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Catalytic co-pyrolysis of lignocellulosic biomass with polymers: a

critical review
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Received 00th January 20xx,

Accepted 00th January 20xx Xuesong Zhang, Hanwu Lei*, Shulin Chen and Joan Wu

Green Chemistry Accepted Manuscript

DOI: 10.1039/x0xx00000x
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Increasing demand for renewable chemicals and fuels requires the exploitation of alternative feedstock to replace
petroleum-derived chemicals and fuels. Lignocellulosic biomass has been considered as the most promising feedstock for
the production of sustainable biofuels. Catalytic fast pyrolysis (CFP) is more amenable to directly convert biomass into high
quality biofuel. However, even in the presence of highly efficient catalyst, CFP of biomass can solely manufacture a low
yield of aromatic hydrocarbon but a high formation of coke. With the addition of hydrogen-rich co-reactant (e.g. waste
plastics) in CFP can significantly improve the yield of aromatics and lower the coke formation. Catalytic co-pyrolysis can
also reduce the disposal of waste polymers (plastics and waste tires) in landfills, solve some environmental issues, and
further increase energy security. In this regard, this article reviews the catalytic co-pyrolysis process from several points of
view, starting from feedstock characteristics and availability, current understanding of the chemistry in non-catalytic co-
pyrolysis, and focusing on the chemistry in catalytic co-pyrolysis of biomass with various categories of polymers. Recent
progress in the experiment studies on both non-catalytic pyrolysis and catalytic co-pyrolysis of biomass with polymers is
also summarized with the emphasis on the liquid yield and quality. In addition, reaction kinetics and several outlooks in
the light of current studies are also presented in the review. Consequently, this review demonstrates both highlights of the
remarkable achievement of catalytic co-pyrolysis and the milestones that necessitate to be garnered in the future.

petroleum resources will be exhausted worldwide after 2042

1. Introduction
Extensive consumption of natural resources (such as coal,
petroleum, and natural gas) is predicted to grow continuously
1 petroleum resources. To control the pollutant emissions and
at the annual rate of 1.6% in the next two decades. The
petroleum fuel resources are recognized as valuable supply of
finite natural energy, because their current depleted rate is
orders of magnitude higher than their corresponding
regeneration cycle. The massive utilization of petroleum fuel
resources results in the augmented emissions of detrimental
pollutants (e.g., sulfur dioxide, oxides of nitrogen, and carbon
dioxide), triggering a sequence of environmental problems.2
Carbon dioxide, as a strong greenhouse gas released into the
atmosphere by means of petroleum resources combustion,
contributes to global warming.3
Despite a variety of environmental issues caused by the
use of petroleum fuel resources, petroleum-derived liquid
hydrocarbons still served as the most attractive and feasible
transportation fuels, including gasoline and jet fuels.4 For
instance, 7 billion barrels of petroleum fuels were consumed
for the United States in 2010; with 71% of petroleum fuels (5.2
billion barrels) went toward satisfying the combined demand
of gasoline, jet, and diesel fuels.5 Within this context, the
without considering projected growth of petroleum fuel
6
consumption.
These issues are inherently attributed to the limitations of
mitigate the energy crisis, several efforts are currently
underway to seek new eco-friendly sources of energy for
3
future generations. The renewable energy sources can not
only dispel the negative environmental impacts, but also
eliminate the dependence on the utilization of petroleum
7
fuels. For the sake of substituting renewable biofuels for
petroleum-derived fuels, the U.S. renewable fuels standard
(RFS2) claimed that the domestic supply of alternative fuels
would increase to 36 billion gallons by 2022; besides the U.S.
Energy Information Administration stated that irrespective of
varied prices of the oil prices the production of renewable
8
biofuels will soar in the next three decades.
In fact, current demand for renewable biofuels originates
from starch-based feedstock, competing with edible
9
resources. Ideally, the second generation biofuels produced
from lignocellulosic biomass (e.g., woods, grass, energy crops,
and agricultural residues) are preferred, which can be
8
compatible with the existing energy infrastructure.
Lignocellulosic biomass has been identified as the most
promising feedstock for the production of renewable
10-15
biofuels. That is because lignocellulosic biomass is the
most abundant and renewable source of non-edible biomass.
A total of 220 billion dry tons of annual lignocellulosic biomass
6
could be sustainably produced worldwide. For the United
States alone, the annual production (1.3 billion dry tons) of
lignocellulosic biomass could offset 50% carbon consumption

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16, 17
for gasoline and diesel. Unlike the petroleum sources,
lignocellulosic biomass has been considered as carbon-neutral
4 22, 31
sources, conducing to mitigating global warming effects. From
the economic point of view, lignocellulosic biomass as the
feedstock to manufacture biofuels is much more inexpensive
than edible biomass (such as corn starch) and crude oil.
Accordingly, the effective implementation of lignocellulosic
biomass necessitates appropriate technologies to produce
3
large amounts of biofuels.
Biochemical conversions of lignocelluloses are not cost-
effective owing to the fact that the biochemical techniques can
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solely take advantages of cellulose and hemicellulose in
19
lignocellulosic biomass. Nevertheless, thermochemical
methods are more energy efficient and cost-effective.
Among the thermochemical routes, pyrolysis is the most cost-
effective and feasible way for the conversion of biomass into
19
liquid fuels. Pyrolysis is the thermal degradation in the
absence of oxygen at 400 – 600 °C. Fast pyrolysis of biomass
could obtain the highest mass yield (up to 80 wt% of dry feed)
of liquid fuel and retain most energy (up to 70%) in the liquid
3, 21
products. Thus the resultant fast pyrolysis oils have been
viewed as the cheapest liquid biofuels and have attracted
crucial attention at research over the past two decades.
Furthermore, fast pyrolysis of biomass is on the verge of
23
commercialization.
Fast pyrolysis oil (usually called bio-oil) is a viscous black
liquid and it is comprised of more than 300 oxygenated
24
compounds. Typical bio-oil primarily consists of three major
categories of compound, i.e., small carbonyl compounds,
sugar-derived compound, and lignin-derived compounds.
The presence of the high water content (15 – 30 wt%) in the
25, 26
bio-oil results in a low heating value. The large amount of
carboxylic acids renders the bio-oil acidic, with low pH values
27
of 2 – 2.5. Under these acidic conditions, the aldehydes and
ketones go through aldol condensation reactions, giving rise to
1 50
a residue (35 – 50 wt% of the primary bio-oil). The instability
of bio-oil is mostly associated with the oxygen-rich nature,
which is recognized as the preliminary difference between
25, 28
hydrocarbon fuels and bio-oils. Due to the detrimental
properties (e.g., low heating value, high acidity, high viscosity,
21, 25
and high reactivity), fast pyrolysis oil cannot be directly
used as transportation fuel in current engine systems.
Improving the quality of pyrolysis oil toward properties
29
identical to those of hydrocarbon fuels is necessary. Efforts
to expel the high oxygen content of bio-oil by certain
21, 24
upgrading technologies is a priority. A variety of studies
have been undertaken to garner this objective through
upgrading techniques. Among them, catalytic deoxygenation
has been widely explored for upgrading bio-oil and dominantly
includes two techniques: catalytic cracking
14
hydrodeoxygenation (HDO). Catalytic cracking is a technique
that involves the introduction of solid acid catalysts to the
pyrolysis process and it is conducted at the atmospheric
30
pressure without the use of hydrogen. However, catalytic
cracking of pyrolysis oil seem to be unpromising due to low
grade products obtained with a low carbon yield and high coke
formation (8 – 25% wt% regarding the feed), resulting in a
6
short catalyst lifetime. HDO of bio-oil adopts petroleum oil
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hydrotreating technique and gain desired hydrocarbons at a
pressurized hydrogen atmosphere by using supported metal
catalysts. This process has been well attracted and
developed owing to the substantial increase in high grade
32
products. Nevertheless, HDO process requires high-severity
18
reaction conditions (such as high reaction temperature and
hydrogen pressure), improving the complexity of the reactor.
High operating cost related to noble catalysts used, significant
catalyst deactivation, and considerable hydrogen consumption
33
are also endured in HDO process.
An alternative way is to directly upgrade pyrolytic volatiles
assisted by a catalyst prior to quenching volatiles to attain bio-
Green Chemistry Accepted Manuscript
oil, which is called catalytic fast pyrolysis (CFP). The in-situ
20
catalytic fast pyrolysis (in-situ CFP) is conducted by combing
the catalyst with biomass; when the catalyst located in a
downstream reactor solely catalyzes the pyrolytic vapors, the
process is referred as ex-situ catalytic fast pyrolysis (ex-situ
34
CFP). CFP is more amenable to directly convert biomass into
high quality bio-oils with enhanced stability, since it can avoid
27, 35-41
polymerization and re-evaporation of pyrolysis oil.
Zeolite-based catalysts (e.g., ZSM-5) have been recognized as
the highest-efficiency catalysts in CFP to produce considerable
22 42-46
petrochemicals (aromatics and olefins). However, even in
the presence of highly efficient catalyst, catalytic pyrolysis of
lignocellulose can solely manufacture low carbon yield (10 –
30%) of aromatic hydrocarbons; large amounts of solid
residues, including both biochar and coke (carbon yields
1, 12, 45, 47, 48
usually above 30%), are achieved in the process. As
aromatics are considered as the high energy-density
25 49
hydrocarbons production, such low carbon yield of aromatic
hydrocarbons from catalytic pyrolysis is not cost-effective to
scale up the process in a biorefinery. Further, the process is
commonly plagued by the high production of coke deposited
on the catalyst because the coke could rapidly deactivate the
catalyst and reduce its lifetime, resulting in the catalytic
process to be impractical. Therefore, these are the huge
challenges in the face of commercializing the catalytic pyrolysis
for the production of renewable petrochemicals.
It is discerned that the petrochemicals with the low carbon
yield of aromatics and high coke formation are mainly
associated with the oxygen-enriched intrinsic nature and
1, 47, 51
hydrogen deficiency of lignocellulosic biomass. In
addition, the hydrogen to carbon effective (H/Ceff) ratio plays a
significant role in coke formation and converting efficiency of
52-54
biomass into advanced biofuels . Thus the hydrogen-
deficient (H/Ceff usually less than 0.3) biomass produces low
carbon yields of petrochemicals and large formation of coke
when the lignocellulose were transformed over zeolite
42, 44
catalysts. In order to improve the carbon efficiency of
and aromatics and minimize the coke formation, it is reasonable
that the incorporation of high H/Ceff ratio co-reactants with
lignocellulosic biomass in the catalytic pyrolysis could help
mitigate these issues. It is observed that co-feeding of
lignocellulosic biomass with hydrogen-rich feedstock in the
catalytic pyrolysis can modify the reaction mechanism of
oxygen
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Fig. 1 Schematic representation of lignocellulosic biomass with the structure of cellulose, hemicellulose and lignin.
removal by substituting decarbonylation and decarboxylation
48, 53, 55, 56
with dehydration.
Synthetic polymers (e.g., waste plastics) represent a
cheaper and abundant hydrogen sources, which can be used
to improve carbon efficiency of aromatics and lower the coke
42, 44, 47, 51, 57
formation in the catalytic co-pyrolysis. Tremendous
quantities of synthetic polymers waste are generated each
year worldwide. For instance, the global generation of waste
electrical and electronic equipment (WEEE) is close to 40
58
million tons per year. These polymers waste cause serious
damage toward the environment and have detrimental impact
44
on human health. Yet the current fate to manage polymers
waste is generally limited by means of landfills and
59, 60
incineration. The state of the art on tertiary recycling
technologies like CFP offers a promising alternative to valorize
61, 62
polymers waste. In the light of these premises, the co-
feeding of lignocellulosic biomass with polymers waste in
catalytic pyrolysis is remarkably beneficial for the environment
and energy recapture.
Numerous comprehensive reviews have reported CFP of
lignocellulosic biomass and CFP of polymers individually. Some
recent reviews have also published fast co-pyrolysis technique
6, 63
to improve oil quality. To the best of our knowledge,
catalytic co-pyrolysis technique of lignocellulosic biomass and
polymers have not been reviewed. This study is the first review
that aims to demonstrate the technique regarding catalytic co-
pyrolysis of lignocellulosic biomass with polymers. This review
will start with the availability of synthetic polymers that can be
supplied for catalytic co-pyrolysis, giving special attention to
the utilization of plastics. Moreover, fundamental chemistry
and kinetics of the reactions in catalytic co-pyrolysis is also
discussed. With the consideration of polymers contribution in
catalytic co-pyrolysis, this review will focus primarily upon
recent advances on the improvement of products quality and
liquid yield for the sake of future commercialization.
2. Feedstock for the co-pyrolysis process
In general, lignocellulosic biomass can be broadly categorized
3
into virgin biomass, waste biomass and energy crops. Virgin
biomass is made up of all naturally occurring terrestrial plants,
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i.e., trees, bushes and grass. Waste biomass is generated as a
by-product from industrial sectors, including agricultural (corn
stover, sugarcane bagasse, straw etc.), forestry (saw mill and
64
paper mill discards). Energy crops are commonly advocated
for the production of second generation biofuels, such as
64
switchgrass and miscanthus.
As for the co-reactant of plastics, synthetic plastics are
mainly classified into two categories: industrial and municipal.
Industrial plastics are tended to more homogeneous and
contamination-free; whilst, municipal polymers are more
65
heterogeneous and have extraneous materials. Municipal
plastics are primarily composed of low-density polyethylene
(LDPE), high-density polyethylene (HDPE), poly(ethylene
terephthalate) (PET), polypropylene (PP), polystyrene(PS),
66
polyvinyl alcohol (PVA) and poly(vinylchloride) (PVC). PVC is
the second most used plastics (after polyethylene) due to its
ow price and durability, and it can be found in drastic
67
quantities in municipal solid waste (MSW). In addition, other
synthetic polymers can also be introduced in catalytic co-
pyrolysis, such as waste tires and waste electrical and
electronic equipment (WEEE). Waste tires from automotive
vehicles are another feedstock with properties similar to those
68
of plastics. However, WEEE is significantly distinct from other
industrial and municipal plastics; both valuable and hazardous
69
materials are included in WEEE.
2.1 Components of lignocellulosic biomass
A fundamental understanding regarding the characteristics of
lignocellulosic biomass is essential to rationally illustrate the
mechanisms of catalytic co-pyrolysis. In this respect, we will
summarize the properties of lignocellulosic biomass in this
section. Lignocellulosic biomass is a complicated biopolymer,
primarily consisting of cellulose, hemicellulose, and lignin (Fig.
70, 71
1). Typically, lignocellulosic biomass contains 40 - 50 wt%
of cellulose, 15 – 30 wt% of hemicellulose, and 15 – 30 wt% of
9
lignin. Cellulose is a linear polysaccharide polymer of glucose
strongly linked by β-1, 4-glycoside linkage, acting as the
framework of lignocellulose cell walls (Fig. 1).
72
A variety of
hydroxyl groups are also presented in cellulose chains, giving
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Table 1 Typical compositions used in tire manufacturing in USA and Europe (percentages of the gross weight of the finished tire).
Compositions (wt%) Truck tire
USA Europe
Nature rubber 27 30
Synthetic rubber 14 15
Carbon black 28 20
Steel 14 – 15 25
Othersa 16 – 17 10
a
Fabric, fillers, accelerators, antiozonants, etc.
75
rise to the formation of hydrogen bonds. Cellulose is made
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up of regions: crystalline (high crystallinity) and amorphous
76
(low crystallinity) regions. Moreover, cellulose microfibrils
are linked to each other by hemicellulose and/or pectin and
75
covered by lignin.
In contrast to cellulose, hemicellulose is more structurally
amorphous, random, and has a heterogeneous composition.
The structure of hemicellulose contains various pentoses
(xylose and arabinose), hexoses (glucose, galactose, mannose,
rhamnose, and fucose), and uronic acids (glucuronic acid,
9 82, 83
methyl glucuronic acid, and galacturonic acid). Short and
branched chains of hemicellulose is conducive to building a
network with cellulose microfibrils and lignin, rendering the
75
lignocellulose matrix extremely rigid. Lignin is the second
abundant organic composition in nature, which is water
insoluble and optically inert. It is a complex aromatic and
hydrophobic amorphous biopolymer of propyl-phenol
77
groups. It is constructed of three basic phenol-containing
components: p-coumaryl, coniferyl, and sinapyl alcohols (Fig.
78
1). These units are bound together by C–O (β-O-4, α-O-4, and
79
4-O-5 linkage) and C–C (β-5, 5-5, β-1, β–β linkage). Lignin also
plays a crucial role in the cross-linking between cellulose and
hemicellulose to garner a rigid three-dimensional structure of
the cell walls. In addition, lignin stores approximately 40% of
energy of lignocellulosic biomass because of its high carbon
78
content. In general, softwood contains more lignin fraction
75
than hardwood and most agricultural residues.
2.2 Selection of synthetic polymers for co-pyrolysis
Although petroleum sources are commonly used as
transportation fuels, which is the end product; some
petroleum sources can still be stored in other forms, including
6 66
plastics and tires. Since a proportion of plastics and tires
cannot be recycled, the challenges of waste polymers
management and extraordinary energy demand can be
simultaneously solved by conversions of waste polymers to
fuels. The waste plastics and tires can be considered as an
option for co-pyrolysis process. Plastics are largely synthetic
polymers derived from petroleum resources. Due to the rich
nature of hydrogen and carbon, plastics are the potential
alternative for the production of hydrocarbon fuels to mitigate
the energy crisis. In particular, the calorific value of liquid
product from fast pyrolysis of plastics could reach to 40
32
MJ/kg; the liquid product is also relatively clean and obtains
80
fuel properties similar to petroleum fuels. Besides, the
addition of plastics in the pyrolysis of lignocellulosic biomass
can further contribute to the heating value through positive
81
synergy.
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73, 74
Passenger car tire
USA Europe
14 22
27 23
28 28
14 – 15 13
16 – 17 14
Tires are another polymers with comparable characteristics
with plastics. Tires is usually composed of these elements:
Green Chemistry Accepted Manuscript
74
liner, plies, bead heel, sidewall, and tread. The compositions
are significantly distant in tires due to their numerous
applications. Fundamental materials make up of tires, i.e.,
74
nature rubber, synthetic rubber, carbon black, and steel.
Table 1 gives the basic material compositions of two tires
(truck tire and passenger car tire) in USA and Europe,
respectively. Pyrolysis of tires is viewed as the most promising
route for the waste tires management, particularly in a large
scale. The technique can be capable of minimizing the
release of contaminates and pollutants, which is more
82
respectful than incineration. Pyrolysis of tires alone can
68
achieve the liquid yield up to 75 wt%, and the heating value
84
of pyrolysis oil can reach up to 44 MJ/kg. In this regard, the
waste tires can be employed during the co-pyrolysis process to
have a synergistic effect at product qualities and liquid yield.
Because the studies regarding the co-pyrolysis of
6
lignocellulosic biomass with waste tires are currently limited,
more efforts should be made to show a clear overview in the
co-pyrolysis of lignocellulosic biomass with waste tires.
2.2.1 Availability of plastics
The availability of plastics as a co-reactant during co-pyrolysis
6
is sufficient for the future sustainability of fuels production.
Plastics are abundantly used in normal life worldwide. For
instance, the total consumption of plastics in Western Europe
was estimated at 33.4 million tons in 1996; while it was
augmented to 48.3 million tons in 2007 by an average
66
increasing rate of 4% per year. After its initial use, less than
85
10% of plastics can be recycled, and the high estimation of
over 60% of solid waste plastics is discarded in open space or
86
landfills worldwide. As reported by World Bank, waste
plastics occupy 8 – 12% of municipal solid waste (MSW)
produced in different counties. It was also evaluated that the
proportion of global waste plastics in MSW will increase to 9 –
13% in 2025. Nevertheless, the disposal of waste plastics
become a major concern in light of damages towards the
environment. Accordingly, the appreciable availability of waste
plastics offers the future use of this polymers in co-pyrolysis
process to minimize the disposal of valuable plastics in
landfills.
2.2.2 Availability of waste tires
It was found that around 2.8 billion tires were manufactured in
87
2012, which correspond to 17 million tons. There tires will
83
eventually categorized or considered as waste tires. In
particular, the considerable tires consumption in Asia and
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Fig. 2 The schematic diagram of lignocellulosic biomass and polymers in the co-pyrolysis system.
Oceania will make these regions become the dominant waste
tires sources in next two decades. Taking China for example,
the waste tires in 2010 was 5.2 million tons, accounting for 60
88
wt% of the global waste tires. Waste tires have a vital
influence in the increase of urban waste stream and threaten
the environment. In general, approximately 64% of waste tires
are disposed in landfills or illegally dumped or stockpiled; no
89
more than 13% of waste tires can be recycled. Since waste
tires are not readily degraded in landfills, yet easily float to the
top over time owing to trapped gases. As a result, the waste
6
tires break landfill covers. Incineration of waste tires liberate
the toxic gas, containing carcinogenic and mutagenic
chemicals. Within the waste refinery concept, the valorization
of waste tires is a preliminary driving force for research and
innovation. Herein, pyrolysis technique have been observed as
a technically feasible way to tackle waste tires and gain
valuable products.
3. Co-pyrolysis chemistry
3.1 Chemistry of non-catalytic co-pyrolysis
The chemistry and steps of co-pyrolysis and normal pyrolysis
are almost the similar. Basically the co-pyrolysis is also
required to be operated in a closed reactor system in the
90
absence of oxygen at 400 – 600 °C. As such, there are three
fundamental steps conducted in the co-pyrolysis system:
samples preparation, co-pyrolysis, and liquid condensation.
63
In order to mimic the co-pyrolysis process, Fig. 2 represents
the schematic diagram of the co-pyrolysis system. In the step
of samples preparation, lignocellulosic biomass and polymers
should be dried to remove the physical moisture and then
ground to the suitable size (usually 2 – 3 mm) for the co-
pyrolysis reactor. In the co-pyrolysis step, inert gas (N2) is
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commonly used to get rid of oxygen in the system and also
facilitate sweeping pyrolytic volatiles to condensers, avoiding
29
secondary reactions and maximizing liquid yield. It was noted
that reaction temperature subjected to the range of 400 – 600
6
°C can garner over 45 wt% of liquid yield. In the condensation
system, pyrolytic vapors generated from co-pyrolysis process
pass through the condensation unit to rapidly obtain the liquid
product.
In contrast to conventional pyrolysis affected by several
parameters (e.g, types of feedstock, heating rate, and reaction
temperature), co-pyrolysis performance is influenced by a
special parameter, namely, the ratio of co-reactants. It was
discerned that the biomass to plastics ratio in the co-pyrolysis
91
process have a significant influence in liquid production.
Furthermore, the effect of biomass to plastics ratio on liquid
yield was found to be more drastic than other effective
92
parameters (temperature and reaction time). The type of co-
pyrolysis reactor chosen also has an important effect on
product yield and distribution. Most studies currently carry out
the co-pyrolysis in a fixed-bed reactor.
69, 93, 94
As the extent of
contact between lignocellulosic biomass and polymers is the
key point to achieve the synergistic effect, the co-pyrolysis is
more likely to be performed in a fixed-bed reactor rather than
95
a fluidized-bed reactor. In comparison with the fixed-bed
reactor, the auger reactor was proved to more effective for
liquid yield than fixed-bed reactor by implementing the co-
pyrolysis of lignocellulosic biomass with waste tires under the
96
same condition. Meanwhile, the characteristics (total acid
number, density, pH value, calorific value, and oxygen content)
of liquid product obtained from auger reactor are superior to
those from fixed-bed reactor.
3.1.1 Importance of non-catalytic co-pyrolysis
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It is well known that simplicity and effectiveness are two key
criteria to develop a technique for the production of liquid
6 102
fuel. Co-pyrolysis is an ideal process by using different
materials as feedstock, which satisfies the aforementioned
criteria. There are a couple of studies showing that co-pyrolysis
of lignocellulosic biomass with polymers have successfully
44, 81, 97
improved product yield and liquid quality. Unlike
catalytic cracking and HDO, co-pyrolysis technique has a
promising application for industrial utilization due to its
attractive outcomes. As mentioned above, the advantages of
the technique mainly depend upon the synergistic effect
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between the reactions of co-reactants during the co-pyrolysis
process. It was manifested that the yield of liquid product with
improved properties, which is derived from the co-pyrolysis of
biomass with plastics, was much higher than that from
32
pyrolysis of biomass alone.
Due to the difference of pyrolysis oil polar nature from
biomass and plastics or waste tires, an unstable form (phase
81
separation) would emerge in the mixed pyrolysis oils. If
biomass and plastics (or waste tires) are pyrolyzed individually,
more energy input is required and the operating cost for liquid
6 103
production will remarkably augment. It was reported that the
interaction of radicals in the co-pyrolysis system could
contribute to the stability of pyrolysis oils, avoiding the
96
phenomenon of phase separation. Therefore the co-pyrolysis
technique is thought to be more reliable for the production of
homogenous pyrolysis oil instead of just blending pyrolysis
oils. Furthermore, it is discerned that polymers waste (waste
plastic and tires) can be appreciably consumed through co-
pyrolysis technique, which can reduce the polymers waste in
landfills, save costs for waste treatment and solve a lot of
98
environmental issues. Hence the co-pyrolysis technique is a
promising alternative for waste management and enhancing
energy security. From an economic point of view, the co-
pyrolysis technique of biomass and polymers is more
99
profitable than pyrolysis of biomass alone; it is a potential
option for the conversion of biomass and polymers waste into
liquid fuels in an industrial scale.
3.1.2 Mechanism of non-catalytic co-pyrolysis
The synergistic effect between biomass and polymers in the
co-pyrolysis process is the main factor for the improvement in
oil quantity and quality. The mechanism corresponding to co-
pyrolysis of lignocellulosic biomass and polymers (plastics and
waste tires) has been widely investigated by a number of
researchers. The mechanism of radical interactions in the co-
pyrolysis reaction contributing to synergistic effect is mostly
proposed. As for co-pyrolysis of lignocellulosic biomass with
plastics, the thermal decomposition mechanisms of biomass
and plastics are relatively different. It was noteworthy that the
pyrolysis of biomass undergoes a sequence of exothermic and
6
endothermic reactions; whilst the thermal degradation of
plastics takes place through a series of radical mechanisms
93
(initiation, propagation, and termination). Since the thermal
stability of biomass is lower than that of plastics during the co-
pyrolysis process, the free radicals from the degradation of
biomass could promote the decomposition of plastics-derived
100, 101
macromolecules. In detail, free radicals generated from
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the degradation of poplar wood participated in the
depolymerization of HDPE in the co-pyrolysis process by using
a micro-scale reactor, yielding more light alkanes. To
summarize, several free radicals could be induced in co-
pyrolysis of biomass with plastics, including initiation,
secondary radicals formation, and termination by radicals
93
disproportionation or recombination. Herein, secondary
radicals formation involves depolymerization, hydrogen
transfer reactions, monomers formation, intermolecular
hydrogen transfer (generation of paraffin and dienes), and
isomerization through vinyl groups.
For the co-pyrolysis of lignocellulosic biomass with waste
69
Green Chemistry Accepted Manuscript
electrical and electronic equipment (WEEE), the hydrogen
donors mechanism was demonstrated as the major factor that
impacts the synergistic effect, playing an important role in the
increase of liquid yield. As lignocellulosic biomass has a much
higher H/C ratio than WEEE, the significantly high hydrogen
content in lignocellulosic biomass could serve as a hydrogen
donor toward WEEE in the co-pyrolysis process. In addition,
water evolved from biomass pyrolysis could also act as a
reactive compound to accelerate further cracking of WEEE tar,
thereby promoting the liquid yield.
During the co-pyrolysis of lignocellulosic biomass with
polyethylene (PE), it is mostly likely that hydrogen abstraction
by biomass-derived oxygenates and reactive free radicals could
facilitate the scission of polymer chains and their
104, 105
derivatives. Comparing with cellulose and hemicellulose,
lignin is the major source of reactive free radicals in the fast
106, 107
pyrolysis of biomass. Therefore, lignin could strongly
influence the decomposition of PE when biomass and PE are
co-pyrolyzed. It was also obtained that the formation of char,
CO, and CO2 were all inhibited during the co-pyrolysis
51
process. These outcomes imply that hydrogen transfers from
PE toward biomass-derived oxygenates could mitigate
polymerization and cross-linking reactions for the formation of
char, and also suppress decarbonylation and decarboxylation
reactions to generate CO and CO2.
Besides the mechanism with respect to co-pyrolysis of
cellulose with polypropylene (PP) was also investigated by
108
using Py-GC/MS and Py-FTIR. During the co-pyrolysis
process, a large amount of alcohols was obtained at 600 °C. It
was indicted that the vapor phase interactions including
cellulose-derived hydroxyl radical abstraction and PP-derived
chain-end scission, β-scission and intramolecular hydrogen
108
abstraction were favored at this condition. It was also
observed that the free radicals, especially hydroxyl radical
formation from the decomposition of cellulose was induced by
the presence of PP; whereas, with the absence of PP, the
degradation of cellulose predominantly involves concerted
109, 110
reactions. Based on these observations, the plausible
mechanism regarding the formation of alcohols during co-
pyrolysis of cellulose and PP is depicted in Fig. 3. In addition, it
was noticeable that PP-derived methyl abstraction and
subsequent hydrogen transfer was a preliminary route for the
generation of less branched linear alcohols; whilst the
formation of long branched alcohols could
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Fig. 3 Proposed mechanism for the production of alcohols during co-pyrolysis of cellulose and polypropylene.
also take place via free radical recombination of an end-chain
111, 112
with mid-chain hydrocarbon radicals.
3.2 Chemistry of catalytic co-pyrolysis
In terms of chemistry and steps for catalytic co-pyrolysis, they
are comparable with those of catalytic fast pyrolysis (CFP).
Basically, catalytic co-pyrolysis is also necessitated to be
carried out in the presence of a catalyst. The presence of a
catalyst could enhance the targeted product yield and
113
selectivity in CFP. Among the widely used catalysts, zeolite-
based catalysts are particularly attractive due to their
35
performances in the increase of aromatic yield. Likewise,
zeolite-based catalysts (e.g., HZSM-5) have been mainly
applied as the catalysts in the catalytic co-pyrolysis of
42, 43, 53, 57, 114
lignocellulosic biomass with plastics. However,
most previous studies regarding catalytic co-pyrolysis of
biomass with plastics have been usually performed by using a
high catalyst to feed ratios (e.g. 10:1) to maximize
petrochemical yields. The co-feeding of biomass and plastics
are commonly subject to catalytic pyrolysis process at the
43, 51, 53
catalytic temperature of 400 – 700 °C.
It is noticed that current catalytic co-feed catalytic pyrolysis
of biomass and plastics are frequently conducted in fixed-bed
6
reactors. By contrast, the continuous feeding fluidized-bed
44, 54
reactor and the tandem micro-pyrolyzer reactor with
51
downstream packed-bed reactor have been applied in the
catalytic co-pyrolysis of biomass with plastics as well. In
addition, a couple of groups implemented the co-feeding of
biomass with plastics in CFP by using micro-pyrolysis
42, 43, 53, 57, 114
reactors. There was a positive synergy between
biomass and plastics in the augment of aromatic yield and
solid residues reduction. For the slow catalytic co-pyrolysis
conducted in abovementioned studies, it is detrimental for
biomass conversions; nonetheless, the extended reaction time
not only enhances the degradation of polymers to small
molecular, but also promotes the catalytic reforming of
biomass-derived oxygenates and polymers-derived olefins to
yield aromatic production.
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108
3.2.1 Importance of catalytic co-pyrolysis
Petrochemicals (aromatics and olefins) produced from
petroleum sources are crucial feedstock for the manufacture
of valuable products, such as solvents, synthetic fibers,
36
plastics, and pharmaceuticals. Meanwhile, benzene, toluene,
and xylenes (BTX) with the light olefins (ethylene, propylene,
and butadiene) are the most important preliminary
42
petrochemicals. As stated above, CFP of biomass over
zeolite-based catalysts is a promising technique that can
convert biomass directly into high-value added aromatics and
olefins. Yet many issues accompanied with valuable products
have also been encountered. For example, coke is rapidly and
dramatically formed in CFP and deposits on the catalyst, block
the micropores and consequently leads to the deactivation of
115
the catalysts. It is worth noting that a relatively low carbon
yield (usually 10 – 30%) of aromatics were observed in CFP. In
the liquid products, a large amount of aromatics belong to
polycyclic aromatic hydrocarbons (PAH). The high
concentration of PAH limit the utilization of liquid product
since PAH are well known to be carcinogenic, mutagenic and
116
environmentally unfriendly.
To increase the petrochemicals yield, improve the aromatic
selectivity, and minimize the coke formation, co-feed catalytic
pyrolysis of biomass with hydrogen-enriched feedstock (such
as plastics and alcohols) is a novel and feasible route to solve
these problems. It was reported that the co-feeding of
117 38
alcohols and light olefins (ethylene and propylene) in the
catalytic pyrolysis of biomass could enhance the yield of
petrochemicals over ZSM-5 catalyst. Plastics as the ideal co-
reactant are usually added in the catalytic pyrolysis of biomass.
Since waste plastics can cause serious environmental issues
and threaten human health, the utilization of waste plastics in
catalytic co-pyrolysis process is not only beneficial for the
reduction of pollutants, but also in favor of energy recovery.
Numerous studies reveal that the co-feed catalytic pyrolysis of
biomass with plastics could enhance petrochemicals yield,
improve the selectivity of
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n
tio ion
ra at
h yd rad
g
De de
al
r m
e
Th
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Green Chemistry Accepted Manuscript

Fig. 4 Schematic presentation for the productions of aromatics from catalytic co-pyrolysis of cellulose with LDPE in the presence of ZSM-
47, 57
5 catalyst.

desired aromatic compounds, and reduce the coke
43, 47, 53, 54, 57, 118, 119
formation. These results evidence that there
is a positive synergetic effect between biomass and plastics in
the co-feed catalytic pyrolysis process. According to state of
the art research, most studies reported the results of
hydrocarbon plastics (e.g., PE, PP, and PS) mixed with biomass
in catalytic co-pyrolysis using HZSM-5 as the catalyst, and
observed a positive synergy in the improvement of aromatic
yield and selectivity and the reduction of coke generation.
Therefore, catalytic co-pyrolysis of lignocellulosic biomass with
polymers should be advocated as the economically feasible
route for the utilization of both lignocellulosic biomass and
polymers in the future.
3.2.2 Mechanism of catalytic co-pyrolysis
The reaction mechanism of catalytic co-pyrolysis can be
relatively complex due to various types of materials introduced
53
in the process. The catalytic co-pyrolysis mechanism can be
classified into two categories: the mechanism among biomass
and polymers during thermal degradation, and the mechanism
51
among the pyrolytic volatiles at the catalytic sites. For
catalytic co-pyrolysis of biomass and plastics model
compounds, it was observed that there was a positive synergy
for aromatic production in the co-feeding of cellulose and
57
LDPE in CFP. The phenomenon was mainly attributed to the
interactions between cellulose-derived oxygenates and LDPE-
42
derived olefins. It was discerned that cellulose-derived
oxygenates could react with LDPE-derived light olefins in the
42
presence of ZSM-5 catalyst. Fig. 4 depicts the reaction
pathway for the conversion of cellulose and LDPE into
aromatic production in the catalytic co-pyrolysis over ZSM-5
catalyst.

O O
Dehydration
Cracking
OH Decarbonylation
Decarbonxylation O OH
O
O O
n OH
tio ion
d ra dat OH
hy gra
De de
al
e rm Decarbonylation
Cellulose Th Dehydration
HO Decarbonxylation
HO O
O
O O Alkylation
O
HO OH HO OH n H2C C CH2

Alkylation

Thermal decomposition

Catlalytic cracking
n
PS
Fig. 5 Possible reaction scheme regarding the formations of naphthalene and indene from catalytic co-pyrolysis of cellulose with PS by
52, 53
using HZSM-5 as the catalyst.

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Fig. 6 Proposed reaction pathways for the conversions of lignocellulosic biomass and plastics in co-feed catalytic pyrolysis.120, 121
It can be seen that furan compound (e.g., furan and
furfural) derived from cellulose could react with light olefins
(ethylene and propylene) evolved from LDPE to form
aromatics (e.g, BTX) through Diels-Alder reactions followed by
dehydration reaction. In the catalytic co-pyrolysis, furan
compounds and light olefins serves as the diene and
52, 55, 122
dienophile compounds, respectively. The Diels-Alder
reactions followed by dehydration reaction can enhance the
aromatics yield and reduce the coke formation via
42, 117
polymerization of furans. It is also evidenced that LDPE-
derived hydrocarbons (such as olefins and alkanes) can also act
as the hydrogen donor for cellulose-derived oxygenates,
resulting in the decrease of coke formation in the zeolite-
123, 124
catalyzed conversions.
Comparing to PE and PP, PS cannot produce enough small
olefins for biomass-derived oxygenates to produce aromatics
in the catalytic co-pyrolysis. The interactions among biomass
and plastics proceeds in a different manner in the co-feed
catalytic pyrolysis. Generally, naphthalenes can be produced
through the Diels-Alder condensation, dehydration of benzene
and furans, and a cascade of alkylation among toluene and
52
intermediate allene. Based on the mechanism of
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naphthalenes formation in CFP, possible reaction scheme for
the formations of naphthalene and indene from catalytic co-
pyrolysis of cellulose with PS by using HZSM-5 as the catalyst is
sketched in Fig. 5. Styrene as a major product from the
thermal degradation of PS could undergo the successive
alkylation with allene derived from furans to form indene in
52
the presence of the catalyst. As such, the indene produced
could further react with allene, giving rise to the generation of
52
naphthalene.
The resultant observations are manifested that the
reaction pathway was much more complicated than those
proposed previously when the real lignocellulosic biomass with
42, 43, 57
plastics are performed in catalytic co-pyrolysis.
According to related results from catalytic pyrolysis of
37, 39, 41, 45, 46, 125, 126 60, 62, 127-130
biomass and plastics alone, and
43, 47, 51, 53, 57, 119
catalytic co-pyrolysis of biomass with plastics;
120
Zhang et al. demonstrated the overall reactions network
(co-feed catalytic pyrolysis of practical lignocellulosic biomass
with hydrocarbon-based plastics over zeolite-based catalysts)
as outlined in Fig. 6. For the dominant route in lignocellulosic
biomass, cellulose could go through a sequence of
dehydration, decarbonylation, and decarboxylation to
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45, 125
generate furan compounds in the thermal degradation.
As such, it is evidenced that hemicellulose was likely to
131
depolymerized into furan compounds, which is comparable
125
with the result of cellulose degradation. Unlike cellulose and
hemicellulose, lignin in lignocellulosic biomass was primarily
decomposed into phenolic compounds. As for the degradation
of plastics in another route, thermal degradation of plastics
usually occurred through two mechanisms (random scission
132, 133
and chain-end scission). The two abovementioned
mechanisms took place simultaneously, generating free
134
radicals together with the long carbon chains. At the same
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are stabilized and the polymerization reaction for the
51, 120
generation of coke could be inhibited. Nonetheless, the
issue of coke formation in the catalytic co-pyrolysis can only be
51, 57, 120, 121
mitigated, rather than being completely eliminated.
It is reinforced by the mechanisms that the biomass-derived
oxygenates and plastics-derived olefins can partially undergo
polymerization reactions to form coke as well.
4. Practical non-catalytic co-pyrolysis of
lignocellulosic biomass with synthetic polymers

time, the radical fragments could be transformed into straight

134 4.1 Plastics as the co-reactant in non-catalytic co-pyrolysis

Green Chemistry Accepted Manuscript

chain hydrocarbons via hydrogen transfer reactions. The
To produce high-grade pyrolysis oil, many efforts have been
hydrogen from the thermal degradation of plastics was
made to explore non-catalytic co-pyrolysis technique by a
provided for biomass-derived oxygenates that acted as the
number of researchers. Most studies regarding non-catalytic
strong acceptor, suppressing the char formation.
co-pyrolysis have chosen plastics as the addition with biomass
The waxes with large molecule weigh from the thermal
for the sake of improving the liquid quantity and quality. The
degradation of plastics can predominantly undergo catalytic
summary of representative studies on non-catalytic co-
cracking over zeolite-based catalysts through two
132, 135 pyrolysis of biomass with plastics is given in Table 2. Based on
carbocationic mechanisms, giving rise to light olefins. On
the categories of plastics, PE are commonly co-fed with
the other hand, a small partial amount of waxes may directly
biomass in the pyrolysis to investigate their synergy in the
suffer the catalytic cracking and oligomerization reaction to
61, 62 process. Pinto et al.138 aimed to valorize rice crop wastes (rice
form liquid alkanes and olefins. The light olefins can
husk and straw) by co-feeding with PE in the process to
thereafter react with furan compounds by the Diels–Alder
produce liquid fuel. The plastic to biomass ratio of 4:1 was the
reaction followed by the dehydration reaction to form
optimal one for both rice husk and straw to maximize the
aromatic hydrocarbons. Meanwhile, these plastics-derived
liquid yields. It was found that the co-pyrolysis of rice husk
olefins could individually subject to cyclization, aromatization,
with PE favored the formation of liquid product, while the
and oligomerization reactions to obtain aromatic
51 utilization of rice straw was in favor of gaseous and solid
hydrocarbons. Likewise, these furan compounds could
products. The liquid products from co-pyrolysis were
individually go through decarbonylation, aromatization, and
composed of a complex mixture of compounds, most of which
oligomerization reactions inside zeolite catalysts pores to form
are aliphatic hydrocarbons (alkanes and alkenes). The authors
aromatic hydrocarbons as well. As previously reported, it is
also pointed out that the recovery of biomass and waste
confirmed that the interaction via the hydrocarbon pool
plastics through co-pyrolysis provided a promising option for
mechanism could be found in addition to Diels–Alder
42 the economic valorization of the wastes.
reaction. Since the carbon yield of liquid organics
Moreover, almond shell was co-pyrolyzed with HDPE at
significantly increased and the coke yield dramatically
500 °C in a fixed bed reactor to evaluate the synergistic effect
decreased, the Diels–Alder reaction was the dominant reaction
on the product yield and composition.93 The maximum liquid
pathway during the co-feed catalytic pyrolysis in comparison
yield from co-pyrolysis was 50.88 wt%, which was strongly
with the hydrocarbon pool mechanism. In addition, phenolic
enhanced. For the properties of the liquid product from co-
compounds were individually converted into aromatic
pyrolysis, the optimal one had higher carbon (26% higher) and
hydrocarbons over zeolite catalysts by the dehydration,
45, 136 hydrogen contents (78% higher), a low oxygen content (86%
cracking, and oligomerization reactions.
less), as well as a higher heating value (38% higher) than those
During the catalytic pyrolysis of lignocellulosic biomass
of bio-oil from the pyrolysis of biomass almond shell alone.
individually, the hydrogen-deficient oxygenates from the
Aliphatic hydrocarbons were dominant in the liquid product
thermal decomposition of cellulose and hemicellulose could
from co-pyrolysis of almond shell with HDPE. In addition, co-
readily polymerize and react with phenolic compounds to
45, 125 pyrolysis of biomass (red oak) and HDPE was also performed in
generate coke; likewise, most phenolic compounds from
a continuous fluidized reactor.81 It was found that when the
the thermal degradation of lignin are too large to enter zeolite
137 pyrolysis temperature was elevated up to 625 °C, the
pores; these phenolic compounds are relatively unstable
maximum liquid yield (57.6 wt%) from co-pyrolysis was
and could easily deposit on the catalyst surface, and further
obtained. There was also a positive synergy at the HHV of
polymerize or react with small-molecule oxygenates to form
51 liquid product from co-pyrolysis, reaching up to 36.66 MJ/kg. It
coke. On the other hand, the resultant furan compounds
was also observed that the co-feeding of HDPE limited the char
could react with plastics-derived olefins via Diels-Alder
formation but improved the HHV of the resultant char.
reactions rather than polymerization reactions, thereby
As for the studies regarding co-pyrolysis of biomass with
reducing the coke formation during the catalytic co-pyrolysis
42, 52 PP, PP co-fed with cellulose via fast pyrolysis was conducted in
of lignocellulosic biomass with plastics. As such, lignin-
a Pyroprobe® reactor to investigate the production of high
derived phenolic compounds could abstract hydrogen atoms
quality biofuel intermediates.108 The effects of cellulose to PP
from evolutions of plastics; hence these phenolic compounds
mass

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Table 2 Summary of studies on non-catalytic co-pyrolysis of biomass with plastics.

Type of materials Reaction conditions Results
Ref.
Biomass plastics Plastics Temp. Reactor Liquid yield Product quality, calorific value
to (°C) (wt%) (MJ/kg) and oxygen content (wt%)
biomass
ratio
Rice husk PE 4:1 – 1:1 350 – Parr reactor Max. ~ 72 HHV = Max. ~ 27, dominant alkanes 138
430 and alkenes
Rice straw 4:1 350 – Max. ~ 66 HHV = Max. ~ 32, dominant alkanes
430 and alkenes
a 139
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Pine cone LDPE 1:1 500 Semi-batch 63.9 GCV = 46.33, O = 5.61
glass reactor

Green Chemistry Accepted Manuscript

a
PP 1:1 500 64.1 GCV = 45.58, O = 1.55
PS 1:1 500 69.7 GCVa = 46.43, O = 6.54
b 93
Almond shell HDPE 1:2 – 2:1 500 Fixed bed Max. 50.88 38% increase of HHV , O = 3.74 ,
reactor mainly aliphatic hydrocarbons
Red oak HDPE 1:4 525 – Continuous Max. 57.6 HHV = Max.36.66, O = Min.13.77, 81
675 fluidized bed mainly carbohydrate derivatives
reactor
b b 94
Potato skin HDPE 1:2 – 2:1 400 – Stainless steel Max. 50.88 HHV = 45.61 , O = 3.69 , mainly
550 retort aliphatic alkenes
Cellulose PP 1:3 – 3:1 500 – Pyroprobe NA HHV = Max. 41, Max. 45% of 108
800 reactor hydrocarbons, Max. 36% of alcohols
Alder wood PP 1:9 – 1:1 500 – Steel batch Max. 73.2 NA 140
700 retort
Pine wood 1:9 – 1:1 500 – Max. 70.6 NA
700
Pinewood PP 1:3 – 1:1 450 Pyrex reactor Max. 61 O = Min. 0.81, mainly aliphatic 141
sawdust hydrocarbons
PS 1:3 – 1:1 450 Max. 67 O = Min. 1.60, mainly aromatic
hydrocarbons
Cellulose PS 1:3 – 3:1 500 Pyrex reactor Max. 80.10 Dominant aromatic hydrocarbons 142

Palm Shell PS 1:1 500 Fixed bed 61.63 HHV = 38.01, O = 7.82, dominant 143
reactor aromatic hydrocarbons
Cellulose PVC 1:1 800 Fixed bed ~ 45 Most PAH decreased, HCl decreased 144
reactor
Xylan 1:1 800 ~ 40 Several PAH decreased, HCl
decreased
Lignin 1:1 800 ~ 37 Several PAH decreased, HCl yield
decreased to 9.3 wt%,
Fir sawdust WEEE 1:4 – 2:1 450 – Fixed bed Max. 62.3 Dominant aromatic hydrocarbons, 69
600 reactor no PBDD/Fs detected
Willow PLA 1:10 – 450 Semi- Max. 55.53 HHV = Max. 19.70 145
2:1 continuous
home-built
reactor
Willow PHB 1:7 – 1:1 450 Semi- Max. 64.24 HHV = Max. 20.22 146
continuous
home-built
reactor
a b
Gross calorific value; at plastic to biomass ratio of 1:1

ratio, temperature, liquid composition, and HHV were
evaluated. It was achieved that a maximum of 36% alcohols
and 45% hydrocarbons were garnered at 600 °C, and the
highest HHV of 41 MJ/kg was also gained from PP-rich mixture.
The char formation was inhibited during the fast co-pyrolysis.
Importantly, the introduction of PP to cellulose substantially
reduced the time taken for the completion of pyrolysis.
Furthermore, the synergistic effect between biomass (alder
wood and pine wood) and PP in the co-pyrolysis was also
140
studied. Interestingly, the addition of PP in the pyrolysis of
biomass not only improved the liquid yield, but also increased
degassing of bio-char. It was found that small amounts of PP
(up to 30 wt%), the appropriate temperature, and biomass
humidity allowed complete coverage of the energy demand

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for the co-pyrolysis. The design of experiments (DOE) method
was also utilized to optimize the compositions of solid, liquid
and gaseous products from the co-pyrolysis process.
In comparison with PE and PP, PS have a low hydrogen
content due to the aromatic nature. In the studies on co-
pyrolysis of biomass with PS, the cellulose combined with PS
were subjected to a pyrolysis to investigate their synergistic
142
effect. The maximum liquid yield from co-pyrolysis was
80.10 wt%, which much higher than bio-oil yield (45.50 wt%)
from the pyrolysis of cellulose alone. With the co-feeding of
PS, the liquid quality was clearly improved, including the
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decrease of acid number, pour point, and density. A dominant
amount of aromatic hydrocarbons were obtained in the liquid
products from the co-pyrolysis of cellulose with PS. Abnisa et
143
al. has investigated the non-catalytic co-pyrolysis of palm
shell with PS to garner a high-grade liquid product. It was
found that the liquid yield considerably increased to 61.63
wt%, comparing to the bio-oil yield (46.13 wt%) from the
pyrolysis of palm shell alone. Besides, the liquid quality was
significantly enhanced when PS was co-fed in the pyrolysis of
palm shell. For instance, the high heating value (HHV) was
improve up to 38.01 MJ/kg, while the HHV of pyrolysis oil from
the pyrolysis of palm shell alone was only 11.94 MJ/kg. It was
also observed that there were a dominant amount of aromatic
hydrocarbons obtained in the co-pyrolysis oil. In the study, it
was concluded that the co-pyrolysis of palm shell with PS is the
key aspect to overcome environmental issues stemming from
the high amount of palm shell waste and assure the energy
security.
The utilization of some special polymers has also attracted
the attention in non-catalytic co-pyrolysis. PVC was used with
biomass components (cellulose, xylan, and lignin) in the co-
pyrolysis at 800 °C in a fixed bed reactor to determine their
144
interactions. During the co-pyrolysis of biomass components
with PVC, it was found that the liquid yield was remarkably
increased and the HCl yield was reversely declined.
Furthermore, most polycyclic aromatic hydrocarbons were
decreased in all co-pyrolysis tars, comparing to the calculated
proportion results. It was also manifested that biomass and
biomass-derived char can act as the catalysts for the
prevention of dehydrochlorination or the promotion of PVC
144
chain fission. However, Zhou et al. stated that the co-
pyrolysis of biomass with PVC should be further researched;
since there were toxic chlorinated compounds existing in the
pyrolysis oils, affecting their subsequent use.
Waste electrical and electronic equipment (WEEE) co-fed
with fir sawdust were co-pyrolyzed to obtain a liquid fuel.69 It
was discerned that the liquid yield (62.30 wt%) from co-
pyrolysis was much higher that liquid yields from pyrolysis of
fir sawdust and WEEE individually (i.e., 46.3% for fir sawdust
and 53.1% for WEEE). It was suggested that there was a
positive synergistic effect between fir sawdust and WEEE
during the co-pyrolysis process. The liquid product stemming
from co-pyrolysis mainly consisted of aromatic hydrocarbons.
In the co-pyrolysis, less than 10% of total bromides distributes
in gas, which is much lower than that emanated from
combustion of WEEE. Interestingly, no polybrominated
dibenzo-p-dioxins and furans (PBDD/Fs) were found in all
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products. It was also revealed that this work paved an
environmentally friendly way for the disposal of WEEE and
resource recovery.
Polylactic acid (PLA) and Polyhydroxybutyrate (PHB) were
leveraged with willow in the co-pyrolysis to produce liquid
145, 146
fuel. The co-pyrolysis was carried out in a semi-
continuous home-built rector at 450 °C. It is noted that there
was a positive synergy between biomass and polymers in the
co-pyrolysis. The liquid yield was dramatically increased in
comparison with the bio-oil from the pyrolysis of willow alone.
Moreover, the water content was reduced, and the HHV of the
co-pyrolysis oil was improved. Given the resultant properties
Green Chemistry Accepted Manuscript
of the co-pyrolysis oils, PHB was considered as the most
potential feedstock for the use in the co-pyrolysis due to the
higher liquid yield and higher HHV.
To summarize, the co-feeding of plastics in the pyrolysis of
biomass can appreciably enhance the liquid yield. Besides, the
qualities of the liquid product have been improved as well. For
example, the energy content of liquid products represented by
HHV showed a considerable increase; all types of plastics were
evidenced to have a benefit in the improvement of the HHV of
liquid products, comparing with the HHV of bio-oil from the
pyrolysis of biomass individually.
4.2 Waste tires as the co-reactant in non-catalytic co-pyrolysis
Apart from the wide attention on waste plastics, there is also
growing interest in the utilization of waste tires as a fuel
source via fast pyrolysis. Several comprehensive reviews
through many aspects regarding the pyrolysis of waste tires for
74, 83, 84, 89
liquid fuels have been reported. To date, studies
focusing on co-pyrolysis of biomass with waste tires are
recently limited. The summary of the studies on non-catalytic
co-pyrolysis of biomass with waste tires is summarized in Table
3. It can be seen that most studies were conducted in a fixed
bed reactor. For example, pine nut shells co-fed with scrap
tires were subjected to the pyrolysis at different blend ratios at
147
500 °C. It was found that the introduction of scrap tires in
the pyrolysis of pine nut shells not only improve the liquid
yield, but also enhanced the liquid qualities when compared to
the pyrolysis of pine nut shells alone. The carbon content in
the liquid products from co-pyrolysis was much higher and
oxygen content was much lower than those in biomass-
derived bio-oil. The HHV of liquid products from co-pyrolysis
was dramatically promoted, reaching up to 43.3 MJ/kg when
the biomass to tires mass ratio was set at 1:4. In the co-
pyrolysis oils, D-limonene and aromatic hydrocarbons were
the preliminary compounds. In addition, the heating value of
gaseous and solid products were both higher than those of the
products from the pyrolysis of pine nut shells individually.
As such, co-pyrolysis of palm shells with scrap tires was
investigated as a function of stepwise co-pyrolysis
temperature and feed ratios in a fixed bed reactor to improve
the quantity and quality of liquid product.68 Two scenarios
were performed at 500 °C and 800 °C respectively in the study.
The scenario with higher temperature and prolonged time
showed an increase in both liquid and gas yields. Likewise, the
second scenario also
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Table 3 Summary of studies on waste tires co-fed with biomass in non-catalytic pyrolysis.
Reaction conditions Results
Biomass Tires to Temp. (°C) Reactor Liquid Product quality, calorific value (MJ/kg) and Ref.
categories biomass ratio yield oxygen content (wt%)
(wt%)
Pine nut 1:4 – 4:1 500 Fixed bed Max. 47.0 HHV = Max. 43.4, O = Min. 7.33, mainly D- 147
shell reactor limonene and aromatic hydrocarbons
Palm shell 1:3 – 3:1 500 Fixed bed Max. HHV = Max.46, O = Min. 0.43 68
reactor 48.06
1:3 – 3:1 800 Max. HHV = Max. 47, O = Min. 0.06
48.22
Sawdust 2:3 – 3:2 500 Fixed bed Max. 47.0 HHV = 42.44, O = Min. ~5, PAH considerably 148
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reactor decreased

Green Chemistry Accepted Manuscript

Oil palm 1:1 500 Fixed bed 42.80 NA 149
empty fruit reactor
bunches
Pine 1:9 – 1:4 500 Fixed bed Max. 48.5 LHV = Max. ~15, O = Min. 51.3, dominant 96
woodchips reactor oxygenates
1:9 – 1:4 500 Continuous Max. 56.0 LHV = Max. 25.0, O = Min. 46.8, dominant
auger reactor oxygenates
microalgae 1:4 – 4:1 290 – 370 Custom-made Max. 65.4 HHV = 42.03, O = Min. 2.49, mainly aliphatic 150
autoclave esters and hydrocarbons

had a higher quality of liquid products, achieving a higher
HHV and lower oxygen content. Furthermore, Cao et al. have
carried out the co-pyrolysis of sawdust and waste tires both in
a fixed bed rector and a continuous auger rector.148 It was
discerned that only one phase was found in the both two
reactors and a positive synergistic effect between
lignocellulosic biomass and waste tires was evidenced. Acidity,
density, oxygen content of the liquid products form co-
pyrolysis are both declined; PAH and HHV were both improved
regarding the merely biomass-derived bio-oil. However, the
positive synergy was more notable in the auger rector,
because a higher liquid yield and qualities with higher HHV and
lower oxygen content was obtained.
More importantly, an attractive and novel topic regarding
co-pyrolysis of microalgae with waste tires was proposed by
Duan et al.150 Waste tire was co-fed with microalgae in
supercritical ethanol at 290 – 370 °C to examine the synergistic
effect between such two feedstock. It was reinforced by the
results that there was a positive synergistic effect between
microalgae and waste tires. The maximum liquid yield was 65.4
wt%, originating from the co-pyrolysis. The most significant
extent for the synergistic effect was 37.8% with microalgae to
waste tire mass ratio of 1:1. The optimal HHV of liquid product
from co-pyrolysis was 42.03 MJ/kg, similar to that of diesel.
The interactions between microalgae and waste tires during
the co-pyrolysis process, ZnO and carbon black in the waste
tire all favored denitrogenation and deoxygenation, thereby
improving the quality of the liquid products. To sum up, this
study paved a novel pathway for the utilizations of microalgae
and waste tires.
5. Practical catalytic co-pyrolysis of lignocellulosic
biomass with synthetic polymers
5.1 Plastics as the co-reactant in catalytic co-pyrolysis
It is indicated that the liquid products from non-catalytic pyrolysis
of biomass with polymers cannot be used as liquid fuels, even
though some properties (e.g., HHV and oxygen content) of liquid
products have been improved to a large extent. To obtain advanced
products, a catalyst should be introduced in the co-pyrolysis so that
the carbon efficiency of aromatics can be enhanced and coke
formation can be correspondingly reduced. To date, a few studies
have pointed out that catalytic co-pyrolysis of biomass with plastics
could be significantly improved the carbon yield of target aromatics.
The summary of representative studies on co-feed catalytic
pyrolysis of biomass with plastics is shown in Table. 5.
Most of the studies leveraged cellulose (a model compound of
lignocellulosic biomass) co-fed with plastics to conduct catalytic
pyrolysis in a micro-pyrolyzer. To be more specific, Li et al. have
investigated the co-feeding of cellulose with LDPE in CFP by using
ZSM-5 as the catalyst to determine their interactions during the
catalytic co-pyrolysis.42 It was obtained that the co-feeding of
cellulose with LDPE in CFP had a much higher carbon yield (47.46%)
of aromatics than CFP of cellulose or LDPE individually; and co-feed
CFP also gave rise to a lower coke formation than CFP of cellulose
alone. Besides, up to 85.1% selectivity toward valuable mono-cyclic
aromatics was achieved during co-feed CFP. Therefore, the co-
feeding of cellulose with LDPE in CFP had a positive synergistic
effect on the improvement of aromatic production and decrease of
coke formation. As such, the difference among LDPE, PP, and PS in
the co-feed CFP over ZSM-5 was also evaluated by Li et al.57 During
co-feed CFP of cellulose with LDPE, PP, and PS, LDPE applied in the
co-feed CFP could generate higher carbon yield of petrochemicals
(aromatics and olefins) and lower carbon yield of solid residues
(coke/char). It was evidenced that cellulose and LDPE had a more
pronounced synergy because of the Diels-Alder reaction between
cellulose-derived furans and linear olefins derived from LDPE during
co-feed CFP.
Moreover, Dorado et al. aimed to produce drop-in fuels from
catalytic co-pyrolysis of biomass (cellulose, xylan, lignin, and

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ARTICLE

Table 4 Summary of studies on catalytic co-pyrolysis of biomass with plastics.

Type of materials Reaction conditions Results
Ref.
Biomass plastics Catalyst Plastics Temp. Reactor Aromatic Aromatic selectivity
to (°C) yield (C
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biomas %)

Green Chemistry Accepted Manuscript

s ratio
Cellulose LDPE HZSM-5 1:1 650 Pyroprobe 47.46 Mainly toluene and xylenes 42
pyrolyzer
Cellulose LDPE HZSM-5 1:4 – 590 Curie-point 33.0 – Mainly BTX 118
1:1 pyrolyzer 34.3
B/HZSM- 1:4 – 590 26.6 – Mainly xylenes and toluene
5 1:1 30.6
Cellulose LDPE HZSM-5 1:2 550 Pyroprobe 48.4 Mainly toluene and xylenes 57
pyrolyzer
PP HZSM-5 1:2 37.5 Mainly toluene and polyaromatics
PS HZSM-5 1:2 54.4 Mainly benzene and polyaromatics
Cellulose LDPE K10 1:3 400 – Horizontal 53 – 70 NA 151
a
500 oven wt%
KSF 1:3 400 – 52 – 69 NA
a
500 wt%
Bentonit 1:3 400 – 62 – 64 NA
a
e 500 wt%
Cellulose LDPE HZSM-5 0.4:1 – 250 - Microwave- 36.05 – Dominant xylenes and 121
1.45:1 500 induced 46.35 trimethylbenzenes
pyrolyzer
Cellulose LLDPE HZSM-5 1:1 500 – Microscale 11.8 – Mainly toluene and xylenes 152
600 online 33.1
b
pyrolyzer wt%
HY ~ 10 – Mainly toluene and xylenes
17.1
wt%b
PP HZSM-5 1:1 500 – 8.3 – ~27 Mainly toluene and xylenes
600 wt%b
HY ~9 – 14.7 Mainly xylenes and other mono-
wt%b aromatics
Cellulose PE HZSM-5 1:1 500 Tandem micro- 25.00 Dominant BTX 51
pyrolyzer
Xylan HZSM-5 1:1 500 17.95 Dominant BTX
Milled HZSM-5 1:1 500 15.19 Dominant BTX
wood
lignin
Red oak HZSM-5 1:1 400 – 15.68 – Dominant BTX
700 21.35
Black- PE LOSA-1 1:1 600 Continuous 29.9 Mainly benzene and naphthalenes 54
liquor Spent 1:1 600 fluidized bed ~20 Mainly benzene and naphthalenes
lignin FCC reactor
γ-Al2O3 1:1 600 ~17 Mainly benzene and naphthalenes
Sand 1:1 600 ~13 Mainly benzene and toluene
PP Spent 1:1 600 ~19 Mainly benzene and naphthalenes
FCC
PS Spent 1:1 600 55.3 Mainly styrene
FCC
Douglas LDPE HZMS-5 0.4:1 – 200 – Microwave- 34.18 – Mainly xylenes and 120
fir pellets 1.45:1 500 induced 42.66 trimethylbenzenes

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pyrolyzer

Pine PE LOSA-1 1:1 600 Continuous 42.5 Dominant benzene and toluene 44
sawdust Spent 1:4 – 400 - fluidized bed 14.7 – Dominant benzene and
FCC 4:1 650 reactor 37.7 naphthalene
γ-Al2O3 1:1 600 25.6 Dominant benzene and
naphthalene
Sand 1:1 600 20 Dominant benzene and toluene
PP Spent 1:1 600 34.7 Dominant benzene and
FCC naphthalene
PS Spent 1:1 600 47 Dominant benzene and
FCC naphthalene
48
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Pine LDPE HZSM-5 1:2 550 Pyroprobe 28.23 Mainly toluene and m-xylene
wood pyrolyzer

Green Chemistry Accepted Manuscript

sawdust
Ga/HZSM 1:2 550 29.52 Mainly toluene and m-xylene
-5
Ga-Al-Si 1:2 550 27.96 – Mainly toluene and p-xylene
29.85
Ga-Si MFI 1:2 550 24.94 – Mainly toluene and p-xylene
27.96
Pine LDPE HZSM-5 1:2 550 Pyroprobe 30.33 Dominant toluene and xylenes 47
wood pyrolyzer
sawdust
P/HZSM- 1:2 550 33.12 Dominant toluene and xylenes
5
P/Ni- 1:4 – 550 32.49 – Mainly BTX
HZSM-5 1:1 36.69
Corn HDPE HZSM-5 1:4 – 550- Pyroprobe NA Dominant xylene and toluene 114
stalk 4:1 800 pyrolyzer
Poplar HDPE P/HZSM- 1:1 450 – Pyroprobe NA Mainly benzenes 153
wood 5 650 pyrolyzer
Switchgr LDPE HZSM-5 1:1 650 Double-shot ~ 6.8c Dominant toluene and p-xylene 43
ass micro pyrolyzer
HDPE HZSM-5 1:1 650 ~ 6.0c Dominant p-xylene and toluene
c
PP HZSM-5 1:1 650 ~ 9.5 Dominant p-xylene and toluene
c
PS HZSM-5 1:1 650 ~ 8.0 Dominate toluene and
ethylbenzene
c
PET HZSM-5 1:1 650 ~ 9.5 Dominant toluene, p-xylene and
naphthalene
Torrefied PS HZSM-5 1:4 500 – Pyroprobe NA Dominant styrene and α- 154
wood 650 pyrolyzer methylstyrene
a b c
bio-oil yield; based on mass yield; carbon yield of six aromatic compounds (toluene, ethylbenzene, o- and p-xylene, naphthalene, and
2-methylnathalene).
switchgrass) with plastics (LDPE, HDPE, PP, PS, and PET) in the presence of PS contributed to the decrease of oxygenated phenolic
43
presence of HZSM-5 catalyst. It was observed that the compounds and the increase of aromatic hydrocarbons. Styrene
enhancement of quantified aromatic hydrocarbons took place in and α-methylstyrene were still the major compounds in the
several cases conversion for the mixture, with aliphatic polymers catalytic co-pyrolysis mainly due to the nature of PS.
(PE and PP) and PET presenting the considerable augment in total Comparing with ZSM-5-based catalysts, Kim et al. have made
aromatic carbon yield. The selectivity toward individual aromatic efforts to determine the effect of zeolite pore size and molecular
compounds varied in the mixture from co-feed CFP in comparison diameter of plastics on aromatic production during catalytic co-
152
with biomass or plastics alone. In addition to switchgrass, corn stalk pyrolysis. The catalytic co-pyrolysis of cellulose with LLDPE or PP
was also used with HDPE in the catalytic co-pyrolysis over HZMS-5 was implemented in the presence of HZSM-5 or HY catalysts. It was
114
to promote carbon efficiency of aromatic hydrocarbons. Several noteworthy that the synergistic aromatic production was readily
factors were taken into account to investigate their effects on the gained over HY for both LLDPE and PP. On the contrary, HZSM-5
relative and economic potential of aromatic hydrocarbons in this showed to be effective for the improvement of aromatics when the
study. It was found that high relative contents and value index (VI) reaction was carried out under a severe condition.
of aromatic hydrocarbons could be gained if H/Ceff of co-reactants To synthesize a more efficient catalytic for catalytic co-pyrolysis,
should be adjusted to be more than 1. Torrefied wood was also Wang’s group have investigated the effect of boron-modified ZSM-5
employed with PS during catalytic co-pyrolysis by using HZSM-5 as on the catalytic performance of cellulose and LDPE in co-feed
154 118
the catalyst to improve the yield of aromatic hydrocarbons. The CFP. It was noted that the carbon yield of monocyclic aromatics

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increased to 24.6% when the co-feed CFP was applied over boron-
modified ZSM-5; while the carbon yield of polycyclic aromatics
declined to 6%, comparing with CFP of cellulose alone catalyzed by
parent ZSM-5. The carbon selectivity of p-xylene was dramatically
improved as well. Moreover, synthesized Ga/ZSM-5, Ga-Al-Si, and
Ga-Si MFI catalysts were also tested in the co-feed CFP of pine
48
wood sawdust with LDPE. Compared with parent ZSM-5 catalyst,
Ga-modified catalysts remarkably improved the carbon yield of
monocyclic aromatics and olefins and reduced the generation of
polycyclic aromatics and alkanes. Notably, Ga-Al-Si and Ga-Si MFI
catalysts generally contributed to higher yield of aromatics and
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selectivity toward valuable p-xylene than Ga/ZSM-5 in the co-feed
CFP. Wang and his co-workers also synthesized P/ZSM-5 and P/Ni-
ZSM-5 for the subsequent use in the catalytic co-pyrolysis of pine
47
wood sawdust with LDPE. Up to 36.69% carbon yield of aromatic
production was obtained by using P/Ni-ZSM-5 as the catalyst. It was
also found that ZSM-5 modification with P and P/Ni could improve
hydrothermal stability and life time of the catalyst during the co-
feed CFP.
P/HZSM-5 acting as the catalyst was also utilized in the catalytic
153
co-pyrolysis of poplar wood with HDPE using a Py-GC/MS. In
general, parent HZSM-5 favored the production of aromatics, whilst
P/HZSM-5 facilitated the generation of light aliphatic hydrocarbons
(C4 – C12). Furthermore, three clay catalysts (K10, KSF, and
Bentonite) were subject to catalytic co-pyrolysis of cellulose with
151
LDPE to produce bio-oil with high yield. K10 was found to be
superior to the other catalysts according to the liquid yield and
qualities. A large amount of hydrocarbons was detected in the
resultant bio-oil when K10 was used as the catalyst.
Unlike the studies conducted the process in a Py-GC/MS, a
tandem micro-pyrolyzer was used to carry out the catalytic co-
51
pyrolysis of biomass with PE using HZSM-5 as the catalyst. During
the catalytic co-pyrolysis of cellulose with PE, the enhancement of
aromatic hydrocarbons was accompanied with the decrease of
small olefins. It was also observed that the carbon yield of aromatic
and aliphatic hydrocarbons were both improved in the catalytic co-
pyrolysis of PE with xylan or lignin. When PE was co-fed with red
oak in CFP, there are a positive synergistic effect on the carbon yield
of aromatic hydrocarbons and coke reduction as well.
By using a continuous fluidized bed reactor, Xiao and his co-
44
workers focused on the catalytic co-pyrolysis of pine sawdust and
54
black-liquor lignin with plastics (PE, PP, and PS). In the light of
LOSA-1, spent FCC, γ-Al2O3, and sand as the catalysts during the
catalytic co-pyrolysis, it was suggested that petrochemical yield
from catalytic co-pyrolysis of PE and lignin was LOSA-1 > spent FCC >
γ-Al2O3 > sand. As such, LOSA-1 present a better catalytic
performance than spent FCC, γ-Al2O3, and sand during the catalytic
co-pyrolysis of pine sawdust with PE. For maximizing the
petrochemical yield, the co-reactant with lignin during the catalytic
co-pyrolysis is PS> PE> PP. Similar trends were also obtained during
the catalytic co-pyrolysis of pine sawdust with these plastics.
Meanwhile, catalytic co-pyrolysis of lignin with PS achieved the
maximum aromatic yield (55.3%). Likewise, the catalytic co-
pyrolysis of pine sawdust with PS also obtained the highest carbon
yield of aromatics (47%).
Interestingly, Lei and his co-workers have leveraged microwave
121
reactor to implement the co-feed catalytic pyrolysis of cellulose
120
and Douglas fir pellets with LDPE. Enhanced carbon yields of
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aromatic hydrocarbons were obtained from the co-feed catalytic
microwave-induced pyrolysis by using the well-promoted HZSM-5
catalyst. It was also observed that cellulose had a more positive
synergistic effect than Douglas fir pellets with LDPE for the
production of aromatic hydrocarbons and reduction of solid
residues (char and coke). The aromatic hydrocarbons with
improved carbon yields were more principally lumped in the jet fuel
range (C8 – C16) from the co-feed catalytic microwave-induced
pyrolysis of both cellulose and Douglas fir pellets with LDPE, which
is mainly due to the unique properties of the catalyst fabricated by
hydrothermal and calcined treatments.
Green Chemistry Accepted Manuscript
5.2 Waste tires as the co-reactant in catalytic co-pyrolysis
In contrast to plastics, waste tires have been rarely employed as a
148, 149
co-reactant together with biomass in catalytic pyrolysis. Cao
et al. have first investigated the catalytic co-pyrolysis of
lignocellulosic biomass with waste tires by using SBA-15, MCM-41
148
and HZSM-5 as the catalysts in a fixed bed reactor. The influences
of the mixture proportion in liquid yield and qualities were
determined in the study. It was evidenced that there was a
synergistic effect between biomass and waste tires, favoring the
promotion of liquid quality. The catalytic co-pyrolysis of biomass
with waste tires could suppress the formation of polycyclic aromatic
hydrocarbons. When biomass to waste tires mass ratio was set at
2:3, the content of PAH presented the lowest in the liquid product.
It was also found that mesoporous catalysts (SBA-15 and MCM-41)
showed better catalytic performance than microporous catalyst
(HZSM-5) in the improvement of liquid qualities, such as HHV and
viscosity. For the mesoporous catalysts, SBA-15 was more
significant than MCM-14 in the aspects of reducing the liquid
density and viscosity, and converting large molecular into small
ones.
Additionally, Alias et al. thereafter investigated the catalytic co-
pyrolysis of oil palm empty fruit bunches with waste tires in a fixed
149
bed reactor at 500 °C with a mass of 1:1. The shredded empty
fruit bunches was impregnated with 10 wt% of cobalt catalyst
solution prior to being fed in the reactor. The objective of this study
was to determine the effects of cobalt catalyst with direct
impregnation into the biomass fibers with respect to the liquid
yield. It was suggested that there was a positive synergistic effect
between biomass and waste tires on the increase of liquid yield. By
using cobalt as the catalyst could result in higher liquid yield during
the catalytic co-pyrolysis, comparing with the outcome from the
direct co-pyrolysis of lignocellulosic biomass with waste tires in the
absence of the catalyst.
5.3 The mechanism of catalysts in catalytic co-pyrolysis
In order to determine the effects of catalyst properties on reaction
chemistry and product distribution during the catalytic co-pyrolysis
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Table 5 Characterizations of various zeolite-based catalysts.a

SBET Vpore Spore dpore ABrönsted ALewis
Catalyst 2 3 2 Ref.
(m /g) (cm /g) (m /g) nm µmol/g µmol/g
118
HZSM-5 372.0 0.114 293.1 - 356.1 56.8
B/HZSM-5 229.6 0.077 194.6 - 242.1 56.7
152
HZSM-5 405 - - 6.36 - -
HY 780 - - 11.24 - -
47
HZSM-5 414.4 0.158 366.8 - 496.1 40.1
P-HZMS-5 327.6 0.118 276.6 - 304.0 75.9
P/Ni-HZSM-5 322.3 0.113 270.7 - 264.9 197.7
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44
LOSA-1 220.2 0.220 - 2.14 - -

Green Chemistry Accepted Manuscript

spent FCC 242.7 0.210 - 4.85 - -
γ-Al2O3 134.7 0.220 - 6.41 - -
48
HZSM-5 403.3 0.161 - - 420.3 134.0
Ga/HZSM-5 372.6 0.138 - - 251.9 114.2
Ga-Al-Si 330.5 0.124 - - 157.4 126.9
Ga-Si 355.6 0.132 - - 132.4 118.8
a
SBET: BET surface area; Vpore: pore volume; Spore: pore surface area; dpore: average pore size; ABrönsted: Brönsted site acidity; ALewis:
Lewis site acidity.

of biomass with polymers, and further design highly efficient and
stable catalysts, the characteristics of representative catalysts are
interpreted in Table 5. As mentioned above, HY achieved a more
positive synergistic effect for the aromatic formation than HZSM-5
in the catalytic co-pyrolysis of biomass with plastics due to the
effectiveness of the large pore size.152 That is possibly because the
diffusion of polymers into the small micropores of HZSM-5 was
inhibited by biomass-derived coke. However, HZSM-5 displayed
better catalytic performance for aromatic production than HY by
increasing the loading of catalyst or catalytic temperature due to its
strong site acidity and proper pore structure for aromatization.152
Regarding the mechanism of LOSA-1, γ-Al2O3, and spent FCC in the
catalytic co-pyrolysis, the LOSA-1 is a microporous catalyst having
special pore structure and activity, which is favorable for mono-
aromatic hydrocarbons production; while γ-Al2O3 as a mesoporous
catalyst has little shape selectivity toward aromatics and olefins.44
The mechanism of zeolites modified by other elements during
the catalytic co-pyrolysis has also been investigated. The properties
of typical catalysts are given in the Table 5 as well. To be more
specific, when the parent HZSM-5 catalyst was impregnated with
boron, the acidity and pore size of the modified B/HZM-5 decreased
with increasing the boron loading.118 However, the B/HZSM-5
preserved sufficient catalytic activities for the generation of
valuable mono-aromatic hydrocarbons. In the co-feed CFP, the pore
narrowing of boron-modified HZSM-5 extensively promoted the
yield of petrochemicals and improved p-xylene production over m-
xylene and o-xylene. This result suggests that slight decrease of
HZSM-5 pore size by impregnating boron can enhance the
selectivity toward valuable products.118 Moreover, P and Ni
modified HZSM-5 decreased the Brönsted acid sites, but increased
its Lewis acid sites.47 Since Lewis acid sites are electron pair
acceptor and have strong affinity for hybrid ions (dehydrogenation),
they can assist to accept the released hydride ions during the
conversion of alkanes to olefins, as well as subsequent intermediate
olefins to aromatic hydrocarbons.155 As a result, P and P/Ni
modified HZSM-5 catalyst could enhance aromatic production in
the co-feed CFP.47
Additionally, it was aforementioned that Ga-containing zeolite
catalysts (i.e. Ga/HZSM-5, Ga-Al-Si, and Ga-Si catalyst) could
significantly increase the petrochemicals yield at the expense of
alkanes in the co-feed CFP.48 It is attributed to the fact that non-
framework Ga oxides (e.g., Ga2O3 and GaO+) in Ga-containing
zeolites can cooperate with Brönsted acid sites and contribute to
catalyzing the dehydrogenation of alkanes to olefins.156 The non-
framework Ga species can be also conducive to converting olefins
to aromatic hydrocarbons.48 In addition, it is found that the pore
mouths of Ga/HZSM-5 may be partially blocked by extra crystalline
Ga2O3 oxides;113 whereas Ga-Al-Si and Ga-Si MFI zeolites have a
narrowed channel because of the deposition of non-framework Ga
oxides in the zeolite channels.48 Accordingly, Ga-containing zeolites
may be able to decrease polycyclic aromatics production by
hindering their formation in the narrowed zeolite pores (as for Ga-
Al-Si and Ga-Si), or preventing them from diffusing out the partially
blocked pores (in terms of Ga/HZSM-5). Nevertheless, Ga-Al-Si and
Ga-Si MFI zeolites are more effective catalysts than Ga/HZSM-5 and
conventional HZSM-5 for petrochemicals production in the co-feed
CFP. That is because the non-framework Ga species of Ga-Al-Si and
Ga-Si MFI zeolites are primarily distributed uniformly inside the
zeolite channels.157 By contrast, Ga dominantly exists as Ga2O3
particles at the external surface of Ga/HZSM-5 or even in a separate
phase.113, 158 In general, zeolite-catalyzed reactions usually take
place inside the zeolites pores as the external surface accounts for
negligible fractions of surface area. Consequently, Ga-Al-Si and Ga-
Si MFI zeolites are more viable catalysts than HZSM-5 and
Ga/HZSM-5 to optimize the product distribution toward more
valuable aromatics via shape selective mechanisms.48
6. Assessments and future prospectives

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Table 6 Advantages and limitations shown by non-catalytic and catalytic co-pyrolysis techniques.
Technique Advantages Disadvantages
32 96
Non-catalytic • Increase in oil yield • Increase of sulfur content in oil
32, 93, 145 144, 147
co-pyrolysis • Improvements in oil qualities • Increase of heteroatom content in oil
81, 96, 159 69, 108
• Improvement in quality of char • Complex compounds in oil
6, 160 144
• Improvement in calorific value of gas • High yield of PAH in oil
• Liquid product cannot directly used as transportation
150
fuels
61, 62 42, 51, 57, 120, 121
Catalytic co- • Beneficial for the environment and energy recapture • Increase of water content in oil
43, 47, 53, 54, 57, 118, 119
pyrolysis • Improvement of petrochemicals yield • Strict requirements of polymers and mixed mass
43, 47, 53, 54, 57, 118, 119 6
• Decrease of coke formation ratio
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51, 120, 121

• Decrease of char production • Liquid product has to be further upgraded before it is
43, 47, 53, 54, 57, 118, 119 161, 162

Green Chemistry Accepted Manuscript

• Improvement in oil qualities used as an automotive fuel

There have been much effort on the application and research of
non-catalytic and catalytic co-pyrolysis techniques. Table 6 lists the
advantages and limitations shown by non-catalytic and catalytic co-
pyrolysis of biomass with polymers. It was revealed that there are
several limitations presented by non-catalytic co-pyrolysis
technique. It was thus conclude that the non-catalytic co-pyrolysis
of biomass with polymers are yet to be fully feasible for biomass
and waste polymers valorization. Herein, a variety of studies have
investigated the potency of catalytic co-pyrolysis technique using
various categories of biomass and polymers. It is reinforced by
these results that catalytic co-pyrolysis of biomass with polymers is
relatively encouraging. The improvement of aromatic production
and decrease of coke formation are observed during catalytic co-
pyrolysis. It is implied that catalytic co-pyrolysis is a promising
technique due to several merits such as reducing the consumption
of petroleum-derived fuels, solving some environmental issues,
improving waste management systems, and enhancing energy
security.
Apart from these advantages, the co-pyrolysis technique can
provide simplicity in design and feasibility with respect to economic
6
analysis. Several studies have evaluated the feasibility of co-
pyrolysis technique from an economic point of view. Kuppens et
99
al. employed the net present value (NPV) to conduct the
economic analysis of the fast co-pyrolysis of lignocellulosic biomass
(willow) with biopolymers (PLA, PHB, corn starch, biopearls, eastar,
solanyl, and potato starch) with the mass ratio of 1:1. It was stated
that NPV is the most important analytic method to select or reject
163-165
an investment in an industrial scale. If the NPV is larger than
or equal to zero, the project will be accepted, otherwise the project
166
will be declined. In this case, the fast co-pyrolysis of
lignocellulosic biomass with any biopolymers was economically
feasible in comparison with the fast pyrolysis of lignocellulosic
biomass alone. That is because the NPV of co-pyrolysis contributed
to positive cash flows for all biopolymers used in the process. Other
estimations (i.e., initial investment expenditure, products cost, and
possible revenues) were in favor of the economic feasibility of the
co-pyrolysis as well. However, the techno-economic analysis of
catalytic co-pyrolysis of biomass with polymers have never been
evaluated so far. In order to scale up the catalytic co-pyrolysis
technique, future efforts should be made to evaluate the economic
feasibility of catalytic co-pyrolysis.
It is worth noting that the ash content (alkali metals) present in
the feedstock plays a dominant effect on product yield and
distribution, with the main alkali metals (sodium and potassium)
167, 168
having much remarkable contribution. These alkali metals
can act as the active catalysts during the pyrolysis, and cause the
secondary cracking of pyrolytic vapors to yield reaction water and
29
further lead to the decrease of liquid yield and qualities. Higher
ash content means more minerals in the feedstock, thus more
169
effective catalytic actions can take place during pyrolysis. It was
observed that the high level of ash content could produce a high
level of reaction water, leading to a decrease of the HHV of the
pyrolysis oil as well as risking phase separation; the yields of char
170, 171
and gas are inversely enhanced. A lower content of alkali
metals can reduce the cracking reaction of volatiles so that more
large-molecule compounds and less reaction water can be found in
170
the pyrolysis oil. For the in-situ catalytic pyrolysis, zeolite-based
catalysts (e.g. HZSM-5) whose surface is acidic could deactivated
the fundamental minerals in the feedstock by acid-base interaction,
169
thereby inhibiting vaporization of feedstock. To remove the ash
content in the biomass, the ash can be managed to some extent by
selecting the species of biomass and harvesting time, but it cannot
29
completely eliminated from the biomass. Although the ash
content in biomass can be effectively reduced by washing in water
or dilute acid, this method is not usually viewed as a feasible
possibility due to the loss of valuable compositions and high
29
complexity of the method.
Furthermore, it is shown that the types and ratios of co-
reactants essentially affect the liquid yield and characteristics. Both
waste plastics and tires can be co-fed with lignocellulosic biomass in
catalytic pyrolysis. Yet there are some pivotal factors that need to
be kept in mind when the co-reactants are fed into the process. For
example, PVC is not recommended as a co-reactant for direct use in
catalytic pyrolysis since it contains approximately 57 wt% chlorine
content. When PVC and biomass are carried out in catalytic co-
pyrolysis, chlorinated compounds (such as chlorinated aromatics
and hydrochloric acid) will generate in the liquid product as well.
Hydrochloric acid is readily corrosive and toxic, thereby significantly
impacting the liquid quality and incurring corrosion toward the
67, 86
pyrolysis equipment. Thus, it is necessary to eliminate the
chlorine content through dechlorination. In general, adsorbents can
be used to remove chlorine content to a large extent prior to
135
catalytic pyrolysis. The dechlorination step was usually conducted
at 300 °C by using the adsorbents (e.g., FeOOH, Fe3O4, and
135, 172
Fe2O3). It was found that the liquid chlorine content by more
173
than 75% could be removed. Wherefore, PVC must be
dechlorinated by introducing a dechlorination step when PVC and
biomass will be conducted in catalytic co-pyrolysis.

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Fig. 7 Promising routes for the conversions of lignocellulosic biomass and polymers into advanced products.
In addition, waste plastics and tires are the limited sources,
whose amount are generally lower than that of lignocellulosic
biomass. Both waste plastics and tires are also more valuable than
lignocellulosic biomass. Although many studies have proved that a
higher ratio of polymers introduced in catalytic pyrolysis of
lignocellulosic biomass could result in the increase of liquid yield
and qualities, it is more important to add less polymers in catalytic
co-pyrolysis to get the optimal result. In this regard, the proportion
of polymers should be designed to be less than that of
lignocellulosic biomass. Accordingly, the waste polymers proportion
in the feedstock should be considered as a vital criterion to
estimate the feasibility of catalytic co-pyrolysis in a large scale.
As for the assessments of products obtained, three main
products from catalytic co-pyrolysis of lignocellulosic biomass with
polymers can have a broad range of applications, as depicted in Fig.
7. After catalytic co-pyrolysis, gaseous fraction generally consists on
a mixture of hydrogen, paraffins, olefins, and trace amounts of
other hydrocarbons. The by-product can be used to supply the heat
required by the process of catalytic co-pyrolysis, as it can be
energetically self-sufficient.74 The ex-situ catalytic co-pyrolysis is
conducive to separate char and catalyst after the reaction. Char
gained from the process can be activated through various physico-
chemical procedures for the production of activation carbon.88, 174
As described above, the liquid fraction from catalytic co-
pyrolysis of biomass with waste plastics or tires commonly contains
high valuable aromatics (such as BTX and D-limonene).89, 175, 176 Even
though the ideal liquid product from catalytic co-pyrolysis of
lignocellulosic biomass with waste polymers contains large amounts
of gasoline-range hydrocarbons, the liquid product has to be
upgraded before it is used as an automotive fuel.161, 162 That is
mainly attributed to the active and detrimental components in the
liquid product, resulting in the liquid product to be unstable. It is
also found that there are still a large amount of PAH in the resulting
liquid product from catalytic co-pyrolysis, which is not capable to be
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Green Chemistry Accepted Manuscript
utilized as a replacement or additive in transportation fuels.
Additionally, there is existing some inorganics in the lignocellulosic
biomass and heteroatoms in the waste polymers, these atoms not
only affect the quality of liquid product but also deactivate the
catalyst rapidly.177 More specifically, waste plastics from the
agricultural sector usually include some heteroatoms such as
Ca, P, S, and N.65 It was shown that the properties of liquid
product from non-catalytic co-pyrolysis were distorted due
to the presence of these contaminants in waste plastics.
However, the introduction of a catalyst during co-pyrolysis
possesses the additional merit of reducing the concentration
of impurities to some extent because some heteroatoms can
attach to the catalyst.65 As for the co-pyrolysis of biomass
with waste tires, it is clearly evident that the addition of
waste tires can enhance the sulfur content in pyrolysis oil.96
Waste tires co-fed in the catalytic pyrolysis could also
contribute to the trace amounts of H2S, SO2 and NH3.178 The
generation of H2S is caused by the volatilization of sulfur
utilized in the vulcanization. The concentration of H2S
augments with the increase of waste tires ratio due to the
general increase of sulfur content in the blend.96 The char
derived from co-pyrolysis is a carbon-enriched solid residue
including the initial carbon black in waste tires and inorganic
compounds (e.g. S, N, Zn, Si, and Ca).84, 174 The elemental
composition of pyrolysis char varies with regard to the
biomass to waste tires blend ratio.147 It is worth noting that
the sulfur content in the char from co-pyrolysis is related to
the waste tire ratio in the blend.
To remove the heteroatoms, stabilize the liquid product, and
further improve the applied value of liquid product,
hydroprocessing is the suitable method that allows for
simultaneously solving the main barriers179 and allow its direct
application as a transportation fuel. Besides, it is noticeable that the
current jet fuels are principally comprised of linear-chain and
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21, 180
branched-chain alkanes in the range of C8 - C16.
known that cycloalkanes in jet fuels can be burned cleanly with high
heats of combustion; that is because cycloalkanes are compact
181, 182
molecules within robust ring strain. To promote the qualities
of current jet fuels, cycloalkanes with the carbon numbers in the jet
fuel range can be synthesized and added into civilian jet fuels.
The promising pathway for the production of cycloalkanes are the
61, 171, 184-186
hydro-cycloaddition of aromatic hydrocarbons.
the studies from catalytic co-pyrolysis, the PAH and large amounts
of benzene substituted by branched chains with the carbon number
are mostly lumped in the range of 8 – 16. These aromatic
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It is well petrochemicals (in particular monocyclic aromatic hydrocarbons),
but also lowers the coke formation in the process. With the
utilization of lignocellulosic biomass, this technique can also reduce
our dependence on petroleum fuels and mitigate global warming
effects. By using waste polymers as the co-reactant, this technique
21, 183
can reduce the disposal of waste polymers in landfills, solve some
environmental issues, and further increase energy security.
Based on Moreover, this technique is also beneficial to obtain highly valuable
by-products (gas and char) in the process.
Based on the current technique from aromatic
hydrocarbons to cycloalkanes conducted under a very mild

compounds are the perfect precursors of renewable cycloalkanes condition, the catalytic co-pyrolysis integrated with

Green Chemistry Accepted Manuscript

for jet fuels. A variety of studies have reported the route from hydrogenation process is significantly meaningful for the
aromatic hydrocarbons to cycloalkanes. Meanwhile, Lei and his production of renewable cycloalkanes. From an economic
colleagues have developed a green catalytically route for the point of view, the improved carbon yield of aromatics can
production of renewable cycloalkanes from lignocellulosic considerably enhance conversion efficiency from feedstock to
171, 184, 185
biomass. The aromatic hydrocarbons evolved from cycloalkanes for jet fuels, finally contributing to the increase of
catalytic microwave-induced pyrolysis were almost hydrogenated ROI. However, current studies are mainly based on the lab-
into cycloalkanes by using home-made Raney Ni as the catalyst scale equipment by using biomass with pure plastics to
under a low-severity reaction condition. Based on these results, the manufacture aromatics. Apparently, the most achievable and
addition of plastics have been added into the microwave-induced economical way is to directly convert lignocellulosic biomass
pyrolysis of biomass to improve the carbon yield of aromatic with waste polymers, rather than pure plastics. Since waste
production and thereafter enhance the carbon yield of renewable polymers are the limited sources, whose amount is generally
120, 121
cycloalkanes for jet fuels. Therefore, the enhanced carbon lower and value is much higher than those of lignocellulosic
yield of aromatic hydrocarbon from catalytic co-pyrolysis can be biomass; the availability of waste polymers and its proportion
upgraded into high valuable cycloalkanes for the use as in the feedstock play a crucial role in the sustainability and
replacements or additives in high density jet fuels (e.g., JP-5) as feasibility of this technique. In this premise, the catalytic co-
sketched in Fig. 7. From an economic point of view, the improved pyrolysis technique remains in the infancy and necessitates
carbon yield of aromatics will elevate the overall conversion continual research work on the scale-up of the process.
efficiency from lignocellulosic biomass and water polymers to jet
fuel range cycloalkanes; consequently the elevated conversion
efficiency will definitely contribute to the increase in the return on 8. List of abbreviations
investment (ROI). BTX Benzene, toluene, and xylenes
It is affirmed that the co-feeding of waste polymers could lower CFP Catalytic fast pyrolysis
the coke formation. Nonetheless, the heteroatoms can significantly GCV Gross calorific value
affect the life time of zeolite-based catalyst during catalytic co- HDO Hydrodeoxygenation
pyrolysis. Therefore, it is required to develop a catalyst that can HDPE High-density polyethylene
mitigate the problems occurring in catalytic co-pyrolysis. In order to HHV High heating value
improve the value of resultant aromatics, catalysts developed LDPE Low-density polyethylene
should facilitate tailored reaction route toward either maximizing LHV Low heating value
the carbon yield of valuable simple aromatics (such as BTX) or jet MSW Municipal solid waste
fuel precursors (C8 – C16 polycyclic aromatics). Moreover, the ideal NPV Net present value
catalysts should be capable of catalyzing a series of desired PAH Polycyclic aromatic hydrocarbons
reactions, including dehydration, decarbonylation, decarboxylation, PBDD/Fs Polybrominated dibenzo-p-dioxins and furans
cracking, and C–C coupling. Catalysts developed should also have PE Polyethylene
appropriate acid sites and acidity for target products through PET Poly(ethylene terephthalate)
certain reaction pathways and to extend the life time of catalysts. PHB Polyhydroxybutyrate
PLA Polylatic acid
PP Polypropylene
7. Conclusions PS Polystyrene
To summarize, this study reviews a state-of-the-art technique on PVA Polyvinyl alcohol
catalytic co-pyrolysis of lignocellulosic biomass with polymers PVC Poly(vinylchloride)
(plastics and waste tires). From the feedstock availability to the RFS2 Renewable fuels standard
chemistry of catalytic co-pyrolysis were specifically demonstrated. It ROI Return on investment
is discerned that catalytic co-pyrolysis of lignocellulosic biomass TGA Thermogravimetric analysis
with waste polymers for the production of aromatics is a much WEEE Waste electrical and electronic equipment
more promising technique than catalytic pyrolysis of lignocellulosic
biomass alone. The technique not only enhances the carbon yield of

20 | J. Name., 2012, 00, 1-3 This journal is © The Royal Society of Chemistry 20xx

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Acknowledgements
This study was supported partially by the Agriculture and Food
Research Initiative of National Institute of Food and
Agriculture, United States Department of Agriculture (Award
Number: 2015-67021-22911; Award Number: 2016-67021-
24533), WSU Office of Commercialization and the Offices of
the President and Provost in conjunction with the Vice
President of Research, the Washington Research foundation,
and Chinese Scholarship Council.
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Catalytic co-pyrolysis of lignocellulosic biomass with polymers: a perspective and

review of recent progress
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