Article

Cite This: Energy Fuels 2020, 34, 460−473 pubs.acs.org/EF

Catalytic Co-pyrolysis of Biomass and Plastics (Polypropylene and

Polystyrene) Using Spent FCC Catalyst
Kanduri Praveen Kumar and Seethamraju Srinivas*
Department of Energy Science and Engineering, Indian Institute of Technology Bombay, Powai, Mumbai 400076, India
*
S Supporting Information

ABSTRACT: In situ catalytic co-pyrolysis (CCP) of mixtures of lignocellulosic biomass (LB) and plastic (polypropylene (PP)
and polystyrene (PS)) with spent FCC catalyst (10% w/w loading) was performed in a semibatch reactor. The experiments
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were carried out using 30 g of feed at 510 °C and three different feed ratios of LB to plastic (1:2, 1:1, and 2:1). The effect of
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feed ratio on bio-oil yield, composition, and carbon yield of products (mainly, aromatics and olefins) was evaluated. A maximum
aromatic selectivity of ∼49%C with PP and ∼82%C with PS was observed at a feed ratio of 0.5. Co-processing LB with PP
produced more valuable chemicals like toluene and xylene at equal mixing ratios. The total yield of monoaromatics and olefins
was maximum (∼73%C) at an LB to PP ratio of 0.5. When LB was co-fed with PS, the more valuable styrene monomers and
ethylbenzene were found significantly in the product at intermediate mixing ratios. While co-feeding PP with LB improved the
(H/C)eff ratio of the pyrolysis liquid, the change in the (H/C)eff ratio was insignificant in the case of biomass and PS mixtures.
The spent FCC catalyst helps in oxygen removal from the bio-oil and improves its quality (higher aromatic fraction) compared
to oil obtained from thermal co-pyrolysis of the biomass and plastic mixtures.

1. INTRODUCTION unstable. Also, oxygenates initiate polymerization reactions and

The global primary energy demand grew by 2.9% in 2018 and
was driven primarily by fossil fuels. On average, the global oil
consumption increased by 1.4 million barrels per day (1.5%),
which led to a growth in carbon dioxide emissions by 2.0%.1
Therefore, in comparison to fossil resources, lignocellulosic
biomass (LB) can be used as an alternative on account of its
renewability, abundant availability, and CO2 neutrality.2,3 Over
the past decade, LB has contributed significantly to the
renewable energy sector by meeting approximately 10% of the
global energy demand.4
Among different biomass conversion alternatives like
pyrolysis, gasification, and hydrothermal liquefaction, pyrolysis
offers an attractive way of transforming the low-energy density
biomass into a high-energy-density liquid called bio-oil. The
thermal breakdown of polymeric biomass components
(cellulose, hemicellulose, and lignin) into smaller fragments
occurs at moderate to relatively high temperatures in an inert
atmosphere during biomass pyrolysis.5−7 The pyrolysis
products include bio-oil, bio-char, and gases like hydrogen,
carbon monoxide, methane, and carbon dioxide. Owing to the
heterogeneity of biomass, the bio-oil yield and composition
varies with the type of feedstock and process conditions
(temperature, heating rate, and residence time). Research
suggests that bio-oil typically contains 45−50 wt % oxygen and
is distributed in oxygenates like hydroxyaldehydes, hydrox-
yketones, carboxylic acids, alcohols, and phenolics. The
presence of oxygen in the bio-oil makes it behave differently
from hydrocarbon fuels (e.g., heavy oil), which contain less
than 1.0 wt % oxygen.2,8 Due to the presence of oxygenates,
the bio-oil has a lower heating value (16−19 MJ/kg) compared
to conventional fuels such as diesel or gasoline (40−45 MJ/
kg).9,10 Further, oxygenates in the bio-oil impart high acidity,
corrosiveness, and high viscosity, which collectively make it
promote aging of bio-oil upon storage. Therefore, upgrading of
bio-oil is necessary for its acceptance as a replacement for
petroleum fuels.2,11,12 Over the past few decades, research has
focused on the use of catalysts in biomass pyrolysis to produce
deoxygenated pyrolysis liquid. However, poor hydrocarbon
yields and high char formation are the major drawbacks of this
process.13−15 Since biomass is hydrogen-deficient (low (H/
C)eff ratio of ∼0.3 only), it results in a low hydrocarbon yield.
Further, most of the hydrogen results in water formation
during the catalytic deoxygenation process. The H2-deficient
environment also leads to rapid char formation, which
eventually deactivates the catalyst.16,17
Since plastics are predominantly hydrocarbons and H2-rich,
co-feeding plastics with biomass during pyrolysis is envisaged
to overcome H2 deficiency. Also, the bio-oil from this process
has better stability and heating value compared to oil produced
from the pyrolysis of LB alone.18,19 Most plastics are
predominantly non-oxygenated hydrocarbons and can serve
as low-cost hydrogen sources during co-pyrolysis with LB. Up
to 2015, approximately 6300 MMT of plastic waste was
generated; 79% of it was landfilled, 12% incinerated, and only
9% recycled.20 One of the advantages of the co-pyrolysis
process is the utilization of waste plastics (including end-of-
life-plastics) and waste biomass as feedstocks; this can reduce
the plastic waste sent to landfill sites. Co-pyrolysis, thus, can
also be an effective waste management strategy.
Conversion of biomass to high-value products needed in the
petrochemical industry instead of fuels is the focus of most
research today; these include olefins and aromatics like
Received: September 13, 2019
Revised: December 10, 2019
Published: December 10, 2019

© 2019 American Chemical Society 460 DOI: 10.1021/acs.energyfuels.9b03135

Energy Fuels 2020, 34, 460−473
Energy & Fuels
Figure 1. Schematic diagram of the co-pyrolysis experimental setup.
benzene, toluene, and xylene, which are the starting materials
for manufacturing a wide range of specialty chemicals.9,17
Catalytic co-pyrolysis (CCP) of biomass and plastics has an
advantage over thermal co-pyrolysis as the reaction mechanism
can be tailored to produce specific fuels and chemicals since
several reactions occur at the catalyst sites, for example,
dehydration, aromatization, isomerization, oligomerization,
alkylation, and cyclization.21 Various zeolite catalysts, and in
particular, HZSM-5, have been extensively used in the
pyrolysis studies for the production of petrochemicals.22−33
Some of these studies are summarized in Table S1 in the
Supporting Information. Spent FCC catalyst is also a zeolite
that can be used in biomass co-pyrolysis. FCC catalyst is used
in the petroleum refineries to convert heavy petroleum
fractions into lighter products such as gasoline, diesel, and
other products. Globally, 150,000−170,000 tons of spent FCC
catalyst is generated as a waste per year and is typically
disposed of in landfills.34 The reuse of this spent FCC catalyst
is expected to decrease the costs involved in the procurement
of fresh catalyst, reduce efforts in the development of
proprietary or new catalysts, and improve overall process
economy.
Groundnut is one of the world’s leading oilseed crops with
an estimated production of ∼46.58 MMT in 2017−2018
according to the USDA.35 Groundnut shells (GS) are a low-
cost byproduct of groundnut processing and are a potential
source of waste biomass for producing renewable fuels. In the
global context, India is the second-largest producer of
groundnuts with an estimated production of ∼5.2 MMT in
2018.36 In India, groundnuts are grown throughout the year
and have the ability to provide residual biomass throughout the
year; this alleviates the seasonal biomass availability issue,
which is otherwise one of the hurdles in biomass utilization.
This study aims to investigate the yield of aromatics from
catalytic co-pyrolysis of groundnut shell (GS) and commonly
used plastics (polypropylene (PP) and polystyrene (PS)) using
spent FCC catalyst. The novelty of the work lies in trying to
valorize waste biomass and plastic streams using a waste
refinery stream (spent FCC catalyst). The effect of plastic
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proportion on the %C selectivity in the bio-oil, mainly,
aromatics, olefins, and oxygenates, was investigated.
2. MATERIALS AND METHODS
2.1. Raw Materials. Groundnut shells were procured from the
local market area, finely ground to a particle size of ∼1 mm, and dried
for 24 h in an oven at 105 ± 2 °C to remove the moisture.
Commercially available polypropylene (PP) and polystyrene (PS)
beads (∼4 mm in diameter) were also purchased from the local
market area. The catalyst used was spent FCC catalyst with a Si/Al
ratio of 1.29 and was supplied in kind by L&T India. The catalyst was
used directly in the experiments without any pretreatment.
2.2. Experimental Setup and Method. Figure 1 shows the
schematic of the experimental setup used for the catalytic co-pyrolysis
(CCP). The reactor is a 15 cm long quartz tube, with 5 cm inner
diameter. An electrical tubular furnace was used to heat the reactor to
the desired temperature, and the set point temperature was
maintained using a PID controller. A condenser with a cooling
water jacket was connected at the exit of the reactor to cool the
pyrolysis vapors. The condensed liquid (bio-oil) was collected in a
round-bottom flask, and the noncondensable gases in gas bags for
analysis.
Initially, 15−30 g of feed mixture consisting of finely ground LB
and plastic was thoroughly mixed with the catalyst (10% w/w of feed)
and loaded into the cylindrical quartz reactor. Subsequently, the
reactor was placed in the electric tubular furnace and purged using N2
to ensure the presence of an inert atmosphere before starting the
experiment. The reactor temperature was set to 510 °C at a heating
rate of 10 °C/min and a holding time of 1 h. The operating
temperature of 510 °C was selected as the major components of
lignocellulosic biomass (cellulose, hemicellulose, and lignin) are
completely pyrolyzed at this temperature.2 Also, this is close to the
temperature used or is the average value of the temperature range
reported in most studies in Table S1. After the completion of the
process, the reactor was allowed to cool down to room temperature,
and the weights of liquid and char were measured. The percentage
yields of liquid, char, and gases were calculated as given in eqs 1−3.
Likewise, each experiment was performed in triplicate to ensure
repeatability and reproducibility.
2.3. Product Analysis. The pyrolysis oil was analyzed using an
Agilent 7890 gas chromatograph (GC) equipped with a Jeol
AccuTOF GCV mass spectrometer (MS). An HP-5 capillary column
(30 m × 0.25 mm ID × 0.25 μm film thickness) was used to separate
the products using He as a carrier gas (flow rate of 1.0 mL/min). The
DOI: 10.1021/acs.energyfuels.9b03135
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split ratio was 10:1. The GC inlet and the MS ion source temperature
was 250 °C. The electron impact ionization was 70 eV. The mass
detection range of MS was 35−650 amu. The GC oven was
programmed to reach 50 °C in the first 2 min, then heated to 140 °C
at 5 °C/min and held for 3 min, further heated to 240 °C at 5 °C/min
and held for 3 min, and finally heated to 280 °C at 10 °C/min. For
each analysis, 0.4 μL of the liquid sample was injected into the GC.
The pyrolysis gas samples were analyzed offline using a gas
chromatograph (NUCON-5765, India) equipped with a thermal
conductivity detector. A Carbosieve column was used to separate H2,
N2, CH4, CO, and CO2. Argon was used as the carrier gas, and a
standard gas mixture with known concentrations of H2, N2, CH4, CO,
and CO2 was used as the reference to find the composition of
pyrolysis gases. For each analysis, 0.5 μL of gas sample was injected
into the GC.
3. RESULTS AND DISCUSSION
The following calculations were used in this study:
weight of liquid
liquid yield (%) = × 100
total weight of the feed
weight of Char
char yield (%) = × 100
total weight of the feed
gas yield (%) = 100 − %liquid yield − %char yield
carbon yield (%C)
number of carbon atoms in a functional group
= corresponding values are ∼350 to 480 °C and ∼350 to 450
total number of carbon atoms in all the functional groups
× 100
aromatic selectivity (%C)
number of carbon atoms in an aromatic product
= from thermal pyrolysis of individual LB and PP samples and
total number of carbon atoms in all the aromatic products
× 100
olefin selectivity (%C)
number of carbon atoms in an olefin product
=
total number of carbon atoms in all the olefin products
× 100
Equation 4 represents the %C for each functional group like
olefins, aromatics, alkanes, etc. Equations 5 and 6 represent the
selectivity of each component within the same functional
group, for example, benzene, toluene, etc., in aromatics.
3.1. Characteristics of Raw Materials. The elemental
analysis of both the biomass and polymer beads was carried
out using T withhermo Finnigan, Italy Flash EA 1112 series
analyzer and is shown in Table 1. The effective hydrogen index
(EHI) or (H/C)eff is an indicator of net hydrogen to carbon
ratio in a feedstock and is calculated according to eq 7.37
Feedstocks with a high EHI [(H/C)eff > 1] are easier to
convert to hydrocarbons, whereas feedstocks with a lower EHI
[(H/C)eff < 1] result in poor hydrocarbon yields and cause
rapid catalyst deactivation due to coke formation during
CCP.16,19 PP has a much higher (H/C)eff ratio of 2.1
compared to those of LB and PS, which have (H/C)eff values
of 0.19 and 0.82, respectively. These values reveal that plastics,
especially PP, are H2-rich, while biomass is H2-deficient.
H − 2O − 3N − 2S
EHI or (H/C)eff =
C (7)
where C, H, O, N, and S indicate the number of atoms per unit
weight of carbon, hydrogen, oxygen, nitrogen, and sulfur,
respectively. The proximate analysis of the LB, PP, and PS
samples is given in Table S2 of the Supporting Information.
3.2. Thermogravimetric Analysis (TGA). The thermal
decomposition behavior of LB, PP, and PS was evaluated by a
thermogravimetric analyzer (model no. STA 449 F3 Jupiter
NETZSCH). For each run, approximately 15 mg of the sample
(1)
was placed in an alumina crucible and pyrolyzed under a N2
atmosphere (80 mL/min flow rate) at a heating rate of 10 °C/
min from 35 to 600 °C for plastic samples and 35 to 950 °C
(2)
for the LB sample. For the LB sample, the N2 atmosphere was
(3)
switched to the O2 atmosphere at 800 °C to determine the
amount of fixed carbon. It was observed that LB decomposed
at a lower temperature than plastics; the degradation
temperature range of LB was ∼200−400 °C, and the
°C for PP and PS, respectively (see Figure S1 in the
(4) Supporting Information). The decomposition temperature
range for PP was higher compared to PS.
3.3. Thermal Pyrolysis of Individual and Mixed Feeds
of LB-PP and LB-PS. Figure 2 summarizes the product yields
their mixtures at three different mixing ratios.
(5)
Thermal pyrolysis (TP) of PP produced ∼62 wt % liquid
yield and ∼38 wt % gases. There was no char formation
observed in the pyrolysis of PP. The primary pyrolysis
products of PP were mainly branched olefins and alkanes,
which result from the random scission of the parent polymer
(6)

Table 1. Elemental Composition of Biomass, Polypropylene

(PP), and Polystyrene (PS) Used

element biomass (wt %) PP (wt %) PS (wt %)

C 47.89 85.19 93.63
H 6.57 14.81 6.36
N 1.13
S
O 44.42 Figure 2. Product yields as a function of feed ratio for thermal
(H/C)eff 0.19 2.1 0.82 pyrolysis (LB and PP).

462 DOI: 10.1021/acs.energyfuels.9b03135

Energy Fuels 2020, 34, 460−473
Energy & Fuels
chain. The olefins accounted for approximately 76% of the
total carbon yield (see Figure 3). In the case of thermal
Figure 3. Distribution of functional groups as a function of feed ratio
for thermal pyrolysis (LB and PP).
pyrolysis of LB, the bio-oil yield was ∼35 wt %, and the gas
yield was ∼28 wt %. Besides, there was significant char
formation (∼37 wt %), which is higher than the liquid and gas
yields. Thermal pyrolysis of LB produced predominantly
oxygenated compounds: carboxylic acids, ketones, furans,
aldehydes, and phenols. These products are mostly the
degraded fragments of cellulose, hemicellulose, and lignin.
Thermal co-pyrolysis of LB and plastic mixtures (TCP)
produced different compounds when compared to pyrolysis of
the individual components only. For TCP of LB and PP
mixtures, the liquid yield was ∼50 wt % at an LB/PP ratio of
0.5 and ∼32 wt % at a ratio of 2 (see Table S3 in the
Supporting Information for phase distribution values between
the organic and the aqueous layers). This is in line with the
expectation since higher amounts of plastic in the mixture
result in higher liquid yields. The gas yields for TCP
experiments were relatively higher than the TP of the
individual components, which indicates the presence of
significant interactions between LB and PP during co-pyrolysis.
As seen in Figure 3, which shows the effect of feed ratio on
the distribution of pyrolysis products in TCP of LB and PP
mixtures, the aromatic content increased with the increase in
LB fraction in the feed. The aromatic yield (∼35%C) was
maximum at an LB/PP ratio of 2 and minimum (∼24%C) at a
ratio of 0.5. However, the aromatics are predominantly
phenolic compounds and are observed at all the feed ratios.
Most of the phenolic compounds are the degradation products
of lignin, for example, catechol, methyl catechol, and
resorcinol. The nonoxygenated monoaromatic (NOMA)
selectivity increased with LB fraction in the feed, the maximum
and minimum selectivity values being ∼22%C and ∼7%C at
the feed ratios of 2 and 0.5, respectively. Toluene and xylene
were the major nonoxygenated monoaromatic compounds
observed, irrespective of the change in the feed ratios. Olefins
were the second most abundant compounds in the TCP of LB
and PP mixtures. The olefins in the pyrolysis liquid are
branched and are mainly produced from the decomposition of
PP. The small changes observed in the olefin and aromatic
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content with the change in the feed ratio are not so significant,
which indicates that there are minimal interactions between LB
and PP components for aromatic formation in the absence of
the catalyst. Therefore, TCP has a minimal effect in improving
the aromatic distribution in the bio-oil.
The thermal pyrolysis (TP) of PS predominantly produced a
liquid product rich in aromatics. The liquid, gas, and char
yields are ∼88, ∼4, and ∼8 wt %, respectively (see Figure 4).
Styrene monomer was the most abundant component found in
the liquid from thermal pyrolysis of PS followed by methyl
styrene, toluene, and ethylbenzene.
Figure 4. Product yields as a function of feed ratio for thermal
pyrolysis (LB and PS).
TCP of LB and PS mixtures produced a higher liquid yield
compared to TCP of LB-PP mixtures. The liquid yield values
in TCP of LB and PS mixtures were in the range of 45−64 wt
% with the maximum yield observed at a high PS loading (LB/
PS ratio of 0.5) (see Table S3 in the Supporting Information
for the phase distribution values). The char yield was
proportional to the biomass fraction in the feed mixture, that
is, higher char yields at a high LB loading (see Figure 4).
Figure 5 summarizes the product distribution in TCP of LB
and PS mixtures. The aromatic yields almost remained
constant and did not change appreciably with changes in the
feed ratio. The aromatics yield was in the range of 77−80%C.
Similar to PS pyrolysis, styrene monomer, methyl styrene,
toluene, and ethylbenzene were found abundantly in the bio-
oil. The selectivity of phenols (product of lignin degradation
from biomass) did not change with the feed ratio; these results
suggest that the change in the feed ratio did not affect the
product distribution in the bio-oil to a significant extent in
TCP. The advantage of using a catalyst in the co-pyrolysis
process is discussed in the next few sections.
3.4. Effect of Feed Composition on Yields and
Selectivity with Polypropylene (PP). Catalytic co-pyrolysis
(CCP) of lignocellulosic biomass (LB) and polypropylene
(PP) mixtures was carried out at three different mass ratios
(1:1, 1:2, and 2:1). The co-pyrolysis experiments were
repeated three times to check the consistency of the results.
Figure 6 compares the percentage yields of liquid, char, and
gases at different LB to PP ratios. The liquid yield was
DOI: 10.1021/acs.energyfuels.9b03135
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Energy & Fuels
Figure 5. Distribution of functional groups as a function of feed ratio
for thermal pyrolysis (LB and PS).
Figure 6. Product yields as a function of feed ratio for CCP of LB and
PP mixtures.
maximum (∼43 wt %) at an LB to PP ratio of 0.5 and
minimum (∼35%) at a ratio of 2. This observation is in line
with the expectation since the pyrolysis of PP gives a
significantly higher liquid yield (∼60 wt %; see Figure 2),
and hence, the mixture with a higher proportion of PP exhibits
the maximum liquid yield. Similarly, it can be argued that
biomass pyrolysis results in a higher char yield compared to
PP, and therefore, the char yields in Figure 6 increase with
biomass fraction in the feed.
The influence of LB on the PP decomposition is explained
as follows. LB begins to degrade at a much lower temperature
than plastic. The thermal breakdown of plastic proceeds as a
radical chain process that includes steps of radical initiation,
chain propagation, and radical termination. During the initial
stage of co-pyrolysis, radicals from the LB components initiate
the chain scission of the plastic polymer chain. Consequently,
the hydrogen transfer takes place from the PP chain to the LB-
derived radicals, which stabilize LB degradation products. This
mechanism, in turn, helps improve the hydrocarbon yield and
restricts char formation.38,39 PP, being a hydrogen-rich
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polymer, provides significant hydrogen to the LB and increases
the hydrocarbon yield. Hence, the liquid yield is expected to
increase at high PP proportions as observed in Figure 6. In all
the co-pyrolysis experiments, phase separation was observed in
the final liquid; one phase was rich in hydrocarbons, and the
other was rich in oxygenates (see Table S3 in the Supporting
Information for phase distribution values). Figure 7 summa-
Figure 7. Distribution of functional groups as a function of feed ratio
for CCP of LB and PP mixtures.
rizes the product distribution in the CCP of LB and PP
mixtures. Increasing the PP proportion in the feed mixture
boosted the formation of useful hydrocarbons (aromatics and
olefins). The combined yield of aromatics and olefins increased
from ∼65 to ∼89%C as the LB to PP ratio varied from 2 to
0.5. The increased PP loading resulted in a decrease in
undesired char, from ∼28 to ∼13 wt % (see Figure 6). Thus,
maintaining a hydrogen-rich environment during CCP has
contributed to the conversion of biomass into more useful
hydrocarbons and lowered the char formation.
3.4.1. Effect of Feed Ratio on Aromatic and Olefin Yields.
Both the aromatic and olefin yields increased at high PP
proportion in the feed. The maximum aromatic yield (∼49 %
C) was obtained for an LB to PP ratio of 0.5, whereas the
minimum (∼32%C) was obtained for an LB to PP ratio of 1.
Though the aromatic yield at an LB to PP ratio of 2 was higher
than the intermediate ratio, the majority of the aromatics at
high biomass fractions were phenolic compounds that
originated from biomass. Though the aromatic formation can
happen in many ways, it is attributed primarily to the
interaction of furans (from cellulose) with PP-derived olefins.
Cellulose is the principal constituent of LB and a polymer of β-
(1→4)-D-glucopyranose units. During pyrolysis, cellulose
depolymerizes into anhydrosugars (mostly levoglucosan) and
other oxygenated compounds.6,40 In the presence of an acid
catalyst, the anhydrosugars undergo dehydration and rear-
rangement reactions to form smaller oxygenates (e.g., furans,
smaller aldehydes, and water) that penetrate the catalyst pores
and undergo a series of reactions (dehydration, dehydrogen-
ation, decarboxylation, decarbonylation, oligomerization, and
isomerization) to form monocyclic aromatics and olefins.2
Moreover, Diels−Alder reaction between furans and olefins
results in the formation of a Diels−Alder adduct, which, upon
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Energy Fuels 2020, 34, 460−473
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dehydration, produces aromatics. The Diels−Alder reaction is
the most desired in biomass co-pyrolysis since it produces C6
ring compounds in a single step (see Figure 8). It is reported
Figure 8. Diels−Alder reaction between furans and olefins in the
presence of spent FCC catalyst.
that the furan acts as a conjugated diene and the olefin as a
dienophile.3,22,41 Furans and olefins are the key reactants for
the aromatic formation in co-pyrolysis, and a low abundance of
either one of them would significantly vary the aromatic yield.
Co-feeding PP, therefore, ensures the presence of olefins in the
pyrolysis reactions, where it aids both in the aromatic
formation and in the stabilization of LB-derived oxygenates.
In addition to their contribution to aromatic formation, the
PP-derived olefins also undergo a series of reactions
(oligomerization, cyclization, and aromatization) within the
catalyst pores.16 However, the rate of olefins to aromatic
formation through PP depolymerization is slow compared to
the LB pyrolysis reactions.
Char formation is a significant competing reaction that
hinders the aromatic formation. It can happen in many ways
via polymerization of degraded cellulosic fragments or
polymerization of furans and aromatics.21,42 LB is rich in
carbon relative to hydrogen, and most of the hydrogen in LB is
bound to oxygen in the form of a hydroxyl group rather than
carbon. During LB pyrolysis, most of this hydrogen is removed
as water, making it more hydrogen-deficient. As a result, the
reaction mechanism shifts toward the char formation due to
the lack of hydrogen availability for hydrocarbon formation.5,43
The decrease in aromatic yields at high biomass fractions is
due to the coverage of the active surface area of the catalyst by
char formation. Co-pyrolysis at high and intermediate biomass
fractions produce more sugars (especially levoglucosan). The
sugar molecules cannot diffuse readily into the catalyst pores
owing to their large molecular size.44,45 They dehydrate on the
external active surface of the catalyst to form furans and other
smaller oxygenates. The furans have to diffuse through the
catalyst pores to further get transformed to aromatics.
However, as time proceeds, char formation happens through
the dehydration of accumulated sugar molecules. The char
buildup on the external surface of the catalyst restricts the
passage of smaller molecules like furans into the catalyst pores
hampering both the aromatic formation and deoxygenation
reactions. Therefore, high amounts of furans (oxygenates) at a
high biomass loading (LB to PP ratio of 2) are observed, as
seen in Figure 7.
Similar to aromatics, the olefin content increased with
increasing PP fraction in the feed. The highest yield of ∼40%C
and the lowest yield of ∼19%C were observed at LB to PP
ratios of 0.5 and 2, respectively. The olefins were mainly in the
range of C7−C12, and C9 fraction was the most dominant.
Most of the unreacted olefins were branched olefins. This is
because PP is a branched polymer, and its thermal breakdown
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predominantly produces branched olefins. It is reported that
the branched olefins are less reactive than linear α-olefins due
to steric hindrance.16 Branched alkanes were observed with a
<7%C yield in all the co-pyrolysis experiments; these are
envisaged to be formed by hydrogenation of the branched
olefins through H2 released during the aromatization process.
Commonly observed alkanes were 1,3,5-trimethylcyclohexane
and 2,6-dimethylnonane.
3.4.2. Effect of Feed Ratio on Aromatic Hydrocarbon
Selectivity. Figure 9 shows the selectivity of the aromatic
Figure 9. Aromatic selectivity as a function of feed ratio for CCP of
LB and PP mixtures.
compounds, which were the most desired in this study.
Toluene, xylene, alkylbenzenes, and phenols (cresols, benze-
nediols, and xylenols) were the main aromatic compounds
detected. The selectivity for toluene peaked (∼24%C) at an LB
to PP ratio of 1. Selectivity toward xylene increased from ∼21
to ∼35%C with an increase in the PP loading in the feed. A
similar behavior was observed by Cheng et al.,46 who reported
that furan and propylene produced a significant amount of
xylenes in the presence of the HZSM-5 catalyst. Although the
overall aromatic selectivity increased with a higher PP content
in the feed, the combined yield of toluene and xylene was
maximum (∼54%C) at an LB to PP ratio of 1. This value
suggests that there exists an optimal LB to PP ratio at which
maximum valuable aromatics are formed. Lignin contains
several methoxy groups in its structure, resulting in the
generation of methyl groups at high temperatures.47 The
absence of benzene and high selectivity for xylenes at high PP
fractions signify that the methyl groups from lignin react with
benzene to form xylene. In addition to xylene and toluene,
alkylbenzenes such as 3-ethyltoluene, trimethylbenzenes, and
their isomers were found substantially at all feed ratios.
However, their trend was not monotonous with the changes in
the feed ratio.
Other monoaromatic compounds like phenols (including
phenols, cresols, and their isomers, benzenediols and their
isomers, and xylenols) are found abundantly in the bio-oil.
Their selectivity was ∼43 %C at high biomass ratios and
decreased to ∼27 %C at a low biomass fraction. Previous
studies have reported that the phenols are formed either by the
breakdown of ether linkages in the main lignin chain or
through the oxidation of aromatic intermediates.22,25 Lignin is
one of the major components of lignocellulosic biomass and is
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Energy & Fuels
itself a cross-linked phenolic polymer that contains alkoxy,
aryloxy, and phenolic subunits. The major pyrolysis products
of lignin are phenols, guaiacols, and syringols. It has been
recently reported that guaiacol acts as a methylating agent and
forms benzenediols, hydroxybenzene, and cresols as final
products in the presence of the H-USY catalyst.48 Our
observations are consistent with this reported trend as
substantial quantities of phenols were formed at a high
biomass fraction in the feed.
Lignin-derived phenols may also be the precursors for the
formation of PAHs (polycyclic aromatic hydrocarbons) and
char. Phenols are relatively thermally stable and are less
reactive compared to other molecules. However, they tend to
dehydrate and polymerize in the presence of an acid catalyst.
Recent studies report that PAH formation is mainly due to the
combination of biomass-derived oxygenates with monoaro-
matics, viz., secondary reactions of pyrolysis products.9,49 In
our study, the PAH selectivity was ∼5% C at the lowest LB to
PP ratio. However, it was negligible for the other two ratios
due to coverage of the active catalyst surface area by char, as
mentioned in section 3.4, at high biomass loading, which
inhibits PAH formation owing to the inaccessibility of the
pores for the dehydration and polymerization reactions.
3.4.3. Effect of Feed Ratio on Oxygenate Distribution.
CCP of LB and PP mixtures resulted in oxygenated
compounds like anhydrosugars, carboxylic acids, aldehydes,
ketones, alcohols, and esters. The cellulose and hemicellulose
are the primary sources for their formation. Table 2 shows the
Table 2. %C Yields of Oxygenated Compounds in Catalytic
Co-pyrolysis of LB and PP
LB/PP ratio
compounds 0.5 1 2
anhydrosugars 0.76 0 0.95
furans 0 9.87 8.37
carboxylic acids 1.07 4.65 0.66
esters 1.92 1.68 4.54
ethers 0 0 4.77
ketones 0 5.97 4.21
alcohols 0.48 4.38 5.79
total 4.23 26.54 29.29
%C selectivity of oxygenated compounds; the major
compounds are furans, hydroxyl, carboxyl, and carbonyl
group compounds. As expected, the amount of oxygenated
compounds diminished as the PP portion in the feed mixture
increased since oxygenates are mainly formed from biomass. In
addition to dehydration, oxygen is also removed by decarbon-
ylation and decarboxylation reactions in the form of CO and
CO2. The significant decrease in carboxyl and carbonyl groups
at high PP loading may be mainly attributed to the better
catalytic activity to disrupt the −COOH and CO bonds to
produce CO2, CO, and hydrocarbons as final products.45
The presence of significant amounts of unconverted furans
and olefins at high LB loading reveals that char buildup on the
catalyst surface had a significant impact on the interaction
between the two classes of compounds. The char formation, in
turn, influenced the aromatic yield as there was less provision
for the molecules to access the acidic sites of the catalyst.
Among the oxygen-containing aromatics, phenols contributed
to around ∼43% of their composition at high biomass loading;
these are primarily the degradation products of lignin. At low
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biomass loading, the absence of furans indicates that the
aromatic formation was greatly enhanced through the Diels−
Alder mechanism, as discussed in the previous subsection.
3.4.4. Effect of Feed Ratio on Olefin Distribution. Figure
10 depicts the olefin distribution during CCP of LB and PP
Figure 10. Olefin distribution as a function of feed ratio for CCP of
LB and PP.
mixtures at different mass fractions. The olefins were widely
distributed ranging from C7 to C12 in all the experiments.
Majority of the unreacted olefins belong to C9, which have
branching in their structures, for example, (Z)-2,4-dimethyl-1-
heptene, (Z)-2,3-dimethyl-3-heptene, and (Z)-2,6-dimethyl-3-
heptene; they constituted ∼50% of the olefin composition at
all the feed ratios. Li et al.16 reported that branched olefins do
not interact appreciably in the Diels−Alder reaction due to
their restricted mobility into the catalyst pores. Apart from
branched olefins, C7 cyclic olefins like 1,3-cycloheptadiene
were also found in abundance at higher and intermediate PP
loading. They represent ∼36% of the olefins composition at an
LB to PP ratio of 0.5. This suggests that cyclic olefins are solely
formed from the PP decomposition and not from the LB
components. The presence of furans in the liquid suggests that
furans interact with the smaller olefins only which are in cis-
conformation.16 The possible reaction mechanisms during
CCP of LB and PP are depicted in Figure 11, which shows the
different routes for formation of furans (e.g., directly from
hemicellulose pyrolysis or by dehydration of cellulose pyrolysis
products), aromatic formation from olefins derived through
cracking of PP or pyrolysis of lignin, etc.; it may be noted that
these reaction pathways are already described previously as
needed in this section.
3.4.5. Hydrogen Utilization. To evaluate the effective
hydrogen utilization at various feed ratios, the (H/C)eff ratios
were calculated and compared with the bio-oil obtained from
the thermal and catalytic pyrolysis of biomass. The (H/C)eff
ratios in Figure 12 were calculated using the results of the
CHNS analysis of the liquid products and eq 7. As expected,
the (H/C)eff ratio in the product from catalytic pyrolysis is
higher than thermal pyrolysis; therefore, it can be inferred that
addition of the spent FCC catalyst has led to an improvement
in the bio-oil quality. It can be observed from Figure 12 that
the CCP product values at LB to PP ratios of 0.5 and 1 are
significantly higher than the products of thermal (TP) or
catalytic (CP) pyrolysis. The trend indicates that hydrogen
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Energy & Fuels
Figure 11. Possible reaction mechanisms during CCP of LB and PP mixtures with spent FCC.
Figure 12. (H/C)eff ratio as a function of feed composition for
pyrolysis of LB and PP mixtures
from plastic was effectively utilized at LB to PP ratios of 0.5
and 1, which implies that CCP of LB and PP improved the H/
C ratio of the bio-oil and the H2 from plastic helped in
lowering the oxygen content of the bio-oil. The low EHI value
at the highest biomass loading (feed ratio of 2) is close to that
of the product from catalytic pyrolysis of biomass; this is a
result of the higher fraction of aromatics in the bio-oil at an LB
to PP ratio of 2, which inherently have a lower H/C ratio (e.g.,
1 for benzene) compared to olefins and alkanes.
3.5. Effect of Feed Ratio on Pyrolysis Gas Distribution
in CCP of LB-PP. Figure 13 represents the pyrolysis gas
distribution as a function of feed ratio. H2, CH4, and carbon
oxides (CO and CO2) were the main gases observed during
TP, TCP, and CCP experiments. In LB pyrolysis, carbon
oxides were the dominant gases comprising ∼56% of the total
gas yield, followed by CH4 and H2 with yield values of ∼24 and
∼20%, respectively. In thermal pyrolysis of PP, CH4 and H2
were the only observed gases with yield values of ∼62 and
∼38%, respectively. No carbon oxides were detected as PP has
only carbon and hydrogen in its structure.
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For co-pyrolysis experiments, CH4 was the most dominating
compound during TCP, whereas carbon oxides were the most
abundant gases during CCP. For TCP, the highest CH4 yield
(∼61%) was observed at an LB/PP ratio of 0.5, while the
corresponding value was ∼13% at an LB/PP ratio of 2 for
CCP. The H2 yield was almost the same for TCP and CCP
runs, with the yield values ranging from ∼21 to 28%. The peak
H2 value (∼26 to 27%) was observed at an LB/PP ratio of 0.5
in the case of the co-pyrolysis experiments. With the addition
of the catalyst, the yield of carbon oxides enhanced greatly with
a simultaneous decrease in CH4 yields. For CCP, the carbon
oxides yields were in the range of ∼63−75% with peak value
(∼74%) at an LB/PP ratio of 1. In the case of TCP, the yield
range of the carbon oxides was only 13 to 37% with peak value
(∼37%) at an LB/PP ratio of 1. These results suggest that the
catalyst addition upgraded the bio-oil by disrupting the
carbonyl (CO) and carboxyl (COOH) functional groups
from biomass and removing the oxygen in the form of CO and
CO2.
3.6. Effect of Feed Composition on Yields and
Selectivity with Polystyrene (PS). Figure 14 compares the
product yields for CCP of lignocellulosic biomass (LB) and
polystyrene (PS) at mixing ratios of 1:1, 1:2, and 2:1. As
expected, the addition of PS to biomass improved the liquid
yield since the stand-alone pyrolysis of PS gives a significant
amount of liquid (>80 wt %; see Figure 4) compared to
biomass. The bio-oil yield was minimum (∼46%) at a ratio of
2 and increased to a maximum (∼65%) with the increase in
the PS content in the feed at an LB to PS ratio of 0.5. Also, the
pyrolysis of PS produces significantly lower residue amounts
than biomass. Hence, the char yields in CCP of LB and PS can
be mainly attributed to LB, and it varies between ∼17 to ∼26%
as the LB fraction in the feed increases.
3.6.1. Comparison of Bio-Oil Component Distribution in
CCP of LB and PS Mixtures. Figure 15 summarizes the product
carbon yields from catalytic co-pyrolysis of LB and PS
mixtures. The aromatic selectivity was almost the same at all
the mixing ratios, and the values are in the range of ∼79−82%
C. The high aromatic content in the liquid is primarily due to
PS, which is an aromatic polymer and its pyrolysis produces
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Energy & Fuels
Figure 13. Gas distribution as a function of feed composition for thermal, thermal co-pyrolysis (TCP), and catalytic co-pyrolysis (CCP) of LB and
PP mixtures.
Figure 14. Product yields as a function of feed ratio for CCP of LB
and PS mixtures.
aromatic compounds. The degradation products of lignin also
contribute to aromatics in the pyrolysis liquid. The aromatic
formation through the Diels−Alder mechanism is not possible
as PS is not capable of producing smaller olefins.33 Similarly,
there was no significant change in the oxygenate content in the
liquid with the changing feed ratio. The oxygenate values were
found to be in the range of ∼18−20%C. It can be inferred that
there were no significant interactions between the PS and LB
components as the aromatic rings are more stable compounds
compared to olefins.
3.6.2. Effect of Feed Ratio on the Aromatic Hydrocarbon
Distribution. The aromatics were the desired compounds of
interest in this study. Styrene, ethylbenzene, α-methyl styrene,
styrene dimers, phenols, alkylbenzenes, naphthalene, and
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Article
Figure 15. Distribution of functional groups as a function of feed ratio
for CCP of LB and PS mixtures.
indene derivatives were the common products during LB-PS
co-pyrolysis. However, their selectivity varied significantly
among the three ratios. The % carbon yields of the aromatic
hydrocarbons during CCP of LB-PS mixtures for the three
ratios are presented in Table 3.
Styrene was the most abundant aromatic product from CCP
of LB-PS mixtures. Its composition was maximum (∼27%C) at
an LB to PS ratio of 1 and minimum (∼16%C) at a ratio of 2.
Polystyrene is a polymer of styrene, and the β-scission of the
C−C bond in its main chain produces styrene. Also, the
presence of an acidic catalyst accelerates the disruption of the
C−C bonds in the PS polymer chain.50,51 The lower selectivity
of styrene monomer at higher biomass loading is attributed to
either limited catalytic activity or further styrene monomer
conversion to compounds such as ethylbenzene, styrene
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Energy & Fuels Article

Table 3. Aromatic Selectivity as a Function of Feed Ratio ethylbenzene, which is reported to occur in the presence of an
for CCP of LB and PS Mixtures acid catalyst.50 The ethylbenzene formation was in the range of
∼14 to ∼17%C as the feed ratio changed.
LB/PS ratio
Alkylaromatics such as α-methylstyrene, α-ethylstyrene, and
aromatic hydrocarbons 0.5 1 2 isopropylbenzene were also observed at all the feed ratios.
styrene 24.02 26.97 15.79 Their formation can be mainly attributed to β-scission and
ethylbenzene 13.92 16.93 15.28 hydrogen transfer to PS.44
styrene dimers 13.63 15.03 13.86 Styrene dimers were also observed in the liquid product at
benzene derivatives 7.67 4.80 14.30 all feed ratios; they are styrene oligomers typically formed by
alkyl styrene 7.75 13.15 1.80
the back-biting reaction of styrene monomers through the free
phenols 6.73 8.12 5.73
radical mechanism followed by β-scission during depolymeri-
PAHs (naphthalene and its derivatives, indene 26.29 15.0 32.88
and its derivatives, and multiring aromatics zation of the styrene polymer.52 The percentage selectivity of
having more than two rings) styrene dimers was ∼14% C on average. The observed styrene
dimers include 2-phenyltetralin, diphenylmethane, 1,3-diphe-
derivatives, and styrene dimers. The formation of ethylbenzene nylpropane, 1,2-diphenylpropane, 1,3-diphenyl-1-butene, 1,2-
suggests that hydrogen transfer happened during co-pyrolysis. diphenylethylene, and 1,5-diphenyl-1-pentene. Among all the
Figure 16 illustrates the reaction of hydrogenation of styrene to styrene dimers, 1,3-diphenylpropane and 1,3-diphenyl-1-
butene were predominant in all the experimental runs. The
maximum yield for 1,3-diphenylpropane (∼5%) was obtained
at low PS loading, and the maximum yield (∼5%) for 1,3-
diphenyl-1-butene was obtained at high PS loading. 1,3-
Diphenylpropane is formed by the reaction between the
styrene radical and benzyl radical, while 1,3-diphenyl-1-butene
is formed by the combination of two styrene free radicals
followed by dehydrogenation.33 The possible reaction path-
Figure 16. Hydrogenation of styrene to ethylbenzene. ways for the formation of various styrene dimers are depicted
in Figure 17.

Figure 17. Reaction pathways for styrene dimer formation during CCP of LB and PS mixtures.33

469 DOI: 10.1021/acs.energyfuels.9b03135

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Energy & Fuels Article

Figure 18. Mechanism of PAH formation during lignin depolymerization.58

Other compounds like benzene derivatives were also found
in the bio-oil, especially in a higher percentage (∼14%) at a
feed ratio of 2. These benzene derivatives include iso-
propylbenzene, propylbenzene, 2-propenylbenzene, 1-prope-
nylbenzene, cyclopropylbenzene, biphenyl, terphenyl, etc.
Apart from the desired monoaromatics, PAHs, which are
extremely undesirable in the bio-oil, are also found. They are
highly susceptible to coke formation in the presence of an acid
catalyst. In this study, PAHs are categorized as naphthalene
and its derivatives, indene and its derivatives, and multiring
aromatic components having more than two rings. The total
PAH selectivity was maximum (∼33%) at high LB loading and
minimum (∼15%) at an equal feed ratio. Among the PAH
observed, two-ring PAH, naphthalenes and indenes, dominated
in all the liquid samples. Phenanthrene and fluorene were the
second most detected three-ring PAHs. Among the two-ring
PAHs, the maximum selectivity for naphthalene derivatives
(∼14%) was observed at high and low PS loadings, while the
maximum for indene derivatives (∼12%) was observed at high
biomass loading. Both the naphthalene and indene derivatives
exhibited a lower selectivity at intermediate mixing ratios (∼7
and 5%, respectively).
Since both PS and lignin are aromatic in nature, there is a
possibility of PAH formation from their degradation products.
Monocyclic aromatics combine with oxygenated fragments
from biomass to form naphthalenes and other higher PAHs.53
It is reported that styrene and benzene also contribute to two-
ring PAHs, and the presence of a catalyst can enhance their
formation.54,55 Styrene monomers via intramolecular hydrogen
transfer and β-scission reactions also lead to PAH formation.56
Among naphthalene derivatives, 2-phenylnaphthalene was
observed at all the LB to PS ratios (∼8%). Though benzene
was not observed in the final liquid product during co-pyrolysis
of biomass and PS, the presence of indene derivatives indicates
the formation of benzene and its cyclization in the presence of
the catalyst to produce indene and its derivatives.57 The
presence of benzene derivatives also supports the formation of
benzene during co-pyrolysis. Further, both the naphthalene
and indene derivatives had methyl groups attached to the ring
and can be attributed to the generation of methyl groups
during lignin depolymerization. The presence of phenols,
cresols, and catechols in the bio-oil indicate that the secondary
pyrolysis reactions of lignin (demethoxylation, dehydroxyla-
tion, and demethylation) occurred during co-pyrolysis.58 The
mechanism of PAH formation during lignin depolymerization
is shown in Figure 18.
470
The high PAH selectivity and low phenolics yield at high
biomass loading indicates a greater possibility of phenols acting
as potential precursors for PAH formation. The major phenolic
compounds identified include phenols, cresols (and their
isomers), and benzenediols (and their isomers), which are of
lignin origin formed via breakage of weak α-ether and β-ether
bonds.59 In the presence of a catalyst, they actively undergo a
series of dehydration and polymerization reactions to form
PAH and char.56 However, the actual mechanism of PAH
formation is quite elusive and yet to be understood completely.
3.6.3. Effect of Feed Ratio on Oxygenate Distribution.
Table 4 shows the %C selectivity of oxygenated compounds in
Table 4. %C Yields of Oxygenated Compounds in Catalytic
Co-pyrolysis of LB and PS
LB/PS ratio
compounds 0.5 1 2
anhydrosugars 3.46 9.48 1.30
furans 1.35 7.97 3.30
carboxylic acids/esters 2.31 1.54
aldehydes/ketones 9.65 2.57 13.32
alcohols 1.64 0.85 0.40
total 18.40 20.87 19.86
the bio-oil. Anhydrosugars, furans, aldehydes, and ketones
were the majority of oxygenates observed in all the feed ratios;
these compounds are mainly the defragmented products of
cellulose and hemicellulose. The oxygenate content almost
remained the same (∼18−21%) at all the feed ratios,
indicating that the PS and LB components did not have
significant interactions. The low amounts of sugars and furans
and high PAH content (see Table 4) at high and low biomass
loading reveal that these oxygenates contributed to PAH
formation.53
3.6.4. Hydrogen Utilization. To evaluate the effective
hydrogen utilization between LB and PS, a (H/C)eff analysis
was performed similar to that of PP in section 3.4.5. Most of
the studies in the literature indicated that PS and biomass did
not exhibit significant interactions during catalytic pyroly-
sis.32,33,60 In our study, the (H/C)eff values of the co-pyrolysis
liquid almost remained the same at all feed ratios (see Figure
19), which signify that PS and LB had minimum interactions
during co-pyrolysis.
Figure 19 also shows that the CCP product (H/C)eff values
are higher than the products of thermal (TP) or catalytic
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Energy & Fuels
Figure 19. (H/C)eff ratio as a function of feed composition for
pyrolysis of LB and PS mixtures.
pyrolysis (CP) at mixing ratios where the plastic proportion is
low. At the highest PS loading, the (H/C)eff value is close to
that of catalytic pyrolysis, possibly due to the formation of
monoaromatics. At other PS loading ratios, the proportion of
alkyl styrenes is higher, which results in (H/C)eff values greater
than one.
3.7. Effect of Feed Ratio on Pyrolysis Gas Distribution
in CCP of LB-PS. Figure 20 shows the pyrolysis gas
Figure 20. Gas distribution as a function of feed composition for
thermal, thermal co-pyrolysis (TCP), and catalytic co-pyrolysis
(CCP) of LB and PS mixtures.
compositions as a function of feed ratio for TP of LB and
PS and co-pyrolysis (thermal and catalytic) of LB and PS
mixtures. H2, CH4, and carbon oxides (CO and CO2) were the
most abundant gases in all the experimental runs. The
percentage of H2 in LB pyrolysis was ∼20%, whereas this
value ranged from ∼11 to 14% and ∼8 to 18% for TCP and
CCP, respectively.
The percentage CH4 yield was maximum (∼24%) for LB
pyrolysis and TCP (∼23%) at a feed ratio of 0.5. Carbon
oxides were the most dominant compounds during TP of LB,
TCP, and CCP of LB-PS mixtures, irrespective of the feed
ratios. There was no significant gas yield in the case of thermal
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pyrolysis of PS. The carbon oxides are mainly the products of
LB decomposition as PS is an aromatic polymer consisting of
carbon and hydrogen only in its structure. The percentage of
carbon oxides varied in the range of ∼56−73% across all the
experiments in Figure 20. These results (particularly carbon
oxide yields) further justify that LB and PS did not have
significant interactions either in TCP or CCP.
4. CONCLUSIONS
In this study, experiments on catalytic co-pyrolysis of
lignocellulosic biomass and plastics (PP and PS) with spent
FCC catalyst were performed at three different mixing ratios to
investigate the effect of plastic composition on the product
yields and selectivity. The increase in plastic proportion in the
feed enhanced the liquid yield. The oxygenate content also
reduced to a significant extent from 30 to 5%C when the
plastic proportion was increased from 33 to 67 wt %, especially
with PP (Figure 7). The results suggest that decarboxylation
and decarbonylation reactions were the primary deoxygenation
pathways during CCP using the spent FCC catalyst. The
maximum yield of monoaromatics and olefins was ∼73% when
PP was used as a co-reactant at an LB to PP ratio of 0.5. Using
PS as a co-feed produced the maximum aromatic yield of
∼82% at the same feed ratio. However, the more valuable
chemicals like toluene, xylene, etc., were found abundant for
PP, and useful aromatics like styrene, ethylbenzene, etc., were
abundantly formed for PS at equal mixing ratios. This suggests
that the optimum feed conditions would tailor the reaction
mechanism toward the formation of more valuable chemicals
due to the presence of active acidic sites of the spent FCC
catalyst. Further, since the best performance in terms of
aromatic yields was obtained at a feed ratio of 0.5, it can be
concluded that having a large excess of plastic in the co-
pyrolysis feed mixture is not beneficial; this is important as
obtaining greater amounts of waste plastic compared to
biomass is challenging. The waste agricultural residue or
biomass generation is much higher than waste plastic
generation. The (H/C)eff ratio of the final liquid products in
the case of PP was comparatively higher than the products of
catalytic pyrolysis of biomass, which suggests oxygen reduction
during CCP process; this is also expected to increase the
calorific value of the oil formed. However, in the case of PS,
the (H/C)eff results show that PS did not have significant
interactions with LB. These results suggest that the product
distribution in CCP of lignocellulosic biomass and plastic
mixtures strongly depends on the feed composition. Also, co-
pyrolysis of a H2-rich feedstock (plastic) and a H2-deficient
feed (biomass) offers synergy in improving the (H/C)eff of the
bio-oil formed in the presence of spent FCC catalyst. Future
studies could consider optimization of the reaction conditions
by investigating the effects of temperature, heating rate, catalyst
loading and residence time together. A continuous process
rather than a batch process might be more amenable and could
be taken up as another future work using auger reactors. This
process helps in valorization of waste plastics and agricultural
residues to make chemicals and in waste management.
However, owing to the logistics involved in the collection,
transport, and storage of these waste resources, it is advisable
to have small-scale and distributed CCP units, which can be
mobile and modular for easy scale-up of the process.
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■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.energyfuels.9b03135.
Table summarizing the use of catalyst in co-pyrolysis of
plastics and biomass; proximate analysis of the feed
components; tables showing the % weight distribution of
organic and aqueous phases in the bio-oil and % yields of
products (liquids, gases, and char) in the catalytic
pyrolysis of LB, PP, and PS; and figure showing the
DTG curves for LB, PP, and PS (PDF)
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: s.srinivas@iitb.ac.in.
ORCID
Seethamraju Srinivas: 0000-0003-0505-1029
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The authors thank IRCC, IIT Bombay for the seed grant
project funding provided to S.S. and MHRD, India for
providing the scholarship to K.P.K. during his graduate
studentship. The authors also thank SAIF, IIT Bombay for
providing the analytical facilities used in this work. The authors
are also thankful to the anonymous reviewers whose comments
helped in improving the quality and presentation of this work.
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473 DOI: 10.1021/acs.energyfuels.9b03135

Energy Fuels 2020, 34, 460−473