Energy Conversion and Management 180 (2019) 60–71

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Energy Conversion and Management

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Catalytic fast co-pyrolysis of bamboo sawdust and waste tire using a tandem T
reactor with cascade bubbling fluidized bed and fixed bed system
⁎
Jia Wanga,b, Zhaoping Zhonga, , Kuan Dinga,c, Mi Lib, Naijia Haob, Xianzhi Mengb, Roger Ruanc,
⁎
Arthur J. Ragauskasb,d,e,
a
Key Laboratory of Energy Thermal Conversion and Control of Ministry of Education, Southeast University, No. 2 Sipailou, Xuanwu District, Nanjing, Jiangsu 210096,
China
b
Department of Chemical & Biomolecular Engineering, University of Tennessee, Knoxville, TN 37996, USA
c
Center for Biorefining and Department of Bioproducts and Biosystems Engineering, University of Minnesota, 1390 Eckles Ave., St. Paul, MN 55108, USA
d
Department of Forestry, Wildlife and Fisheries, Center for Renewable Carbon, The University of Tennessee, Institute of Agriculture, Knoxville, TN 37996, USA
e
Joint Institute for Biological Science, Biosciences Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831, USA

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

Keywords: Catalytic fast co-pyrolysis (co-CFP) of bamboo sawdust and waste tire over HZSM-5 and MgO was conducted
Catalytic fast co-pyrolysis using a tandem pyrolysis and upgrading system which consists of a bubbling fluidized bed and a fixed bed
Bamboo sawdust reactor. HZSM-5 mixed and sequential with MgO modes were studied to explore the additive effect for the
Waste tire promotion of aromatic hydrocarbons. Experimental results indicated that co-CFP of bamboo sawdust with waste
HZSM-5 and MgO
tire over pure HZSM-5 increased the yields of pyrolysis oil and char, while the gas yield decreased with the
Additive effect
increasing of waste tire percentage in the feedstock blends. The product distribution of pyrolysis oil obtained
from co-CFP of bamboo sawdust and waste tire over pure HZSM-5 was dominated by aromatic hydrocarbons,
and the relative concentration increased from 26.71 to 71.50% as the waste tire percentage elevated from 0 to
60 wt%. Co-CFP of bamboo sawdust and waste tire using HZSM-5 mixed with MgO mode produced a higher yield
of pyrolysis oil than the sequential mode when HZSM-5/MgO mass ratio was raised from 1:4 to 1:1. However,
the sequential mode was proved to be more effective in the promotion of aromatic hydrocarbons than the mixed
mode at a higher HZSM-5 proportion. A positive additive effect for alkylbenzenes was found when the sequential
mode was used at varying HZSM-5/MgO mass ratios. Regarding the olefins, C10 olefins were main products, and
limonene selectivity increased at first and then decreased with the highest selectivity of 38.87% occurring at
HZSM-5/MgO of 2:3 in the mixed mode case. The additive effect of HZSM-5 and MgO indicated that both the
mixed and sequential modes inhibited the formation of polycyclic aromatic hydrocarbons with the most sig-
nificant additive effect obtained at HZSM-5/MgO mass ratio of 1:1 using the mixed mode.

1. Introduction into alternative fuels, such as thermochemical conversion to produce

Thermochemical conversion of fossil-based and bio-based wastes
into alternative liquid fuels provides a promising approach to realize
waste management and environmental protection [1–4]. Among the
fossil-based wastes, waste tires are one of the most important materials.
The production of tires reaches to 1.5 billion tons each year, and a
considerable amount of waste tire (800 million tons) needs to be dis-
posed of [5]. Due to the nonbiodegradable and non-destructible prop-
erties of waste tire, post-treatment and/or recycling are difficult. In
addition, landfill of waste tire is prohibited in many countries in Europe
[6]. Therefore, efforts should be made to effectively convert waste tires
liquid products [7–9], gasification to generate flue gases [10,11], and
incorporating into cement concrete to replace some of the natural ag-
gregates [12,13].
Among the thermochemical techniques employed to convert bio-
based and fossil-based wastes into liquid products, fast pyrolysis and
catalytic fast pyrolysis (CFP) are the most commonly used ones
[14–17]. Studies on the pyrolysis of waste tires have been conducted
extensively to investigate the effect of pyrolysis temperature, heating
rate and reactor configuration on the product yields and chemical
fractions in the pyrolysis oil [8,18–24]. In addition, catalytic fast co-
pyrolysis (co-CFP) of waste tire with lignocellulosic biomass also has

⁎
Corresponding authors at: Key Laboratory of Energy Thermal Conversion and Control of Ministry of Education, Southeast University, No. 2 Sipailou, Xuanwu
District, Nanjing, Jiangsu 210096, China (Z. Zhong).
E-mail addresses: zzhong@seu.edu.cn (Z. Zhong), aragausk@utk.edu (A.J. Ragauskas).

https://doi.org/10.1016/j.enconman.2018.10.056
Received 14 August 2018; Received in revised form 26 September 2018; Accepted 17 October 2018
Available online 05 November 2018
0196-8904/ © 2018 Elsevier Ltd. All rights reserved.
J. Wang et al. Energy Conversion and Management 180 (2019) 60–71

Table 1
Reaction conditions for co-pyrolysis of biomass with waste tire.
Feedstocks co-pyrolyzed with waste tire Reactor Catalyst Tem.a/°C Yield (wt%) Ref.

Pyrolysis oil Char Gas

Wheat straw Fixed bed Non 500 44.13 37.65 18.22 [31]
Pine wood chips Fixed bed Non 500 48.51 24.84 26.65 [6]
Pine wood chips Auger reactor Non 500 56.04 26.72 17.24 [6]
Pine nut shell Fixed bed Non 500 47.08 36.67 16.25 [26]
Wood biomass Fixed bed SBA-15 500 46.45 – – [32]
Bamboo sawdust Microwave-assisted reactor HZSM-5 550 37.86 40.39 21.72 [33]
Lignite Fixed bed Non 500 31.69 42.83 25.48 [34]
Lignite Heinze reactor Non 500 25.13 47.37 27.50 [34]
Palm shell Fixed bed Non 500 48.06 36.16 15.78 [35]
Coal Fixed bed Non 850 32.25 48.16 19.56 [36]
Coal Rotary oven Non 850 12.55 30.57 56.88 [36]
Soap stock Microwave-assisted reactor HZSM-5 550 35.47 33.06 31.47 [7]
Pistachio seeds Fixed bed Ni-Mo/γ-Al2O3 500 60.14 20.03 19.83 [37]
Oily waste Fixed bed Red mud 500 46.19 40.53 13.28 [38]
Corn stalk Fixed bed Non 550 34.95 – – [39]

a
Tem. = Reaction temperature.

attracted much attention as shown in Table 1. Various bio-based raw
materials such as wheat straw, pine wood chips, and corn stalk, have
been used in catalytic co-pyrolysis with waste tires (Table 1). Abnisa
et al. [25] co-pyrolyzed palm shell and waste tire in a fixed bed reactor
at 500 °C, and they found that the addition of scrap tire in the pyrolysis
of palm shells improved both the quantity and quality of pyrolysis oil.
Uçar et al. [26] conducted co-pyrolysis of pine nut shells and scrap tires
at different blend ratios, and it was observed that compared to the bio-
oil obtained from pyrolysis of pine nut shells alone, the pyrolysis oil
derived from co-pyrolysis process had higher amounts of carbon and
lower concentration of oxygen.
Concerning the reactor configurations used in the co-CFP of biomass
and waste tire, a number of pyrolysis reactors such as fixed bed, mi-
crowave assisted reactor, auger reactor, and heinze reactor, have been
used to study the co-pyrolysis process (shown in Table 1). Dai et al. [27]
used a microwave assisted pyrolysis reactor to conduct the co-pyrolysis
of soap stock and waste tire, and the effects of pyrolysis temperature,
catalyst/feedstock mass ratio, soap stock/waste tire mass ratio on
product distribution were studied. It was observed that waste tires
could act as hydrogen donor which significantly promoted the pro-
duction of pyrolysis oil and the formation of aromatic hydrocarbons. In
addition, Martínez et al. [6] compared the pyrolysis oil characteristics
obtained from co-pyrolysis of forestry wastes and waste tires using a
fixed bed and a continuous auger reactor at 500 °C, and they found that
co-pyrolysis experiments conducted by the auger reactor showed more
significant synergistic effect than that of the fixed bed reactor. How-
ever, to the best of our knowledge, there is no study using a bubbling
fluidized bed tandem with a fixed bed reactor to conduct the co-CFP of
biomass and waste tire. Compared to the fixed bed system, the bubbling
fluidized bed reactor provides better mass and heat transfers which are
beneficial to biomass pyrolysis [28]. Huber et al. [29,30] concluded
that the production of aromatic hydrocarbons in pyrolysis oil obtained
from CFP of biomass using fluidized bed is the highest at optimal re-
action conditions.
On the other hand, catalysts used during the co-CFP of biomass and
waste tire were focused on HZSM-5, SBA-15, and red mud with HZSM-5
being the most commonly used (Table 1). Nolte et al. [40] reported that
acidic zeolites significantly promoted dehydration reactions in the
deoxygenation of cellulose pyrolysis. However, base catalysts such as
CaO or MgO favored the fragmentation reactions more which facilitated
the production of lower molecular weight pyrolytic products
[15,41,42]. Wang et al. [41] reported that the use of alkali metal oxides
during the catalytic fast pyrolysis of lignocellulosic biomass could de-
of lower-molecular-weight oxygenates and light hydrocarbon com-
pounds by fragmentation and CeC bonding (such as ketonization and
aldol condensation) reactions. Subsequently, the smaller oxygenates
can enter the micropores of HZSM-5 zeolites to be converted into aro-
matic hydrocarbons. Therefore, a combination of acidic zeolite and
base catalyst might result in dehydration reactions and low molecular
weight pyrolytic products. To test this hypothesis, in this study, a
bubbling fluidized bed connected with a fixed bed reactor was used to
conduct the co-CFP of bamboo sawdust and waste tire, and HZSM-5 and
MgO were used as catalysts. Two catalytic modes, namely HZSM-5
mixed with MgO (mixed mode) and HZSM-5 sequential with MgO
(sequential mode) were investigated. The effect of bamboo sawdust/
waste tire mass ratio and HZSM-5/MgO mass ratio on the pyrolytic
product yields and distribution was studied. In addition, the additive
effect between HZSM-5 and MgO in terms of promoting the formation
aromatic hydrocarbons was also explored.
2. Materials and experiments
2.1. Materials
Waste tire powder with 100 screen mesh (∼0.15 mm) was pur-
chased from a tire recycling plant in Guangdong province, China, and
they were used as received. Bamboo sawdust was obtained from
Zhejiang province, China, and they were ground and sieved with a 100
screen mesh (∼0.15 mm). Prior to the pyrolysis experiments, the
feedstocks were dried at 105 °C for 24 h. The elemental analysis of the
samples was conducted by Vario EL II elemental analyzer (Germany),
and the results are summarized in Table 2. In addition, MgO (high
purity, > 98%) was provided by Nanjing Chemical Reagent Co. Ltd.
HZSM-5 was purchased from the Catalyst Plant of Nankai University,
Tianjin, China, and the physicochemical properties are shown in Table
S1.
Table 2
Elemental analysis of bamboo sawdust and waste tire.
Ultimate analysisa (%) C H Ob N S
Bamboo Sawdust 51.51 6.12 42.05 0.21 0.11
Waste tire 88.62 6.18 0.63 2.62 1.95

oxygenate the carboxylic acids, linear aldehydes and bulky oxygenates a

Dry-ash free basis.
such as anhydrosugars (mainly levoglucosan), leading to the production b
By difference.

61
J. Wang et al.
Fig. 1. Schematic of the tandem cascade bubbling fluidized bed and fixed bed reactor system.
2.2. Experimental methods
A tandem cascade bubbling fluidized bed and fixed bed reactor was
used to conduct the co-CFP of bamboo sawdust and waste tire experi-
ments. The bubbling fluidized bed with an inner diameter of 32 mm and
a height of 480 mm, was used for co-pyrolysis of bamboo sawdust/
waste tire blends, and then the pyrolytic vapors were catalyzed over
HZSM-5/MgO catalysts in the fixed bed reactor (32 mm in diameter and
380 mm in height) as shown in Fig. 1. Two catalytic modes, i.e., HZSM-
5 mixed with MgO (mixed mode) and HZSM-5 sequential with MgO
(sequential mode), were studied in this work. Specifically, for the mixed
mode, HZSM-5 and MgO were physically mixed (3 g for each run) be-
fore each experiment, and then the catalyst blends were fixed in the
upgrader by a 200 mesh sieve (∼0.075 mm). While for the sequential
mode, HZSM-5 and MgO were separately placed in the upgrader, the
pyrolytic vapors first underwent the MgO layer and subsequently were
catalyzed by the HZSM-5 zeolites. Silica sand (0.15–0.2 mm size,
15 mL) were utilized as bed materials. High purity nitrogen (99.99%)
was used as carrier gas with a flow rate of 100 L/h (∼2.8 times of
theoretical minimum fluidization rate 34.7 L/h) and was heated up to
350 °C prior to each experiment. The bamboo sawdust and waste tire
blends (10 g for each run) were fed into the bubbling fluidized bed by a
screw feeder with a weight hourly space velocity (WHSV) of 4.83 h−1.
The catalytic upgrading vapors were condensed by an ice-cooled water
condenser and the non-condensable gases were collected by gas bags.
A gas chromatography/mass spectrometry (GC/MS, 7890A/5975C,
Agilent) was used to identify the chemical fractions in the pyrolysis oil
(heavy ends). The organic phases were separated by a capillary column
(HP-5MS, 0.25 mm × 0.25um × 30 m), and the column was controlled
at 1 mL/min with a split ratio of 1:20. High pure analytical helium
(99.999%) was used as carrier gas. The injector and interface tem-
peratures were kept at 275 °C and 300 °C, respectively. The GC column
62
Energy Conversion and Management 180 (2019) 60–71
oven was programmed to increase from 40 °C (3 min) to 180 °C (2 min)
with a heating rate of 5 °C/min, and then was increased to 280 °C at
10 °C/min. The electron ionization (EI) was kept at 70 eV, and the ions
were detected by mass-to-charge (m/z) ratios in the range of 28–350.
The identification of the pyrolytic components was conducted by
comparing the mass spectra with the NIST MS library database, and the
area percentage of the chromatogram peaks was used to analyze the
relative concentration of identified products as recently reported by
Zhang et al. [43], Ma et al. [44], and Wang et al. [45].
2.3. Evaluation method
The weight difference of the condensation system was used to de-
termine pyrolysis -oil yield (wt%). The yield of char (wt%) was calcu-
lated by the weight change in cyclone and bed materials, and the coke
yield was calculated by the weight difference of catalysts before and
after each experiment. The mass balance was then used to determine
the gas yield.
Furthermore, the relative selectivity of aromatic hydrocarbons or
olefins (Sao) was calculated based on related studies, shown as below:
[46,47]
Ps
Sao =
∑ Pao (1)
where Ps is the peak area of specific products, ΣPao is the total peak
areas of aromatic hydrocarbons or olefins.
J. Wang et al.
55
Liquid oil
50 Char+Coke
Gas
45
Yield (wt%)
40
35
30
25
20
15
0 20 40 60 80 100
WT Percentage (wt%)
Fig. 2. Yields of pyrolytic products as a function of waste tire percentage ob-
tained from co-CFP of bamboo sawdust and waste tire over pure HZSM-5:
Pyrolysis/catalytic upgrading temperature: 550/500 °C.
3. Results and discussion
3.1. Catalytic fast co-pyrolysis of bamboo sawdust and waste tire over pure
HZSM-5
3.1.1. Effect of waste tire percentage on the yields of pyrolytic products
It’s well known that pyrolysis and catalytic upgrading temperatures
generally play a determining role in the products yield and distribution
during the thermal conversion of biomass. In this study, we first con-
ducted fast pyrolysis of bamboo sawdust with/without HZSM-5 to ex-
plore the optimal reaction temperatures using the bubbling fluidized
bed/fixed bed reactor, and it was observed that a pyrolysis temperature
of 550 °C and catalytic upgrading temperature of 500 °C optimized the
pyrolysis oil yield and quality as shown in Figs. S1 and S2 [48].
Therefore, for the co-CFP of bamboo sawdust and waste tire experi-
ments, the pyrolysis and catalytic upgrading temperatures were kept at
550 and 500 °C, respectively. Fig. 2 presents the yields of pyrolytic
products derived from co-CFP of bamboo sawdust and waste tire over
pure HZSM-5. As indicated, liquid oil yield increased from 26.71% to
42.32% with the increasing of waste tire proportion in feedstock blends.
Previous studies regarding the pyrolysis of waste tire illustrated that the
liquid oil yield was distinctly affected by the type of reactor config-
urations [7,9]. Martinez et al. [6] reported that the yield of liquid
products derived from pyrolysis of waste tire ranged from 27.50 to
58.10 wt%, depending on the pyrolysis temperature and reactor type
used. In this study, the yield of liquid oil produced from the catalytic
fast pyrolysis of waste tire was 42.32%, which was in good agreement
with existing studies. In addition, among the co-CFP of bamboo sawdust
and waste tire runs, the highest yield of liquid oil was achieved when
the waste tire percentage was 80 wt%. Similar results were also found
by Uçar et al [26] who reported that an addition of scrap tires into pine
nut shells resulted in a positive synergistic effect which increased the
yield of liquid oil during the co-pyrolysis of pine nut shells and scrap
tires in a fixed bed reactor at 500 °C. Regarding char and coke produced
from the co-CFP of bamboo sawdust and waste tire using pure HZSM-5,
it could be observed from Fig. 2 that the yield of char and coke in-
creased as the waste tire percentage increased from 0 to 100 wt%. This
could be ascribed to the higher percentage of fixed carbon and lower
percentage of volatile matter in waste tire than that in the biomass [26].
Moreover, the gas yield decreased significantly when the waste tire
percentage was raised, which agreed well with previous studies
[33,37].
63
Energy Conversion and Management 180 (2019) 60–71
40% WT (Exp.) 50% WT (Exp.) 60% WT (Exp.) 80% WT (Exp.)
80 40% WT (Theo.) 50% WT (Theo.) 60% WT (Theo.) 80% WT (Theo.)
70 BS only
Relative Content (%)
WT only
60
50
40
30
20
10
0
Aromatic hydrocarbons Olefins Aromatic oxygenates
Fig. 3. Chemical components in liquid oil obtained from co-CFP of bamboo
sawdust (BS) and waste tire (WT) over pure HZSM-5: Pyrolysis/catalytic up-
grading temperature: 550/500 °C; Aromatic hydrocarbons = benzene, toluene,
ethylbenzene, xylenes, naphthalene and its derivates; Olefins = C6–C10 olefins;
Aromatic oxygenates = phenol, alkylphenols, methoxy phenols, 2,3-dihydro-
benzofuran. Exp. = experimental results; Theo. = calculated results.
3.1.2. Chemical fractions in liquid oil
Fig. 3 shows the components of liquid oil derived from co-CFP of
bamboo sawdust and waste tire over pure HZSM-5. As observed, the
dominated products in the CFP of bamboo sawdust alone were aromatic
oxygenates including phenol, alkylphenols, methoxy phenols and ben-
zofuran (shown in Fig. S2). Furthermore, a number of aromatic hy-
drocarbons such as benzene, toluene, ethylbenzene, xylenes, naphtha-
lene and its derivates, were produced when HZSM-5 was used in the ex-
situ CFP of bamboo sawdust, and no olefins were detected. However,
when the waste tire was added to co-CFP with bamboo sawdust over
pure HZSM-5, the formation of hydrocarbons (including aromatic hy-
drocarbons and olefins) was significantly promoted. For instance, the
relative concentration of aromatic hydrocarbons increased from 26.71
to 71.50% as the waste tire percentage elevated from 0 to 60 wt%,
which corresponds to a ∼62.64% relative increment. Moreover, to
make a specific comparison, the theoretical concentrations of aromatic
hydrocarbons, olefins, and aromatic oxygenates, which was calculated
by the linear superposition of individual feedstock with the assumption
of no interactions, were also shown in Fig. 3. As indicated, the addition
of waste tire into bamboo sawdust resulted in a positive “synergistic
effect” as the experimental relative concentrations of aromatic hydro-
carbons and olefins were higher than the theoretical ones for all runs at
different waste tire percentages. The highest positive synergistic effect
for aromatic hydrocarbons was observed in the run with waste tire
percentage of 40 wt%, while for olefins, the synergistic effect was
maximized when waste tire percentage was 80 wt%.
Regarding aromatic oxygenates, as exhibited in Fig. 3, compared to
the HZSM-5 catalyzed bamboo sawdust only run, an addition of waste
tire into the bamboo sawdust decreased the relative concentration of
aromatic oxygenates accompanied with an increased formation of hy-
drocarbons. Furthermore, the experimental concentrations of aromatic
oxygenates were lower than the theoretical ones when waste tire per-
centage increased from 40 to 80 wt%, indicating the synergistic effect
not only promoted the formation of aromatic hydrocarbons but also
inhibited the production of aromatic oxygenates. Mullen et al. [6]
studied the effect of acidity and structure of HZSM-5 on the formation
of aromatic hydrocarbons and phenols, they concluded that there was a
competitive pathway between alkylphenols and aromatic hydrocarbons
when HZSM-5 was used. Therefore, the competitive pathway described
above might be responsible for the decrease of aromatic oxygenates and
the increase of aromatic hydrocarbons when co-pyrolysis of bamboo
sawdust and waste tire was catalyzed by HZSM-5.
J. Wang et al. Energy Conversion and Management 180 (2019) 60–71

40
40 (a) Mixed Mode (b) Mixed Mode
35 Sequential Mode

Yield of liquid product (wt%)

35 Sequential Mode
30

Yield of Char (wt%)

30
25
25

20 20

15 15

10 10

5 5

0 0
1:4 2:3 1:1 3:2 4:1 1:4 2:3 1:1 3:2 4:1
HZSM-5:MgO HZSM-5:MgO
2.0 45
(C) (d) Mixed Mode
Mixed Mode 40 Sequential Mode
Sequential Mode
35
Yield of Coke (wt%)

1.5

Yield of Gas (wt%)

30
25
1.0
20
15
0.5 10
5
0.0 0
1:4 2:3 1:1 3:2 4:1 1:4 2:3 1:1 3:2 4:1
HZSM-5:MgO HZSM-5:MgO
Fig. 4. Effect of HZSM-5 and MgO catalytic modes on the pyrolytic product yields: (a) bio-oil; (b) char; (c) coke; (d) Gas. Pyrolysis/catalytic upgrading temperature:
550/500 °C; Waste tire percentage in the feedstock blends: 60 wt%.

3.2. Effect of HZSM-5 and MgO catalytic modes on the product distribution
3.2.1. Yield of pyrolytic products
Fig. 4 presents the yields of pyrolytic products produced from co-
CFP of bamboo sawdust and waste tire over HZSM-5 and MgO using
different catalytic modes (waste tire percentage in the feedstock blends:
60 wt%). As shown, the use of varying HZSM-5 and MgO modes af-
fected the yields of pyrolytic products. For the HZSM-5 mixed with MgO
mode, the yield of bio-oil decreased as HZSM-5/MgO mass ratio ele-
vated from 1:4 to 4:1, while the yields of char and gas increased at first
and then decreased. Moreover, coke yield presented an opposite trend
within the studied HZSM-5/MgO mass ratios, and the lowest yield was
obtained when HZSM-5/MgO mass ratio was 1:1. For the HZSM-5 and
MgO sequentially processed catalytic mode, the yield of bio-oil in-
creased from 26.43 to 33.42% when the HZSM-5/MgO mass ratio in-
creased from 1:4 to 3:2 as shown in Fig. 4, however, further increasing
the mass ratio to 4:1 decreased the bio-oil yield. Moreover, the yield of
char slightly increased with the increasing of HZSM-5 proportion in the
catalysts, while the gas yield exhibited an opposite trend. Concerning
the yield of coke, it could be observed that HZSM-5/MgO mass ratio of
2:3 lowered the yield to the most extent, which might show great
promise for the inhibition of HZSM-5 deactivation.
Regarding the comparison of mixed and sequential catalytic modes
on the pyrolytic product yields, the use of mixed mode produced a
higher yield of bio-oil than the sequential mode when HZSM-5/MgO
mass ratio was raised from 1:4 to 1:1. Conversely, further increasing the
mass ratio to 3:2 and 4:1 led to an opposite variation in the yield of bio-
oil. In addition, the mixed mode produced more char and coke than the
sequential one for all runs with different HZSM-5/MgO ratios. In par-
ticular, the lowest coke yield of 0.34 wt% (based on feedstocks) was
achieved when HZSM-5/MgO mass ratio was 2:3 using the sequential
catalytic mode.
3.2.2. Chemical fractions in bio-oil
As described above, the pyrolytic products produced from co-CFP of
bamboo sawdust and waste tire could be classified into aromatic hy-
drocarbons, olefins and aromatic oxygenates. Fig. 5 shows the chemical
fractions in bio-oil as a function of HZSM-5/MgO mass ratios using both
mixed and sequential modes. The theoretical values were also em-
bedded to make a comparison. As observed, similar to co-CFP of
bamboo sawdust and waste tire over pure HZSM-5, aromatic hydro-
carbons were still the predominant pyrolytic products when MgO and
HZSM-5 were used at different mass ratios and followed by olefins.
Moreover, the relative concentrations of aromatic hydrocarbons and
olefins produced from both the mixed and sequential modes were in-
creased to varying levels compared to the theoretical ones depending
on the HZSM-5/MgO mass ratios applied, which indicated that MgO
with mesoporous property not only facilitated the deoxygenation of
oxygenated products but also favored the diffusion of pyrolytic vapors,
resulting in an enhanced mass transfer during the catalytic upgrading
process. The use of sequential mode at HZSM-5/MgO mass ratio of 2:3
promoted the relative concentration of aromatic hydrocarbons to the
most extent, while the highest relative concentration of olefins could be
obtained under the mixed mode trial with HZSM-5/MgO ratio of 4:1.
Furthermore, a comparison between mixed mode and sequential mode
indicated that the sequential one was proved to be more effective in the

64
J. Wang et al. Energy Conversion and Management 180 (2019) 60–71

72.0 72.0
HZSM-5 : MgO = 1:4 HZSM-5 : MgO = 2:3
63.0 63.0

Theoretical Theoretical
Relative Content (%)

Relative Content (%)

54.0 54.0
Mixed Mode Mixed Mode
45.0 Sequential Mode 45.0 Sequential Mode

36.0 36.0

27.0 27.0

18.0 18.0

9.0 9.0

0.0 0.0
Aromatic hydrocarbons Olefins Aromatic oxygenates Aromatic hydrocarbons Olefins Aromatic oxygenates

72.0 72.0
HZSM-5 : MgO = 1:1 HZSM-5 : MgO = 3:2
63.0 63.0

Theoretical Theoretical
Relative Content (%)

Relative Content (%)

54.0 54.0
Mixed Mode Mixed Mode
45.0 Sequential Mode 45.0 Sequential Mode

36.0 36.0

27.0 27.0

18.0 18.0

9.0 9.0

0.0 0.0
Aromatic hydrocarbons Olefins Aromatic oxygenates Aromatic hydrocarbons Olefins Aromatic oxygenates

72.0
HZSM-5 : MgO = 4:1
63.0

Theoretical
Relative Content (%)

54.0
Mixed Mode
45.0 Sequential Mode

36.0

27.0

18.0

9.0

0.0
Aromatic hydrocarbons Olefins Aromatic oxygenates

Fig. 5. Chemical fraction in bio-oil derived from co-CFP of bamboo sawdust and waste tire over HZSM-5 and MgO: effect of HZSM-5/MgO mass ratio.

promotion of aromatic hydrocarbons than the mixed one at a higher
HZSM-5 proportion (> 40 wt%). However, the use of sequential and
mixed modes produced a comparable concentration of olefins when
HZSM-5/MgO mass ratio varied from 1:4 to 3:2.
Typically, during the CFP of biomass over HZSM-5 zeolites, Diels-
Alder reaction and hydrocarbon pool mechanism are responsible for the
production of aromatic hydrocarbons [49–51]. Huber and Cheng [49]
concluded that co-pyrolysis of furanic products with olefins promoted
the formation of aromatic hydrocarbons via Diels-Alder condensation
followed by dehydration reactions. In addition, Lu et al. [52] reported
that alkali metal oxides were effective for the production of furan and 2-
methylfuran during the CFP of woody biomass. Therefore, in this study,
an enhanced Diels-Alder cycloaddition might occur when MgO and
HZSM-5 were used simultaneously during the co-CFP of bamboo saw-
dust and waste tire. Specifically, CFP of bamboo sawdust over MgO
promoted the formation of furans, and the pyrolysis of waste tire re-
sulted in the production of olefins which could act as hydrogen donor to
enhance the Diels-Alder reaction as shown in Fig. 6, thus more aromatic
hydrocarbons were produced. Moreover, the furanic products can also
undergo oligomerization and decarbonylation to form hydrocarbon
pool when HZSM-5 zeolite was used [41]. Nevertheless, it’s well known
that biomass is a hydrogen-deficient material with a low H/C effective
ratio (0–0.3, bamboo sawdust in this study: 0.18), which largely sup-
pressed the hydrocarbon pool towards the formation of aromatic

65
J. Wang et al.
Fig. 6. Proposed reaction pathway for the production of aromatic hydrocarbons using MgO and HZSM-5 as catalysts.
hydrocarbons and olefins [53,54]. Therefore, an addition of waste tire
(H/C effective ratio is 0.80) into the bamboo sawdust increased the
average H/C effective ratio of feedstocks, thus an enhanced hydro-
carbon pool was obtained which was beneficial for the promotion of
aromatic hydrocarbons. On the other hand, Kabir et al. [42] reported
that syringol could be converted into aromatic hydrocarbons along with
the formation of CO2, CO and H2O via deoxygenation and decarbox-
ylation in the presence of metal oxides. Therefore, the deoxygenation of
phenolic products over base catalysts via hydrodeoxygenation, hydro-
cracking, demethoxylation and demethylation reactions also facilitated
the formation of aromatic hydrocarbons as shown in Fig. 6.
Regarding the formation of aromatic oxygenates obtained from co-
CFP of bamboo sawdust and waste tire using the mixed and sequential
modes, compared to the theoretical value, both the use of mixed and
sequential modes during the co-CFP of bamboo sawdust and waste tire
decreased the concentration of aromatic oxygenates as shown in Fig. 5.
For the mixed mode run, the lowest concentration of aromatic oxyge-
nates was achieved under HZSM-5/MgO ratio of 4:1, while the mass
ratio of 1:1 in the sequential mode reduced the formation of aromatic
oxygenates to the most extent. In this study, it should be noted that the
product distribution of aromatic oxygenates obtained from co-CFP of
bamboo sawdust and waste tire over HZSM-5 and MgO was dominated
by 2,5-dimethyl-benzenemethanol and 2,3-dihydro-benzofuran, and
only trace concentrations of ketones, acetic acids, aldehydes, and cre-
sols were detected during the co-CFP of bamboo sawdust and waste tire
when the mixed and sequential modes were used (detailed products
shown in Tables S2 and S3), which showed encouraging catalytic
deoxygenation performance in terms of the upgrading of bio-oil.
3.2.3. Distribution of aromatic hydrocarbons
The aromatic hydrocarbons produced from co-CFP of bamboo
sawdust and waste tire over HZSM-5 and MgO mainly include benzene,
toluene, ethylbenzene, xylenes, alkylbenzenes (such as 1,3,5-trimethyl-
benzene and 1-ethyl-3-methyl-benzene), and PAHs (mainly naphtha-
lene and its derivates). Fig. 7 shows the distribution of aromatic
66
Energy Conversion and Management 180 (2019) 60–71
hydrocarbons as a function of HZSM-5/MgO mass ratios using both the
mixed and sequential modes. As observed, alkylbenzenes and xylenes
were the main aromatic hydrocarbons and followed by PAHs and to-
luene. For instance, the relative selectivity of alkylbenzenes in the se-
quential catalytic mode was 53.90%, 45.70%, 46.55%, 43.61%, 45.76%
for HZSM-5/MgO mass ratio of 1:4, 2:3, 1:1, 3:2 and 4:1, respectively
(Fig. 8a), while only a small amount of benzene and ethylbenzene were
obtained (relative selectivity < 3%, shown in Fig. 8a and b). Com-
pared to the theoretical concentrations of benzene, toluene, ethylben-
zene, and xylenes (BTEX), both the mixed and sequential modes ex-
hibited positive additive effect on the formation of BTEX as the
experimental concentrations were higher in all cases. In addition, the
mixed mode was more beneficial to the formation of BTEX than the
sequential mode when HZSM-5/MgO ratio varied from 1:4 to 3:2.
However, sequential mode tended to be more effective in the produc-
tion of BTEX at a higher HZSM-5 proportion (80 wt%, HZSM-5/MgO
ratio: 4:1).
In the case of alkylbenzenes, as observed in Fig. 7, for the sequential
mode, the experimental concentration of alkylbenzenes was higher than
the theoretical one at various HZSM-5/MgO mass ratios, which illu-
strated a positive additive effect between HZSM-5 and MgO for the
production of alkylbenzenes. However, for the mixed mode, it could be
found that the experimental concentration was lower than the theore-
tical one when HZSM-5 was loaded at a low percentage (< 50 wt% in
catalyst mixture), indicating a negative additive effect might occur
under these conditions. Moreover, the concentration of PAHs obtained
from either the mixed mode or the sequential mode was lower than the
theoretical value in all cases at different HZSM-5/MgO mass ratios. It’s
well known that PAHs are the precursors of coke during the CFP of
biomass [55]. Therefore, the decrease of PAHs was accompanied with
the reduction of coke formed in the co-CFP of bamboo sawdust and
waste tire using the mixed and sequential modes as reflected in Fig. 4,
which might provide a promising way to suppress HZSM-5 deactivation
during the catalytic conversion of biomass [56].
J. Wang et al. Energy Conversion and Management 180 (2019) 60–71

35 35
HZSM-5 : MgO = 1:4 HZSM-5 : MgO = 2:3
28 Theoretical 28 Theoretical
Mixed Mode Mixed Mode
Relative Content (%)

Relative Content (%)

Sequential Mode Sequential Method
21 21

14 14

7 7

0 0
e es zene lenes s
zene AHs
ene oluene ylbenzen ylenes lbenzen PAHs ene oluene lben lben
Benz T Eth X Alky Benz T Ethy Xy Alky
P

35 35
HZSM-5 : MgO = 1:1 HZSM-5 : MgO = 3:2
28 Theoretical 28 Theoretical
Mixed Mode Mixed Mode
Relative Content (%)
Relative Content (%)

Sequential Mode Sequential Mode

21 21

14 14

7 7

0 0
e es s
ene oluene ylbenzen ylenes lbenzen PAHs ene oluene zene lenes zene AHs
Benz T Eth X Alky Benz lben Xy lben P
T Ethy Alky

35
HZSM-5 : MgO = 4:1
28 Theoretical
Mixed Mode
Relative Content (%)

Sequential Mode
21

14

0
zene lenes s
ene oluene lben zene AHs
Benz T Ethy Xy lben P
Alky

Fig. 7. Distribution of aromatic hydrocarbons using mixed and sequential modes during the co-CFP of bamboo sawdust and waste tire: effect of HZSM-5/MgO mass
ratios.

3.2.4. Distribution of olefins dimethylcyclopentene, 1-methyl-1,4-cyclohexadiene), C8 (such as 1,3-

As described above, besides the formation of aromatic hydrocarbons
in the co-CFP of bamboo sawdust and waste tire, a number of olefins
were also produced. Fig. 9 shows the distribution of olefins obtained
from co-CFP of bamboo sawdust and waste tire using different HZSM-5/
MgO catalytic modes. It should be noted that the major olefins detected
in the bio-oil were C7 such as (5-methyl-1,4-hexadiene, 3,5-
dimethyl-1-cyclohexene, 2,3-dimethyl-cyclohexa-1,3-diene, 1,5-di-
methyl-1,4-cyclohexadiene), and C10 (mainly limonene) olefins. As
indicated in Fig. 9, the relative concentration of C7 olefins decreased
gradually within the studied HZSM-5/MgO regions using the mixed
mode, while the relative concentration of C10 olefins tended to present
an opposite trend. Concerning the formation of C8 olefins, it could be

67
J. Wang et al. Energy Conversion and Management 180 (2019) 60–71

HZSM-5:MgO=1:4 HZSM-5:MgO=2:3 HZSM-5:MgO=1:1 HZSM-5:MgO=3:2 HZSM-5:MgO=4:1

45.7% 46.55% 43.61% 45.76%

53.9%

14.26% 14.62% 16.49% 15.54%

12.7%
26.34% 26.91% 26.92% 25.14%
6. 3 9.44% 0.67% 10.12% 0.85% 10.88% 0.99%
1% 1.04% 11.1% 0.86%
24.26%

1.75% 1.81% 2.01% 1.68%

1.8%

(a) Sequential mode

HZSM-5:MgO=1:4 HZSM-5:MgO=2:3 HZSM-5:MgO=1:1 HZSM-5:MgO=3:2 HZSM-5:MgO=4:1

38.84% 47.53%
43.09% 40.47% 42.06%

14.44% 15% 12.33% 15.96% 14.11%

31.97%
26.75% 28.19%
27.55% 25.34%
9.85% 0.92%
12.18% 1.07% 12.82% 1.14% 13.51% 0.99% 11.62% 0.86%

2.47% 2.25%
2.39% 2.36% 1.95%

(b) Mixed mode

Benzene Toluene Ethylbenzene Xylenes

Alkylbenzenes PAHs
Fig. 8. Relative selectivity of aromatic hydrocarbons using sequential and mixed modes during the co-CFP of bamboo sawdust and waste tire.

observed that the relative concentration of C8 olefins fluctuated as the
HZSM-5/MgO mass ratio increased from 1:4 to 4:1. On the other hand,
when the sequential mode was taken into consideration, the production
of C10 olefins was reduced with an increased loading of HZSM-5 in the
catalysts. In addition, the use of sequential mode produced higher
concentration of C10 olefins as HZSM-5/MgO mass ratios ranged from
1:4 to 3:2 compared to the mixed mode. Conversely, the sequential
mode was less effective in the formation of C7 olefins than the mixed
mode when HZSM-5/MgO mass ratio was lower than 1:1.
Fig. 10 presents the relative selectivity of olefins obtained from co-
CFP of bamboo sawdust and waste tire using mixed and sequential
modes. As shown, the product distribution of olefins was dominated by
C10 olefins, and in the mixed mode catalytic run, the relative selectivity
of C10 increased with an elevated HZSM-5 proportion in the catalyst
blends. While the relative selectivities of C7 and C8 olefins decreased
within the studied HZSM-5/MgO ratio regions. In addition, the main
product in C10 olefins was limonene, which was a typical product ob-
tained from the thermal conversion of waste tire. Similarly, previous
studies reported that the decomposition of polyisoprene was re-
sponsible for the production of limonene during the pyrolysis of waste
tire [26]. As indicated in Fig. 10, the selectivity of limonene increased
at first and then decreased with the highest selectivity of 38.87% oc-
curring at HZSM-5/MgO of 2:3 in the mixed mode case. Regarding the
relative selectivity of olefins using the sequential mode, the limonene
selectivity was maximized when the HZSM-5/MgO ratio was kept at
1:1. Furthermore, both the relative selectivities of C7 and C8 olefins
fluctuated slightly as the sequential mode was used at different HZSM-
5/MgO ratios.
3.3. Additive effect on the promotion of aromatic hydrocarbons
As mentioned in Section 3.2, there was a significant additive effect
for the production of aromatic hydrocarbons when HZSM-5 and MgO
were simultaneously used during the co-CFP of bamboo sawdust and
waste tire. In order to investigate the effect of various HZSM-5/MgO
mass ratios on the promotion of aromatic hydrocarbons, an additive
effect (Ad, %) was defined and calculated by the following equation and
the results are shown in Fig. 11.
Experimental − Theoretical
Ad = × 100%
Experimental
As indicated in Fig. 11, HZSM-5/MgO mass ratio played a de-
termining role in the additive effect for aromatic hydrocarbons. For
instance, the additive effect of benzene in the mixed mode run was
higher than that in the sequential run when HZSM-5/MgO mass ratio
increased from 1:4 to 3:2. However, further increased HZSM-5/MgO
ratio to 4:1, the use of sequential mode proved to be more effective for
the production of benzene. Similar results could be found for toluene
and xylenes. Therefore, it could be concluded that the mixed mode was
more beneficial for the formation of BTX (benzene, toluene and xy-
lenes) than the sequential one when HZSM-5/MgO mass ratios ranged
from 1:4 to 3:2, while at higher HZSM-5 loading of 80 wt% (HZSM-5/
MgO = 4:1), the use of sequential mode was more effective. Moreover,
the additive effects of mixed mode and sequential mode were com-
parable for the formation of ethylbenzene when HZSM-5/MgO ratio
was 3:2, while at other HZSM-5/MgO mass ratios, the additive effects of
ethylbenzene in mixed mode cases were higher than those in the se-
quential mode runs. Conversely, for the additive effect of alkylben-
zenes, it’s interesting to find that the use of sequential mode showed
positive additive effect for the formation of alkylbenzenes at all HZSM-
5/MgO mass ratios with the maximum additive effect obtained at 1:4.
Whereas the mixed mode was proved to be negative with HZSM-5/MgO
ratio varying from 1:4 to 1:1. With respect to the additive effect of
PAHs, both the mixed and sequential modes decreased the formation of
PAHs as the additive effects obtained at different HZSM-5/MgO ratios
were negative. Specifically, for the sequential mode case, it could be
observed that the most prominent additive effect of PAHs was achieved
at 1:4, while for the mixed mode run, HZSM-5/MgO ratio of 1:1

68
J. Wang et al. Energy Conversion and Management 180 (2019) 60–71

3.6 3.6
(a) C7 Olefins Mixed Mode (b)C8 Olefins Mixed Mode
Sequential Mode Sequential Mode
2.7
Relative Content (%)

Relative Content (%)

2.7

1.8 1.8

0.9 0.9

0.0 0.0
1:4 2:3 1:1 3:2 4:1 1:4 2:3 1:1 3:2 4:1
HZSM-5:MgO HZSM-5:MgO

25
Mixed Mode
(c) C10 Olefins
Sequential Mode
20
Relative Content (%)

15

10

0
1:4 2:3 1:1 3:2 4:1
HZSM-5:MgO
Fig. 9. Distribution of olefins obtained from co-CFP of bamboo sawdust and waste tire using the mixed and sequential modes.

81 81
72 (a) Mixed Mode 72
(b) Sequential Mode
63 63
Relative Selectivity (%)

Relative Selectivity (%)

54 54
45 45
36 36 C7 Olefins
C8 Olefins
D-Limonene
C10 Olefins (Total)
9 C7 Olefins 9
C8 Olefins
D-Limonene
C10 Olefins (Total)
0 0
1:4 2:3 1:1 3:2 4:1 1:4 2:3 1:1 3:2 4:1
HZSM-5:MgO HZSM-5:MgO
Fig. 10. Relative selectivity of olefins obtained from co-CFP of bamboo sawdust and waste tire using different catalytic modes: (a) mixed mode; (b) sequential mode.

69
J. Wang et al. Energy Conversion and Management 180 (2019) 60–71

HZSM-5:MgO=1:4 HZSM-5:MgO=1:4
HZSM-5:MgO=1:4
(a) Benzene 45
(b) Toluene 64 (c) Ethylbenzene 54
40 48
56
35 42
48 36
30

= 4: 1
= 4: 1

HZS
=4:1
H ZS
40

HZS
25 30
32

MgO
24
M gO

20

M - 5:
MgO
M -5 :

M-5:
15 24 18

M - 5:
M -5 :

MgO
12

M gO
10 16

M-5:

MgO
5 8 6

HZ S
H ZS

= 2: 3
HZS
= 2 :3

=2:3
HZSM-5:MgO=3:2 HZSM-5:MgO=1:1 HZSM-5:MgO=3:2 HZSM-5:MgO=1:1 HZSM-5:MgO=3:2 HZSM-5:MgO=1:1

HZSM-5:MgO=1:4 HZSM-5:MgO=1:4
(d) Xylenes
HZSM-5:MgO=1:4
56
(e) Alkylbenzenes 12 (f) PAHs -80
-70
49 8
-60
42 4
4: 1

= 4: 1
HZS
-50

H ZS
= 4: 1

35 0
H ZS

gO=

-40

M gO
M
28 -4

M -5 :
M gO

-30
M - 5:

-5:M
M

21 -8
M-5:

-20

M -5 :

M gO
14 -12
M-5:

M gO

gO=
7 -10
HZS

H ZS

= 2 :3
H ZS

= 2: 3

HZSM-5:MgO=3:2 HZSM-5:MgO=1:1 HZSM-5:MgO=3:2 HZSM-5:MgO=1:1 2: 3 HZSM-5:MgO=3:2 HZSM-5:MgO=1:1

Mixed Mode Sequential Mode

Fig. 11. Additive effect of HZSM-5 and MgO using mixed and sequential modes for the production of aromatic hydrocarbons.

increased the additive effect to the most extent. Acknowledgements

4. Conclusions
In summary, compared to CFP of bamboo sawdust alone, co-CFP of
bamboo sawdust with waste tire over pure HZSM-5 increased the pyr-
olysis-oil and char yields and the highest pyrolysis-oil yield was
achieved when the waste tire percentage was 80 wt%. An addition of
waste tire into bamboo sawdust resulted in a positive synergistic effect
as the experimental relative concentrations of aromatic hydrocarbons
and olefins were higher than the theoretical ones for all runs at different
waste tire percentages. Moreover, the relative concentrations of aro-
matic hydrocarbons and olefins produced from both the mixed and
sequential modes were increased to varying levels compared to the
theoretical ones, depending on HZSM-5/MgO mass ratios employed.
The use of sequential mode at HZSM-5/MgO mass ratio of 2:3 promoted
the relative concentration of aromatic hydrocarbons to the greatest
extent, while the highest relative concentration of olefins could be
obtained under the mixed mode trial with HZSM-5/MgO ratio of 4:1.
Compared to the theoretical concentrations of BTEX, both the mixed
and sequential modes exhibited positive additive effect on the forma-
tion of BTEX as the experimental concentrations were higher for all
cases. Concerning the olefins obtained from co-CFP using the two cat-
alytic modes, the product distribution was dominated by C10 olefins,
and in the mixed mode catalytic run, the relative selectivity of C10
increased with an elevated HZSM-5 proportion in the catalyst blend.
The authors are grateful for the National Natural Science Fund
Program of China (No. 51776042), the Scientific Research Foundation
of Graduate School of Southeast University (YBJJ1646), the Scientific
Innovation Research Program of College Graduate in Jiangsu Province
(KYLX16_0204) as well as the Financial Support from the Program of
China Scholarships Council (No. 201706090032).
Appendix A. Supplementary material
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.enconman.2018.10.056.
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