Bioresource Technology 293 (2019) 122076

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

Catalytic pyrolysis of biomass-plastic wastes in the presence of MgO and T

MgCO3 for hydrocarbon-rich oils production
⁎
Rui Yuana, Yafei Shena,b,
a
Jiangsu Key Laboratory of Atmospheric Environment Monitoring and Pollution Control (AEMPC), School of Environmental Science and Engineering, Nanjing University of
Information Science and Technology (NUIST), Nanjing 210044, China
b
Collaborative Innovation Center of Atmospheric Environment and Equipment Technology, NUIST, Nanjing 210044, China

G R A P H I C A L A B S T R A C T

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

Keywords: This work comparatively studied the catalytic effect of MgO and MgCO3 on pyrolysis of rice husk (RH). The
Catalytic pyrolysis apparent activation energy (E) was reduced significantly by pyrolysis of RH with MgCO3, thus lowering the
Rice husk (RH) decomposition temperature during pyrolysis. MgO could not obviously influence the gas evolution during
Bio-oil pyrolysis, while MgCO3 had a better performance on the syngas (H2 and CO) generation at around 600–700 °C.
MgO
Also, the generation of CO2 was suppressed by the RH pyrolysis with MgCO3. The phenols were the dominant
MgCO3
compounds in the bio-oil derived from RH. Furthermore, co-pyrolysis of RH and polyvinyl chloride (PVC) in the
presence of MgO or MgCO3 at 600 °C could improve the oils quality by decreasing the acids content and in-
creasing the hydrocarbons content. Particularly, the resulting oils had high hydrocarbons content (> 35%) and
low acids content (< 2%). The decrease of acids, alcohols, and phenols contributed to the increase of hydro-
carbons.

1. Introduction Yoshikawa, 2013). Nevertheless, the quality of oil produced from the
non-catalytic pyrolysis of biomass was low due to high oxygen content
Biomass has been known as one of the attractive sources that be with low heating value (Xiang et al., 2018). Agro-forestry residues
used for renewable biofuels (e.g., biochar, bio-oil) production due to its produced in considerable quantities can be utilized as attractive,
biodegradable, cheap, carbon neutrality and low greenhouse gas carbon-neutral and nonedible lignocellulosic biomass that are con-
emission (Loy et al., 2018). Generally, biomass pyrolysis is performed in verted into fuels (e.g., oil, syngas) and chars via pyrolysis (Yuan et al.,
inert environment to maximize the yield of oil or syngas (Shen and 2019; Sfakiotakis and Vamvuka, 2018). The pyrolysis process and its

⁎
Corresponding author.
E-mail address: [email protected] (Y. Shen).

https://doi.org/10.1016/j.biortech.2019.122076
Received 31 July 2019; Received in revised form 24 August 2019; Accepted 26 August 2019
Available online 28 August 2019
0960-8524/ © 2019 Elsevier Ltd. All rights reserved.
R. Yuan and Y. Shen Bioresource Technology 293 (2019) 122076

parameters (e.g., final temperature, pressure, heating rate, and re- 2. Materials and methods
sidence time) can influence the quality of biochar (Shen, 2015; Tripathi
et al., 2016). 2.1. Feedstock and chemicals
Fast pyrolysis is an economically feasible process for converting
biomass into liquid product, which always contains a large amount of The feedstock of rice husk (RH) was collected from a grain-proces-
reactive, oxygenated species and is a mixture including organic acids, sing factory at Nanjing (China). The received RH were initially ground
(dehydrated) carbohydrates, aldehydes, ketones, (depolymerized) and sieved to obtain the fine particles with uniform sizes (< 1 mm).
lignin fragments, aromatics, and alcohols. Two catalytic strategies of in- Before use, the sample was dried at 105 °C for 10 h. The chemical
situ and ex-situ catalysis have been widely exploited for pyrolysis va- properties including proximate analysis, ultimate analysis and ash
pour upgrading through deoxygenation and cracking (Nolte and composition of biomass feedstock was presented in the E-
Shanks, 2016; Venderbosch, 2015). In-situ catalysis (also called cata- Supplementary data. In addition, the chemical reagents including MgO
lytic pyrolysis) has been considered as one of the most promising ways (> 98%) and MgCO3 (MgO: 40–47%, MgCO3: > 50%) were purchased
for production of liquids with a better quality (e.g., low oxygen content from Sigma-Aldrich (China).
and high hydrocarbon content) than the pyrolysis bio-crude
(Venderbosch, 2015). It is known that use of catalysts in fast pyrolysis 2.2. Pyrolysis tests
has a high potential for production directly of hydrocarbons from bio-
mass than the conventional in relation to its use in the pyrolysis-cata- 2.2.1. Thermogravimetric analysis (TGA)
lytic upgrading processes (i.e., ex-situ catalysis). The significant ad- The pyrolysis kinetics of RH with MgO and MgCO3 can be evaluated
vantage of this integrated process is that re-evaporation of the liquid by the TGA. The RH sample and MgO/MgCO3 were blended with a mass
products can be avoided (Venderbosch, 2015). A wide variety of zeo- ratio of 1 by ball-milling. For each pyrolysis test, 5 mg of the sample
lites, particularly HZSM-5, have been applied in catalytic pyrolysis was placed into a ceramic crucible and then heated from 30 to 850 °C
process (Hu et al., 2017; Mullen and Boateng, 2015; Sebestyén et al., (heating rate: 20 °C/min) under the highly purified N2 (2.1 bar; flow
2017). Here zeolite-type catalysts are effective in the deoxygenation of rate: 30 ml/min) condition. Each sample was tested triple times to en-
bio-oil, but the liquid yield is relatively low. Moreover, zeolites can sure the data reliability. To further study the effect of MgO and MgCO3
deactivate rapidly by coking due to both their surface acidity and pore on the pyrolysis gas (e.g., CO2, CO, H2, C2H4 and CH4), the TG coupled
structure (Lin et al., 2018). In recent years, metal oxides such as tran- with an in-situ mass spectrometry (MS, Pfeiffer, MS GSD 320) was used.
sition and base metals have attracted more attentions in catalytic pyr- For the kinetics study, the evolution of weight loss (TG) and weight loss
olysis due to their low cost and accessibility as well as good deox- rate (DTG) with temperature was obtained. And the kinetic study of
ygenation performance (Shen et al., 2015; Wang et al., 2017). Ding catalytic pyrolysis was conducted according to the reported work (Yuan
et al. studied a dual-catalyst bed of CaO and HZSM-5 for improving et al., 2019; Zhang et al., 2016).
hydrocarbon yield from catalytic fast co-pyrolysis of hemicellulose and
plastics (Ding et al., 2018). CaO as base catalysts have been widely 2.2.2. Py-GC/MS analysis
developed for biomass pyrolysis (Chen et al., 2019b) including biofuels A pyrolysis reactor coupled with a gas chromatography/mass
upgrading (Yang et al., 2018). spectrometer (namely Py-GC/MS) was employed to identify the com-
With regard to the carbon efficiency of the process, the composition ponents of bio-oil derived from fast pyrolysis of RH. The pyrolysis re-
of bio-oil and its downstream upgrading, the use of base catalysts has actor is a CDS 5250 (Chemical Data Systems, USA), and the GC/MS in-
been regarded as new ways in fast pyrolysis of biomass (Stefanidis strument is a Trace DSQ II (Thermo Scientific, USA). RH and the mixture
et al., 2016). Among metal oxides, magnesium oxide (MgO) is one of were pyrolyzed in 600 °C for 10 s at 20 °C/ms. Firstly, each sample
the most attractive candidates as a base catalyst for biomass pyrolysis (0.5 mg) was packed as sandwich by quartz wool and put into quartz
(Kalogiannis et al., 2018; Ryu et al., 2019; Chen et al., 2019a,b,c; Zeng sample tube. To avoid the condensation of pyrolysis vapour before
et al., 2018). On one hand, the base catalysts can promote the deox- GC–MS, the valve oven and transfer line between pyrolyzer and GC–MS
ygenation of pyrolysis vapors via the production of CO2, which is a were controlled at 290 °C and 280 °C, respectively. After passing
more efficient ways with respect to carbon conservation than the pro- through the valve oven and transfer line, pyrolysis vapour was sepa-
duction of CO that the acid catalysts promote. On the other hand, they rated using GC/MS with a capillary column (Agilent: HP-5MS, 19091S-
can reduce the production of H2O, thus conserving hydrogen in bio-oil 433; length, 30 m; internal diameter, 250 μm; film thickness, 0.25 μm). The
and increasing its energy density (Kalogiannis et al., 2018). It was GC injector temperature used was 280 °C. The flow rate of carrier gas
proved that the use of MgO supported on carbon (MgO/C) can produce (Helium) for the column was 1.0 ml/min and the split ratio was 80:1.
a high yield of aromatic hydrocarbons during the pyrolysis of lignin, The film in the column was formed of bonded 5% phenyl and 95%
due to its well-balanced acid/base sites and high surface area. More- methyl siloxane. The GC oven temperature was initiated at 40 °C for
over, MgO/C showed a strong positive synergy toward the production 2 min, heated up to 200 °C at 5 °C/min and further to 280 °C at 10 °C/
of aromatic hydrocarbons during co-pyrolysis of biomass (e.g., lignin) min for 2 min. Finally, most of the peaks were identified by the NIST
and plastics (e.g., low-density polyethylene). It suggested that a metal library. The peak areas were obtained by automatic integration with
oxide with base properties supported on high-surface-area carbon could Agilent ChemStation under the same standard. Each experiment was
be an efficient catalyst for producing bio-oil with high energy density conducted triple times to ensure the reproducibility. The peak area (%)
fuel additives from the lignin (Stefanidis et al., 2016). Chen et al. can represent the yield and selectivity of each product.
(2019a) investigated the catalytic pyrolysis of biomass with metal
oxides (e.g., MgO) for selective deoxygenation to balance the quality 2.2.3. Pyrolysis in a fixed-bed reactor
and yield of bio-oil. Due to its lower cost, magnesium carbonate The experimental apparatus for the pyrolysis process is composed of
(MgCO3) present in natural magnesite can act as a good candidate to four parts: carrier gas system, pyrolysis reactor (vertical furnace),
produce MgO by thermal decomposition at a relatively low temperature condenser and gas collection. The sample was fed into the pyrolysis
(around 400–500 °C). So far, pyrolysis of biomass with MgCO3 has not reactor. Before the pyrolysis process, the N2 gas (flow rate: 0.5 l/min)
yet been reported. This work will comparatively study the catalytic was continuously introduced from the top of the reactor for 30 min to
pyrolysis of biomass in the presence of MgO and MgCO3 for biofuels remove air and to keep the gas flow stability. As the pyrolysis process
production. The experimental scheme is presented in Fig. 1. started, the terminal temperature was controlled at 600 °C (heating
rate: 20 °C/min). The residence time was 2 h to ensure a complete de-
composition. The pyrolysis products including oil, gas and char were

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R. Yuan and Y. Shen Bioresource Technology 293 (2019) 122076

Fig. 1. Investigation pathways of biomass pyrolysis in the presence of MgO or MgCO3 by TG/DTG analysis, Py-GC/MS analysis and fixed-bed pyrolysis.

collected separately. The condensable oil was absorbed by isopropyl (Fig. 3b), it can be seen that the pyrolysis of RH and RH-MgO showed
alcohol (IPA) in the ice water. The non-condensable gas was collected two main DTG peaks including the first stage dehydration (about
by an air bag. 30–150 °C) and second stage volatiles decomposition (about
150–550 °C). A wide temperature range for biomass pyrolysis was at-
2.2.4. Analytical methods tributed to the decomposition of lignin in a wide temperature range
The proximate analysis of biomass was performed by the TGA (TGA- (Chen et al., 2019b). It was noteworthy that a mall DTG peak appeared
4000, PerkinElmer, USA). The ultimate analysis of biomass was per- at around 300 °C, indicating the decomposition of RH occurring at
formed by the elemental analyzer (VARIO EL III, Element, Germany). lower temperatures in the presence of MgCO3. Additionally, a narrow
Metal oxides in biomass were determined by the X-ray fluorescence DTG peak appeared at around 400–600 °C was attributed to the de-
(Olympus Innovex X-5000, Canada). Bio-oil derived from biomass pyr- composition of MgCO3 (Fig. 3d). The linear model was obtained by
olysis was analyzed by a GC/MS (Shimadzu GCMS-QP2020, Japan) with plotting ln[−ln(1 − x)T2] versus 1/T for pyrolysis of RH with MgO/
a capillary column (DB-Wax) (length: 30 m; internal diameter: MgCO3 as shown in Fig. 3c. The results could be well fitted by the linear
0.25 mm; film thickness: 0.25 mm). The bio-oil sample (0.5 μl) was in- models. And the corresponding kinetic parameters such as apparent
troduced to the injection port (250 °C) with a split ratio of 50:1. activation energy (E) and pre exponential factor for RH, RH-MgO, and
Initially, the column temperature was kept at 35 °C for 3 min and then RH-MgCO3 during pyrolysis were presented in Table 1. The R2 of the
was increased to 250 °C (10 °C/min). The column temperature soaped at linear models were larger than 0.95, indicating the first-order reaction
250 °C for 5 min. The flow rate of carrier gas (Helium) for the column mechanism fitting well. The apparent activation energy (E) of RH-
was 4.0 ml/min. The main compounds in bio-oils could be identified MgCO3 (55.2 kJ/mol) were much lower than those of RH (122 kJ/mol)
according to the spectra in the GC–MS library (NIST 2015) and then be and RH-MgO (115 kJ/mol), indicating the high catalytic effect of
confirmed by injecting standards if available. MgCO3 in the pyrolysis process. In general, the decomposition tem-
perature of RH could be reduced by pyrolysis with MgCO3.
3. Results and discussion From the thermogravimetric parameters, biomass samples could
reach the maximum mass loss peak earlier in the presence of MgO/
3.1. XRD analysis of MgO and MgCO3 MgCO3, thus enhancing the pyrolysis of lignocellulosic biomass to a
certain degree. The pyrolytic products required further investigation.
The crystal structures of the Mg catalysts (MgO and MgCO3) were As shown in the MS profiles (the E-Supplementary data), the evolution
determined by the XRD analysis. As shown in Fig. 2a, remarkable of gaseous products from the RH pyrolysis with MgO had no significant
characteristic peaks (37.2°, 43.5° and 62.5°) was observed, indicating its change, suggesting that MgO could not influence the gas evolution
high purity and crystal structure. However, the MgCO3 catalyst showed during pyrolysis. However, the MgO catalysts were proved for im-
a tanglesome XRD pattern with two characteristic peaks of MgCO3 and proving the bio-oil quality via deoxygenation during pyrolysis
Mg3O(CO3)2, indicating a composite of MgO and MgCO3 (Fig. 2b). (Stefanidis et al., 2016). Compared to MgO, MgCO3 showed an obvious
change on the evolution of pyrolysis gas (especially for C2H2 and CO2).
Generally, two major representative peaks of C2H2 occurred at the
3.2. TG-MS analysis
temperature ranges of 300–600 °C and 600–800 °C. Only one peak oc-
curred with a maximum peak at around 500 °C, indicating the inhibi-
The TG and DTG curves can be used to study the effect of MgO and
tion of small molecular olefins generation during pyrolysis of RH with
MgCO3 on the weight loss characteristics of biomass pyrolysis.
MgCO3. In usual, pyrolysis of biomass is performed at a medium tem-
Generally, the decomposition of RH in the absence of MgO and MgCO3
perature range (e.g., 400–700 °C). In this work, the generation of CO2
occurred with a higher weight loss. However, the higher residual
was remarkably suppressed by the RH pyrolysis with MgCO3, which
weight of the RH-MgO pyrolysis was attributed to a high content of the
could also suppress the generation of CO2 during pyrolysis of biomass at
stable MgO in the char (Fig. 3a). From the weight loss rate (DTG) curves

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R. Yuan and Y. Shen Bioresource Technology 293 (2019) 122076

Fig. 2. XRD patterns of the Mg catalysts: MgO (a) and MgCO3 (b).

a medium temperature. production and identify the major compounds in pyrolysis, the Py-GC/
MS analysis was conducted at 600 °C (20 °C/ms) to ensure a complete
3.3. Py-GC/MS analysis decomposition of RH. From the total ion chromatogram in the E-
Supplementary data, a large number of peaks (> 160) in RH was de-
The Py-GC/MS analysis can be used for the semi-quantitatively tected, indicating many types of compounds in the pyrolysis products.
analysis of pyrolysis products (Rahman et al., 2019; Chen et al., 2019c). However, the number of peaks decreased by pyrolysis of RH with MgO
In order to confirm the feasibility of RH towards hydrocarbon biofuels or MgCO3. Correspondingly, the identified compounds were given in

Fig. 3. (a) TG, (b) DTG, and (c) Fitting curves of ln[−ln(1 − x)/T2] versus 1/T for the RH pyrolysis with MgO or MgCO3; (d) DTG curve of MgCO3.

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R. Yuan and Y. Shen Bioresource Technology 293 (2019) 122076

Table 1
Kinetic parameters for catalytic pyrolysis of RH with MgO or MgCO3.
Feedstock Temperature (°C) E (kJ/mol) A (min−1) R2

RH 280–400 122 9.89 × 109 0.974

RH-MgO 280–405 115 1.76 × 109 0.985
RH-MgCO3 255–400 55.2 6.54 × 103 0.983

Fig. 5. Selectivity (relative peak area, %) of the identified compounds in bio-

oils from the RH pyrolysis with PVC in the presence of MgO or MgCO3.

Furthermore, the identified compounds in bio-oil could be divided into

several groups, such as phenols, acids, alcohols, hydrocarbons (e.g.,
Fig. 4. Relative content of different groups in bio-oils from the RH pyrolysis in alkanes, aromatics), esters, ketones, furans, etc. As shown in Fig. 5, the
the presence of MgO or MgCO3 using Py-GC/MS. phenols in bio-oil derived from RH were the dominant compounds with
a high content above 25%. It was found that both MgO and MgCO3 had
the E-Supplementary data. A number of oxygenated compounds with little effect on the conversion of phenols. The results accorded with the
reactive molecules, such as ketone, alkene, and carboxylic acid were Py-GC/MS analysis. The contents of alcohols and ketones were in-
derived from hemicellulose and cellulose. Moreover, phenols and cre- creased by pyrolysis of RH with MgO or MgCO3. Similar to CaO, MgO
sols were main phenolic compounds derived from lignin (Rahman et al., reacted with sugars at low temperatures, and high temperatures pro-
2019). The compounds from biomass pyrolysis could be divided into moted the dehydration and ring-opening reaction of anhydrosugars to
several groups, such as aldehydes, acids, furans, ketones, phenols, and form furans, alcohols and ketones. During pyrolysis of lignin, MgO
hydrocarbons (e.g., alkanes, aromatics) (as shown in Fig. 4). Amongst, could also react with phenolic compounds at low temperatures, and
the phenols were the dominant compounds, which took up a high promote the free radical reactions, thereby leading to a more complex
fraction (more than 28%) in the pyrolysis products from RH. The composition of bio-oil at high temperatures (Chen et al., 2019b). Thus,
phenols derived from RH-MgO and RH-MgCO3 were decreased to 16% these oxygenated compounds could not be efficiently transformed
and 25%, respectively. Compared to MgCO3, MgO was more effective during the catalytic pyrolysis with MgO in lower heating rates and re-
for conversion of the phenols to aromatic hydrocarbons during pyr- sidence times.
olysis. It is noted that hydrocarbons with higher heating value could be Furthermore, it was noted that co-pyrolysis of RH and PVC in the
applied as biofuels increased by pyrolysis of RH with MgO. Further- presence of MgO or MgCO3 could significantly decrease the content of
more, the oxygen-compounds (e.g., alcohols, phenols) and N-com- acids and increase the content of hydrocarbons (Fig. 5). Particularly,
pounds were decreased by pyrolysis of RH with MgO as a base catalyst, pyrolysis of RH-PVC-MgO and RH-PVC-MgCO3 could result in high
which was more beneficial for production of bio-oil with a higher hy- quality of bio-oils with high content of hydrocarbons (> 35%) and low
drocarbons content. However, the fraction of hydrocarbons was still content of acids (< 2%). Moreover, the alcohols had been fully trans-
low, which would be enhanced by the co-pyrolysis of biomass and formed. The decrease of acids, alcohols, and phenols contributed to the
plastics in the further work. Compared to the RH-MgO, the pyrolysis of increase of hydrocarbons. Consequently, both MgO and MgCO3 had a
RH-MgCO3 could achieve a lower yield of CO2 corresponding to the considerable performance on co-pyrolysis of biomass and plastics at
results of the TG-MS analysis. intermediate temperatures (e.g., 600 °C) to produce fuel oils with lower
acidity and higher hydrocarbons content.

3.4. Bio-oil analysis by GC–MS

4. Conclusions
The bio-oil product from biomass pyrolysis in the fixed-bed reactor
was analyzed by the GC–MS. In this study, the co-pyrolysis of RH and This work comparatively studied the effect of MgO and MgCO3 on
polyvinyl chloride (PVC) plastic was performed to improve the yield of pyrolysis of RH for bio-oils production. The apparent activation energy
hydrocarbons. The total ion chromatogram and the identified com- (E) was reduced by RH pyrolysis with MgCO3. The decomposition
pounds were given in the E-Supplementary data. Similar to the Py-GC/ temperature of RH was decreased by pyrolysis with MgCO3. Phenols
MS analysis, a large number of peaks were observed, indicating many (> 25%) were the dominant components in bio-oil. Co-pyrolysis of RH
types of compounds in bio-oil derived from RH. The number of peaks in and PVC with MgO/MgCO3 significantly decreased the content of acids
bio-oils derived from RH-MgO and RH-MgCO3 was decreased sig- and increase the content of hydrocarbons. Pyrolysis of RH-PVC-MgO
nificantly. The base catalyst (e.g., MgO) could take a considerable and RH-PVC-MgCO3 resulted in oils with high content of hydrocarbons
catalytic effect on the bio-oil transformation during biomass pyrolysis. (> 35%) and low content of acids (< 2%). The decrease of acids,

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alcohols, and phenols contributed to the increase of hydrocarbons. Nolte, M.W., Shanks, B.H., 2016. A perspective on catalytic strategies for deoxygenation
in biomass pyrolysis. Energy Technology 5, 7–18.
Rahman, Md.M., Chai, M., Sarker, M., Nishu, Liu, R., 2019. Catalytic pyrolysis of pine-
Acknowledgements wood over ZSM-5 and CaO for aromatic hydrocarbons: analytical Py-GC/MS study. J.
Inst. Energy. https://doi.org/10.1016/j.joei.2019.01.014.
Supports by the National Natural Science Foundation of China Ryu, H.W., Lee, H.W., Jae, J., Park, Y.-K., 2019. Catalytic pyrolysis of lignin for the
production of aromatic hydrocarbons: effect of magnesium oxide catalyst. Energy
(Grant 21607079), the Natural Science Foundation of the Jiangsu 179, 669–675.
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