Bioresource Technology 344 (2022) 126096

Contents lists available at ScienceDirect

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

Review

Co-pyrolysis of microalgae and other biomass wastes for the production of

high-quality bio-oil: Progress and prospective
Guangcan Su a, Hwai Chyuan Ong b, c, *, Yong Yang Gan a, Wei-Hsin Chen d, Cheng Tung Chong e,
Yong Sik Ok f
a
Department of Mechanical Engineering, Faculty of Engineering, University of Malaya, 50603 Kuala Lumpur, Malaysia
b
Centre for Green Technology, Faculty of Engineering and IT, University of Technology Sydney, NSW 2007, Australia
c
Future Technology Research Center, National Yunlin University of Science and Technology, 123 University Road, Section 3, Douliou, Yunlin 64002, Taiwan
d
Department of Aeronautics and Astronautics, National Cheng Kung University, Tainan 701, Taiwan
e
China-UK Low Carbon College, Shanghai Jiao Tong University, Lingang, Shanghai 201306, PR China
f
Korea Biochar Research Center, APRU Sustainable Waste Management Program & Division of Environmental Science and Ecological Engineering, Korea University,
Seoul 02841, Republic of Korea

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

• Synergistic effects of microalgae co-

pyrolysis has been critically analyzed.
• Co-pyrolysis enhances the overall py­
rolysis performance and bio-oil
properties.
• CaO and Cu/HZSM-5 promote the
quality of bio-oil effectively.
• Co-pyrolysis of microalgae and other
biomass wastes is economic and
feasible.

A R T I C L E I N F O A B S T R A C T

Keywords: Microalgae are the most prospective raw materials for the production of biofuels, pyrolysis is an effective method
Microalgae to convert biomass into bioenergy. However, biofuels derived from the pyrolysis of microalgae exhibit poor fuel
Biofuels properties due to high content of moisture and protein. Co-pyrolysis is a simple and efficient method to produce
Co-pyrolysis
high-quality bio-oil from two or more materials. Tires, plastics, and bamboo waste are the optimal co-feedstocks
Catalytic effect
based on the improvement of yield and quality of bio-oil. Moreover, adding catalysts, especially CaO and Cu/
Environmental sustainability
HZSM-5, can enhance the quality of bio-oil by increasing aromatics content and decreasing oxygenated and
nitrogenous compounds. Consequently, this paper provides a critical review of the production of bio-oil from co-
pyrolysis of microalgae with other biomass wastes. Meanwhile, the underlying mechanism of synergistic effects
and the catalytic effect on co-pyrolysis are discussed. Finally, the economic viability and prospects of microalgae
co-pyrolysis are summarized.

* Corresponding author.
E-mail addresses: ong1983@yahoo.com, HwaiChyuan.Ong@uts.edu.au (H.C. Ong).

https://doi.org/10.1016/j.biortech.2021.126096
Received 16 August 2021; Received in revised form 2 October 2021; Accepted 4 October 2021
Available online 6 October 2021
0960-8524/© 2021 Elsevier Ltd. All rights reserved.
G. Su et al.
1. Introduction
With the rapid development of industrialization and urbanization,
the energy demand is growing dramatically, while the finite conven­
tional fossil fuels cannot meet the requirement (Liu et al., 2020a). Based
on the Annual Energy Outlook 2020 from the United States Energy In­
formation Agency, crude oil and coal reserves are estimated to be
depleted in 2042 and 2112, respectively, as global energy demand will
rise by 56% in 2040 (EIA, 2020). Furthermore, the reckless consumption
of natural resources and the uninterrupted expenditure of fossil fuels
have led to a series of grave problems including air pollution, global
warming, acid rain, ozone layer loss, and desertification, which have
constituted an enormous threat to the existence and development of
mankind. It is urgent and essential to search for clean, alternative, and
sustainable energy to reduce the degree of reliance on fossil fuels (Uzar,
2020).
Renewable and sustainable energy sources such as solar, wind, nu­
clear, geothermal, and hydro have been successfully utilized to decrease
the consumption and dependency on fossil fuels (Benedek et al., 2018).
However, those energy sources are intermittent and non-dispatchable,
their output power is hard to satisfy the fluctuating electricity needs
of society at any time owing to the change of power generation. Bio­
energy originated from biomass has overcome the above problem, the
primary products including biochar and biofuels, can be used as vital
and stable backup energy for storage and transportation (Chen et al.,
2021b). Moreover, biomass is the most promising energy source, which
has drawn attention globally because of its low cost, sustainability,
availability, and environmental friendliness (Ong et al., 2020). Various
kinds of materials have been employed as feedstocks for the production
of biofuels, such as corn, wood, wheat straw, sewage sludge, plastics,
tires, kitchen waste, and microalgae (Lu et al., 2020). Currently, biofuels
are classified into four generations according to different biomass
sources. First-generation biofuels are mainly manufactured from animal
fats or oil-based plants, but the application causes many serious conse­
quences like water crises, ecosystem damage, and food versus fuel
debate (Stamenković et al., 2020). Second-generation biofuels have
been extensively implemented by exploiting agricultural, industrial,
municipal, and household waste as feedstocks to overcome the problems
raised by the first generation biofuels. However, there are still some
commercial restrictions, especially the high cost of transportation, pre­
treatment, and conversion (Lee et al., 2015). Third-generation biofuels
are derived from microalgae, which exhibit numerous advantages
including high photosynthetic efficiencies, good CO2 capture ability,
high oil content, exponential growth rates, and non-selective growth
condition. Thus, microalgae have been suggested as the most promising
and sustainable raw materials for the production of biofuels, pharma­
ceuticals, chemicals, and other high-value products, but they are still
constrained by low productivity and high cost of cultivation and harvest
(Gan et al., 2018). Additionally, fourth-generation biofuels employ
genetically modified microalgae to produce biofuels. Genetic modifi­
cation is utilized to increase the output of microalgae by raising the
photosynthetic efficiency, decreasing the photoinhibition, and
improving the light penetration. While it is an emerging technology,
which is in its infancy and requires more in-depth research (Abdullah
et al., 2019).
Simultaneously, a proper treatment process is required to utilize
microalgae as an energy source. There are two main categories of
biomass conversion methods including thermochemical conversion
(pyrolysis, torrefaction, combustion, gasification, and liquefaction) and
biochemical conversion (fermentation and digestion) (Lee et al., 2020b).
Presently, many conversion techniques, such as gasification, torre­
faction, combustion, and hydrothermal liquefaction, have been exten­
sively explored. Gasification is a versatile thermochemical technology,
which utilizes air, oxygen, steam, or supercritical water to convert
microalgae biomass into syngas (H2, CO, CO2, and CH4) at a temperature
range of 700 to 1000 ◦ C. However, high energy input and toxic gases
2
Bioresource Technology 344 (2022) 126096
emission hamper its development. Dry or wet torrefaction can transform
microalgae biomass into solid product, but it is used as a pretreatment
method to reduce the moisture content and improve grinding and hy­
drophobicity of biomass for pyrolysis (He et al., 2018). The combustion
of microalgae can produce heat or electricity, but low thermal efficiency
and the release of noxious gas and ash hinder its further development.
Hydrothermal liquefaction can directly convert wet microalgae at a
moderate temperature (300–400 ◦ C) and high pressure environment
(10–25 MPa) into bio-oil, biochar, and biogas without any pretreatment
process. Nevertheless, huge capital costs, low security, and unobserv­
able reaction process impede its promotion (Chiaramonti et al., 2017).
Pyrolysis is regarded as the most popular thermochemical conver­
sion technology, which thermally degrades the organic materials by the
cracking of chemical bonds in the absence of oxygen. Pyrolysis is cate­
gorized as slow, fast, and flash pyrolysis based on various operating
conditions including temperature, heating rate, and residence time,
whereas the product distribution can be highly controllable by tailoring
those pyrolysis parameters (Ong et al., 2019). Moreover, it is a cheap
and effective route to produce biofuels and valuable chemicals because
of the superiorities of abundant feedstocks, unstrict conditions, high
conversion efficiency, and eco-friendliness, thus it is on the edge of
commercialization right now. However, owing to the high oxygen and
nitrogen contents in bio-oil, some barriers have impeded the process,
such as low caloric value, high acidity, low stability, nitrogen pollution,
and corrosiveness. To eliminate the obstacles and enhance the quality of
bio-oil, many researchers have explored in-depth and focused on co-
pyrolysis, proving that co-pyrolysis is an efficient way to solve the
above problems (Su et al., 2021).
Co-pyrolysis involves two or more different materials, the interaction
between various radicals possesses a promotional effect on the forma­
tion of homogenous bio-oil and leads to synergistic effects, which are the
crux to improve the properties of biofuels. During the co-pyrolysis
process, tires, plastics, and bamboo waste have exhibited the best syn­
ergistic effects on the enhancement of yield and higher heating value
(HHV) of bio-oil with microalgae (Dai et al., 2018b). Meanwhile, due to
the significant advantages of simplicity and effectiveness, co-pyrolysis is
also treated as an ideal waste management technology. The utilization of
waste materials including rural solid waste, kitchen waste, wood
sawdust, peanut shell, and sewage sludge as co-feedstocks with micro­
algae has also achieved remarkable results (Bong et al., 2020; Chang
et al., 2018; Chen et al., 2018a). Furthermore, plenty of studies have
indicated that catalysts can further facilitate the selectivity of the py­
rolysis process and the properties of bio-oil by limiting product distri­
bution, lowering the activation energy, reducing acidity, and cutting
down the oxygenated and nitrogenous compounds (Xiang et al., 2018).
As the enormous advantages of microalgae and catalytic co-pyrolysis
process, catalytic co-pyrolysis of microalgae and other biomass wastes
will have a crucial influence on the energy market and play a key role in
the future. Numerous literature works on the conventional pyrolysis, co-
pyrolysis, hydrothermal liquefaction, and catalytic pyrolysis of micro­
algae have been published (Chen et al., 2015; Enamala et al., 2018;
Fakayode et al., 2020). Nevertheless, a review of the non-catalytic and
catalytic co-pyrolysis of microalgae and other biomass wastes is limited
in the literature, even with the above advantages. Consequently, this
paper reveals a critical and comprehensive review of the co-pyrolysis of
microalgae with other biomass wastes. Furthermore, the mechanism of
synergistic effects between various materials and the catalytic effect on
co-pyrolysis are provided. Finally, the economic viability, challenges,
and prospects of co-pyrolysis are fully discussed.
2. Microalgae and other biomass wastes characterization
As the oldest living unicellular microorganisms (1–400 μm) on earth,
microalgae have been available for about 3 billion years with approxi­
mately 20,000 species (Levasseur et al., 2020). Moreover, microalgae
have relatively low requirements for growth environment, which can be
G. Su et al. Bioresource Technology 344 (2022) 126096

Table 1
Elemental and proximate analyses of microalgae and other biomass wastes.
Biomass Elemental Analysis (dry basis, wt%) Proximate Analysis (wt%) HHV(MJ/kg) Reference
C H O N S VM MO FC Ash

Microalgae
Chlorella vulgaris 46.82 8.63 32.03 11.05 0.29 77.23 1.98 12.35 8.44 22.82 (Chen et al., 2018a)
Nannochloropsis sp. 53.39 7.75 21.27 6.97 0.61 79.61 4.01 10.38 6.00 24.01 (Chen et al., 2017a)
Nannochloropsis sp. 50.61 7.31 28.46 6.68 0.64 79.21 4.23 10.26 6.30 21.51 (Tang et al., 2020b)
Isochrysis sp. 49.26 7.50 31.74 6.24 0.96 79.79 1.69 11.63 6.89 23.52 (Wang et al., 2016)
Spirulina platensis 47.27 7.05 21.53 10.99 0.62 82.03 7.48 5.43 5.06 21.21 (Chen et al., 2018c)
Spirulina platensis 47.58 6.33 28.15 11.26 0.51 81.13 7.62 5.08 6.17 18.68 (Tang et al., 2020b)
Scenedesmus sp. 45.60 6.50 36.30 11.10 0.48 75.20 12.10 7.10 5.60 23.40 (Nyoni et al., 2020)
Dunaliella salina 48.10 7.10 23.30 9.40 0.90 76.30 4.00 12.50 7.20 21.20 (Gong et al., 2014)
Dunaliella salina 45.75 6.91 43.08 4.11 0.15 81.80 – 17.98 0.22 – (Chen et al., 2021a)
Mougeotia 41.51 5.59 27.03 5.40 0.51 64.49 5.14 10.41 19.96 16.63 (Sharara et al., 2014)
Arthrospira platensis 46.75 6.97 35.11 10.62 0.55 71.50 7.60 15.93 4.97 20.75 (Anand et al., 2016)
Dunaliella tertiolecta 43.31 5.96 29.90 4.33 – 64.70 1.60 17.20 16.50 17.81 (Wu et al., 2015)
Isochrysis galbana 48.35 7.24 36.82 7.60 – 64.02 2.27 10.12 23.56 16.52 (Azizi et al., 2020)
Botryococcus braunii 51.50 8.90 31.90 7.50 – 76.10 3.50 17.90 2.40 21.50 (Ali et al., 2018)
Cyanobacteria sp. 33.56 5.16 25.89 5.85 0.62 61.78 – 9.32 28.92 14.48 (Huang et al., 2016)
Chlorella sp. 49.00 7.14 28.97 8.59 0.77 79.17 – 15.41 5.42 – (Lv et al., 2021)
Chroococcus sp. 24.28 3.98 25.35 4.17 1.08 49.23 6.77 4.20 39.80 – (Varsha et al., 2021)
Lignocellulosic biomass
Bamboo 41.97 5.89 43.18 0.27 0.15 80.57 6.22 10.89 2.32 16.86 (Chen et al., 2017a)
Wood sawdust 47.10 6.63 46.13 0.15 0.00 79.76 5.32 14.21 0.72 18.42 (Chen et al., 2019b)
Peanut crust 43.80 5.70 34.00 1.80 0.40 72.40 5.80 13.20 8.50 18.30 (Sattar et al., 2020)
Palm kernel shell 50.70 6.00 42.80 0.40 0.10 75.20 0.00 22.70 2.10 – (Chang et al., 2018)
Walnut shell 61.09 6.42 29.81 0.16 0.16 74.53 1.06 22.05 2.36 – (Zhu et al., 2018)
Cornstalk 42.89 5.94 43.11 0.91 – 72.74 3.46 16.65 7.15 – (Li et al., 2017)
Non-lignocellulosic biomass
Rural solid waste 51.03 7.43 27.93 1.31 0.14 75.26 0.00 10.64 12.16 22.39 (Tang et al., 2020a)
Kitchen waste 45.15 8.57 36.31 1.53 0.00 80.27 2.47 16.07 1.19 18.74 (Chen et al., 2018a)
Municipal solid waste 55.67 7.57 33.99 2.77 0.43 75.73 7.13 6.38 16.75 – (Varsha et al., 2021)
Low-quality coal 79.31 4.72 13.38 1.03 1.30 30.56 4.18 49.88 15.38 – (Wu et al., 2018a)
Semi-anthracite coal 63.15 4.74 8.84 0.78 0.92 33.12 0.00 45.31 21.57 26.32 (Chen et al., 2012)
Colombian coal 79.50 5.00 13.20 1.60 0.00 43.20 0.00 56.10 0.70 32.20 (Fermoso et al., 2018)
Coal 63.60 3.64 30.70 1.57 0.49 20.90 2.80 60.10 16.20 27.80 (Nyoni et al., 2020)
LDPE 84.32 15.47 0.00 0.00 0.21 99.99 0.00 0.00 0.00 47.29 (Tang et al., 2020b)
PVC 38.09 5.22 – – – 93.77 0.00 6.06 0.17 20.07 (Dai et al., 2018b)
PP 84.31 15.30 0.00 0.31 0.08 99.60 0.40 0.00 0.00 47.46 (Azizi et al., 2018b)
PS 92.07 7.89 0.00 0.01 0.03 99.57 – 0.39 0.04 – (Chen et al., 2021a)
PET 61.80 4.55 33.55 0.02 0.08 84.80 0.00 14.80 0.40 – (Chen et al., 2021a)
Waste rubber tires 78.70 7.47 1.63 1.40 1.90 72.00 0.00 19.00 9.00 36.09 (Duan et al., 2015)
Tire 78.95 6.73 1.62 0.72 1.78 60.33 0.00 29.47 10.20 – (Fang et al., 2018)
Waste cooking oil 78.31 11.46 10.01 0.00 0.08 97.57 – 0.39 0.14 39.93 (Wu et al., 2020)
Waste lubricant oil 83.90 14.20 0.44 0.70 0.76 99.09 – – 0.91 43.10 (Uçar et al., 2005)
Oil shale 37.34 4.90 51.99 1.47 4.30 38.52 3.63 5.38 52.47 – (Hu et al., 2016)
Sewage sludge 34.77 4.27 24.69 2.59 0.00 60.22 2.44 2.49 34.85 13.04 (Wang et al., 2016)
Textile dyeing sludge 24.75 3.80 3.93 3.26 10.44 41.33 – 4.85 53.82 – (Peng et al., 2015)

VM: Volatile matter; MO: Moisture; FC: Fixed carbon; HHV: Higher heating value (MJ/kg); LDPE: Low-density polyethylene; PP: Polypropylene; PS: Polystyrene; PET:
Polyethylene terephthalate.

cultivated in freshwater, brackish water, marine area, and even land.
With the help of chloroplasts, microalgae possess the ability to produce
rich organic matters, fix carbon, and release oxygen with high photo­
synthetic efficiency, which are treated as a promising carbon sink (Saj­
jadi et al., 2018). Microalgae are mainly composed of lipids, proteins,
and carbohydrates, with other minor components including vitamins,
fatty acids, pigments, and antioxidants. The content of major compo­
nents is primarily related to the species, cultivation methods, and
environmental conditions (Nagappan et al., 2019). The proteins content
of microalgae is in the interval of 14.00 to 65.20 wt%, which is widely
used in the field of pharmacy vaccine, nutrition, and adhesives (Mene­
gazzo & Fonseca, 2019). Lipids are the most valuable components with
the content of 1.10–51.00 wt%, which are suitable for the production of
high-value oil-based products (Katiyar & Arora, 2020). Moreover, the
content of carbohydrates is between 3.28 and 30.21 wt%, which are the
feedstock for valuable chemicals (Klein et al., 2018). The microalgae
production industry still faces several challenges like enormous capital
investments, high running costs, and huge energy consumption, espe­
cially in the cultivation and harvesting process. In 2019, the cost of
biocrude based on microalgae is approximately $7.50 per gallon, which
is much higher than conventional fuels (Yang et al., 2019).
In addition, as the low-cost and most abundant carbon source,
lignocellulosic biomass is deemed to be an economically feasible,
environmental-friendly, and carbon–neutral raw material for the pro­
duction of biofuels (Dai et al., 2020). Currently, there are about 5 billion
metric tons of crop residues generated across the world annually. In
contrast to microalgae, the chief components of lignocellulosic biomass
are cellulose (40–60%), hemicellulose (15–30%), and lignin (10–25%),
with little extractives and ash, and the composition mainly depends on
the type of source (softwood, hardwood, or herbaceous plant) (Sankaran
et al., 2020). Meanwhile, more attention has been paid to non-
lignocellulosic biomass such as municipal solid waste, plastics, tires,
coal, and sewage sludge. The global municipal solid waste has increased
to 2.01 billion tons in 2016, which is estimated to rise to about 3.4
billion tons by 2050 (Istrate et al., 2020). In addition, over 300 million
tons of plastics are produced annually, resulting in plenty of plastics
waste (Kasar et al., 2020). Furthermore, non-biodegradable waste tires
are another global environmental problem, more than 1.5 billion tires
are scrapped annually (Mohajerani et al., 2020). The disposal of these
wastes is a huge global challenge, which possesses a serious threat to the
environment and human survival without proper treatment. Co-
pyrolysis is an effective and simple solution, it not only can reduce the

3
G. Su et al.
amount of waste, but also generates valuable products.
Table 1 presents the elemental and proximate analyses of various
kinds of materials. Most microalgae species possess high nitrogen and
oxygen content. The content of nitrogen in microalgae is much higher
than other materials owing to the existence of protein, Spirulina platensis
possesses the highest nitrogen content of 11.26 wt%. Meanwhile,
microalgae species are medium in volatile matter, moisture, fixed car­
bon, ash, and HHV. Moreover, the oxygen content of lignocellulosic
biomass is also high, while the carbon and hydrogen content are rela­
tively low and lead to low HHV, the nitrogen and sulfur content are close
to zero. For non-lignocellulosic biomass, polypropylene (PP), coal, and
tires possess high carbon content of 84.31, 79.31, and 78.70 wt%,
respectively. Additionally, PP possesses the highest hydrogen content,
volatile matter, HHV, and the lowest ash content. Sewage sludge has the
highest ash content and the lowest HHV, while coal has the maximum
fixed carbon content and the minimum volatile matter content.
3. Co-pyrolysis of microalgae and other biomass wastes
Co-pyrolysis possess the superiorities of simplicity and effectiveness,
while microalgae exhibit the strengths of environmental friendliness,
high photosynthetic efficiencies, high oil content, and exponential
growth rates. Therefore, the combination of co-pyrolysis and microalgae
will have a huge impact on the biomass industry, while numerous re­
searchers at home and abroad have devoted themselves to related
studies and yielded fruitful results.
3.1. Co-pyrolysis process
Co-pyrolysis entails the thermal degradation of two or more mate­
rials. It is analogous to conventional pyrolysis which is carried out in a
closed reactor system by utilizing moderate operating temperature and
oxygen-free environment. The transition from pyrolysis to co-pyrolysis
does not need any modification of existing equipment but positively
influences the pyrolysis process and end-products (Lee et al., 2020a).
The whole process of co-pyrolysis is divided into three major steps
including pretreatment, co-pyrolysis, and condensation. Pretreatment is
a pivotal step in biomass conversion due to the complex nature and
structure of biomass materials, which can improve the usability of
components for an extensive range of applications (Soltanian et al.,
2020). Pretreatment is classified as physical (milling, freezing, and
extrusion pretreatments), chemical (acid, alkaline, organic solvent,
oxidative, and ionic liquid pretreatments), physical–chemical (steam
explosion, liquid hot water, wet oxidation, CO2 explosion, and ultra­
sound pretreatments), biological (microbial consortium, bacterial,
fungal, and enzymatic pretreatments), thermal (torrefaction, drying,
and microwave irradiation) and combined pretreatments (Huang et al.,
2020). Drying, torrefaction, milling, and sieving are the most common
pretreatment methods to obtain small and homogenous samples. High
moisture content in biomass can affect the quality of bio-oil negatively.
Thus, drying is the most common technique to reduce the moisture
content of biomass (Carvalho et al., 2020). Meanwhile, torrefaction can
also alter the structure and composition of biomass and improve its
grinding, hydrophobicity, and pyrolysis performance (He et al., 2018).
Additionally, small particles are conducive to ameliorate the reaction
efficiency and promote the production of biofuels on the basis of surface
chemistry. Therefore, dry biomass particles with the moisture content of
less than 10 wt% need to be smaller than 1 mm to achieve the optimum
effect of fast pyrolysis, while flash pyrolysis requires even smaller
biomass particles (less than 0.2 mm) (Kumar et al., 2020). In general,
pretreatment is the most expensive process because of large energy
consumption, different kinds of pretreatment should be selected based
on the properties of biomass, capital cost, production condition, and
environmental impacts (del Río et al., 2020).
During the co-pyrolysis process, biomass mixtures are heated to a
temperature that exceeds their thermal stability threshold under
4
Bioresource Technology 344 (2022) 126096
anaerobic condition, a range of chemical reactions, such as decarbox­
ylation, decarbonylation, dehydration, and dehydrogenation, occur to
form carbonyl, carboxyl, hydroxyl, and other functional groups. Biomass
mixtures are then converted into biochar and biogas, while some volatile
components are condensed into liquid products (Tripathi et al., 2016).
Pyrolysis is highly affected by various operating parameters, such as
temperature, reaction time, heating rate, types of inert gas, sweeping
rate, and particulate size. While co-pyrolysis possesses an extra impor­
tant interfering factor, that is blending ratio of different raw materials.
Furthermore, those conditions require to be adjusted according to the
characteristic of feedstocks and the optimization of the target product.
Condensation is another vital step to isolate bio-oil. In a typical
workflow of the fixed-bed reactor, pyrolysis volatiles are condensed into
bio-oil by a water-cooled condenser, solid residues are left in the reactor,
while the non-condensable gases are collected in a gas bag or released
into the atmosphere after filtration. Three stages condensation system is
widely employed during the pyrolysis experiment (He et al., 2019).
3.2. Synergistic effects on the co-pyrolysis process
Synergistic effects are the crux to modify the existing pyrolysis
process and ameliorate the properties of bio-oil. The sufficient contact of
volatiles produced by each material plays a crucial role in synergistic
effects during the co-pyrolysis process. A large number of research
groups have delved into the phenomenon, especially on the mechanism
of synergistic effects and the improvement of target product during
microalgae co-pyrolysis (Sun et al., 2019a).
3.2.1. Mechanism of synergistic effects
The underlying mechanism of synergistic effects between microalgae
and plastics has been explored and summarized by Tang et al. (2020b)
and Qi et al. (2018). With the aid of pyrolysis–gas chromatography-mass
spectrometry, Tang et al. (2020b) detected that a strong interaction
between microalgae and low-density polyethylene (LDPE) promoted the
formation of esters and long-chain alcohols, whereas hindered the pro­
duction of oxygenated and nitrogenous compounds in the bio-oil. The
free radicals from LDPE enhanced the dehydroxylation and C− C bond
cleavage of long-chain carboxylic acids from the hydrolysis of proteins
and lipids. Hydration, decarboxylation, and dehydration reforming re­
actions made carbohydrates generate formic acid, acetic acids, OH
radicals, and release H2O, CO2, hinder the formation of furans, phenol,
and long-chain fatty acids. Meanwhile, OH radicals reacted with formic
acid and acetic acids to form esters, or further combined with the long-
chain CH radicals from the cleavage of LDPE to generate long-chain
alcohols. Moreover, Qi et al. (2018) observed a sharp rise of aromatic
hydrocarbons content in the bio-oil due to violent synergistic effects
between Nannochloropsis sp. and PP with the help of HZSM-5. There are
three major routes of the mechanism for the production of aromatic
hydrocarbons. Firstly, olefins from the pyrolysis of PP reacted with fu­
rans from the cracking of microalgae carbohydrates to generate aro­
matic hydrocarbons by the Diels-Alder and dehydration reactions, then
further formed compounds with six-membered ring structures on the
surface of HZSM-5. Secondly, small organic moieties were deoxygenated
and decomposed into olefins, while triglycerides were cracked into
heavy oxygenated hydrocarbons, then underwent decarboxylation and
decarbonylation reactions to form olefins. Moreover, with the help of
HZSM-5, the volatiles originated from the pyrolysis of microalgae and
the olefins generated from the cracking of PP entered the hydrocarbon
pool and were converted into aromatic hydrocarbons through the hy­
drocarbon pool mechanism. Thirdly, olefins generated from the pyrol­
ysis of PP were transformed into aromatic hydrocarbons through HZSM-
5 via aromatization, cyclization, and oligomerization reactions.
According to Table 1, microalgae have a very high content of ni­
trogen, which will cause high nitrogen content in the bio-oil and sub­
sequent nitrogen pollution. Thus, it is essential to inhibit the formation
of nitrogenous compounds (Liu et al., 2016). Meanwhile, proteins are
G. Su et al. Bioresource Technology 344 (2022) 126096

Table 2
Synergistic effects of the co-pyrolysis of microalgae with other biomass wastes.
Microalgae Co- Conditions Reactor Relevant results and observation Reference
feedstock

Nannochloropsis sp. Bamboo 600 ◦ C, 30 min, Ar Fixed-bed The increase of microalgae ratio enhances the content of long-chain fatty acids, (Chen et al.,
reactor nitrogenous compounds, decreases the content of phenol, acetic acids, and 2017a)
oxygenated compounds dramatically in the bio-oil.
Nannochloropsis sp. Palm kernel 600 ◦ C, 15 min, N2 Fixed-bed The increase of microalgae ratio decreases the content of phenolic compounds, (Chang et al.,
shell reactor while the content of aromatic hydrocarbons increases first and then decreases. 2018)
Chlorella vulgaris Waste 900 ◦ C, 60 min, N2 Fixed-bed Co-pyrolysis with 50 wt% waste glycerol increases the content of alcohol to (Wang et al.,
glycerol reactor 72.30 wt%, decreases the content of nitrogenous compounds and phenols. 2019a)
Chlorella vulgaris Kitchen 500–700 ◦ C, 25 Fixed-bed The increment of microalgae ratio enhances the hydrocarbons content and (Chen et al.,
waste min, CO2 reactor activation energy, decreases the carboxylic acids, causes a higher bio-oil HHV. 2018a)
Chlorella vulgaris PVC 800 W/1 kW, 40 Microwave The growth of PVC ratio boosts the aromatic hydrocarbons content and HHV, (Dai et al.,
min, N2 reactor decreases oxygenated and nitrogenous compounds in the bio-oil. 30 wt% PVC 2018b)
is the optimum ratio.
Nannochloropsis sp. LDPE 600 ◦ C, 30 min, Ar Fixed-bed The addition of LDPE with high EHI reduces the content of oxygenated and (Tang et al.,
reactor nitrogenous compounds. The aliphatic hydrocarbons content in the oil rises to 2019)
77.40 wt% with 25 wt% LDPE.
Isochrysis sp. Sewage 5, 10, 15, 20 and Thermal Significant synergistic effects are observed at 550 to 700 ◦ C. The addition of (Wang et al.,
sludge 25 ◦ C/min, N2 analyzer microalgae decreases the content of hydrocarbons and nitrogenous 2016)
compounds, increases the content of aldehyde and ketones in the bio-oil.
Dunaliella salina PP, PS, PET, 800 ◦ C, 20 ◦ C/min, Thermal The coating effect of the molten plastics enhances the pyrolysis of microalgae; (Chen et al.,
PVC N2 analyzer the hydrogenation reaction between microalgae and PP, PS, and PET reduces 2021a)
the solid residue; the activation energies of PP, PS, PET, and PVC are decreased
largely after adding microalgae.
Chlorella sp. PP 550 ◦ C, 20 s, Ar Fixed-bed The addition of PP reduces the activation energy remarkably; The increase in (Lv et al.,
reactor the PP ratio in the mixture raises the hydrocarbons content and decreases the 2021)
oxygenated compounds largely.
Chlorella, Low-rank 25–850 ◦ C, Thermal The presence of microalgae enhances the release of volatiles from coal; (Wu et al.,
Nannochloropsis coal 10–40 ◦ C/min, N2 analyzer Different species of microalgae influences the decomposition of coal distinctly; 2018b)
sp. synergistic effects cut down the activation energy.
Chlorella pyrenoidosa Waste 290–370 ◦ C, Mini-batch 50% microalgae and 50% waste tire induce the most violent synergistic effects, (Duan et al.,
rubber tire 10–120 min, He reactor which promote denitrogenation and deoxygenation, thereby improving the 2015)
quality of bio-oil.

EHI: Effective hydrogen index.

the primary component of microalgae and the chief nitrogen source,
while amino acids are the basic structural units of protein. Therefore, the
mechanism of synergy between microalgae and lignocellulosic biomass
can be revealed through the co-pyrolysis of amino acids and lignocel­
lulosic biomass (Chen et al., 2017b). Consequently, Chen et al. (2019a)
pyrolyzed amino acids with bamboo waste and reported that the in­
clusion of lignocellulosic biomass into microalgae increased phenols and
oxygenated compounds significantly while cutting down nitrogenous
compounds sharply. The large number of –NH2 groups in proteins was
the main reason for the increment of phenols, which provided numerous
H+, then facilitated the scission of lignin fragments via β-O-4 linkage
breaking reaction. Additionally, the Maillard reaction and ketonization
reaction caused the growth of oxygenated compounds in the bio-oil,
− C=O groups from bamboo waste reacted with − NH2 groups easily.
After − NH2 groups from amino acids were removed, oxygenated com­
pounds were formed, while the Maillard reaction produced new
nitrogenous compounds (Moens et al., 2004). Owing to the large amount
of NH3 released during the co-pyrolysis, amino acids generated
numerous intermediates which contain –COOH group, then reacted with
each other to produce ketones via ketonization reaction directly
(Resasco & Crossley, 2015). As the reason for the decline of nitrogenous
compounds, numerous − NH2 groups were released out as NH3, while
some nitrogenous compounds concentrated in the biochar as the forms
of pyrrolic-N, pyridinic-N, and quaternary-N.
Moreover, Chen et al. (2017a) conducted the co-pyrolysis of bamboo
with Nannochloropsis sp. and observed a sharp growth of long-chain fatty
acids and a sharp decline of acetic acids in the bio-oil. The acidic unit
(− COOH) in hemicellulose of bamboo and basic unit (− NH2) in the
proteins of microalgae induced condensation reaction during the co-
pyrolysis process, which inhibited the formation of acetic acids. Simul­
taneously, co-pyrolysis inhibited the generation of acetic acids through
violent decarboxylation reactions by releasing a large volume of CO2. As
for the increase of long-chain fatty acids, the cracking of lipids in
microalgae underwent C− O cleavage through acyl or alkoxy during
pyrolysis. Therefore, pyrolysis can enhance the cleavage of the alkoxy
bond and generate a great number of long-chain fatty acids.
Other researchers reported that the synergistic effects of co-pyrolysis
could be attributed to the formation of H and OH radicals, materials with
high hydrogen content acted as hydrogen donors. Those radicals shifted
from biomass to char structure and led to the decomposition of char
(Meng et al., 2016). Duan et al. (2015) pyrolyzed waste rubber tires with
Chlorella pyrenoidosa in supercritical ethanol and observed positive
synergistic effects between two raw materials, which favored deni­
trogenation and deoxygenation to ameliorate the quality of bio-oil.
Microalgae could form solid material then acted as free radical donors
to induce the polyisoprene and poly chain scission. The hydrogen
transferred from polyisoprene and poly chain to microalgae-derived
radicals, which stabilized the primary product of microalgae thermal
degradation. Microalgae-derived radicals took part in the termination of
polymer radicals to produce bio-oil, biochar, and biogas.
3.2.2. Synergistic effects on the bio-oil
As mentioned above, co-pyrolysis exhibits a positive effect on the
formation of high-grade bio-oil, synergistic effects are the primary fac­
tor. Meanwhile, the performance of pyrolysis and the properties of bio-
oil are prone to be influenced by various factors, which have been fully
discussed in the literature (Abnisa & Wan Daud, 2014; Azizi et al.,
2018a; Fakayode et al., 2020). Thus, this section mainly introduces the
influence of synergistic effects on the yield and quality of bio-oil. As
summarized in Table 2, synergistic effects favor the improvement of the
bio-oil properties during the co-pyrolysis process. The utilization of raw
materials with high volatile matter content is instrumental in the gen­
eration of bio-oil, whereas the application of co-feedstocks with high ash
content hinders the process, but promotes the production of biochar and
biogas (Dhyani & Bhaskar, 2018). Table 1 indicates plastic materials like
PP and polyvinyl chloride (PVC) possess the high volatile matter of

5
G. Su et al. Bioresource Technology 344 (2022) 126096

Table 3
Synergistic effects on the yield and HHV of bio-oil.
Microalgae Co-feedstock T(◦ C) Catalyst Bio-oil yield (wt%) HHV (MJ/kg) Reference
MA CO 1:1E 1:1D MA CO 1:1E 1:1D

Nannochloropsis sp. Bamboo 600 ◦ C − 62.50 61.00 66.63 4.88 – – – – (Chen et al., 2017a)
Nannochloropsis sp. Bamboo waste 600 ◦ C − 53.00 42.00 51.00 3.50 27.52 20.03 24.19 0.42 (Chen et al., 2018c)
Nannochloropsis sp. Bamboo waste 600 ◦ C Biochar 53.00 42.00 35.00 − 12.50 27.52 20.03 29.72 5.95 (Chen et al., 2018c)
Spirulina platensis Bamboo waste 600 ◦ C − 55.00 42.00 52.00 3.50 21.44 20.03 20.17 − 0.56 (Chen et al., 2018c)
Spirulina platensis Bamboo waste 600 ◦ C Biochar 55.00 42.00 37.00 − 11.50 21.44 20.03 25.10 4.37 (Chen et al., 2018c)
Chlorella vulgaris Rural solid waste 500 ◦ C − 53.77 48.88 47.23 − 4.10 23.80 32.20 32.18 4.18 (Tang et al., 2020a)
Chlorella vulgaris Rural solid waste 500 ◦ C CaO 50.29 47.50 48.01 − 0.88 26.60 33.60 35.80 5.70 (Tang et al., 2020a)
Chlorella vulgaris Rural solid waste 500 ◦ C MgO 49.25 46.17 48.47 0.76 25.20 31.80 30.08 1.58 (Tang et al., 2020a)
Chlorella vulgaris Rural solid waste 500 ◦ C HZSM-5 53.33 45.83 46.32 − 3.26 27.20 30.60 32.92 4.02 (Tang et al., 2020a)
Chlorella vulgaris Kitchen waste 600 ◦ C − 55.00 56.00 30.00 − 25.50 30.30 12.00 33.90 12.75 (Chen et al., 2018a)
Chlorella vulgaris PVC 800 W − 40.80 16.20 25.20 − 3.30 32.71 36.95 37.11 2.28 (Dai et al., 2018b)
Chlorella vulgaris PVC 1 kW − 50.60 24.40 41.20 3.70 33.54 30.95 37.46 5.22 (Dai et al., 2018b)
Chlorella vulgaris Waste glycerol 900 ◦ C − 56.90 73.70 58.50 − 6.80 29.50 20.03 24.25 − 0.52 (Wang et al., 2019a)
Chlorella vulgaris Wood sawdust 1 kW SiC 49.30 20.20 44.40 9.65 23.61 28.66 17.97 − 8.17 (Chen et al., 2019b)
Chlorella vulgaris Wood sawdust 1 kW AC 45.30 21.20 37.10 3.85 19.93 29.30 15.02 − 9.60 (Chen et al., 2019b)
C. pyrenoidosa Waste tire 330 ◦ C − 52.50 25.30 53.60 14.70 33.68 42.90 38.96 0.67 (Duan et al., 2015)
Chlorella Tire (Under N2) 1 kW AC 53.60 22.80 36.20 − 2.00 – – – – (Fang et al., 2018)
Chlorella Tire (Under CO2) 1 kW AC 50.20 20.40 32.60 − 2.70 – – – – (Fang et al., 2018)
Isochrysis sp. Sewage sludge 500 ◦ C − 42.60 25.20 34.37 0.47 38.00 36.50 37.90 0.65 (Wang et al., 2016)

MA: Microalgae; CO: Co-feedstock; E: Experimental value; D: Difference between experimental and theoretical value.

99.60 and 93.77 wt%, while the ash content is close to zero, followed by
lignocellulosic biomass. While sewage sludge has the highest ash con­
tent and coal possesses the lowest volatile matter. Therefore, co-
pyrolysis of microalgae with plastics or lignocellulosic biomass can
facilitate the production of bio-oil, whereas the usage of coal or sewage
sludge as a co-feedstock is difficult to raise the yield of bio-oil.
Some studies have reported that synergistic effects are beneficial to
increase the yield of bio-oil. Chen et al. (2017a) performed co-pyrolysis
of Nannochloropsis sp. with bamboo. The yield of bio-oil went up to
66.63 wt% using 50 wt% of bamboo in the mixture at 600 ◦ C, while the
bio-oil generated from the sole pyrolysis of bamboo and microalgae
were just 60.05 and 61.85 wt%, respectively. Duan et al. (2015) ob­
tained a similar conclusion via the co-pyrolysis of Chlorella pyrenoidosa
and waste rubber tires. The yield of bio-oil from the pyrolysis of pure
microalgae was only 52.8 wt%, which was twice as high as that of waste
rubber tires. Nevertheless, the highest value of 57.2 wt% was reached
through the co-pyrolysis of microalgae with 20 wt% of waste rubber
tires. This was because co-pyrolysis inhibited the secondary cracking of
pyrolysis volatiles, thereby limiting the generation of biogas.
Nevertheless, some researchers have pointed out that the synergistic
effects can hinder the formation of bio-oil. Tang et al. (2020a) reported
that the bio-oil yield declined during the co-pyrolysis of Chlorella vulgaris
and rural solid waste, only 47.23 wt% bio-oil was obtained, which was
lesser than each sole pyrolysis. Meanwhile, an analogous result was
gained by Chen et al. (2018a), via the co-pyrolysis of Chlorella vulgaris
and kitchen waste. The highest bio-oil yield of 56.00 wt% was gained by
sole pyrolysis of kitchen waste, while only 30.00 wt% bio-oil was ob­
tained by using 50 wt% kitchen waste. The main reason was the sec­
ondary reaction, which converted part of bio-oil into biogas. Moreover,
after mixing, feedstocks pertained high H/C ratio, and increased the
hydrogen-related chemical groups significantly, which was instrumental
in the formation of biogas too.
In addition, based on the perspective of the application, hydrocar­
bons are the most significant chemical composition of biofuels, bio-oil
with high content of hydrocarbons can be used as transport fuel addi­
tives and industrial chemicals directly (Fan et al., 2020; Liu et al.,
2020b). The high content of oxygenated compounds in bio-oil possesses
a deleterious effect on the gasoline engine, which will cause several
problems owing to high acidity. Consequently, it is necessary to increase
the content of hydrocarbons and reduce the content of oxygenated
compounds to produce high-quality bio-oil (Mei et al., 2020). Conse­
quently, EHI has been introduced to assess the relative hydrogen content
of different samples as shown in Eq. (1) (Bertero et al., 2019; Dai et al.,
2018b).
EHI = (H − 2O − 2S − 3N)/C (1)
The H, O, S, N, and C refer to the moles of hydrogen, oxygen, sulfur,
nitrogen, and carbon.
Furthermore, HHV is another crucial criterion for the quality of bio-
oil. The high contents of carbon and hydrogen will produce bio-oil with
high HHV, whereas the high contents of oxygen and nitrogen have an
inverse effect (Ahmed et al., 2020). Many researchers have demon­
strated that synergistic effects can positively influence the quality of bio-
oil by decreasing the content of oxygenated and nitrogenous compounds
and carboxylic acids, and increasing the HHV. In general, the addition of
co-feedstocks with high EHI is favorable to improve the quality of bio-
oil. Xie et al. (2015) pyrolyzed Nannochloropsis sp. with scum and
detected the positive synergistic effects on the yield and aromatics
proportion of bio-oil when the ratio of Nannochloropsis sp. to scum was
less than 2:1. As a hydrogen donor, scum raised the EHI of the mixture to
boost the formation of aromatics. Simultaneously, oxygenated com­
pounds in the volatiles from the pyrolysis of Nannochloropsis sp. pro­
moted the cracking of scum, further enhanced the yield and quality of
bio-oil. Moreover, Tang et al. (2019) conducted the co-pyrolysis of
Nannochloropsis sp. with LDPE and found significant synergistic effects.
The growth of the LDPE ratio reduced the content of oxygenated and
nitrogenous compounds, while prominently rose the aliphatic hydro­
carbons content in the bio-oil. Oxygenates tended to evolve as H2O and
CO, while nitrogenous compounds were prone to be transformed into
gas products. Meanwhile, the addition of biomass with high EHI facili­
tated the quality of bio-oil was also confirmed by Fang et al. (2018) and
Qi et al. (2018).
Furthermore, synergistic effects positively influenced the HHV of
bio-oil while reducing the yield of bio-oil. Chen et al. (2018a) saw a
decline in the bio-oil yield during the co-pyrolysis of kitchen waste and
Chlorella vulgaris. The synergistic effects between different materials
increased the hydrocarbons content and decreased the carboxylic acids
in the bio-oil, resulted in the growth of HHV to 33.9 MJ/kg. The same
phenomenon that synergistic effects ameliorated the bio-oil quality and
reduced the bio-oil yield was also witnessed by Tang et al. (2020a), Dai
et al. (2018b), and Chen et al. (2018c). Nevertheless, synergistic effects
sometimes adversely affect the quality of bio-oil. According to the
research conducted by Chen et al. (2019b), the bio-oil HHV was 29.30
MJ/kg and 19.93 MJ/kg from the pyrolysis of pure wood sawdust and
Chlorella vulgaris with activated carbon, respectively. However, the HHV
of bio-oil originated from the co-pyrolysis fell to the bottom of 15.02
MJ/kg, but the yield of bio-oil increased owing to the high volatile

6
G. Su et al.
Fig. 1. Synergistic effects on the yield and HHV of bio-oil (Chen et al., 2018a;
Chen et al., 2019b; Chen et al., 2018c; Dai et al., 2018b; Duan et al., 2015; Tang
et al., 2020a; Wang et al., 2019a; Wang et al., 2016). *NS: Nannochloropsis sp.;
CP: C. pyrenoidosa; CV: Chlorella vulgaris; IS: Isochrysis sp.; PVC: Polyvi­
nyl chloride.
Fig. 2. Chemical composition of bio-oil from the co-pyrolysis of Chlorella vul­
garis (CV) with other biomass wastes (Chen et al., 2019b; Wang et al., 2019a;
Yuan et al., 2015).
matter content of two raw materials. Nevertheless, the phenomenon was
not common during the co-pyrolysis process.
Synergistic effects can be realized through the interaction of free
radicals, while the characteristics of various feedstocks and their
blending ratio are the primary factors influencing the synergistic effects
and resulting in complex and varied pyrolysis (Wang et al., 2019b; Zhao
et al., 2020). Usually, the difference between the theoretical and
experimental results of co-pyrolysis is a vital criterion to determine the
synergistic effects.
YT = W1X1 + W2X2 (2)
YD = YE- YT (3)
As shown in Eq. (2) and Eq. (3), W1 and W2 represent the mass
proportion of each raw material in the mixture samples, respectively. X1
and X2 refer to the product or physic-chemical properties of every single
raw material, YE and YT are the experimental value and the theoretical
7
Bioresource Technology 344 (2022) 126096
value, respectively. If YD greater than 0, suggesting positive synergistic
effects on pyrolysis; while if YD less than 0, indicating negative syner­
gistic effects on pyrolysis (Yao et al., 2017).
Table 3 summarizes the synergistic effects of co-pyrolysis of micro­
algae with other biomass wastes on the yield and HHV of bio-oil. Syn­
ergistic effects have a complex effect on the bio-oil yield but induce a
positive influence on the bio-oil HHV in most cases. Fig. 1 depicts the
influence of synergistic effects originated from the co-pyrolysis of
microalgae with some representative materials on the bio-oil properties,
the accession of plastics and tires presented great strengths, which
increased the yield and HHV of bio-oil by 3.7 wt% and 5.22 MJ/kg, 14.7
wt% and 0.67 MJ/kg, respectively. The inclusion of bamboo waste also
brought a decent result, increased the yield and HHV of bio-oil by 3.50
wt% and 0.42 MJ/kg, while the usage of sewage sludge had a tiny
enhancement on the yield and HHV of bio-oil. Other materials also
exhibited impressive performances, the addition of rural solid waste and
kitchen waste enhanced the bio-oil HHV, whereas the application of
wood sawdust raised the bio-oil yield without the amelioration on the
bio-oil HHV due to its high volatile matter content and low EHI. In short,
tires, plastics, and bamboo waste are suitable co-feedstocks for the py­
rolysis of microalgae.
Fig. 2 presents the chemical composition of bio-oil generated from
the co-pyrolysis of Chlorella vulgaris with other materials. The addition of
50 wt% different raw materials possessed a dramatic effect on the
chemical composition of bio-oil. At first, there was a remarkable
reduction of nitrogenous compounds after adding each material, as
numerous nitrogenous compounds were released into the air or
concentrated in the biochar. Additionally, the percentage of hydrocar­
bons increased significantly during the co-pyrolysis of microalgae with
kitchen waste and wood sawdust. Synergistic effects between those
materials promoted aromatization and deoxygenation reactions. How­
ever, the addition of waste glycerol reduced the content of hydrocarbons
sharply with the prominent increment in the content of alcohols. This
was ascribed to that glycerol was pyrolyzed into ethylene glycol, then
further dehydrated to form alcohols. Moreover, additional ester com­
pounds were generated with the drop of ketones and aldehydes during
the co-pyrolysis process (Wang et al., 2019a).
In brief, the addition of co-feedstocks with high volatile matter
content is conducive to the formation of bio-oil. While the application of
materials with high EHI can induce a series of reactions, such as Diels-
Alder, dehydration, hydrogen transfer, Maillard, ketonization, conden­
sation, denitrogenation, aromatization, and deoxygenation reactions,
which inhibits the generation of oxygenated and nitrogenous com­
pounds and promotes the production of aromatic hydrocarbons, thereby
improving the quality of bio-oil. Simultaneously, as a substitute for fossil
fuel, bio-oil is the most economically and environmentally important
product. The large-scale production of bio-oil is the only way to achieve
the commercialization and industrialization of related industries.
Consequently, it is particularly important to search and develop excel­
lent and low-cost co-feedstocks. Many materials with high volatile
matter content and EHI, such as medical waste, waste cooking oil, and
waste lubricating oil, need to be studied to further ameliorate the
properties of bio-oil from the pyrolysis of microalgae.
4. Catalytic effects on the co-pyrolysis process
Catalytic pyrolysis is a prospective technique to facilitate the existing
co-pyrolysis process and the properties of bio-oil. Furthermore, the
application of catalysts is conducive to lower the activation energy,
reduce acidity, shorten the reaction time, and affect the product distri­
butions (Lee et al., 2020a). The catalytic pyrolysis process is categorized
as in-situ and ex-situ modes. For the in-situ process, raw materials and
catalysts are mixed before co-pyrolysis, while for the ex-situ process, the
pyrolysis volatiles pass through the catalyst at an operational tempera­
ture (Yu et al., 2019). Table 4 summarizes catalytic effects on the co-
pyrolysis of microalgae and other biomass wastes. Numerous studies
G. Su et al. Bioresource Technology 344 (2022) 126096

Table 4
Catalytic effects on the co-pyrolysis of microalgae and other biomass wastes.
Microalgae Co- Catalyst Conditions Reactor Catalyst performance Reference
feedstock

Chlorella vulgaris Rural solid CaO 500 ◦ C, 25 Fixed-bed • Increases the activation energy and HHV. (Tang et al.,
waste min, N2 reactor • Raises the content of aliphatic hydrocarbons. 2020a)
• Reduces acids and nitrogenous compounds.
Chlorella vulgaris Rural solid HZSM-5 500 ◦ C, 25 Fixed-bed • Reduces the activation energy. (Tang et al.,
waste min, N2 reactor • Increases the aromatic hydrocarbons and nitrogenous 2020a)
compounds content in the bio-oil.
Chlorella vulgaris Rural solid MgO 500 ◦ C, 25 Fixed-bed • Increases the hydrocarbons content in the bio-oil. (Tang et al.,
waste min, N2 reactor • Reduces the activation energy. 2020a)
Nannochloropsis sp. Palm kernel Cu/HZSM-5 600 ◦ C, 15 Fixed-bed • Increases the aromatics content in the bio-oil. (Chang et al.,
shell min, N2 reactor • Cu reduces the number of strong acid sites of HZSM-5. 2018)
Nannochloropsis sp. Palm kernel CaO/HZSM- 600 ◦ C, 15 Fixed-bed • Increases the aromatics content in the bio-oil. (Chang et al.,
shell 5 min, N2 reactor • Generates lower peak area values of specific aromatics than 2018)
other catalysts.
Chlorella vulgaris Kitchen CaO 900 ◦ C, 40 ◦ C/ Fixed-bed • Decreases the acids content sharply. (Chen et al.,
waste min, N2 reactor • Increases the aromatic hydrocarbons content. 2018b)
Chlorella vulgaris Kitchen CaCO3 900 ◦ C, 40 ◦ C/ Fixed-bed • Decreases the acids content. (Chen et al.,
waste min, N2 reactor • Improves the benzene, toluene, ethylbenzene, xylenes for all 2018b)
samples and hydrocarbons in the bio-oil for sole microalgae
and mixture, except kitchen waste.
Chlorella vulgaris Kitchen Permutit 900 ◦ C, 40 ◦ C/ Fixed-bed • Lowers the initial temperature. (Chen et al.,
waste min, N2 reactor • Results in less residues. 2018b)
• Shows unfavorable selectivity on the products.
Chlorella vulgaris Kitchen SiO2 900 ◦ C, 40 ◦ C/ Fixed-bed • Shows an unsatisfied product distribution. (Chen et al.,
waste min, N2 reactor • Hinders the formation of hydrocarbons and benzene, 2018b)
toluene, ethylbenzene, xylenes.
• Promotes the generation of oxygenated and nitrogenous
compounds.
Chlorella vulgaris Wood Activated 1 kW, 25 min, Microwave • Increases the gas yield and aromatic hydrocarbons content in (Chen et al.,
sawdust carbon N2 reactor the bio-oil. 2019b)
• Possesses a better absorptive capacity of microwave
irradiation.
Chlorella vulgaris Wood SiC 1 kW, 25 min, Microwave • Raises the bio-oil and biochar yield. (Chen et al.,
sawdust N2 reactor • Increases the content of aliphatic hydrocarbons and phenols 2019b)
in the bio-oil.
Nannochloropsis sp. Scum HZSM-5 550 ◦ C, 30 Microwave • Increases the gas yield and hydrocarbons content. (Xie et al.,
min, He reactor • Decreases oxygenated and nitrogenous compounds in the 2015)
bio-oil.
Spirulina platensis, Bamboo Biochar 600 ◦ C,30 min, Two-stage fixed- • Facilitates the decomposition of long-chain fatty acids and (Chen et al.,
Nannochloropsis sp. waste Ar bed reactor O− species in the bio-oil. 2018c)
• Enhances the production of phenols and aromatics in the bio-
oil.
• Reduces oxygenated compounds content in the bio-oil.

have reported that the presence of catalysts has a positive effect on the
pyrolysis process and product properties.
4.1. Catalytic effect of zeolites
At present, over 60 natural zeolites and 230 zeotype frameworks
with special characteristics and porous structures have been discovered
and designed. There are various kinds of zeolites including ZSM-5,
HBEA, HZSM-5, and permutit, which have been utilized in the co-
pyrolysis of microalgae and other biomass wastes. Carbohydrates, al­
cohols, acids, aldehydes, furans, ketones, and other functional groups
can easily diffuse into the zeolite molecular sieve channels, participate
in a series of reactions to produce oxygen, aromatics, and coke (Zhang
et al., 2016).
As a consequence of the existence of proteins and high moisture
content, the bio-oil originated from the pyrolysis of microalgae possesses
high oxygen and nitrogen contents. Therefore, HZSM-5 has been widely
used owing to its characteristics of deoxygenation, denitrogenation, and
aromatization. HZSM-5 is manufactured from ZSM-5 via calcined and
hydrothermal treatments and manifests strong acidity and favorable
deoxygenation effect because of active hydrogen, which can facilitate
the formation of aromatic hydrocarbons and hinder the generation of
oxygenated compounds like acids, alcohols, and ketones (State et al.,
2019). Qi et al. (2018) conducted the co-pyrolysis of PP with Nanno­
chloropsis sp. and witnessed a sharp growth in the content of aromatic
hydrocarbons from 43.38 to 93.29 wt%, a notable drop in the content of
olefins from 33.19 to 2.29 wt% and a severe decline in the content of
nitrogenous compounds from 18.37 to 0.59 wt%, when the mass ratio of
catalyst/feedstock raised from 1 to 10. They elucidated the phenomenon
that volatiles fully reached the surface of HZSM-5, the intermediate
polar product was produced by degradation during the pyrolysis of
Nannochloropsis sp., the nonpolar compounds and hydrocarbons were
formed by the destruction of nitrogenous functional groups. Addition­
ally, the conclusion of HZSM-5 can greatly decrease the nitrogenous
compounds and improve aromatics selectivity in the bio-oil was also
supported by Zhang et al. (2017) and Yang et al. (2011). On top of that,
Xie et al. (2015) studied the effect of HZSM-5 on the properties of bio-oil
during the co-pyrolysis of Nannochloropsis sp. and scum. The bio-oil
yield declined with the presence of catalyst as the thermal cracking re­
action converted the condensable gas into non-condensable gas. Mean­
while, the content of polycyclic aromatic hydrocarbons and aromatic
hydrocarbons raise sharply, while the content of aliphatic hydrocarbons,
oxygenated, and nitrogenous compounds declined. Due to its unique
structure, HZSM-5 manifested excellent shape-selectivity to the aro­
matics and drove the cracking and deoxidation of oxygenated com­
pounds. Furthermore, a similar conclusion was also gained in the
pyrolysis of lignocellulosic biomass (Mihalcik et al., 2011).
However, many studies have revealed that the HZSM-5 can poly­
merize a considerable number of oxygenated compounds to form coke
on the surface of the catalyst, thus reduces its catalytic activity (Wu

8
G. Su et al.
et al., 2015). To overcome the barrier, the utilization of modified HZSM-
5 has attracted attention rapidly. The chemical liquid deposition tech­
nique is applied to ameliorating the catalytic performance of HZSM-5 by
narrowing the pore openings and reducing the number of external acid
sites, which has advantages of simple apparatus, easy operation, and low
cost (Dai et al., 2018a). Chang et al. (2018) performed the co-pyrolysis
of Nannochloropsis sp. and palm kernel shell with HZSM-5, CaO/HZSM-
5, and modified HZSM-5 with Cu. These three types of catalysts raised
the aromatics content from 30.39 to 40.19, 36.12, and 42.16 wt%,
respectively. The results revealed that Cu/HZSM-5 was the best catalyst
which enhanced the quality of bio-oil effectively, as Cu cut down the
number of strong acid sites on the surface of HZSM-5 and improved the
catalytic activity, while pore structures of HZSM-5 facilitated the for­
mation of aromatics. In addition, HZSM-5 has displayed great perfor­
mance in the reduction of activation energy during the co-pyrolysis
process. Bong et al. (2020) and Dai et al. (2019) reported that the
average activation energy fell from 142.56 to 131.37 kJ/mol and 258.72
to 198.66 kJ/mol using the Flynn-Wall-Ozawa model with the help of
HZSM-5 for co-pyrolysis of Chlorella vulgaris with peanut shell and the
co-pyrolysis of Spirulina with oil shale, respectively. Furthermore, Tang
et al. (2020a) obtained the same result that the co-pyrolysis of Chlorella
vulgaris and rural solid waste using HZSM-5 catalyst has decreased the
activation energy from 258.33 to 222.64 kJ/mol via Kissinger-Akahira-
Sunose method.
Except for HZSM-5 and its derivatives, other zeolite was also
employed in the co-pyrolysis but did not achieve ideal results. Chen et al.
(2018b) pyrolyzed the Chlorella vulgaris and kitchen waste with the aid
of permutit and ascertained that the catalyst had a predominant pro­
moting effect on the reduction of initial temperature and residue mass,
but did not show positive selectivity on the final products.
4.2. Catalytic effect of metal oxides
Metal oxides exhibit Lewis acid and Bronsted base because of the
positive metal ions and negative oxygen ions. They have been explored
excessively to improve the properties of bio-oil with the characteristics
of acid base and redox. CaO, MgO, CaCO3, ZnO, and SiO2 are the most
commercial metal oxides applied in the co-pyrolysis of microalgae and
other biomass wastes, which can be divided into basic metal oxides
(CaO, MgO) and acidic metal oxides (SiO2) (Chan & Tanksale, 2014).
Generally, the basic metal oxides are suitable for aldol condensation and
ketonization of carbonyl compounds and carboxylic acid, while the
acidic metal oxides present better catalytic activity during the deoxy­
genation process.
Microalgae possess a high content of oxygen and nitrogen, thus the
catalyst with the ability of denitrogenation and deoxygenation is
essential for the pyrolysis of microalgae. Among metal oxides, CaO
manifests the best performance on the reduction of acids and nitrides
and the improvement of hydrocarbons in the bio-oil. Tang et al. (2020a)
carried out the co-pyrolysis of Chlorella vulgaris and rural solid waste
with the assistance of three different catalysts. CaO raised the activation
energy of the overall reaction, while HZSM-5 and MgO diminished it.
Furthermore, CaO increased aliphatic hydrocarbons content especially
light fraction, reduced acids and nitrogenous compounds content. MgO
boosted the increase of hydrocarbons and the decrease of carboxylic
acids and nitrogenous compounds for sole pyrolysis of microalgae but
failed to the pyrolysis of rural solid waste and all mixtures. Moreover,
HZSM-5 raised aromatic hydrocarbons content, but unfortunately, also
increased nitrogenous compounds content. The analogous experimental
result was obtained by Chen et al. (2018b), via the co-pyrolysis of
Chlorella vulgaris and kitchen waste with the aid of CaCO3, CaO, SiO2,
and permutit. The process was favored by CaO without exception, the
content of hydrocarbons in the bio-oil increased for all mixed samples.
Moreover, the acids yield decreased sharply by 2.4 times for pure
kitchen waste, 6.1 times for pure microalgae, and 4.5 times for the
mixture, the metal cation Ca2+ from CaO was capable to neutralize
9
Bioresource Technology 344 (2022) 126096
acids. While the utilization of CaCO3 did not improve the hydrocarbons
content in the bio-oil from the pyrolysis of pure kitchen waste, the
addition of SiO2 presented an unfavorable product distribution, and the
presence of permutit did not display any obviously admirable selectivity
on the final products.
Tang et al. (2020a) carried out the co-pyrolysis of Chlorella vulgaris
and rural solid waste with the aid of three kinds of catalysts (HZSM-5,
MgO, and CaO) and detected that non-catalytic co-pyrolysis had an
inhibitory influence on the bio-oil yield, primarily related to the sec­
ondary reaction to form biogas. While the addition of catalysts allevi­
ated the situation, the presence of MgO even reversed the trend and
generated positive synergistic effects on the bio-oil yield. As for the
HHV, synergistic effects influenced the HHV of bio-oil positively, CaO
further enhanced the tendency due to its strong deoxygenation, deni­
trogenation, and aromatization capacity. Based on the above analysis,
CaO showed the best catalytic performance based on the amelioration of
bio-oil yield and quality.
4.3. Catalytic effect of carbon-based catalysts
Carbon-based catalysts also play critical roles in the co-pyrolysis of
microalgae and other biomass wastes. Carbon-based catalysts are effi­
cient catalysts owing to the carbonaceous matter and unique surface
area, while mineral content (Al2O3, MgO, and Fe2O3) and metal (Na, Mg,
K, Al, Ca, and P) can further facilitate its catalytic activity (Gao et al.,
2020). Furthermore, carbon-based catalysts such as biochar, SiC, acti­
vated carbon, and graphite are widely utilized in microwave-assisted
pyrolysis as absorbents with admirable microwave absorptivity.
Numerous studies have demonstrated that biochar possesses strong
nitrogen fixation ability and deoxidation power. Chen et al. (2018d)
pyrolyzed Nannochloropsis sp. and cellulose under the aid of biochar.
They ascertained that HCN, NH3, and nitrogenous intermediates had
reactions with high active oxygen species, promoted the formation of
pyrrolic-N, pyridinic-N, amine/amide-N, and quaternary-N on the sur­
face of the catalyst, which made the high concentration of nitrogen in
the char and the reduction of N-containing gas, amines, and nitriles.
Chen et al. (2018c) noticed that the usage of biochar in the co-pyrolysis
of bamboo waste and Spirulina platensis had a huge impact on the
product distribution, which reduced the bio-oil yield from 52 to 37 wt%,
while increasing the biogas yield from 12 to 20 wt%. Simultaneously,
the addition of biochar enhanced the content of phenol and long-chain
fatty acids and hindered the formation of oxygenated and nitrogenous
compounds in the bio-oil, rose the bio-oil HHV to 25.10 MJ/kg.
Furthermore, other carbon-based additives also exhibited great perfor­
mance on denitrogenation and deoxygenation. Chen et al. (2019b) re­
ported the carbon-based additives improved the quality of bio-oil by
deoxygenation and aromatization through the microwave-assisted co-
pyrolysis of Chlorella vulgaris with wood sawdust. The presence of SiC
raised the yield of bio-oil and biochar, while the application of activated
carbon increased the biogas yield due to the good absorptive capacity of
microwave irradiation. Moreover, both additives had a positive impact
on the aromatization and deoxygenation by increasing the content of
aliphatic hydrocarbons and phenols in the bio-oil, but denitrogenation
was not detected during the co-pyrolysis process.
In summary, the addition of CaO and Cu/HZSM-5 exhibits great
advantages in previous researches, which can facilitate the formation of
aromatics and inhibit the generation of oxygenated and nitrogenous
compounds. The overall bio-oil quality has been improved effectually
because Ca2+ in CaO neutralizes acids. Meanwhile, the pore structure
and surface acidity of HZSM-5 possess strong deoxygenation, deni­
trogenation, and aromatization capabilities, the usage of Cu cuts down
the number of strong acid sites of the catalyst. Modified HZSM-5 hinders
the formation of coke and ameliorates the activity of catalysts, which
can be a prospective research direction for the co-pyrolysis of micro­
algae and other materials. Additionally, some studies have proven the
effectiveness of acid and alkali coexist bifunctional catalyst in the
G. Su et al.
reduction of acid content, the inhibition of coke formation, and the
growth of bio-oil yield. Yu et al. (2020) utilized coexist bifunctional
catalyst based on SBA-15 to conduct the pyrolysis of waste cooking oil
and achieved satisfying results. Microalgae possess the drawbacks of
high oxygen and ash content. Hence, the acid and alkali coexist
bifunctional catalyst can be explored in the microalgae co-pyrolysis.
Moreover, the relationship between the product properties and cata­
lysts still requires additional studies, whereas the suitable catalyst for
specific microalgae and other biomass wastes needs to be further
developed.
5. Economic viability of the co-pyrolysis process
Many studies have shown the great techno-economic strengths of co-
pyrolysis in comparison with sole pyrolysis. The equipment of co-
pyrolysis is similar to sole pyrolysis, which shows simplicity in design
and operation, but the result is considerably profitable owing to the
reduction of feedstocks cost and the improvement of products properties
(Ozyuguran et al., 2018).
Meyer et al. (2020) conducted the economic and environmental
benefits analysis for the conversion of 11 biomass feedstocks to biofuels
through fast pyrolysis or co-pyrolysis. The study concluded that capital-
related costs (including capital depreciation, return on investment, and
income tax) was the maximum cost contributed with 30–40% of the
minimum fuel selling price, followed by feedstock cost (30%), hydro­
treating catalyst cost (13–18%), and labor cost (12–15%). Woody and
herbal mixed raw materials with reasonable product yield, little risk,
low raw materials price, and low transportation costs display tremen­
dous advantages over single raw materials. Kuppens et al. (2010)
analyzed the profitability of the co-pyrolysis of biopolymers with willow
and indicated that co-pyrolysis can obtain better economic benefits in
comparison with sole pyrolysis of willow, the net present value of cash
flow raised by at least 0.405 MEUR because of the growth of high-value
crotonic acid. Zhang et al. (2015) pyrolyzed corn stalk and HDPE in the
presence of HZSM-5 and performed an economic assessment. Value
index formula was used to analyze the economic potential of aromatic
hydrocarbons and found that high content of aromatic hydrocarbons
was achieved when the hydrogen to carbon effective ratio of feedstock
was more than 1. Co-pyrolysis was superior to sole pyrolysis because of
high-quality products and subsequent economic benefits.
As for the production of microalgae, the high cost of cultivation and
the low production capacity of microalgae are the primary barriers to
the commercialization of the microalgae production industry. Many
scholars have devoted themselves to the techno-economic assessment of
microalgae cultivations and made a substantial number of achieve­
ments. Rezvani et al. (2016) took a techno-economic assessment on the
microalgae cultivations and concluded that the selling price is between
$440–1028/t when photosynthetic efficiency is 4%. Yang et al. (2019)
demonstrated that with the rapid development of cultivation technology
last decade, the cost of biocrude of microalgae was decreased to
approximately $7.50 per gallon, while the low productivity of micro­
algae was still the main bottleneck.
A feasibility and economic analysis of microalgae-based biodiesel
production in China was conducted by Sun et al. (2019b). The produc­
tion cost of microalgae-based biodiesel was calculated as USD 2.29/kg
according to the 100 ha of production facilities, which was far more than
that of conventional fuel. The main obstacles were the low productivity
of microalgae and product benefits. Additionally, Xin et al. (2016)
performed a techno-economic analysis of biofuel production from the
pyrolysis of wastewater-based algal. Capital, land, operation, chemical
coagulation harvesting costs, and reasonable bio-oil yield and revenue
were calculated. The estimated break-even selling price of biofuels was
USD 2.23 per gallon, which was within an acceptable range. Meanwhile,
if breakthroughs could be made in the three key components of culti­
vation, harvesting, and downstream transformation, this method would
obtain better overall benefits and the internal rate of return would raise
10
Bioresource Technology 344 (2022) 126096
to 18.7%. Jonker and Faaij (2013) treated microalgae as feedstocks for
the production of bioenergy and found the production cost of biofuels
was 136 €/GJ for raceway ponds and 153 €/GJ for horizontal tubular
systems, which was far more than diesel and gasoline (5–20 €/GJ), even
the costs could be reduced by a quarter via possible improvement op­
tions during the production process. Nevertheless, co-pyrolysis with
low-cost raw materials and co-production of bioenergy and high-value
products has not been taken into consideration.
The techno-economic assessment for co-pyrolysis of microalgae and
other biomass wastes was conducted by Wang et al. (2016) and Chen
et al. (2018c). Wang et al. (2016) detected that the inclusion of Isochrysis
sp. cut down the energy consumption and facilitated energy efficiency.
Co-pyrolysis saved energy costs and improved the energy conversion
and stability of sewage sludge pyrolysis. Moreover, Chen et al. (2018c)
performed an economic assessment for the mass production of biofuels
via the co-pyrolysis of microalgae and bamboo waste. However, co-
pyrolysis did not show great advantages, sole pyrolysis of Spirulina
platensis earned the most profit of 33.6 million RMB annually, followed
by sole pyrolysis of Nannochloropsis sp. with 32.8 million RMB every
year, while the third one was the co-pyrolysis of Spirulina platensis and
bamboo waste with 31.6 million RMB per year. However, the input and
output were only taken into account, while the positive social, eco­
nomic, and environmental effects owing to the disposal of bamboo waste
were not considered in the study. In addition, anther raw materials with
low cost would push the co-pyrolysis process forward.
6. Challenges and prospects of the co-pyrolysis process
As mentioned above, the economic feasibility of microalgae-based
biodiesel is still poor due to the high cost of microalgae and low prod­
uct benefits. However, the cost of microalgae is expected to decline
significantly in the foreseeable future with the support of government
policies and various capitals. For instance, the Chinese government has
initiated many national key research and development projects for
microalgae biomass and biofuels to regulate and incentivize the devel­
opment of the microalgae industry. In 2009, the “Key technologies in
CO2 to oil algae to biodiesel” project received 3.2 million US dollars
funding from the Chinese government. In 2013, ENN Group got a loan of
46.5 million US dollars from the China Development Bank to scale up
the microalgae farm to 280 Hectares in Inner Mongolia (Chen et al.,
2020). The U.S. government has launched many microalgae programs to
support the target of 17% of transportation fuels in the United States can
be replaced by microalgae-based biofuels (Su et al., 2017). Meanwhile,
in the background of global warming, carbon neutrality and low-carbon
economy are the themes of sustainable development in the world. The
microalgae industry is closely linked to the topic and will receive more
attention and strong support from governments of all countries. Because
the cultivation and utilization of microalgae can bring numerous social,
economic, and environmental benefits, like carbon dioxide reduction,
wastewater treatment, and environmental improvement, which will
gain benefits from variegated policy arbitrations like second-generation
biomass, such as tax break, economic support, subsidies for production
and infrastructure (Sajjadi et al., 2018). Additionally, many microalgae
companies have aroused the attention of commercial capital. For
example, Xiaozao Tech in China has completed a round of Series B
funding (15.5 million US dollars) in 2021 to expand production scale
and increase market share. Therefore, the cost of microalgae will be
decreased sharply in the future with the joint endeavors from various
parties.
In addition, further valorization of microalgae through deep pro­
cessing is vital to the microalgae industry. Microalgae possess a wide
range of applications and enormous economic value. For instance,
polysaccharides are used for human nourishment, cosmetics, pharma­
ceuticals, and therapeutics. Lipids in the microalgae are applied to
neutraceutics, food technology, and medicine. Bioactive compounds are
extensively employed in antibiotics, agronomic chemistry, vaccines, and
G. Su et al.
Fig. 3. Flow diagram of microalgae biorefinery and biofuels production.
chemicals. Proteins are the raw material for pharmacy vaccines, nutri­
tion, and recombinant protein. Pigments have wide application in
fragrance, cosmetics, and medicine (Dasan et al., 2019). Consequently, a
biorefinery system is required to realize the valorization of microalgae.
Vanthoor-Koopmans et al. (2013) proposed an effective microalgae
biorefinery scheme, which adopted pulsed electric field as a cell
disruption technique and ionic liquids to separate hydrophilic and hy­
drophobic compounds. Gerardo et al. (2014) held a view that membrane
filtration was a promising technology and would play a key role in the
recovery of proteins, lipids, and carbohydrates from microalgae.
Furthermore, Banu et al. (2020) proposed three biorefinery routes
including biodiesel production, pigments, animal feed, biogas, bio-
hydrogen production, and concluded that process integration was
conductive to reduce the cost and increase the profit effectively.
Nevertheless, present research of conventional or advanced pyrolysis of
microalgae is still in the laboratory stage, large-scale production of
bioproduct is essential to achieve its industrialization and commercial­
ization. Therefore, the expansion of research is necessitated to complete
the industrial production and subsequent market applications of bio-oil
from microalgae pyrolysis. Meanwhile, the economic assessment of
microalgae pyrolysis on a large scale is also important, because the
positive result will absorb capital and talent, thereby stimulating the
development of related industries.
As the growth, survival, and reproduction organisms in aquatic
ecosystems, microalgae possess high moisture content, which is unfa­
vorable to the production of high-quality bio-oil. Accordingly, pre­
treatment processes, like drying or torrefaction, are imperative to
ameliorate the bio-oil quality. However, the implementation of drying
or torrefaction will substantially increase the production cost since they
are energy-intensive processes. The application of microwave-assisted
pyrolysis can combine drying and pyrolysis processes due to the polar
nature of water, which will simplify the equipment and reduce the cost.
It is reported that the release of water occurs between ambient tem­
perature to 200 ◦ C (Sait & Salema, 2015). Meanwhile, vacuum pyrolysis
requires further exploration to increase the bio-oil yield and reduce the
production cost, because the condition of negative pressure can cut
down the boiling point of bio-oil, thereby promoting the generation of
bio-oil. Lam et al. (2019) conducted the co-pyrolysis of plastics with
waste oils using inert gas and vacuum pump, then obtained a result that
the production cost under vacuum environment was 20.47% less than
that under N2 environment. Moreover, it is necessary to achieve excess
energy in the final product due to the endothermic characteristics of
pyrolysis. Further studies on the selection of cheap and excellent co-
feedstocks, development of effective catalysts, and mechanism of syn­
ergistic effects behind the co-pyrolysis of microalgae and other materials
will contribute to accomplishing the goal.
As depicted in Fig. 3, the economic advantages of co-pyrolysis and
microalgae biorefinery are supposed to be combined, a comprehensive
facility consisted of microalgae cultivation, biorefinery, and biofuels
production system will achieve the target. During cultivation, micro­
algae will absorb CO2 released by vehicles using biofuels, while micro­
algae will be used as raw materials for the production of biofuels. The
carbon cycle based on microalgae conforms to the principle of sustain­
able development and circular economy. After cultivation, microalgae
will be sent into biorefinery systems and downstream industries, the
11
Bioresource Technology 344 (2022) 126096
residues will be employed in the co-pyrolysis process to produce bio­
fuels. While biogas can be reused for the pretreatment process to cut
down the storage, transportation, and heating cost, bio-oil and biochar
are the main products for industry and transportation, biochar can also
be utilized in the co-pyrolysis process as a catalyst. The comprehensive
facility inherits the advantages of co-pyrolysis and microalgae, which
will maximize the value of microalgae and accelerate the speed of
commercialization of related industries (van Schalkwyk et al., 2020).
7. Conclusions
Co-pyrolysis of microalgae and other biomass wastes is an effective
way to produce high-quality biofuels. The positive synergistic effects
between various materials and the improvement of the target product
have verified the strength and effectiveness of co-pyrolysis. Simulta­
neously, the addition of catalysts has significantly facilitated the quality
of bio-oil by reducing the content of oxygenated and nitrogenous com­
pounds, while increasing the HHV and the content of aromatic hydro­
carbons in the bio-oil. Meanwhile, a comprehensive facility that inherits
the superiorities of co-pyrolysis and microalgae has been proposed to
realize the valorization of microalgae and promote the commercializa­
tion of related industries.
CRediT authorship contribution statement
Guangcan Su: Investigation, Formal analysis, Writing – original
draft. Hwai Chyuan Ong: Conceptualization, Writing – review & edit­
ing, Supervision. Yong Yang Gan: Validation, Writing – review &
editing. Wei-Hsin Chen: Resources, Writing – review & editing. Cheng
Tung Chong: Formal analysis, Validation. Yong Sik Ok: Visualization,
Writing – review & editing.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
References
Abdullah, B., Syed Muhammad, S.A.F.a., Shokravi, Z., Ismail, S., Kassim, K.A., Mahmood,
A.N., Aziz, M.M.A. 2019. Fourth generation biofuel: A review on risks and mitigation
strategies. Renewable and Sustainable Energy Reviews, 107, 37-50.
Abnisa, F., Wan Daud, W.M.A., 2014. A review on co-pyrolysis of biomass: An optional
technique to obtain a high-grade pyrolysis oil. Energy Conversion and Management
87, 71–85.
Ahmed, Mohamed H.M., Batalha, Nuno, Mahmudul, Hasan M.D., Perkins, Greg,
Konarova, Muxina, 2020. A review on advanced catalytic co-pyrolysis of biomass
and hydrogen-rich feedstock: Insights into synergistic effect, catalyst development
and reaction mechanism. Bioresource Technology 310, 123457. https://doi.org/
10.1016/j.biortech.2020.123457.
Ali, I., Naqvi, S.R., Bahadar, A., 2018. Kinetic analysis of Botryococcus braunii pyrolysis
using model-free and model fitting methods. Fuel 214, 369–380.
Anand, V., Sunjeev, V., Vinu, R., 2016. Catalytic fast pyrolysis of Arthrospira platensis
(spirulina) algae using zeolites. Journal of Analytical and Applied Pyrolysis 118,
298–307.
Azizi, K., Keshavarz Moraveji, M., Abedini Najafabadi, H., 2018a. A review on bio-fuel
production from microalgal biomass by using pyrolysis method. Renewable and
Sustainable Energy Reviews 82, 3046–3059.
G. Su et al.
Azizi, K., Keshavarz Moraveji, M., Abedini Najafabadi, H., 2018b. Simultaneous pyrolysis
of microalgae C. vulgaris, wood and polymer: The effect of third component
addition. Bioresource Technology 247, 66–72.
Azizi, K., Keshavarz Moraveji, M., Arregi, A., Amutio, M., Lopez, G., Olazar, M., 2020. On
the pyrolysis of different microalgae species in a conical spouted bed reactor: bio-
fuel yields and characterization. Bioresource Technology 123561.
Banu, J.R., Preethi, Kavitha, S., Gunasekaran, M., Kumar, G. 2020. Microalgae based
biorefinery promoting circular bioeconomy-techno economic and life-cycle analysis.
Bioresource Technology, 302, 122822.
Benedek, J., Sebestyén, T.-T., Bartók, B., 2018. Evaluation of renewable energy sources
in peripheral areas and renewable energy-based rural development. Renewable and
Sustainable Energy Reviews 90, 516–535.
Bertero, M., García, J.R., Falco, M., Sedran, U., 2019. Equilibrium FCC catalysts to
improve liquid products from biomass pyrolysis. Renewable Energy 132, 11–18.
Bong, J.T., Loy, A.C.M., Chin, B.L.F., Lam, M.K., Tang, D.K.H., Lim, H.Y., Chai, Y.H.,
Yusup, S., 2020. Artificial neural network approach for co-pyrolysis of Chlorella
vulgaris and peanut shell binary mixtures using microalgae ash catalyst. Energy 207,
118289.
Carvalho, J.C., Magalhães, A.I., de Melo Pereira, G.V., Medeiros, A.B.P., Sydney, E.B.,
Rodrigues, C., Aulestia, D.T.M., de Souza Vandenberghe, L.P., Soccol, V.T., Soccol, C.
R., 2020. Microalgal biomass pretreatment for integrated processing into biofuels,
food, and feed. Bioresource Technology 300, 122719.
Chan, F.L., Tanksale, A., 2014. Review of recent developments in Ni-based catalysts for
biomass gasification. Renewable and Sustainable Energy Reviews 38, 428–438.
Chang, G., Miao, P., Wang, H., Wang, L., Hu, X., Guo, Q., 2018. A synergistic effect
during the co-pyrolysis of Nannochloropsis sp. and palm kernel shell for aromatic
hydrocarbon production. Energy Conversion and Management 173, 545–554.
Chen, C., Ma, X., He, Y., 2012. Co-pyrolysis characteristics of microalgae Chlorella
vulgaris and coal through TGA. Bioresource Technology 117, 264–273.
Chen, H., Wang, X., Wang, Q., 2020. Microalgal biofuels in China: The past, progress and
prospects. GCB Bioenergy 12 (12), 1044–1065.
Chen, H., Xie, Y., Chen, W., Xia, M., Li, K., Chen, Z., Chen, Y., Yang, H., 2019a.
Investigation on co-pyrolysis of lignocellulosic biomass and amino acids using TG-
FTIR and Py-GC/MS. Energy Conversion and Management 196, 320–329.
Chen, L., Yu, Z., Fang, S., Dai, M., Ma, X., 2018a. Co-pyrolysis kinetics and behaviors of
kitchen waste and chlorella vulgaris using thermogravimetric analyzer and fixed bed
reactor. Energy Conversion and Management 165, 45–52.
Chen, L., Yu, Z., Liang, J., Liao, Y., Ma, X., 2018b. Co-pyrolysis of chlorella vulgaris and
kitchen waste with different additives using TG-FTIR and Py-GC/MS. Energy
Conversion and Management 177, 582–591.
Chen, L., Yu, Z., Xu, H., Wan, K., Liao, Y., Ma, X., 2019b. Microwave-assisted co-pyrolysis
of Chlorella vulgaris and wood sawdust using different additives. Bioresource
Technology 273, 34–39.
Chen, R., Zhang, S., Yang, X., Li, G., Zhou, H., Li, Q., Zhang, Y., 2021a. Thermal
behaviour and kinetic study of co-pyrolysis of microalgae with different plastics.
Waste Management 126, 331–339.
Chen, W.-H., Lin, B.-J., Lin, Y.-Y., Chu, Y.-S., Ubando, A.T., Show, P.L., Ong, H.C.,
Chang, J.-S., Ho, S.-H., Culaba, A.B., Pétrissans, A., Pétrissans, M., 2021b. Progress in
biomass torrefaction: Principles, applications and challenges. Progress in Energy and
Combustion Science 82, 100887.
Chen, W., Chen, Y., Yang, H., Xia, M., Li, K., Chen, X., Chen, H., 2017a. Co-pyrolysis of
lignocellulosic biomass and microalgae: Products characteristics and interaction
effect. Bioresource Technology 245, 860–868.
Chen, W., Li, K., Xia, M., Yang, H., Chen, Y., Chen, X., Che, Q., Chen, H., 2018c. Catalytic
deoxygenation co-pyrolysis of bamboo wastes and microalgae with biochar catalyst.
Energy 157, 472–482.
Chen, W., Lin, B.J., Huang, M.Y., Chang, J.S., 2015. Thermochemical conversion of
microalgal biomass into biofuels: a review. Bioresource Technology 184, 314–327.
Chen, W., Yang, H., Chen, Y., Li, K., Xia, M., Chen, H., 2018d. Influence of Biochar
Addition on Nitrogen Transformation during Copyrolysis of Algae and
Lignocellulosic Biomass. Environmental Science & Technology 52 (16), 9514–9521.
Chen, W., Yang, H., Chen, Y., Xia, M., Chen, X., Chen, H., 2017b. Transformation of
Nitrogen and Evolution of N-Containing Species during Algae Pyrolysis.
Environmental Science & Technology 51 (11), 6570–6579.
Chiaramonti, D., Prussi, M., Buffi, M., Rizzo, A.M., Pari, L., 2017. Review and
experimental study on pyrolysis and hydrothermal liquefaction of microalgae for
biofuel production. Applied Energy 185, 963–972.
Dai, G., Wang, S., Huang, S., Zou, Q., 2018a. Enhancement of aromatics production from
catalytic pyrolysis of biomass over HZSM-5 modified by chemical liquid deposition.
Journal of Analytical and Applied Pyrolysis 134, 439–445.
Dai, L., Zhou, N., Li, H., Deng, W., Cheng, Y., Wang, Y., Liu, Y., Cobb, K., Lei, H., Chen, P.,
Ruan, R., 2020. Recent advances in improving lignocellulosic biomass-based bio-oil
production. Journal of Analytical and Applied Pyrolysis 104845.
Dai, M., Xu, H., Yu, Z., Fang, S., Chen, L., Gu, W., Ma, X., 2018b. Microwave-assisted fast
co-pyrolysis behaviors and products between microalgae and polyvinyl chloride.
Applied Thermal Engineering 136, 9–15.
Dai, M., Yu, Z., Fang, S., Ma, X., 2019. Behaviors, product characteristics and kinetics of
catalytic co-pyrolysis spirulina and oil shale. Energy Conversion and Management
192, 1–10.
Dasan, Y.K., Lam, M.K., Yusup, S., Lim, J.W., Lee, K.T., 2019. Life cycle evaluation of
microalgae biofuels production: Effect of cultivation system on energy, carbon
emission and cost balance analysis. Science of The Total Environment 688, 112–128.
del Río, P.G., Gomes-Dias, J.S., Rocha, C.M.R., Romaní, A., Garrote, G., Domingues, L.,
2020. Recent trends on seaweed fractionation for liquid biofuels production.
Bioresource Technology 299.
12
Bioresource Technology 344 (2022) 126096
Dhyani, V., Bhaskar, T., 2018. A comprehensive review on the pyrolysis of lignocellulosic
biomass. Renewable Energy 129, 695–716.
Duan, P., Jin, B., Xu, Y., Wang, F., 2015. Co-pyrolysis of microalgae and waste rubber tire
in supercritical ethanol. Chemical Engineering Journal 269, 262–271.
EIA, 2020. Annual Energy Outlook 2020 with projections to 2050. U.S. DOE Energy
Information Administration, Washington, DC.
Enamala, M.K., Enamala, S., Chavali, M., Donepudi, J., Yadavalli, R., Kolapalli, B.,
Aradhyula, T.V., Velpuri, J., Kuppam, C., 2018. Production of biofuels from
microalgae - A review on cultivation, harvesting, lipid extraction, and numerous
applications of microalgae. Renewable and Sustainable Energy Reviews 94, 49–68.
Fakayode, O.A., Aboagarib, E.A.A., Zhou, C., Ma, H., 2020. Co-pyrolysis of
lignocellulosic and macroalgae biomasses for the production of biochar – A review.
Bioresource Technology 297, 122408.
Fan, L., Ruan, R., Li, J., Ma, L., Wang, C., Zhou, W., 2020. Aromatics production from fast
co-pyrolysis of lignin and waste cooking oil catalyzed by HZSM-5 zeolite. Applied
Energy 263, 114629.
Fang, S., Gu, W., Dai, M., Xu, J., Yu, Z., Lin, Y., Chen, J., Ma, X., 2018. A study on
microwave-assisted fast co-pyrolysis of chlorella and tire in the N2 and CO2
atmospheres. Bioresource Technology 250, 821–827.
Fermoso, J., Corbet, T., Ferrara, F., Pettinau, A., Maggio, E., Sanna, A., 2018. Synergistic
effects during the co-pyrolysis and co-gasification of high volatile bituminous coal
with microalgae. Energy Conversion and Management 164, 399–409.
Gan, Y.Y., Ong, H.C., Show, P.L., Ling, T.C., Chen, W.-H., Yu, K.L., Abdullah, R., 2018.
Torrefaction of microalgal biochar as potential coal fuel and application as bio-
adsorbent. Energy Conversion and Management 165, 152–162.
Gao, N., Kamran, K., Quan, C., Williams, P.T., 2020. Thermochemical conversion of
sewage sludge: A critical review. Progress in Energy and Combustion Science 79,
100843.
Gerardo, M.L., Oatley-Radcliffe, D.L., Lovitt, R.W., 2014. Integration of membrane
technology in microalgae biorefineries. Journal of Membrane Science 464, 86–99.
Gong, X., Zhang, B., Zhang, Y., Huang, Y., Xu, M., 2014. Investigation on Pyrolysis of
Low Lipid Microalgae Chlorella vulgaris and Dunaliella salina. Energy & Fuels 28
(1), 95–103.
He, C., Tang, C., Li, C., Yuan, J., Tran, K.-Q., Bach, Q.-V., Qiu, R., Yang, Y., 2018. Wet
torrefaction of biomass for high quality solid fuel production: A review. Renewable
and Sustainable Energy Reviews 91, 259–271.
He, Q., Guo, Q., Ding, L., Wei, J., Yu, G., 2019. Rapid co-pyrolysis of lignite and biomass
blends: Analysis of synergy and gasification reactivity of residue char. Journal of
Analytical and Applied Pyrolysis 143, 104688.
Hu, Z., Ma, X., Li, L., 2016. The synergistic effect of co-pyrolysis of oil shale and
microalgae to produce syngas. Journal of the Energy Institute 89 (3), 447–455.
Huang, Ming, Ma, Zhongqing, Zhou, Bingliang, Yang, Youyou, Chen, Dengyu, 2020.
Enhancement of the production of bio-aromatics from renewable lignin by combined
approach of torrefaction deoxygenation pretreatment and shape selective catalytic
fast pyrolysis using metal modified zeolites. Bioresource Technology 301, 122754.
https://doi.org/10.1016/j.biortech.2020.122754.
Huang, Yanqin, Chen, Yupeng, Xie, Jianjun, Liu, Huacai, Yin, Xiuli, Wu, Chuangzhi,
2016. Bio-oil production from hydrothermal liquefaction of high-protein high-ash
microalgae including wild Cyanobacteria sp. and cultivated Bacillariophyta sp. Fuel
183, 9–19.
Istrate, I.-R., Iribarren, D., Gálvez-Martos, J.-L., Dufour, J., 2020. Review of life-cycle
environmental consequences of waste-to-energy solutions on the municipal solid
waste management system. Resources, Conservation and Recycling 157, 104778.
Jonker, J.G.G., Faaij, A.P.C., 2013. Techno-economic assessment of micro-algae as
feedstock for renewable bio-energy production. Applied Energy 102, 461–475.
Kasar, P., Sharma, D.K., Ahmaruzzaman, M., 2020. Thermal and catalytic decomposition
of waste plastics and its co-processing with petroleum residue through pyrolysis
process. Journal of Cleaner Production 265, 121639.
Katiyar, R., Arora, A., 2020. Health promoting functional lipids from microalgae pool: A
review. Algal Research 46, 101800.
Klein, B.C., Bonomi, A., Maciel Filho, R., 2018. Integration of microalgae production
with industrial biofuel facilities: A critical review. Renewable and Sustainable
Energy Reviews 82, 1376–1392.
Kumar, R., Strezov, V., Weldekidan, H., He, J., Singh, S., Kan, T., Dastjerdi, B., 2020.
Lignocellulose biomass pyrolysis for bio-oil production: A review of biomass pre-
treatment methods for production of drop-in fuels. Renewable and Sustainable
Energy Reviews 123, 109763.
Kuppens, T., Cornelissen, T., Carleer, R., Yperman, J., Schreurs, S., Jans, M., Thewys, T.,
2010. Economic assessment of flash co-pyrolysis of short rotation coppice and
biopolymer waste streams. Journal of Environmental Management 91 (12),
2736–2747.
Lam, S.S., Wan Mahari, W.A., Ok, Y.S., Peng, W., Chong, C.T., Ma, N.L., Chase, H.A.,
Liew, Z., Yusup, S., Kwon, E.E., Tsang, D.C.W., 2019. Microwave vacuum pyrolysis
of waste plastic and used cooking oil for simultaneous waste reduction and
sustainable energy conversion: Recovery of cleaner liquid fuel and techno-economic
analysis. Renewable and Sustainable Energy Reviews 115, 109359.
Lee, Jechan, Kwon, Eilhann E., Park, Young-Kwon, 2020a. Recent advances in the
catalytic pyrolysis of microalgae. Catalysis Today. 355, 263–271.
Lee, D.-J., Chang, J.-S., Lai, J.-Y., 2015. Microalgae–microbial fuel cell: A mini review.
Bioresource Technology 198, 891–895.
Lee, D.-J., Lu, J.-S., Chang, J.-S., 2020b. Pyrolysis synergy of municipal solid waste
(MSW): A review. Bioresource Technology 123912.
Levasseur, W., Perré, P., Pozzobon, V., 2020. A review of high value-added molecules
production by microalgae in light of the classification. Biotechnology Advances
107545.
G. Su et al.
Li, K., Zhang, L., Zhu, L., Zhu, X., 2017. Comparative study on pyrolysis of lignocellulosic
and algal biomass using pyrolysis-gas chromatography/mass spectrometry.
Bioresource Technology 234, 48–52.
Liu, G., Wright, M.M., Zhao, Q., Brown, R.C., Wang, K., Xue, Y., 2016. Catalytic pyrolysis
of amino acids: Comparison of aliphatic amino acid and cyclic amino acid. Energy
Conversion and Management 112, 220–225.
Liu, R., Sarker, M., Rahman, M.M., Li, C., Chai, M., Nishu, Cotillon, R., Scott, N.R. 2020a.
Multi-scale complexities of solid acid catalysts in the catalytic fast pyrolysis of
biomass for bio-oil production – A review. Progress in Energy and Combustion
Science, 80, 100852.
Liu, Y., Zhai, Y., Li, S., Liu, X., Liu, X., Wang, B., Qiu, Z., Li, C., 2020b. Production of bio-
oil with low oxygen and nitrogen contents by combined hydrothermal pretreatment
and pyrolysis of sewage sludge. Energy 203, 117829.
Lu, J.-S., Chang, Y., Poon, C.-S., Lee, D.-J., 2020. Slow pyrolysis of municipal solid waste
(MSW): A review. Bioresource Technology 123615.
Lv, X., Liu, H., Huang, Y., Yao, J., Yuan, H., Yin, X., Wu, C., 2021. Synergistic effects on
co-pyrolysis of low-temperature hydrothermally pretreated high-protein microalgae
and polypropylene. Energy Conversion and Management 229, 113772.
Mei, Deqing, Guo, Dongmei, Wang, Cheng, Dai, Pengfei, Du, Jiayi, Wang, Junfeng, 2020.
Evaluation of esterified pyrolysis bio-oil as a diesel alternative. Journal of the Energy
Institute 93 (4), 1382–1389.
Menegazzo, M.L., Fonseca, G.G., 2019. Biomass recovery and lipid extraction processes
for microalgae biofuels production: A review. Renewable and Sustainable Energy
Reviews 107, 87–107.
Meng, Haiyu, Wang, Shuzhong, Chen, Lin, Wu, Zhiqiang, Zhao, Jun, 2016. Study on
product distributions and char morphology during rapid co-pyrolysis of platanus
wood and lignite in a drop tube fixed-bed reactor. Bioresource Technology 209,
273–281.
Meyer, Pimphan A., Snowden-Swan, Lesley J., Jones, Susanne B., Rappé, Kenneth G.,
Hartley, Damon S., 2020. The effect of feedstock composition on fast pyrolysis and
upgrading to transportation fuels: Techno-economic analysis and greenhouse gas life
cycle analysis. Fuel 259, 116218. https://doi.org/10.1016/j.fuel.2019.116218.
Mihalcik, D.J., Mullen, C.A., Boateng, A.A., 2011. Screening acidic zeolites for catalytic
fast pyrolysis of biomass and its components. Journal of Analytical and Applied
Pyrolysis 92 (1), 224–232.
Moens, L., Evans, R.J., Looker, M.J., Nimlos, M.R., 2004. A comparison of the Maillard
reactivity of proline to other amino acids using pyrolysis-molecular beam mass
spectrometry. Fuel 83 (11), 1433–1443.
Mohajerani, A., Burnett, L., Smith, J.V., Markovski, S., Rodwell, G., Rahman, M.T.,
Kurmus, H., Mirzababaei, M., Arulrajah, A., Horpibulsuk, S., Maghool, F., 2020.
Recycling waste rubber tyres in construction materials and associated environmental
considerations: A review. Resources, Conservation and Recycling 155, 104679.
Nagappan, S., Devendran, S., Tsai, P.-C., Dinakaran, S., Dahms, H.-U., Ponnusamy, V.K.,
2019. Passive cell disruption lipid extraction methods of microalgae for biofuel
production – A review. Fuel 252, 699–709.
Nyoni, B., Duma, S., Bolo, L., Shabangu, S., Hlangothi, S.P., 2020. Co-pyrolysis of South
African bituminous coal and Scenedesmus microalgae: Kinetics and synergistic
effects study. International Journal of Coal Science & Technology 7 (4), 807–815.
Ong, H.C., Chen, W.-H., Farooq, A., Gan, Y.Y., Lee, K.T., Ashokkumar, V., 2019. Catalytic
thermochemical conversion of biomass for biofuel production: A comprehensive
review. Renewable and Sustainable Energy Reviews 113, 109266.
Ong, H.C., Chen, W.-H., Singh, Y., Gan, Y.Y., Chen, C.-Y., Show, P.L., 2020. A state-of-
the-art review on thermochemical conversion of biomass for biofuel production: A
TG-FTIR approach. Energy Conversion and Management 209, 112634.
Ozyuguran, A., Akturk, A., Yaman, S., 2018. Optimal use of condensed parameters of
ultimate analysis to predict the calorific value of biomass. Fuel 214, 640–646.
Peng, X., Ma, X., Lin, Y., Guo, Z., Hu, S., Ning, X., Cao, Y., Zhang, Y., 2015. Co-pyrolysis
between microalgae and textile dyeing sludge by TG–FTIR: Kinetics and products.
Energy Conversion and Management 100, 391–402.
Qi, P., Chang, G., Wang, H., Zhang, X., Guo, Q., 2018. Production of aromatic
hydrocarbons by catalytic co-pyrolysis of microalgae and polypropylene using
HZSM-5. Journal of Analytical and Applied Pyrolysis 136, 178–185.
Resasco, D.E., Crossley, S.P., 2015. Implementation of concepts derived from model
compound studies in the separation and conversion of bio-oil to fuel. Catalysis Today
257, 185–199.
Rezvani, S., Moheimani, N.R., Bahri, P.A., 2016. Techno-economic assessment of CO2
bio-fixation using microalgae in connection with three different state-of-the-art
power plants. Computers & Chemical Engineering 84, 290–301.
Sait, H.H., Salema, A.A., 2015. Microwave dielectric characterization of Saudi Arabian
date palm biomass during pyrolysis and at industrial frequencies. Fuel 161, 239–247.
Sajjadi, B., Chen, W.-Y., Raman, A.A.A., Ibrahim, S., 2018. Microalgae lipid and biomass
for biofuel production: A comprehensive review on lipid enhancement strategies and
their effects on fatty acid composition. Renewable and Sustainable Energy Reviews
97, 200–232.
Sankaran, R., Parra Cruz, R.A., Pakalapati, H., Show, P.L., Ling, T.C., Chen, W.-H.,
Tao, Y., 2020. Recent advances in the pretreatment of microalgal and lignocellulosic
biomass: A comprehensive review. Bioresource Technology 298, 122476.
Sattar, Hamed, Muzaffar, Imran, Munir, Shahid, 2020. Thermal and kinetic study of rice
husk, corn cobs, peanut crust and Khushab coal under inert (N2) and oxidative (dry
air) atmospheres. Renewable Energy 149, 794–805.
Sharara, M.A., Holeman, N., Sadaka, S.S., Costello, T.A., 2014. Pyrolysis kinetics of algal
consortia grown using swine manure wastewater. Bioresource Technology 169,
658–666.
Soltanian, S., Aghbashlo, M., Almasi, F., Hosseinzadeh-Bandbafha, H., Nizami, A.-S.,
Ok, Y.S., Lam, S.S., Tabatabaei, M., 2020. A critical review of the effects of
13
Bioresource Technology 344 (2022) 126096
pretreatment methods on the exergetic aspects of lignocellulosic biofuels. Energy
Conversion and Management 212, 112792.
Stamenković, O.S., Siliveru, K., Veljković, V.B., Banković-Ilić, I.B., Tasić, M.B.,
Ciampitti, I.A., Đalović, I.G., Mitrović, P.M., Sikora, V.Š., Prasad, P.V.V., 2020.
Production of biofuels from sorghum. Renewable and Sustainable Energy Reviews
124, 109769.
State, R.N., Volceanov, A., Muley, P., Boldor, D., 2019. A review of catalysts used in
microwave assisted pyrolysis and gasification. Bioresource Technology 277,
179–194.
Su, G., Ong, H.C., Ibrahim, S., Fattah, I.M.R., Mofijur, M., Chong, C.T., 2021. Valorisation
of medical waste through pyrolysis for a cleaner environment: Progress and
challenges. Environmental Pollution 116934.
Su, Y., Song, K., Zhang, P., Su, Y., Cheng, J., Chen, X., 2017. Progress of microalgae
biofuel’s commercialization. Renewable and Sustainable Energy Reviews 74,
402–411.
Sun, C., Li, C., Tan, H., Zhang, Y., 2019a. Synergistic effects of wood fiber and polylactic
acid during co-pyrolysis using TG-FTIR-MS and Py-GC/MS. Energy Conversion and
Management 202, 112212.
Sun, J., Xiong, X., Wang, M., Du, H., Li, J., Zhou, D., 2019b. Microalgae biodiesel
production in China: A preliminary economic analysis. Renewable and Sustainable
Energy Reviews 104.
Tang, F., Yu, Z., Li, Y., Chen, L., Ma, X., 2020a. Catalytic co-pyrolysis behaviors, product
characteristics and kinetics of rural solid waste and chlorella vulgaris. Bioresource
Technology 299, 122636.
Tang, Z., Chen, W., Chen, Y., Yang, H., Chen, H., 2019. Co-pyrolysis of microalgae and
plastic: Characteristics and interaction effects. Bioresource Technology 274,
145–152.
Tang, Z., Chen, W., Hu, J., Li, S., Chen, Y., Yang, H., Chen, H., 2020b. Co-pyrolysis of
microalgae with low-density polyethylene (LDPE) for deoxygenation and
denitrification. Bioresource Technology 311, 123502.
Tripathi, M., Sahu, J.N., Ganesan, P., 2016. Effect of process parameters on production of
biochar from biomass waste through pyrolysis: A review. Renewable and Sustainable
Energy Reviews 55, 467–481.
Uçar, S., Karagöz, S., Yanik, J., Saglam, M., Yuksel, M., 2005. Copyrolysis of scrap tires
with waste lubricant oil. Fuel Processing Technology 87 (1), 53–58.
Uzar, U., 2020. Political economy of renewable energy: Does institutional quality make a
difference in renewable energy consumption? Renewable Energy 155, 591–603.
van Schalkwyk, D.L., Mandegari, M., Farzad, S., Görgens, J.F., 2020. Techno-economic
and environmental analysis of bio-oil production from forest residues via non-
catalytic and catalytic pyrolysis processes. Energy Conversion and Management 213,
112815.
Vanthoor-Koopmans, M., Wijffels, R.H., Barbosa, M.J., Eppink, M.H.M., 2013.
Biorefinery of microalgae for food and fuel. Bioresource Technology 135, 142–149.
Varsha, S.S.V., Vuppaladadiyam, A.K., Shehzad, F., Ghaedi, H., Murugavelh, S.,
Dong, W., Antunes, E., 2021. Co-pyrolysis of microalgae and municipal solid waste:
A thermogravimetric study to discern synergy during co-pyrolysis process. Journal of
the Energy Institute 94, 29–38.
Wang, S., Shang, H., Abomohra, A.E.-F., Wang, Q., 2019a. One-step conversion of
microalgae to alcohols and esters through co-pyrolysis with biodiesel-derived
glycerol. Energy Conversion and Management 198, 111792.
Wang, X., Ma, D., Jin, Q., Deng, S., Stančin, H., Tan, H., Mikulčić, H., 2019b. Synergistic
effects of biomass and polyurethane co-pyrolysis on the yield, reactivity, and heating
value of biochar at high temperatures. Fuel Processing Technology 194, 106127.
Wang, X., Zhao, B., Yang, X., 2016. Co-pyrolysis of microalgae and sewage sludge:
Biocrude assessment and char yield prediction. Energy Conversion and Management
117, 326–334.
Wu, Tu, J., Cai, Y., Wu, Z., Li, Z. 2020. Biofuel production from pyrolysis of waste
cooking oil fried sludge in a fixed bed. Journal of Material Cycles and Waste
Management, 22(4), 1163-1175.
Wu, X., Wu, Y., Wu, K., Chen, Y., Hu, H., Yang, M., 2015. Study on pyrolytic kinetics and
behavior: The co-pyrolysis of microalgae and polypropylene. Bioresource
Technology 192, 522–528.
Wu, Zhiqiang, Yang, Wangcai, Li, Yaowu, Yang, Bolun, 2018a. Co-pyrolysis behavior of
microalgae biomass and low-quality coal: Products distributions, char-surface
morphology, and synergistic effects. Bioresource Technology 255, 238–245.
Wu, Zhiqiang, Yang, Wangcai, Yang, Bolun, 2018b. Thermal characteristics and surface
morphology of char during co-pyrolysis of low-rank coal blended with microalgal
biomass: Effects of Nannochloropsis and Chlorella. Bioresource Technology 249,
501–509.
Xiang, Zhongping, Liang, Jianghui, Morgan, Hervan Marion, Liu, Yuanyuan,
Mao, Hanping, Bu, Quan, 2018. Thermal behavior and kinetic study for co-pyrolysis
of lignocellulosic biomass with polyethylene over Cobalt modified ZSM-5 catalyst by
thermogravimetric analysis. Bioresource Technology 247, 804–811.
Xie, Q., Addy, M., Liu, S., Zhang, B., Cheng, Y., Wan, Y., Li, Y., Liu, Y., Lin, X., Chen, P.,
Ruan, R., 2015. Fast microwave-assisted catalytic co-pyrolysis of microalgae and
scum for bio-oil production. Fuel 160, 577–582.
Xin, C., Addy, M.M., Zhao, J., Cheng, Y., Cheng, S., Mu, D., Liu, Y., Ding, R., Chen, P.,
Ruan, R., 2016. Comprehensive techno-economic analysis of wastewater-based algal
biofuel production: A case study. Bioresource Technology 211, 584–593.
Yang, C., Li, R., Zhang, B., Qiu, Q., Wang, B., Yang, H., Ding, Y., Wang, C., 2019.
Pyrolysis of microalgae: A critical review. Fuel Processing Technology 186, 53–72.
Yang, W.Y., Zeng, Y., Luo, J., Tong, D., Qing, R.W., Fan, Y., hu, C. 2011. Production of
bio-oil by direct and catalytic pyrolysis of Nannochloropsis sp. Ranliao Huaxue
Xuebao/Journal of Fuel Chemistry and Technology, 39, 664-669.
G. Su et al.
Yao, Z., Ma, X., Wu, Z., Yao, T., 2017. TGA–FTIR analysis of co-pyrolysis characteristics
of hydrochar and paper sludge. Journal of Analytical and Applied Pyrolysis 123,
40–48.
Yu, D., Hui, H., Li, S., 2019. Two-step catalytic co-pyrolysis of walnut shell and LDPE for
aromatic-rich oil. Energy Conversion and Management 198, 111816.
Yu, S., Cao, X., Wu, S., Chen, Q., Li, L., Li, H., 2020. Effective pyrolysis of waste cooking
oils into hydrocarbon rich biofuel on novel mesoporous catalyst with acid and alkali
coexisting. Industrial Crops and Products 150, 112362.
Yuan, T., Tahmasebi, A., Yu, J., 2015. Comparative study on pyrolysis of lignocellulosic
and algal biomass using a thermogravimetric and a fixed-bed reactor. Bioresource
Technology 175, 333–341.
14
Bioresource Technology 344 (2022) 126096
Zhang, Bo, Zhong, Zhaoping, Ding, Kuan, Song, Zuwei, 2015. Production of aromatic
hydrocarbons from catalytic co-pyrolysis of biomass and high density polyethylene:
Analytical Py–GC/MS study. Fuel 139, 622–628.
Zhang, J., Wang, K., Nolte, M.W., Choi, Y.S., Brown, R.C., Shanks, B.H., 2016. Catalytic
Deoxygenation of Bio-Oil Model Compounds over Acid-Base Bifunctional Catalysts.
ACS Catalysis 6 (4), 2608–2621.
Zhang, X., Lei, H., Zhu, L., Qian, M., Yadavalli, G., Wu, J., Chen, S., 2017. From plastics
to jet fuel range alkanes via combined catalytic conversions. Fuel 188, 28–38.
Zhao, Y., Cao, H., Yao, C., Li, R., Wu, Y., 2020. Synergistic effects on cellulose and lignite
co-pyrolysis and co-liquefaction. Bioresource Technology 299, 122627.
Zhu, X., Zhang, Y., Ding, H., Huang, L., Zhu, X., 2018. Comprehensive study on pyrolysis
and co-pyrolysis of walnut shell and bio-oil distillation residue. Energy Conversion
and Management 168, 178–187.