Bioresource Technology 342 (2021) 126067

Contents lists available at ScienceDirect

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

Fast hydropyrolysis of biomass Conversion: A comparative review

Shinyoung Oh a, 1, Jechan Lee b, 1, Su Shiung Lam c, 1, Eilhann E. Kwon d, 1, Jeong-Myeong Ha a, 1,
Daniel C.W. Tsang e, Yong Sik Ok f, Wei-Hsin Chen g, h, i, Young-Kwon Park j, *
a
Clean Energy Research Center, Korea Institute of Science and Technology, Seoul 02792, Republic of Korea
b
Department of Environmental and Safety Engineering & Department of Energy Systems Research, Ajou University, Suwon 16499, Republic of Korea
c
Pyrolysis Technology Research Group, Higher Institution Centre of Excellence (HICoE), Institute of Tropical Aquaculture and Fisheries (AKUATROP), Universiti
Malaysia Terengganu, 21030 Kuala Nerus, Terengganu, Malaysia
d
Department of Environment and Energy, Sejong University, Seoul 05006, Republic of Korea
e
Department of Civil and Environmental Engineering, The Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong, PR China
f
Korea Biochar Research Centre, APRU Sustainable Waste Management Program & Division of Environmental Science and Ecological Engineering, Korea University,
Seoul 02841, Republic of Korea
g
Department of Aeronautics and Astronautics, National Cheng Kung University, Tainan 701, Taiwan
h
Research Center for Smart Sustainable Circular Economy, Tunghai University, Taichung 407, Taiwan
i
Department of Mechanical Engineering, National Chin-Yi University of Technology, Taichung 411, Taiwan
j
School of Environmental Engineering, University of Seoul, Seoul 02504, 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

• Studies on hydropyrolysis and catalytic

hydropyrolysis were critically reviewed.
• The pyrolysis/hydropyrolysis and non-
catalytic/catalytic processes were
compared.
• Integrated hydrotreating processes were
developed to enhance hydrocarbon
yield.
• Combined hydropyrolysis process could
economically produce amounts of
hydrocarbons.

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

Keywords: Recent studies show that fast hydropyrolysis (i.e., pyrolysis under hydrogen atmosphere operating at a rapid
Hydropyrolysis heating rate) is a promising technology for the conversion of biomass into liquid fuels (e.g., bio-oil and C4+
Pyrolysis hydrocarbons). This pyrolysis approach is reported to be more effective than conventional fast pyrolysis in
Biofuels
producing aromatic hydrocarbons and also lowering the oxygen content of the bio-oil obtained compared to
Hydrocarbons
Biorefinery
hydrodeoxygenation (a common bio-oil upgrading method). Based on current literature, various non-catalytic
and catalytic fast hydropyrolysis processes are reviewed and discussed. Efforts to combine fast hydropyrolysis
and hydrotreatment process are also highlighted. Points to be considered for future research into fast hydro­
pyrolysis and pending challenges are also discussed.

* Corresponding author.
E-mail address: catalica@uos.ac.kr (Y.-K. Park).
1
These authors are co-first authors because they contributed equally to this work.

https://doi.org/10.1016/j.biortech.2021.126067
Received 26 August 2021; Received in revised form 27 September 2021; Accepted 29 September 2021
Available online 1 October 2021
0960-8524/© 2021 Elsevier Ltd. All rights reserved.
S. Oh et al.
1. Introduction
Liquid fuels comprise hydrocarbon mixtures with the advantages of
high-energy density and ease of use. The production of high-value liquid
fuels from non-fossil resources to reduce fossil fuel consumption has
become an imperative need. Biomass is a sustainable, renewable, and
near carbon–neutral source that has the potential to substitute for pe­
troleum via hydrocarbon fuel production (Ahmad et al., 2021). The
production of hydrocarbon-based liquid fuels or chemicals from biomass
(including waste biomass) has been studied widely, as the utilization of
renewable hydrocarbons obtained from biomass conversion could
circulate the carbon and this reduces global warming (Jung et al., 2020).
Among various biomass conversion processes, thermochemical conver­
sion shows potential for commercialization (Shahabuddin et al., 2020).
Pyrolysis is a thermochemical conversion process that can be per­
formed with various reactor types, inert gas types, residence times, and
heating rates (Jung et al., 2018). This process is applicable to the
treatment of various types of biomass (Moogi et al., 2020), organic waste
(Kwon et al., 2018), municipal solid waste (Lee et al., 2020a), plastics
(Hassan et al., 2019), and industrial waste (Chen et al., 2020a). Among
different pyrolysis processes, fast pyrolysis is widely employed to pro­
duce liquid fuels from biomass (e.g., bio-oil). Fast pyrolysis typically
operates at moderate temperatures (400–600 ◦ C), rapid heating rate
(>100 ◦ C min− 1), and short residence time of pyrolytic vapors (0.5–2 s)
(Lee et al., 2019). High contents of oxygen in bio-oil leads to thermal
instability and corrosiveness of bio-oil and lowers the heating value
compared to petroleum-derived oil (Lee et al., 2020b). To tackle the
problems of bio-oil, it needs to be upgraded properly to improve its
quality. One bio-oil upgrading route involves passing the vapor from the
pyrolysis process through a catalyst bed prior to condensing the vapor to
form bio-oil (Mo et al., 2020). Typically, zeolites are used in this type of
upgrading process (referred as catalytic fast pyrolysis) (Kumar et al.,
2019). Hydrotreatment upgrading is becoming a major refinery process
for reducing the oxygen content and producing high-quality biofuels
(Mahesh et al., 2021).
Hydrotreatment is conducted mostly under high hydrogen pressures
(100–170 bar), temperatures at 310–375 ◦ C, and low space velocities
(0.1–0.2 of LHSV, liquid hourly space velocity) in the presence of
catalyst. The use of catalysts can enhance hydrogenation of the
oxygenated compounds produced from the pyrolysis, leading to a higher
H/C ratio of bio-oil (Ahmed et al., 2020). For example, while a typical
effective H/C ratio of biomass ranges from 0 to 0.3, in situ hydrogena­
tion over a Ru/C catalyst leads to a bio-oil having the ratio of > 1 (Huang
et al., 2016). This process, however, produces a large quantity of coke,
which deactivates the catalyst active sites and clogs the reactor, result­
ing in additional cost to regenerate the catalyst (Wu et al., 2020).
Hydropyrolysis (HP) is a pyrolysis process performed under H2 at­
mosphere, developed to obtain high quality liquid hydrocarbon fuels
while increasing the efficiency of hydrogen utilization. Fast hydro­
pyrolysis (FHP) process to produce hydrocarbon products such as ole­
fins, cycloalkanes, and alkanes, has recently been investigated (Resende,
2016). Even though recent research has suggested that FHP is a prom­
ising way to produce liquid hydrocarbon fuels from renewable resources
such as biomass, only limited number of studies is available, and the HP
process is not well-understood. In this regard, this review focuses on the
effectiveness of HP process for the production of hydrocarbon chemicals
and provides a comparison of HP with conventional pyrolysis. The
application of catalytic fast hydropyrolysis (CFHP) compared to con­
ventional catalytic fast pyrolysis (CFP) is also discussed. The challenges
in hydrocarbon production via HP process are discussed, and the future
perspectives are also provided.
2. Mechanism of fast hydropyrolysis
The initial reactions taking place in FHP should be similar to that
occurred in conventional fast pyrolysis, which are mostly associated
2
Bioresource Technology 342 (2021) 126067
with thermal decomposition of biomass. The presence of hydrogen in
FHP, however, results in the addition of complex hydrotreating re­
actions that occur simultaneously or successively (Stummann et al.,
2020a). Such reactions can involve C–C coupling, hydrocracking,
alkylation, decarboxylation, decarbonylation, hydrogenation, hydro­
deoxygenation (HDO), and recombination (Stummann et al., 2021).
Fig. 1 describes reaction chemistries and mechanisms for conventional
fast pyrolysis, non-catalytic fast hydropyrolysis (NCFHP), and CFHP of
biomass samples (He et al., 2020). The effect of HDO caused by hy­
drocracking and deoxygenation is more pronounced in NCFHP and
CFHP than in conventional fast pyrolysis. The use of a bifunctional
catalyst (e.g., Rh/ZrO2) increases alkanes and decreases oxygenates,
indicating that CFHP is more effective at removing oxygen from pyrol­
ysis bio-oil and improving bio-oil quality than NCFHP.
C–C coupling reactions lead to the production of light compounds
present in both gaseous and liquid phase but cause polymerization and
coke formation on the catalyst. Hydrocracking reactions reduce the
carbon chain length of pyrolytic products to a length within the range
C4–C21, representing the range comparable to gasoline, jet-fuel, and
diesel-range hydrocarbons. However, they also facilitate the formation
of light non-condensable C1–C3 hydrocarbons, which deteriorates
overall hydrocarbon yield in bio-oil.
Acid catalyzed alkylation is favorable to occur at temperatures at
which FHP is conducted. This reaction can enhance carbon recovery in
condensable organic phase by incorporating short hydrocarbons into
aromatic compounds (Resasco et al., 2016). Alkylation reactions also
occur via alcohols or olefins generated during the FHP (Resasco et al.,
2016).
Decarboxylation and decarbonylation reactions also occur during
FHP and in turn decrease the oxygen content in the condensable com­
pounds by removing CO2 and CO. These reactions help stabilizing the
reactive oxygenated phase in bio-oil before the reactive species are
polymerized. Although the concentrations of CO2 and CO are highly
associated with hydrogen partial pressure (Stummann et al., 2019c),
water–gas shift reaction also has effect on the concentrations of CO2 and
CO, which can be catalyzed by the catalysts employed for FHP. There­
fore, it could be hard to experimentally prove the effects of decarbox­
ylation and decarbonylation reactions on FHP.
Hydrogenation and HDO reactions also occur in FHP because
hydrotreating catalysts are often employed for FHP (Stummann et al.,
2018). They are likely to be the most important reactions in FHP because
they substantially contribute to the decrease in oxygen content of the
bio-oil obtained (Kim et al., 2019a). In HDO, oxygen contained in
organic species is reacted with hydrogen to form water. Thus, there is no
carbon loss in removing the oxygen, and it allows a high yield of carbon
in bio-oil at the expense of a high hydrogen consumption compared with
decarboxylation and decarbonylation. HDO of oxygenated aromatics (e.
g., phenolic compounds) occurs via deoxygenation, retaining aroma­
ticity, and hydrogenation; these reactions saturate the aromatic ring
before the deoxygenation (Liu et al., 2021a). For HDO reactions, a high
hydrogen pressure (e.g., >50 bar) is often needed to operate the process
at a high temperature (e.g., >250 ◦ C) (Kim et al., 2019a). Major reaction
pathways involved in HDO are highly dependent upon the components
of catalyst (Kim et al., 2019a). Jin et al. recently reported a catalytic
system comprising Mo-promoted Ir/SiO2 and HZSM-5 for the production
of C5 and C6 alkanes from cellulose via hydrogenation and hydro­
genolysis (Jin et al., 2020).
When using molybdenum sulfide-based catalysts for FHP of biomass,
H2S could be produced during the FHP process. In such cases, recom­
bination between olefins and H2S takes place resulting in generation of
organosulfur compounds such as thiols. Thiols can be further converted
into thiophenes via acid catalyzed reaction with carbenium ions
(Leflaive et al., 2002). Given that the incorporation of sulfur is catalyzed
by acid sites, the use of a catalyst having a low acid density might help
reducing the S content of bio-oil produced from the FHP. Recombination
reactions increase the S content in bio-oil, while the S content can be
S. Oh et al. Bioresource Technology 342 (2021) 126067

Fig. 1. Reaction chemistries and mechanisms for conventional fast pyrolysis, non-catalytic fast hydropyrolysis, and catalytic fast hydropyrolysis of biomass samples
(abbreviations inside the figure: HCR – hydrocracking; HDO – hydrodeoxygenation; DDO - direct deoxidation; DCO – decarboxylation; DME – demethylation; MT –
transmethylation; DE – deoxygenation extent; HLE – hydrogen-loss extent). Reprinted from (He et al., 2020), Copyright (2019), with permission from Elsevier.

readily reduced through subsequent hydrotreating of the bio-oil.
Occurrences of the aforementioned reactions are highly influenced
by temperature and pressure in FHP process, thereby affecting the
product selectivities (Venkatesan et al., 2020). For example, an increase
in temperature increases the ratio of aromatic/aliphatic hydrocarbons.
At low temperatures, hydrogenation of unsaturated double bonds (e.g.,
olefins, aldehydes, and ketones) occurs to stabilize bio-oil, whereas HDO
takes place at higher temperatures to eliminate furanic and phenolic
oxygen-containing compounds (Wang et al., 2013). As seen in Fig. 2,
olefins, aldehydes, and ketones are hydrogenated to alcohols at low
temperatures. Alcohols then undergo both catalytic hydrogenation and
thermal dehydration between 150 ◦ C and 200 ◦ C to form olefins. Car­
boxylic groups, phenolic ethers, and phenols are reactive between
300 ◦ C and 350 ◦ C. As hydrogen partial pressure increases, the ratio of
aromatic/aliphatic hydrocarbons decreases. Hydrogen partial pressure
also plays a critical role in transforming oxygen-rich pyrolytic volatiles
to hydrocarbons. An increase in the proportion of H2O and light non-
condensable compounds such as CO, CO2, and CH4 proves the occur­
rence of deoxygenation via dehydration, decarboxylation, and decar­
bonylation reactions.
3. Non-catalytic fast hydropyrolysis
Among the diverse biomass to liquid conversion processes, fast py­
rolysis is one of the most preferred process. During fast pyrolysis process,
the feedstock is converted to pyrolytic vapors via rapid heating for a
short residence time, followed by the pyrolytic vapors quenched to form
liquid bio-oil (Liu et al., 2021b). The short residence time and rapid
quenching could minimize the secondary reactions and generate the
maximum amount of liquid bio-oil by limiting the gas production
(Dabros et al., 2018). Bio-oil can be used widely for heating, generating
electricity, or producing value-added chemicals (Wang et al., 2021). On
the other hand, some features of bio-oil, such as low energy density, high
oxygen content (ca. 40 wt%), high water content (ca. 20 wt%), high
acidity (acid number:100–200 mg of KOH per g of bio-oil), high vis­
cosity, instability, and immiscibility with petroleum, make the bio-oil
unsuitable for use as transportation fuel (Marker et al., 2012). Given
that the disadvantages of bio-oil are generally due to the presence of
oxygenated compounds (e.g., acids and aldehydes), bio-oil obtained
from fast pyrolysis requires further upgrading via hydrotreatment (Kong
et al., 2020). According to a previous study, the H/C ratio of the most
deoxygenated bio-oil is approximately unity, and this value is similar to
that of coal and better than that of petroleum blends. Therefore, in-situ
or ex-situ hydrotreatment can improve the bio-oil composition (Gamliel

3
S. Oh et al. Bioresource Technology 342 (2021) 126067

Fig. 2. Reactivity scale of oxygenated groups in bio-oil according to tempera­
ture. Reprinted from (Wang et al., 2013), Copyright (2013) American Chemi­
cal Society.
et al., 2018).
HP was initially studied for coal (Canel et al., 2005; Chareonpanich
et al., 2002), and then extended to produce hydrocarbons from biomass
(Galiasso et al., 2014; Onay et al., 2006). HP can be conducted using
only hydrogen gas, or with hydrogen diluted in an inert gas (Ven­
katakrishnan et al., 2014). Under a hydrogen atmosphere, the free
radicals and olefins causing bio-oil instability are not formed due to the
capping of reactive volatile intermediates by hydrogen radicals (Melli­
gan et al., 2013; Thangalazhy-Gopakumar et al., 2012). The reaction of
biomass with hydrogen during HP at elevated temperatures can produce
a hydrocarbon-rich intermediate with a low oxygen content (Dayton
et al., 2013). The hydrogen pressure required in HP (around 30–50 bar)
is typically much lower than that required in bio-oil hydrotreatment
(over 100 bar is required). HP is generally performed at 30 bar of
hydrogen pressure. The partial hydrogen pressures are also recorded,
and>50 bar of hydrogen pressure has also been studied (Ven­
katakrishnan et al., 2014), and bio-oil hydrotreatment requires high
hydrogen pressures (100–170 bar) (Marker et al., 2012; Marker et al.,
2014).
Apart from typical hydrotreatment (conducted with high pressure at
around 100–170 bar to reduce coke formation and plugging problem
and the enhancement in the CH4 yield was most substantial with a
sweeping-gas flow rate at 150 mL min− 1. The CH4 was produced mainly
through hydrogenation of tar. The presence of alkaline species promoted
the hydrogenation reaction. In Table 1, the advantages and disadvan­
tages of conventional non-catalytic fast pyrolysis and NCFHP are
compared.
FHP produces two phases of liquid products, referred to as the top
organic phase (target products consisting of a hydrocarbon mixture) and
the aqueous phase (based on the dehydrated water), as well as char and
gases (Marker et al., 2012; Resende, 2016). The organic phase obtained
from FHP has a relatively low oxygen level and is of better quality than
the bio-oil produced from conventional fast pyrolysis under an inert
atmosphere (Balagurumurthy & Bhaskar, 2014). NCFHP results in the
generation of large amounts of CH4, CO, and CO2 gases as by-products
with a tar-like char (Venkatakrishnan et al., 2014) because of insuffi­
cient hydrogenation of the oxygenated volatiles. The level of deoxy­
genation of the products, especially the targeted liquid phase, varies
with the operating conditions (e.g., reaction temperature, hydrogen
pressure, and the type of catalyst). For example, hydrogen can react with
pyrolytic volatiles under harsh conditions (above 500 ◦ C and 30 bar) to
generate low molecular weight hydrocarbons (i.e., the cracking reaction
is promoted by increasing hydrogen pressure) (Dayton et al., 2013).
Previous study reported that the HP of cellulose at high temperatures
(580 ◦ C) combined with high hydrogen pressures (50 bar) suppressed
the formation of light oxygenated compounds (e.g., glycoaldehyde and
formic acid) (Venkatakrishnan et al., 2014).
Table 2 lists the representative experimental conditions and the re­
sults of NCFHP. It can be found that the yields of pyrolytic products vary
depending upon NCFHP temperature and hydrogen partial pressure.
This indicates that the temperature and hydrogen partial pressure affect
the extent of devolatilization and stabilization of volatiles during the
NCFHP of biomass.
4. Catalytic fast hydropyrolysis
During CFP, the components of biomass (e.g., cellulose, hemicellu­
lose, and lignin) are degraded to form vapors at temperatures of
300–600 ◦ C under an inert atmosphere. CFP can be performed in either
two units (ex situ) or single unit (in situ) pyrolysis reactors (Chandler &
Resende, 2019). When CFP is carried out in a typical fluidized bed
reactor, the bed material inside the reactor can act as a heat-transfer
material and also catalyze the various reactions simultaneously (Dab­
ros et al., 2018). Typically, CFP is accomplished under atmospheric
conditions with zeolite catalysts (HZSM-5 (Li et al., 2020; Xu et al.,
Table 1
Comparison of advantages and disadvantages of different pyrolysis types.
Pyrolysis type Advantage Disadvantage

during re-vaporization of bio-oil), fast pyrolysis under hydrogen atmo­ Non-catalytic - Relatively simple reactor design - High oxygen content in
sphere (i.e., FHP) was developed to overcome the problems mentioned fast pyrolysis bio-oil
- Low selectivity toward
above and produce hydrocarbon-based liquid products. FHP, whereby
target products
the organic material is decomposed rapidly under a hydrogen atmo­ CFP - High selectivity toward target - Catalyst deactivation
sphere (approximately 500 ◦ C s− 1), has been studied as the hydro­ products (e.g., BTX)
pyrolysis process uses a long residence time and low heating rates - Lower downstream hydrotreating
cost than non-catalytic fast
(Venkatakrishnan et al., 2015). Similar with fast pyrolysis, FHP can be
pyrolysis
performed with fluidized bed reactors (Dayton et al., 2013; Marker et al., NCFHP - Biofuels with low oxygen content - Need for expensive
2012; Marker et al., 2014), cyclone reactors (Venkatakrishnan et al., and high quality pyrolysis agent such as
2014), and micropyrolysis systems such as Py-GC/MS (pyroprobe-gas - Eliminating the need for H2
chromatography/mass spectrometry) (Jan et al., 2015; Thangalazhy- reheating
- Lessening undesired reactions
Gopakumar et al., 2012), which allows short residence times (<2 s).
- Producing biofuel with low
Tian et al. has recently suggested a partial NCFHP process operating oxygen content and high quality
at temperatures between 700 ◦ C and 900 ◦ C under 0% to 30% hydrogen CFHP - Higher selectivity toward - Need for expensive
atmosphere (Tian et al., 2021). An increase in the H2 concentration in hydrocarbons than NCFHP pyrolysis agent such as
pyrolysis medium led to enhancing the yields of CH4, C2H6, and light tar, - Higher deoxygenation extent then H2
NCFHP - Catalyst deactivation

4
S. Oh et al. Bioresource Technology 342 (2021) 126067

Table 2 decreased coke formation due to the combination of Ni metal sites and
Summary of non-catalytic fast hydropyrolysis studies reported in earlier zeolite acid sites (Iliopoulou et al., 2012; Valle et al., 2010; Veses et al.,
literature. 2015). As a transition metal, Ni can promote oligomerization and
Feedstock Conditions Performance Ref. dehydration (Iliopoulou et al., 2012), as well as increasing the hydro­
Pinewood and 300–700 ◦ C; High pressure (40–70 bar) (Galiasso et al.,
thermal stability and cost-effectiveness of the catalyst (Gamliel et al.,
lignin 70 bar cracked much of the 2014) 2017a). The HZSM-5 catalyst is also known as effective in producing
lighter compounds compatible hydrocarbons, such as aromatics (e.g., benzene, toluene, and
Eucalyptus 450 ◦ C; 100 s Deeper bed (high pressure) (Onay et al., xylene), while these aromatics may form coke during reforming at low
wood waste produced a lighter, less 2006)
temperature (<200 ◦ C) or remain inside the zeolite pores. Those coke
oxygenated, and more
stable tars/oils formations should be prohibited since the coke could block the active
Sugarcane 600 ◦ C; 70 Almost 30 wt% liquid (Venkatakrishnan sites of the catalyst and cause its deactivation (Carlson et al., 2011). CFP
bagasse bar product is obtained et al., 2014) of sawdust at the temperature ranging from 500 to 670 ◦ C with a weight
Sunflower 400–700 ◦ C High hydrogen pressure (Melligan et al., hourly space velocity (WHSV) of 0.1–1.7 h− 1 resulted in decreased
pressed (>50 bar) increased the oil 2013)
bagasse yields (~10 wt%)
toluene and xylene production, whereas naphthalene production
Mixed wood, 350–480 ◦ C; 20.6–46.3 wt% liquid (Mohan et al., increased with increasing WHSV. A maximum aromatic hydrocarbon
bagasse, 14–35 bar yield with over 90% 2006) yield of 14% was obtained at 600 ◦ C and 0.1 h− 1 (Carlson et al., 2011).
corn stover, carbon recovery The formation of a stable liquid product under inert conditions (i.e.,
microalgae,
pyrolysis without using hydrogen as carrier gas) is an advantage of CFP,
seaweed
Euphorbia 400–650 ◦ C; Liquid product yield of (Marker et al., but coke formation is a major disadvantage of CFP. For example, only
rigida, 50 bar 30–40 wt%; maximum 2014) 10–30 wt% of carbon could be recovered as a liquid product, with
sunflower yield achieved at 520 ◦ C approximately 30 wt% of the carbon loss as coke deposited on the
oil, catalyst active sites (Agblevor et al., 2010; Resende, 2016). The oxygen
industrial
content remained at a significant level between 10 wt% and 20 wt%
waste, pure
cellulose after the CFP process (Stummann et al., 2020b; Venderbosch, 2015).
Pine wood 550 ◦ C; 5.5 Biomass to catalyst ratio (Jan et al., 2015) Therefore, to overcome this limitation, introduction of hydrogen gas
chips bar from 1:4 to 1:9 reduced the into the pyrolysis process was suggested (Gamliel et al., 2018).
oxygenated compounds
FHP in the presence of a HDO catalyst for deoxygenation and hy­
and increased the aromatic
compounds drogenation under a partial hydrogen atmosphere is termed CFHP (Chen
Loblolly pine 375–450 ◦ C; Increased hydrogen partial (Anuar Sharuddin et al., 2020b; Linck et al., 2014). The main effect of using hydrogen in
3.4–20 bar pressure promoted liquid et al., 2016) FHP is to reduce the coke yield and increase the generation of liquid
production hydrocarbons and gaseous olefins. The addition of a catalyst favored the
Pine sawdust, 700–900 ◦ C; CH4, C2H6, and light tar (Tian et al., 2021)
deoxygenation pathway compared to the non-catalytic system, resulting
reeds, 0–30% H2 yields increased with
Sargassum increasing H2 in relatively low oxygen content in bio-oil (4 wt%) (Stummann et al.,
horneri concentration 2019b), and the generation of aromatic hydrocarbons as the primary
Pine sawdust 400–600 ◦ C; Higher yield of (Venkatesan product in the organic liquid phase. Table 1 compares the advantages
1–20 bar condensables than typical et al., 2020)
and disadvantages of CFP and CFHP are compared.
pyrolysis; More
hydrocarbons at high H2
CFHP may unavoidably lead to coke production (even small amounts
partial pressures; more of coke was produced at the optimal condition), which deactivates the
pyrolysates and less char catalyst activity (Marker et al., 2012; Resende, 2016). For example,
were produced as CFHP with HZSM-5 at 400 ◦ C and 35 bar could produce 8.9 gallon of
temperature increased
liquid hydrocarbons (mostly consisted of BTX) per ton of biomass,
Poplar 500 ◦ C; It had a significant (He et al., 2020)
sawdust, atmospheric hydrodeoxygenation whereas 6.0 gallon of liquid hydrocarbons per ton of biomass was ob­
rice husk pressure effect, compared with tained with CFP (Chandler & Resende, 2019).
conventional fast pyrolysis For the CFHP of lignin model compounds, ReOx/MCM-41, ZrO2, and
ReOx/ZrO2 supports could effectively reduce coke formation compared
with HBeta (Sirous-Rezaei et al., 2018; Sirous-Rezaei & Park, 2020).
2021; Zhang et al., 2019)) or alumina-based catalysts (Foong et al.,
During the CFHP process, oxygen is removed by conversion to water or
2021; Mante et al., 2016; Nguyen et al., 2017). When catalytic fast py­
gases (e.g., CO and CO2), which minimizes the undesirable reactions,
rolysis was performed with the zeolite, approximately 25% carbon re­
such as acid catalyzed polymerization, aromatization, and coking re­
covery in the form of hydrocarbons, mainly as olefins and aromatics,
actions, promoting the hydrocarbon production by addition of hydrogen
was obtained (Lappas et al., 2012). In particular, biomass was pyrolyzed
to the hydrocarbon structure using the active catalyst (Balagurumurthy
to produce hydrocarbon ca. 15–25 wt% using ZSM-5 as a catalyst (Liu
et al., 2013). Furthermore, the active catalyst used in CFHP can promote
et al., 2014). To enhance the hydrocarbon yield and reduce the oxygen
the addition of hydrogen to the hydrocarbon structure, resulting in hy­
content, ZSM-5 was modified and utilized in the CFP (Che et al., 2019;
drocarbon production (Balagurumurthy et al., 2013). During those un­
Dai et al., 2019; Shang et al., 2021). The pyrolytic vapors were hydro­
desirable reactions, the intermediates may undergo polymerization and
treated immediately in the catalyst bed reactor (placed after the fast
generate carbon-based coke. On the other hand, the hydrogen, added to
pyrolysis reactor) to achieve a certain level of deoxygenation (Jiang
the CFHP process, can cap the active sites of the intermediates and
et al., 2020; Pirbazari et al., 2019; Wang et al., 2019). Therefore, the
reduce coke formation (Melligan et al., 2013; Thangalazhy-Gopakumar
selection or design of an appropriate catalyst for the CFP process is
et al., 2012). To enhance the deoxygenation reaction, elevated pressure
critical in catalytic fast pyrolysis to produce high yield of hydrocarbons.
was applied to the CFHP process. This elevated pressure resulted in
The catalyst used in CFP must have a capacity to remove the oxygen-
deoxygenation reaction, with the high energy recovery and a highly
containing functional groups and add hydrogen atoms into the feedstock
deoxygenated liquid product (Venderbosch, 2015).
(Alonso et al., 2012; Huber et al., 2006; Kloekhorst et al., 2015). The CFP
According to a model compound study, anisole was converted to
process can produce more aromatic hydrocarbon than non-catalytic
cyclohexane over Ni/ZSM-5 at low temperatures and high pressures,
process (Dabros et al., 2018; Venderbosch, 2015). Studies on CFP with
whereas high temperatures could produce naphthalenes or poly­
Ni/ZSM-5 reported an enhanced yield of aromatic compounds and
aromatic hydrocarbons via polymerization (Gamliel et al., 2018). When

5
S. Oh et al. Bioresource Technology 342 (2021) 126067

pine was subjected to catalytic fast hydropyrolysis at 650 ◦ C and 28 bar
with pyroprobe GC/MS using various metals supported on ZSM-5, it was
suggested that the metals catalyzed the hydrogenation process, whereas
ZSM-5, which has a number of acid sites, notably influenced the deox­
ygenation reaction (Santana Junior et al., 2019; Thangalazhy-
Gopakumar et al., 2012). When the CFHP experiments were conduct­
ed with laboratory scale pyroprobe GC/MS, the yield of aromatic hy­
drocarbons increased at 600 ◦ C and 31 bar with M/ZSM-5 (M = Ni, Pd,
or Ru) (Gamliel et al., 2017a; Gamliel et al., 2017b; Xue et al., 2020),
and at 650 ◦ C and 17 bar with Pd/HZSM-5 (Jan et al., 2015), compared
to the case of HZSM-5 (Dabros et al., 2018). Previous research using two-
stage upgrading of CFHP followed by a hydrotreatment over Pd/ZSM-5
concluded that single catalytic fast hydropyrolysis is thermodynamically
insufficient for alkane formation and highlighted the need for additional
ex-situ upgrading process (Gamliel et al., 2018; Gamliel et al., 2017b;
Jan et al., 2015; Perkins et al., 2019). The CFHP of silvergrass at 600 ◦ C,
followed by fixed-bed upgrading at low temperatures over Ni/ZSM-5
could effectively produce alkanes with increasing hydrogen pressure
(Melligan et al., 2012; Melligan et al., 2013). M/H-ZSM-5 (M = 5 wt%
Ni, Co, or Mo or 0.5 wt% Pt) converted lignin effectively to aromatic
hydrocarbons at hydrogen pressures of>20 bar (Thangalazhy-Gopaku­
mar et al., 2012). At 1 wt% of Pd loading, Pd/H-ZSM-5 produced 44%
more aromatic hydrocarbons than those obtained with H-ZSM-5 at
650 ◦ C and 17.2 bar, with a high catalyst to lignin ratio as 20:1 (Jan
et al., 2015; Resende, 2016). On the other hand, CFHP using HZSM-5
under mild conditions (catalyst to biomass ratio of 5:1 and pressure of
5.5 bar) produced a similar yield of aromatic hydrocarbons under a
helium atmosphere, even at higher pressures of about 27.5 bar (Resende,
2016; Thangalazhy-Gopakumar et al., 2012). The selectivity toward
toluene increased with enhancing the pressure due to the occurrence of
simultaneous cracking and hydrogenation, whereas the production of
m/p-xylenes decreased. This result suggests that the reaction between
the methyl group of m/p-xylenes and hydrogen may form CH4 gas
(Resende, 2016; Thangalazhy-Gopakumar et al., 2012).
The CFHP of loblolly pine using a pre-reduced commercial hydro­
treatment catalyst placed in a fluidized bed reactor at 375 ◦ C and 3 bar
of hydrogen pressure reached a 90.3% degree of deoxygenation, despite
a liquid product yield of only 10 wt% (Dayton et al., 2013). The hy­
drocarbon distribution of the liquid product depends significantly on the
bed materials used in the pyrolysis reactor. When MgAl2O4 or a mixture
of HZSM-5 and Al2O3 was used as the bed material, the CFHP of loblolly
pine produced char (18.7–21.1 wt% yield), CO (18.9 wt% yield), and
CO2 (20.0 wt% yield), as well as 17.8–20.4 wt% of condensed organics
over C4 as a liquid product (Dayton et al., 2013). In addition, CoMo/
MgAl2O4 and a mixture of NiMo/zeolite and Al2O3 could decrease the
char yield significantly to 11.4–13.1 wt%; the condensed organics
increased to 21.5 wt% using CoMo/MgAl2O4 and to 24.0 wt% using a
NiMo/zeolite and Al2O3 mixture (Stummann et al., 2020b). Sulfided
CoMo and NiMo could convert beech wood into upgraded biofuel
(18.7–21.5 wt%) with low oxygen level (<0.01 wt%) (Stummann et al.,
2019c). Table 3 provides an overview of various CFHP processes
available in earlier literature.

Table 3
Summary of previous studies on catalytic fast hydropyrolysis.
Feedstock Conditions Reactor Catalyst Ref.

Rice husk 450–650 ◦ C; atmospheric Fluidized bed Ni/Al2O3, Ni/LY, dolomite, CoMo/Al2O3 (Meesuk et al., 2011;
pressure Resende, 2016)
Rice husk 700 ◦ C Py-GC/MS Thermoplastic bituminous coal (Zhang et al., 2018)
Pine wood 650 ◦ C; 5.5–28 bar Py-GC/MS HZSM-5, Co/ZSM-5, Ni/ZSM-5, Pt/ZSM-5 (Thangalazhy-
Gopakumar et al., 2012)
Beech wood 450 ◦ C; 26 bar Fluidized bed Mo/MgAl2O4, CoMo/MgAl2O4, NiMo/ (Stummann et al., 2019d)
MgAl2O4
Poplar sawdust 450–550 C; 3–5 s
◦
Py-GC/MS Rh/ZrO2 (He et al., 2020)
Lignin 650 ◦ C and < 25.8 bar Py-GC/MS Pd/HZSM-5 (Jan et al., 2015)
m-cresol and Guaiacol 350 ◦ C; 1 bar Py-GC/MS NiReOx/CeO2, NiReOx/ZrO2, NiReOx/ZrCeO2 (Sirous-Rezaei et al.,
2019)
Woody residue 375–450 ◦ C; 3.4–20 bar Fluidized bed Commercial hydrotreating catalyst, (Dayton et al., 2013)
commercial FCC catalyst
Green algae (Oscillatoria) 550 ◦ C; 1 bar Tubular TiO2 and ZnO (Kawale & Kishore, 2019)
Algae 260–450 ◦ C Fluidized bed MoS2 (Lee et al., 2020c; Love
et al., 2005)
Algal consortium (Chlorella 150–300 ◦ C; 25 bar Batch K2CO3 (Choudhary et al., 2020)
and Phormidium sp.)
Seaweed (Enteromorpha 550 ◦ C; atmospheric pressure Fixed bed MCM-41, ZSM-5 (Hu et al., 2021)
clathrate)
Lignin extracted from corn 600 ◦ C; atmospheric pressure Two-stage consisting of non- HZSM-5, MoO3/ZSM-5, Ni/ZSM-5 (Xue et al., 2020)
stover, loblolly pine, red catalytic reactor and fixed-bed
oak reactor in series
Pine sawdust 400–600 ◦ C; 1–20 bar Packed bed Sulfided metal catalysts (Venkatesan et al., 2020)
Beech wood ~450 ◦ C; >90 vol% H2 in N2 Fluid bed CoMo/MgAl2O4, MgAl2O4, olivine sand, bog (Stummann et al., 2020b)
iron, a HZSM-5/Al2O3 mixture, NiMO/HZSM-
5/Al2O3 mixture
Beech wood 450 ◦ C; 94 vol% H2 in N2 Fluid bed CoMo/MgAl2O4, CoMo/HZSM-5/Al2O3 (Stummann et al., 2020a)
Kraft lignin First zone: 600 ◦ C, second zone: Tandem micro-reactor with two HY, HBeta, Fe/HBeta, FeReOx/MCM-41, Fe/ (Sirous-Rezaei & Park,
350–550 ◦ C; atmospheric zones ZrO2, ReOx/ZrO2, FeReOx/ZrO2, NiReOx/ 2020)
pressure ZrO2, PdReOx/ZrO2
Poplar sawdust, rice husk 500 ◦ C; atmospheric pressure Py-GC/MS Rh/ZrO2 (He et al., 2020)
Mixture of pine sawdust/ 360–420 ◦ C; 5–20 bar Packed bed HZSM-5 (Chen et al., 2020b)
HDPE
Arundo donax 400 ◦ C; 35 bar Fluidized bed NiMo/HZSM-5 (Chandler & Resende,
2019; Chandler et al.,
2020)
Beech wood ~450 ◦ C; >90 vol% H2 in N2 Fluid bed Sulfided NiMo/MgAl2O4 (Stummann et al., 2019c)
Kraft lignin 450–650 ◦ C; 6.9 bar Py-GC/MS ZSM-5, HY-340 (Santana Junior et al.,
2019)
Microalgae > 120 ◦ C Batch Mo2C (Azizi et al., 2018; Chang
et al., 2015)

6
S. Oh et al.
A catalytic route to produce liquid alkane from biomass (giant cane)
using a NiMo/H-ZSM-5 catalyst was suggested, involving methane for­
mation promoted by nickel, oligomerization of methane to aromatic
compounds catalyzed by molybdenum, and hydrogenation of aromatic
compounds to cycloalkanes catalyzed by nickel (Chandler et al., 2020).
The highest hydrocarbon yield was 7.9 wt% at 400 ◦ C under 35 bar H2,
which corresponds to 15 gallons of hydrocarbons per ton of biomass.
The increase in Ni loading in the catalyst suppressed coke formation at
the expense of an increase in the yield of C2–C3 alkanes.
To produce high-quality bio-oil, reduce the energy load on coal, and
utilize waste plastic, the co-pyrolysis of biomass and coal (or waste
plastics) has been performed and recommended (Klose & Stuke, 1993;
Sharma & Ghoshal, 2010). On the other hand, the co-pyrolysis of
biomass and coal could form heavy tar that can lead to operational
problems, such as pipe blocking and tar aerosol formation. The co-HP of
coal/synthetic polymer mixtures (Sharypov et al., 2007; Yasuda et al.,
2014) and biomass/synthetic polymer mixtures (Pinto et al., 2016;
Sharypov et al., 2006) is expected to improve the hydrocarbon yield.
The co-HP of rice husk and thermoplastic bituminous coal improved the
higher heating value and enhanced the BTX (benzene, toluene, and
xylene) yield, whereas the production of corrosive acids, such as
methanoic acid, acetic acid, and propanoic acid, decreased by 89%
under 50 bar of hydrogen (Zhang et al., 2018).
He et al. used a modified lab-scale micro-pyrolyzer system to
compare conventional fast pyrolysis, NCFHP, and CFHP over a Rh/ZrO2
catalyst (Rh loading of 0.5 wt%) (He et al., 2020). In terms of the
selectivity towards hydrocarbons and the extent of deoxygenation,
CFHP showed the best performance among the three processes. For
poplar sawdust, CFHP showed a 49.1% selectivity towards hydrocar­
bons, while NCFHP and conventional fast pyrolysis showed ~ 10% and
~ 1% selectivities, respectively. The extent of deoxygenation decreased
in an order of CFHP > NCFHP > conventional fast pyrolysis. When using
the feedstock with a high ash content (e.g., rice husk), NCFHP showed
the performance comparable to CFHP, most likely because the mineral
elements contained in ash bring about unexpected and uncontrollable
catalytic effects (Carpenter et al., 2014; Li et al., 2016).
Based on the results reported in various studies, the employment of a
right catalyst for FHP process is essential to achieve a high carbon re­
covery from raw biomass with a low oxygen content. However, catalyst
deactivation is a major challenge for the CFHP, which is possibly caused
by transfer of alkali metals from biomass feedstock to catalyst (Stum­
mann et al., 2019a), catalyst attrition/entrainment (Dayton et al., 2016),
and metal poisoning. In addition, crushed catalyst due to attrition is
impossible to separate from char after the HP. This might constitute a
serious challenge because some HP catalysts (e.g., sulfide catalysts) are
toxic, thereby the char unseparated from the used catalyst being toxic
waste. Therefore, the development of stable and non-toxic catalysts for
FHP should be more encouraged.
5. HFP combined with hydrotreatment process
Since C6 to C8 aromatic hydrocarbons can be used as high-octane
gasoline additives, transportation fuel itself, and intermediates of
manufacturing polymers. HDO is an effective upgrading process because
it removes oxygen and leads to an atomic H/C ratio (1.75) of bio-oil that
is close to that of gasoline (Gamliel et al., 2018; Morvay & Gvozdenac,
2008). Direct HDO of biomass with multifunctional Pt/NbOPO4 catalyst
yielded 28.1 wt% of liquid alkanes (Xia et al., 2016). Typically, the HDO
process was performed with bio-oil produced from fast pyrolysis, and
complete HDO required large amounts of hydrogen with high pressure.
CFHP primarily produces aromatic hydrocarbons, but appropriate
conditions with hydrotreatment can also produce alkanes and naph­
thalenes. FHP and CFHP can be combined with flowthrough vapor-
phase HDO for effective upgrading in a fixed bed reactor (Dabros
et al., 2018; Saraeian et al., 2019). The hydropyrolytic vapors from
biomass are upgraded to hydrocarbons by HDO in a catalytic packed
7
Bioresource Technology 342 (2021) 126067
bed. On the other hand, the operating conditions of HP and HDO may be
dissimilar; the reaction temperature is higher in HP (480–580 ◦ C) than
HDO (300–375 ◦ C), but the pressure is lower in HP (<70 bar) than HDO
(≥70 bar) (Nguyen & Clausen, 2019).
Compared to CFHP, NCFHP can produce a high yield of hydrocar­
bons without pronounced catalyst deactivation (Resende, 2016).
Therefore, H2Bioil, a process combining NCFHP, vapor-phase catalytic
hydrotreatment, and HDO, has been proposed as an alternative process
for producing hydrocarbon fuels (Agrawal & Singh, 2009; Singh et al.,
2010). In this process, biomass is hydropyrolyzed rapidly at around
480–580 ◦ C and the vapor products are then hydrodeoxygenated at
300–375 ◦ C under high hydrogen pressure (~200 bar), resulting in high
efficiency hydrocarbon production (Nguyen & Clausen, 2019; Ven­
katakrishnan et al., 2015). The reactive oxygenated compounds could be
upgraded effectively via HDO before undesirable secondary reactions
could occur, and this process could result in the strikingly reduced ox­
ygen containing compounds (Venkatakrishnan et al., 2015). This H2Bioil
process is estimated to show high carbon recovery (up to 70%) as well as
a high energy efficiency up to 75%. When the H2Bioil process was
performed with cellulose or with biomass feedstock (e.g., poplar), the
carbon recoveries for C1–C8+ hydrocarbons reached up to 73% with
cellulose and 54% with poplar while the yield of C4+ hydrocarbons
within the liquid fuel range was up to 55% and 32%, respectively
(Venkatakrishnan et al., 2015). This was notably a higher amount of
hydrocarbons (17.8–20.4 wt%) compared with that produced from
CFHP (Dayton et al., 2013). According to the economic analysis, this
H2Bioil is also economically attractive in both small and large scale
process (USD 0.62 to 0.73 per liter), since it can result in a high yield of
hydrocarbons that can be employed as transportation fuel without
further treatment after HP (Zhang et al., 2017).
Another integrated process developed by the Gas Technology Insti­
tute (GTI), IH2®, consists of bubbling fluidized bed reactor HP at
335–480 ◦ C, followed by downstream HDO (345–400 ◦ C) of the vapor
type products in a fixed bed reactor, with a 20–30 bar of hydrogen
pressure in both reactors to sustain deoxygenation reactions (Marker
et al., 2012; Marker et al., 2014). This IH2® pilot unit could continu­
ously convert 50 kg per day of feedstock, with long term performance of
catalyst (endure almost 700 h of operation) in 2012, and the process
expanded to 2,000 metric tons per day of wood. Through this process,
the oxygen content of the liquid product was typically<0.5 wt% and the
energy recovery was approximately 65% with a liquid product yield of
26–30 wt% (Dabros et al., 2018). Non-condensable hydrocarbons such a
(e.g., CH4, C2H6, and C3H8) produced from the IH2® process are not
suitable for transportation fuel. Therefore, those hydrocarbons were sent
to a steam reformer as a vapor phase to produce H2 and CO2, which
could then be sent back into the process (Dabros et al., 2018). The liquid
products obtained via the IH2® process can have higher contents of
carbon (C: 85–88 wt%) and hydrogen (H: 12–14 wt%) and lower oxygen
content (O: <2.2 wt%) than those obtained via HDO (C: 76–87 wt%; H:
9.7–13 wt%; O: 0.02–14.2 wt%) or CFP (C: 77–90 wt%; H: 9.6–12 wt%;
O: 0.5–14 wt%) (Dabros et al., 2018; Marker et al., 2012; Marker et al.,
2014; Singh et al., 2010). The higher heating value (HHV) of the liquid
product produced via the IH2® process (55 MJ kg− 1) is also higher than
that of the liquid product produced via HDO process (41–46 MJ kg− 1)
(Meesuk et al., 2011). From techno-economic assessment of the IH2®
process, it was estimated that the product prices ranged from USD 0.43
to 0.50 per liter (Tan et al., 2014), whereas the techno-economic
assessment estimated the value of bio-oil produced from conventional
fast pyrolysis-based process to be around USD 0.82 per liter (Wright
et al., 2010).
Xie et al. reported an integrated HP/hydrotreatment sequenced
batch process for the conversion of microalgae (Auxenochlorella pyr­
enoidosa) and used engine oil into sulfur-free liquid fuel (Xie et al.,
2019). For the first step of the integrated process, a blend of microalgae
and used engine oil was processed at 400 ◦ C under 60 bar H2 for 4 h in
the presence of a Pt/C catalyst, resulting in production of light and
S. Oh et al.
heavy oil. The light oil was recovered and processed in the second step of
the integrated process at the same condition to that used in the first step.
The light oil obtained in the second step was also recovered and pro­
cessed repeatedly until the fourth step. The yields of light oil achieved
from four runs were between 83 wt% and 89 wt%. The contents of O, N,
and S decreased when the integrated process was applied. The light oil
obtained after the fourth processing had fuel properties that are similar
to gasoline (zero sulfur content, 2 ppm of nitrogen, acid number of 1.89,
density of 0.8 kg m− 3, kinematic viscosity of 1.89 × 10− 3 m2 s− 1, and
HHV of 46.4 MJ kg− 1). This study showed that HP process combined
with hydrotreatment can be effective at producing gasoline-like fuels
from biomass resources.
6. Research needs and perspectives
FHP is a promising process to make renewable hydrocarbons that
have a potential to replace fossil hydrocarbons. This process shows
beneficial features to overcome the disadvantages of conventional fast
pyrolysis (production of low-quality bio-oil) as well as catalytic hydro­
treatment (requirement of high hydrogen pressure). The application of
CFHP shows potential to prolong the catalyst lifetime via suppression of
the coke formation as well as demonstrating high hydrocarbon selec­
tivity by minimizing the occurrence and extent of undesirable reactions.
Fast pyrolysis represents a thermochemical conversion process that
can produce bio-oil and hydrocarbons (e.g., aromatic hydrocarbons such
as benzene, toluene, ethylbenzene, and xylenes). Although conventional
fast pyrolysis is commercially available, the utilization of bio-oil as a
boiler fuel or in industrial applications is restricted (Butler et al., 2011;
Huber et al., 2006; Perkins et al., 2018). As a solution to tackle the issue,
it was suggested that bio-oil is hydrotreated followed by co-processing
with petroleum-derived hydrocarbons such as fuel oil (Lappas et al.,
2009; Pinho et al., 2015); however, bio-oil is immiscible with such liquid
hydrocarbon due to its high oxygen content and causes coke formation
during its hydrotreating process (Talmadge et al., 2014). To optimize the
production of high concentration of C6 to C8 aromatic hydrocarbon for
use as transportation fuel or gasoline additives, integrated processes
coupled with FHP and HDO (e.g., H2Bioil and IH2® processes) have been
commercially developed. Compared with the technoeconomic analysis
of bio-oil production, a commercial IH2® process is estimated to be
competitive.
CFHP system could effectively enhance the product quality and
produce large amounts of hydrocarbons (e.g., aromatic hydrocarbons)
which can be employed as a boiler fuel and a transportation fuel
(Khodier et al., 2009; No, 2014). The addition of a catalytic conversion
unit (e.g., CFHP and HDO) is required to obtain a high yield of bio-oil
with a low oxygen content. The formulation of the catalyst used in
CFHP is essential, and issues related to catalyst deactivation (e.g.,
catalyst poisoning, coke formation, and leaching), catalyst regeneration,
as well as reactor breakdown, need to be addressed (Dabros et al., 2018).
To maximize the hydrocarbon yield for utilization as a fuel or chemicals,
it is important to design active, selective, and stable catalysts (Kim et al.,
2019b). The complex reaction mechanism of biomass HP or catalytic
conversion causes the process and product to differ in each case.
Therefore, a detailed study, including the kinetic parameters depending
on the different kinds of target products should be performed (Bala­
gurumurthy et al., 2013). Various catalysts apart from zeolite and HDO
catalysts must be screened, and their corresponding reaction mecha­
nisms in each process need to be evaluated.
The price of gasoline and diesel produced from conventional fast
pyrolysis followed by hydrotreatment or hydrocracking was estimated
to be USD 0.54 per liter in 2007 based on the data from the Pacific
Northwest National Laboratory (Jones et al., 2009). However, it is
difficult to perform a direct comparison of renewable hydrocarbon fuels
made via FHP with fossil hydrocarbon fuels because of the varied fuel
prices and different investments for each process (Nguyen & Clausen,
2019). Moreover, the existing policies have imposed a duty on fossil
8
Bioresource Technology 342 (2021) 126067
fuels (energy use, CO2 and SO2 emissions, etc.) or encouraged in­
vestments related to the renewable energy (Abdmouleh et al., 2015). For
instance, Australia (Renewable Energy Demonstration Program; REDP),
China (Global Environmental Facility; GEF) and China Renewable En­
ergy Scale-Up Program; CRES), Indonesia (Integrated Micro hydro
Development and Application Program; IMIDAP), Sri Lanka (Renewable
Energy for Rural Economic Development Project; RERED), Nepal
(Biogas Support Program; BSP), and Europe (Austria, Ireland, Portugal,
and Spain) provide financial support for renewable energy development
(Abdmouleh et al., 2015). According to IEA/IRENA (International En­
ergy Agency/International Renewable Energy Agency) Joint Policies
and Measures database, nine countries (Angola, Bulgaria, El Salvador,
Denmark, Paraguay, Poland, Fiji, India, and France) implemented
financial support policies toward bioenergy in force from 2010 to 2017.
Therefore, although few studies have already been available (Zupko,
2019), more studies into technoeconomic analysis, life cycle assess­
ments, as well as carbon and energy analysis for integrated HP and
hydrotreatment processes should be conducted to make them more
industrially viable.
7. Conclusions
Herein, an effective bio-oil upgrading process, HP, is reviewed. It is a
process of pyrolysis operating under H2 environment. Although slow HP
has been investigated for many years, FHP has been primarily reported
only over the last few years. Aromatic hydrocarbons are primary prod­
ucts of CFHP, while alkanes and cycloalkanes are also produced when an
ex-situ hydrotreating unit is applied. CFHP results in higher yields of
hydrocarbons and slower catalyst deactivation than conventional CFP.
This shows that FHP is a promising option to upgrade renewable alter­
native biofuels to more realistic fuels.
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.
Acknowledgments
This study was supported by the National Research Foundation of
Korea (NRF) grant funded by the Korea government (MSIT) (No. NRF-
2020M1A2A2079801, NRF-2021R1A2C3011274).
References
Abdmouleh, Z., Alammari, R.A.M., Gastli, A., 2015. Review of policies encouraging
renewable energy integration & best practices. Renew. Sust. Energ. Rev. 45,
249–262.
Agblevor, F.A., Mante, O., Abdoulmoumine, N., McClung, R., 2010. Production of stable
biomass pyrolysis oils using fractional catalytic pyrolysis. Energy Fuel. 24 (7),
4087–4089.
Agrawal, R., Singh, N.R., 2009. Synergistic routes to liquid fuel for a petroleum-deprived
future. AIChE J. 55 (7), 1898–1905.
Ahmad, M.S., Liu, C.-G., Nawaz, M., Tawab, A., Shen, X., Shen, B., Mehmood, M.A.,
2021. Elucidating the pyrolysis reaction mechanism of Calotropis procera and
analysis of pyrolysis products to evaluate its potential for bioenergy and chemicals.
Bioresour. Technol. 322, 124545.
Ahmed, M.H.M., Batalha, N., Mahmudul, H.M.D., Perkins, G., Konarova, M., 2020.
A review on advanced catalytic co-pyrolysis of biomass and hydrogen-rich feedstock:
Insights into synergistic effect, catalyst development and reaction mechanism.
Bioresour. Technol. 310, 123457.
Alonso, D.M., Wettstein, S.G., Dumesic, J.A., 2012. Bimetallic catalysts for upgrading of
biomass to fuels and chemicals. Chem. Soc. Rev. 41 (24), 8075–8098.
Anuar Sharuddin, S.D., Abnisa, F., Wan Daud, W.M.A., Aroua, M.K., 2016. A review on
pyrolysis of plastic wastes. Energy Convers. Manag. 115, 308–326.
Azizi, K., Keshavarz Moraveji, M., Abedini Najafabadi, H., 2018. A review on bio-fuel
production from microalgal biomass by using pyrolysis method. Renew. Sust. Energ.
Rev. 82, 3046–3059.
Balagurumurthy, B., Bhaskar, T., 2014. Hydropyrolysis of lignocellulosic biomass: state
of the art review. Biomass Conv. Bioref. 4 (1), 67–75.
S. Oh et al.
Balagurumurthy, B., Oza, T.S., Bhaskar, T., Adhikari, D.K., 2013. Renewable
hydrocarbons through biomass hydropyrolysis process: challenges and
opportunities. J. Mater. Cycles Waste Manag. 15 (1), 9–15.
Butler, E., Devlin, G., Meier, D., McDonnell, K., 2011. A review of recent laboratory
research and commercial developments in fast pyrolysis and upgrading. Renew. Sust.
Energ. Rev. 15 (8), 4171–4186.
Canel, M., Mısırlıogˇlu, Z., Sınagˇ, A., 2005. Hydropyrolysis of a Turkish lignite
(Tunçbilek) and effect of temperature and pressure on product distribution. Energy
Convers. Manag. 46 (13), 2185–2197.
Carlson, T.R., Cheng, Y.-T., Jae, J., Huber, G.W., 2011. Production of green aromatics
and olefins by catalytic fast pyrolysis of wood sawdust. Energy Environ. Sci. 4 (1),
145–161.
Carpenter, D., Westover, T.L., Czernik, S., Jablonski, W., 2014. Biomass feedstocks for
renewable fuel production: a review of the impacts of feedstock and pretreatment on
the yield and product distribution of fast pyrolysis bio-oils and vapors. Green Chem.
16 (2), 384–406.
Chandler, D.S., Resende, F.L.P., 2019. Comparison between catalytic fast pyrolysis and
catalytic fast hydropyrolysis for the production of liquid fuels in a fluidized bed
reactor. Energy Fuel. 33 (4), 3199–3209.
Chandler, D.S., Seufitelli, G.V.S., Resende, F.L.P., 2020. Catalytic route for the
production of alkanes from hydropyrolysis of biomass. Energy Fuel. 34 (10),
12573–12585.
Chang, Z., Duan, P., Xu, Y., 2015. Catalytic hydropyrolysis of microalgae: influence of
operating variables on the formation and composition of bio-oil. Bioresour. Technol.
184, 349–354.
Chareonpanich, M., Boonfueng, T., Limtrakul, J., 2002. Production of aromatic
hydrocarbons from Mae-Moh lignite. Fuel Process. Technol. 79 (2), 171–179.
Che, Q., Yang, M., Wang, X., Yang, Q., Rose Williams, L., Yang, H., Zou, J., Zeng, K.,
Zhu, Y., Chen, Y., Chen, H., 2019. Influence of physicochemical properties of metal
modified ZSM-5 catalyst on benzene, toluene and xylene production from biomass
catalytic pyrolysis. Bioresour. Technol. 278, 248–254.
Chen, L., Ma, X., Tang, F., Li, Y., Yu, Z., Chen, X., 2020a. Comparison of catalytic effect
on upgrading bio-oil derived from co-pyrolysis of water hyacinth and scrap tire over
multilamellar MFI nanosheets and HZSM-5. Bioresour. Technol. 312, 123592.
Chen, W., Lu, J., Zhang, C., Xie, Y., Wang, Y., Wang, J., Zhang, R., 2020b. Aromatic
hydrocarbons production and synergistic effect of plastics and biomass via one-pot
catalytic co-hydropyrolysis on HZSM-5. J. Anal. Appl. Pyrolysis 147, 104800.
Choudhary, P., Malik, A., Pant, K.K., 2020. Exploration of a novel biorefinery based on
sequential hydropyrolysis and anaerobic digestion of algal biofilm: a comprehensive
characterization of products for energy and chemical production. Sustain. Energy
Fuels 4 (3), 1481–1495.
Dabros, T.M.H., Stummann, M.Z., Høj, M., Jensen, P.A., Grunwaldt, J.-D., Gabrielsen, J.,
Mortensen, P.M., Jensen, A.D., 2018. Transportation fuels from biomass fast
pyrolysis, catalytic hydrodeoxygenation, and catalytic fast hydropyrolysis. Prog.
Energy Combust. Sci. 68, 268–309.
Dai, L., Wang, Y., Liu, Y., Ruan, R., Duan, D., Zhao, Y., Yu, Z., Jiang, L., 2019. Catalytic
fast pyrolysis of torrefied corn cob to aromatic hydrocarbons over Ni-modified
hierarchical ZSM-5 catalyst. Bioresour. Technol. 272, 407–414.
Dayton, D.C., Carpenter, J., Farmer, J., Turk, B., Gupta, R., 2013. Biomass hydropyrolysis
in a pressurized fluidized bed reactor. Energy Fuel. 27 (7), 3778–3785.
Dayton, D.C., Hlebak, J., Carpenter, J.R., Wang, K., Mante, O.D., Peters, J.E., 2016.
Biomass hydropyrolysis in a fluidized bed reactor. Energy Fuel. 30 (6), 4879–4887.
Foong, S.Y., Chan, Y.H., Cheah, W.Y., Kamaludin, N.H., Tengku Ibrahim, T.N.B.,
Sonne, C., Peng, W., Show, P.-L., Lam, S.S., 2021. Progress in waste valorization
using advanced pyrolysis techniques for hydrogen and gaseous fuel production.
Bioresour. Technol. 320, 124299.
Galiasso, R., González, Y., Lucena, M., 2014. New inverted cyclone reactor for flash
hydropyrolysis. Catal. Today 220–222, 186–197.
Gamliel, D.P., Bollas, G.M., Valla, J.A., 2017a. Bifunctional Ni-ZSM-5 catalysts for the
pyrolysis and hydropyrolysis of biomass. Energy Technol. 5 (1), 172–182.
Gamliel, D.P., Bollas, G.M., Valla, J.A., 2018. Two-stage catalytic fast hydropyrolysis of
biomass for the production of drop-in biofuel. Fuel 216, 160–170.
Gamliel, D.P., Wilcox, L., Valla, J.A., 2017b. The effects of catalyst properties on the
conversion of biomass via catalytic fast hydropyrolysis. Energy Fuel. 31 (1),
679–687.
Hassan, H., Lim, J.K., Hameed, B.H., 2019. Catalytic co-pyrolysis of sugarcane bagasse
and waste high-density polyethylene over faujasite-type zeolite. Bioresour. Technol.
284, 406–414.
He, Y., Zhao, Y., Chai, M., Zhou, Z., Sarker, M., Li, C., Liu, R., Cai, J., Liu, X., 2020.
Comparative study of fast pyrolysis, hydropyrolysis and catalytic hydropyrolysis of
poplar sawdust and rice husk in a modified Py-GC/MS microreactor system: insights
into product distribution, quantum description and reaction mechanism. Renew.
Sust. Energ. Rev. 119, 109604. https://doi.org/10.1016/j.rser.2019.109604.
Hu, Y., Li, J., Wang, S., Xu, L., Barati, B., Cao, B., Wang, H., Xie, K., Wang, Q., 2021.
Catalytic fast hydropyrolysis of seaweed biomass with different zeolite catalysts to
produce high-grade bio-oil. Process Saf. Environ. Prot. 146, 69–76.
Huang, Y., Qiu, S., Oduro, I.N., Guo, X., Fang, Y., 2016. Production of high-yield bio-oil
with a high effective hydrogen/carbon molar ratio through acidolysis and in situ
hydrogenation. Energy Fuel. 30 (11), 9524–9531.
Huber, G.W., Iborra, S., Corma, A., 2006. Synthesis of transportation fuels from biomass:
chemistry, catalysts, and engineering. Chem. Rev. 106 (9), 4044–4098.
Iliopoulou, E.F., Stefanidis, S.D., Kalogiannis, K.G., Delimitis, A., Lappas, A.A.,
Triantafyllidis, K.S., 2012. Catalytic upgrading of biomass pyrolysis vapors using
transition metal-modified ZSM-5 zeolite. Appl. Catal. B: Environ. 127, 281–290.
Jan, O., Marchand, R., Anjos, L.C.A., Seufitelli, G.V.S., Nikolla, E., Resende, F.L.P., 2015.
Hydropyrolysis of lignin using Pd/HZSM-5. Energy Fuel. 29 (3), 1793–1800.
9
Bioresource Technology 342 (2021) 126067
Jiang, L., Wang, Y., Dai, L., Yu, Z., Wu, Q., Zhao, Y., Liu, Y., Ruan, R., Ke, L., Peng, Y.,
Xia, D., Jiang, L., 2020. Integrating pyrolysis and ex-situ catalytic reforming by
microwave heating to produce hydrocarbon-rich bio-oil from soybean soapstock.
Bioresour. Technol. 302, 122843.
Jin, L., Li, W., Liu, Q., Ma, L., Hu, C., Ogunbiyi, A.T., Wu, M., Zhang, Q.i., 2020. High
performance of Mo-promoted Ir/SiO2 catalysts combined with HZSM-5 toward the
conversion of cellulose to C5/C6 alkanes. Bioresour. Technol. 297, 122492. https://
doi.org/10.1016/j.biortech.2019.122492.
Jones, S.B., Valkenburt, C., Walton, C.W., Elliott, D.C., Holladay, J.E., Stevens, D.J.,
Kinchin, C., Czernik, S. 2009. Production of gasoline and diesel from biomass via fast
pyrolysis, hydrotreating and hydrocracking: a design case. Pacific Northwest
National Laboratory (PNNL).
Jung, J.-M., Oh, J.-I., Baek, K., Lee, J., Kwon, E.E., 2018. Biodiesel production from waste
cooking oil using biochar derived from chicken manure as a porous media and
catalyst. Energy Convers. Manag. 165, 628–633.
Jung, S., Lee, J., Park, Y.-K., Kwon, E.E., 2020. Bioelectrochemical systems for a circular
bioeconomy. Bioresour. Technol. 300, 122748.
Kawale, H.D., Kishore, N., 2019. Production of hydrocarbons from a green algae
(Oscillatoria) with exploration of its fuel characteristics over different reaction
atmospheres. Energy 178, 344–355.
Khodier, A., Kilgallon, P., Legrave, N., Simms, N., Oakey, J., Bridgwater, T., 2009. Pilot-
scale combustion of fast-pyrolysis bio-oil: ash deposition and gaseous emissions.
Environ. Prog. Sustainable Energy 28 (3), 397–403.
Kim, S., Kwon, E.E., Kim, Y.T., Jung, S., Kim, H.J., Huber, G.W., Lee, J., 2019a. Recent
advances in hydrodeoxygenation of biomass-derived oxygenates over heterogeneous
catalysts. Green Chem. 21 (14), 3715–3743.
Kim, S., Tsang, Y.F., Kwon, E.E., Lin, K.-Y.-A., Lee, J., 2019b. Recently developed
methods to enhance stability of heterogeneous catalysts for conversion of biomass-
derived feedstocks. Korean J. Chem. Eng. 36 (1), 1–11.
Kloekhorst, A., Shen, Y., Yie, Y., Fang, M., Heeres, H.J., 2015. Catalytic
hydrodeoxygenation and hydrocracking of Alcell® lignin in alcohol/formic acid
mixtures using a Ru/C catalyst. Biomass Bioenergy 80, 147–161.
Klose, W., Stuke, V., 1993. Comparison of the pyrolysis of different types of biomass and
coals. Fuel Process. Technol. 36 (1), 283–289.
Kong, L., Zhang, L., Gu, J., Gou, L., Xie, L., Wang, Y., Dai, L., 2020. Catalytic
hydrotreatment of kraft lignin into aromatic alcohols over nickel-rhenium supported
on niobium oxide catalyst. Bioresour. Technol. 299, 122582.
Kumar, R., Strezov, V., Lovell, E., Kan, T., Weldekidan, H., He, J., Dastjerdi, B., Scott, J.,
2019. Bio-oil upgrading with catalytic pyrolysis of biomass using Copper/zeolite-
Nickel/zeolite and Copper-Nickel/zeolite catalysts. Bioresour. Technol. 279,
404–409.
Kwon, E.E., Lee, T., Ok, Y.S., Tsang, D.C.W., Park, C., Lee, J., 2018. Effects of calcium
carbonate on pyrolysis of sewage sludge. Energy 153, 726–731.
Lappas, A.A., Bezergianni, S., Vasalos, I.A., 2009. Production of biofuels via co-
processing in conventional refining processes. Catal. Today 145 (1), 55–62.
Lappas, A.A., Kalogiannis, K.G., Iliopoulou, E.F., Triantafyllidis, K.S., Stefanidis, S.D.,
2012. Catalytic pyrolysis of biomass for transportation fuels. WIREs Energy Environ.
1 (3), 285–297.
Lee, D.-J., Lu, J.-S., Chang, J.-S., 2020a. Pyrolysis synergy of municipal solid waste
(MSW): a review. Bioresour. Technol. 318, 123912.
Lee, J., Kwon, E.E., Park, Y.-K., 2020b. Recent advances in the catalytic pyrolysis of
microalgae. Catal. Today 355, 263–271.
Lee, J., Sarmah, A.K., Kwon, E.E., 2019. Production and formation of biochar. In: Ok, Y.
S., Tsang, D.C.W., Bolan, N. (Eds.), Biochar from Biomass and Waste. Elsevier, J.M.
Novak, pp. 3–18.
Lee, X.J., Ong, H.C., Gan, Y.Y., Chen, W.-H., Mahlia, T.M.I., 2020c. State of art review on
conventional and advanced pyrolysis of macroalgae and microalgae for biochar, bio-
oil and bio-syngas production. Energy Convers. Manag. 210, 112707.
Leflaive, P., Lemberton, J.L., Pérot, G., Mirgain, C., Carriat, J.Y., Colin, J.M., 2002. On
the origin of sulfur impurities in fluid catalytic cracking gasoline—reactivity of
thiophene derivatives and of their possible precursors under FCC conditions. Appl.
Catal. A: Gen. 227 (1-2), 201–215.
Li, C., Aston, J.E., Lacey, J.A., Thompson, V.S., Thompson, D.N., 2016. Impact of
feedstock quality and variation on biochemical and thermochemical conversion.
Renew. Sustain. Energ. Rev. 65, 525–536.
Li, K., Zhang, G., Wang, Z.-X., Hu, B., Lu, Q., 2020. Calcium formate assisted catalytic
pyrolysis of pine for enhanced production of monocyclic aromatic hydrocarbons
over bimetal-modified HZSM-5. Bioresour. Technol. 315, 123805.
Linck, M., Felix, L., Marker, T., Roberts, M., 2014. Integrated biomass hydropyrolysis and
hydrotreating: a brief review. WIREs Energy Environ. 3 (6), 575–581.
Liu, C., Wang, H., Karim, A.M., Sun, J., Wang, Y., 2014. Catalytic fast pyrolysis of
lignocellulosic biomass. Chem. Soc. Rev. 43 (22), 7594–7623.
Liu, Q., Bai, Y., Chen, H., Chen, M., Sang, Y., Wu, K., Ma, Z., Ma, Y., Li, Y., 2021a.
Catalytic conversion of enzymatic hydrolysis lignin into cycloalkanes over a gamma-
alumina supported nickel molybdenum alloy catalyst. Bioresour. Technol. 323,
124634.
Liu, Y., Wu, S., Zhang, H., Xiao, R., 2021b. Fast pyrolysis of torrefied holocellulose for
producing long-chain ether precursors in a fluidized bed. Bioresour. Technol. 341,
125770.
Love, G.D., Bowden, S.A., Jahnke, L.L., Snape, C.E., Campbell, C.N., Day, J.G.,
Summons, R.E., 2005. A catalytic hydropyrolysis method for the rapid screening of
microbial cultures for lipid biomarkers. Org. Geochem. 36 (1), 63–82.
Mahesh, D., Ahmad, S., Kumar, R., Chakravarthy, S.R., Vinu, R., 2021. Hydrothermal
liquefaction of municipal solid wastes for high quality bio-crude production using
glycerol as co-solvent. Bioresour. Technol. 339, 125537.
S. Oh et al.
Mante, O.D., Dayton, D.C., Gabrielsen, J., Ammitzboll, N.L., Barbee, D., Verdier, S.,
Wang, K., 2016. Integration of catalytic fast pyrolysis and hydroprocessing: a
pathway to refinery intermediates and “drop-in” fuels from biomass. Green Chem. 18
(22), 6123–6135.
Marker, T.L., Felix, L.G., Linck, M.B., Roberts, M.J., 2012. Integrated hydropyrolysis and
hydroconversion (IH2) for the direct production of gasoline and diesel fuels or
blending components from biomass, part 1: proof of principle testing. Environ. Prog.
Sustain. Energy 31 (2), 191–199.
Marker, T.L., Felix, L.G., Linck, M.B., Roberts, M.J., Ortiz-Toral, P., Wangerow, J., 2014.
Integrated hydropyrolysis and hydroconversion (IH2®) for the direct production of
gasoline and diesel fuels or blending components from biomass, part 2: continuous
testing. Environ. Prog. Sustain. Energy 33 (3), 762–768.
Meesuk, S., Cao, J.-P., Sato, K., Ogawa, Y., Takarada, T., 2011. Fast pyrolysis of rice husk
in a fluidized bed: effects of the gas atmosphere and catalyst on bio-oil with a
relatively low content of oxygen. Energy Fuel. 25 (9), 4113–4121.
Melligan, F., Hayes, M.H.B., Kwapinski, W., Leahy, J.J., 2012. Hydro-pyrolysis of
biomass and online catalytic vapor upgrading with Ni-ZSM-5 and Ni-MCM-41.
Energy Fuel. 26 (10), 6080–6090.
Melligan, F., Hayes, M.H.B., Kwapinski, W., Leahy, J.J., 2013. A study of hydrogen
pressure during hydropyrolysis of Miscanthus x giganteus and online catalytic vapour
upgrading with Ni on ZSM-5. J. Anal. Appl. Pyrolysis 103, 369–377.
Mo, L., Dai, H., Feng, L.i., Liu, B., Li, X., Chen, Y., Khan, S., 2020. In-situ catalytic
pyrolysis upgradation of microalgae into hydrocarbon rich bio-oil: effects of nitrogen
and carbon dioxide environment. Bioresour. Technol. 314, 123758. https://doi.org/
10.1016/j.biortech.2020.123758.
Mohan, D., Pittman, C.U., Steele, P.H., 2006. Pyrolysis of wood/biomass for bio-oil: a
critical review. Energy Fuel. 20 (3), 848–889.
Moogi, S., Jae, J., Kannapu, H.P.R., Ahmed, A., Park, E.D., Park, Y.-K., 2020.
Enhancement of aromatics from catalytic pyrolysis of yellow poplar: role of
hydrogen and methane decomposition. Bioresour. Technol. 315, 123835.
Morvay, Z., Gvozdenac, D., 2008. Applied Industrial Energy and Environmental
Management. John Wiley & Sons.
Nguyen, T.-V., Clausen, L.R., 2019. Techno-economic analysis of polygeneration systems
based on catalytic hydropyrolysis for the production of bio-oil and fuels. Energy
Convers. Manag. 184, 539–558.
Nguyen, T.S., Duong, T.L., Pham, T.T.T., Nguyen, D.T., Le, P.N., Nguyen, H.L., Huynh, T.
M., 2017. Online catalytic deoxygenation of vapour from fast pyrolysis of
Vietnamese sugarcane bagasse over sodium-based catalysts. J. Anal. Appl. Pyrolysis
127, 436–443.
No, S.-Y., 2014. Application of bio-oils from lignocellulosic biomass to transportation,
heat and power generation—a review. Renew. Sust. Energ. Rev. 40, 1108–1125.
Onay, O., Gaines, A.F., Kockar, O.M., Adams, M., Tyagi, T.R., Snape, C.E., 2006.
Comparison of the generation of oil by the extraction and the hydropyrolysis of
biomass. Fuel 85 (3), 382–392.
Perkins, G., Batalha, N., Kumar, A., Bhaskar, T., Konarova, M., 2019. Recent advances in
liquefaction technologies for production of liquid hydrocarbon fuels from biomass
and carbonaceous wastes. Renew. Sust. Energ. Rev. 115, 109400.
Perkins, G., Bhaskar, T., Konarova, M., 2018. Process development status of fast pyrolysis
technologies for the manufacture of renewable transport fuels from biomass. Renew.
Sust. Energ. Rev. 90, 292–315.
Pinho, A.d.R., de Almeida, M.B.B., Mendes, F.L., Ximenes, V.L., Casavechia, L.C. 2015.
Co-processing raw bio-oil and gasoil in an FCC Unit. Fuel Process. Technol., 131,
159-166.
Pinto, F., Miranda, M., Costa, P., 2016. Production of liquid hydrocarbons from rice crop
wastes mixtures by co-pyrolysis and co-hydropyrolysis. Fuel 174, 153–163.
Pirbazari, S.M., Norouzi, Omid, Kohansal, Komeil, Tavasoli, Ahmad, 2019. Experimental
studies on high-quality bio-oil production via pyrolysis of Azolla by the use of a three
metallic/modified pyrochar catalyst. Bioresour. Technol. 291, 121802. https://doi.
org/10.1016/j.biortech.2019.121802.
Resasco, D.E., Wang, B., Crossley, S., 2016. Zeolite-catalysed C-C bond forming reactions
for biomass conversion to fuels and chemicals. Catal. Sci. Technol. 6 (8), 2543–2559.
Resende, F.L.P., 2016. Recent advances on fast hydropyrolysis of biomass. Catal. Today
269, 148–155.
Santana Junior, J.A., Menezes, A.L., Ataíde, C.H., 2019. Catalytic upgrading of fast
hydropyrolysis vapors from industrial Kraft lignins using ZSM-5 zeolite and HY-340
niobic acid. J. Anal. Appl. Pyrolysis 144, 104720.
Saraeian, A., Nolte, M.W., Shanks, B.H., 2019. Deoxygenation of biomass pyrolysis
vapors: Improving clarity on the fate of carbon. Renew. Sust. Energ. Rev. 104,
262–280.
Shahabuddin, M., Krishna, Bhavya B., Bhaskar, Thallada, Perkins, Greg, 2020. Advances
in the thermo-chemical production of hydrogen from biomass and residual wastes:
Summary of recent techno-economic analyses. Bioresour. Technol. 299, 122557.
https://doi.org/10.1016/j.biortech.2019.122557.
Shang, J., Fu, G., Cai, Z., Feng, X., Tuo, Y., Zhou, X., Yan, H., Peng, C., Jin, X., Liu, Y.,
Chen, X., Yang, C., Chen, D., 2021. Regulating light olefins or aromatics production
in ex-situ catalytic pyrolysis of biomass by engineering the structure of tin modified
ZSM-5 catalyst. Bioresour. Technol. 330, 124975.
Sharma, S., Ghoshal, A.K., 2010. Study of kinetics of co-pyrolysis of coal and waste LDPE
blends under argon atmosphere. Fuel 89 (12), 3943–3951.
Sharypov, V.I., Beregovtsova, N.G., Kuznetsov, B.N., Baryshnikov, S.V., Cebolla, V.L.,
Weber, J.V., Collura, S., Finqueneisel, G., Zimny, T., 2006. Co-pyrolysis of wood
biomass and synthetic polymers mixtures: Part IV: Catalytic pyrolysis of pine wood
and polyolefinic polymers mixtures in hydrogen atmosphere. J. Anal. Appl. Pyrolysis
76 (1), 265–270.
Sharypov, V.I., Beregovtsova, N.G., Kuznetsov, B.N., Cebolla, V.L., Collura, S.,
Finqueneisel, G., Zimny, T., Weber, J.V., 2007. Influence of reaction parameters on
10
Bioresource Technology 342 (2021) 126067
brown coal–polyolefinic plastic co-pyrolysis behavior. J. Anal. Appl. Pyrolysis 78
(2), 257–264.
Singh, N.R., Delgass, W.N., Ribeiro, F.H., Agrawal, R., 2010. Estimation of liquid fuel
yields from biomass. Environ. Sci. Technol. 44 (13), 5298–5305.
Sirous-Rezaei, P., Jae, J., Cho, K., Ko, C.H., Jung, S.-C., Park, Y.-K., 2019. Insight into the
effect of metal and support for mild hydrodeoxygenation of lignin-derived phenolics
to BTX aromatics. Chem. Eng. J. 377, 120121.
Sirous-Rezaei, Pouya, Jae, Jungho, Ha, Jeong-Myeong, Ko, Chang Hyun, Kim, Ji Man,
Jeon, Jong-Ki, Park, Young-Kwon, 2018. Mild hydrodeoxygenation of phenolic
lignin model compounds over a FeReOx/ZrO2 catalyst: zirconia and rhenium oxide
as efficient dehydration promoters. Green Chem. 20 (7), 1472–1483.
Sirous-Rezaei, P., Park, Y.-K., 2020. Catalytic hydropyrolysis of lignin: suppression of
coke formation in mild hydrodeoxygenation of lignin-derived phenolics. Chem. Eng.
J. 386, 121348.
Stummann, M.Z., Elevera, E., Hansen, A.B., Hansen, L.P., Beato, P., Davidsen, B.,
Wiwel, P., Gabrielsen, J., Jensen, P.A., Jensen, A.D., Høj, M., 2020a. Catalytic
hydropyrolysis of biomass using supported CoMo catalysts – effect of metal loading
and support acidity. Fuel 264, 116807.
Stummann, M.Z., Høj, M., Davidsen, B., Hansen, A.B., Hansen, L.P., Wiwel, P.,
Schandel, C.B., Gabrielsen, J., Jensen, P.A., Jensen, A.D., 2020b. Effect of the
catalyst in fluid bed catalytic hydropyrolysis. Catal. Today 355, 96–109.
Stummann, M.Z., Høj, M., Davidsen, B., Hansen, L.P., Beato, P., Gabrielsen, J., Jensen, P.
A., Jensen, A.D., 2019a. Deactivation of a CoMo catalyst during catalytic
hydropyrolysis of biomass. part 2: characterization of the spent catalysts and char.
Energy. Fuel. 33 (12), 12387–12402.
Stummann, M.Z., Høj, M., Gabrielsen, J., Clausen, L.R., Jensen, P.A., Jensen, A.D., 2021.
A perspective on catalytic hydropyrolysis of biomass. Renew. Sust. Energ. Rev. 143,
110960.
Stummann, M.Z., Høj, M., Hansen, A.B., Beato, P., Wiwel, P., Gabrielsen, J., Jensen, P.A.,
Jensen, A.D., 2019b. Deactivation of a CoMo catalyst during catalytic hydropyrolysis
of biomass. part 1. product distribution and composition. Energy. Fuel. 33 (12),
12374–12386.
Stummann, M.Z., Høj, M., Hansen, A.B., Davidsen, B., Wiwel, P., Gabrielsen, J.,
Jensen, P.A., Jensen, A.D., 2019c. New insights into the effect of pressure on
catalytic hydropyrolysis of biomass. Fuel Process. Technol. 193, 392–403.
Stummann, M.Z., Høj, M., Schandel, C.B., Hansen, A.B., Wiwel, P., Gabrielsen, J.,
Jensen, P.A., Jensen, A.D., 2018. Hydrogen assisted catalytic biomass pyrolysis.
effect of temperature and pressure. Biomass Bioenergy 115, 97–107.
Stummann, M.Z., Hansen, A.B., Hansen, L.P., Davidsen, B., Rasmussen, S.B., Wiwel, P.,
Gabrielsen, J., Jensen, P.A., Jensen, A.D., Høj, M., 2019d. Catalytic hydropyrolysis of
biomass using molybdenum sulfide based catalyst. effect of promoters. Energy. Fuel.
33 (2), 1302–1313.
Talmadge, M.S., Baldwin, R.M., Biddy, M.J., McCormick, R.L., Beckham, G.T.,
Ferguson, G.A., Czernik, S., Magrini-Bair, K.A., Foust, T.D., Metelski, P.D.,
Hetrick, C., Nimlos, M.R., 2014. A perspective on oxygenated species in the refinery
integration of pyrolysis oil. Green Chem. 16 (2), 407–453.
Tan, E.C.D., Marker, T.L., Roberts, M.J., 2014. Direct production of gasoline and diesel
fuels from biomass via integrated hydropyrolysis and hydroconversion process—a
techno-economic analysis. Environ. Prog. Sustain. Energy 33 (2), 609–617.
Thangalazhy-Gopakumar, S., Adhikari, S., Gupta, R.B., 2012. Catalytic pyrolysis of
biomass over H+ZSM-5 under hydrogen pressure. Energy Fuel. 26 (8), 5300–5306.
Tian, Y., Li, J., Wei, W., Zong, P., Zhang, D., Zhu, Y., Qiao, Y., 2021. Parametric effect of
biomass partial hydropyrolysis process in a downer reactor to co-produce high-
quality tar and syngas. Bioresour. Technol. 320, 124401.
Valle, B., Gayubo, A.G., Aguayo, A.T., Olazar, M., Bilbao, J., 2010. Selective production
of aromatics by crude bio-oil valorization with a nickel-modified HZSM-5 zeolite
catalyst. Energy Fuel. 24 (3), 2060–2070.
Venderbosch, R.H., 2015. A critical view on catalytic pyrolysis of biomass.
ChemSusChem 8 (8), 1306–1316.
Venkatakrishnan, V.K., Degenstein, J.C., Smeltz, A.D., Delgass, W.N., Agrawal, R.,
Ribeiro, F.H., 2014. High-pressure fast-pyrolysis, fast-hydropyrolysis and catalytic
hydrodeoxygenation of cellulose: production of liquid fuel from biomass. Green
Chem. 16 (2), 792–802.
Venkatakrishnan, V.K., Delgass, W.N., Ribeiro, F.H., Agrawal, R., 2015. Oxygen removal
from intact biomass to produce liquid fuel range hydrocarbons via fast-
hydropyrolysis and vapor-phase catalytic hydrodeoxygenation. Green Chem. 17 (1),
178–183.
Venkatesan, K., Prashanth, F., Kaushik, V., Choudhari, H., Mehta, D., Vinu, R., 2020.
Evaluation of pressure and temperature effects on hydropyrolysis of pine sawdust:
pyrolysate composition and kinetics studies. React. Chem. Eng. 5 (8), 1484–1500.
Veses, A., Puértolas, B., Callén, M.S., García, T., 2015. Catalytic upgrading of biomass
derived pyrolysis vapors over metal-loaded ZSM-5 zeolites: effect of different metal
cations on the bio-oil final properties. Microporous Mesoporous Mater. 209,
189–196.
Wang, C., Lei, H., Zou, R., Qian, M., Mateo, W., Lin, X., Ruan, R., 2021. Biochar-driven
simplification of the compositions of cellulose-pyrolysis-derived biocrude oil coupled
with the promotion of hydrogen generation. Bioresour. Technol. 334, 125251.
Wang, H., Male, J., Wang, Y., 2013. Recent advances in hydrotreating of pyrolysis bio-oil
and its oxygen-containing model compounds. ACS Catal. 3 (5), 1047–1070.
Wang, Jing-Xian, Cao, Jing-Pei, Zhao, Xiao-Yan, Liu, Sheng-Nan, Ren, Xue-Yu,
Zhao, Ming, Cui, Xin, Chen, Qiang, Wei, Xian-Yong, 2019. Enhancement of light
aromatics from catalytic fast pyrolysis of cellulose over bifunctional hierarchical
HZSM-5 modified by hydrogen fluoride and nickel/hydrogen fluoride. Bioresour.
Technol. 278, 116–123.
Wright, M.M., Daugaard, D.E., Satrio, J.A., Brown, R.C., 2010. Techno-economic analysis
of biomass fast pyrolysis to transportation fuels. Fuel 89, S2–S10.
S. Oh et al.
Wu, Qiuhao, Wang, Yunpu, Jiang, Lin, Yang, Qi, Ke, Linyao, Peng, Yujie, Yang, Sha,
Dai, Leilei, Liu, Yuhuan, Ruan, Roger, 2020. Microwave-assisted catalytic upgrading
of co-pyrolysis vapor using HZSM-5 and MCM-41 for bio-oil production: co-feeding
of soapstock and straw in a downdraft reactor. Bioresour. Technol. 299, 122611.
https://doi.org/10.1016/j.biortech.2019.122611.
Xia, Q., Chen, Z., Shao, Y., Gong, X., Wang, H., Liu, X., Parker, S.F., Han, X., Yang, S.,
Wang, Y., 2016. Direct hydrodeoxygenation of raw woody biomass into liquid
alkanes. Nat. Commun. 7 (1), 11162.
Xie, L.-F., Wang, F., Zhai, L.-L., Xu, Y.-P., Duan, P.-G., 2019. A sequenced batch process
for integrated hydropyrolysis and hydrotreatment of a microalgae and used engine
oil blend. Fuel Process. Technol. 190, 47–54.
Xu, Lujiang, He, Zijian, Zhang, Huan, Wu, Shenghong, Dong, Chengyu, Fang, Zhen, 2021.
Production of aromatic amines via catalytic co-pyrolysis of lignin and phenol-
formaldehyde resins with ammonia over commercial HZSM-5 zeolites. Bioresour.
Technol. 320, 124252. https://doi.org/10.1016/j.biortech.2020.124252.
Xue, Y., Sharma, A., Huo, J., Qu, W., Bai, X., 2020. Low-pressure two-stage catalytic
hydropyrolysis of lignin and lignin-derived phenolic monomers using zeolite-based
bifunctional catalysts. J. Anal. Appl. Pyrolysis 146, 104779.
11
Bioresource Technology 342 (2021) 126067
Yasuda, H., Yamada, O., Kaiho, M., Nakagome, H., 2014. Effect of polyethylene addition
to coal on hydrogasification enhancement. J. Mater. Cycles Waste Manag. 16 (1),
151–155.
Zhang, Jie, Zheng, Nan, Wang, Jie, 2018. Comparative investigation of rice husk,
thermoplastic bituminous coal and their blends in production of value-added
gaseous and liquid products during hydropyrolysis/co-hydropyrolysis. Bioresour.
Technol. 268, 445–453.
Zhang, L., Gong, K., Lai, J., Alvey, P., 2017. Chemical composition and stability of
renewable hydrocarbon products generated from a hydropyrolysis vapor upgrading
process. Green Chem. 19 (15), 3628–3641.
Zhang, X., Yuan, Z., Yao, Q., Zhang, Y., Fu, Y., 2019. Catalytic fast pyrolysis of corn cob
in ammonia with Ga/HZSM-5 catalyst for selective production of acetonitrile.
Bioresour. Technol. 290, 121800.
Zupko, R., 2019. Life cycle assessment of the production of gasoline and diesel from
forest residues using integrated hydropyrolysis and hydroconversion. Int. J. Life
Cycle Assess. 24 (10), 1793–1804.