Journal of Analytical and Applied Pyrolysis 147 (2020) 104780

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Journal of Analytical and Applied Pyrolysis

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Impact of feedstock composition on pyrolysis of low-cost, protein- and T

lignin-rich biomass: A review
Feng Cheng, Hengameh Bayat, Umakanta Jena, Catherine E. Brewer*
Department of Chemical and Materials Engineering, New Mexico State University, P.O. Box 30001 MSC 3805, Las Cruces, NM 88003, USA

ARTICLE INFO ABSTRACT

Keywords: Bio-energy is a major component of the global renewable energy market due to the low requirement for energy
Pyrolysis infrastructure modification and the high bio-energy productivity. Bio-ethanol production from sugar-rich bio-
Protein-rich mass, biodiesel production from lipid-rich biomass, and biogas production from volatile-matter-dense feedstock
Lignin-rich have been commercialized. A substantial fraction of biomass waste, however, is still discarded due to high
Biomass waste
processing costs and low end-product values. This fraction includes agricultural wastes, dedicated plants, spent
Bio-oil
grains, de-oiled seed cakes, forestry wastes, food wastes, municipal wastes, and digestated residues. Such wastes
generally contain fewer digestible compounds (e.g. fatty acids and sugars), and more proteins and recalcitrant
lignin, which require more severe reaction conditions to extract valuable compounds. Pyrolysis is a potential
inexpensive extraction option for these compounds with the needed reaction severity, easy operation, and high
compatibility with diverse feedstocks. Here, pyrolysis reactions of protein- and lignin-rich biomass wastes are
compared in terms of feedstock composition, degradation mechanism, and yield and quality of bio-oils. Overall,
agricultural wastes, dedicated plants, seed cakes, digestates, and municipal wastes are recommended for pyr-
olysis in terms of higher yields and higher quality of bio-oils. Denitrogenation upgrading strategies can further
improve the potential of the produced bio-oils.

1. Introduction
Developing renewable energy as an alternative to fossil-based en-
ergy is inevitable to enable energy security, environmental protection,
and economic improvement. In 2017, < 15 % of the global primary
energy consumption was from clean energy sources (Table 1) [1]. The
renewable energy industry, however, has been experiencing high an-
nual growth (16.2 %) relative to other energy sources. According to the
International Energy Agency (IEA), the global renewable electricity
capacity is projected to expand 43 % by 2022 based on current levels
[2]. Based on previous levels, the International Renewable Energy
Agency (IRENA) and the IEA expect energy-related CO2 emissions to
fall by more than 70 % by 2050; renewable energy is expected to ac-
count for 44 % of the decrease [3].
In the U.S., up to 45 % of total renewable energy consumption came
from biomass-derived energy in 2017 (Table 2), much higher than other
forms of renewable energy sources (e.g., wind, geothermal, and solar)
[4]. In addition to the opportunity for a carbon-neutral cycle and re-
latively mature infrastructure [5], biomass energy has the advantages
of high feedstock diversity and strong adaptability to widespread land
resources [6]. In 2016, 10.5 % of the global energy supply was from a
total biomass supply of 62.5 EJ (1 EJ=1012 MJ) with an annual growth
rate of 2.5 % since 2010 [7]. The total global biomass potential is
projected to reach 150 EJ by 2035 (Table 3). Without cropland ex-
pansion, current biomass potential worldwide will considerably exceed
the 2050 demand through increasing cropping intensities and spatially
reallocating crops [8].
1.1. Current status of biofuels
Biofuel is the most efficient form of biomass-derived energy
worldwide due to the economically competitive processes and the drop-
in nature of the fuels relative to the most popular fossil-based fuels [9].
Regular biofuel mainly contains mono-alkyl esters of long chain fatty
acids derived from energy crops, vegetable oils, animal fats and lig-
nocellulose-derived components, and meets the standard requirements
of ASTMD 6751 [10,11]. The biofuel share has been rising annually
since 2000 (Table 4) [12]. In 2016, 4 % of global road transportation
fuels was supplied by liquid biofuels [13], when 129 million liters were
produced [14] and 2.9 % of the total land area was used for dedicated

⁎
Corresponding author.
E-mail address: cbrewer@nmsu.edu (C.E. Brewer).

https://doi.org/10.1016/j.jaap.2020.104780
Received 27 August 2019; Received in revised form 10 January 2020; Accepted 30 January 2020
Available online 03 February 2020
0165-2370/ © 2020 Elsevier B.V. All rights reserved.
F. Cheng, et al. Journal of Analytical and Applied Pyrolysis 147 (2020) 104780

Table 1
The consumption, annual growth rate and share of various energy sources worldwide [1].
Primary Energy Source Type Oila Natural Gasb Coalc Nuclear Energyd Hydro-Electrice Renewablesf Totalg

Consumption in 2017 (Million tons oil equivalent) 4622 3156 3731 596 919 487 13511
Annual Growth Rate (%) 2017 1.69 2.97 0.96 1.15 0.87 16.96 2.18
2006–2016 1.05 2.34 1.27 −0.70 2.91 16.22 1.68
Share in 2017 (%) 34.2 23.4 27.6 4.4 6.8 3.6 100

a
Inland demand plus international aviation and marine bunkers and refinery fuel and losses. Consumption of bio-gasoline (such as ethanol), biodiesel and
derivatives of coal and natural gas are also included.
b
Excludes natural gas converted to liquid fuels but includes derivatives of coal as well as natural gas consumed in Gas-to-Liquids transformation.
c
Commercial solid fuels only, i.e. bituminous coal and anthracite (hard coal), and lignite and brown (sub-bituminous) coal, and other commercial solid fuels.
d
Based on gross generation and not accounting for cross-border electricity supply. Converted on the basis of thermal equivalence assuming 38 % conversion
efficiency in a modern thermal power station.
e
Based on gross primary hydroelectric generation and not accounting for cross-border electricity supply. Converted on the basis of thermal equivalence assuming
38 % conversion efficiency in a modern thermal power station.
f
Based on gross generation from renewable sources including wind, geothermal, solar, biomass and waste, and not accounting for cross-border electricity supply.
Converted on the basis of thermal equivalence assuming 38 % conversion efficiency in a modern thermal power station.
g
Primary energy comprises commercially-traded fuels, including modern renewables used to generate electricity.

Table 2
The annual growth rate and share of various bioenergy sources in the U.S. [4].
Energy Consumption Annual Growth Rate (%) Share in 2017 (%)

2006-2016 2017

Total Biomass Wood 3.89 0.34 0.00 0.64 44.60 19.47

Waste 1.85 −4.12 4.38
Biofuels 11.04 0.31 20.75
Total Renewablesa 4.82 7.37 100

a
Based on gross generation from renewable sources including wind, geothermal, solar, wood, waste, and biofuels.

Table 3
Global potential of various biomass resources in 2012 and 2035 [16].
Biomass type Global Potential (EJ)

2012 – 2016 2035 – Range 2035 – Average

Agriculture Dedicated crops 5.6 3.5 56 – 72 26 – 34 64 30

Residuesa 2.1 30 – 38 34
Forestry 48.9 72 – 84 78
Organic waste 1.7 6 – 10 8
Total 56.2 134 – 166 150

a
Including manure.

Table 4 1.2. 2 G biofuels

Global transportation energy consumption, annual growth rate, and consump-
tion share of various energy sources [12]. Bioethanol and biodiesel are produced from edible raw materials
Transport Energy Source Type Oil Gas Electricity Othera Total (e.g., corn, sugarcane and oilseeds) in the current infrastructure (e.g.,
wet milling plants) [18], and used in the commercial engines via
Consumption in 2020 (million tons 2593 66 39 131 2829 blending with fossil fuels in a certain proportion [19]. Such first-gen-
oil equivalent) eration (1 G) biofuels accounted for 94 % of total biofuels in 2017,
Annual Growth Rate 2020 1.85 9.33 4.89 4.83 2.15
(%) 2000-2020 2.04 25.41 5.98 11.97 2.40
reaching 142.1 million liters [20]. Issues related to food-versus-fuel
Share in 2020 (%) 91.66 2.33 1.36 4.65 100 [21] and low greenhouse gas (GHG) abatement (e.g., cleaning forest for
cropland [22]) are driving the transition from 1 G biofuels to second-
a
Includes biofuels, gas-to-liquids, coal-to-liquids, and hydrogen. generation (2 G) biofuels [23], which are primarily produced from non-
edible lignocellulosic biomass [24]. 2 G biofuels are projected to supply
half of total biofuels by 2050 [3]. Technologies for lignocellulose con-
biofuel crops [15]. Annual biofuels productivity is projected to reach
version development enable a wider range of feedstocks (e.g., leaves,
500 million liters by 2030 [3], and approximately 5 % of farmland will
stem, bark, and seeds), blending ratios in any proportion with fossil-
be used to grow dedicated energy crops for biofuels and solid-biomass-
based fuels, and use in unmodified diesel engines. Lignocellulosic
derived energy by 2035 [16]. Transport sector energy consumption is
feedstock for producing 2 G biofuels can be cultivated on marginal
expected to account for 27.4 % of the world’s total energy consumption
farmland, barren and arid lands, and offset 3.5–4 billion metric tons of
by 2040. In 2018, the global direct and indirect jobs created by the
carbon annually [25]. Compared to fossil fuels, 2 G biofuels have lower
liquid biofuels sector were 1.93 million [17], suggesting the opportu-
carbon footprints from direct combustion [26], and better fuel prop-
nity for substantial economic improvement as the biofuels industry
erties, such as higher cetane number, higher flash point, and better
develops.
lubricity [9]. One of the primary barriers to 2 G biofuel

2
F. Cheng, et al.
commercialization is high cost of the feedstock [27,28]. To reduce
feedstock cost, low-input dedicated plants grown on marginal/de-
graded land [25,29], agricultural residues, and organic wastes from
industrial, municipal, and forest sectors need to be considered for 2 G
biofuels production [30,31].
1.3. Protein- and lignin-rich biomass wastes for biofuels
Ideally, municipal, agricultural, and industry-derived biomass is
fully used for producing a variety of edible products, high-value che-
micals, and biofuels [32,33]. Easily digestible and processable compo-
nents (e.g., starch and fats) are extracted from biomass, while protein-
derived nitrogen and lignin-derived aromatics are enriched in solid
residues. For example, bioethanol and biodiesel industries generate
protein- and lignin-rich distiller’s/spent grains and de-oiled seedcakes,
respectively; the pulp and paper industry produces recalcitrant lignin-
rich residue; forest and urban areas generate protein-rich fallen leaves;
and household and restaurant kitchens generate food wastes including
uneaten meat/proteins, fats, peel, and undigestible fibers. This leaves a
vast quantity of non-edible, nitrogen- and lignin-rich wastes that are
disposed of by landfilling or incineration [34–36]. In 2017, the global
availability of agricultural residues reached 2.45 billion tons [37], and
the availability of total solid waste reached 2.12 billion tons [38]. Most
of discarded N- and lignin-rich resources are discarded rather than
valorized (e.g. as bioactive peptides [39], phenolic monomers [40],
etc.) due to the low efficiency and high cost of protein/lignin selective
extraction from biomass [41–43], and the limited market demand and
low quality for biomass-derived N-containing products [42,44]. Pyr-
olysis may be able to effectively convert this protein- and lignin-rich
biomass into energy-dense biofuel [45]. In pyrolysis, N can be recycled
in the form of ammonia from the pyrolysis aqueous phase [46] to
compensate N lost during crop cultivation, as a potential alternative to
fossil-based N-containing fertilizers [47], which offsets the life-cycle
energy benefit [22]. Recycling N resources can also reduce nitrous
oxide emissions [48]. As a natural source of phenolics, lignin can be
decomposed and upgraded into jet-fuel-range fuels rich in aromatic
hydrocarbons [49]. Therefore, recycling and upgrading protein- and
lignin-rich biomass from the existing sectors (e.g., agriculture, forestry,
food industry, municipal water treatment, etc.) to 2 G biofuels are ex-
pected to reduce the biorefinery cost, close the N loop, and minimize
the requirement of fossil energy-derived N fertilizers.
1.4. Organization of review
The objective of this review is to compare the availability and
pyrolysis performance of different classes of under-utilized protein- and
lignin-rich biomass waste to fill in the gap between waste disposal/
recycling and bio-energy production. Pyrolysis performance is based on
bio-oil productivity and quality, followed by the potential for im-
proving bio-oil composition by denitrogenation and for recycling va-
luable nitrogenous compounds for applications. Section 2 describes the
characteristics and availability of non-edible wastes that are lipid- and
(poly)saccharide-deficit, and protein- and lignin-rich. Sections 3 and 4
compare and evaluate the pyrolysis performance of the protein- and
lignin-rich wastes for yield and composition of bio-oil. Section 5 pro-
vides perspectives for bio-oil upgrading techniques, in particular cata-
lytic denitrogenation, to improve bio-oil quality and minimize en-
vironmental impact. Emphasis is placed on bio-oil as a precursor for
drop-in biofuel in terms of productivity, component distribution, and
formation mechanism, rather than on the influences of operating con-
ditions, reactor configuration, and accessory treatment.
2. Feedstocks
Protein- and lignin-rich biomass wastes with significant availability
and appropriate composition were grouped into seven categories
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Journal of Analytical and Applied Pyrolysis 147 (2020) 104780
Fig. 1. Low-cost protein-rich lignocellulosic biomass types. SS: sewage sludge.
MSW: municipal solid waste. a [308], b [309,310], c [311], d [312], e [313], f
[314], and g [315].
(Fig. 1): 1) whole dedicated plants (e.g., legumes, grasses, and oilseeds)
and unprocessed agricultural residues (e.g., straw, stems, husks and
leaves); 2) spent grains from bioethanol production; 3) de-oiled seed-
cakes from biodiesel production; 4) sewage sludges (SS) from municipal
wastewater treatment and the organic fraction of municipal solid
wastes (OFMSW); 5) solids from anaerobic digestion; 6) protein-con-
taining forestry wastes, and 7) lignocellulosic food wastes.
Algae valorization was not included here as there are many path-
ways developed for conversion of algae into biodiesel, biogas, value-
added proteins, etc. [50–52]. Algae contains less of the recalcitrant
components (in particular, lignin, or crystalline cellulose) as energy/
chemical barrier to conversion [53], thus, high-protein, lignin-free
algae is less of an under-utilized biomass waste with respect to bio-
chemical composition and energy content [54].
2.1. Dedicated crops and unprocessed agricultural wastes
Agricultural wastes (e.g. corn stover) usually contain ∼35 wt.%
cellulose, ∼24 wt.% hemicellulose, and ∼22 wt.% lignin, while dedi-
cated plants (e.g. herbaceous crops) have more cellulose (> 38 wt.%)
and less lignin (∼19 wt.%) [55–57]. Dedicated plants, grown for a
longer time before harvest (e.g. legumes and wetland plants), have
higher biomass production rates with higher contents of glucans, xy-
lans, and lignin, and less ash [58–60], leading to higher bio-oil yield
and energy recovery [61]. As a typical perennial legume used as forage
for animals, alfalfa (Medicago sativa) contains abundant crude protein,
lignocellulosic fiber, minerals, and vitamins. Due to the symbiotic re-
lationship with a soil bacterium, Sinorhizobium meliloti, alfalfa produc-
tion leads to strong biological N2 fixation (150 kg of N/(ha·year) on
average) [62]. Alfalfa stems have been used to produce electricity/li-
quid biofuels [63,64]. Alfalfa stems were found to have superior com-
bustion characteristics, including low volatiles and ash contents com-
pared to coals [65]. Switchgrass (Panicum virgatum) is used as a protein-
rich forage (∼17 %) [66,67], and has shown great potential as a per-
ennial energy crop, needing low inputs of pesticides and fertilizer with
no annual reseeding [68]. Milkweed (Asclepias spp.), another dedicated
energy crop, has higher energy content, can be harvested three times
per year, and can be grown at the large scale without competing with
F. Cheng, et al.
edible crops [69]. Wetland plants, such as narrowleaf cattail (Typha
angustifolia), alligator weed (Alternanthera philoxeroides), and water
dropwort (Oenanthe javanica), are widely distributed in temperate
zones. They have high growth rates, high nutritional intakes, and short
growth cycles, making them highly suitable for cleaning wastewater
[70]. Their N-rich biomass has been used as livestock feed or feedstock
of anaerobic digestion, however, inferior quality of available biomass
storage options and high transportation costs have limited the valor-
ization of wetland plants [71,72].
2.2. Spent grains from ethanol production
Spent grain, including distiller's dried grains (DDG) and DDG with
solubles (DDGS), is the primary co-product of the dry mill ethanol
process. DDGS’ high contents of protein, nutrients, simple sugars, and
digestible fiber has made DDGS a valuable livestock feed. More re-
cently, as DDGS production has increased rapidly, overfeeding of DDGS
and price fluctuations have led to unhealthy growth in animals, a net
increase in greenhouse gas emissions, and a vulnerability to the corn
ethanol market [73–75]. Some specific types of DDGS, especially from
barley, contain small amounts of mycotoxin, meaning that another
disposal method (e.g. biofuel production) rather than animal feed might
be needed [76]. Spent grains from the beer brewing process (30 g dry
basis/L beer) are much wetter than DDGS (∼90 % moisture content)
and are becoming more abundant as the craft brewing industry expands
[77]. Without drying, brewers spent grains deteriorate in a short time
[57]; biofuel production may be one way to manage excess spent
grains.
2.3. De-oiled seed cakes
De-oiled seedcake is the main co-product from bio-diesel production
after crude glycerol. The presence of residual oils in the seedcakes
usually mean that they have higher energy content than other lig-
nocellulosic wastes [78]. Common seedcakes available include those
from pennycress, canola, and Jatropha curcas. Pennycress (Thlaspi ar-
vense) is a winter annual weed distributed throughout the northern
American corn-belt. Pennycress can be grown as a dedicated crop in
corn or soybean rotation cycles, but does not require additional farm-
land or compete with food crops. Pennycress produces high yields of
oil-rich seeds ∼1000 kg seed/acre, which consist of 36 wt.% oil and
640 kg seedcake/acre, more than that of soybeans [27,79,80]. Jatropha
curcas is a semi-evergreen shrub from which oil can be extracted; that
oil can be used directly in diesel engines or upgraded into bio-diesel.
Use of the residual seedcake after oil extraction for bio-oil production
has the potential to improve the economics of the bio-diesel industry
[81].
2.4. Organic fraction from municipal solid wastes and sewage sludges
Municipal solid waste includes yard trimmings, rubber and leather,
paper, plastics, and textiles.
Sewage sludge is an ash-rich solid residue generated from waste-
water treatment plants. Agricultural reuse, landfilling, and incineration
are the three most common disposal methods to decrease waste volume
(by ∼70 %), stabilize the waste, and recover energy from municipal
solid waste and sewage sludge [82,83]. There were about 260 million
tons of municipal solid waste generated in the U.S. in 2015. More than
half of municipal solid waste was disposed by landfilling, while only a
quarter of the total was recycled [84]. The presence of heavy metals,
pathogens, and toxic chemicals (e.g. polychlorinated biphenyls, poly-
aromatic hydrocarbons, and dioxins) [85,86] in municipal solid waste
and sewage sludge have caused serious environmental issues like soil
contamination, air pollution, and greenhouse gas emissions, [87,88],
and has resulted in stringent regulations and limited land application
options [89]. Novel techniques for conversion of sewage sludge into
4
Journal of Analytical and Applied Pyrolysis 147 (2020) 104780
energy have been studied, especially anaerobic digestion and thermo-
chemical processes [90].
2.5. Anaerobic digestates
Anaerobic digestate is the solid residue generated from biogas
plants, generally accounting for 30–50 % of the original organic ma-
terial [91]. Approximately 80 million tons of digestate are produced in
Europe each year [92]. Digestate is biologically stable and contains
abundant organic molecules, N and P [93,94]. Digestate has been used
as solid fuel, organic soil amendment, and fertilizer [95]. Since some
digestates may not be completely biodegraded, there is potential for
soil/air contamination caused by pathogenic bacteria, and inorganic/
organic heterogenous compounds [96]. By converting the digestates
into bio-oil through pyrolysis, most of pathogens and chemicals of
concern can be decomposed into oily compounds and fly ash (carbon-
poor biochar) to be used for other applications (e.g. catalyst for oil
upgrading [97]).
2.6. Protein-containing forestry wastes
Forestry wastes are abundant in terms of mass and energy
throughout the world. In Nigeria, wood logging and sizing operations
consume about 9 million hectares of forest, generating 7 million m3/
year of forestry wastes [98]; much of the excessive generation wastes is
attributed to outdated milling machines [99]. In Spain, 11–16 million
tons of forestry waste are produced annually [100], representing 1.3
billion MJ/year of energy potential [101]. In regions of India, Nepal,
and Bhutan, about 7.6 million hectares is covered by pine trees, con-
taining 48–49.5 million tons forestry waste, particularly pine needles
[102]. Forestry wastes primarily contain wood, bark, and leaves. The N
content of bark and leaves are higher due to the presence of chlorophyll
and proteins. Bark also has higher contents of pectin, phenolic com-
pounds, suberins, and ash [103]. Forestry waste over-accumulation,
with its high flammability, greatly increases the risk of uncontrollable
forest fires and CO2 emissions [104,105]. In western North America,
Douglas fir (Pseudotsuga menziesii) is one of the main tree species, and a
substantial amount of forestry waste is generated and pelletized [106]:
approximately 1.5 million tons of wood pellets are conventionally
combusted for heat and power each year [107]. The N in wood pellets
forms gaseous nitrogen oxides during direct burning, creating the op-
portunity to explore other methods for valorizing the higher-nitrogen
waste.
2.7. Food wastes
Food waste consists of a wide and heterogeneous range of compo-
nents, most of which are obtained from household kitchens [108]. For
example, from pre-consumer food processing alone, 0.5 million tons of
apricot (Prunus armeniaca L.) waste and ∼43 million tons of potato
skins are produced every year [109–112]. Given the increasingly im-
portant role this waste can have on environmental and health problems,
effective disposal methods are critical. Landfill and incineration are the
common methods, however, rapid food residue decay, soil contamina-
tion, and air pollution are stimulating the transformation of conven-
tional methods into more environmental-friendly methods [113]. Food
waste normally contains abundant lipids, proteins, and digestible su-
gars, indicating the potential for conversion into energy-dense bio-oil
by thermochemical processes [114].
3. Pyrolysis of protein- and lignin-rich biomass for bio-oil
production
3.1. General effects of pyrolysis operating conditions
The yield and composition of bio-oil from pyrolysis depend on
F. Cheng, et al.
operating conditions [81], reactor configuration, and the nature of the
feedstock. Typically, bio-oil formation is favored by intermediate tem-
peratures of 450–550 °C [115], short vapor residence times (∼5 s)
[116], higher heating rates (30‒30,000 °C/min) [117], and a suitable
reaction atmosphere such as off-gases [116] or steam [118].
Temperature plays the most significant role on biomass decom-
position and bio-oil production. Below 200 °C, biomass dehydration
occurs, and small volatiles like formic acid, acetic acid, glyoxal, and
CO2, are released. As temperature increases to 260 °C, biomass starts to
char, emitting water, formic acid, acetic acid, glyoxal, and non-con-
densable gases. The reactions under < 260 °C are basically en-
dothermic. At 260–500 °C, mostly exothermic pyrolysis reactions occur,
accelerating the temperature increases during this period. More energy-
dense gases and volatiles (e.g. CO, CH4, H2, aldehydes, acids, alcohols,
ketones, and phenols), along with biochar, are generated via dec-
arbonylation, decarboxylation, aromatization, isomerization, deami-
nation, etc. Above 500 °C, volatiles, with a wide range of molecular
weights, released from both liquid and solid phases are fragmented into
smaller gaseous products, including H2, CH4, and C2H6. As secondary
reactions (e.g. H2-abstraction-C2H2-addition) occur, polycyclic aro-
matic hydrocarbons and other repolymerized products form and attach
to the outer layer of the biochar [119–121].
Bio-oil, a highly heterogeneous liquid mixture, contains ∼75 % of
the energy from the feedstock [122], and consists of carboxylic acids,
alcohols, aldehydes, ketones, esters, ethers, furans, phenols, aliphatics
(e.g. alkanes, alkenes, naphthene, etc.), N- and S-containing compounds
(e.g. amines, amides, heterocyclic aromatics, etc.), water, and fine
biochar particles [115,116,123]. Bio-oil molecular weight ranges from
370 to 1000 g/mol [124]. Operating within an optimal range of con-
ditions leads to lower oil kinematic viscosity, higher water content
[116], fewer carboxylic acids, and increased lignin-derived phenols
(alkyl and alkoxy) [115], which has been found to stabilize bio-oil
[125]. Fast pyrolysis with higher heating rates (300‒30,000 °C/min)
further improves bio-oil yield compared to slow/flash pyrolysis [126].
3.2. Effect of feedstock type on pyrolysis process
Feedstock affects the product distribution of pyrolysis, the reaction
rate, and the physical and chemical properties of the bio-oil. Among the
feedstock characteristics that have been shown to have effect are the
particle shape, particle size, bulk density, and thermal conductivity (for
example, 1.8–2.0 mm, 0.06–0.1 g/cm3, and 0.1-0.5 W·m−1 K−1, re-
spectively) [127]; proximate, ultimate, and chemical composition (e.g.
lignocellulosic fiber, protein, lipid, extractives, ash, and moisture con-
tents ≤60 %) [128–130]; and energy content (≤28 MJ/kg). Biomass
physical properties can be modified by physical pretreatment (drying,
grinding, and pelletization) [122]. Feedstock composition can be tuned
by harvesting method and timing [131,132], storage method [55],
chemical/thermochemical pretreatment, and mixing with other mate-
rials (e.g. coal and oil shale) for co-pyrolysis [133–135].
3.2.1. Pyrolysis of biomass macromolecules
The general pathways of pyrolysis of protein are shown in Fig. 2.
Compared to biological and chemical conversion techniques, thermo-
chemical conversion techniques require more energy to stretch and split
the rigid structures of all components, rather than selectively extracting
less recalcitrant components. In theory, all organic biomass components
are available for bio-oil production through thermochemical conver-
sion. The mechanisms for the conversion of the different molecules into
the desired bio-oil compounds are not completely understood, thus,
additional work is needed to enable higher yield and higher quality of
bio-oil for each feedstock.
Protein is the primary source of diverse types of nitrogenous com-
pounds in bio-oil [136,137]. Some (21–38 %) of the N is transferred
from the feedstock to the bio-oil phase, while most (36–62 %) enters the
gas phase as NH3 or HCN [138]. At the beginning of pyrolysis (< 300
5
Journal of Analytical and Applied Pyrolysis 147 (2020) 104780
°C), protein is mainly decomposed into peptidic, tryptophanic, prolinic,
and other types of protein-derived fragments with abundant amino and
amide functional groups [139]. Under more severe conditions
(300–550 °C), the more labile peptidic derivatives (e.g. alanine, valine,
leucine, and glycine), break into amides (e.g. acetamide), pyridines,
pyrrolidines (e.g. 3-pyridinol), pyrroles (e.g. pyrrole), and diketopi-
perazines [140]. Simultaneously, tryptophanic, asparaginic, and mela-
noidinic fragments degrade into indoles [141–143]; prolinic and pyr-
rolysinic derivatives decompose into pyrrolidines and pyrroles [144].
Such heterocyclic compounds are also generated from cyclization and
condensation of unstable intermediates (by Diels-Alder reactions)
[145], Amadori compounds (by Maillard reactions) [144], and protein-
derived fragments (e.g. amines) [139,140]. With longer vapor residence
times, smaller products, such as amines (e.g. 1,3-propanediamine, N-
methyl-), oxime ethers, amides, and a few nitriles (e.g. aromatic nitriles
and acetonitrile) [146], are generated from the heterocyclic compounds
(e.g. pyridines, pyrrolidines, pyrroles, indoles, and diketopiperazines)
and amides [138,139]. Secondary reactions form nitrogenous poly-
cyclic aromatic compounds from small unsaturated molecules (e.g.
olefins, nitriles, etc.), lowering bio-oil yield [141]. At temperatures >
550 °C, amines and heterocyclic compounds from bio-oil further frag-
ment into NH3 by deamination and bimolecular reactions, and HCN by
ring opening, respectively [139,147]. Notably, bio-oil yield is propor-
tional to the yields of amines and heterocyclic compounds, indicating
that these compounds may represent the most abundant nitrogenous
species for bio-oil formation.
Lignin, a recalcitrant biopolymer consisting of propylphenol units, is
broken into non-condensable gases (e.g. CO2), char, alcohols, acetic and
formic acids, furans, acetaldehyde, acetone, smaller hydrocarbons (CH4
and C2H6), and phenol derivatives (e.g. alkylphenols, alkylguaiacols,
alkylsyringols, sinapyl alcohol, etc.) [148–150], most of which con-
tribute to the formation of pyrolysis liquid with higher molecular
weight, higher viscosity, but lower water content [151]. The phenolic
monomers are prone to re-oligomerize into heavier asphalt or even char
in the presence of acetic acid [150,152]. The primary decomposition of
lignin occurs under a wide range of operating conditions [153]; only 60
wt.% of lignin decomposes below 800 °C [154]. The pyrolysis reaction
rate of lignin is lower than that of cellulose [155] due to the more
complex and thermally stable molecular structures within lignin [156].
Apart from protein and lignin, there are cellulose, hemicellulose,
and ash as well. Cellulose is a crystalline, linear polysaccharide, com-
posed of anhydro-D-glucose units, and is embedded in a matrix linked
with lignin and hemicellulose by strong inter- and intra-molecular hy-
drogen bonds [157]. The activation energy of cellulose (187–235 kJ/
mol) is higher than that of hemicellulose (41–68 kJ/mol) and lignin
(97–150 kJ/mol) [81]. Approximately 90 wt.% of cellulose is degraded
between 250 and 430 °C [154]. During pyrolysis, cellulose is broken
down to form anhydro-sugar intermediates, predominantly levoglu-
cosan, acids, ketones (e.g. levulinate), aldehydes, furans, and non-
condensable gases [149,158,159].
Hemicellulose is an amorphous branched polysaccharide [160],
made of monosaccharides including glucose, galactose, xylose, arabi-
nose, mannose, and uronic acids [161]. Around 70 wt.% of hemi-
cellulose reacts between 180 and 350 °C [154]. Most hemicellulose
decomposes into anhydrosugars, acids, furans, ketones, aldehydes, hy-
drocarbons (e.g. olefins), non-condensable gases, and char under pyr-
olysis conditions [148,162].
Ash content in biomass varies greatly depending on feedstock type,
from as low as 1 wt.% in agricultural wastes [163] to as high as 57 wt.%
in digestated sewage sludges [164]. Ash mainly contains calcium, so-
dium, potassium, magnesium, silicon, phosphorus, chlorine, carbo-
nates, phosphates, nitrates, oxyhydroxides, sulfates, silicates, and
chlorides [165]. Excessive ash hampers pyrolysis, causing higher char
yield, lower bio-oil yield, and higher bio-oil viscosity
[150,151,162,166]. Trace amounts of alkali and alkaline metals (< 0.1
wt.%) can catalyze fragmentation of cellulose and hemicellulose via
F. Cheng, et al.
Fig. 2. Pyrolytic pathway of protein into bio-oil, adapted from [138].
reducing the activation energy of reactions (e.g. ring opening)
[154,167–169]. Phosphorus facilitates whole biomass decomposition
and a higher content of fixed carbon [170]. Potassium can crack an-
hydrosugars into smaller oxygenated compounds, and stimulate lignin
degradation and char generation [171]. Calcium oxide was reported to
deoxygenate bio-oil, inhibit char formation, and lower bio-oil acidity
[172].
3.2.2. Comparing pyrolysis data
In Table 5, pyrolysis data from 77 feedstock types in 51 publications
were evaluated in terms of feedstock and bio-oil elemental composition,
bio-oil yield, and energy recovery (energy in the bio-oil relative to the
total energy in the feedstock). When comparing pyrolysis data from
previous publications, researchers must note that: 1) elemental and
proximate data are presented on different bases (e.g. as received, dry, or
dry-ash-free basis); 2) the definition of bio-oil varies; 3) bio-oil yield
and quality data were generated under different operating conditions;
and 4) different analytical methods are used to characterize different
proportions of bio-oil. Here, elemental and proximate data were con-
verted to a dry basis. Bio-oil, as a highly heterogeneous product, is
generally comprised of three proportions: a watery phase (containing
volatile, high-polarity organic compounds), a transition phase (con-
sisting of moderate-polarity organic compounds and some water), and
an organic phase (rich in low-polarity compounds and almost no
moisture) [103,173]. Among different studies, bio-oil has been defined
as the whole pyrolysis liquid, or as an organic phase extracted from the
whole pyrolysis liquid by low-polarity solvents (e.g. hexane or di-
chloromethane) [174]. In most cases, bio-oil was collected from simple
phase separation (separating a watery phase from both transition and
organic phases). In this review, both transition and organic phases were
defined as bio-oil so that yield and energy recovery can be compared on
a more uniform basis. Yield and composition of bio-oils were compared
under the study-defined optimal conditions, even though those condi-
tions differed between studies. Finally, categories of oily components
were compared in terms of functional structures and heteroatoms.
6
Journal of Analytical and Applied Pyrolysis 147 (2020) 104780
Typically, studies used gas chromatography–mass spectrometry
(GC–MS) to characterize the relative abundances of organic molecules
in bio-oils. GC-detectable oily compounds account for only 30–50 % of
whole bio-oil, and detection varies between studies [175]. Thus, bio-oil
characterization data (particularly the concentrations of specific oily
components) from different publications could not be compared di-
rectly.
4. Pyrolysis of specific wastes
4.1. Pyrolysis of agriculture wastes and dedicated plants
Agriculture wastes and dedicated plants generally contained more
volatile matter (73–88 wt.%) and have comparable energy content
(15–28 MJ/kg) relative to the other biomass wastes considered here,
indicating the potential for high bio-oil yields. The wide range of ash
content in the biomass (1–49 wt.%) dramatically affected bio-oil yield,
chemical composition, and energy recovery [169]. The average bio-oil
yield and energy recovery from pyrolysis of agricultural waste and
dedicated plants were 46 wt.% and 63 %, respectively. The bio-oil
contained a considerable number of oxygenated compounds (e.g. le-
voglucosan, hydroxyacetaldehyde, methanol, phenols, non-aromatic
ketones, and carboxylic acids) (41–56 %) due to the high contents of
cellulose and hemicellulose in the feedstock [174,176,177]. Most of
these oxygenated compounds were present as water-soluble com-
pounds, accounting for 65–75 % of bio-oils; the remainder of the bio-oil
was made up of water-insoluble compounds, including lignin-derived
oligomers and phenolic compounds (e.g. syringols, guaiacols, eugenols,
cresols, etc.) [178]. A certain amount of aromatics (e.g. methyl-
naphthalene) and other heteroatom-containing compounds (e.g. ben-
zylnitrile, indole, amino acid-derived amines, and alkaloid-derived
pyridines and pyrroles) were found and varied with different types of
nitrogenous compounds in feedstock [177,178]. Water content in the
bio-oil ranged from 14 % to 24 % [174,178].
F. Cheng, et al. Journal of Analytical and Applied Pyrolysis 147 (2020) 104780

Table 5
Elemental composition of feedstock and bio-oil, bio-oil yields and energy recovery.
Feedstock Elemental analysis (wt.% d.b.) HHV (MJ/ Feedstock Proximate analysis Bio-oil Yield Energy Recovery Ref.
kg) (wt.% d.b.) (wt.% d.b.) (%)

C H N S O Ash VM

Empty Fruit Bunches Biomass 49.07 6.48 0.70 < 0.1 38.29 19.35 5.36 83.86 34 64 [286]
Bio-oil 69.35 9.61 0.74 None 20.02 36.06
Soybean Biomass 48.00 5.84 0.84 N.D. 41.40 18.90 3.95 N.A. 53 74 [287]
Bio-oil 50.45 4.38 1.43 N.D. 43.74 26.55
Soybean Biomass 46.85 5.45 0.92 N.D. 40.92 18.98 3.43 N.A. 53 74 [287]
Bio-oil 56.26 4.29 1.49 N.D. 41.57 26.65
Mesua ferrea Seed Cover Biomass 42.76 5.31 1.56 N.A. 47.42 16.32 2.82 77.28 29 53 [288]
Bio-oil 56.12 6.97 1.83 N.A. 31.87 29.45
Pongamia glabra Seed Cover Biomass 46.92 5.36 1.14 N.A. 45.34 18.34 1.22 79.86 28 50 [288]
Bio-oil 60.05 7.11 1.45 N.A. 29.08 32.63
Tobacco Residue Biomass 45.40 5.45 1.80 N.A. 35.25 16.87 12.10 73.35 26 46 [289]
Bio-oil 66.02 8.50 3.02 N.A. 22.46 29.59
Corn Stover Biomass 47.82 5.11 0.84 0.21 41.12 18.37a 4.90 N.A. 40 53 [180]
Bio-oil 53.97 6.92 1.18 < 0.05 37.94 24.30
Corn Stalk Biomass 42.65 5.57 1.49 < 0.10 42.41 16.24 6.75 82.58 66 79 [238]
Bio-oil 44.30 6.30 0.60 0.30 47.50 19.60
Corn Cob Biomass 43.32 6.02 0.93 < 0.10 46.13 16.99 3.24 88.43 57 56 [238]
Bio-oil 51.90 7.00 0.80 N.D. 40.30 16.80
Corn Cob Biomass 43.60 5.80 0.70 N.A. 48.60 16.90 1.20 80.60 56 52 [99]
Bio-oil 38.10 8.00 0.70 N.A. 53.20 15.80
Rice Straw Biomass 26.73 4.05 1.02 0.28 17.24 12.26 49.33 49.24 60 90 [238]
Bio-oil 65.68 7.66 1.08 N.D. 25.58 18.43
Rice Straw Biomass 44.12 6.05 0.73 N.A. 39.12 16.59 9.98 75.39 37 58 [290]
Bio-oil 42.19 13.44 1.25 N.A. 43.12 25.87
Cocoa Pod Husk Biomass 43.87 5.82 2.23 0.57 35.25 17.93 12.05 76.32 53 50 [238]
Bio-oil 46.50 7.30 0.20 0.10 49.80 17.20
Sugarcane Bagasse Biomass 44.31 5.73 0.63 < 0.10 44.84 16.88 4.27 86.85 61 84 [238]
Bio-oil 45.77 7.86 0.18 N.D. 46.19 23.30
Barley Straw Biomass 46.86 6.15 0.78 0.15 43.69 16.60 2.37 N.A. 56 81 [183]
Bio-oil 50.78 3.20 1.37 0.00 44.42 24.20
Barley Hulls Biomass 44.21 5.82 1.03 0.00 42.73 17.60 6.22 N.A. 49 67 [183]
Bio-oil 54.73 5.32 1.79 0.09 38.49 24.10
Jatropha Residues Biomass 46.01 6.50 4.49 N.A. 42.18 19.33b 0.82 86.96 9 15 [163]
Bio-oil 67.20 8.79 5.57 N.A. 17.33 32.16
Spent Mushroom Substrate Biomass 36.79 4.43 1.03 N.A. 47.56 12.87b 10.19 80.74 11 30 [135]
Bio-oil 69.05 9.65 N.A. N.A. 18.53 33.79c
Milkweed Biomass 37.22 5.33 2.64 N.A. 43.61 16.67 11.20 79.15 26 49 [69]
Bio-oil 69.07 8.81 5.52 N.A. 16.60 31.28
Switchgrass Biomass 47.53 6.81 0.51 0.00 42.54 20.16 2.61 83.41 60 54 [178]
Bio-oil 47.47 6.96 0.36 N.A. 45.19 18.45
Switchgrass Biomass 47.40 6.79 0.55 0.21 42.45 20.11a 2.60 N.A. 57 66 [180]
Bio-oil 52.97 6.43 0.38 0.00 39.13 23.10
Eel Grass Biomass 39.60 5.08 2.08 0.35 40.30 15.38a 12.60 N.A. 38 66 [180]
Bio-oil 69.20 7.31 3.81 0.07 19.61 26.10
Alfalfa Stems Biomass 42.06 5.73 2.37 0.19 40.85 17.01a 8.80 N.A. 41 79 [180]
Bio-oil 53.88 8.47 4.59 0.05 32.73 33.10
Alfalfa Stems (Early Bud) Biomass 41.98 5.73 2.39 0.21 40.85 19.48 8.74 73.39 45 59 [61]
Bio-oil 53.76 8.45 4.58 0.05 32.66 25.85
Alfalfa Stems (Full Flower) Biomass 43.41 5.84 1.51 0.08 43.26 19.85 5.83 75.29 53 70 [61]
Bio-oil 57.00 7.89 3.75 0.07 31.30 26.54
Alfalfa (Early Bud) Biomass 44.30 5.43 2.52 0.22 38.20 17.71a 8.74 73.39 45 65 [178]
Bio-oil 53.88 8.47 4.59 0.05 32.73 25.85
Alfalfa (Full Flower) Biomass 45.97 5.52 1.60 0.09 40.58 18.22a 5.83 75.29 53 77 [178]
Bio-oil 56.84 7.86 3.73 0.07 31.30 26.54
Linseed Biomass 64.90 9.04 2.45 N.A. 30.00 28.03 6.00 82.53 64 90 [127]
Bio-oil 75.77 10.76 3.16 N.A. 10.80 39.23
Mahua Seed Biomass 59.90 8.22 4.03 0.72 24.94 26.69 2.19 84 49 71 [291]
Bio-oil 69.32 9.12 2.53 0.89 18.14 39.02
Rapeseed Biomass 58.68 8.60 3.69 N.A. 23.53 26.70 5.50 81.7 68 96 [292]
Bio-oil 72.80 10.80 3.30 N.A. 13.10 37.90
Rapeseed Biomass 52.25 8.06 3.91 N.A. 35.78 28.36 5.73 86.04 46 62 [293]
Bio-oil 74.04 10.29 3.97 N.A. 11.70 38.40
Barley DDGS Biomass 51.15 7.09 4.42 0.54 32.14 21.30 4.67 N.A. 48 74 [183]
Bio-oil 74.02 8.92 5.05 0.35 6.24 32.90
Barley DDGS Biomass 51.24 7.10 4.38 0.46 32.22 22.81a 4.60 N.A. 48 70 [180]
Bio-oil 74.02 8.92 5.05 0.35 6.24 32.90
DDGS Biomass 46.79 6.01 3.19 0.85 37.12 23.30 6.03 81.14 35 51 [78]
Bio-oil N.A. N.A. 2.18 1.57 N.A. 34.14
Brewers Spent Grains Biomass 44.32 6.51 3.37 0.70 40.19 18.91a 4.89 84.78 48 73 [184]
Bio-oil 62.57 8.12 1.41 2.01 25.79 28.90
(continued on next page)

7
F. Cheng, et al. Journal of Analytical and Applied Pyrolysis 147 (2020) 104780

Table 5 (continued)

Feedstock Elemental analysis (wt.% d.b.) HHV (MJ/ Feedstock Proximate analysis Bio-oil Yield Energy Recovery Ref.
kg) (wt.% d.b.) (wt.% d.b.) (%)

C H N S O Ash VM

Brewers Spent Grains Biomass 46.41 5.95 3.86 0.09 36.68 18.55 6.81 64.36 53 68 [188]
Bio-oil 52.80 5.94 8.49 < 0.1 32.66 24.07
Wheat Spent Grains Biomass 42.18 6.35 4.39 0.10 44.72 18.35 2.36 80.51 45 55 [188]
Bio-oil 50.86 5.82 6.06 < 0.1 37.26 22.80
Digested Sewage Sludge Biomass 39.40 5.60 7.80 0.80 28.60 18.50 17.80 68.1 36 71 [229]
Bio-oil 65.20 8.60 8.40 0.40 17.40 36.40
Digested Sewage Sludge Biomass 34.02 5.39 5.74 1.12 23.80 16.60 30.00 59.50 28 45 [175]
Bio-oil 58.50 8.20 12.30 1.80 19.20 27.00
Digested Sewage Sludge Biomass 47.19 7.50 6.64 1.36 37.31 12.74 41.30 49.36 28 51 [173]
Bio-oil 44.59 9.00 7.50 0.70 38.19 22.80
Digested Sewage Sludge Biomass 20.48 3.41 3.54 0.56 15.21 8.40a 56.80 40.10 19 61 [164]
Bio-oil 58.30 7.40 8.30 1.10 24.90 26.48a
Digested Lignocellulosic Biomass 42.50 6.08 1.43 N.A. 37.29 17.96b 12.70 72.10 58 76 [294]
Biomass Bio-oil 58.25 5.52 1.20 N.A. 34.78 23.50
Digestate Biomass 48.11 5.85 2.60 0.56 35.76 14.00 21.06 54.47 12 29 [295]
Bio-oil 69.75 7.06 4.55 1.11 9.84 34.40
Albizia Sawdust Biomass 46.40 5.80 0.60 N.A. 45.50 17.40 1.80 72.70 54 53 [99]
Bio-oil 41.90 7.40 0.60 N.A. 50.10 16.90
Mesquite Sawdust Biomass 53.00 4.80 0.60 N.A. 41.60 15.40 0.6 [48] N.A. 11 18 [237]
Bio-oil 59.40 5.80 0.30 N.A. 34.50 24.00a
Pine Sawdust Biomass 47.75 6.30 1.27 N.A. 44.37 19.28 0.31 N.A. 19 21 [296]
Bio-oil N.A. N.A. N.A. N.A. N.A. 21.29
Pine Needles Biomass 49.57 7.20 1.05 0.10 34.12 20.42 8.06 71.71 28 40 [102]
Bio-oil 63.78 9.69 1.63 0.10 24.80 28.64
Wood Chip Biomass 51.54 6.18 0.30 < 0.1 41.67 20.70 0.30 85.94 35 46 [175]
Bio-oil 58.50 8.20 12.30 1.80 19.20 27.00
Oak Biomass 48.75 6.11 0.95 0.43 41.17 19.93a 2.60 N.A. 51 57 [180]
Bio-oil 56.54 6.00 0.61 0.00 36.84 22.10
Evergreen Oak Biomass 44.20 6.30 0.50 0.04 45.40 19.60 3.60 N.A. 3 6 [297]
Bio-oil 72.20 7.00 2.60 0.30 17.90 32.80
Vine Shoots Biomass 47.80 6.20 0.60 0.05 41.20 19.20 4.08 N.A. 4 8 [297]
Bio-oil 78.60 7.20 2.50 0.30 11.40 35.50
Brown Forestry Residue Biomass 51.10 5.90 0.50 N.A. 38.70 20.50 3.80 73.20 61 51 [103]
Bio-oil 43.00 7.40 0.10 N.A. 49.00 17.40
Green Forestry Residue Biomass 51.40 6.00 0.50 0.04 40.00 20.80 2.10 76.70 64 52 [103]
Bio-oil 43.90 7.50 < 0.1 N.A. 48.00 16.90
Sewage Sludge Biomass 25.50 4.46 4.84 2.07 25.87 11.10 37.20 54.20 48 90 [217]
Bio-oil 45.00 8.80 6.60 0.70 39.00 20.72
Dried Granulated Sewage Biomass 30.20 4.30 4.80 1.20 17.17 13.42 42.33 54.22 13 31 [212]
Sludge Bio-oil 65.20 7.60 7.60 1.20 4.50 31.86
Broiler Litter Biomass 29.16 4.64 3.76 0.85 41.95 14.32 17.35 N.A. 38 80 [298]
Bio-oil 60.16 8.90 8.30 0.37 22.10 29.70
Pig Compost Biomass 40.82 5.45 4.17 0.56 29.35 15.90 19.80 67.37 25 42 [175]
Bio-oil 58.50 8.20 12.30 1.80 19.20 27.00
AmmoSoak Biomass 35.62 5.51 0.50 0.05 57.52 12.98 1.11 N.A. 45 88 [298]
Bio-oil 65.15 6.70 0.61 < 0.05 27.32 25.30
Apricot Kernel De-oiled Cake Biomass 51.43 7.78 6.08 N.A. 33.41 22.88 1.30 87.28 32 55 [199]
Bio-oil 74.19 11.18 1.03 N.A. 13.60 39.12
Canola Seed Press Cake Biomass 47.93 6.73 5.14 0.84 32.80 23.60 6.56 77.24 30 44 [78]
Bio-oil N.A. N.A. 10.87 1.08 N.A. 34.75
Camelina Press Cake Biomass 50.89 6.99 6.23 0.90 29.97 22.80a 5.00 N.A. 53 74 [180]
Bio-oil 69.75 69.80 8.55 0.37 12.69 32.00
Pennycress Press Cake Biomass 46.74 5.55 5.91 1.25 28.46 19.69a 12.10 N.A. 36 60 [180]
Bio-oil 69.01 8.35 7.14 0.76 15.63 32.00
Defatted Pennycress Press Biomass 43.47 5.59 6.09 0.58 31.98 18.16a 12.30 N.A. 41 66 [180]
Cake Bio-oil 58.39 6.83 10.48 1.27 23.04 29.10
Cottonseed Cake Biomass 49.29 5.59 1.23 N.A. 38.67 17.99 5.22 83.81 29 55 [299]
Bio-oil 68.46 9.36 6.06 N.A. 16.12 33.73
Soybean Cake Biomass 55.89 6.57 9.29 N.A. 28.25 23.25 6.14 78.15 31 39 [118]
Bio-oil 62.16 8.33 7.47 N.A. 22.04 29.03
Soursop Seed Cake Biomass 50.20 5.82 2.47 N.A. 38.86 19.00 1.38 90.69 18 33 [300]
Bio-oil 70.80 9.20 2.40 N.A. 17.60 33.80
Black Cumin Seed Cake Biomass 51.17 7.95 5.32 0.45 35.11 22.46 5.06 74.71 45 78 [192]
Bio-oil 75.21 10.35 3.70 0.20 10.54 38.48
Safflower Seed Press Cake Biomass 48.02 6.69 2.91 N.A. 39.38 24.80 3.00 83.00 35 50 [301,302]
Bio-oil 66.98 6.29 4.58 N.A. 22.15 36.00
Raspberry Seed Cake Biomass 51.99 6.33 1.85 0.29 36.90 20.30 2.64 69.54 53 49 [194]
Bio-oil 51.90 6.50 2.10 0.10 39.40 18.60
Rapeseed Oil Cake Biomass 42.68 5.77 6.41 0.82 37.27 19.49 7.05 75.28 18 31 [210]
Bio-oil 66.80 8.72 9.05 0.59 14.84 33.17
Mahua De-oiled Cake Biomass 49.65 5.71 3.34 0.61 40.69 21.00 4.55 92.25 41 51 [303]
Bio-oil 63.20 8.74 4.04 0.38 23.64 26.30
(continued on next page)

8
F. Cheng, et al. Journal of Analytical and Applied Pyrolysis 147 (2020) 104780

Table 5 (continued)

Feedstock Elemental analysis (wt.% d.b.) HHV (MJ/ Feedstock Proximate analysis Bio-oil Yield Energy Recovery Ref.
kg) (wt.% d.b.) (wt.% d.b.) (%)

C H N S O Ash VM

Sesame De-oiled Cake Biomass 43.26 7.23 6.95 0.69 37.59 19.78 4.28 92.26 58 75 [206]
Bio-oil 55.80 8.34 7.00 0.17 28.91 25.50
Mustard De-oiled Cake Biomass 43.58 5.26 5.66 1.60 35.72 20.50 8.19 89.40 53 65 [206]
Bio-oil 58.46 8.52 5.86 0.49 26.67 25.10
Neem De-oiled Cake Biomass 37.99 4.04 1.67 1.16 44.49 18.20 10.65 84.44 40 66 [206]
Bio-oil 73.81 8.79 1.88 0.24 15.59 30.00
Sunflower De-oil Cake Biomass 49.59 6.38 6.75 N.A. 31.03 22.30 6.25 78.18 42 63 [304]
Bio-oil 68.50 9.90 5.60 N.A. 16.00 33.70
Potato skin Biomass 71.32 6.13 2.57 N.A. 9.38 34.99 10.60 78.55 24 22 [110]
Bio-oil 58.82 8.54 1.22 N.A. 31.41 32.00
Apricot Pulp Biomass 48.78 5.47 2.39 N.A. 38.12 18.48 5.24 80.22 21 31 [112]
Bio-oil 61.50 7.80 1.74 N.A. 28.96 26.82

d.b.: dry basis; DDGS: distiller's dried grains with solubles; energy recovery = bio-oil yield × (bio-oil HHV/feedstock HHV) × 100 %; VM: volatile matter; FC: fixed
carbon.
a
Calculated using [305].
b
Calculated using [306].
c
Calculated using [307].

4.2. Pyrolysis of spent grains
Spent grains contained more protein (20–30 wt.%) and fewer
polysaccharides than other biomass feedstocks [154,179,180]. Spent
grains have traditionally been used as livestock feed [181], however,
when there is a local surplus, an appropriate pyrolysis process can be
used to improve the economic feasibility of the crop-to-ethanol bior-
efinery by offering another pathway to biofuel, co-producing biochar as
a soil amendment [182]. Table 5 shows that spent grains generally have
low ash content (2–7 wt.%) and favorable energy content (18–23 MJ/
kg). Compared to other agricultural wastes and dedicated crops, dry
spent grain has lower decomposition activation energy [154], and si-
milar average bio-oil yield (46 wt.%) and energy recovery (66 %)
(Table 5).
Bio-oil from spent grain pyrolysis has relatively high energy content
(> 30 MJ/kg), attributed to spent grain’s fatty acid derivatives (e.g.
palmitic acid, linoleic acid, di-acylglycerides, tri-acylglycerides, and
undecanoic acid methyl esters) [183,184]. The protein content of the
spent grain also leads to a higher level of deoxygenation in the bio-oil
due to the tendency of protein-derived nucleophilic amine groups to
substitute for electrophilic oxygen groups (e.g. carbonyl and hydroxyl
groups, Fig. 4) [180]. Spent grain-derived bio-oil contains less acetol,
hydroxyacetaldehyde, furfural, and acetic acid (< 1 %), and more
protein-derived fragments (phenyl-acetonitrile, undecane-nitrile, ben-
zylnitrile, indoles, pyrrole, pyridinol, 2-pyrrolidinone, and tetramethyl-
4-piperidone), and N bases (amides and amines). This leads to a more
neutral bio-oil pH (6.5) compared to the pH of other bio-oils (2–3),
meaning the bio-oil is less likely to cause corrosion [180,183,184]. By
substituting amine groups for oxygen (e.g. through Maillard reactions),
spent grain bio-oil contains fewer reactive oxygenated compounds: le-
voglucosan, phenolic compounds, and cellulose-derived furfuryl al-
cohol formed via cleavage of formyl group from hydroxymethylfurfural
[180,185]. Spent grain bio-oil does contain C5-C19 alkanes (e.g. tride-
cane), alkenes (e.g. hexene), and aromatic hydrocarbons (e.g. benzene,
toluene, xylene, and cyclooctatetraene) [184]. Due to the lower lignin
content in spent grain, the bio-oil has fewer phenolic compounds
(guaiacols, syringols, cresols, isoeugenol, etc.) compared to bio-oils
derived from agriculture wastes [183].
The high protein content in spent grain does create some dis-
advantages for pyrolysis. The pyrolytic degradation rate of spent grain
is slower than those of agriculture wastes and dedicated plants [154].
Spent grain-derived bio-oil is less stable than bio-oils from agriculture
wastes, dedicated plants, and seed cakes due to cross-linking reactions
(e.g. polymerization) between protein-derived amino/amine groups
with active O-containing groups (ketones, carboxylic acids, and alde-
hydes) [180,186]. These reactions lead to the formation of two het-
erogeneous, viscous phases, which makes downstream processing more
difficult [183,184].
Optimization of reaction conditions can mitigate some of the dis-
advantages of bio-oil derived from spent grain. Ateş et al. observed that
increased pressure decreased the bio-oil yield but increased the fatty
acid content [78]. Microwave-assisted pyrolysis improved bio-oil re-
covery (bio-oil yields of ∼51 %) and chemical composition, especially
for alkane and aromatic hydrocarbon content [187]. Studies on cata-
lytic pyrolysis of spent grains found that the presence of alumina-based
catalyst resulted in higher bio-oil yield, higher contents of olefins and
aromatics, and lower contents of heteroatoms [188–190]. Recently, a
microwave-assisted catalytic study on co-pyrolysis of spent grain and
plastic waste found a higher carbon yield of hydrocarbons in the bio-oil
with the aid of zeolite catalysts [191].
4.3. Pyrolysis of seed cakes
Seed cakes are an oily solid residue, including abundant lipids (2–20
%) [118,192,193], high protein content (12–44 %) [118,194], high
volatile matter content (70–92 %), and low ash content (1–12 %)
(Table 5). Toxicity of some seed cakes make them unusable as animal
feed, however, they have potential for improving the overall energy
efficiency of biodiesel production if they can be used for additional
renewable energy production [27]. Seed cake-derived bio-oils have an
average yield of 39 wt.% and an average energy recovery of 57 %,
lower than those of agriculture wastes, dedicated plants, and dry spent
grains (Fig. 3). The lower yield is offset by the higher quality of seed
cake-derived bio-oil with higher heating values (HHV) of 25–39 MJ/kg
and lower oxygen contents of 10.5–29 wt.% (Table 5). The high content
of fatty acid derivatives in the bio-oil contribute to the higher energy
content but can also the increase in the viscosity, which can negatively
impact the flowability and combustion performance in engines under
lower temperature conditions [195,196]. The water content and density
of seed cake bio-oil were approximately 31 % and 1040 kg/m3, re-
spectively [197]. Compared to other biomass-derived bio-oils, the sta-
bility of seed cake-derived bio-oil is higher [180], because the stable
oily components rarely oligomerize and the bio-oil viscosity remains
unchanged during storage [27]. Intermediate pH values (3.3–8.9) and
low total acid numbers (TAN, 64–96 mg of KOH/g) in seed cake-derived
bio-oil are more favorable than those from forestry wastes, dedicated

9
F. Cheng, et al.
Fig. 3. Impact of feedstock type on elemental ratio change, bio-oil yield, and energy recovery during pyrolysis (data from Table 5). Diff X/C = (X/Cbio-oil-X/
Cfeedstock)/(X/Cfeedstock)×100 %, where X = H, O, or N.
plants and agricultural wastes (pH of 2–3.2 and TAN of 124–157 mg of
KOH/g); these properties are attributed to higher contents of organic
nitrogenous compounds (4–11 wt.%) [27,198,199]. As with spent grain
bio-oils, much of the stability of seed cake bio-oils is attributed to the
absence of active oxygenated functional groups, achieved by sub-
stituting the oxygen atom on the active functional groups by the nu-
cleophilic amino groups from protein-derived molecules (Fig. 4). Car-
bonyl group-containing compounds (e.g. furfural, acetol, and
hydroxyacetaldehyde) are the most active compounds facilitating the
aging/oligomerization of bio-oils, and are rarely detected in seed cake-
derived bio-oils [186,200].
Similar to bio-oils derived from other protein-rich lignocellulosic
wastes, seed cake-derived bio-oils contain C4-C28 oily components, in-
cluding oxygenated compounds (e.g. carboxylic acids, ketones, alde-
hydes, esters, furfuryl alcohol, and phenolic compounds), hydrocarbons
(e.g. alkanes, alkenes, and alkynes), nitrogenous compounds (e.g. ni-
triles, fatty acid amides, amines, indoles, pyridines, pyrroles, piper-
idines, quinolines, pyrazines, etc.) [27,180,195,201], and S-containing
compounds (e.g. disulfide and thiophenes) [202]. Alkanes and alkenes
are produced from triglycerides through hydrolysis, decarbonylation
and decarboxylation [202]; aromatics form via Diels–Alder addition of
Fig. 4. Synergetic effect between cellulose and protein fragments during pyrolysis, adapted from [180].
10
Journal of Analytical and Applied Pyrolysis 147 (2020) 104780
carboxylic acids and conjugated dienes [203]. Among these chemical
components, seed cake-derived bio-oil contains more stable non-aro-
matic and aromatic compounds (53–77 %, mainly C15-C19 fatty acids
derivatives and phenols) [204–206], than bio-oils from forestry waste
and spent grains [27,199,207].
The main disadvantage of bio-oils derived from seed cakes is their
high N content (2–11 %) (Table 5), causing problems similar to those of
spent grain-derived bio-oils. Most of nitrogenous compounds exist in
the bio-oil in the form of amides with long alkyl chains [208]. Steam
pyrolysis can increase bio-oil yield and the concentrations of saturated
hydrocarbons (e.g. alkanes) and aromatic compounds (e.g. toluene,
methoxy toluene, psoralen) compared to traditional pyrolysis
[209,210]. Catalytic fast pyrolysis was used to produce high-purity
aliphatic and aromatic hydrocarbons (∼99 %) via dehydration, dec-
arbonylation, and decarboxylation in the presence of zeolite USY cat-
alyst [193]. In a recent study on Ru charcoal-supported catalyst [208],
seed cake-derived bio-oil was upgraded into long aliphatic hydro-
carbons with lower heteroatom contents (< 15 wt.%) and higher en-
ergy contents (37 MJ/kg) relative to traditional lignocellulosic biomass-
derived bio-oils. All catalyst candidates completely removed sulfur,
whereas no catalyst was able to effectively eliminate N from bio-oil.
F. Cheng, et al.
4.4. Pyrolysis of the organic fraction of municipal solid waste and sewage
sludge
Organic fraction of municipal solid waste (OFMSW) and sewage
sludge (SS) are generated from municipal waste sorting/recycling
plants and wastewater treatment plants, respectively. Pyrolysis is con-
sidered as a competitive thermochemical conversion for valorization of
OFMSW and SS due to evidence of: 1) stabilization of organic matter in
sludge; 2) reduction of nitrogen oxide and dioxin emissions; 3) reduc-
tion of waste volume by 50 %; and 4) transfer of heavy metals into the
biochar [211–214]. OFMSW and SS are characterized by high hetero-
geneity (containing paper, oils and fats, fecal material, plant residues,
plastics, soil, etc.) [215], relatively high content of inorganics (17–42
wt.%), lower HHV, and low levels of volatile matter (54–67 wt.%, in-
cluding proteins, lipids and polysaccharides) [216] (Table 5). On
average, bio-oil yield is lower (34.2 wt.%) and energy recovery is si-
milar (66.7 %) for pyrolysis of OFMSW and SS, compared to pyrolysis of
agriculture wastes, dedicated plants, spent grains, and seed cakes
(Fig. 3). Unlike other biomass-derived bio-oils, OFMSW and SS bio-oils
have higher pH values (8–10), owing to a greater amount of amine and
amino groups-containing compounds (from microbial biomass) [173].
The density of OFMSW and SS-derived bio-oils is lower (1.04–1.08 kg/
m3) than that of other lignocellulosic biomass-derived bio-oils [173].
Combining these properties, OFMSW and SS-derived bio-oils are ex-
pected to be less corrosive with better pumpability and flowability.
OFMSW and SS-derived bio-oil is normally a single phase, with
mostly O-, N- and S-containing compounds, a few aliphatic and aro-
matic compounds, and steroids [211,215,217]. The oxygenated com-
pounds include long-chain and phenyl carboxylic acids, alcohols, ke-
tones, furans and phenols [211,218]. Much of the N (4–5 wt.%) in the
OFMSW and SS feedstock transfers into bio-oil during pyrolysis, re-
sulting in high bio-oil N content (7–12 wt.%).
N-containing compounds include acyclic (C13‒C18 nitriles, fatty acid
amides, amines, acetamide, and carbamide), and heterocyclic species
(pyrroles, indoles, pyridine, benzimidazole, carbazole β-Carbolines, and
lactams), mostly derived from proteins and pyridine structure-con-
taining compounds [211,219,220]. The protein and pyridine structure-
containing compounds in OFMSW and SS feedstock primarily fragment
into nitrogenous gases (NH3, HCN, and minor N2) [137], and water-
insoluble N-containing compounds, which can be further cracked into
water-soluble molecules as secondary reactions under more severe
conditions [216]. S-containing compounds include sulphides and sulf-
oxides [218].
Just as with spent grain- and seed cake-derived bio-oils, high N
content in the OFMSW and SS-derived bio-oil causes environmental
problems [221]. Most attempted pretreatment methods (e.g. acids and
bases pretreatments, catalytic pyrolysis, upgrading of bio-oils, etc.) do
not improve bio-oil yields [116,221]. Sulfided NiMo/Al2O3 and CaO/
La2O3 effectively remove N and Cl, respectively, from OFMSW and SS-
derived bio-oils [116,222]. Wang et al. found a synergistic effect during
co-pyrolysis of SS and carbon-rich wheat straw, leading to higher bio-
oil yield and lower pyrolysis heat requirements [223].
4.5. Pyrolysis of digestates
Digestate, the solid residue from anaerobic digestion, is mostly de-
rived from sewage sludge (SS) after wastewater treatment. Digestate
has relatively high contents of non-biodegradable fibers (e.g. lignin),
pathogens and heavy metals. More severe conversion techniques,
therefore, are required to kill pathogens, convert energy-rich compo-
nents into bio-oil, and concentrate non-energy components into the
char fraction [224–226]. Similar to the physical and chemical proper-
ties of OFMSW and SS, digestate has more ash (18–57 wt.%) and less
oxygen (15–37 wt.%) than other feedstocks (Table 5). Digestate has
also a comparable energy content (8–19 MJ/kg) to that of the raw SS.
The average bio-oil yield and energy recovery for digestate pyrolysis
11
Journal of Analytical and Applied Pyrolysis 147 (2020) 104780
were 30.5 wt.% and 56 %, respectively, both slightly lower than that of
SS-derived bio-oil (Fig. 3). The difference in energy is attributed to the
energy converted to biogas during anaerobic digestion of SS.
Digestate-derived bio-oil has pH values of 6.8–6.9, density of
1.05–1.09 g/mL, viscosity of 2.5–3.1 cSt, and water content of 23–27
wt.% [227–229]. The single-phase bio-oil contains aliphatic and aro-
matic hydrocarbons, oxygenated compounds, nitrogenous compounds,
and minor S-containing and halogenated compounds [227,228]. The
aliphatic and aromatic hydrocarbons include C6-C26 straight chain/
branched alkanes and alkenes, benzene, alkylbenzenes (e.g. toluene),
1,3-diphenylpropane, and polycyclic aromatic compounds (e.g. naph-
thalene) [164]. The oxygenated compounds mainly include fatty acids
and esters, phenolic compounds (e.g. alkyl-phenols and benzenediols),
alcohols, ketones (e.g. cyclopentenones), aldehydes, ethers, steroids,
and cholestene derivatives [228]. The nitrogenous compounds include
pyrroles, amides with C12-C19 aliphatic chains, nitriles, amines, pyr-
idines, pyrazines, indoles, quinoline, carbazole, and lactams (e.g. pyr-
imidinones and pyrazinones) [164,228]. The aliphatic compounds are
mostly formed from decarboxylation and decarbonylation of fatty acids
[230]. Aromatic compounds are produced from Diels–Alder reactions
and dehydrogenation of unsaturated compounds [227]. Phenolic com-
pounds are produced from devolatilization of carbohydrates and pro-
teins, and incomplete hydrolysis of lignin [231]. Pyrroles, nitriles, and
pyridines/pyrazines form via cyclization of amides, dehydrogenation of
amines, and decomposition of heterocyclic nucleic and amino acids,
respectively, under more severe conditions [228,232,233].
Use of digestate-derived bio-oils is inhibited by higher NOx emis-
sions, more carcinogenic nitrogenous aromatic compounds, and low
bio-oil yields due to the high contents of N and ash [130]. Acid pre-
treatments (e.g. acid-infusion and acid-washing), catalytic pyrolysis,
and high-pressure pyrolysis can enhance the removal of N, O, and ash
from digestate-derived bio-oils for the production of hydrocarbon-rich
biofuels and value-added chemicals [234,235].
4.6. Pyrolysis of forestry waste
Forestry waste has two drivers for utilization [102]: it is a potential
fire hazard [105], and it has carbon-rich lignocellulosic component
content and low ash content (0.3–4 wt.%, Table 5). Relatively low
feedstock HHV (15.4–20.7 MJ/kg), low cellulose content [122,178],
high lignin content (20–30 wt.%), and high water content in bio-oil
(25–30 wt.%) [103], render the average bio-oil yield (35.1 wt.%) and
energy recovery (37.2 %) from pyrolysis waste lower than those of most
other protein- and lignin-rich biomass wastes (Table 5).
Forestry waste-derived bio-oil is highly heterogeneous (normally
separating into a viscous oily phase and a polar liquid phase) [103],
with a viscosity of 11–15 cSt [102,103]. The bio-oils contain a sub-
stantial fraction of oxygenated compounds, minor nitrogenous com-
pounds (like pyridine and alkyl-oxazolidines), aliphatic, aromatic and
polycyclic aromatic hydrocarbons (e.g. alkenes, sesquiterpene, ben-
zenes, naphthalene), and no S-containing compounds [102,175,236].
The oxygenated compounds mainly consist of phenolic compounds (e.g.
guaiacyl and syringyl compounds), carboxylic acids (e.g. acetic acid),
ketones (e.g. hydroxyl-propanone), aldehydes (e.g. hydroxyl-acet-
aldehyde), anhydrosugars (e.g. levoglucosan), esters (e.g. triglycerides),
furans, pyrans, and trace amounts of ethers and alcohols (e.g. sterol)
[99,102,237]. Compared to the N distribution in pyrolysis of other
lignocellulosic wastes, most of N from forestry waste fractionates into
gaseous NH3 and HCN [138], leading to lower content of N (0.1–2.6 wt.
%,) in forestry bio-oil (Table 5). The lower N content and higher car-
boxylic acid content give forestry waste-derived bio-oil a much lower
pH (2.1–3.3) [238] than bio-oil from spent grain, seed cakes, OFMSW
and SS, and digestates [239]. This low pH creates corrosion challenges
for reactor design. Carboxylic acids, alcohols, water, hydroxy ketones,
and furfur-aldehyde are produced from degradation of hemicellulose
[240]. Acetic acid specifically is generated via removal of acetyl groups
F. Cheng, et al. Journal of Analytical and Applied Pyrolysis 147 (2020) 104780

from hemicellulose-derived glucuronoxylan; water is produced from Energy recovery= YieldBio ×

HHVBio oil
× 100%
oil
dehydration of the polysaccharides [99]. Hydroxyl-acetaldehyde and HHVFeedstock
levoglucosan form during cellulose degradation; 1,4:3,6-di-anhydro-α-
where X is H, O, or N; X/CBio-oil is the ratio in the bio-oil; and X/
D-glucopyranose is obtained from further levoglucosan dehydration
CFeedstock is the ratio in the feedstock. YieldBio-oil is the bio-oil yield on
[99,178]. Most of the methoxy phenols (e.g. vanillin, isoeugenol, and
dry basis (d.b.). HHVBio-oil and HHVFeedstock are the higher heating va-
guaiacol) and minor catechols (e.g. hydroquinone and methyl-benze-
lues (d.b.) of the bio-oil and feedstock, respectively. If the value of X/
nediol) are derived from lignin [99]. The K and Ca (400–1000 mg/kg)
CChange is positive, that element (X) is concentrated in bio-oil. If X/
in forestry waste [103] can facilitate the decarbonylation of lignin and
CChange is negative, that X element fractionates into the other pyrolysis
the dehydration of cellulose and hemicellulose, resulting in higher char
products.
yield, and higher selectivity towards phenols and catechols in bio-oils
Changes of H/C ratio (black bar) are weakly correlated with feed-
[99].
stock type, while O/C ratio changes (green bar) are negative across
The high content of active functional groups in forestry waste-de-
most of the range of feedstock types, indicating that O atoms were in-
rived bio-oil, particularly holocellulose-derived carbonyl and carboxyl
hibited from entering the oily phase during pyrolysis (Fig. 3). Changes
groups and lignin-derived phenolic intermediates, promote poly-
of N/C ratio (blue bar) vary by feedstock type: most of the N/C ratio
merization reactions [241], leading to much higher-molecular-weight
changes for the pyrolysis of agriculture wastes and dedicated plants are
bio-oils relative to SS- and seed cake-derived bio-oils [242]. These
positive, while all of the N/C ratio changes are negative for pyrolysis of
oxygenated functional groups are detrimental to bio-oil quality, redu-
seed cakes.
cing HHV, increasing corrosiveness, accelerating aging, reducing
In Fig. 3, average bio-oil yields (yellow and red dots) of agriculture
thermal stability, and declining miscibility with petroleum-derived
wastes, dedicated plants, spent grains, seed cakes, digestates, and
fuels [27,243]. Numerous strategies, including pretreatment, micro-
OFMSW and SS are higher than those of forestry waste and food waste
wave-assisted pyrolysis, co-pyrolysis, and catalytic upgrading of bio-oil
(31–46 wt.% vs. 23–34 wt.%, respectively); average energy recovery
have been used to eliminate active carbonyl groups, reduce phenolic
shows a similar trend (purple dashed lines, 56–67 % vs. 27–35 %). If
compounds (coke precursors), remove heteroatoms and ash, and in-
energy recovery is determined only on a bio-oil basis, energy recovery
crease hydrocarbon concentration [30,236,237,244,245]. The compli-
averages are higher for pyrolysis of OFMSW, SS and digestate, in-
cated structures of forestry waste-derived bio-oil limit the ability of
dicating that energy-rich components were more effectively extracted
noble metal catalysts to deoxygenate the bio-oil, relative to their per-
from OFMSW, SS and digestate to form bio-oil, compared to the pyr-
formance for upgrading of agricultural waste-derived bio-oil [245].
olysis of other protein- and lignin-rich biomass wastes. Based on energy
efficiency, bio-oil stability, bio-oil composition and ease of upgrading,
4.7. Pyrolysis of food waste the most appropriate feedstocks for pyrolysis are agricultural wastes,
dedicated plants, seed cakes, digestate, OFMSW and SS.
Compared to pyrolysis of other protein-rich lignocellulosic wastes,
pyrolysis of food waste has rarely been studied for bioenergy produc-
5. Challenges and perspectives
tion because: 1) the components of food waste vary greatly with loca-
tion, season, and collection method; 2) high contents of protein and
Protein helps to deoxygenate bio-oil compounds by replacing the
water are not favorable for bio-oil properties; and 3) other value-added
active functional groups, particularly carbonyl groups, during pyrolysis.
components can be extracted from food waste using lower-cost tech-
However, protein- and lignin-rich biomass wastes face problems caused
niques under milder conditions [246,247].
by incorporation of protein-derived N into the bio-oil and under-de-
Özbay et al. found that pyrolysis of apricot pulp gave an optimal
composition of lignin.
bio-oil yield of 22 wt.% [112]; pyrolysis of potato skin gave a bio-oil
N-rich bio-oil has undesirable properties in terms of combustion:
yield of 25 wt.% [110]. Due to the high HHV of the food wastes (18–35
greater NOx emissions, inferior atomization, and lower calorific values
MJ/kg) and low HHV of their bio-oils (27–32 MJ/kg), the energy re-
[248]. Thus, upgrading is needed to remove N and improve these
coveries in both cases were below 32 % (Table 5). Food waste-derived
combustion properties. Catalytic pyrolysis is the most common method
bio-oil is comprised of oxygenated compounds (e.g. carboxylic acids,
to denitrogenate bio-oil using different types of catalysts, including
aldehydes, ketones, alcohols, and phenolic compounds), some ni-
zeolites and noble metals [249]. Zeolite H-ZSM-5, which is effective at
trogenous compounds (e.g. C16‒C19 nitriles and amides), and minor
reducing O content in bio-oil, seldom eliminates N from bio-oil [250],
C11–C28 aliphatic, aromatic, and polycyclic aromatic hydrocarbons
due to the higher stability of N-containing cyclic compounds relative to
[110,112,138]. Steam pyrolysis has been studied as an effective method
O- and S-containing compounds [251–253]. Nitrogenous compounds
to increase bio-oil yield, inhibit secondary cracking reactions, reduce
also lead to coke formation on catalyst active sites [254]. Zeolite cat-
char yield, and increase the concentration of aliphatic hydrocarbons in
alysts, into which external metal (e.g. Li) were introduced, enhance N
food waste-derived bio-oil relative to conventional pyrolysis under an
removal [255]. Novel catalyst synthesis procedures (e.g. microwave-
N2 atmosphere [110]. Co-catalytic pyrolysis of food waste and agri-
assisted) [256,257] for these catalysts lead to final bio-oil N content
culture waste using ZSM-5 zeolite increased aromatics content and the
below 1 wt.%, and favor aromatics and olefins [255,257]. Hydrotalcite
effective hydrogen index of the bio-oil due to the synergetic effects
and Ce-based alumina catalysts have also been studied for eliminating
between the two feedstocks [31].
nitrogenous compounds [258,259]. To improve the economic feasi-
bility of bio-oil catalytic upgrading, researchers have looked to a variety
4.8. Comparison of inexpensive industrial wastes (e.g. lime mud and fly ash) as catalysts
with some success [260–262]. Nitrogenous compound content in Pon-
Pyrolysis performance among different types of protein-rich lig- gamia waste-derived bio-oil was decreased to nearly 0 wt.% with fly ash
nocellulosic wastes can be compared using changes to elemental ratios introduced into zeolite X catalyst [260]. Denitrogenation of bio-oil is
(H/C, O/C and N/C), bio-oil yield, and energy recovery (Fig. 3). Change affected by other factors beyond catalyst type, including catalyst
of elemental ratio and energy recovery are defined using the following amount, particle size, acidity, pore structure, operating temperature,
equations, respectively. and reaction atmosphere. Bio-oil N removal is favored by higher
amounts of catalyst with smaller particle size, higher temperature, and
X/CBio oil X/CFeedstock
X/CChange = × 100% methane as reaction gas [193,255,262–264].
X/CFeedstock
Fig. 5 shows a general denitrogenation pathway for the diverse

12
F. Cheng, et al.
Fig. 5. Proposed catalytic denitrogenation pathway for bio-oil produced from pyrolysis of N-rich biomass, adapted from [266,267,269].
acyclic and cyclic N-containing compounds based on previous studies of
possible mechanisms for catalytic pyrolysis of protein- and lignin-rich
biomass, and N-rich model compounds. Specifically, acyclic amines
were denitrogenated into hydrocarbons via disproportionation and
deamination over Ni-based catalysts [265]. Some amines and nitriles
may be prone to form N-cyclic compounds, as dehydrogenation, de-
hydration, deamination, and aromatization occurred under hydrogen
radical participation [264,266]. Other nitriles are denitrogenated into
hydrocarbons via scissoring CeC bonds and forming hydrogen cyanide;
acyclic amino acids are less likely to form coke via polymerization and
dehydration relative to cyclic amino acids [267,268]. Cyclic com-
pounds, such as aromatic amines, indole, quinoline and pyrrole deri-
vatives, are converted into aromatic hydrocarbons through hydrogen
radical-assisted ring opening and deamination over Ni-based zeolite
catalyst with high acidity [266,267,269], or hydrogenated into alicyclic
compounds over the sulfided Mo-based alumina catalysts [270]. Addi-
tion of transition metals (e.g. Ni and Co) into the catalyst further de-
nitrogenates different types of N-containing intermediate species into
olefins and hydrogen cyanide/ammonia over catalyst acid sites
[266,267]. Aromatic hydrocarbons are generated through both cycli-
zation and aromatization (e.g. Diels-Alder reaction and dehydrogena-
tion) of olefins, whereas over-reaction may cause formation of poly-
aromatic hydrocarbons via polymerization [267].
Introducing additives for co-pyrolysis, feedstock pretreatment, and
bio-oil post-treatment have significant influences on bio-oil deni-
trogenation. Pyrolysis biochar was observed to effectively transfer ni-
trogenous compounds from bio-oil and gaseous phases into the solid
phase due to condensation/cyclization reactions between N-containing
compounds and O-containing functional groups (e.g. ester, hydroxyl,
and carboxyl groups) on the biochar surface, leading to higher quality
of bio-oil and less emission of nitrogenous gases [271]. Hydrogen-rich
industrial wastes have been found to eliminate N by hydrogen supplied
from the mid-chain β-scission in the wastes, thereby increasing energy
content in the bio-oils [272,273]. Hydrothermal carbonization as a
feedstock pretreatment helps transfer nitrogenous compounds from the
feedstock into the aqueous phase, resulting in a dramatic reduction
(from 11 % to 0.2 %) of N-containing compounds, in particular nitriles,
in bio-oil during catalytic pyrolysis compared to the untreated feed-
stock [274]. Acid-infused pretreatment was found to promote N re-
moval from bio-oil in the form of gaseous ammonia, which can po-
tentially be recycled as fertilizer or other N-containing chemical
precursors [234]. Catalytic upgrading under a high-pressure reducing
atmosphere has been the most frequently studied post-treatment. Both
13
Journal of Analytical and Applied Pyrolysis 147 (2020) 104780
noble metal-based catalysts and zeolites were observed to remove N
with low efficiency, while those same catalysts were more effective at
removing O, which may be attributed to the higher stability of ni-
trogenous compounds, as well as catalyst deactivation caused by re-
polymerization of nitrogen-containing oily compounds [275,276].
New strategies are needed and have been attempted to further im-
prove denitrogenation. Table 6 summarizes N content reduction in
during catalytic upgrading, showing that N can be more completely
removed when bio-oil is mixed with carbon- and hydrogen-rich model
fuels, relative to reactions without introducing such additives. A non-
polar solvent, xylene, was incorporated into catalytic upgrading of bio-
oil, leading to complete N removal from bio-oil through hydrogenation,
cleavage of CeN bonds within nitro-cyclic compounds, and subsequent
deamination [277]. A two-stage catalytic upgrading process was used to
reduce bio-oil N content to < 50 ppm over sulfided CoMo/γ-Al2O3
catalyst, producing > 70 vol.% aliphatic and aromatic hydrocarbons in
the upgraded fuel [278]. Ionic liquids (ILs) have also been used to re-
move almost half of the N in bio-oil by simple mixing [279].
In addition to thermochemical methods, physiochemical methods
have been investigated to denitrogenate bio-oil using acid-treated
carbon adsorbents with desired functional groups, which have high
affinity for N -containing compounds [280]. Nitro-cyclic compounds
are selectively bound to the adsorbent through the interaction between
the electron charges donated from π complexation of nitrogenous
compounds and the vacant s-orbital in the adsorbent, as well as the
interaction between the antibonding π orbital of nitrogenous com-
pounds and the electron charges back-donated from the D-orbitals of
metals in the adsorbent [281]. Adsorption performance is impacted by
the acidity/basicity of the adsorbent, and can be tuned through grafting
of specific functional groups onto the adsorbent surface [282].
Pretreatments that soften/split rigid structures of recalcitrant com-
ponents in the feedstock should be considered. Under-utilization of
lignin during pyrolysis results in generally low bio-oil yields regardless
of feedstock, driving ongoing research in the field of lignin degradation
into valuable chemicals [283–285]. Rahimi et al. found that formic acid
can lower the reaction barrier and accelerate lignin hydrolysis under a
redox-neutral condition without consuming the formic acid; they ob-
served an dramatic increase in monoaromatic yield from 11.6 %–61.3
% [284]. Shuai et al. observed that formaldehyde can effectively miti-
gate repolymerization of lignin through formation of 1,3-dioxane
structures between formaldehyde and hydroxyl groups in lignin side-
chains, and through masking reactive positions on benzene rings (an-
ions); using this method, the lignin monomer yield significantly
F. Cheng, et al. Journal of Analytical and Applied Pyrolysis 147 (2020) 104780

increased from 47 % to 78 % [285].

N Content Reduction (%)

6. Conclusions

Agricultural wastes, dedicated plants, spent grains, and OFMSW and

> 99.72
SS are more favorable for pyrolysis and have higher bio-oil yield than
97.81

99.76
69.07

69.76

99.73

80.36

26.92
10.77
27.27
the other feedstocks considered. Seed cake-, digestate-, and OFMSW
100

100
100

100
and SS-derived bio-oils possess better properties, including higher
content of fatty acid-like molecules, fewer active oxygenated functional
N Content of Upgraded Oil (of Parent Oil)

Model diesel oil A consisted of hexadecane (70 wt.%), tetralin (30 wt.%), and S-containing compounds (2500 ppm; 95 % dibenzothiophene and 5 % 4,6-dimethyldibenzothiophene).
groups, and more neutral pH values. Substantial condensation of light
molecules does occur in spent grains-derived bio-oil during storage.
Considering the negative effects of protein and lignin on the decom-
position of bio-oil, novel techniques and strategies, such as acid/base
< 50 ppm (1.76 wt.%) pretreatment and catalytic upgrading, are needed to improve the yield
1.80 wt.% (5.82 wt.%)

1.76 wt.% (5.82 wt.%)

0.11 wt.% (0.56 wt.%)

wt.%)
wt.%)
wt.%)
wt.%)
and quality of bio-oil.
49ppm (1.80 wt.%)
57ppm (2600 ppm)

0ppm (2600 ppm)

0ppm (2450 ppm)

0ppm (2450 ppm)
6ppm (2450 ppm)

(0.50
(2.86
(3.62
(1.10
Declaration of Competing Interest
(wt.%/ppm)

wt.%
wt.%
wt.%
wt.% The authors declare that they have no known competing financial
0.00
2.09
3.23
0.80
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
350 °C, 7 MPa H2, 1.5 h−1 WHSV, Fixed-bed
400 °C, 2 h, 7 MPa H2, Slurry bed, Distillate

400 °C, 2 h, 7 MPa H2, Slurry bed, Distillate

Fixed-bed
Fixed-bed
Fixed-bed
Fixed-bed

Acknowledgement
350 °C, 5 h, 7 MPa H2, Fixed-bed
350 °C, 5 h, 7 MPa H2, Fixed-bed

LHSV,
LHSV,
LHSV,
LHSV,
500 °C, 45 min, 250 mL/min N2

Funding was received from the U.S. Department of Agriculture

330 °C, 3 h, 5 MPa H2, Batch

330 °C, 3 h, 5 MPa H2, Batch

330 °C, 3 h, 5 MPa H2, Batch

330 °C, 3 h, 5 MPa H2, Batch

h−1
h−1
h−1
h−1

“Sustainable Bioeconomy for Arid Regions (SBAR)” grant (#2017-

68005-2686).
10
10
10
10
H2,
H2,
H2,
H2,

Appendix A. Supplementary data

MPa
MPa
MPa
MPa
at 240-360 °C
at < 240 °C
Conditions

2
2
2
2

Supplementary material related to this article can be found, in the

°C,
°C,
°C,
°C,
Denitrogenation of bio-oil by catalytic upgrading using different catalysts and under different operating conditions.

350
350
350
350

online version, at doi:https://doi.org/10.1016/j.jaap.2020.104780.

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