Renewable and Sustainable Energy Reviews 57 (2016) 1126–1140

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Renewable and Sustainable Energy Reviews

journal homepage: www.elsevier.com/locate/rser

Lignocellulosic biomass pyrolysis: A review of product properties

and effects of pyrolysis parameters
Tao Kan n, Vladimir Strezov, Tim J. Evans
Department of Environmental Sciences, Faculty of Science and Engineering, Macquarie University, Sydney, NSW 2109, Australia

art ic l e i nf o a b s t r a c t

Article history: Pyrolysis is one of the thermochemical technologies for converting biomass into energy and chemical
Received 4 February 2015 products consisting of liquid bio-oil, solid biochar, and pyrolytic gas. Depending on the heating rate and
Received in revised form residence time, biomass pyrolysis can be divided into three main categories slow (conventional), fast and
23 September 2015
flash pyrolysis mainly aiming at maximising either the bio-oil or biochar yields. Synthesis gas or
Accepted 17 December 2015
Available online 8 January 2016
hydrogen-rich gas can also be the target of biomass pyrolysis. Maximised gas rates can be achieved
through the catalytic pyrolysis process, which is now increasingly being developed. Biomass pyrolysis
Keywords: generally follows a three-step mechanism comprising of dehydration, primary and secondary reactions.
Biomass pyrolysis Dehydrogenation, depolymerisation, and fragmentation are the main competitive reactions during the
Mechanism
primary decomposition of biomass. A number of parameters affect the biomass pyrolysis process, yields
Bio-oil
and properties of products. These include the biomass type, biomass pretreatment (physical, chemical,
Biochar
Pretreatment and biological), reaction atmosphere, temperature, heating rate and vapour residence time. This
Pyrolysis parameters manuscript gives a general summary of the properties of the pyrolytic products and their analysis
methods. Also provided are a review of the parameters that affect biomass pyrolysis and a summary of
the state of industrial pyrolysis technologies.
& 2016 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1127
2. Pyrolysis mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1127
3. Properties and applications of products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1127
3.1. Bio-oil. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1127
3.2. Biochar . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1128
3.3. Pyrolytic gas. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1130
3.4. Analysis of pyrolysis products. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1132
4. Parameters influencing biomass pyrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1132
4.1. Biomass type . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1132
4.2. Biomass pretreatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1132
4.2.1. Physical pretreatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1132
4.2.2. Thermal pretreatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1133
4.2.3. Chemical pretreatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1133
4.2.4. Biological pretreatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1134
4.3. Effects of reaction conditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1134
4.3.1. Reaction atmosphere . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1134
4.3.2. Temperature. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1134
4.3.3. Heating rate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1134
4.3.4. Vapour residence time. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1134

n
Corresponding author. Tel.: þ 61 2 9850 7950.
E-mail address: tao.kan@mq.edu.au (T. Kan).

http://dx.doi.org/10.1016/j.rser.2015.12.185
1364-0321/& 2016 Elsevier Ltd. All rights reserved.
 T. Kan et al. / Renewable and Sustainable Energy Reviews 57 (2016) 1126–1140
5. Biomass pyrolysis reactors and state-of-arts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1135
6. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1135
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1136
1. Introduction
With the rapid increase in global energy demand and increas-
ing environmental and sustainability challenges, biomass fuels as
renewable energy sources have increasingly been considered as a
key option to substitute conventional fossil fuels. Currently, bio-
mass and waste contribute to around 10% of the global energy
supply [1]. The full estimated potential of annual biomass avail-
ability is predicted to be as high as 1.08  1011 toe (tons of oil
equivalent), which is almost 10 times the world's current energy
need [2,3]. The abundant biomass reserves, its renewability, CO2
neutrality, and technical grafting from coal industries have been
the main driving forces for research and utilisation of biomass.
Thermochemical technologies for converting biomass into
energy or chemicals mainly consist of combustion, pyrolysis,
gasification, and high-pressure liquefaction [4]. Biomass pyrolysis
with a long history of use, initially for the production of charcoal
(biochar), has emerged as a frontier research domain. Biomass
pyrolysis is generally defined as the thermal decomposition of the
biomass organic matrix in non-oxidising atmospheres resulting in
liquid bio-oil, solid biochar, and non-condensable gas products.
Depending on the heating rate and solid residence time, bio-
mass pyrolysis can be divided into three main types including slow
(conventional) pyrolysis, fast pyrolysis and flash pyrolysis [5,6].
Some other pyrolysis processes may also be conducted between
these typical pyrolysis types [7]. Slow pyrolysis, termed carboni-
sation, has been conventionally applied for the production of
charcoal. Due to the long residence time (lasting hours to days),
relatively low temperature (  300–700 °C), and the acceptance of
a wide range of particle sizes (5–50 mm) [8], the thermal
decomposition of biomass (mostly lignocellulosic types) proceeds
under a very low heating rate with sufficient time allowed for
repolymerisation reactions to maximise the solid yields. Fast pyr-
olysis typically involves high heating rates (4 10–200 °C/s) and
short residence times (0.5–10 s, typically o2 s) [8]. Bio-oil yield
(dry biomass basis) can be as high as 50–70 wt%. The flash pyr-
olysis process is characterised by higher heating rates of 103–
104 °C/s and shorter residence times (o 0.5 s), resulting in very
high bio-oil yields which can achieve up to 75–80 wt% [9–11].
The future of research on biomass pyrolysis toward achieve-
ment of high energy efficiencies and tailoring the conditions to
produce the desired product types takes into consideration the
experience and knowledge of the influences of pyrolysis para-
meters on the process performance, including reaction rate, pro-
duct selectivities and yields, product properties and energy effi-
ciency [12]. The pyrolysis parameters for consideration involve
feedstock type selection (biomass type, particle size, biomass
pretreatment), reaction conditions (pyrolysis temperature, pres-
sure, particle heating rate, residence time), reactor configurations
and processes, and miscellaneous variables, such as the addition of
catalysts and vapour condensation mechanisms [13]. This paper
aims to review the properties and applications of pyrolysis pro-
ducts, as well as the effects of pyrolysis parameters on biomass
pyrolysis product yields and properties.
1127
2. Pyrolysis mechanism
The complexity of biomass pyrolysis arises from the difference
in decomposition of the biomass components with varying reac-
tion mechanisms and reaction rates which also partly depend on
the thermal processing conditions and reactor designs. Interac-
tions between the major constituents of the woody biomass, such
as the cellulose, hemicelluloses, and lignin, during pyrolysis have
been confirmed previously [14], which makes prediction of bio-
mass pyrolysis characteristics simply based on the thermal beha-
viour of the three individual components very difficult. For
example, the interaction between hemicellulose and lignin pro-
motes production of lignin-derived phenols while hinders the
generation of hydrocarbons [15]. Lignin also significantly interacts
with cellulose during pyrolysis as lignin hinders the polymerisa-
tion of levoglucosan from cellulose thus reducing biochar forma-
tion, while the cellulose-hemicellulose interaction has a lower
effect on the formation and distribution of pyrolysis products [16].
During biomass pyrolysis, a large number of reactions take
place in parallel and series, including dehydration, depolymerisa-
tion, isomerization, aromatisation, decarboxylation, and charring
[12,17,18]. It is generally accepted that the pyrolysis of biomass
consists of three main stages: (i) initial evaporation of free
moisture, (ii) primary decomposition followed by (iii) secondary
reactions (oil cracking and repolymerisation) [19]. These stages are
intermingled, with a possibility to observe their transitional
behaviour through thermal analysis. The apparent specific heat of
biomass during pyrolysis and the corresponding heats of reactions
during different pyrolysis stages have been extensively studied in
the past using computer-aided thermal analysis (CATA) under
different heating rates [20–26].
Biomass decomposition generally occurs during the primary
decomposition to form solid char at 200–400 °C, which is
responsible for the largest degradation of biomass [27]. The sec-
ondary reactions proceed to take place within the solid matrix
with further rising of the temperature [27].
The degradation pathways of the main biomass components have
been investigated separately. Decomposition of hemicellulose, gen-
erally represented by xylan, mainly takes place between 250 and
350 °C, followed by cellulose decomposition, which primarily occurs
between 325 and 400 °C with levoglucosan as the main pyrolysis
product [28,29]. Lignin is the most stable component which
decomposes at higher temperature range of 300–550 °C [30].
Among the three major biomass constituents of cellulose, hemi-
celluloses, and lignin, the decomposition of cellulose has been most
widely analysed and best comprehended [31]. Fig. 1 illustrates the
simplified reaction pathway of cellulose pyrolysis, which is the gen-
erally accepted Waterloo-mechanism [32]. Dehydrogenation, depo-
lymerisation and fragmentation are the main competitive reactions
dominant at different temperature ranges.
3. Properties and applications of products
3.1. Bio-oil
When bio-oil production is the primary product of interest,
fast or flash pyrolysis are the conditions of choice to maximise the
1128 T. Kan et al. / Renewable and Sustainable Energy Reviews 57 (2016) 1126–1140
k Char, water, CO ,
Dehydration CO, etc.
(dominant at T< 250°C and slow heating
rates)
Anhydrosugars
k
(levoglucosan, etc.)
Cellulose
k
Active cellulose
Low degree of
polymerisation k heavy fuel oil, including moisture content (15–30 wt% vs. 0.1 wt%),
Carbonyls, acids,
alcohols, etc.
Fig. 1. Waterloo-mechanism of primary decomposition of cellulose [31].
bio-oil yields. The essential principles of fast pyrolysis generally
involve moderate pyrolysis temperature (450–650 °C), biomass
particle sizes of less than 2 mm, very high heating rates (103–
105 °C/s), very short vapour residence time (o 2 s), and rapid
quenching of pyrolytic vapours to suppress secondary reactions
[5,33–35]. Fast removal of primary char is a general requirement as
it acts as a catalyst for cracking primary organic vapours to form
secondary char, gas, and water, leading to lower bio-oil yields [35].
The fast pyrolysis process typically results in bio-oil, gas, and char
yields of 60–70 wt%, 13–25 wt%, and 12–15 wt%, based on dry
biomass feed weight [36]. Flash pyrolysis requires typical feed
particle sizes of not more than 200 mm and higher temperatures of
around 800–1000 °C, giving a typical bio-oil yield of 75 wt%, and
gas and char yields of 12–13 wt% [5,10].
Bio-oil is also referred to as pyrolysis oil, pyrolysis liquid, pyr-
olysis tar, bio-crude, wood liquid, wood oil or wood distillate
[7,37]. It is a dark brown, free flowing organic liquid mixture,
which generally comprises of a great amount of water (usually 15–
35 wt%) and hundreds of organic compounds, such as acids,
alcohols, ketones, aldehydes, phenols, ethers, esters, sugars, fur-
ans, alkenes, nitrogen compounds and miscellaneous oxygenates
[38], as well as solid particles [39]. The final water content of the
bio-oils depends on the initial moisture content of the feedstock
and water formation during pyrolysis relating to the reaction
parameters. It is very hard to achieve chemically accurate identi-
fication of some individual components in the bio-oils due to the
existence of pyrolytic lignins with molecular weights as high as
5000 amu or even more [40].
The higher heating value (HHV) of the bio-oils typically ranges
between 15 and 20 MJ/kg which is only 40–50% of the conven-
tional petroleum fuels' HHV (42–45 MJ/kg) [41]. This is due to the
considerable oxygen content which is in the extent of 35-40 wt%
on dry basis weight. The HHV of the bio-oils can be approximately
calculated from elemental analysis by the following empirical
correlation:


HHV MJ=kg ¼ 0:3491  C þ 1:1783  H þ 0:1005  S – 0:1034
 O – 0:0151  N – 0:0211  A
[42],
or simplified as:



HHV MJ=kg ¼ ð338:2  C þ 1442:8  H–O=8 Þ  0:001
[43]
where C, H, S, O, and N are the weight percent of carbon,
hydrogen, sulphur, oxygen, and nitrogen, and A is weight percent
of ash.
The lower heating value (LHV) can be calculated by the pro-
posed equation:
LHV ðkJ=kgÞ ¼ HHV  218:3  H%ðwt%Þ
[44].
Apart from the high oxygen content, the other undesirable
characteristics of the pyrolysis bio-oils are low pH value of 2–3.7
due to the presence of the carboxylic acids. Hence bio-oils are
potentially corrosive to common structures, high instability during
storage due to the ongoing chemical reactions to form larger
molecules (mainly polymerisation, etherification and esterifica-
tion) [45], and solids retention with a proportion of 0.01–1 wt% of
the bio-oils [46]. The detailed comparisons between bio-oil and
specific gravity (1.2 vs. 0.94), elemental composition, and some
other fuel indexes, such as pour point (  33 °C vs.  18 °C), were
presented by Mohan et al. [7]
Bio-oils were extensively tested as candidate combustion fuels
for electricity and heat production in boilers, furnaces, and com-
bustors [47,48], diesel engines [49,50], and gas turbines [51,52].
Bio-oils were successfully fired in a diesel test engine with limited
operation time, whereas long-term operation is not possible due
to the poor quality of the bio-oils, such as poor volatility, high
viscosity, high corrosiveness and coking [35].
It is generally accepted that further upgrading of the bio-oils is
needed prior to their practical application in engines [46,53,54].
Production of transportation liquid fuels from bio-oils has been
demonstrated after upgrading through catalytic cracking tech-
nologies [55–59] and high-pressure hydroprocessing [60–66].
Combustible syngas and hydrogen can be produced through steam
reforming and gasification [67–80]. Butler et al. [81] and Xiu et al.
[82] provided comprehensive reviews of bio-oil upgrading
through steam reforming and gasification. In addition, bio-oils can
be used as a feedstock for production of chemicals, such as phenols
for resin production, additives in fertilising and pharmaceutical
industries, flavouring agents (such as glycolaldehyde) in food
industries and other special chemicals [53,83].
3.2. Biochar
Biochar (also called charcoal) is the major solid product, which
contains unconverted organic solids and carbonaceous residues
produced from the partial or complete decomposition of biomass
components, as well as a mineral fraction. The physical, chemical,
and mechanical properties of chars depend on the feedstock type
and pyrolysis operating conditions. Slow pyrolysis (typical product
yields: bio-oil 30 wt%, biochar 35 wt%, and gas 35 wt%) at pyrolysis
temperatures ranging from 300 to 800 °C favours the production
of biochar by reducing the yields of bio-oil. Demirbas [84,85]
summarised the elemental composition (carbon content ranging
from 53% to 96%), HHVs (20–36 MJ/kg), and yields (30–90 wt%) of
biochars from pyrolysis of several biomass feedstock, and pyrolysis
at different heating rates and temperatures. The high HHV makes
chars attractive in some fuel applications as substitutes for coal.
The microscopic surface structure of biochars formed during
pyrolysis endows their potential for filtration and adsorption of
organic and inorganic pollutants [85,86], especially after the chars
are physically or chemically activated. The optimal biochar prop-
erties for filtration purposes (surface area of 1400 m2/g and
micropore volume of 0.7 cm3/g) was obtained from coconut shells
with a particle diameter of 1.55 mm, reaction temperature of
850 °C and a retention time of 1.5 h under steam using a fluidised
bed reactor [87]. A biochar with similar properties (surface area of
1690 m2/g and micropore volume of 0.7 cm3/g) was achieved by
pyrolysing olive seed waste in a fixed bed heated under N2 at
800 °C for 1 h and activating the produced biochar with KOH [88].
More details about the activation conditions (reaction atmosphere,
temperature and retention time) and characteristics (BET surface
area, micropore volume and ratio of micropore volume to total
pore volume) of different activated biochars have been given by
Manyà [89].
Table 1
Nutrient concentration of biochars produced from different lignocellulosic biomass.

Feedstock Reaction conditions Biochar yield Total concentration of nutrient elements (mg/kg) Ref.
(wt%)
Macronutrients Micronutrients

T. Kan et al. / Renewable and Sustainable Energy Reviews 57 (2016) 1126–1140

Pyrolysis T Heating rate (°C/min) or residence time (s) N P K Ca Mg S Na Mn Cu Fe Se Mo Zn
(°C)

Switchgrass (Panicum virgatum 525 Residence time of 90 s / / 815 3622 4055 2504 498 498 / / / / / / [92]
L.)
Switchgrass 450 Residence time of 30 s 31.3 12800 1963 11309 10439 9637 1257 248 246 14 457 4.4 2.3 102 [93]
600 16.9 11300 2400 16452 14611 11802 1338 208 341 46 797 5.6 5.7 115
800 11.4 8600 4046 16734 17513 15022 1917 220 374 61 633 5.1 6.0 155
Pine wood 450 Residence time of 30 s 26.6 2300 162 1684 2318 730 153 56 195 ND 202 3.8 0.5 49
600 15.2 2300 281 2889 4158 1281 214 104 324 6 167 7.2 1.9 71
800 9.5 2600 439 4237 4915 1952 270 129 488 18 164 5.7 4.6 445
Wheat straw 300 7–10 °C/min heating rate and 20 min resi- 48a 13800 2600 30000 6300 4500 / / 106 / 158 / / 47 [94]
400 dence time at peak temperature 38a 9400 3000 32000 8300 5600 / / 117 / 259 / / 59
500 33a 8500 3400 36000 8700 6900 / / 163 / 422 / / 70
Rice straw 300 45 a 11500 1100 36000 9100 8100 / / 396 / 195 / / 67
400 36 a 9800 1300 41000 9800 9600 / / 554 / 341 / / 89
500 32 a 8500 1400 48000 13300 11300 / / 649 / 521 / / 98
Miscanthus (Miscanthus x 700 / / 3400 820 18330 / 1520 340 / / / / / / [95]
giganteus) straw
Willow wood (Salix sp.) 450 / / 9100 1560 5180 / 1830 160 / / / / / /
Switchgrass b 500 Fast pyrolysis in a fluidised bed / / 9202 27184 14235 6367 2100 284 495 / 4469 / / / [96]
Corn stover b 500 Fast pyrolysis in a fluidised bed / / 2582 16620 13490 7553 600 737 390 / 10009 / / /
Hardwood b 500 15 °C/min to 500 °C / / 121 1557 22210 502 500 62 697 / 3533 / / /
Corn stover 500 Fast pyrolysis in a fluidised bed 17.0 14700 12940 23460 20130 14240 1070 650 / 15950 / / / [97]
Birch (Betula pendula) wood 450 For 4 h 28.7 / 225 750 / 300 19 100 5.5 1.7 8.7 / / 28 [98]
700 For 4 h 26.7 / 230 785 / 315 19 75 6.5 1.9 10 / / 25
Oil palm empty fruit bunch 300-350 / / 16300 2100 53000 1100 1300 / / / / / / / / [99]
Rice husk 500 / / 2300 3600 7200 200 800 / / / / / / / /

ND: not detected.

a
On basis of as received.
b
Concentration values of nutrient elements are calculated from the data in the corresponding references.

1129
1130 T. Kan et al. / Renewable and Sustainable Energy Reviews 57 (2016) 1126–1140

Biochars contain a range of plant nutrients, making them
valuable as soil amendments [90] and they can also contribute to
carbon sequestration to mitigate atmospheric carbon [91]. Table 1
lists the range of nutrient contents (macro- and micronutrients) of
biochars produced from different feedstock. The concentration of
respective nutrient elements varies in a wide range, depending
primarily on the biomass type and pyrolysis conditions. The
increase in pyrolysis temperature results in the increased con-
centrations of nutrient elements in the biochars due to loss of
mass of the biomass at higher temperatures. Nitrogen is more
volatile than the other nutrients and the concentrations may
change differently, depending on the biomass type and the
chemistry of the nitrogen in the feedstock.
3.3. Pyrolytic gas
Gases released from biomass pyrolysis may consist of carbon
dioxide (CO2), carbon monoxide (CO), hydrogen (H2), low carbon
number hydrocarbons such as methane (CH4), ethane (C2H6), and
ethylene (C2H4), and small amounts of other gases, such as

Table 2
Analysis methods employed on the biomass and pyrolysis products.

Pyrolysis Properties Analysis methods Ref.

products

Bio-oil Water content ASTM E203 or ASTM D-1744 by Karl-Fischer titration [111,112]
Carbon residue ASTM E203 by Destructive distillation method [111]
Qualitative and quantitative Gas chromatography–mass spectrometry (GC–MS), high performance liquid chromatography (HPLC) [111]
identification of bio-oil
compounds
Molecular weight Gel permeation spectroscopy (GPC), [113,114]
distributions Matrix-assisted laser desorption/ionisation (MALDI) mass spectroscopy [22,23]
Gross calorific value (GCV)/ ASTM D4809 [111,115]
Higher heating value (HHV) Theoretical calculation [116]
Elemental composition (CHN ASTM D5373 [111,115]
and O by difference)
Sulphur content ASTM D4294 by Energy dispersive X-ray fluorescence (EDXRF) spectrometry, or ASTM D4239 by Infrared [111]
measurement of SOx after combustion of bio-oils
Functional groups Infrared techniques including near-IR (NIR) and Fourier transform infrared (FT-IR) spectroscopy [117]
Types of hydrogens or car- Nuclear magnetic resonance (NMR) spectroscopy [118,119]
bons in specific structures
Acid number ASTM D664 by potentiometric titration method, or ASTM D974 by colour-indicator titration [111]
Density at 15 °C (kg/m3) ASTM D4052 by digital density metre [111]
Kinematic viscosity (mm2/s) ASTM D445–03 [111]
Flash point, pour point, and ASTM D93, D97, and D2887, respectively [111]
boiling range (°C)
Water insolubles FT-IR, 13C NMR, and column chromatography [117]
Biomass/ Proximate analysis (moist- ASTM D1762-84, 2007 [92,96,120]
Char ure, ash, volatile matter, and
fixed carbon contents)
Ultimate analysis (elemental ASTM standard D3176-89, 2002 [120,121]
analysis of CHN, and O by
difference)
Metal content X-ray fluorescence (XRF), inductively coupled plasma mass spectrometry (ICP-MS), inductively coupled [96,122,123]
plasma atomic emission spectroscopy (ICP-AES)
Elemental surface Scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM/EDX) [121,124]
distribution
Functional groups FT-IR [89,96]
13
Aromaticity C NMR [96,125,126]
Mass/heat change during Thermogravimetric analysis with differential scanning calorimetry (TGA/DSC) [121,127–129]
heating in different atmo-
spheres (N2, O2, air, etc.)
Crystalline phases, and their X-ray diffraction (XRD) [128,130]
qualitative and semi-quanti-
tative data
Brunauer–Emmet–Teller Nitrogen gas sorption [96,121]
(BET) surface area, porous
structure
Surface morphology SEM [99,128,131]
Particle size distribution Laser sizing equipment [132]
Electrical conductivity (EC) Conductivity metre [128,133]
Particle size distribution Microscopy, particle counter laser sizing equipment [132]
Surface acidity and alkalinity Boehm titration [134]
Organic carbon DPI in-house method 236 [134,135]
Cation exchange capacity Ion chromatography (IC) [137]
[136]
Gas Gases species and Gas chromatography (GC); mass spectrometry (MS); non-dispersive infrared (NDIR) analysis [23,73,137,138]
concentrations
Functional groups FT-IR [139,140]
Lower heating value (LHV) Calculation from gas composition: LHV(MJ/m3) ¼ [141]
(107.98  H2 þ126.36  COþ358.18  CH4 þ59.036  C2H4 þ 63.772  C2H6)/1000, where gas species
represent the respective volumetric fractions
H2S content Lead sulphur precipitate through reaction between H2S and lead nitrate [142]
Tar content and composition Cold trapping; solid phase adsorption (SPA) [143,144]
Size distribution of particles Scanning mobility particle sizer (SMPS) [145]
Table 3
Cellulose, hemicelluose, lignin, and extractives in selected groups of biomass, and pyrolysis behaviour of biomass [146–149].

Biomass groups Cellulose (%) Hemicellulose (%) Lignin (%) Extractives (%) Pyrolysis behaviour

Species Pyrolysis conditions Product yields (wt%) Oil composition Ref.

Liquid Char Gas

Hardwood 45–50 20–25 20–25 2–4 Mixture of various Eastern tree Two-step vacuum pyr- 50–55 25–27 Others C 36–38%, H 8%, O [160]
species olysis (200 –275 °C for 53–55%
30–45 min, and then
450 °C for 1 h)

T. Kan et al. / Renewable and Sustainable Energy Reviews 57 (2016) 1126–1140

Hardwood shavings Fast pyrolysis with 63.3 12.7 24.0 C 55.2%, H 6.5%, N [161]
τ o 5 s, T ¼ 500 °C o 0.5%, O 37.6%
Aspen poplar þwhite birch Vacuum pyrolysis 53.9 26.2 19.9 / [112]
Sweet Gum Heating rate at 1000 °C/s, 52.5 / / C 53.9%, H 5.9%, O [162]
 620 °C 37.1%
Softwood 35–40 20–25 27–30 1–10 De-barked Lodgepole pine Two-step vacuum pyr- 50–55 25–27 Others C 33–36%, H 8%, O [160]
(Pinus contorta) and Douglas Fir olysis (200–275 °C for 55–60%
(Pseudotsuga menziesii)wood 30–45 min, and then
450 °C for 1 h)
White spruceþ balsam Vacuum pyrolysis 45 27.6 27.4 C 62.6%, H 7.0%, N [112]
fir þ larch 1.05%, O 29.0%
Softwood Flash pyrolysis 75 / / C 55%, H 7% [163]
Spruce wood (Picea orientalis) Final T of 750 °C in a 39.7 32.4 28.9 C 69.3%, H 8.6%, N [164]
horizontal cylindrical 0.7%, O 21.4%
reactor
Lignin containing crop resi- 38 26–29 15–19 5 Single-pass corn stover τ ¼ 1.5 s, 500 °C in a free- 55 25.5 16.2 C 46.7%, H 14.7%, [165]
dues (corn stover, wheat (ensiled) fall pyrolyzer N 0.5%, O 38.1%
straw) Corn stover 400 °C for 20 min in in a 31 37 15 C 78%, H 9%, N [166]
batch pressure reactor 1.9%, O 10.6%
Corn stover Fast pyrolysis at 500 °C 61.6 17 21.9 C 54%, H 6.9%, N [97]
in a fluidized bed 1.2%, O 37.9%
Wheat straw 400 °C and τ ¼ 1 s in a 46 47 7 C 34.5%, H 8.2%, N [167]
CFB reactor 0.8%, O 56.5%
Acid-treated wheat straw 400 °C and τ ¼ 1 s in a 57 38 5 C 41.3%, H 7.5%, N [167]
CFB reactor 0.9%, O 50.3%
Lignin free crop residues 31–42 15–25 – 3–7 Soybean cake 5 °C/min to 550 °C in 30 [168] þ 25 25 C 62.2%, H 8.3%, N [169]
(soybean, rye straw) sweeping N2 20 (water) 7.5%, O 22.0%
Soybean (Glycine max L.) 400 °C with a heating 25.81 23.56 Others C 67.9%, H 7.8%, N [170]
rate of 50 °C/min 10.8%, O 13.5%
Soybean cake 300 °C/min to 550 °C in 39 [168] þ 21 18 C 67.2%, H 9.0%, N [171]
sweeping N2 22 (water) 10.8%, O 13.0%
Lignin containing warm 37–43 24–29 18–19 3–6 Switchgrass (Panicum virgatum) 6 °C/min to 600 °C and 37 25 26 (syn-gas) C 50%, H 9.3%, N [172]
season grasses (switch- then 20 min at 600 °C 1.5%, S 0.6%, O 37%
grass, mischantus, big Switchgrass (Cave-in-Rock 480 °C in fluidized bed 60.7 12.9 11.3 / [173]
bluestern) variety) (noncondensable)
Lignin free warm season 35–40 30–33 – 0–3 / / / / / / /
grasses
Cool season grasses 25–35 30–35 – 3–15 / / / / / / /

1131
1132 T. Kan et al. / Renewable and Sustainable Energy Reviews 57 (2016) 1126–1140
propane (C3H8), ammonia (NH3), nitrogen oxides (NOx), sulphur
oxides (SOx) and alcohols of low carbon numbers. The typical LHVs
of the pyrolytic gases range between 10 and 20 MJ/N m3,
depending on their practical composition. As the primary products
of biomass pyrolysis, CO2 and CO mainly originate from the
decomposition and reforming of carbonyl (C ¼ O) and carboxyl
(COO) groups [23,100]. Light hydrocarbons (primarily CH4) are
primarily attributed to the decomposition of weakly bonded
methoxyl ( O CH3) and methylene (  CH2 ) groups as well as
the secondary decomposition of the oxygenated compounds,
while H2 results from secondary decomposition and reforming of
the aromatic C ¼C and C–H groups at high temperatures [101,102].
Synthesis gas or hydrogen-rich gas, can be produced from
biomass pyrolysis. Wet biomass could give up to 40% higher H2
yield and content in the gas, compared to the dried biomass [103].
Temperature and catalysts can further enhance the hydrogen
production from biomass [104]. Catalysts which can promote H2
production and adjust the gas composition for downstream
applications (e.g., Fischer–Tropsch synthesis) include ZnCl2, dolo-
mite, K2CO3, Na2CO3, Ni/Al, Ni/Fe, CaO, Fe2O3, Cr2O3 and Rh/CeO2
[105–109]. Prior to practical use of the pyrolytic gas, some treat-
ments are required to reduce or eliminate the undesired con-
stituents which may include tars, dust/aerosols, evaporated heavy
metals, steam, HCN, NH3, and H2S.
The pyrolysis gas has multiple potential applications, such as
direct use for production of heat or electricity (e.g., gas combustion
in spark ignition and compression ignition engines [110]), either
directly or co-fired with coal, production of individual gas com-
ponents, including CH4, H2 or other volatiles, or in production of
liquid bio-fuels through synthesis. In some applications, the hot
pyrolytic gas can be used to preheat the inert sweeping gas or can
be returned to the pyrolysis reactor as a carrier gas.
3.4. Analysis of pyrolysis products
A number of analysis methods have been employed to chemi-
cally and physically characterise the bio-oil, char, and bio-gas
products of pyrolysis. Table 2 summarises the properties of these
products as well as the corresponding analysis methods.
4. Parameters influencing biomass pyrolysis
4.1. Biomass type
Lignocellulosic biomass is composed of cellulose (25–50 wt%),
hemicellulose (15–40 wt%), lignin (10–40 wt%), extractives (0–
15 wt%), and generally a small fraction of inorganic mineral matter
[146–149]. The biomass type influences the pyrolysis process and
products in several ways. Firstly, the relative mass ratios of the
organic and inorganic components vary with biomass types,
Table 4
Effect of biomass particle size on pyrolysis products distribution.
Feedstock Pyrolysis conditions Particle size range, in mm (liquid, biochar and gas yields, wt%)
1
Cotton stalk 550 °C, heating rate: 7 °C min in 0.225–0.425 (21,
a fixed bed 27.5, 31.1)
1
Hazelnut bagasse 10 °C min to 500 °C in a fixed bed 0.224–0.425 (30.7,
27.8, 28.5)
Rapeseed 30 °C min  1 to 550 °C in a fixed bed o 0.425 (42.7, 23,
without sweeping gas 26)
Oil mallee 500 °C in a fluidised bed 1–2 (52.0, 18.8, 19.4)
Cylindrical wood 500 °C in a fluidised bed 4 (64.2, /, /)
particles
growth environment and harvesting time. Pyrolysis of each con-
stituent features unique reaction pathways and thermochemical
characteristics, and produces different products [29,140,150–152].
Cellulose and hemicelluloses contribute to the bio-oil production
yield, while lignin yields larger proportion of solid char [153].
Higher lignin content may increase the average molecular weight
and viscosity but decrease the water concentration of the bio-oils
[154]. Extractives in lignocellulosic biomass refer to the non-
structural materials that can be extracted by solvents (e.g., water,
ethanol, acetone, benzene and toluene), such as fatty acids, simple
sugars, waxes and sterols [155,156]. Wang et al. [157] found that
the extractives could benefit the bio-oil yield and suppress the
char and gas production when using corn stalk and wheat straw as
the feedstocks for pyrolysis. The bio-oils from the extracted sam-
ples with reduced extractives also exhibited higher oxygen and
lower alkane contents than those from the original samples. In
another study, the extractives were confirmed to lower the acti-
vation energy and the yields of CO2, CO and aldehydes while
enhance and acid generation during the pyrolysis of Mongolian
pine and manchurian ash [158]. The structural combination of the
components generally differ from biomass to biomass (Table 3),
which makes the interactions among components change with
biomass types, and subsequently affects the pyrolysis perfor-
mance. Additionally, the mineral matter composition and content
in the biomass types can also be factors that influence distribution
and properties of products due to its catalytic effect during bio-
mass pyrolysis [154,159].
4.2. Biomass pretreatment
The biomass feedstock usually requires some form of pre-
treatment before its pyrolysis. The aim of the pretreatment is to
change or even destruct the lignocellulosic structure so that the
pyrolysis efficiency can be enhanced. The technologies for biomass
pretreatment can be divided into five main categories, including 1)
physical (e.g., milling/grinding and extrusion); 2) thermal (e.g.,
torrefaction, steam explosion/liquid hot water pretreatment and
ultrasound/microwave irradiation); 3) chemical (e.g., treatment
with acids, bases and ionic liquids); 4) biological (e.g., fungal,
microbial consortium and enzymatic); and 5) above combined
pretreatments [174].
4.2.1. Physical pretreatment
Milling or grinding of biomass to smaller particles is a con-
ventional treatment to facilitate the biomass feeding into reactors
and improve the pyrolysis performance. As biomass is generally a
poor conductor of heat, the temperature gradient across the par-
ticle will influence the biomass pyrolysis mechanism [175,176].
Generally, smaller particles promote the heat and mass transfer to
form uniform temperature within particles during pyrolysis,
thereby enhancing the bio-oil production by restraining the char
Ref.
0.425–0.850 (22, 0.850–1.80 (23.8, 41.80 (22.5, / [177]
27.8, 30.5) 27.1, 28.6) 26.6, 28.5)
0.425–0.6 (33.2, 0.6–0.85 (32.5, 0.85–1.8 (31.9, / [178]
27.9, 29) 27.5, 29.7) 27.4, 31)
0.6–0.85 (48, 17.5, 0.85–1.25 (49, 16, 1.25–1.8 (48, 17.5, 41.8 (46, 21, [179]
27.5) 29) 27.5) 26.5)
2.0–3.35 (47.5, 4.75–5.6 (51.0, / / [180]
18.8, 28.4) 20.2, 24.0)
6 (64.6, /, /) 9 (64.0, /, /) 12 (63.0, /, /) 15 (61.2, /, /) [181]
 T. Kan et al. / Renewable and Sustainable Energy Reviews 57 (2016) 1126–1140
formation and secondary cracking of vapours. However, particle
size reduction can be costly and significantly increase the overall
cost of the biomass pyrolysis operation. Table 4 summarises the
effect of biomass particle size on production of liquid, biochar and
gas yields in fixed and fluidised bed reactors.
Extrusion of biomass under higher pressure produces biomass
pellets which generally take the shape of small cylinders,
increasing the volumetric energy density of biomass, while
decreasing the moisture content [182]. Xue et al. [183] found that
larger pellet diameters increased the char and gas yields as well as
the char density, but lowered the tar yield. Similar phenomena
were also observed by Erlich et al. [182]. Pellets of mixed biomass
materials may also be used in the pyrolysis practices. Zabaniotou
et al. [184] mixed pine (25%), fir (25%) wood and cotton (50%) or
corn (50%) to form pellets, and the results of pyrolysis at 400–
750 °C showed that gas products with high CO and H2 and low CO2
contents were generated and the gas heating value was around
14–15 MJ/m3.
4.2.2. Thermal pretreatment
Biomass drying prior to pyrolysis increases the energy effi-
ciency of the pyrolysis process and improves the quality of the bio-
oil products. There are various different industrial dryers applic-
able for biomass drying [185] which are designed to reuse the
fugitive heat released during the heating pyrolysis process and
remove the moisture from the biomass. When the thermal pre-
treatment is conducted at temperatures between 200 and 300 °C,
process termed as torrefaction, the water content is fully removed
and the oxygen content is partially reduced from the biomass
[186]. Compared to untreated biomass, torrefied biomass pos-
sesses several advantages. It is higher in energy density, it has
improved grindability, lower hygroscopicity when stored in open
air, lowers the risk of biological degradation and self-ignition, and
improves feeding in the reactors [187,188]. During torrefaction,
some decomposition reactions begin to take place, forming CO2,
CO, acetic acid and levoglucosan [189,190]. Boateng et al. [190]
found that the fast pyrolysis of torrefied hardwood and switch-
grass pellets in a fluidized bed produced bio-oils with lower
acidity and higher energy density but lower liquid yield and car-
bon conversion than the oils from untreated biomass. Higher
quality and lower yield of bio-oils from pyrolysis of torrefied
biomass were also confirmed by others [191,192]. Torrefaction was
found to improve the quality of produced syngas via reduction of
its CO2 content and increase in H2 and CH4 contents [193].
Steam explosion (SE) is a process consisting of exposure of
biomass to saturated steam at generally 1.5–5 MPa and 150–260 °C
for seconds to minutes in a sealed vessel followed by a sudden
depressurisation to ‘explode’ the biomass structure [194–197]. SE
causes the breakage of carbohydrate linkages and also alters the
physical properties of lignocellulose [198], thus changing the
behaviour of biomass pyrolysis and product properties. Biswas et
al [194] investigated the pyrolysis of willow chips after SE pre-
treatment at 205 °C through thermogravimetric analysis at 10 °C/
min, and observed increased cellulose crystallinity compared to
the untreated material. During this process, the degradation of
hemicellulose shifted to lower temperature region and became
more active but the thermal stability of cellulose and lignin
increased. Wang et al [199] pretreated loblolly pine chips by SE
(1.3 MPa and 173–193 °C) and the untreated and pretreated
materials were then separately pyrolysed in a proprietary auger
reactor. Results showed that, in comparison to the untreated
feedstock, the chips after SE pretreatment had increased cellulose
and lignin contents while reduced hemicellulose content. The SE
pretreatment also resulted in a bio-oil product with different acid
value from 90.1 to 64.2, viscosity (cSt at 40 °C) from 6.5 to 3.9, and
water content (%) from 20.8 to 29.3. Similarly, hot liquid water is
1133
sometimes ultilised to partially remove the hemicellulose in the
biomass feedstock, which is beneficial to the decrease in acetic
acid content and the stabilisation of bio-oils [188].
Ultrasound and microwave irradiation are unconventional ther-
mal methods for biomass pretreatment. The ultrasound is mostly
used to enhance the anaerobic digestion and biogas (mainly
methane) production from sludge [200]. Several studies have also
been performed on lignocellulosic biomass. Yachmenev et al. [201]
applied ultrasound to efficiently accelerate the enzymatic hydrolysis
of cellulose in corn stover and sugar cane bagasse to generate
sugars due to the cavitation effects which could enhance the
movement of enzyme molecules and the opening up of the sub-
strates surface [201]. Sun et al. [202] used KOH solution and ultra-
sonic irradiation to extract hemicellulose from the wheat straw and
found that the ultrasound assistance produced hemicellulose with
larger linearity and less acidity than those obtained from conven-
tional KOH extraction. The effect of ultrasound pretreatment on the
biomass pyrolysis needs further investigation. Microwave irradia-
tion is nowadays a common alternative to traditional heating of
lignocellulosic biomass, and it is able to generate ‘hot spots’ in the
biomass [200,203]. Although microwave-assisted pyrolysis of bio-
mass has been widely studied [204], biomass pretreatment by
microwave irradiation prior to the pyrolysis is not well investigated
[205]. Microwave drying at 600 W and 6 min was proposed to
improve the bio-oil and char yields with performance showing
better yields than conventional electrical oven drying due to the
suppression of secondary reactions during pyrolysis after biomass
drying in a microwave oven [205].
4.2.3. Chemical pretreatment
The presence of inorganic minerals, especially the alkali (K, Na,
etc.) and alkaline-earth (Mg, Ca, etc.) metal salts, is believed to
affect the mechanism of biomass pyrolysis [206,207]. For example,
K in the biomass mineral matter catalytically promotes the for-
mation of lower molecular weight compounds and suppresses the
formation of levoglucosan during the primary pyrolysis of cellu-
lose [208]. The cations, acting as catalysts, induce the fragmenta-
tion of the biomass monomers rather than the depolymerisation,
which favours char formation and lowers bio-oil yields [208–211].
The deposit of salts onto the reactor and pipeline inner walls also
causes corrosion and engineering difficulties [212]. Besides, the
presence of ash in bio-oils affects the subsequent applications of
bio-oils and accelerates their aging.
The above shortcomings can be improved by reducing the ash
content through water or acid washing. Water washing is used to
remove the dirt and minerals on the surface of biomass particles
during biomass harvesting, transport and storage. However, the
structural minerals will still remain within the biomass matrix.
Washing by acids, such as HNO3 and HF, can further reduce the ash
content [213]. Blasi et al. [214] examined the effect of water
washing on pyrolysis characteristics of straw, and found that water
washing increases the bio-oil yields while char formation is
decreased. Phosphoric acid was applied to pretreat cellulose
feedstock to obtain higher production of levoglucosan and levo-
glucosenone in the bio-oils [215]. In some cases, concentrated
acids (e.g., H2SO4) were applied to hydrolyse and solubilise car-
bohydrates in biomass to extract lignin [216], and alkaline solu-
tions (e.g., NaOH) were used to remove lignin, hemicellulose, and/
or cellulose [174].
Ionic liquids are a series of recently emerging compounds
mainly consisting of organic cations and inorganic/organic anions
and can take the form of/turn into liquids at temperatures below
100 °C (especially room temperature) [217]. They are regarded as
green solvents with unique physical and chemical characteristics,
such as low vapour pressure, strong chemical stability, and non-
flammability [218–220]. Ionic liquids have found applications in
1134 T. Kan et al. / Renewable and Sustainable Energy Reviews 57 (2016) 1126–1140
not only various industrial areas applications, such as catalysis,
chemical synthesis and engineering fluids, but also the decon-
struction and dissolution of cellulose, hemicellulose and lignin
[221]. Ionic liquids have been used to pretreat lignocellulosic
biomass for the production of sugars from enhanced enzymatic
hydrolysis of oil palm fronds [222], renewable chemicals of
vanillin, syringyl and allyl guaiacol from eucalyptus, switchgrass
and pine respectively [223], levulinic acid from cellulose [224], and
biogas from improved anaerobic digestion of water hyacinth, rice
straw, mango leaves and spruce[225]. The thermal behaviour of
biomass materials can also be changed after their pretreatment by
ionic liquids. Zhang et al. [226] found that after the pretreatment
by 1-butyl-3-methylimidazolium acetate ([C4mim][OAc]), the
Avicel and switchgrass samples showed higher thermal resistance
due to the crystal change of cellulose and the removal of minerals,
respectively [226].
4.2.4. Biological pretreatment
Comparing physical and chemical pretreatments, biological
methods are slower but less energy-consuming and with better
environmental footprint [227]. Fungal pretreatment of lig-
nocellulose prior to pyrolysis has been proved to improve the
efficiency of the pyrolysis performance. White-rot fungus has been
selected to pretreat the natural lignocellulose as it could selec-
tively decompose the refractory lignin component during pyrolysis
[228,229]. Yang et al. [230] employed three different species of
white-rot fungus (Pleurotus ostreatus BP2, Echinodontium taxodii
2538, and Irpex lacteus CD2) to biopretreat corn stover and then
studied its thermal characteristics during pyrolysis in a TGA
instrument. Results showed that this biopretreatment could
effectively lower the pyrolysis temperature by 1–35 °C and
decrease the emission of toxic SOx through reduction of the sul-
phur content in the feedstock by 30–45%. Yu et al. [227] investi-
gated fast pyrolysis of corn stover pretreated by white-rot fungus I.
lacteus CD2 in the presence of ZSM-5 zeolite, and observed 10%
improvement in valuable aromatics product yields and 20%
reduction in deposition of undesired coke on catalysts.
Microbial consortium has been generally used to pretreat lig-
nocellulosic biomass to enhance the biogas production. It employs
certain microbes selected from the natural environment which
mainly degrade the cellulose and hemicellulose components [174].
The process lasts for several hours to several days with the ability
of increasing the methane yield by 25% to nearly 100% [174].
Enzymes have been proposed as a pre-treatment for hydrolysis
of lignin prior to its pyrolysis in order to enhance production of
aromatic phenols and hydrocarbons [231]. The produced chars
also appeared to be highly porous with vesicles.
4.3. Effects of reaction conditions
4.3.1. Reaction atmosphere
Biomass pyrolysis is typically carried out under inert atmo-
sphere. Other gases can be also introduced to modify the pyrolysis
process. For instance, steam can weakly oxidise the biomass and
provide partial gasification. In a recently developed pyrolysis
process, referred to as steam pyrolysis, the steam is used as the
carrier gas, which may also take part in the reactions. The steam
for biomass pyrolysis has several advantages. Primarily, it can
upgrade the yield of organic oxygenated products by preventing to
some extent the secondary cracking reactions in the gas phase
[232]. Zhang et al. [233] studied the effects of N2, CO2, CO, CH4 and
H2 atmospheres on biomass pyrolysis in a fluidised bed reactor. It
was found that CH4 atmosphere gave the highest bio-oil yields
(58.7%) with the lowest yield in CO (49.6%). Lower methoxy-
containing compounds and larger monofunctional phenols in the
bio-oils were detected when applying CO and CO2 as the sweeping
gas. Under H2 atmosphere, the HHV of the bio-oils could reach the
highest value of 24.4 MJ/kg and more oxygen in biomass was
converted into H2O comparing to other atmospheres. The char
obtained in the CO2-containing atmosphere had increased surface
area and different chemical composition [234] compared to the
chars produced under inert atmosphere.
4.3.2. Temperature
Pyrolysis temperature significantly influences the distribution
and properties of products [235–237]. Generally, the bio-oil yields
reach their peak concentrations at temperatures between 400 and
550 °C, and then decline after proceeding with heating. At tem-
peratures higher than 600 °C, the bio-oils and char products are
converted into gas due to the dominant secondary cracking reac-
tions [238]. The polar, aliphatic and aromatic fractions in the bio-
oils enhance with increased temperatures from 300–500 °C to
600–800 °C [239]. Generally, temperatures exceeding 700 °C
increase the carbon content of the bio-oils in the form of polycyclic
aromatic hydrocarbons (PAHs), such as pyrene and phenanthrene,
due to the decarboxylation and dehydration reactions [153]. The
variation of gas yields and composition (CO, CO2, CH4, H2, etc.)
with pyrolysis temperature has been reviewed by Uddin et al.
[101]. The physicochemical characteristics (e.g., surface area,
electrical conductivity, concentration of inorganic elements, car-
bon content, aromatic structure, and HHV) of biochars from bio-
mass fast pyrolysis at different temperatures were also investi-
gated in the past [128,240–242].
4.3.3. Heating rate
Heating rate is a fundamental parameter that defines the type
of biomass pyrolysis, i.e., flash, fast, and slow pyrolysis. Fast
heating rates favour quick fragmentation of the biomass and yield
more gases and produce less char. Bio-oil production is also
enhanced at fast heating rates due to the reduction in mass and
heat transfer limitations, and short time available for secondary
reactions [153]. The effect of heating rate on yields and properties
of products has been determined previously [176,243,244]. Salehi
et al. [245] observed that an increase in heating rate from 500 °C/
min to 700 °C/min increased the bio-oil yields from sawdust by 8%,
however, no obvious change in the bio-oil yields was detected
when further increasing the heating from 700 to 1000 °C/min due
to the overcoming of mass and heat transfer limitations. Similarly,
rapid increase in liquid yield for pyrolysis of cottonseed cake was
observed when elevating the heating rate from 5 °C/min (26 wt%)
to 300 °C/min (35 wt%), where as no obvious change of liquid yield
was found when further increasing the heating rate from 300 °C/
min to 700 °C/min [246].
4.3.4. Vapour residence time
Shorter residence time favours bio-oil production due to the
quick removal of organic vapours from reactors which minimises
the secondary reactions [247]. For the pyrolysis of raw sorghum
bagasse at 525 °C Scott et al. [248] observed that an increase in
vapour residence time from 0.2 to 0.9 s resulted in a decrease in
the bio-oil yields from 75% to 57%, while the char and gas yields
increased. Similarly, during the pyrolysis of sweet gum hardwood
at 700 °C, the oil yield dropped from 22 wt% to 15 wt% by
increasing the vapour residence time from 0.7 s to 1.7 s [247].
Although the effect of vapour residence time on product dis-
tribution is well studied, the interaction between vapour residence
time and pyrolysis temperature on not only product yields but also
product quality needs further clarification [101].
 T. Kan et al. / Renewable and Sustainable Energy Reviews 57 (2016) 1126–1140 1135

5. Biomass pyrolysis reactors and state-of-arts

Ash formation in circulating solids leads to

Gas can contain particulates and tar, may be Lower process temperatures (400 °C); heat
Heat transfer to bed has yet to be proven at

biomass particles on the hot reactor wall;

transfer at large scales may be a problem

Simple reactor design; clogging and foul-

Water and some ash and charcoal particles High heat transfer and high pressure of
Quick char removal is essential; special

loss of bio-oil yield; acceptance of very

designs are required to minimise tem-

ing of gas handling system due to tars

perature and concentration gradients
Modern reactor configurations for biomass pyrolysis mainly
Advantages and disadvantages
comprise of fixed bed, fluidised bed, heated kiln, rotating cone,
ablative, screw feeder/auger and vacuum pyrolysers [33,249].
Typical industrial pyrolysis processes for various reactor config-

rapid removal of volatiles

urations have been well reviewed in the past [33,250]. Mohan
et al. [7] also reviewed the properties of bio-oils produced from

large throughputs
pyrolysis of various biomass feedstock in different reactor designs.

Demonstration
Table 5 summarises the characteristics and current status of

large scales
common pyrolysis reactors. Three reactor types, including bub-
bling and circulating fluidised beds and rotating cone, have been
commercialised in the market while others still remain at the
stage of demonstration, pilot or even laboratory research. Table 6
Water and high level of ash and charcoal

Water and high level of ash and charcoal

very acidic. High moisture content in gas

lists the typical examples of pyrolysis facilities at commercial
Commercial 200–2000 kg/h Water, ash and charcoal particles in oils.

scales. During the period of 1994–2002 the cost of production of

and/or oil if feed is not dried before

bio-oil was estimated to range between US$0.62 and US$1.40 per
gallon. [251].
Beside the above-mentioned pyrolysis processes, there is also a
range of other technologies at research and development stage
which are being considered for industrial biomass pyrolysis
operations, including microwave-assisted pyrolysis [204,253–256],
particles in oils.

particles in oils.
Product quality

hydrothermal pyrolysis [257–259], catalytic pyrolysis [260–263],

and integration of biomass pyrolysis with other processes, such as
pyrolysis
in oils.

iron ore reduction [264] and NOx reduction systems [265].

200–2000 kg/h Hard

Biomass pyrolysis in now a promising technology for generat-

/

ing energy, fuels and chemicals. Although rapid progress in the

biomass pyrolysis field has been achieved, a number of barriers
Commercial o 4000 kg/h

20–200 kg/h

and challenges are still to be overcome to unleash the full potential

1–20 kg/h
Commercial 2–20 t/h

Commercial 2–20 t/h

of various pyrolysis processes, including limitations in unsatisfying

Scale

overall energy efficiency relating to feedstock pretreatment,

reliability of reactors and processes, poor product quality, com-
Laboratory

plete product standards for producers and customers, and reactor

scalability [10,266]. Additional technology development is
Status

Pilot

required on the integration of biomass pyrolysis process and

downstream upgrading of pyrolytic products aiming at final pro-
ducts with high added value. The science and engineering devel-
difficulty
Complexity Scale-up

Medium

Medium

opment of biomass pyrolysis is expected to address the production

Hard
Easy

Easy

of designed fuels or chemicals from specific biomass materials

with finer control of the pyrolysis process (e.g., pyrolysis para-
/

meters and addition of catalysts), simpler pyrolysis procedures and

Medium

Medium

reduction of the production cost.

High

High

High

High
Low

6. Conclusions
Bio-oil
yield

75%

75%

75%

60%

60%
70%
/

This paper reviews the parameters and pre-treatment pro-

Characteristics and current status of pyrolysis reactors [7,250,252].

Carrier gas

cesses that influence biomass pyrolysis. Heating rate and tem-

perature are the two the most studied process conditions. Higher
need

High

High

Low

Low

Low

Low

heating rates promote production of higher liquid yields, while

/

lower heating rates are applied for enhanced biochar yields. The
optimum temperature for maximised liquid and solid product
moisture

yields is in the range of 400–550 °C. Bio-gas is now increasingly

o 10%

o 10%

o 10%

o 10%

o 10%

o 10%

o 10%
Feed

being considered as a product of choice from biomass pyrolysis,

mainly for production of hydrogen rich synthetic gas. High tem-
perature catalytic pyrolysis is proposed for achieving high yield
o 0.2–6 mm
requirement

and quality of bio-gas. Reaction atmosphere and residence time

o 20 mm
5–50 mm

Auger/screw feed 5–50 mm

5–50 mm
Feed size

o 2 mm

o 6 mm

both significantly affect the products of biomass pyrolysis. Slightly

oxidising atmospheres and increased residence times promote
gasification and reduce the bio-oil yields. Significant improve-
ments to the pyrolysis process can be achieved through pre-
Circulating flui-

treatment of the biomass prior to pyrolysis. Physical, thermal,

Rotating cone
Bubbling flui-
Reactor type

dised bed

dised bed

Heated kiln

chemical and biological pre-treatments have been developed to

Ablative

Vacuum

tailor for the desired properties of the pyrolysis products. Physical

Table 5

pre-treatment involves reduction of particle size to promote

intraparticle heat and mass transfer and enhance bio-oil
1136 T. Kan et al. / Renewable and Sustainable Energy Reviews 57 (2016) 1126–1140
Table 6
Examples of pyrolysis facilities at commercial scales [250].
Company name Location Pyrolysis type
Dynamotive West Lorne, Ontario, Flash pyrolysis
Canada
Guelph, Ontario, Flash pyrolysis
Canada
Mitsubishi Heavy Industries/ Mie Prefecture, Japan Slow pyrolysis
Mie Chuo Kaihatsu
Ensyn Rhinelander, Fast pyrolysis
Wisconsin
Renfrew, Canada Fast Pyrolysis
BTG Malaysia Fast pyrolysis
Choren Germany Slow pyrolysis and
gasification
production yields. Thermal pre-treatment involves reduction in
the intrinsic moisture and oxygen content in the biomass, gen-
erally utilising the waste heat from the pyrolysis process, in order
to improve the energy efficiency and product quality. Chemical
pre-treatment reduces the mineral matter content, while biologi-
cal pre-treatment has been trialled to reduce the lignin content,
generally the most thermally resistant compound in the lig-
nocellulosic biomass, so that the pyrolysis bio-oil yields can be
enhanced. Generally, biomass pyrolysis is currently at the mature
stage of development with several technologies already achieving
full commercialization stage. Their input into the global energy
production is expected to achieve the full potential in the near
future.
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