Egyptian Journal of Petroleum 27 (2018) 1305–1311

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Egyptian Journal of Petroleum

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Full Length Article

Developing a free-fall reactor for rice straw fast pyrolysis to

produce bio-products
A.M. Shoaib a,⇑, R.A. El-Adly b,c, M.H.M. Hassanean a, A. Youssry d, A.A. Bhran a,e
a
Petroleum Refining and Petrochemical Engineering Department, Faculty of Petroleum and Mining Engineering, Suez University, Suez, Egypt
b
Process Design & Development Department, Egyptian Petroleum Research Institute, Cairo, Egypt
c
Chemistry Department, Faculty of Science, Taif University, Saudi Arabia
d
Suez Oil Petroleum Company, Suez, Egypt
e
Chemical Engineering Department, College of Engineering, Al Imam Mohammad Ibn Saud Islamic University IMSIU, Al Riyadh, Saudi Arabia

a r t i c l e i n f o a b s t r a c t

Article history: Recently, the world energy demand is increasing due to the growing world population. Accordingly,
Received 2 February 2018 many research works are directed toward the new resources of renewable energy in order to compensate
Revised 19 July 2018 the shortage in petroleum based products. The use of biomass as a source for renewable energy is of
Accepted 5 August 2018
growing importance. One of the most problematic agriculture wastes in Egypt is rice straw which is gen-
Available online 3 September 2018
erated in huge amounts over a limited harvesting period. In this study the main objective is to develop
and design a new rice straw fast pyrolysis reactor that improves some inefficiencies in traditional reactors
Keywords:
while maintaining high bio-oil yields. To accomplish this target, a laboratory scale plant with a free-fall
Fast pyrolysis
Rice straw
reactor was designed to avoid lack of moving parts; Compared it with other plants, the designed under
Free fall reactor investigation plant has the advantage of simple design. Two basic principles were combined in the design
Pyrolysis products of the free-fall reactor; the first principle dealt with the particle heating rate, while the second considered
the particle’s free-fall velocity. Based on this developed and designed free-fall reactor, the fast pyrolysis
process of rice straw was carried out at temperatures ranging from 450 °C to 700 °C. The obtained bio-
products from this process are liquid bio-oil, bio char and non-condensable gases. The characterization
and chemical composition of the bio-oil and non-condensable gases were determined, respectively. It
was concluded that the above mentioned free-fall reactor can be used for producing useful bio-
products from rice straw and sharing to solve the most problematic agriculture waste.
Ó 2018 Egyptian Petroleum Research Institute. Production and hosting by Elsevier B.V. This is an open
access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction considered as biomass feedstock; such as wood, agricultural and

Nowadays, there is a growing demand for sustainable energy
resources to overcome the increased cost of fuel and depletion of
petroleum products with increasing population. Renewable
energy, especially biomass, is a promising solution for these chal-
lenges. This will consequently reduce the resulting environmental
hazards from fossil fuels; especially, great emissions of CO2, SOx
and NOx [1].
Biomass could be defined as any hydrocarbon that consists basi-
cally of carbon, hydrogen, oxygen and nitrogen, in addition to sul-
fur in less percentage [2]. Many natural and derived materials are
Peer review under responsibility of Egyptian Petroleum Research Institute.
⇑ Corresponding author.
E-mail addresses: abeer.shoaib@suezuniv.edu.eg (A.M. Shoaib), refeladly@
hotmail.com (R.A. El-Adly), mhassanean@yahoo.com (M.H.M. Hassanean),
mada_eng2009@yahoo.com (A. Youssry), abhrane@yahoo.com (A.A. Bhran).
industrial residues (e. g. bagasse, rice straw, saw dust, waste paper,
food processing wastes, animal wastes, aquatic plants and wood
ship) [3,4].
Biomass conversion into valuable hydrocarbons could be
achieved through three alternative routes; biochemical, thermo-
chemical and biological processes [4]. Thermochemical processing,
aiming at biomass conversion into bio-oil, a solid charcoal like
material named char or bio-char and a non-condensable gas,
includes gasification, liquefaction, combustion and pyrolysis.
Among these processes, pyrolysis is a promising process for bio-
mass conversion into alternative energy in forms of biochar, bio-
oil and combustible gases. It is an oxygen-free thermochemical
decomposition of biomass to produce such valuable alternative
fuels efficiently and economically [5,6]. This process could be clas-
sified into slow (conventional), fast and/or flash pyrolysis, based on
the operating conditions, like heating rate and pyrolysis time [7,8].
When the process is aimed to produce charcoal as a main product

https://doi.org/10.1016/j.ejpe.2018.08.002
1110-0621/Ó 2018 Egyptian Petroleum Research Institute. Production and hosting by Elsevier B.V.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
1306 A.M. Shoaib et al. / Egyptian Journal of Petroleum 27 (2018) 1305–1311
and chemicals like methanol and acetic acid, conventional pyroly-
sis would be applied [9].
Fast pyrolysis has gained more attention as a flexible and attrac-
tive way for the production of bio-oil as a main product to be an
alternative to transportation fuels [10,11]. Besides, there is a major
advantage for fast pyrolysis over thermal liquefaction and gasifica-
tion; liquid fuels could be directly produced at atmospheric pres-
sure, thus, reducing the high cost of high pressure systems and
allowing for the use of simple reactor design [6,12]. Additionally,
unlike other bio renewable energy platforms, it does not require
expensive catalysts or enzymes but rather uses heat to breakdown
lignocellulosic biomass. Another advantage of biomass fast pyroly-
sis over other renewable energy platforms (wind and solar for
example) is the fact that a liquid energy carrier is produced.
In fast pyrolysis, for maximum yield of bio-oil, heat is quickly
injected into biomass particles, while condensable compounds
are collected efficiently and quickly from the existing stream
[13]. Biomass, in this process, undergoes a very quick decomposi-
tion generating mostly vapors and aerosols and some charcoal
and gas. A homogeneous dark brown oil is produced with a lower
heating value than fuel oil. As the feed ash content is lower, a
higher liquid yield is gained [11].
Among biomass feedstock varieties, Rice straw is concerned in
this study, as it is one of the most problematic wastes, produced
in huge amounts seasonably in Egypt; more than 3 million tons/
year [14]. In addition, it has limitation toward its application in
paper making or animal fodder due to its high silica content. Fur-
ther benefits could be ascribed to the converting of rice straw bio-
mass to biofuels such as: Agricultural soil improvement, waste
management, renewable energy production and climate change
mitigation. Many research works have paid attention to the pro-
duction of biofuel from rice straw. The effect of catalyst on the dis-
tribution of product yield and bio-oil characterization has been
studied by Ahmed et al. [15], while Zolghadr [14] concerned the
characteristics of the produced bio-oil experimentally on a pilot
scale. Sukumar [2] has introduced a review for the various work
carried out on feedstock of biomass, taking into consideration
pyrolysis type, reactor type and bio-oil upgrading techniques. Xiu-
juan et al. [16] have studied physicochemical properties of bio-oil
obtained from fast pyrolysis of rice husk. A complete review for
work achieved on product properties and effects of biomass pyrol-
ysis parameters have been introduced by Kan et al. [17].
Many types of reactors have been reported in literature for the
fast pyrolysis of biomass such as Circulating fluidized beds, Bub-
bling fluidized bed, Fixed bed, Auger reactor Rotating cone pyroly-
zer, Ablative pyrolyzer, Heinze-type reactor, Vacuum pyrolysis, and
transport reactor [2]. Punsuwan and Tangsathitkulchai [18] intro-
duced a study for the biomass pyrolysis in a free-fall reactor.
Jahirul et al. [19] introduced an overview for the various fast pyrol-
ysis reactor types, indicating advantages and disadvantages of each
of them. Among various introduced reactor types, free-fall reactor
has been selected to be used in this work due to lots of advantages;
mean residence time as like mass balance could be determined
simply and straightforward. Residence time could also be moder-
ately controlled. High heating rate could be provided efficiently
and the kinetic parameters could be conveniently examined from
the pyrolysis results [18,20].
Biomass is an abundant organic material composed of cellulose,
hemicellulose and lignin. It may be converted into useful products
to offset petroleum based products. Accordingly, the goal of this
work is to develop a new biomass fast pyrolysis reactor that
improves upon inefficiencies in traditional reactors while main-
taining high bio-oil yields. The obtained bio-oil characteristics have
been studied, in addition to that the complete analysis of the pro-
duced non-condensable gases.
2. Experimental
2.1. Materials
The feeds of the investigated laboratory scale plant are rice
straw and pure nitrogen (99%) gas as an inert gas for the process.
Rice straw obtained from delta region in Egypt is dried and
grinded, then, sieved to a particle size less than 1 mm. Table 1
addresses the characteristics of rice straw feedstock.
2.2. Pyrolysis of the rice straw
Before pyrolysis, rice straw was cut and milled to a diameter
about 1 mm. After that, the sample was dried in a vacuum oven
at 105 °C for 24 h. Fast pyrolysis experiments of rice straw were
carried out in Pyrolysis pilot plant at temperatures 400 °C to
700 °C. This process was fitted with a nitrogen purge (1 L/min flow
rate) and a thermocouple for temperature measurement. The
residual bio-char particles were collected as total yield of the
pyrolysis process. The total yield was determined by the difference
between the weight of sample before and after the pyrolysis exper-
iment. The bio-oil was collected through the condensation system.
2.3. Pyrolysis pilot plant description
The pilot plant used in this study consists of a screw feeding
system connected to a reactor, char catch, carbon filters (cyclone),
placed for gas clean-ups, and a series of two condensing canisters
(H-shaped, vapor condensers) those are cooled by water. Nitrogen
gas cylinder was used as the inert gas for the process. A Free fall
reactor was chosen to carry out the fast pyrolysis process at tem-
peratures in the range of 400–700 °C for converting raw rice straw
biomass into bio-oil, bio-char and non-condensable gas. The reac-
tor was heated by an electric ceramic heater. Temperature and
pressure measurements were respectively carried out using ther-
mocouples and a pressure indicator. Temperature readings in the
reactor were taken at many points and the averages were
computed.
The process begins by placing biomass into the feed hopper
located on top of the reactor. A ball valve type is located between
the feed hopper and the top of the reactor, where biomass is
allowed to travel through the reactor by free falling when this
valve is open. The biomass flow rate is controlled by adjusting
the valve opening. It is noticed that the first design of feeding sys-
tem shown in Fig. 1 has many problems during operation which
can be summarized in the difficulty of biomass falling through
the ball valve opening. As a result, a new feeding system has been
installed instead of this ineffective one.
The new feeding system presented in Fig. 2 consists of capacity
hopper that stores biomass, and an auger of 2.54 cm inside diame-
ter that serves for metering and injecting biomass into the reactor
manually. The biomass is agitated and encouraged to exit the fee-
der by the walls of the hopper which flex alternately at the same
Table 1
Analysis of Egyptian rice straw (on dry basis).
Rice Straw Component wt %
Pectin 2.3
Holocellulose 71
a-cellulose 34.94
b- hemicellulose 36.06
Lignin 12.3
Soluble materials 14.17
Total 100
 A.M. Shoaib et al. / Egyptian Journal of Petroleum 27 (2018) 1305–1311
Fig. 1. First design of feeding system.
Fig. 2. New design of feeding system.
speed as the metering auger. The feeder has a transparent lid to
view the condition of the biomass during operation and it is fitted
with a nitrogen purge inlet. By purging a small amount of nitrogen
through the hopper, a slight positive pressure is provided to dis-
courage the back flow of pyrolysis vapors into the hopper.
The injection auger feed tube of 2.54 cm inside diameter is con-
nected horizontally to the reactor; below this connection point, the
reactor is wrapped with a water cooling jacket. This jacket task is
to remove heat conducted from the reactor to ensure that the bio-
mass does not begin decomposing prematurely. The cooling water
is entering at room temperature, and the flow rate is manually con-
trolled. The reactor was made of stainless steel (type 316) with
2.54 cm inner diameter (schedule 40) and 2 m height. The reactor
heated length of 1.5 m is radioactively heated using ceramic hea-
ters capable of raising the temperature up to 1000 °C.
A nitrogen cylinder is connected to the purge line feeding into
the top of the reactor and feeder. The carrier gas serves to remove
all oxygen from the system before starting the feeder. K-type ther-
mocouples are located in 0.30 m increments along the reactor. The
thermocouples serve to monitor the temperature of the biomass
particles that are rapidly heated as they fall through the reactor.
On average, over 98% of the produced char is collected at the
bottom of the reactor in a stainless steel catch of 0.076 m diameter
and 0.20 m height. This catch is heated by a ceramic barrel heater
to prevent condensation of vapors. The vapors and non-
condensable gas which are produced from the high-temperature
reaction exit the reactor from two separated vapor ports and enter
a heated cyclone particulate filter to remove any entrained char.
The first vapor port is located at 1 m from the reactor top which
1307
is the designed length for a complete pyrolysis of rice straw parti-
cles. The other port is located at 1.5 m from the top of the reactor
heated length to serve the decomposition of any other types of bio-
mass or a larger particles of rice straw that did not decompose
through the 1 m heated length of the reactor.
Vapors leaving the cyclone enter a bio-oil collection system.
Two bio-oil fractions are collected in two double pipes water
cooled condenser made of stainless steel and arranged in a capital
‘‘H” shape. Cooling water flows from the bottom to the top and it is
controlled manually. The two bio- oil fractions are collected in two
drains connected to ball valves and the non-condensable gases
leaves through an exit line to atmosphere.
2.4. Reactor design
As indicated before, the reactor type used in the current work
for producing bio oil from rice straw feedstock is a free fall reactor.
The selection of this reactor type was due to its simplicity and the
absence of moving parts. Various configurations and sizes of free-
fall reactors have been used in a wide range of applications. Even
so, very few free-fall reactors have been constructed for the pro-
duction of bio-oil via fast pyrolysis of biomass. Designing the
free-fall reactor required a multi-disciplinary approach. The only
restriction on the design was a specified biomass feed rate of
1 kg/h. The reactor was designed in this study and constructed at
Suez oil processing company (SOPC). Reactor design and its calcu-
lations are discussed in the following sections.
2.4.1. Design principles
Two basic principles were combined in the design of the free-
fall reactor; the first principle dealt with the particle heating rate,
while the second considered the particle’s free-fall velocity. After
integrating both of these concepts, either the required wall tem-
perature of the reactor as well as its length for complete conversion
can be determined.
2.4.2. Particle heating rate
It is reported in literature that the optimum operating temper-
ature for fast pyrolysis is in the range of 475–525 °C [21,22]. By
assuming that complete pyrolysis has taken place once the center
of a spherical biomass particle reaches 500 °C, the time needed for
the particle to reach this temperature should be calculated. Ignor-
ing all effects due to shrinking and changing particle density, a
lumped capacitance method can be used for determining the tran-
sient heating time [23]. The lumped capacitance approach assumes
a uniform temperature distribution throughout the body. Since this
can only be the case if the conductive resistance within a solid
body is zero, lumped capacitance is assumed accurate for small
ratios of convection at the surface of the body over conduction
within the body. This ratio is a non-dimensional value and gener-
ally represented by the Biot number [23], Bi, as shown in Eq. (1).
hLc
Bi ¼ ð1Þ
k
where,
h: the convective heat transfer coefficient at the surface of the
body
k: the conductive heat transfer coefficient within the body; it is
also called as thermal conductivity.
Lc: The characteristic length; it is defined as the ratio of an
objects volume, V, to its surface area, As, as given in Eq. (2) [23]:
V
Lc ¼ ð2Þ
As
In general, the lumped capacitance method is applicable if Bi
0.1. In order to find the Biot number, the convective and conductive
1308 A.M. Shoaib et al. / Egyptian Journal of Petroleum 27 (2018) 1305–1311

heat transfer coefficients as well as the particle size must be
defined. Since the biomass particles would be free-falling through
a heated reactor tube, the only heat transfer to the particles is due
to convection and radiation.
Bohn and Benham, 1984 concluded that radiation heat transfer
is the primary means by which particles are heated within an
entrained flow reactor. To account for this, a radiation heat transfer
coefficient, hrad, was derived as shown in the following equation
[23]:

 
r T 2pþ T 2wall T pþ T wall
hrad ¼ ð3Þ
1
ep  1 þ F112
where r is the Stefan-Boltzmann constant, Tp is the particle tem-
perature, Twall is the reactor wall temperature, ep is the emissivity
of the particle and F12 is the view factor from the particle to the
reactor wall. The view factor can be estimated by defining the bio-
mass particle as a cube. Assuming the particle cannot touch the
reactor wall through the top and bottom faces of the cube due to
the other particles falling before and after it, the view factor can
be approximated to be somewhere between 2/3 and 1. By choosing
a view factor of 0.7 and assuming that the biomass particle enters
the reactor at room temperature and that the particle is a black-
body, only the wall temperature is undefined.
Assuming that complete pyrolysis occurs when the particle
reaches 500 °C, the next step is to calculate the time required for
a particle to reach that temperature. Using a lumped capacitance
approach, Eq. (4) can be solved for t (the time required to reach a
specified temperature) as a function of temperature T(t) as
described below [23]:
TO  T1
¼ ebt ð4Þ
Ti  T1
where, T1 is the fluid temperature. It could be assumed that the
fluid temperature is equal to the wall temperature. Ti is the initial
particle temperature and b is the time constant that can be calcu-
lated as below [23].
hrad :As
b¼ ð5Þ
q:v :Cp
2.5. Design case
The next sections are directed to the design of a lab scale unit
that can be used for converting rice straw biomass into valuable
biofuels such as bio-char which is produced in a large amount.
The important design parameters is the calculation of radiation
heat transfer coefficient, time required to heat the particle to
500 °C, particle terminal settling velocity, produced amount of
char, and the char collector size.
2.5.1. Calculation of radiation heat transfer coefficient
Design first step considers the calculation of radiation heat
transfer coefficient (hrad) assuming the following: The reactor
diameter D = 900 lm, Tp = 298 °K, Twall = 923 °K (maximum wall
temperature), r ¼ 5:67x108 mW (Stephan Boltzmann constant),
2 :k4
ep = 1, and view factor = 0.7. According to the above mentioned
assumptions, the calculated hrad with regarding to Eq. (3) is 45.6
W
m2 :k
.
2.5.2. Calculation of required time
The time required to heat the particle to 500 °C is calculated
according to the lumped system method. To apply this method,
the Biot number should be lower than or equals to 0.1
h:Lc 45:6  900
Bi ¼ ¼ ¼ 0:1
k 0:068  6  106
As the Biot number is equal to 0.1; thus lumped capacitance
analysis can be applied for the present case. With T O ¼ 773;
T i ¼ 298, qricestraw ¼ 200 mkg3 , and specific heat capacity of biomass
kJ
C p ¼ 1:3 kgK , the value of time constant b can be estimated as
below:
45:6
b¼ ¼ 1:17
200  103  16  900  1:3
From energy balance of a solid over a finite time interval, T wall
can be used instead of T 1 in Eq. (4) [23] and the time required to
reach temperature of 773 °K can be obtained.

Replacing hrad in Eq. (5) with the radiation heat transfer coeffi-
cient presented in Eq. (3) while specifying a particle density (q), a
specific heat (Cp), and a particle diameter, Eq. (4) can be solved for
t, the time to reach 500 °C. Note that only the radiation heat trans-
fer coefficient is substituted to be conservative.
2.4.3. Particle Free-fall velocity
Knowing the restrictions on particle size set by rapid heating to
500 °C in 2 s or less, the length of the reactor can be determined. To
be conservative, all effects due to particle heating, such as changing
density and loss of mass were ignored. Assume that the particle
free-fall velocity is the terminal settling velocity which is defined
as follow [24]:
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
4:g:2:ro: ðqp  qf Þ
lnð500650Þ
t¼ 25650
¼ 1:21sec
1:17
2.5.3. Calculation of particle terminal settling velocity
The particle terminal settling velocity can be calculated accord-
ing to Stokes’ Law. The following properties of air and particles
should be considered. Air density and dynamic viscosity at
450 °C are qf ¼0.4880 mkg3 and l = 3.415  105 m:s kg
respectively. It
should be noticed that the air density at 450 °C is less than that
of pyrolysis vapors, therefore particle will have a higher terminal
velocityut . The particle outer radius and rice straw particles densi-
ties are:r o ¼ 900  106 m, andqp ¼ qricestraw ¼ 200 mkg3 . By substituting
2

ut ¼ ð6Þ with the above mentioned properties of air and particle, the value
3:qf :C D of particle terminal settling velocity can be calculated as follows:

where, ut is the particle settling velocity, r is the Stokes radius, g is vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi

u
gravity, qp is density of the particle, qf is the density of the fluid, and u 4  9:81  900  106 ð200  0:488Þ
ut ¼ u
u :7
CD is the drag coefficient. t3  0:488fð 24
Þð1 þ :14½0:48890010
6
ut
 Þg
0:488900106 u t 3:415105
By calculating the time t required to heat a biomass particle to 3:415105

500 °C, ut can be obtained by solving Eq. (6) and then the reactor
length can be calculated. When particle is falling for time t (s) from
rest, it will travelling near ut (m/s) during falling a distance L (m)
that can be calculated by L = ut  t. This is the length required for
the reactor to heat the particle to 500 °C.
By solving this equation by trial and error, the calculated value
of ut is 1:289 m/s. then, the minimum length required for the reac-
tor to heat a 900 lm rice straw particle to 500 °C isL ¼ 1:21x
1:289  1:55m.
 A.M. Shoaib et al. / Egyptian Journal of Petroleum 27 (2018) 1305–1311
2.5.4. Calculation of the produced amount of char
The produced amount of char can be estimated by assuming
that 25% of biomass feed will be converted to char with a bulk den-
sity of 400 kg/m3 [25]. The amount of the produced char could be
determined by applying the following equation:
o:25xbiomassfeedrate
Char produced ¼ t ð7Þ
qchar
According to the above equation and after 1 h, it is found that
the calculated value of the produced bio-char is 625 cm3 at bio-
mass feed rate of 1 kg/h,
2.5.5. Calculation of char collector size
It is assumed that 2/3 of the char container volume is filled after
1 h. This assumption is provided to prevent the particles escaping
from the container in case of its volume is completely filled; this
consequently helps the particles to be re-entrained. For a radius
(r) of the char collector equals 3.81 cm, the container cross section
area (Across) will be 45.6 cm2 and the collector height can be
1:5char
obtained as following: h ¼ Acrossproduced
¼ 1:5625
45:6
¼ 20:6 cm. Accord-
ingly, the char collector volume V = 45.6  20.6 = 939.3 cm3.
2.6. Methodology
A schematic of the pilot plant included the free fall reactor that
was designed to produce a bio-oil from a biomass feed stock is
shown in Fig. 3. As illustrated in this Figure, the production process
starts by placing 500 g of each rice straw samples in the feeding
system. When the temperature of the reactor reached the specified
run temperature, the flushing of nitrogen gas was initially allowed
to flow for about 1 min. This action is taken to remove all the oxy-
gen from the system in order to ensure an inert atmosphere in the
reactor tube. Then, the feeding screw is operated manually for
moving up the rice straw sample to the heated reactor. After pyrol-
ysis of biomass sample inside the reactor, produced streams com-
posed of volatiles and bio-char residues passed through the carbon
filters (cyclone) where the bio-char residues were separated. The
purified volatile streams then flowed through the condensers
Fig. 3. Schematic of the investigated pilot plant with a free fall reactor: 1- nitrogen line, 2-feeding system, 3-reactor tube, 4-char catch, 5- cyclone, 6- condenser, and 7- gas
exit line.
1309
where they were condensed into bio-oils. The condensed volatiles
were finally collected in two circular tubes drains.
After each run, the bio-char was obtained as a by-product and
separated from the char catch and the cyclone. The weight of the
produced char was determined, then char yield was calculated.
The non-condensable gas, together with the carrier gas (nitrogen)
was vented or collected by gas sample bags and analyzed by gas
chromatography (GC).
3. Results and discussion
The chemical composition of the rice straw under investigation
is summarized in Table 2, indicating the higher organic material
(lignocellulosic compounds) and high silica content. This reveals
that the higher content of ash content.
Experimental data show that the obtained products from fast
pyrolysis of the rice straw are bio-oil, bio-char and non-
condensable gas (NCG). Fig. 4 shows the yields of these products
as a function of process temperature in temperature range of
450–700 °C.
As addressed in Fig. 4, the bio-oil liquid yields are increased
from 39.2 to 46.0 wt% as the temperature increases from 450 to
500 °C. However, after 500 °C, the yield is decreased with increas-
ing temperature and its value is reduced to 36.3 wt% at 700 °C. The
maximum bio-oil yield of 46.0 wt% was obtained at 500 °C. Unlike
to bio-oil, the NCG yield is increased continuously as the tempera-
ture increases from 450 to 700 °C. Nevertheless, the char yield is
decreased as the temperature increases for the whole temperature
range of 450–700 °C.
Three correlations relating bio-gas, bio-oil and bio-char yield to
temperature have been extracted using regression analysis. The
adjusted R2 for the three proposed correlations are very close to
1, while the standard errors are very close to zero. This confirms
the good agreement between the experimental and the predicted
results using the proposed correlations. Table 3 summarize these
results.
The desired product from fast pyrolysis process under investi-
gation is a dark brown liquid known as pyrolysis oil, bio-oil or
1310 A.M. Shoaib et al. / Egyptian Journal of Petroleum 27 (2018) 1305–1311

Table 2 Table 4
Chemical composition of rice straw. Characteristics of the bio-oils achieved by the
fast pyrolysis process.
Component Percentage (%)
Characteristic Value
Moisture 22
Lignin 14.5 Bio-oil yield (wt %) 40.5–46
Cellulose 34 Calorific value (MJ/kg) 18
Nitrogen-free extract 4.2 Density, kg/m3 1010
Ash 19.5 Viscosity@ 50 °C (mm2 s1) 15
Silica 14 pH 3–3.7
Calcium 0.17 Flash point (°C) 70
Phosphor 0.10
Potassium 0.20
Magnesium 0.11
Sulfur 0.08 corrosion inhibitor, or separating the highly acidic compounds
Cobalt 0.05(mg/kg) such acetic and formic acids. As it is presented in Table 2, the den-
Copper 0.50(mg/kg)
Manganese 0.40(mg/kg)
sity of bio-oils derived from rice straw is 1010 kg/m3 which is den-
ser than that of either light petroleum oil (diesel oil) or heavy fuel
oil with densities of 854 and 963 kg/m3 respectively. The viscosity
of the achieved bio-oil is 15 mm2/s which is lower than that of the
60 fossil fuel oil with approximately 300 mm2/s as a kinetic viscosity.
The considered bio-oil has a low heating value and it is often
50 reported around 40%–50% less than the heating value of petroleum
Product yield, wt %

40
30
20
10
0 emits very low sulfur emissions compared to fossil fuels [27].
450 500 550
Temperature, ºC
Fig. 4. Fast pyrolysis products yields in relation to the process temperature.
liquid smoke. Bio-oil has a distinct odor similar to smoke from a
wood fire, and it is often quite pungent. The most important spec-
ifications of the investigated bio-oil are higher heating value, den-
sity, viscosity, flash point, and pH. Table 4 showed the physical
characteristics of the produced bio-oils that was obtained from
the rice straw at 500 °C (maximum yield). The maximum yields
of bio-oil derived from the rice straw ranged from 40.5 to 46%. This
yield of bio oil is lower than that achieved by wood pyrolysis (75%).
This can be attributed to lower organic and high ash contents in
rice straw compared with their corresponding values in wood. In
addition, the presence of some metallic components can partici-
pate in lowering the bio-oil yield by catalytic decomposition of
oil portion.
The obtained bio-oils has pH range of 3–3.7. These lower values
of pH indicate that the produced bio-oils are highly acidic com-
pared with light petroleum oil with a pH of 5.7. This could be
attributed to the presence of acids such as acetic acid and formic
acid. The highly acidity of the considered bio-oil can cause corro-
sion problems for its metallic storage containers. However, the
acidity of this bio-oil can be reduced by neutralization, adding of
based fuel-oils. This can be ascribed to the high oxygen and water
contents in the produced bio-oil [26]. It can be noticed that the
obtained bio-oils have bad fuel properties than both diesel and
heavy oils. However, their sulfur and nitrogen contents are 0.009
and 0.08 wt% respectively, which are low, compared to light and
heavy fuel oils of 0.9 and 2.1 wt% respectively. This consequently
gives the produced bio-oils an advantage over these conventional
fuels since they would emit less SO2 and NO2 during combustion.
So, bio-oil combustion may be considered carbon neutral and
600 700 Direct combustion in boilers, engines and turbines has been tested
with various results. Due to its heterogeneity, viscosity and corro-
sive nature, most equipment requires some modification in order
to efficiently process bio-oil including a preheating section [28].
Upgrading of boi-oil would improve their characteristics as a
fuel. These characteristics include oxygen and moisture contents,
ignition temperature, acidity and stability. Upgrading would con-
vert the bio-oils to either green gasoline or green diesel oil depend-
ing on the process employed, making them suitable for use as
alternative fuels for transportation and stationary engine applica-
tions. Bio-oil large scale production would be cost-effective since
it is based on lignocellulosic biomass such as bagasse, rice straw
and other agriculture waste, which currently offers little value.
Also, the re-use of the co products, i.e. char and NCG as process
heat would be valuable.
The gaseous products from fast pyrolysis will be referred to as
non-condensable gas (NCG) rather than syngas. The NCG fraction
from fast pyrolysis is a combustible mixture, and contains many
species. The main components in product gas are methane, hydro-
gen, CO and CO2. Ethene and ethane was other important compo-
nents in the product gas. For a purpose of getting the NCG
composition, the gas sample was taken in a lap balloon which
was connected to the exit of the free fall reactor. The compositions
of the obtained product gases were analyzed by a gas chro-
matograph and the results are reported in Table 5.

Table 3
Statics for the proposed correlations.

Item Bio-Gas yield Bio-Oil yield Bio-Char yield

correlation Y = 75.47 + 0.3 T-0.00017 T2 Y = -151.05 + 0.9 T-0.0015 T2 + 8.49E-07 T3 + 2.54E-06 T4 Y = 639.06–2.84 T + 0.0043 T2-2.2E-06 T3
R2 0.98325 1 0.995432
Adjusted R2 0.966501 1 0.981728
Standard Error 1.820437 0 1.174757
 A.M. Shoaib et al. / Egyptian Journal of Petroleum 27 (2018) 1305–1311 1311

Table 5  It is also recommended to investigate other types of potential

NCG composition determined by a gas chromatograph. lingo cellulosic biomass as feedstock for bio-fuel production
Component wt % using fast pyrolysis.
Hydrogen (H2) 35.33  Finally, it is necessary also to study pyrolysis process parame-
Carbon dioxide (CO2) 20.80 ters to maximize bio-oil yields with high quality.
Carbon monoxide (CO) 11.67
Methane (CH4) 16.28
Ethane (C2H6) 1.34
Ethene (C2H4) 3.11
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