INTERNATIONAL JOURNAL OF ENERGY RESEARCH

Int. J. Energy Res. 2014; 38:16241634

Published online 13 July 2014 in Wiley Online Library (wileyonlinelibrary.com). DOI: 10.1002/er.3244

Mathematical modelling of a hydrocracking reactor for

triglyceride conversion to biofuel: model establishment
and validation
A. A. Forghani1,2,*,, M. Jafarian2, P. Pendleton3 and D. M. Lewis1
1
Micro-algae Engineering Research Group, School of Chemical Engineering, The University of Adelaide, Adelaide, SA 5005,
Australia
2
Centre for Energy Technology, The University of Adelaide, Adelaide, SA 5005, Australia
3
Center for Molecular and Materials Sciences, Sansom Institute, University of South Australia, Adelaide, SA 5000, Australia

SUMMARY
In the study, a 2D, non-isothermal, heterogeneous model of a triglyceride hydrocracking reactor is investigated. The inter-
nal heat and mass transfer within the phases in the reactor were considered using the lm theory. The conservation
equations for energy and mass were solved simultaneously using appropriate numerical techniques whose reliability was
assessed by comparison of the results with previously reported experimental data. The modelling was performed with
consideration of two proposed hydrocracking kinetic models. The model predictions showed reasonable correlation with
published experimental data and conversion rates. The calculations indicated that at feed temperature of 380 C, liquid
hourly space velocity of 8 h
1 and hydrogen : feed ratio of 1500:1, the total triglyceride conversion was 82.54% for four
major classes of hydrocarbons (light, middle, heavy and oligomerised). In addition, the concentration distribution and
temperature prole along the reactor were investigated. The product concentrations along the reactor show that higher rates
of production at the beginning of the reactor were achieved because of high concentration of triglyceride due to the
exothermic hydrocracking reactions and counter-current ow modes of triglyceride and hydrogen; a jump of 90 C was
shown at the beginning of the reactor temperature prole. Copyright 2014 John Wiley & Sons, Ltd.
KEY WORDS
triglyceride conversion; hydrocracking kinetics; reactor modelling; biofuel

Correspondence
*A. A. Forghani, Micro-algae Engineering Research Group, School of Chemical Engineering, The University of Adelaide, Adelaide, SA
5005, Australia.

E-mail: amir.forghani@adelaide.edu.au

Received 25 March 2014; Revised 5 June 2014; Accepted 1 July 2014

1. INTRODUCTION low aromatics and sulfur content of produced fuel, lower

The combustion of fossil fuels over the last hundred years
has led to a signicant increase in greenhouse gas emis-
sions, which is considered to be linked to the simultaneous
increase in the global mean temperature [1]. However,
despite the urgent need to decrease these emissions, fossil
fuels still account for ~80% of the world energy demand
[2,3]. The dependency on these sources of energy in the
mid-to-long term will result in the depletion of natural
reserves of fossil fuels and subsequently increase their cost
[1,2]. Consequently, renewable and sustainable fuel
sources are receiving increased attention. One such
sustainable resource is micro-algae from which triglycer-
ides may be extracted and reduced to a fuel source [4,5].
Several factors promote micro-algae feedstock: potentially
air pollution on burning compared with fossil fuels, the
potential abundance of micro-algae, their relatively low cost
of nourishment and their overall environmental compatibil-
ity [4,69]. One of several ways to convert triglyceride to
different ranges of hydrocarbons is via hydrocracking [10].
Therefore, the overall aim of this work is to investigate the
production of three types of fuels (light, middle and heavy
ranges of hydrocarbon) by hydrocracking triglyceride
substrates within a trickle-bed reactor [11].
Single-step and multi-step processes have been
proposed to convert triglyceride and bio-oil to different
ranges of hydrocarbon [12,13]. Hydrocracking is a
relatively efcient, single-step conversion process in terms
of energy consumption and process simplicity [6,9,13].
The hydrocracking process produces primarily linear

1624 Copyright 2014 John Wiley & Sons, Ltd.

Analysis of a hydrocracking reactor for triglyceride conversion
alkanes from micro-algal oil via three major reactions:
de-oxygenation, selective cracking and isomerisation
towards light (gasoline and kerosene) and middle hydro-
carbon (jet fuel) production [7]. In this process, large
hydrocarbon molecules are fragmented to smaller
components over specic catalysts in a hydrogen-rich
atmosphere. The rate and selectivity of each reaction
depends on both the properties of the selected catalyst
and the reaction conditions [11].
There is increasing interest in the different aspects of
catalytic hydro-reforming of micro-algae oil [12,1417].
To optimise the conversion reforming reactions, localised
experimental measurements are required at high pressure
and temperature. The large number of reaction design op-
tions renders empirical optimisation both time-consuming
and costly. Alternatively, numerical analysis provides an
appropriate and complementary methodology to investi-
gate reaction kinetics and identify how to improve the total
conversion efciency. Of the recent numerical modelling
methods, Bhaskar et al. [18] presented a three-phase
heterogeneous model that was applied to simulate the per-
formance of a trickle-bed reactor for hydro-desulfurisation
of diesel fractions of crude oil [18]. They investigated the
inuence of temperature and feed-rates on the hydro-
treating reactions and products and analysed the perfor-
mance of the reactor under various operating conditions
[18]. A mathematical model of a heterogeneous trickle-
bed reactor for the hydro-treatment of vacuum gas oil
was presented by [19]. In this model, the two-lm theory
was applied to assess the performance of the reactor in
terms of temperature, pressure, space velocity and the
gas/oil ratio [19]. Also they found from their model that
incomplete catalyst wetting and low feed velocity lead to
poor conversion of crude oil hydro-treating reactions in
the pilot-plant reactor. Alvarez and Ancheyta [20] deve-
loped a heterogeneous plug-ow model for a hydro-
processing xed bed reactor to describe the behaviour of
the crude oil residue. In their model, the gasliquid and
liquidsolid mass transfer and experimental kinetic data
were considered for validation of their model using
pilot-plant data. Their model results showed good agree-
ment with the experimental data, and a higher (818%)
performance could be achieved by the scaling up their
pilot-plant reactors. No operational performance of a
hydrocracking trickle-bed reactor for micro-algal bio-oil
has been reported in the literature. Therefore, a clear aim
of the reported work is to present a heterogeneous plug-
ow model of a trickle-bed reactor for hydrocracking of
micro-algal bio-oil.
The major section in setting up a reliable trickle-bed re-
actor model is dening a reliable reaction kinetic. Several
studies investigated the reaction pathway of hydrocracking
of triglyceride, which is the major component of bio-oil.
For instance, Benson et al. and Kloprogge et al. studied
the reaction pathways of triglyceride cracking and
upgrading over acidic zeolitic structures [15,21]. The
mechanism of hydrocracking of jathropha oil at different
temperatures was discussed by Anand and Sinha [14].
Int. J. Energy Res. 2014; 38:16241634 2014 John Wiley & Sons, Ltd.
DOI: 10.1002/er
A. A. Forghani et al.
They proposed seven different reaction mechanisms to
model triglyceride hydrocracking over alumina-supported
CoMo mixed catalysts. In their study, they grouped reac-
tants and products into various assortments, referred to as
lumps; for example, the reactant triglyceride was identied
as a lump consisting of four major components as stearic
acid, palmitic acid, linoleic acid and oleic acid. They also
used four product lumps: light hydrocarbons (LC), middle
hydrocarbons (MC), heavy hydrocarbon (HC) and
oligomerised products (OC). The rate of reaction as a func-
tion of both temperature and concentrations for each lump
was identied [14]. However, they proposed that each re-
action kinetics model is appropriate for a specic range
of temperature.
In the reported studies, the simulation strategy were
applied to model the reaction kinetics in the reactor, vali-
date the reactor model with experimental data and check
the inuence of operating conditions on the reactions
and reactor performance. A primary aim of this work is
to develop and validate the most appropriate reaction
kinetic models for triglyceride hydrocracking and thus
simulate and investigate the performance of a proposed
hydrocracking reactor.
2. MODEL DESCRIPTION
A schematic representation of the trickle-bed reactor is
shown in Figure 1(a). The system for which mass and
energy balances were developed consisted of a catalyst
bed enclosed in a thermally conductive reactor, allowing
isothermal operation under steady-state conditions. To op-
erate the reactor in an isothermal condition, a heating
jacket was needed to maintain the reactor temperature.
The triglyceride, as a rich, dense feed, entered from the
top and hydrogen gas entered from the bottom of the reac-
tor allowing counter-current ow over and around the sta-
tionary, solid phase supported catalyst, which promoted a
well-mixed continuous (uid) phase. Throughout the reac-
tor, hydrogen was assumed to be absorbed by the liquid
phase and transfers to the liquidsolid interface, promoting
hydrocracking reactions. The reaction products as LC,
MC, HC and OC dispersed through the gas and liquid
phases, transporting up or down the reactor, with their re-
spective (average) densities, and thus direction, depending
on the operating temperature and pressure. An element of
the reactor with length z, shown in Figure 1(c), was
employed in deriving the mass and energy balance expres-
sions for the model.
3. MATHEMATICAL MODEL OF THE
HYDROCRACKING TRICKLE-BED
REACTOR
Modelling is one of the most efcient ways to evaluate
plant performance. Recently, models were employed to
optimise the impact of changes in design variables. The
1625
A. A. Forghani et al.
Figure 1. (a) Schematic representation of the trickle-bed reactor, (b) lm theory over the catalyst and (c) the selected element of the
trickle-bed reactor for development of the governing equations.
rst step to make an efcient model is the formation of the
appropriate mass and energy balance equations. To this set
of equations, suitable kinetic equations that represent the
rate of reaction/s are added [22].
In the reported study, the model was developed for a
lab-scale trickle-bed reactor by using a two-lm theory,
which incorporated mass transfer at the gasliquid and
liquidsolid interfaces, and employed previously published
[20,18,23,24,19]. This reactor model enabled optimisation
of the operational conditions of hydrocracking processes at
lab-scale and estimated the scalability of the hydrocracking
at large scale. The following assumptions were made for
the three-phase heterogeneous reactor model:
1. Plug ow along the reactor with no radial concentra-
tion gradient;
2. The trickle-bed reactor operated at steady-state
conditions;
3. The reactor operated isothermally;
4. Axial heat dispersion was negligible;
5. Light components phase change was negligible; and
6. All reactions occurred at the liquidcatalyst surface
interface.
All the assumptions are valid and reasonable to apply in
the mathematical model. For example, because the ratio of
length per diameter of reactor (diameter is 1.3 cm and
length is 30 cm) has a large number, then the rst and fth
assumptions are justied. The experimental data were col-
lected at the steady-state condition by a lab-scale trickle-
bed reactor, and also the lab-scale of trickle-bed reactor
was operated isothermally to obtain experimental data;
therefore, the fourth section is justied. For justication
of the seventh section, according to the temperature and
pressure of hydrocracking reactions in the trickle-bed
1626
Analysis of a hydrocracking reactor for triglyceride conversion
reactor, all components such as triglyceride and all lump
products remained in the liquid phase thermodynamically.
4. MODEL EQUATION
The large number of components produced within the hy-
drocracking synthesis was classied using ve lumps.
The triglyceride lump (Tg) consisted of four components:
stearic acid, oleic acid, palmitic acid and linoleic acid.
The four product lumps as LC, MC, HC and OC is shown
in Figure 2, which is separated into two reaction kinetics
models A1 and A7, extracted from Anand and Sinhas
[14] analyses because these were relevant to the modelled
triglyceride conversion at temperatures >360 C, the mini-
mum temperature of our proposed process [14]. In model
A1, triglyceride was converted directly to LC, MC, HC
and OC via distinct reactions with discrete rate constants.
The A7 model (Figure 2 (b)) considered a more compre-
hensive process, wherein four primary reactions again con-
vert the triglyceride to LC, MC, HC and OC directly,
followed by two subordinate reactions, which further con-
vert HC to MC and MC to LC. In the model, each reaction
rate constant was identied as ki . However, Anand and
Sinha [14] proposed various kinetic models for hydro-
cracking of triglyceride, but in this study, we investigated
their model and data for reactor modelling and validation.
Differential mass and energy balance expressions were
developed using the aforementioned assumptions general-
ised expression for mass distribution along the reactor for
transfer from the gasliquid interface to the gas phase for
each considered lump and hydrogen gas is given in Eq.
1. For each lump, an evaporation model for an ideal mix-
ture was employed.
Int. J. Energy Res. 2014; 38:16241634 2014 John Wiley & Sons, Ltd.
DOI: 10.1002/er
Analysis of a hydrocracking reactor for triglyceride conversion A. A. Forghani et al.

Figure 2. A1 (a) and A7 (b) reaction kinetics models that are proposed by Anand and Sinha [14] for triglyceride conversion.

For lipid and triglyceride as the feedstock (Tg): For hydrogen (H2):

!
PgTg K lTg :a:Ac PgH 2 K l :a:Ac R:T g PgH 2
ug :A:
xTg PTg
PgTg ; (1)
H2
ClH 2 ; (6)
z R:T g z ug hH 2

For LC:
where, ug, xi, Pgi and K gi are the gas velocity, ith lump,
i = LC, MC, HC and OC, liquid mole fraction in the gas
PgLC K l :a:Ac

ug :A:
LC xLC PLC
PgLC ; (2) and liquid interface, partial pressure and mass transfer
z R:T g coefcients in gas phase, respectively.

4.1. Mass balance equations in liquid phase

For MC:
The differential equations of mass balance for the concentra-
tions of hydrogen and light, middle, heavy and oligomerised
PgMC K l :a:Ac
 hydrocarbon in the liquid phase can be written by equating
ug :A:
MC xMC PMC
PgMC ; (3) the concentration gradients for the mass transfer of Tg,
z R:T g
LC, MC, HC, OC and H2 across the gasliquid interface
as follows:
For and triglyceride as the feedstock (Tg),
For HC:

PgHC K l :a:Ac
 C LTg K gTg :a:Ac

ug :A:
HC xHC PHC
PgHC ; (4) uL :A:
r LL xTg PTg
PgTg : (7)
z R:T g z R:T g

For OC: For LC,

PgOC K l :a:Ac
 ClLC K l :a:Ac


ug :A:
OC xOC POC
PgOC ; (5) uL :A: r LC LC xLC PLC
PgLC : (8)
z R:T g z R:T g

Int. J. Energy Res. 2014; 38:16241634 2014 John Wiley & Sons, Ltd. 1627
DOI: 10.1002/er
A. A. Forghani et al. Analysis of a hydrocracking reactor for triglyceride conversion

For HC: Table I. Lump reaction rate constants and activation energy
values.
C lHC K l :a:Ac

uL :A: r HC HC xHC PHC
PgHC ; (9) Lump reaction Activation
z R:T g Reactant and rate constant energy

1
product lumps (h ) (kJ/mol)
2
Triglycerides (Tg) 31.97 10 26
For OC: 5
Lighter hydrocarbons (LC) 62.62 10 83
10
Middle hydrocarbons (MC) 4.2 10 127
ClOC K l :a:Ac
 4
uL :A: r OC OC xOC POC
PgOC ; (10) Heavy hydrocarbons (HC) 13.73 10 47
z R:T g Oligomerised hydrocarbon (OC) 14.58 10
4
47

4.3. Energy balance equation for the

reaction bed
where uL, C Li , ri,
and Pgi Pi
are the liquid velocity, ith lump,
i = LC, MC, HC and OC, liquid concentration, rate of reaction The energy balance equations for the liquid and gas phases
for each lump, partial pressure in the gas phase and saturation were developed to assess the temperature variation in the
pressure in the liquidgas phase interface, respectively. catalyst bed of the reactor as the reaction bed.
For liquid phase:
4.2. Chemical reaction model
T L X

Triglyceride hydrocracking reaction kinetic model devel- mg C lP r i H i Ac
hG aA T g
T l
z
opment has been hindered by its overall complexity

2r in hl T w
T l : (19)
[14,15,21]. More recently, a comprehensive suite of possi-
ble reaction pathway was developed in 2012 [14,15,21],
with each path depending on the reaction conditions. For
the proposed reactor development, the reaction pathways For gas phase,
summarised in Figure 2 were appropriate. The reaction rate
expressions for model A1 are listed as follows: T g

mg C gP hG a:A T g
T l

r LL k1 k2 k 3 k4 CTg ; (11) z



2r in 1
hl T w
T g ; (20)
r LC k1 C Tg ; (12)

r MC k2 C Tg ; (13) where mg, Clp, TL, Tg, Tw, hG, , hl and Hi are mass ow-
rate, specic heat capacity of liquid phase, liquid tempera-
r HC k3 C Tg ; (14) ture, gas temperature, reactor wall temperature, gas heat
transfer coefcient, bed porosity, liquid heat transfer coef-
r OC k4 CTg : (15) cient and enthalpy of reaction for each lump, respec-
tively. Also the calculation of the enthalpy of each lump
For model A7, two subordinate cracking reactions between reaction is shown:
HC and MC are needed to be considered. The rst reaction (as X X
reaction 5) cracks HC to MC, and the second (as reaction 6) H i H p
H r : (21)
Products Reactants
cracks MC to LC. The rate of reaction expressions are as follows:
Here Hp and Hr are the enthalpy of all products and
r HC
MC k 5 CHC ; (16) reactants, respectively, which are triglyceride and hydrogen.

r MC
LC k 6 C MC ; (17)
where ki and Ci, ith lump, i = LC, MC, HC and OC are rate con-
stants and liquid concentration, respectively. The reaction rate
constant for each lump was estimated from the Arrhenius equa-
tion using data summarised in Table I.
The percentage yield of each lump during hydrocrack-
ing was dened as follows:
4.4. Energy balance equation for the tube of
the reactor
In this section, temperature variation of the reactor tube (reac-
tor wall) was considered in the model, where the reactor tube
temperature variation was considered in two dimensions in the
model. The reactor conguration was assumed as a vertical
cylinder, and the energy balance for the reactor tube (wall) is

mass of each lump 2 T w 1 T w

Yi *100% (18) K K: 0: (22)
mass of triglycerides z2 r r r

1628 Int. J. Energy Res. 2014; 38:16241634 2014 John Wiley & Sons, Ltd.
DOI: 10.1002/er
Analysis of a hydrocracking reactor for triglyceride conversion A. A. Forghani et al.

The boundary conditions are as follows: 4.6. Molecular diffusivity

T
At r r out
K hout T
T amb ; (23) In order to determine the gasliquid mass transfer coefcient,
r it is essential to calculate the molecular diffusivity of each
T
 lump and hydrogen in the liquid and gas. The diffusivity
At r r in
K hin T
T f ; (24)
r was determined by the Fuller correlation [25].

T DAB 110
8 :T 1:75 1=M A 1=M B 0:5

At z 0&z L 0; (25) X 1 X 1 2 (29)
r P i =3 i =3 ;
A B

where Tamb and Tf are the ambient and uid temperature re-
spectively and hin and hout are the heat transfer coefcients in- where P, Mi and vi are the total pressure, molecular weight of
side and outside of the reaction side of the reactor. each lump and the specic volume of each lump, respec-
tively. The aforementioned parameters for each component
4.5. Gasliquid mass transport analyses were derived from Perrys handbook, and then they were
calculated for lumps by applying the rule of mixtures [26].
Because all the hydrocracking reactions were taken place
in the liquidcatalyst interface, the transportation of mass
between gas and liquid phase should be considered in the 5. NUMERICAL SOLUTION
model. The correlation for the estimation of the gasliquid
mass transfer coefcients is [19] To solve these sets of partial differential equations, the mass
and energy balance equations were discretised and solved
0:765 0:365
jD 0:82
0:386 (26) simultaneously using the modied GaussSeidel iteration
Re Re technique [27]. The numerical algorithm is illustrated in
Sh Figure 3. According to the algorithm, the input parameters
jD (27) such as feed temperature, pressure, ow-rate and H2 : feed ra-
Re:Sc1 =3
tio were specied. Initial distribution of temperature and lump
concentrations was assumed along the reactor. Conservation
K:dp
Sh (28) equations for energy and mass balances are discretised and
DAB solved simultaneously using modied GaussSeidel iteration
method to determine the temperature and concentration distri-
Here , DAB, Sh, Re and Sc are porosity, molecular bution along the reactor. This process continued until conver-
diffusion, Sherwood, Reynolds and Schmidt numbers, gence was reached. The output of the model provides the lump
respectively. concentration and temperature distribution along the reactor.

Figure 3. Numerical algorithm that was applied in the hydrocracking reactor model.

Int. J. Energy Res. 2014; 38:16241634 2014 John Wiley & Sons, Ltd. 1629
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A. A. Forghani et al. Analysis of a hydrocracking reactor for triglyceride conversion

The catalyst specications and operating conditions that were was performed by using the experimental data reported
applied in the model are listed in Table II. The production yield by Anand and Sinha [14]. The model was run with two
of three major lumps of LC, MC and HC were the target for different kinetics models of A1 and A7 using different
the model validation and optimisation. The model sensitivity temperatures for validation. The product lumps of LC,
analysis was performed and reported in the second section. MC, HC and OC were considered as major products. In
the Figure 4 and Table III, the reactor model based on
A1 and A7 kinetic models was compared with the exper-
imental data in terms of yields versus temperature. To
6. MODEL VALIDATION obtain the validation results, the reactor model was run
with a xed temperature. For all major product lumps,
To evaluate the accuracy and validity of the mathematical the A7 kinetic model has a good agreement with
model, validation is essential. Validation of the model experimental data in terms of the average deviation from
experimental data. The average errors of the applied A1
and A7 kinetic models in the reactor model were
Table II. The operating conditions and catalyst specications
43.42% and 26.6%, respectively for the LC lump, 20.9%
chosen for the simulation of the hydrocracking reactor [14].
and 8.2%, respectively for the MC lump, and 11.4% and
Catalyst 4% CoO, 16% MoO3, 2.8%, respectively for the HC lump. According to previ-
1% P2O5 on -Al2O3 ously reported literature for reactor modelling [2729], the
Catalyst mass 2g aforementioned error values show good agreement of the
Catalyst volume 2.4 ml A7 kinetic model to reality, and the large deviation of A1
Catalyst shape Powder kinetics model from the experimental data was attributed
Feed inlet temperature 380 C to failure consideration of subordinate reactions between
Reactor pressure 80 bar the lump products and minor differences in model assump-

1
LHSV 8h
tions. Therefore, the A7 kinetic model was deemed to be
H2 : feed ratio 1500
2 suitable for the investigation of the yield of products and
Heat ow 1000 W/m
reaction temperature.

Figure 4. Comparison of product yields of (a) light hydrocarbon lump (LC), (b) middle hydrocarbon lump (MC) and (c) heavy hydrocar-
bon lump (HC) by A1 and A7 kinetic models with experimental data [14].

1630 Int. J. Energy Res. 2014; 38:16241634 2014 John Wiley & Sons, Ltd.
DOI: 10.1002/er
Analysis of a hydrocracking reactor for triglyceride conversion A. A. Forghani et al.

Table III. Experimental products yield of LC, MC and HC temperature prole, and the gas temperature prole is
versus. A1 and A7 kinetic models. less than the liquid, because of the difference in their
Experimental A1 kinetic A7 kinetic
heat transfer coefcient [14,30,13].
Temperature (C) data model model As shown in Figure 1, triglyceride and hydrogen were
injected from the top and bottom of the reactor, respec-
Low hydrocarbon production yield (LC) tively (counter-current ow). Therefore, the gas inlet point
300 0.081 0.2095 0.172 is at the end of the reactor where the gas temperature
340 0.572 0.6856 0.5856 prole varied linearly along the reaction bed. From these
360 0.873 0.9818 0.9218 data, it is clear that the triglyceride-cracking reactions
380 1.715 1.4006 1.461 started after entering the reactor. The hydrogen and cata-
Middle hydrocarbon production yield (MC)
lyst bed were maintained at an appropriate temperature to
300 0.083 0.2155 0.112
allow the required heat ux to control the temperature of
320 0.473 0.5026 0.7026
the reactor. The gas phase temperature increased linearly
340 2.092 1.1006 1.5006
along the reactor because the gas physical properties
360 3.994 2.2758 2.8758
remain constant between 380 and 450 C. The liquid
Heavy hydrocarbon production yield (HC)
320.00 50.23 44.6926 49.8936
temperature increased rapidly to 470 C because of low
340.00 37.07 31.8451 40.8451 liquid ow-rate and rapid heat absorption at the beginning
360.00 72.47 65.8153 71.8153 of the hydrocracking endothermic reactions. The liquid
temperature then decreased with the same trend of wall
temperature prole as the triglyceride concentration dimin-
ished along the reactor to about 420 C, and heat was
7. RESULTS AND DISCUSSION absorbed during the hydrocracking reactions.
The concentration, mole fraction and the yield of pro-
To show the result of the model, the calculation param- duction for all lumps along the reactor are shown in
eters were assessed at the inlet temperature of 380 C, Figure 6. In the assumptions, it was mentioned that the
liquid hourly space velocity (LHSV) of 8 h
1, pressure reactions are taken place in the liquid phase, and all the
of 80 bar and H2 : feed ratio of 1500, and the A7 results about lump productions along the reactor were in
kinetic model based on the validation results was the liquid phase. As shown in Figure 6(a), the triglyceride
selected because of low deviation from the experimen- concentration, as one of the reactants, decreased from
tal data. 2.246 to 0.39 mol/m3, along the reactor and residual tri-
In the lab-scale hydrocracking unit, the trickle-bed glyceride exited the reactor. This decrease in triglyceride
reactor was situated in a furnace to control the reactor concentration had a higher rate at the reactor entrance,
temperature by a constant heat ow. A constant heat and then the slope of triglyceride consumption decreased
ux along the reactor surface was assumed in the along the reactor. For example, from the reactor entrance
model, and the obtained temperature prole along the to X/L0 of 0.2, the mole fraction of triglyceride decreased
reactor is shown in Figure 5. The applied parameter from 1 to 0.6068, but from the X/L0 of 0.2 to 0.4, the mole
of X/L0 is the dimensionless form of the reactor length. fraction varied from 0.6068 to 0.3689. The reasons for the
A constant heat ow of 1000 W/m2 was considered in higher rate of triglyceride consumption at the beginning of
the model. The inlet temperatures of triglyceride (liquid the reactor demonstrate adequate triglyceride concentration
phase) and hydrogen (gas phase) were both 380 C. The and a high pre-heated volume of hydrogen with the temper-
liquid temperature prole is less than the wall ature above 400 C. The aforementioned reasons improve
the hydrocracking reactions and lead to higher rate of
triglyceride consumption and higher rate of hydrocarbon
production at the preliminary length of the reactor.
According to concentration and mole fraction data
(Figure 6(a and b)), the conversion of triglyceride to hydro-
carbon was 82.54%. The majority of the triglyceride
conversion moved forward to heavy (diesel range) and
oligomerised range of hydrocarbons. The rate of production
increased rapidly at the preliminary length of the reactor,
and the production rate decreased from X/L0 of 0.4.
In Figure 6(c), the production yields of heavy and
oligomerised range of hydrocarbons were greater than light
and middle range of hydrocarbons. With the current
operating conditions (Tin = 380 C, LHSV = 8 h
1 and H2/
feed = 1500), the hydrocracking synthesis conducted the
Figure 5. The reactor wall, liquid and gas temperature proles triglyceride conversion towards biodiesel production
along the reactor. because of the high HC production yield.

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A. A. Forghani et al. Analysis of a hydrocracking reactor for triglyceride conversion

Figure 6. (a) Concentration, (b) mole fraction and (c) yield of production for ve lumps of triglyceride, LC, MC, HC and OC.

Figure 7. (a) Mole fraction and (b) partial pressure of LC, MC, HC and OC in the gas phase (evaporation).

Evaporation or mass transfer of different lumps from the
liquid phase to gas phase is shown in Figure 7. At an inlet
temperature of 380 C and pressure of 80 bar, evaporation
of different lumps was very low because of high pressure
along the reactor. As shown in Figure 7(a), all lump evapora-
tions were in order of 10
4, and most of the products were
coming out from the reactor in liquid form. As shown in
Figure 7, at the end of the reactor (X/L0 of 0.8 to 1), the max-
imum conversion was achieved in the reactor, and most of
the reactants converted to HC and OC, so the evaporation
rate of OC and HC lumps were very low, but the evaporation
of LC was very high. From the X/L0 of 0.8 to the reactor en-
trance, the evaporation rate, because of temperature increase
along the reactor, increased rapidly for the LC, MC and HC
fractions. These levels of increase were higher in LC because
of low vapour pressures of its components, in comparison
with other lumps. Also the OC has the lower evaporation rate
because its components have higher vapour pressures.
8. CONCLUSION
A three-phase non-isothermal heterogeneous model was
considered to analyse a triglyceride hydrocracking reactor.
In the hydrocracking reactor, triglyceride and hydrogen en-
tered the reactor counter-currently, and after reaction with

1632 Int. J. Energy Res. 2014; 38:16241634 2014 John Wiley & Sons, Ltd.
DOI: 10.1002/er
Analysis of a hydrocracking reactor for triglyceride conversion A. A. Forghani et al.

the supported catalyst, four lumps of hydrocarbons were H2 = hydrogen

produced such as LC, MC, HC and OC. Two kinetic HC = heavy hydrocarbons
models of hydrocracking reactions, A1 and A7, were i = each lump index
applied in the modelling of the reactor. According to the in = inside
results, the A7 kinetic model was close to the reality, and L, l = liquid
the yield of major product lumps based on A7 the kinetics LC = light hydrocarbons
model had a good correlation with the average error of MC = middle hydrocarbons
12.53% in comparison with the experimental data. The OC = oligomerised products
temperature variations of liquid, solid and gas phases were out = outside
also investigated. The gas temperature increased linearly Tg = triglyceride
along the reactor because of the gas physical properties. w = wall
The liquid temperature increased rapidly to 470 C because
of low liquid ow-rate and rapid heat absorption at the
entrance of the reactor due to endothermic reactions. The
liquid temperature decreased with the same trend of wall ACKNOWLEDGEMENTS
temperature prole as the triglyceride concentration
decreased along the reactor. The triglyceride conversion The rst author is grateful for the support of an Adelaide
of the modelled reactor was 82.54%, and most of the Scholarship International (ASI) from The University of
triglyceride converted to HC and OC indicates good Adelaide, and also the authors wish to acknowledge Emeritus
potential for biodiesel production. This modelling can be Prof. Keith King for his grateful support. Also this research
applied for scale-up design of biodiesel production using was supported under Australian Research Councils Linkage
a single-step hydrocracking process. Projects funding scheme (Project LP100200616) with
industry partner SQC Pty Ltd and the Australian Renewable
Energy Agency advanced biofuels investment readiness
programme funding agreement number Q00150.
NOMENCLATURE
a = specic surface area of catalyst (m2/m3)
C Li = liquid concentration of each lump (mol/m3)
REFERENCES
Clp = liquid specic heat capacity (J/kg.K)
hG = gas heat transfer coefcient (W/m2.K) 1. Gross M. Looking for alternative energy sources.
hl = liquid heat transfer coefcient (W/m2.K) Current Biology 2012; 22(4):R103R106. doi:10.1016/
ki = rate constant of major reactions (1/s) j.cub.2012.02.002.
K gi = mass transfer coefcients in gas phase (m/s) 2. Hosseini SE, Abdul Wahid M. The role of renewable
ki = rate constant of internal reactions (1/s) and sustainable energy in the energy mix of Malaysia:
L0 = reactor length (m) a review. International Journal of Energy Research
LHSV = liquid hourly space velocity (1/h) 2014. doi:10.1002/er.3190.
mg = gas mass ow-rate (kg/s)
3. Mokhtar M, Ali MT, Khalilpour R, Abbas A, Shah N,
Pgi = partial pressure (Pa)
Hajaj AA, Armstrong P, Chiesa M, Sgouridis S. Solar-
Pi = saturation pressure in the liquidgas phase
interface (Pa) assisted post-combustion carbon capture feasibility study.
ri = rate of reaction (mol/m3.s) Applied Energy 2012; 92:668676. doi:10.1016/j.
R = universal gas constant (J/mol.K) apenergy.2011.07.032.
Re = Reynolds number 4. Brennan L, Owende P. Biofuels from microalgaea
Sc = Schmidt number review of technologies for production, processing, and
Sh = Sherwood number extractions of biofuels and co-products. Renewable and
TL = liquid phase temperature (K) Sustainable Energy Reviews 2010; 14(2):557577.
Tg = gas phase temperature (K) doi:10.1016/j.rser.2009.10.009.
Tw = reactor wall temperature (Tube) (K) 5. Srensen B. A renewable energy and hydrogen scenario
X = each point along the reactor length (m)
for northern Europe. International Journal of Energy
Y(i) = yield of each lump
Research 2008; 32(5):471500. doi:10.1002/er.1376.
Hi = enthalpy of reaction for each lump (kJ/mol)
= bed porosity 6. Sharif Hossain ABM, Salleh A. Biodiesel fuel produc-
tion from algae as renewable energy. American Journal
of Biochemistry and Biotechnology 2008; 4(3):250254.
Superscripts and subscripts 7. Luque R, Herrero-Davila L, Campelo JM, Clark JH,
Hidalgo JM, Luna D, Marinas JM, Romero AA. Biofuels:
amb = ambient a technological perspective. Energy & Environmental
g = gas phase Science 2008; 1(5):542564. doi:10.1039/B807094F.

Int. J. Energy Res. 2014; 38:16241634 2014 John Wiley & Sons, Ltd. 1633
DOI: 10.1002/er
A. A. Forghani et al.
8. Satyanarayana KG, Mariano AB, Vargas JVC. A
review on microalgae, a versatile source for sustainable
energy and materials. International Journal of Energy
Research 2011; 35(4):291311. doi:10.1002/er.1695.
9. Shi F, Wang P, Duan Y, Link D, Morreale B. Recent
developments in the production of liquid fuels via
catalytic conversion of microalgae: experiments and
simulations. RSC Advances 2012; 2(26):97279747.
doi:10.1039/C2RA21594B.
10. Lestari S, Mki-Arvela P, Beltramini J, Lu GQ,
Murzin DY. Transforming triglycerides and fatty acids
into biofuels. ChemSusChem 2009; 2(12):11091119.
doi:10.1002/cssc.200900107.
11. Ash M, Ash I. Handbook of Textile Processing
Chemicals. Synapse Information Resources: Endicott,
New York, 2000.
12. Chen L, Liu T, Zhang W, Chen X, Wang J. Biodiesel pro-
duction from algae oil high in free fatty acids by two-step
catalytic conversion. Bioresource Technology 2012;
111:208214. doi:10.1016/j.biortech.2012.02.033.
13. Verma D, Kumar R, Rana BS, Sinha AK. Aviation fuel
production from lipids by a single-step route using hierar-
chical mesoporous zeolites. Energy & Environmental Sci-
ence 2011; 4(5):16671671. doi:10.1039/C0EE00744G.
14. Anand M, Sinha AK. Temperature-dependent reaction
pathways for the anomalous hydrocracking of triglyc-
erides in the presence of sulded CoMo-catalyst.
Bioresource Technology 2012; 126:148155.
doi:10.1016/j.biortech.2012.08.105.
15. Benson TJ, Hernandez R, French WT, Alley EG,
Holmes WE. Elucidation of the catalytic cracking path-
way for unsaturated mono-, di-, and triacylglycerides
on solid acid catalysts. Journal of Molecular Catalysis
A: Chemical 2009; 303(12):117123. doi:10.1016/j.
molcata.2009.01.008.
16. Benson TJ, Hernandez R, White MG, French WT, Alley
EE, Holmes WE, Thompson B. Heterogeneous cracking
of an unsaturated fatty acid and reaction intermediates
on H + ZSM-5 catalyst. CLEAN Soil, Air, Water
2008; 36(8):652656. doi:10.1002/clen.200800050.
17. Pragya N, Pandey KK, Sahoo PK. A review on harvest-
ing, oil extraction and biofuels production technologies
from microalgae. Renewable and Sustainable Energy Re-
views 2013; 24:159171. doi:10.1016/j.rser.2013.03.034.
18. Bhaskar M, Valavarasu G, Sairam B, Balaraman KS,
Balu K. Three-phase reactor model to simulate the per-
formance of pilot-plant and industrial trickle-bed
reactors sustaining hydrotreating reactions. Industrial
& Engineering Chemistry Research 2004; 43(21):
66546669. doi:10.1021/ie049642b.
19. Korsten H, Hoffmann U. Three-phase reactor model for
hydrotreating in pilot trickle-bed reactors. AIChE Journal
1996; 42(5):13501360. doi:10.1002/aic.690420515.
1634
Analysis of a hydrocracking reactor for triglyceride conversion
20. Alvarez A, Ancheyta J. Modeling residue
hydroprocessing in a multi-xed-bed reactor system.
Applied Catalysis A: General 2008; 351(2):148158.
doi:10.1016/j.apcata.2008.09.010.
21. Kloprogge JT, Duong LV, Frost RL. A review of the
synthesis and characterisation of pillared clays and
related porous materials for cracking of vegetable oils
to produce biofuels. Environmental Geology 2005;
47(7):967981. doi:10.1007/s00254-005-1226-1.
22. Ingham T, Walker RW, Woolford RE. Kinetic param-
eters for the initiation reaction RH + O2 R + HO2.
Symposium (International) on Combustion 1994;
25(1):767774. doi:10.1016/S0082-0784(06)80709-5.
23. Jarullah AT, Mujtaba IM, Wood AS. Kinetic parame-
ter estimation and simulation of trickle-bed reactor
for hydrodesulfurization of crude oil. Chemical Engi-
neering Science 2011; 66(5):859871. doi:10.1016/j.
ces.2010.11.016.
24. Jarullah AT, Mujtaba IM, Wood AS. Whole crude oil
hydrotreating from small-scale laboratory pilot plant
to large-scale trickle-bed reactor: analysis of opera-
tional issues through modeling. Energy & Fuels
2011; 26(1):629641. doi:10.1021/ef201406r.
25. Fuller EN, Schettler PD, Giddings JC. New method for
prediction of binary gas-phase diffusion coefcients.
Industrial & Engineering Chemistry 1966; 58(5):
1827. doi:10.1021/ie50677a007.
26. Perry JH. Chemical engineers handbook. Journal of
Chemical Education 1950; 27(9):533. doi:10.1021/
ed027p533.1.
27. Forghani AA, Elekaei H, Rahimpour MR. Enhancement
of gasoline production in a novel hydrogen-
permselective membrane reactor in FischerTropsch
synthesis of GTL technology. International Journal of
Hydrogen Energy 2009; 34(9):39653976. doi:10.1016/
j.ijhydene.2009.02.038.
28. Forghani AA, Rahimpour MR. A novel approach in
enhancement of gasoline (C5+) production by a
dual-type reactor and a H2-permselective membrane
reactor in Fischer-Tropsch synthesis. International
Journal of Separation for Environmental Sciences
2012; 1(1):128.
29. Rahimpour MR, Forghani AA, Mostafazadeh AK,
Shariati A. A comparison of co-current and counter-
current modes of operation for a novel hydrogen-
permselective membrane dual-type FTS reactor in
GTL technology. Fuel Processing Technology 2010;
91(1):3344. doi:10.1016/j.fuproc.2009.08.013.
30. Sharma RK, Anand M, Rana BS, Kumar R, Farooqui SA,
Sibi MG, Sinha AK. Jatropha-oil conversion to liquid hy-
drocarbon fuels using mesoporous titanosilicate supported
sulde catalysts. Catalysis Today 2012; 198(1):314320.
doi:10.1016/j.cattod.2012.05.036.
Int. J. Energy Res. 2014; 38:16241634 2014 John Wiley & Sons, Ltd.
DOI: 10.1002/er