ACIPET

CFD analysis of the heat transfer in a trickle bed reactor used for palm oil
hydrotreatment

J.F. Vlez. Universidad Nacional de Colombia Sede Medelln, Facultad de Minas, Bioprocesos y Flujos reactivos,
Medelln, Colombia.
C. C. Mendoza. Universidad Nacional de Colombia Sede Medelln, Facultad de Minas, Bioprocesos y Flujos reactivos,
Medelln, Colombia.
S. Lpez. Universidad Nacional de Colombia Sede Medelln, Facultad de Minas, Bioprocesos y Flujos reactivos,
Medelln, Colombia.
A. Molina. Universidad Nacional de Colombia Sede Medelln, Facultad de Minas, Bioprocesos y Flujos reactivos,
Medelln, Colombia.

Artculo Tcnico
Tesis Pregrado
Tesis Posgrado

Derechos de Autor 2013, ACIPET

Este artculo tcnico fue preparado para presentacin en el XV Congreso Colombiano del Petrleo organizado por ACIPET en Bogot D.C. Colombia, 20 - 22 de Noviembre de 2013.
Este artculo fue seleccionado para presentacin por el comit tcnico de ACIPET, basado en informacin contenida en un resumen enviado por el autor(es).

Abstract: A CFD (ANSYS Fluent) simulation of heat transfer during the hydrotreatment of palm oil in a trickle bed reactor (catalyst
diameter = 1.8 mm, molar ratio H2/palm = 24 and LHSV = 2h-1) showed that distributed H2 injection can prevent the formation of hot
spots.
Introduction
Climate change and the high price of fossil fuels have raised a strong interest in supplying a significant portion of liquid fuels from
renewable sources. Industrial biofuels production, after significant research efforts, currently contributes to this aim1,2 with ethanol
(via glucose-rich syrup fermentation) and biodiesel (from vegetable oils transesterification). Previous studies36 indicate that biodiesel
produced via transterification presents restrictions in its use because its high viscosity and density and low cetane number and energy
content. These limitations are solved by using mixtures of 5-7%vol biodiesel in petroleum-derived diesel3.
Hydrotreatment (HDT) is one of the most important processes in crude petroleum refining, because it removes pollutant agents of
fossil fuels7. Biodiesel produced by HDT presents advantages such as lower viscosity, higher heat content and cetane number2,3,8 when
compared to biodiesel from transesterification. Recently HDT 2,8 has been used, at laboratory and pilot plant scale, to convert
vegetable oils to biofuels and propane gas. Widespread industrial production of biodiesel via HDT, however, still requires better
understanding of the interaction of the reactive phases.

J.F VLEZ, C.C. MENDOZA, S. LOPEZ, A. MOLINA

Previous studies have proposed mechanisms for the HDT of palm oil from a thermodynamic point of view1,2 and have, mostly, studied
the performance of various catalyst that are currently being tested in this area 2,911. However, there have been few studies about the
performance of the reactor itself. In Colombia, in particular, some authors 12 have modeled HDT of regular crude oil but, in the
refereed literature, none has addressed heat transfer when hydrotreating vegetable oil.
In HDT three phases (hydrogen, oil and catalyst) react in a Trickle Bed Reactor (TBR). Typically the gas and liquid phases move
concurrent downflow through the catalyst1,7. The addition of gas (H2) at high pressures and temperatures breaks weak bonds and
cracks and isomerizes molecules. The high exothermicity of the reaction is of major concern as high temperature (above 375C)
degrades the HDT products1. This paper presents results from Computational Fluid Dynamis (CFD) simulations carried out with the
aim of having a preliminary understanding of heat transfer during HDT of palm oil.
Methodology
The simulations were carried out with the commercial software Ansys-Fluent 13.0 in 3D. This section gives details of the simulation
parameters as well of the material properties and process conditions.
Stoichiometry and reaction rate parameters
In the refereed literature, the expression by Sebos et al.8 was the only reported for the hydrotreatment of vegetable oil (cotton seed).
Sebos et al. simplified the complex vegetable oils HDT mechanism2 to one single global reaction (Eq. A-1). Understanding that it is a
very simplified view of the HDT process, Reaction-1 and the kinetic expression by Sebos et al. were selected for the CFD simulations.
Reaction-1
(Tripalmitin)

(Hydrogen)

(n-Pentadecane)

(Propane)

(Carbon Dioxide)

The heat of reaction for Reaction-1 is -96.36 kJ/mol H2, smaller when compared with the saturation of olefins (-113 kJ/mol H2) but
greater than that of aromatics (-69 kJ/mol H2)13.
Geometry, boundary and operating conditions
Table 1 summarizes the parameters and operating conditions used in the CFD simulation. Because of its high production in Colombia,
940.8 103 in 201114, the selected feedstock was refined bleached deodorized palm oil (RBDPO). The reactor modeled was of pilotplant scale, i.e.10 bbl/day of RBDPO. According to the stoichiometry in Eq. A-1, this corresponds to 2.54
kg/s of hydrogen if
a 24.14 molar ratio2 between hydrogen and oil is assumed. A typical2 Liquid Hourly Space Velocity (LHSV) of 2 h-1 was selected to
define the total reactor volume. The operating temperature (330C) and pressure (88.82) atm are as well standard values for these
systems. The porosity of the bed was 0.52, as calculated from an expression that relates the reactor geometry with catalyst size. The
reactor has cylindrical shape with length 0.49 m and diameter 0.29 m. The length to diameter ratio was assumed as 5/3. The catalyst
has spherical equivalent diameter of 1.8 cm.
In order to expedite calculations the reactor was simulated as a quarter, given the symmetry of the system as becomes evident in
Figure 1. The simulation assumes isotropic flow, i.e. constant fixed bed properties through the reactor volume. The boundary
conditions in Figure 1a, are valid for all simulations with axial H2 injection. Basically there is an injection with a constant flow of H 2
while the walls stay at 330C. The output was considered as a pressure outlet. The boundary conditions are basically the same when a
fraction of H2 enters the reactor through radial injections (Figure 1, b). In this case the diameter of the line where H2 enters radially
through four ports uniformly spaced in the reactor located 0.087 m from the reactors main input stream, was 0.0254 m. 23.22% of
the total H2 enters through the radial streams15,16.

CFD ANALYSIS OF THE HEAT TRANSFER IN A TRICKLE BED REACTOR USED FOR PALM OIL HYDROTREATMENT

Table 1. Reactor parameters and operating conditions

Parameter
Value
Feedstock
10 bbl/day RBDPO
H2 Mass flow
2.54
kg/s
LHSV
2 h-1
Temperature
330 C
Pressure
88.82 atm
0.52
Porosity
Geometry, L/D ratio
5/3

Comments
Regular pilot-plant scale hydrotreating reactor
Assumes a 24.14 H2/oil molar ratio
Ref. 2
Ref. 1,2,8
Ref. 2
Ref. 17

b
Figure 1. Geometry and boundary conditions for the TBR reactor. (a) H2 entering through centerline.
injection

(b) Partial H2 radial

J.F VLEZ, C.C. MENDOZA, S. LOPEZ, A. MOLINA

Thermophysical properties

Table 2 presents the properties relevant for the design of the reactor. Gas density was estimated by the ideal gas law and the density of
n-Pentadecane and tripalmitin from commercial process software and some correlations. Viscosity was taken from the NIST
Chemistry Webbook and the heat capacity from the database of Ansys-Fluent.
Table 2. Thermo-physical properties
Property (Units)

Density

Viscosity

(kg/m3)

(kg/m s)

Heat Capacity
(J/kg K)

Thermal Conductivity
k
(W/m K)

Compounds
H2
C15H32
C3H8
CO2
CoMo or NiMo/Al2O3
C57H98O6
H2
C15H32
C3H8
CO2
C57H98O6
H2
C15H32
C3H8
CO2
CoMo or NiMo/Al2O3
C57H98O6
Hydrogen H2
n-Pentadecane C15H32
Propane C3H8
Carbon Dioxide CO2
CoMo/Al2O3 Catalyst
NiMo/Al2O3 Catalyst
C57H98O6

Value
3.62
380.73
79.02
79.02
3957.86
771.71
1.45 10-5
1.03 10-4
2.71 10-5
2.83 10-5
6.78 10-4
Polynomial
2859.85
Polynomial
Polynomial
1008.21
2568
0.33
0.0675
0.0678
0.0427
42.95
46.25
0.0596

Comments
18

Ref.

19

Process software
Ref. 20
Ref. 19
Process software
Process software
Ref. 19
Ref. 20
Fluent 13.0 18
Process software
Fluent 13.0 18
Fluent 13.0 18
Ref. 19
Ref. 20
19

Process software
Process software
Ref. 19
Ref. 19
Ref. 19
Ref. 20

Constitutive equations, meshing and boundary conditions

Ansys Fluent solves, as all commercial CFD code, the mass, momentum and energy balance equations as described in Ref. 18. The
selection, however, of constitutive equations that help in the design, are particular of each modeling exercise and, for the TBR, are
described below. Because of the low Reynolds number (Rep (gas) = 1.86), a laminar flow was assumed. For the gas phase, the mixture
rules suggested by the Fluent Manual21 were activated.
To simplify the flow system, the CFD simulation did not consider the entrance of tripalmitin into the reactor. The reaction was then
simulated with a User Defined Function (UDF) that represents the mass and heat exchange between reactive species. Assuming that
the flow of tripalmitin in the reactor is similar to that in a plug flow reactor (PFR), the conversion of the ester fraction in the reactor
can be approximated as in Eq A 2 (all terms are described in the Nomenclature section).
(

Eq A - 2

CFD ANALYSIS OF THE HEAT TRANSFER IN A TRICKLE BED REACTOR USED FOR PALM OIL HYDROTREATMENT

With Eq A 2 it is possible to determine, according to the reactor volume, the volume of palm oil that remains in the reactor.
Knowledge of the tripalmitin conversion allows calculation of the concentration of other species based on stoichiometry. In the same
way one can calculate the contribution of the reaction to the energy balance (E1 A 3).
(

Eq A - 3

In this way the UDF gives, as a source, the heat produced in the reactor and the mass flow of carbon dioxide, n-pentadecane and
propane and as a sink, the total consumption of hydrogen.

Results and discussion

Figure 2 compares the profiles of temperature and mass fraction of H2 in the center of the reactor for L/D 5/3, for different mesh sizes.
As the results for meshes with 76590 and 128790 cells are very similar, the mesh with 76590 cells was used to represent the heat
transfer in the reactor. The simulation with H2 quenching required more cells (185383) given the detail that the hydrogen injection
port required.

Figure 2. Evaluation of mesh size independence. Profiles along the reactors center as predicted for different mesh sizes. (a)
Temperature. (b) H2 mass fraction

Figure 3 shows how the temperature changes in the reactor. After a fast rise in temperature in the first section of the reactor, a hot spot,
i.e. a zone where the temperature is higher than 360 C, forms. Towards the end of the reactor, the temperature decreases because of
heat exchange with the cold walls (at 330 C). The mass fraction of C15H32 at the exit of the reactor is 0.68. This value, however, does
not consider any degradation of the products because of the existence of the hot spot as the simplified kinetics used in the CFD
analysis do not consider any degradation reactions.

J.F VLEZ, C.C. MENDOZA, S. LOPEZ, A. MOLINA

Figure 3. Predicted variation of temperature in the TBR. (a) Contours of constant temperature.
along the centerline.

(b) Temperature variation

Figure 4 shows that, when 23.22% of the hydrogen flows through the radial streams, the temperature in the reactor stays below 390 C
as the hydrogen quenching decreases the tripalmitin concentration and cools the reactor. A lower temperature prevents excessive
hydrocracking of the feed, enhancing the desired product yield and decreasing the production of gases. While the maximum
temperature in Figure 4b, of the order of 388C is still higher than the desired maximum of 360C, further refinement of the
temperature of H2 radial injection or in the proportion between both streams would guarantee an even lower temperature. The lower
temperature for the case in Figure 4, however, decreases as well the reaction rate which causes a lower mass fraction of C15H32 (0.61)
at the exit of the reactor. This reduction, however, can be upset as product degradation decreases because of the lower temperature.

Figure 4. Predicted variation of temperature in the TBR with hydrogen injection in the radial direction.
temperature. (b) Temperature variation along the centerline.

(a) Contours of constant

CFD ANALYSIS OF THE HEAT TRANSFER IN A TRICKLE BED REACTOR USED FOR PALM OIL HYDROTREATMENT

Conclusions
Coupling a UDF that predicts the conversion of ester as a function of the reactor length into a CFD allows the simulation of heat
transfer during hydrotreating. The simulation suggests the existence of a hot spot in the reactor, just after injection, if hydrogen is
injected in the reactors entrance. However, quenching of hydrogen in the radial direction can prevent the formation of the hot spot,
maintaining the temperature and preventing product degradation while obtaining an acceptable conversion of ester.
Nomenclature
The nomenclature used in this paper is shown in Table 3
Table 3. Nomenclature, symbols and units

]
Hydrogen mass flow[
Bed porosity
Reactor Diameter [ ]
]
density[
Mass Fraction
]
Heat capacity [
Viscosity [kg/m s]
]
Thermal conductivity[
]
Ester reaction rate [
]
Reaction hydrodeoxigenation constant[
]
Initial ester concentration [
Ester conversion
[
]
]
Delta enthalpy of reaction [
Wall temperatura [ ]

Acknowledgements
The authors thank financial support from Instituto Colombiano del Petrleo, ECOPETROL (Colombian Oil Company) ECOPETROL
(Colombian Oil Company) under Convenio de Cooperacin Tecnolgica No. 004, Colciencias with the scholarships Colciencias,
Jvenes investigadores 2009, 2010 and 2012 as well as to DIME - Universidad Nacional - Sede Medelln, Facultad de Minas
Universidad Nacional - Sede Medelln.
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