Computers and Chemical Engineering 67 (2014) 26–32

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Computers and Chemical Engineering

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

Modeling of a microreactor for propylene production by the catalytic

dehydrogenation of propane
Juan S. Riaño Z, Hugo R. Zea R ∗
Departamento de Ingeniería Química y Ambiental, Facultad de Ingeniería, Universidad Nacional de Colombia, Carrera 30 45-03, Edificio 412, of.201,
Bogotá, Colombia

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

Article history: A model of a microreactor was proposed to analyze the production of propylene by the propane dehy-
Received 2 October 2013 drogenation using a catalytic surface of V2 O5 /TiO2 doped with Rb. The reactor is a 50 mm length tube
Received in revised form 22 March 2014 of 2 mm diameter whose wall is a catalytic surface, modeled using finite volume method in cylindrical
Accepted 27 March 2014
coordinates over a tangential plane. Dehydrogenation kinetics is reported by Grabowski (2004). First, a
Available online 4 April 2014
mesh independence analysis was done to assure the adequate cell size. Second, a parametric analysis
changing Reynolds number at different temperatures and propane-oxygen relations was done to find the
Keywords:
Reynolds range to effectively use the reactor length (Re from 1 to 10). Then at the later Reynolds interval a
Microreactor
Microreactor modeling parametric analysis involving temperature and composition was done to create productivity surfaces to
Catalytic dehydrogenation find the highest productivity operation conditions. Finally, an analysis varying pressure at the maximum
Propane dehydrogenation productivity conditions (Re = 1, T = 500 K, C3 H8 /O2 = 2) was developed.
Propylene production © 2014 Elsevier Ltd. All rights reserved.
Vanadia-titania catalyst

1. Introduction surface, they also described the mechanism of oxygen adsorption

(Grabowski et al., 2002). Grabowski et al. examined propane dehy-
Propylene is primarily produced by naphtha cracking. In this drogenation over catalytic surfaces with Li, K and Rb (Grabowski
process the main products are ethylene and propylene. Since the et al., 1995). Khodakov et al. presented a comparative study of dif-
demand of propylene has overcome that of ethylene, research on ferent catalyst alternatives, in which TiO2 /V2 O2 doped with Rb had
new technologies to produce propylene are a main concern to a higher selectivity in comparison to other materials (Khodakov
avoid a long term propylene shortage. Catalytic propane dehy- et al., 1999). Grabowski fitted a SSAM-Eley-Rideal model for
drogenation is a promising route to produce propylene thanks to propane dehydrogenation using a catalytic surface of TiO2 /V2 O2
the occurrence of increasing natural sources which are reducing doped with Rb (Grabowski, 2004). However, heat and mass transfer
propane price (INTRATEC, 2013). Propane dehydrogenation is an problems as hot spots, intra-particle mass transfer and axial effects
equilibrium reaction, which has a higher dependency on selectiv- are still a challenge to obtain a higher productivity (Levenspiel,
ity and conversion caused by the effects of multiple side reactions 1999).
and coke formation. These kind of chemical reactions are diffi- Different reactor alternatives have been proposed to overcome
cult to operate in packed bed reactors due to the occurrence of these difficulties. Sugiyama et al. used a microreactor with a cal-
heat and mass transfer problems which are easily overcome in a cium hydroxyapatite and magnesium ortho-vanadate catalysts for
micro-reactor system. Theoretically, micro-reactors are a suitable propane dehydrogenation, to suppress the oxidation of the resul-
configuration for this kind of reactions (Ehrfeld et al., 2000). tant propylene to CO and CO2 (Sugiyama et al., 2010). Genser
Several types of heterogeneous catalysts have been stud- et al. studied a mechanism based on the proposition of Oyama
ied to increase propylene productivity and selectivity increasing for propane dehydrogenation using a packed bed reactor (Genser
propane conversion. Sloczynski studied the mechanism of reduc- and Pietrzyk, 1999). Grabowski fitted a SSAM-Eley-Rideal model
tion and oxidation reactions of alkali metals promoted by from data obtained using a packed bed reactor (Grabowski, 2004).
vanadium–titanium catalysts (Sloczynski, 1996). Grabowski et al. Due to its control, manipulation, and predictability, capillary reac-
considered propane dehydrogenation using a TiO2 /V2 O5 catalytic tors are used to make kinetic analysis. An example is presented by
Zamaniyan et al. for syngas production (Zamaniyan et al., 2010).
In the present work, a model of a microreactor for propyl-
∗ Corresponding author. Tel.: +57 1 316 5000. ene production by propane dehydrogenation, carried out over a
E-mail address: hrzear@unal.edu.co (H.R. Zea R). titanium–vanadium doped with Rb catalysts is proposed in Fluent®

http://dx.doi.org/10.1016/j.compchemeng.2014.03.023
0098-1354/© 2014 Elsevier Ltd. All rights reserved.
 J.S. Riaño Z, H.R. Zea R / Computers and Chemical Engineering 67 (2014) 26–32 27

using a SSAM-Eley-Rideal model adjusted by Grabowski (2004). 3.1. Conservation equations

Once a mesh independence analysis has been done, the model is
used to examine in detail the behavior of conversion, selectivity Continuity, momentum, energy, and mass conservation equa-
and productivity by a comprehensive parametric analysis in which tions were solved for all variables except pressure using
wall temperature, inlet composition and pressure conditions are Flexible-cycle (including the effects of concentration gradient and
changed to obtain the highest productivity operation condition. thermal diffusion); pressure was solved using v-cycle in radial and
axial directions (Bird et al., 2006).

2. Materials and methods 3.2. Surface chemistry model

The micro reactor is modeled using the finite volume method The mechanism includes 6 chemical reactions, it was deduced
(Fluent® ) over a 2D axisymmetric tube. It is supposed that from the SSAM-Eley-Rideal model for the propane dehydrogena-
the reactor is at a steady state, and that the flow is in tion process adjusted by Grabowski (2004). The later model just
laminar regimen. Transport coefficients and the specific heat involves surface chemical reactions. In our model we assume that
capacities are evaluated using kinetic theory models. The gas an equilibrium steady state occurs in the catalytic surface, and so,
pressure–volume–temperature behavior is calculated using the the surface oxygen concentration does not change with time. This
ideal gas law. As the model is run at low wall temperatures assumption is used to deduce an equation for superficial oxygen
(lower than 700 K), volumetric reactions do not have an appreciable concentration .
    
−CC3 H8 r1 − 2 Co2 ros + (CC3 H8 r1 + 2 Co2 ros )(CC3 H8 r1 + 2 Co2 ros ) + 8 Co2 ros (3CC3 H6 r2 (1 + x) + CC3 H8 r4 (4 + 3x))
= (1)
6CC3 H6 r2 (1 + x) + 2CC3 H8 r4 (4 + 3x)

x = p + 2(1 − p) (2)
6CC3 H8 + 7CC3 H6
p= (3)
rate and it is supposed that only surface reactions are occurring at 15CC3 H8 + 17CC3 H6
a significant rate. Aspen properties was used to calculate density at
inlet conditions. For all models inlet temperature is fixed at 280 K, where ros is the rate of oxygen adsorption, and x is the stoi-
and pressure is set at 1 bar except in the pressure analysis. Table 1 chiometric coefficient of the theoretical compound COx which
shows inlet conditions imposed to obtain the highest productivity. represents a mixture of CO2 and CO produced by combustion
reactions (Grabowski, 2004). The stoichiometric coefficient x is cal-
culated by the addition of each of the fractional productions of CO2
2.1. Geometry of the reactor and CO multiplied by the oxygen content of each compound. Defin-
ing p as the fractional production of CO in a mixture of CO2 and CO,
The reactor is a 50 mm length tube of 2 mm diameter whose the fractional production of CO2 is calculated as (1 − p). Then, the
wall is a catalytic surface, similar to the reactor of Zamaniyan et al. stoichiometric coefficient x is calculated using Eq. (2).
(2010) used to produce syngas. The reactor is modeled in cylindrical Fractional production p, is calculated using Eq. (3); fractional
coordinates over a tangential region of the reactor, and consists of production p is expressed as the amount of atomic oxygen required
an inlet (left side), an outlet (right side), a catalytic fixed tempera- for the combustion of one mole of C3 H8 and one of C3 H6 to produce
ture wall condition on the upper side, and a symmetry condition on CO and H2 O (reactions 2 and 4), divided by the addition of the oxy-
the opposite side. A parallel quadrilateral mesh is used as velocity, gen required for the combustion of one mole of C3 H8 and one of
temperature, pressure and concentration variations are uniform C3 H6 to produce CO and H2 O (reactions 2 and 4) and the oxygen
over the transversal section. required for the combustion of one mole of C3 H8 and one of C3 H6
to produce CO2 and H2 O (reactions 3 and 5).

3. Theory 3.3. Convective and diffusive mass transfer comparison

In this section the implemented equations for a system in lam- For multicomponent systems Sherwood number can be used to
inar conditions are described, based on a kinetic proposed by compare convective and diffusive mass transfer. Sherwood number
Grabowski (2004). The chemical reactions were separated to repre- can be calculated using mathematical expression as a function of
sent the combustion phenomena in a set of four chemical reactions. Reynolds, Schmidt numbers and the geometry of the region where
mass transfer occurs. Sherwood number equations for a pipe is
suitable to compare mass transfer mechanisms in a tubular micro-
Table 1 reactor (Welty et al., 2007).
Summary of inlet conditions for the highest productivity condition.
Dv
Re = (4)
Tin (K) 280 
Tw (K) 500

C3 H8 /O2 2 Sc = (5)
D (m) 0.002 Da,b 
L (m)
v (m/s)
0.05
0.0024 D 1/3  1/3
D2 v
 (Kg/m3 ) 2.2080 Sh = 1.86 Re Sc = 1.86 (6)
q (m3 /s) 7.44E−09 L L Da,b
 (Kg/s m) 1.05E−05
Dab (m2 /s) 1.08E−05 where Re is the Reynolds number, Sc is the Schmidt number, Sh
Re 1.000 is the Sherwood number, D is the diameter and L the length of
Sc 0.441 the microreactor. v is the fluid mean velocity,  the density, ␮ the
Sh 0.484
viscosity, and Da,b the diffusivity of the inlet mixture. Sherwood
28 J.S. Riaño Z, H.R. Zea R / Computers and Chemical Engineering 67 (2014) 26–32

Fig. 1. Sherwood number versus Reynolds number at different inlet compositions.

number represents the rate of convection to diffusive mass trans- outlet moles C3 H6
P =X ∗S = (9)
port. Eq. (6) shows that Sherwood number depends on v and Da,b inlet moles C3 H8
for a fixed geometry.
C 3 H8 C3 H8 inlet concentration
Fig. 1 shows how at low Reynolds numbers between 0 and 50 = (10)
Sherwood number increases from 1 to 2 independently of compo- O2 O2 inlet concentration
sition. At Reynolds between 50 and 500 Sherwood number growths
at a lower rate and increases with oxygen content. At higher 4.1. Mesh independence analysis
Reynolds Sherwood increases with a lower rate and almost the
same dependence on composition. An analysis of Sherwood versus At different cell sizes, a single set of reactor conditions was
Reynolds number in the first range of Reynolds (From 0 to 50) shows imposed and the system was run until convergence. Then for each
that diffusive transport is of the same order of magnitude at very cell size the average value of velocity, temperature and composi-
low Reynolds (between 1 and 10). tion was reported. A system is considered mesh independent when
Our calculations show diffusivity suffers minimal changes in the the error of all average properties is less than 5%.
composition range used, suggests that Sherwood number depends As pressure and velocity profiles are related by a single solution
strongly on velocity (Reynolds number). The difference behavior scheme, the average pressure relative error is of the same order.
in Sherwood versus Reynolds number plots at different compo- From Table 3, a model with 0.1 mm mesh size is enough to repro-
sition can be explained by velocity variations caused by density duce the velocity, temperature and composition profiles with an
differences. acceptable error. The decrease in average errors with further refine-
ments implies that the profiles with finer meshes are not different
from the profiles obtained using a mesh of 0.1 mm.
4. Calculation
5. Results
Fluent was used to solve transport equations. The standard
method was used for pressure discretization, and second order
The objective of the parametric analysis was to find operation
upwind was used for momentum, species and energy discre-
conditions that maximize productivity. Our first objective was to
tization. The simple scheme was used to solve simultaneously
find the dependence of productivity on Reynolds number, inlet
continuity and momentum. Equations were solved using default
velocity was change from Reynolds 0.1 to 500 at a constant inlet
under-relaxation factors until a residual convergence of 1.0 × 10−6 .
temperature of 280 K, operation pressure of 1 bar, and inlet compo-
A symmetry condition was employed.
sition proportional to the stoichiometric relation. Calculations were
First, a mesh independence analysis was done to assure the
performed at different wall temperatures, results indicate that at
adequate cell size. Second, a parametric analysis (59 models)
low Reynolds numbers (below 10) productivity increases and tends
changing Reynolds number at different wall temperatures and
to increase with temperature (Fig. 2).
propane–oxygen relations was done to find the Reynolds range
to effectively use the reactor length (Re from 1 to 10); then, in
the previous determinate Reynolds range, a parametric analysis
was performed to create productivity surfaces (81 models) involv-
ing wall temperature and composition changes to find the highest
productivity operation conditions. Finally, a parametric analysis
varying pressure (36 models) at the maximum productivity con-
ditions obtained (Re = 1, T = 500 K, C3 H8 /O2 = 2) was done to fully
understand the reactor behavior. Propane conversion, propylene
selectivity, propylene productivity and stoichiometric feed ratio are
defined as:

converted moles C3 H8
X= (7)
inlet moles C3 H8

outlet moles C3 H6
S= (8)
converted moles C3 H8 Fig. 2. Productivity versus Reynolds at different wall temperatures.
 J.S. Riaño Z, H.R. Zea R / Computers and Chemical Engineering 67 (2014) 26–32 29

Fig. 5. Selectivity versus wall temperature at different inlet compositions, and

Fig. 3. Productivity versus Reynolds at different inlet compositions.
Reynolds equal to 1.

Fig. 3 shows productivity dependence on Reynolds for three

and 600 K. Productivity plots at different inlet compositions (Fig. 6)
different values of C3 H8 /O2 ratio, it can be observed that at low
reveal that the highest productivity occurs around 500 K and
Reynolds values productivity tends to increase independently of
C3 H8 /O2 equal to 2. Productivity versus temperature plot of each
the value of C3 H8 /O2 ratio, on the other hand for Reynolds above
inlet composition has a maximum; before 500 K productivity
10 there is an important effect of C3 H8 /O2 ratio as productivities
increases until a maximum, after 500 K, productivity decrease
differentiates revealing that the highest productivity occurs when
almost at the same pace for each inlet composition. It is interesting
C3 H8 /O2 ratio is equal to 2; these results confirm the fact that low
the fact that at 450 K productivity is almost independent of inlet
Reynolds are required for higher productivities.
composition.
Once a suitable range values of Reynolds (between 0.1 and 10)
Results at Reynolds 0.1, 1 and 10 confirm that the highest
has been established (Figs. 2 and 3); the objective of the next set
productivity occurs at Reynolds 1 (Fig. 7). At lower Reynolds pro-
of models is to analyze the dependence of conversion, selectivity
ductivity does not increase significantly. The highest productivity
and productivity on temperature. For these simulations C3 H8 /O2
occurs at 500 K and C3 H8 /O2 ratio equal to 2, on the contrary, for
ratio and temperature values were varied from 1 to 3 and from 400
the case of Reynolds 10 this maximum does not happen.
to 600 K respectively, as show in Fig. 4 at Reynolds 1; similar cal-
In order to understand the effect of inlet pressure in the reac-
culation were done for Reynolds of 0.1 and 10. The results reveal
tors behavior extra calculation at pressure values different to 1 bar
that below 440 K conversion increases and is almost independent
were performed (0.5 and 1.5 bar), in these calculations C3 H8 /O2
of inlet composition (Fig. 4). After 470 K conversion proportionally
ratio and temperature values were varied from 1 to 3 and from 400
increases as the fraction of oxygen increases at reactor inlet. Con-
to 600 K respectively. The results indicate that productivity is not
version versus temperature plot of each inlet composition has a
as strongly dependent on pressure as it dependent on temperature
maximum at a temperature that increases as the amount of oxygen
(Figs. 8 and 6). In term of the effect of C3 H8 /O2 ratio is observed that
decreases at the reactor inlet.
neither has a strong dependency but the stoichiometric inlet ratio
Selectivity versus temperature (Fig. 5) has an inverse tendency
of 1 produces the highest productivity, however the results confirm
in comparison to conversion (Fig. 4). Between 400 and 450 K
that the highest productivity is obtained around 500 K (Fig. 9). It is
selectivity decreases and is almost independent of inlet compo-
interesting to point out that for a temperature of 600 K, productivity
sition. Between 450 and 500 K, selectivity still decreases, but its
is independent of pressure.
dependence on composition is stronger and the separation between
profiles at different inlet composition is bigger. After 500 K selectiv-
ity proportionally decreases as the fraction of oxygen increases at 6. Discussion
the reactor inlet. Selectivity plot attains its minimum at the highest
temperature of the range analyzed. Results indicate the highest productivity occurs at Reynolds
Conversion and selectivity tendencies suggest that the high- equal to 1 (Fig. 1); Sherwood number (convective over diffusive
est productivity will occur at a wall temperature between 400 K mass transfer) depends higher on Reynolds than on Schmidt num-
ber (Bird et al., 2006), then oxygen profiles at Reynolds numbers

Fig. 4. Conversion versus wall temperature at different inlet compositions, and

Reynolds equal to 1. Fig. 6. Productivity versus wall temperature at different inlet compositions.
30 J.S. Riaño Z, H.R. Zea R / Computers and Chemical Engineering 67 (2014) 26–32

Fig. 7. Surfaces of productivity versus wall temperature and inlet composition at different Reynolds.

different that 1 must show concentration profiles with distinct con- molecules in the fluid core do not have enough time to attain the
vective/diffusional effects; a comparison of these profiles explains wall (Fig. 10). Conversely at Reynolds 1 or lower diffusion occurs in
the highest productivity at Reynolds equal to 1. A plot of oxygen an order of magnitude equal to convection and reactants including
concentration for Reynolds 1 and 10 at the reactor inlet shows oxygen have enough time to arrive to the catalytic wall (Fig. 11).
that for Reynolds 10 or higher convective effect dominates and There is a minimum Reynolds value for which selectivity and
conversions do not change, a further Reynolds reduction at any
reactions conditions is equivalent to a volumetric flow reduction
or to a lower mass flow; that is, lower Reynolds implies lower mass

Fig. 8. Productivity versus pressure at different wall temperatures at Reynolds equal

to 1.
Fig. 10. Oxygen molar concentration profile (kmol/m3 ) at wall temperature of 500 K,
C3 H8 /O2 equal to 2, pressure of 1 bar, and Reynolds equal to 10.

Fig. 11. Oxygen molar concentration profile (kmol/m3 ) at wall temperature of 500 K,
Fig. 9. Productivity versus pressure at different inlet compositions. C3 H8 /O2 equal to 2, pressure of 1 bar, and Reynolds equal to 1.
 J.S. Riaño Z, H.R. Zea R / Computers and Chemical Engineering 67 (2014) 26–32 31

Table 2
Detailed reaction mechanism and kinetic coefficients used in this study.

n Reaction kn (s−1 ) E (kJ/mol) r

1 C3 H8 + 0.5O2 → C3 H6 + H2 O 28.1 25.0 k1 CC3 H8 

2 C3 H6 + 3O2 → 3CO + 3H2 O 1.27 × 10−3 30.0 k2 CC3 H6  2 p
3 C3 H6 + 4.5O2 → 3CO2 + 3H2 O 1.27 ×10−3 30.0 k3 CC3 H6  2 (1 − p)
4 C3 H8 + 3.5O2 → 3CO + 4H2 O 1.37 ×10−3 49.0 k4 CC3 H8  2 p
5 C3 H8 + 5O2 → 3CO2 + 4H2 O 1.37 ×10−3 49.0 k5 CC3 H8  2 (1 − p)
Os O2 → Os 1.1 ×107 74.0 –

Table 3
Error for each variable average value at different cell sizes.

Cell size (mm) V rel. error % T rel. error % Mass fraction error %

C3 H8 C3 H6 O2 CO2 CO H2 O

0.500 10.573 0.023 0.876 25.186 5.162 37.144 33.889 31.666

0.250 1.784 0.043 0.232 7.789 1.523 12.277 7.778 7.854
0.100 0.500 0.035 0.002 2.007 0.112 2.459 2.470 1.237
0.050 0.505 0.018 0.040 0.898 0.125 0.256 4.776 1.947
0.025 0.307 0.007 0.005 0.156 0.413 1.114 6.440 1.458

rates but not higher productivities. This is confirmed comparing the and that propylene production depends on oxygen concentration,
results at Reynolds 1 and 0.1 (Figs. 11 and 12). product distribution and selectivity depend on C3 H8 /O2 ratio.
There is a difference between concentration profiles at Reynolds Productivity is expected to be strongly dependent on tempera-
1 and 0.1 (Figs. 11 and 12). At Reynolds 0.1, the reactor length ture due to the fact that both conversion and selectivity are also
is totally used. From diffusion flow definition, diffusion decrease strongly depended on temperature (Fig. 6). Productivity reflects
with barycentric velocity, this implied a reduction in the molecules the inverse tendencies of conversion and selectivity respect to
kinetic energy (de Groot & Mazur, 1969). Higher oxygen and temperature (conversion increases with temperature selectivity
propane concentrations in the entire reactor imply higher rates of decreases); the productivity profiles shown a maximum at inter-
propylene production, but at the same time combustion reactions mediate temperature (around 500 K); although the behavior of the
are catalyzed. Productivities of system at Reynolds 0.1 and 1 are productivity is not as dependent of inlet composition as it is of
almost equal, but the net production of propylene at Reynolds 1 is temperature, it is important to highlight that this maximum in
higher. productivity also happens for a C3 H8 /O2 ratio equal to 2, where
Besides residence time, temperature affects the most the reactor probability of collision of propane to oxygen is higher.
profiles. Conversion and reaction rates increase with tempera- Once the effect of Reynolds, temperature and inlet composition
ture. Conversion depends on the number of molecular collision of on productivity were determined, the only variable left to analyze
reactants at the catalytic surface, different C3 H8 /O2 ratios imply is pressure (Fig. 7); an increment on operating pressure implies an
different collision probabilities, therefore the change of conversion increase in reactants concentration, higher oxygen concentrations
at different inlet mixtures observed in Fig. 4. As the proportion of will raise surface oxygen concentration and higher  value; it can be
oxygen in the inlet mixture increases, there will be more molecu- observed in Table 2 that all kinetic equations but reaction 1 (dehy-
lar collisions between oxygen and propane and then the extent of drogenation) are dependent to the power of 2 of , therefore when
dehydrogenation and combustion reactions will increase until the  values increase its effect on kinetic Eq. (1) will be stronger than
stoichiometric ratio is reached. on kinetic Eqs (2)–(5), thus dehydrogenation will be faster than
On the contrary, selectivity decreases with temperature (Fig. 5). combustion reactions at higher pressures, making productivity also
Molecular kinetic energy is proportional to temperature, at higher higher (Fig. 9).
temperatures molecules have more energy and are able to surpass At any pressure the highest productivity occurs around 500 K
the activation energy. Dehydrogenation reaction has the lowest (Fig. 8), this happens due to the combined effect of conversion and
activation energy and is favored at low temperatures. As temper- selectivity versus temperature; constant productivity at 600 K is
ature increases reactants have enough energy to overcome the caused by the facts that C3 H8 /O2 at the reactor inlet is constant at
activation energies of combustion and thus selectivity decrease any pressure and that all the kinetic rates are faster at 600 than
with temperature. Taking into account that the amount of oxygen at 500 K, which make combustion and dehydrogenation reaction
required for propane combustion is different of that for propylene, occur only near the reactor inlet and until oxygen depletion.

7. Conclusions

After a suitable mesh was obtained from the mesh independence

analysis, a parametric analysis was performed to obtain the highest
productivity operation condition. As the rate of reaction depends on
the reactants concentration near the catalytic wall and radial mass
transfer is diffusive controlled, at low Sherwood and low Reynolds
numbers there will be higher productivity. Highest net productivity
was obtained at Reynolds 1; Further velocity reductions did not rep-
resent a significant increases in productivity (decreasing Reynolds
from 1 to 0.1 generates a 0.02% productivity increment).
Fig. 12. Oxygen molar concentration profile (kmol/m3 ) at wall temperature of 500 K, Due to the occurrence of side reactions, the highest produc-
C3 H8 /O2 equal to 2, pressure of 1 bar, and Reynolds equal to 0.1. tivity will occur at a wall temperature in which a maximum
32 J.S. Riaño Z, H.R. Zea R / Computers and Chemical Engineering 67 (2014) 26–32

difference between the rates of propylene production and con- de Groot SR, Mazur P. de Groot SR, Mazur P, editors. Non-equilibrium thermody-
sumption (dehydrogenation and combustion reactions) is reached. namics. North-Holland; 1969.
Ehrfeld W, Hessel V, Löwe H. Microreactors: new technology for modern chemistry.
A plot of productivity against wall temperature, the highest pro- Weinheim, Germany: Wiley; 2000.
ductivity condition is the maximum of the productivity parabola Genser F, Pietrzyk S. Oxidative dehydrogenation of propane on V2 O5 /TiO2
which results from the opposite tendencies of selectivity and con- catalysts under transient conditions. Chem Eng Sci 1999;54(20):4315–25,
http://dx.doi.org/10.1016/S0009-2509(99)00134-7.
version. This wall temperature for the titanium–vanadium catalyst
Grabowski R. Kinetics of the oxidative dehydrogenation of propane on vana-
modeled is around 500 K. dia/titania catalysts, pure and doped with rubidium. Appl Catal A: Gen
The productivity of the system is also affected by the inlet 2004;270(1–2):37–47, http://dx.doi.org/10.1016/j.apcata.2004.04.021.
composition and pressure. The analysis performed showed that Grabowski R, Grzybowska B, Samson K, Sloczynski J, Stoch J, Weisto K. Effect of alka-
line promoters on catalytic activity of V2O3/TiO2 and MoO2/TiO2 catalysts in
productivity tends to be higher at C3 H8 /O2 ratios near 2, the stoi-
oxidative dehydrogenation of propana and in isopropanol decomposition. Appl
chiometric relation. The analysis also predicts that productivity Catal A: Gen 1995;125(1)., http://dx.doi.org/10.1016/0926-860x(94)00274-276,
increases with pressure. This is in agreement with the fact that all 129–129.
kinetic equations but reaction 1 (dehydrogenation) are dependent Grabowski R, Pietrzyk S, Sloczynski J, Genser F, Wcislo K, Grzybowska-wierkosz
B. Kinetics of the propane oxidative dehydrogenation on vanadia/titania
to the power of 2 of  (oxygen surface coverage), thus at high pres- catalysts from steady-state and transient experiments. Appl Catal A: Gen
sure dehydrogenation kinetic rate tends to be faster than all of the 2002;232(1–2):277–88, http://dx.doi.org/10.1016/s0926-860x(02)00117-125.
combustion reactions. INTRATEC. Propylene via propane dehydrogenation. In: LLC IS, editor. Technology
In summary, the parametric analysis at different temperatures economics; 2013 [United States of America].
Khodakov A, Olthof B, Bell AT, Iglesia E. Structure and catalytic properties of
and inlet compositions demonstrates how changes on these vari- supported vanadium oxides: support effects on oxidative dehydrogenation reac-
ables have higher influence than changes on pressure. The highest tions. J Catal 1999;181(2):205–16, http://dx.doi.org/10.1006/jcat.1998.2295.
productivity is 8.6%, it occurs at 1.5 bar, with conversion of 20% and Levenspiel O. Chemical reaction engineering. New York, USA: Wiley; 1999.
Sloczynski J. Kinetics and mechanism of reduction and reoxidation of the alkali metal
selectivity of 43%.
promoted vanadia-titania catalysts. Appl Catal A: Gen 1996;146(2):401–23,
http://dx.doi.org/10.1016/s0926-860x(96)00172-180.
Acknowledgements Sugiyama S, Sugimoto N, Ozaki A, Furukawa Y, Nakagawa K, Sotowa K-I.
Application of a microreactor in the oxidative dehydrogenation of propane
to propylene on calcium hydroxyapatite and magnesium ortho-vanadate
Acknowledgment is made to the company ESSS Colombia for doped and undoped with palladium. J Chem Eng Japan 2010;43(7):575–80,
providing the license and technical support to use Ansys-Fluent for http://dx.doi.org/10.1252/jcej.43.575.
this project. Welty J, Wicks CE, Rorrer GL, Wilson RE. Fundamentals of momentum, heat and
mass transfer. New York, USA: Wiley; 2007.
Zamaniyan A, Behroozsarand A, Mehdizadeh H, Ghadirian HA. Modeling of microre-
References actor for syngas production by catalytic partial oxidation of methane. J Nat Gas
Chem 2010;19(6):660–8, http://dx.doi.org/10.1016/s1003-9953(09)60135-3.
Bird B, Stewart W, Lightfoot E. Transport phenomena. 2nd ed. New York, USA: John
Wiley & Sons, Inc.; 2006 [Revised].