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articleinfo abstract
Article history: The oxidative dehydrogenation of ethane (ODH-Et) seems the most promising alternative to produce ethy-
Received 5 March 2015 lene compared to conventional processes. Nevertheless, there is not even a pilot plant for ODH-Et world-
Received in revised form 20 May 2015 wide nowadays. This work presents the simulation of the catalytic behavior of a highly active and selective
Accepted 22 May 2015 MoVTeNbO catalyst for the ODH-Et in a wall-cooled industrial-scale packed-bed reactor with a tube to
Available online 6 June 2015
particle diameter ratio equal to 3.12. The feasibility of using this complex yet necessary reactor design,
as well as the influence of operating conditions on conversion and yield along the reactor are analyzed.
Keywords:
The simulations are carried out using a two-dimensional pseudo-heterogeneous model, which makes
Oxidative dehydrogenation reaction
use of both a reliable kinetic model and reliable transport parameters. Specifically, the kinet ic model,
Low dt/dp packed bed reactor
Hydrodynamics
obtained from lab-scale experimental data, is coupled to the reactor model accounting for transport phe -
Ethylene nomena wherein the effect of hydrodynamics on heat transfer is assessed from independent experiments
Reaction kinetics in absence of reaction in an industrial-scale reactor. The developed kinetics successfully accounts for both
MoVTeNbO catalyst the inhibiting effect of adsorbed water on oxidative dehydrogenation and total oxidations and the effect of
the inlet partial pressure of oxygen and ethane on conversion and selectivity. Besides, the reactor model
elucidates the importance of accounting for the role of the hydrodynamics on the heat transport in order to
have reliable conversion and yield predictions. From the parametric sensitivity study, the temperature of
the coolant fluid and the inlet ethane concentration are variables for tuning the reactor performance.
© 2015 Elsevier B.V. All rights reserved.
Abbreviations: BIC, Bayesian information criterion; BLA, boundary layer approximation; CA, classical approach; dt/dp, tube-to-particle diameter ratio; ER, Eley–Rideal; GC,
gas chromatograph; HTP, heat transport parameters; LHHW, Langmuir–Hinshelwood–Hougen–Watson; MvK, Mars-van Krevelen; ODEs, ordinary differential equations; ODH-
Et, oxidative dehydrogenation of ethane; PL, power law.
⇑ Corresponding author. Tel.: +52 55 5804 4648.
E-mail addresses: gamaliel.che@gmail.com (G. Che-Galicia), coca@xanum.uam.mx (C.O. Castillo-Araiza).
http://dx.doi.org/10.1016/j.cej.2015.05.128
1385-8947/© 2015 Elsevier B.V. All rights reserved.
G. Che-Galicia et al. / Chemical Engineering Journal 280 (2015) 682–694 683
Nomenclature
kg interfacial mass transfer coefficient, m 3f m—s2 h—1 qf fluid density, kgf m—f 3
effective material since it presents an outstanding activity and method is used. From XRD pattern using Rietveld refinement, the
selectivity to ethylene, apparently attributed to the presence of crystalline phase composition (wt%) is analyzed to be the M1 major
the M1 crystalline phase. Particularly, V species are the active sites crystalline phase present in the catalyst (92 wt% M1 and 8 wt% M2
—1
in ethane activation, Mo species enhance the catalytic activity of V crystalline phase) [18]. A specific surface area of 7 m 2 gcat is
atoms, Te species are associated with the formation of the active obtained from N 2 physisorption in an AUTOSORB-I instrument.
and selective crystalline phase M1, and Nb species leads to enhance Details concerning the preparation as well as the physicochemical
the selectivity to ethylene [11,13,20–23]. From this end, envisaging characteristics of this catalyst are given elsewhere [18].
a possible future application of this material in ODH-Et to a com-
mercial scale requires, as a first step, of the conceptual design of 2.2. Experimental data
the catalytic reactor technology. Nevertheless, owing to the
exothermicity of the ODH-Et reaction, mainly related to the The data used in the kinetic modeling is obtained from experi-
unavoidably heat released during the formation of COX (CO and ments carried out in a laboratory isothermal fixed-bed reactor at
CO2) out of ethane and ethylene, the reactor design is as yet a com- atmospheric pressure. The fixed-bed reactor, made of quartz, has an
plex chemical engineering assignment, as it is analyzed in the internal diameter of 1.0 × —2 m and length of 4.0 10×—2 m.
10
following. Experiments were performed using a bed consisting of 0.60 g of
The wall-cooled catalytic reactor with low tube-to-particle catalyst with average particle size of 150 lm. The reaction feed-
diameter ratio (dt/dp < 5) seems a suitable option to commercially stock was composed of a mixture of ethane (or ethylene), oxygen
achieve the ODH-Et over the MoVTeNbO formulation [24,25], since and nitrogen with a varying composition depending on the exper-
this configuration and catalyst design promote the fast removal of iment. The experimental conditions and conversion ranges are
the heat generated, maximize the desirable product yield, and listed in Table 1. The reactor effluent was analyzed online period-
avoids strong catalyst deactivation by a sintering process [26–34], ically by gas chromatography (GC). A detailed description of the
as observed for other well-known studied exothermic partial oxida- equipment has been reported in a previous study [57].
tion reactions. In fact, several researches [35–41] have considered
the wall-cooled packed bed catalytic reactor for simulating the pos- 2.3. Reaction rates
sible performance of the ODH-Et over catalytic systems different to
the MoVTeNbO formulation. Nevertheless, these studies are ques- The reaction network for ODH-Et over MoVTeNbO catalysts is
tionable since they do not make use of reliable kinetic models and proposed taking into account the experimental observations given
neglect the effect of the low dt/dp on the void fraction profile and, in [57]. Both parallel and consecutive reactions are considered, in
hence, on velocity field and its role on the heat transport [42–46]. which the species detected by GC (ethane, ethylene, carbon
The conceptual design of the industrial reactor for the ODH-Et monoxide and carbon dioxide) are only included. In this regard:
over a MoVTeNbO catalyst requires of both a reliable kinetic model Ethylene is produced from oxidative dehydrogenation of ethane
and reliable transport parameters. A few number of kinetic models (r1):
have been developed to describe the macroscopic mechanism of
C2 H6 þ 0:5O 2 ! C 2H 4 þ H 2O ð1Þ
ODH-Et, namely power law (PL), Langmuir–Hinshelwood–Houge
n–Watson (LHHW), Eley Rideal (ER), Mars-van Krevelen (MvK) or Ethane can also be oxidized to form CO 2 (r2) and/or CO (r3):
a combination of MvK and LHHW (MvK–LHHW) [47–58], neverthe-
less, these models are specific for every catalyst formulation. C2 H6 þ 3:5O2 ! 2CO2 þ 3H 2 O ð2Þ
Specifically for the MoVTeNbO catalyst, the LHHW model, devel-
oped by our research group, is one of the most suitable one nowa- C2 H6 þ 2:5O 2 ! 2CO þ 3H 2O ð3Þ
days [57] since other kinetic models present a lack of statistical Ethylene can also react to form CO 2 (r4) and/or CO (r5).
and phenomenological significance. Notwithstanding LHHW is a
potential kinetic model to overcome the conceptual design of the C2 H4 þ 3O 2 ! 2CO 2 þ 2H 2O ð4Þ
industrial ODH-Et reactor using the MoVTeNbO catalytic system,
some aspects need to be accounted for, i.e., the relatively weak effect C2 H4 þ 2O 2 ! 2CO þ 2H 2O ð5Þ
of oxygen partial pressure on reaction rates, the high affinity of Table 2 shows the reaction mechanism considered for building
water to adsorb on active sites affecting negatively reaction rates the kinetic model. The mechanism accounts for some of the partic-
and the significative effect of inlet partial pressure of ethane on ular aspects of the MoVTeNbO formulation reported in the litera-
reaction rates. ture [57], namely a relatively weak effect of oxygen partial
The aim of this study is to model the industrial performance of a pressure on reaction rates, a high tendency of water to adsorb on
highly active/selective MoVTeNbO catalyst for the production of active sites and the significative effect of inlet partial pressure of
ethylene out of ethane via ODH-Et in a wall-cooled packed bed cat-
alytic reactor presenting a dt/dp equal to 3.12. This industrial-scale
reaction system is simulated using a two-dimensional pseudo- Table 1
Range of experimental conditions during the steady state in the ODH-Et experiments.
heterogeneous model coupled to a kinetic model devel- oped
herein for MoVTeNbO formulation and accounts, in some detail, Operational condition Unit Range
for the effect of hydrodynamics on heat transfer through the pC2 H6 ;o kPa 5–22
proper estimation of heat transport parameters from pilot plant pC2 H4 ;o kPa 5–22
experiments in absence of reaction. pO2 ;o kPa 5–22
cC H ¼ yO ;oy—1
26 2C H ;o
2 6 molO2;omol
—1
C2 H6 ;o 0.5–2.0
cC H ¼ yO ;oy—1
24 2C H ;o
2 4 mol Omol
2 ;o
—1
C2 H4 ;o
0.5–2.0
2. Reaction kinetics Wcat F—C21H6 ;o 1
gcat h mol—C2 H6 ;o 10–140
5
X
ethane on conversion and selectivity. Thus, the model accounts for Rn ¼ mn;i ri ð15Þ
the following assumptions: (i) there is a single type of active sites i¼1
(S) on the catalyst surface, (ii) the only compounds adsorbed on the
where mn;i is the stoichiometric coefficient of the component n in the
active sites are oxygen and water, (iii) oxygen adsorption is disso-
i-th reaction, vide Eqs. (1)–(5). In order to reduce the correlation
ciative (step A) while water adsorption is associative (step B), (iv)
between activation energies and pre-exponential factors as well
surface reaction steps (steps 1–5) are considered to be fast taking
as standard adsorption enthalpies and entropies during the param-
place over a finite number of active sites, (v) since the construction
eters estimation procedure, both Arrhenius and van’t Hoff equations
of the model is based on the pseudo equilibrium approach, surface
reactions are the rate-determining steps and adsorption and des- are used Σin their reparametrized
. ΣΣ form.
EA;i 1 1
orption steps are quasi-equilibrated. In Table 2, rj is the so-called k ¼ exp A0 — — ð16Þ
i i
Horiuti number, that describes the times that every adsorption– R T Tm
desorption and/or reaction steps need to occur in order to com-
plete a single catalytic cycle comprising the overall reactions Σ . ΣΣ
DSno DHno 1 1
(Eqs. (1)–(5)). Notice that the adsorption of molecular O 2 (step A) Kn ¼ exp — — ð17Þ
R R T Tm
is a crucial stage for the surface reactions to take place (steps 1–5).
The equations that describe the rate of reactions for ODH-Et over where A0i is the natural logarithm of the pre-exponential factor for
MoVTeNbO are given through Eqs. (6)–(10), and are written as a the i-th reaction, EA,i is the activation energy factor for the i-th reac-
function of the partial pressures of the gas phase components tion, T is the reaction temperature, T* is the averaged reaction tem-
according to the reaction mechanism. The calculation of ri involves perature, DSno is the standard adsorption entropy of component n,
a rate coefficient denoted by ki, an adsorption equilibrium coeffi- DHno is the standard adsorption enthalpy of component n and R is
cient for the n-th component represented by Kn, the partial pres- the universal gas constant.
sure of the reactant n represented by pn, the fraction coverage of
oxygen denoted by hO and the reaction order related to the partial 2.3.1. Laboratory reactor model
pressure of the gas phase denoted by mi: The continuity equation for component n at the steady state
assumes that the flow pattern in the laboratory reactor is of plug
flow type and that there is no radial temperature or concentration
r 1 ¼ k1 pC2 H6 hO ð6Þ
gradient as corroborated elsewhere [57]:
r 2 ¼ k2 pC H h m2 ð7Þ dF
n
26 O
¼ Rn ð18Þ
dW cat
r 3 ¼ k3 pC 2 H6 hm
O
3
ð8Þ
with the following initial conditions:
m4
r 4 ¼ k4 pC H h ð9Þ F n ¼ F no ; for W cat ¼ 0 ð19Þ
2 4 O
m5
where Fn is the molar flow rate of component n, Fno is the inlet
r5¼ k p5 C2 H4 hO ð10Þ molar flow rate of component n and Wcat is the mass of the catalyst
Since the fraction coverage of different species on the catalytic loaded into the reactor.
surface is conserved through time, the global balance of the frac-
tion sites corresponds to Eq. (11): 2.3.2. Parameter estimation
The development of a kinetic model must account for a proper
assessment of the model parameters from both physicochemical
hm þ hO þ hH2 O ¼ 1 ð11Þ and statistical perspectives since these evaluations are essential
The fraction coverage of a specific component is defined as the for carrying out a reliable chemical reactor design. The kinetic
number of sites occupied by such a species relative to the total parameters are estimated by minimization of the following
number of available sites corresponding to Eq. (12) for oxygen weighted objective function:
and Eq. (13) for water: n resp nexp
X X 2 b ;b ;...;b
RSSðbÞ ¼ w ðF k;n — F^k;n Þ 1 —2! n min ð20Þ
n¼1 k¼1
1
hO ¼ ðK O2 pO2 Þ hm 2
ð12Þ
where b is an optimal parameter vector, nexp is the number of inde-
hH O ¼ K H O p h ð13Þ pendent experiments, nresp is the number of responses, Fk,n and F^ k;n
2 2 H2 O m
are the n-th experimental and predicted responses for the k-th
where the adsorption equilibrium coefficient for the n-th compo- observation, respectively; and wn is the weight factor assigned to
nent is represented by Kn, the partial pressure of the reactant n is the n-th response.
686 G. Che-Galicia et al. / Chemical Engineering Journal 280 (2015) 682–694
of orthogonal collocation using 5 and 50 interior collocation points C2H4 Kinetic model
60
at the radial and axial coordinates, respectively, employing shifted CO
CO2
Legendre polynomials [70]. The resulting set of ordinary differen-
tial equations is, then, solved by a Runge–Kutta method [71]. 40
The results are divided in two sections. Section 4.1 discusses the
0
kinetics of ODH-Et on MoVTeNbO catalytic system. The model reli-
0 20 40 60 80 100
ability is firstly discussed, in terms of the statistical significance of
both the regression and the parameters; thus, the parameter values Ethane conversion [%]
are analyzed to evaluate whether they are physically meaningful or
Fig. 1. Selectivity to ethylene, CO2, and CO versus ethane conversion. Full lines
not. An analysis on the adsorption phenomena of both water and are calculated with the kinetic model (T = 400–480 °C; space-time = 23–70 gcat
oxygen on the active sites from MoVTeNbO catalytic formulation
h mol— 1 ; nominal inlet molar ratio C /O /N = 9/7/84).
ethane 22 2
688 G. Che-Galicia et al. / Chemical Engineering Journal 280 (2015) 682–694
40 5
ODH-Et observations since it leads to a lower value of BIC (110.7)
than the LHHW model (159.6), obtaining an absolute difference
0 (DBIC) of ca. 49 [79]. Experimental data reported elsewhere [57]
30 0 5 10 15
elucidated how the inlet partial pressure of ethane gives rise to a
C2H6
positive effect on ethane conversion due to its over oxidation to
O2
20 carbon oxides rather than its adsorption on catalytic active sites.
C2H4
CO In this respect, the developed kinetics accounts for the effect of
10 CO2 inlet partial pressure of ethane on reaction rates; a situation that is
H2O
not possible when the LHHW model since it was insensitive to the
0 inlet partial pressure of ethane [57]. Therefore, statistical and
0 10 20 30 40 50 experimental evidences do indicate that the kinetic model devel-
Fn observed [mmol/h] oped in this study is the most suitable to be evaluated during
industrial-scale reactor simulations.
Fig. 2. Parity plot comparing experimental with calculated reactor outlet molar The estimated values for the adsorption equilibrium constants
flow rates for the kinetic model. The full lines are the first bisector and the dashed for oxygen and water, vide Table 4, indicate that standard
lines represent a deviation of 10%.
adsorption enthalpies are negative with water being the compo-
nent with the smallest standard adsorption enthalpy (DH○n = —128.2
kJ mol—1). This suggests that water binds more strongly to
Table 4
MoVTeNbO catalyst formulation than oxygen (DH○n = —45.6 kJ mol—
Kinetic parameters values and corresponding 95% probability confidence intervals of
1). Furthermore, Boudart0 s criteria are totally satisfied since the
the kinetic model used to describe the ODH-Et over the MoVTeNbO catalyst.
values of standard adsorption entropies are between 41.8 J (mol K)—
Parameter Estimated Lower Upper t-Value
1 and the corresponding gas phase molec- ular standard entropy.
value limit limit
The magnitude of the estimated standard
A01 ; mmol (gcat h)— 1 5.50E+00 5.49E+00 5.52E+00 7.59E+02
adsorption enthalpies is similar to those values reported in litera-
A02 ; mmol (gcat h)— 1 6.86E-01 6.84E-01 6.88E-01 6.79E+02
A03 ; mmol (gcat h)— 1 1.58E+00 1.57E+00 1.58E+00 6.61E+02
ture [57,75–77]. For instance, the standard adsorption enthalpy of
oxygen is reported from —19 to —98 kJ mol—1 [75] and the adsorp-
A40 ; mmol (g cat h)—1 2.60E+00 2.59E+00 2.61E+00 4.80E+02
A05 ; mmol (gcat h)— 1 7.87E-01 7.84E-01 7.90E-01 5.14E+02 tion heat of water, measured on various metal oxides surfaces,
EA;1; kJ mol—1 9.05E+01 9.02E+01 9.07E+01 7.90E+02 ranges between — — kJ mol —1 [76,77]. According to the
36 and 113
EA;2; kJ mol—1 1.65E+02 1.64E+02 1.66E+02 5.43E+02 estimated activation energies, the rate of formation of ethylene
EA;3; kJ mol—1 1.50E+02 1.49E+02 1.50E+02 7.91E+02
from ethane, vide Eq. (1), is the reaction that presents the lowest
EA;4; kJ mol—1 1.39E+02 1.38E+02 1.39E+02 5.31E+02
activation energy i.e., 90.5 kJ mol —1. In contrast, the formation of
EA;5; kJ mol—1 1.32E+02 1.31E+02 1.32E+02 4.96E+02
—DSOo2; J (mol K)—1 2.15E+02 2.14E+02 2.16E+02 8.33E+02
COX from both ethane and ethylene, vide Eqs. (2)–(5), require acti-
—DSHo2;OJ (mol K)—1 4.20E+01 4.19E+01 4.21E+01 6.75E+02 vation energies ranging from 131.8 kJ mol—1 to 165.0 kJ mol—1.
—DH —1
4.56E+01 4.55E+01 4.57E+01 8.56E+02 Specifically, ethylene is the principal contributor to COX because
O2 ; kJ mol
o —1
Ho2 O
—DH ; kJ mol— 1 1.28E+02 1.28E+02 1.28E+02 7.48E+02 total oxidations from ethane (ca. 150 kJ mol ) require even more
m2 9.22E-01 9.19E-01 9.24E-01 7.37E+02 energy than the total oxidations from ethylene (ca. 130 kJ mol —1).
m3 9.06E-01 9.03E-01 9.08E-01 7.23E+02 Our estimated values of activation energies, ranging from 90.5 to
m4 1.23E+00 1.22E+00 1.23E+00 5.79E+02 165.0 kJ mol—1, are similar to the values reported in the literature
m5 9.05E-01 9.02E-01 9.08E-01 6.37E+02
for different catalytic systems for the ODH-Et (from 50 to
Note: F value = 7642, Ftab = 2.79, ttab = 1.97 at 1-a = 0.95 and 396° of freedom. 150 kJ mol—1) [53,57,78]. The reaction orders associated to the par-
tial pressure of oxygen are found to be below 1.0, indicating that
reaction rates are weakly affected by changes in oxygen partial
between experimental points at any of the different operating con- pressure.
ditions studied.
Table 4 presents the F-value of the regression, and the esti-
mated parameters along with the 95% confidence interval and t-
value. The calculated F-value amounts to 7642, a value three orders 4.1.1. Fractional surface coverage
of magnitude larger than the tabulated one (2.79), corrobo- rating Adsorption phenomenon on MoVTeNbO formulation seems a
the satisfactory global significance of the model regression. Besides, key aspect to be analyzed during a proper kinetic study since reac-
all parameters are statistically significant since their con- fidence tant and product adsorptions affect significantly reaction rates and,
interval is significantly narrow and their t-value (ca. 240– hence, catalyst activity and selectivity. Fig. 3 displays the predicted
435) is higher than the t-value tabulated (1.97). All parameters surface coverage of adsorbed oxygen and adsorbed water as a func-
are not statistically correlated since their binary correlations coef- tion of temperature and space-time, which are calculated from Eqs.
ficients (qij) are always lower than 0.5. (12) and (13), respectively. The MoVTeNbO active sites are mostly
As commented earlier the LHHW model has been the most suit- covered with adsorbed water (ca. 0.95) rather than with adsorbed
able one nowadays for describing the ODH-Et on the MoVTeNbO oxygen (ca. 0.0). Thus, the present kinetics accounts properly for
catalytic formulation [57], since other kinetic models present a lack the negative effect of adsorbed water on reaction rates since the
of statistical significance. In this regard, a statistical analysis is car- high levels of water concentration and its affinity on active sites,
ried out to discriminate between this previously reported LHHW based on the highest water adsorption enthalpy, do indeed inhibit
model and the kinetic model developed in this study. oxidative dehydrogenation and total oxidations. Besides, the low
Notwithstanding the proposed kinetic model presents a slightly fraction coverage of oxygen on catalyst active sites and the low
better F-value (7642) than the LHHW model (7567), both models are reaction orders associated to the partial pressure of oxygen, indi-
evaluated through the Bayesian information criterion (BIC) cate that the kinetics accounts satisfactorily for the weak effect
G. Che-Galicia et al. / Chemical Engineering Journal 280 (2015) 682–694 689
1.00 1.0
(a) (b)
0.8
0.00 0.0
400 420 440 460 480 0 10 20 30 40 50 60 70
Temperature [ºC] Wcat/Fethane,o [gcat h/molethane,o]
Fig. 3. (a) Fractional surface coverage versus temperature at inlet molar ratio C2H6/O2/N2 = 9/7/84 and space-time of 70 gcat h mol—ethane,o
1 ; and (b) Fractional coverage versus
space-time at inlet molar ratio C2H6/O2/N2 = 9/7/84 and T = 440 °C.
of the inlet partial pressure of oxygen on ethane conversion and during the modeling of the ODH-Et in a wall-cooled catalytic reac-
selectivity to ethylene [57]. tor packed with MoVTeNbO catalyst externally deposited on a non-
The presence of oxygen is, as observed, crucial for the oxidative porous support of TiO 2. Particularly, the boundary layer
dehydrogenation of ethane and total oxidations to occur. Although approximation is used to estimate keff and hw from heat transfer
catalytic studies [80,81] over V materials for other reactions sug- observations in absence of reaction, thus, these parameters con-
gest that bulk lattice oxygen participates in the reaction and it is taining the hydrodynamic information are used to model the
replaced by catalyst reoxidation with oxygen from the gas phase, industrial scale reactor by means of the classical model, vide Eqs.
for the current catalyst the superficial lattice oxygen seems to be (24)–(34). This approach uses a less expensive numerical scheme
the main species participating on several reactions [14,57,81–84], since it only contains heat and mass balances instead of momen-
which explains the high selectivity to ethylene. The activity of V tum, heat and mass balances which computationally speaking is
catalysts mainly depends on the oxygen’s lability, nevertheless this very time-consuming.
lability is a function of catalyst chemical composition and crys- In order to be judicious on the modeling approach applied to
talline structure [14,57,82,83]. In this respect, MoVTeNbO formula- elucidate the role of MoVTeNbO externally deposited on TiO 2 for
tion presents a relatively large capacity for oxygen recombination the ODH-Et in a wall-cooled catalytic reactor with low dt/dp, we
in its active M1 phase [14,57,82,83], i.e. the oxygen species are present the simulations of an industrial-scale reactor for the cat-
immediately used for oxidation reactions from the first lattice lay- alytic o-xylene partial oxidation using the aforementioned
ers and are overtaken from the gas phase. This might be the reason approach. The o-xylene partial oxidation is selected since observa-
why the proposed mechanism, vide Table 2, adequately represents tions at industrial-scale with and without reaction are available
the observed kinetic phenomenon for MoVTeNbO rather the well- from studies carried out by the research group [33,34,68].
known Mars and van-Krevelen redox mechanism [85]. Kubo et al., Moreover, this reaction system presents the same geometric (L and
[84], during the evaluation of propane ammoxidation with lattice dt/dp) and operational conditions (Rep) that are used for the
oxygen from Mo–V–O-based complex metal oxide catalysts, ODH-Et reaction in this work, vide Table 3. From this end, Fig. 4
observed that the migration rate of the oxygen from the bulk to displays temperature profiles for two oxidation reactions, let0 s
superficial lattice is too slow in comparison with the consumption say, the o-xylene partial oxidation used herein as a reference
rate of oxygen from the surface lattice. In this respect, a relatively (Fig. 4a), and the ODH-Et (Fig. 4b). Both reaction cases compare
small amount of oxygen is demanded to reoxidize the metallic temperature profiles along the reactor using distinct effective
sites that are reduced after the propane oxidation reactions, thus, HTP estimated from the same set of experiments in absence of
explaining the high selectivity to ethylene of this type of mixed reaction: (i) parameters estimated via the classical approach (CA)
oxide catalysts. Namely, a low amount of oxygen on surface lattice assuming an uniform velocity profile with constant void fraction
along with a low reaction temperature give rise to ethylene forma- [68,72–74] and (ii) parameter estimated via the boundary layer
tion out of ethane rather than total oxidations. approximation (BLA) in which the role of void fraction profile
and velocity field are assessed [33,34,45]. Table 3 presents the
4.2. Industrial-scale reactor predictions numerical values of hw and keff estimated via the BLA and CA from
the same experimental dataset. These HTP are larger for BLA,
The adequate consideration of heat transport phenomena in the reflecting differences in the estimated rates of radial heat transport
model of a wall-cooled packed bed catalytic reactor with low dt/dp through the core of the packed bed and close to the wall. To this
is, undoubtedly, one of the most essential aspects to be accounted end, the predictions of measured temperature profiles in Fig. 4a
for during the conceptual design of this type of reaction systems. for the o-xylene partial oxidation case elucidate the suitability of
There are several approximations that have been used to model the HTP values from the BLA, giving better predictions than when
heat transport in a wall-cooled catalytic reactor with low dt/dp. HTP values using the CA approach are employed in the reactor
Some studies [33,34,45] suggest that the inclusion of velocity pro- model, vide, i.e. Eqs. (24)–(34). Therefore, hw and keff are effective
files improves heat transport description; however, others studies parameters that through BLA lump differently the hydrodynamic
[68,72–74] have neglected the influence of the hydrodynamics in and heat-transport phenomena in the packed bed leading to better
the modeling of this type of reactors. In this regard, a practical predictions. Fig. 4b presents temperature profiles for the ODH-Et.
but reliable approach, developed by our research group, is herein As expected, when the reactor model makes use of HTP estimated
applied to account for the role of hydrodynamics on heat transport considering plug flow, there is the presence of a higher hot spot
690 G. Che-Galicia et al. / Chemical Engineering Journal 280 (2015) 682–694
460
550 (a) (b)
500 450
Temperature [ºC]
Temperature [ºC]
450
440
400
430
Experimental observation
350 HTP estimated with BLA
HTP estimated with BLA
HTP estimated with CA
HTP estimated with CA
300 420
0.0 0.5 1.0 1.5 2.0 2.5 0.0 0.5 1.0 1.5 2.0 2.5
Reactor length [m] Reactor length [m]
Fig. 4. Axial temperature profiles in the reactor using different HTP: (a) Comparison between prediction and observation for the parti al oxidation of o-xylene on a V2O5/TiO2
catalyst at: Tb = 376 °C, inlet molar ratio o-xylene/air = 1/99 and To = 190 °C [33]; and (b) Predictions for the oxidative dehydrogenation of ethane on MoVTeNbO/TiO 2 catalyst
at: Tb = 440 °C, inlet molar ratio C2H6/O2/N2 = 9/7/84 and To = 200 °C.
560 1.0
Tb=480 ºC
480
0.8 - - - - Initial steady state
0.2 - - - - Transient state
Tb=440 ºC
440
Tb=400 ºC 0.1
400
Initial steady state Second steady state
Final steady state Transient state
360 0.0
0.0 0.5 1.0 1.5 2.0 2.5 0.0 0.5 1.0 1.5 2.0 2.5
Reactor length [m] Reactor length [m]
1.0 1.0
- - - - Final steady state
0.9 (c) (d) - - - - Transient state
1- Conversion and Yield
0.8
0.8
0.7 0.6
- - - - Second steady state
- - - - Transient state
0.3 0.4
0.2
0.2
0.1
0.0 0.0
0.0 0.5 1.0 1.5 2.0 2.5 0.0 0.5 1.0 1.5 2.0 2.5
Reactor length [m] Reactor length [m]
Fig. 5. Reactor model predictions when Tb is increased 40 °C in a ramp change with an inlet molar ratio C2H6/O2/N2 = 9/7/84: (a) Temperature profiles; (b) Conversion and
yield profiles at Tb = 400 °C; (c) Conversion and yield profiles at Tb = 440 °C; (d) Conversion and yield profiles at Tb = 480 °C (For (b)–(d): (d) C2H6 conversion; (h) O2
conversion; (s) C2H4 yield; (j) H2O yield; (N) CO yield and (4) CO2 yield).
since the role of hydrodynamics on heat transfer mechanisms is parametric sensitivity study for the performance of MoVTeNbO
neglected. Owing to the above, the following sections present the system during the ODH-Et in an industrial scale wall-cooled
simulations of the industrial-scale reactor for ODH-Et considering packed bed reactor, this section is aimed at simulating the reactor
those HTP estimated from BLA. when perturbations of cooling bath temperature and inlet ethane
concentration are considered. The first case, illustrated in Fig. 5,
4.2.1. Parametric sensitivity study shows the predicted dynamic response when reactor starts up at
The behavior of a reactor is a function of the initial process con- Tb of 400 °C with an inlet molar ratio C 2H6/O2/N2 = 9/7/84, once
ditions, reactor disturbances and the trajectories of the manipu- the steady state is reached, it is followed by perturbations of the
lated reactor variables. In order to analyze an open-loop cooling bath temperature, namely 440 °C and 480 °C. The second
G. Che-Galicia et al. / Chemical Engineering Journal 280 (2015) 682–694 691
480 1.0
Initial steady state
(a) Second steady state
Third steady state
(b)
470
Temperature [ºC]
Transient state
460
40 mole % of ethane 0.6
18 mole % of ethane - - - - Initial steady state
450 - - - - Transient state
9 mole % of ethane
0.4
440
1 mole % of ethane
0.2
430
420 0.0
0.0 0.5 1.0 1.5 2.0 2.5 0.0 0.5 1.0 1.5 2.0 2.5
Reactor length [m] Reactor length [m]
1.0 1.0
(c) (d)
1- Conversion and Yield
0.6 0.6
- - - - Second steady state - - - - Third steady state
- - - - Transient state - - - - Transient state
0.4 0.4
0.2 0.2
0.0 0.0
0.0 0.5 1.0 1.5 2.0 2.5 0.0 0.5 1.0 1.5 2.0 2.5
Reactor length [m] Reactor length [m]
1.0
(e)
1- Conversion and Yield
0.8
0.6
- - - - Final steady state
- - - - Transient state
0.4
0.2
0.0
0.0 0.5 1.0 1.5 2.0 2.5
Reactor length [m]
Fig. 6. Reactor model predictions when ethane feed concentration is increased at different% mole in a ramp change with a Tb = 440 °C: (a) Temperature profiles; (b)
Conversion and yield profiles at 1% mole of ethane; (c) Conversion and yield profiles at 9% mole of eth ane; (d) Conversion and yield profiles at 18% mole of ethane; (e)
Conversion and yield profiles at 40% mole of ethane (For (b)–(e): (d) C2H6 conversion; (h) O2 conversion; (s) C2H4 yield; (j) H2O yield; (N) CO yield and (4) CO2 yield).
case, illustrated in Fig. 6, displays the predicted dynamic response 400 °C or 440 °C leads to mild hot spots of ca. 1 °C or 7 °C respec-
when reactor starts up at Tb of 440 °C with an inlet molar ratio of tively whereas a Tb equal to 480 °C provokes a pronounced hot spot
C2H6/O2/N2 = 1/7/92, once the steady state is reached, it is followed with a temperature rise of ca. 56 °C. In the latter, the rate of heat
by perturbations of the inlet molar ratio of ethane, specifically removal is minor in comparison with the rate of heat generated.
C2H6/O2/N2 = 9/7/84, C2H6/O2/N2 = 18/7/75 and Besides Figs. 5b–d display the effect of coolant temperature on
C2H6/O2/N2 = 40/7/53. the overall consumption rates of the reactants. The increment of Tb
Fig. 5 displays transient and steady state temperature, conver- favors both ethane and oxygen conversions. Analyzing the pro-
sion (ethane and oxygen) and yield (ethylene, CO X and water) pro- duct distribution, an increase in Tb brings out a positive effect on
files along the reactor length at different coolant temperatures the yield of ethylene out of ethane. However, a higher Tb leads to
maintaining a fixed inlet molar ratio C2H6/O2/N2 = 9/7/84. So far, higher carbon oxides yields, which are the responsible of both
an increment in coolant temperature causes an increase in the the formation of hot spots and the decrease in the selectivity to
magnitude of the hot spot, vide Fig. 5a. Specifically a Tb equal to ethylene. In this regard, a lower Tb is recommended for a
692 G. Che-Galicia et al. / Chemical Engineering Journal 280 (2015) 682–694
0.0 5. Conclusions
0.0 0.5 1.0 1.5 2.0 2.5
Reactor length [m]
The implementation of a new catalytic material at industrial
Fig. 7. Fractional surface coverage along the reactor at differ bath temperatures level requires the knowledge from the conceptual design of the
with an inlet molar ratio C2H6/O2/N2 = 9/7/84. reactor technology. Modeling has been the most reliable engineer-
ing tool to carry out the preliminary reactor design. In this regard,
this work shows through modeling the catalytic performance of
satisfactory ethane conversion along with ethylene selectivity MoVTeNbO catalyst for ODH-Et in a wall-cooled industrial-scale
avoiding catalyst damage due to high temperatures [23]. The catalytic packed bed reactor presenting a low dt/dp ratio. To have
behavior of the industrial scale reactor presented in Fig. 5 shows a confidence on model simulations, a proper determination of both
similar tendencies as those of the typical industrial-scale packed kinetic parameters and heat transport parameters from indepen-
bed reactors used to perform highly exothermic reactions dent experiments should be carefully carried out. In terms of the
[24,30,33,34,67,68]. kinetics, an adequate agreement between model and experimental
In the design of this type of complex reactors it is necessary to values is observed, wherein the obtained parameters are physically
operate without the presence of drastic hot spots in order to meaningful and are found to be statistically significant. The pro-
decrease the irreversible deactivation of the catalysts by a sintering posed kinetics addresses several aspects observed experimentally,
phenomenon [86]. Particularly, the stability of the MoVTeNbO cat- namely it accounts for both the negative effect of adsorbed water
alyst is restricted to operate below 500 °C, due to energy saving on reaction rates and the weak effect of the inlet partial pressure
but, mainly, because operations above 500 °C leads to the irre- of oxygen on ethane conversion and selectivity to ethylene. In this
versible loss of catalytic activity as a consequence of the removal respect, even the presence of oxygen is crucial for the oxidative
of tellurium from the MoVTeNbO catalytic formulation [23], i.e. dehydrogenation of ethane and total oxidations to occur, the
specifically, the lost of Te from MoVTeNbO material occurs prefer- superficial lattice oxygen from the MoVTeNbO catalyst seems to
entially from the end section of the M1 crystal phase, across the be the main species participating on reactions, explaining, thus, its
[001] plane. The removal of Te species modifies the crystal phase high selectivity to ethylene.
composition of the M1 phase causing the partial destruction of In terms of the industrial-scale reactor, the simulations suggest
the MoVTeNbO with the simultaneous formation of the MoO2 that hydrodynamics is an essential aspect to be considered during
phase and, in consequence, the activity and selectivity to ethylene the modeling of this type of reaction systems presenting a low dt/-
are affected as elucidated elsewhere [23]. dp. The coolant temperature is the main variable affecting ethane
Fig. 6 compares transient and steady state temperature, conver- conversions and yield to ethylene. For instance, coolant tempera-
sion (ethane and oxygen) and yield (ethylene, CO X and water) pro- tures larger than 440 °C lead to hot spot magnitudes that could
files along the reactor length at different ethane inlet cause the damage to the MoVTeNbO structure. As observed from
concentrations at Tb equals to 440 °C. The position of the hot spot laboratory experiments, water formation affects conversion and
is located toward the first meter of reactor length, a zone with selectivity, and catalyst is weakly oxidized along the reactor
higher concentration of ethane. An increment in the inlet ethane length, giving insights on the highly selectivity of the MoVTeNbO
concentration causes a slight increment of the magnitude of the catalytic formulations.
hot spot, vide Fig. 6a. Particularly, 1% or 9% of ethane in the feed- On the basis of the results obtained herein, the wall-cooled
stock leads to mild hot spots of ca. 1 °C or 7 °C, respectively, packed-bed reactor represents a promising alternative for petro-
whereas 18% or 40% of ethane causes hot spots with a temperature chemical industry to carry out the ODH-Et over a MoVTeNbO cat-
rise of ca. 12 °C or 34 °C, respectively. Figs. 6b–e show the effect of alyst, which is highly selective to ethylene. Besides, the model
inlet ethane concentration on ethane conversion and product developed in this work, in general, and the modeling strategy
yields. An increase in ethane inlet concentration causes a rapid oxy- based on laboratory and pilot plant experiments in absence of reac-
dehydrogenation (r1), but mainly of the total oxidations (r2–r5) tion, in particular, are potential tools to be used in future studies
reactions, thus, provoking large amounts of heat generation. for the conceptual design and scale-up of industrial reactor system
Therefore, the increase in ethane inlet concentration favors reactant for the ODH-Et on MoVTeNbO material.
conversions and product yields rather than ethylene selectivity
(vide Figs. 6b–e). Acknowledgments
Finally, a brief analysis of the influence of the adsorption of both
water and oxygen on catalytic reactor performance is presented. As This study was supported by El Consejo Nacional de Ciencia y
observed in Fig. 7, the catalyst surface is mainly occupied by water Tecnología (CONACYT) under Project No. 181104. Gamaliel Che-
and vacancy sites, since the surface coverage of oxygen is found to Galicia also thanks CONACYT for providing a postgraduate fel-
be negligibly small along the reactor length, as elucidated from lab- lowship. We also acknowledge to Eng. J.C. Castillo-Rodriguez, Eng.
oratory experiments in Section 4.1.1. The reactions occurring on C. Tzompantzi-Flores and Eng. O. Romero-Pérez for the technical
the MoVTeNbO catalytic formulation are a function of the surface support and discussion on the developed kinetic model. Authors
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