Monte-Carlo Methods For Simulating The Catalytic Oxidative Dehydrogenation of Propane Over Vmgo Catalyst
Monte-Carlo Methods For Simulating The Catalytic Oxidative Dehydrogenation of Propane Over Vmgo Catalyst
Abstract
The oxidative dehydrogenation of propane (ODHP) has been extensively studied by non-steady-state kinetic experiments and by
various experimental characterization techniques under conditions as close as possible to reaction conditions. It can be described in
terms of the Mars}Van Krevelen mechanism. This work reports on Monte-Carlo simulations of the ODHP over VMgO catalysts,
aimed at relating the main experimental insights obtained previously on the catalytic reaction to a theoretical description of the
working catalyst. The `theoretical "eld of catalysisa is explored by handling new Monte-Carlo models with a catalytic reaction graph,
2D pattern recognition of adsorbed molecules, 3D oxygen bulk di!usion and "nally the description of the selective, non-selective
routes of the ODHP process. 1999 Elsevier Science Ltd. All rights reserved.
Keywords: Monte-Carlo simulation; Oxidative dehydrogenation of propane; Pattern recognition; Mars}Van Krevelen mechanism; VMgO catalyst
0009-2509/99/$ - see front matter 1999 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 0 9 - 2 5 0 9 ( 9 9 ) 0 0 1 4 7 - 5
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2.1. Model 1: Theoretical view of the elementary as necessary for the alkane reaction with oxygen (four for
catalytic steps C H , Table 2), in all the 2D space orientations, are
considered. If there is an exact topological match be-
A "rst approach of the bare surface mechanism, with- tween the grid and a pattern, i.e., if any carbon atom or
out bulk oxygen lattice motion, was carried out with hydrogen atom of the molecule can react with an oxygen
a system of 11 elementary steps occurring on the catalyst of the catalytic surface, and if this reaction is kinetically
surface only, this assumes that the 11 kinetic constants selected by the MC process, then the complete reaction
are known. The Monte-Carlo simulation is made on occurs on the catalytic site; if the match is not perfect for
a 225;225 grid of atoms representing the bare surface, any pattern, no reaction occurs.
adsorbed species and catalytic reaction products. The idea beneath these four patterns is the possibility
The pseudo-elementary steps of the catalytic process for the catalyst surface to give in one step all the neces-
are described in Table 1. sary reactants to the colliding molecule for the speci"ed
The theoretical graph of reactions in Table 1 matches reaction. This means that the sub-steps of one pseudo-
the main mechanistic features described in (Pantazidis elementary reaction (k for example) are orders of magni-
and Mirodatos, 1996b) and Pantazidis et al., 1998a). tude faster than the mobilities of the catalytic species.
They can be summarized as follows: These patterns have been selected because they corres-
(i) the selective propane-to-propene route occurs on pond to `ensemble of atomsa in the closest shape of
a surface site formed of lattice surface oxygen and anionic a circular site of the surface which are found to be
vacancy, necessary by experimentalists to develop such kind of
(ii) the non selective propane-to-CO degradation reactions (magnetism measurements).
V
route occurs on adsorbed electrophilic oxygen but also During the simulation, the spatial 2D behaviour of the
likely involves lattice oxygen in further steps, oxide catalyst can interactively be followed from the
(iii) the secondary propene-to CO route involves both initial contact between reactants and the catalytic surface
V
types of surface oxygen species, (Fig. 2), i.e., under unsteady state conditions until the
(iv) the site regeneration occurs by means of surface steady state is achieved, i.e. it implies that there is neither
dehydroxylation into water (from OH groups formed chaos nor oscillations (Qin Feng et al., 1998), by examin-
upon the previous steps) and lattice vacancies reoxida- ing the time evolution of the reaction rates. Thus, it is
tion by gaseous oxygen. observed in Fig. 3 that due to the still increasing surface
In this MC model 1, we use `pattern recognition tech- di!usion M of adsorbed electrophilic oxygen [O3 ], the
I
niquesa to randomly decide if a catalytic site can undergo steady state is not yet reached after more than a thousand
degradation reactions leading to CO (the pattern is here of MC seconds. Fig. 4 gives the spatial 2D description
an ensemble of surface atoms). As many surface patterns of the catalytic surface with an interactive summary
Y. Boudeville et al. / Chemical Engineering Science 54 (1999) 4295}4304
Fig. 1. Left: Oxygen (blue) and vacancies (yellow) volume di!usion in bulk oxide; Upper Right: supposed reactive face (}cyan}"lattice surface oxygen atoms); Lower Right: supposed face of
O gas adsorption and dissociation on two neighbouring lattice vacancy sites (}yellow}).
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Y. Boudeville et al. / Chemical Engineering Science 54 (1999) 4295}4304
Fig. 2. First view of the [1 0 0] surface catalyst at the time"1 for the Model 1; Ox: means lattice oxygen; Oh: Hydroxyl groups; Oo: adsorbed electrophilic oxygen species; Va: means
Vanadium induced oxygen vacancy; Pr: is used to label the surface sites where a Propene has been selectively made at one time of the interactive Monte-Carlo simulation.
Y. Boudeville et al. / Chemical Engineering Science 54 (1999) 4295}4304 4299
Table 2
Surface selected patterns for recognition of the reaction k (one
example)
Pattern 1 1 2 3 4 5
1 [.] [.] [.] [.] [.]
2 [.] [O ] [O ] [O ] [.]
I I I
3 [O ] [O ] [O3 ] [O ] [O ]
I I I I I
4 [.] [O ] [O ] [O ] [.]
I I I
5 [.] [.] [.] [.] [.]
Pattern EEWW.
Pattern 2 1 2 3 4 5
1 [.] [.] [O ] [.] [.]
I
2 [.] [O ] [O ] [O ] [.]
I I I
3 [.] [O ] [O3 ] [O ] [.]
I I I
4 [.] [O ] [O ] [O ] [.]
I I I
5 [.] [.] [O ] [.] [.]
I
Pattern NNSS.
Pattern 3 1 2 3 4 5
1 [.] [.] [.] [O ] [.]
I
2 [.] [.] [O ] [O ] [O ]
I I I Fig. 5. Time curves: Model 1. Variation in time of the di!erent surface
3 [.] [O ] [O3 ] [O ] [.]
I I I species coverages (between 0.0 and 1.0) and rate curves of reactants and
4 [O ] [O ] [O ] [.] [.]
I I I products. [A] a: Propane consumption; b: Propene rate of formation; c:
5 [.] [O ] [.] [.] [.]
I CO formation; d: CO . [B] e: [C] empty site coverage; f: [O ] site; g:
Pattern NESW. I
[OH ] site; h: [O3 ] site coverage.
I I
Pattern 4 1 2 3 4 5
1 [.] [O ] [.] [.] [.]
I
2 [O ]
I
[O ]
I
[O ]
I
[.] [.] 225;225 atoms, is su$cient to have a small enough
3 [.] [O ] [O3 ] [O ] [.] random noise that concentration curves can be followed
I I I
4 [.] [.] [O ] [O ] [O ]
I I I without ambiguity. No physical meaning can be derived
5 [.] [.] [.] [O ] [.]
I from these curves since all the rate constants were taken
Pattern NWSE.
as 1 for this "rst MC model, a large part of these con-
stants being not available from any kinetic experiments.
A similar assumption was considered in the Zi!, Gulari,
Barshad ZGB model, where all the probability functions
are equal to 1.
Fig. 4. Model 1, spatial representation of the catalytic surface at time"1000 Mcs. The caption for surface species has been de"ned in Fig. 2. Number of Reaction 00 is the total number of
reactions that have occurred on the solid catalyst.
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