Carbon Deposition in Heterogeneous Catalysis: Solved With Comsol Reaction Engineering Lab 3.5A

carbon_deposition.
book Page 1 Monday, December 8, 2008 10:26 AM
Carbon Deposition in Heterogeneous Catalysis

SOLVED WITH COMSOL REACTION ENGINEERING LAB 3.5a
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carbon_deposition.book Page 1 Monday, December 8, 2008 10:26 AM
Carbon Deposition in Heterogeneous

Catalysis
Introduction
Carbon deposition onto the surface of solid catalysts is commonly observed in
hydrocarbon processing. Carbon deposits can affect both the activity of catalysts as
well as the flow of gas through a catalyst bed.
This example investigates the thermal decomposition of methane into hydrogen and
solid carbon. In the first model you look at the isothermal process occurring in an ideal
reactor, simulated in the Reaction Engineering Lab. The influence of carbon
deposition on catalyst activity is also considered. In the second model, you study the
effect that the carbon deposits have on the fluid flow. The second simulation takes
place in COMSOL Multiphysics, taking both time and space dependencies into
account.
Model Definition
CHEMISTRY
Methane decomposes over a Ni/Al2O3 catalyst according to the overall chemical

reaction:
CH4
C +
2H2
(1)
The following reaction rate expression has been reported in the literature (Ref. 1):
2
p H2
p CH4 --------Kp
r = k ---------------------------------------2( 1 + k H pH2 )
(2)
where
k = 2,31 10
mol
104200 J/mol
exp 20,492 -------------------------------------- --------------------3
Rg T
m sbar
CARBON DEPOSITION IN HETEROGENEOUS CATALYSIS
1 2
163200 J/mol
k H = exp -------------------------------------- 22.426 (bar)
R T
g
and
5
91200 J/mol bar
K p = 5.088 10 exp ---------------------------------
R T
g
IDEAL REACTOR MODEL
You set up the first model in the Reaction Engineering Lab. This model treats the
isothermal decomposition of methane (Equation 1) in a perfectly mixed reactor with
constant volume. The species mass balances are summarized by
dc
--------i = R i
dt
The rate term, Ri (mol/(m3s), takes into account the reaction stoichiometry, i, the
reaction rate, r (mol/(m3s), and the catalyst activity, a:
R i = i ra
The mass balances of the reacting species are then
dc CH4
---------------- = ra
dt
dc
---------C- = ra
dt
dc H2
------------- = 2ra
dt
The time dependence of the catalytic activity is expressed by the ODE
2
da
------- = k a r c C a
dt
(3)
where
3 3
m
J/mol- 32.007 --------k a = exp 135600
------------------------------------s
mol
Rg T
Solving the mass balances provides the evolution of the species concentrations over
time. The fact that carbon is in the solid phase is taken into account by removing its
effect on gas phase physical properties. The pressure in the reactor is a function of only
the methane and hydrogen concentrations:
p = R g T ( c CH4 + c H2 )
SPACE- AND TIME-DEPENDENT MODEL
The second model is solved in COMSOL Multiphysics and takes both fluid flow and
the chemical reaction into account.
The flow reactor is set up in 2D, as illustrated below:
wall
porous catalytic bed
Inlet
outlet
wall
Figure 1: A flow reactor is set up in 2D. Methane enters from the left and reacts in the
porous catalytic bed in the mid-section of the geometry.
Methane first flows through a free section of the reactor, and then encounters a porous
catalytic bed where the decomposition reaction takes place.
Momentum Balances
The flow in the free channel section is described by the Navier-Stokes equations:
T
u
------- + [ ( u + ( u ) ) + pI ] = ( u )u
t
(4)
u = 0
where denotes density (kg/m3), u represents the velocity (m/s), is the dynamic
viscosity (Pas)), and p refers to the pressure (Pa). In the porous domain, the Brinkman
equations govern the flow:
u
T
----- ------- + ---- ( u + ( u ) ) + pI = --- u

p t
k
p
(5)
u = 0
Here p is the porosity and k denotes permeability (m2) of the porous medium. As you
can see in Equation 4 and Equation 5, the momentum-balance equations are closely
related. The term on the right-hand side of the Navier-Stokes formulation corresponds
to momentum transported by convection in free flow. In the Brinkman formulation,
this term is replaced by a contribution associated with the drag force experienced by
the fluid as it flows through a porous medium. COMSOL Multiphysics automatically
combines free and porous-media flow to solve the equations simultaneously.
The boundary conditions for the flow are:
u n = u0
inlet
u = 0
p = 0
walls
outlet
Mass transport in the reactor is described by the diffusion-convection equations:

c i
------- + ( D i c i + c i u ) = R i
t
where Di denotes the diffusion coefficient (m2/s) and ci is the species concentration
(mol/m3). The term Ri (mol/(m3s)) corresponds to the species net reaction rates.
In the free channel, the inlet conditions are equal to the inlet concentrations
c = c in
At the outlet, use the convective flux condition
n ( D c ) = 0
All other boundaries, use the insulating or symmetry condition
n ( D c + cu ) = 0
Balance for Void Fraction

The void fraction of the catalytic bed decreases as carbon is deposited. This, in turn,
affects the flow through the reactor. A balance for the void fraction, or porosity, of the
bed is given by:
d
r
------ = ---------------------dt
M C soot
(6)
This equation can be implemented in the PDE, General Form application mode of
COMSOL Multiphysics, resulting in porosity distribution across the catalytic bed as a
function of time. The initial porosity of the bed is assumed to be = 0.4.
The porosity is related to the permeability of the porous domain by the expression
(Ref. 2):
3.55
k = k 0 -----
0
(7)
In this way, the porosity balance couples the mass and momentum balances describing
the reacting system.
Results
IDEAL REACTOR MODEL
The upper graph of Figure 2 shows the concentration transients of methane,

hydrogen, and deposited carbon as methane decomposes over a Ni/Al2O3 catalyst.
The lower graph is a plot of the reactor pressure. Deactivation of the catalyst is not
taken into account at this point.
Figure 2: Upper plot: Concentration transients of methane decomposition over a Ni/

Al2O3 catalyst. Lower plot: Reactor pressure. Deactivation of the catalyst is not considered.
Taking catalyst deactivation into account (Equation 3) produces the results shown in
Figure 3. Under the simulated conditions a moderate drop in activity is noted (upper
graph), leading to a largely unaffected overall process, as can be seen by comparing

with the concentration transients of the previous model (lower graph).
Figure 3: Upper plot: Catalyst activity drops off as carbon deposits at the catalyst surface.
Lower plot: Concentration transients of methane, hydrogen, and deposited carbon with no
deactivation present (solid lines) and with deactivation taken into account (dashed lines).
SPACE- AND TIME-DEPENDENT MODEL
The following results concern a space- and time-dependent model simulated in

COMSOL Multiphysics. Methane decomposition occurs in a porous region where
solid catalyst particles are packed. Figure 4 shows the velocity field across the reactor
prior to carbon deposition. The 2D plot shows that the velocity profile is parabolic in
the free channel sections and close to constant in the porous domain. The line plot in
the bottom graph in Figure 4 shows the velocity along the reactor centerline.
Figure 4: Upper plot: Velocity flow field in the 2D reactor domain. Lower plot: Gas velocity
along the reactor centerline.
Reactions take place in the packed catalytic bed located in the reactors mid section.
Figure 5 shows the concentration profiles along the centerline of the bed.
Figure 5: Methane and hydrogen concentrations as a function of the bed position.

The methane and hydrogen concentrations are equal approximately 0.18 m into the
bed. Figure 4 shows that the velocity in the bed is about 0.67 mm/s, corresponding
to a residence time of 270 s. This result agrees with the findings from the ideal reactor
simulation, shown in Figure 2.
Now, consider the effects as methane is constantly supplied to the reactor for
1000 seconds. The initial permeability is a constant 1109 m2 across the bed. Note
how the permeability at the front end of the bed changes by four orders of magnitude
during the first 1000 s of carbon deposition.
Figure 6: Permeability of the packed catalytic bed as the decomposition of methane proceeds
for 1000 s. The time interval between each line is 100 s.
As carbon deposits in the reacting bed, the pressure distribution across the reactor is
affected. Figure 7 shows a small, linear pressure drop as unreacting gas passes through
a clean catalyst bed.
Figure 7: Distribution of pressure as an nonreacting gas passes a clean catalyst bed.Upper

plot: Pressure distribution across the 2D reactor domain. Lower plot: Pressure drop along
the packed catalyst bed.
10
Figure 8 shows the pressure distribution across the reactor after methane
decomposition has occurred for 1000 s. The pressure drop is notably greater and
occurs across the first 10 cm of the bed.
Figure 8: Distribution of pressure when methane decomposition has been allowed to occur
for 1000 s. Upper plot: Pressure distribution across the 2D reactor domain. Lower plot:
Pressure drop along the packed catalyst bed.
11
References
1. S.G. Zavarukhin and G.G. Kuvshinov, J. Appl. Catal. A, vol. 272, p. 219, 2004.
2. E.A. Borisova and P.M. Adler, Phys. Rev. E, vol. 71, p. 016311-1, 2005.
12

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carbon_deposition.

book Page 1 Monday, December 8, 2008 10:26 AM

Carbon Deposition in Heterogeneous Catalysis

carbon_deposition.book Page 1 Monday, December 8, 2008 10:26 AM

Carbon Deposition in Heterogeneous

Methane decomposes over a Ni/Al2O3 catalyst according to the overall chemical

CARBON DEPOSITION IN HETEROGENEOUS CATALYSIS

carbon_deposition.book Page 2 Monday, December 8, 2008 10:26 AM

IDEAL REACTOR MODEL

CARBON DEPOSITION IN HETEROGENEOUS CATALYSIS

carbon_deposition.book Page 3 Monday, December 8, 2008 10:26 AM

CARBON DEPOSITION IN HETEROGENEOUS CATALYSIS

carbon_deposition.book Page 4 Monday, December 8, 2008 10:26 AM

----- ------- + ---- ( u + ( u ) ) + pI = --- u

Mass transport in the reactor is described by the diffusion-convection equations:

CARBON DEPOSITION IN HETEROGENEOUS CATALYSIS

carbon_deposition.book Page 5 Monday, December 8, 2008 10:26 AM

Balance for Void Fraction

The upper graph of Figure 2 shows the concentration transients of methane,

CARBON DEPOSITION IN HETEROGENEOUS CATALYSIS

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Figure 2: Upper plot: Concentration transients of methane decomposition over a Ni/

CARBON DEPOSITION IN HETEROGENEOUS CATALYSIS

carbon_deposition.book Page 7 Monday, December 8, 2008 10:26 AM

graph), leading to a largely unaffected overall process, as can be seen by comparing

The following results concern a space- and time-dependent model simulated in

CARBON DEPOSITION IN HETEROGENEOUS CATALYSIS

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CARBON DEPOSITION IN HETEROGENEOUS CATALYSIS

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Figure 5: Methane and hydrogen concentrations as a function of the bed position.

CARBON DEPOSITION IN HETEROGENEOUS CATALYSIS

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Figure 7: Distribution of pressure as an nonreacting gas passes a clean catalyst bed.Upper

CARBON DEPOSITION IN HETEROGENEOUS CATALYSIS

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CARBON DEPOSITION IN HETEROGENEOUS CATALYSIS

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CARBON DEPOSITION IN HETEROGENEOUS CATALYSIS

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