1

The tubular reactor

(2 lectures)
Processes in tubular
reactors
Empty tube Thermal cracking (ethane)
Packed bed Catalytic gas phase reactions
SO
2
oxidation
Ammonia synthesis
Methanol synthesis
Gas-liquid reactions
Absorption (where the tube is tilted 90 degrees,
i.e. a tower reactor..)
Packed bed or fluidized
bed?
Packed bed
+ Good contact
between gas phase
and fluid phase
+ High degree of
conversion (if 1/r
increases with x)
+ The catalyst
remains in the reactor
- Poor heat transfer
- Large pressure drop
Fluidized bed
+ Good heat
transfer
+ Low pressure drop
- Risk of by-passing
in the reactor
-Low degree of
conversion (if 1/r
increases with x)
- Need for catalyst
separation
The basic equations heat
and mass balances
Why?
Calculation of degrees of conversion
Reactor sizing
Design of cooling
Optimizing temperature profiles
Cases
isothermal, adiabatic, non-
isothermal/adiabatiskt
Dynamics is not the same issue as for a
CSTR
PFR the ideal reactor
dV = a very very tiny reactor segment
F
A
= inflow of A
into the segment
F
A0
F
A,ut
F
A
+ dF
A
= outflow of A
from the segment
Mass balance - steady-state

= + +
i
i Ai A A A
dV r dF F F 0 ) ( v
}

=
i
i Ai
A
r
dF
V
v
in
out
Net formed
acc.
) ,..., ( T c r r
A i i
=
NOTE! Must be taken into account
2
Heat balance
(adiabatic case one reaction only)
0 ) ( ) ( ) ( = A +

+
Adz H r T T c F T T c F
dz z
ref pi i
z
ref pi i

~ const c F
pi i

A
=
pi i
i
c F
A H r
dz
dT ) (

A
+ =
pi i
A A
c F
H x F
T T
) (
0
0
For the adiabatic case (Only then) we get by combining
M.B. and H.B
Cross sectional area
Temperature variation with z
Adiabatic
temperature
increase
Example
AB r =k*c
A
Data:
k = k
0
exp(-Ea/RT)
k
0
= 2.6 10
20
min
-1
Ea = 30 kcal/mol
AH = -20 kcal/mol
C
p
= 1000 cal/lit
C
A0
= 2 mol/liter
Compare an adiabatic CSTR and an adiabatic PFR!
The real tubular reactor
What causes deviation from the ideal PFR?
Everything that gives non plug-flow!
Common complications:
Dispersion
Pressure drop
Heat conduction (poor such..)
More complicated mathematical expressions
necessarily arise from considering these
factors. Analytical solutions are no longer
possible, but numerical approaches must be
used..
The tubular reactor
The mathematics
Derivations
general case
special cases
klassification of process
Causes of deviations to plug flow
Dispersion
Heat conduction
Pressure drop
Numerical treatment
Nothing in life is to be feared. It is only
to be understood
Marie Curie
Mass balances
A general derivation
n =normal to the surface
Ytan S
(som omger volymen V)
j
i
=flux vector for
species i
The mass balances for V can be written as usual, i.e.
Acc =In Out +formed - consumed
3
Mass balance general
derivation
}} }}} }}}
+ =
c
c
S
i
V
i
rdV jdS n dV c
t
v
Accumulated
Net flow (in out)
Net produced (formed minus consumed)
the net flow consists of two terms; diffusiv (Ficks law) and convective transport
}} }} }}
V =
S S S
i i i
u c n c D n jdS n
The surface integrals can be transformed into volume integrals by the
Green Gauss Ostrogradskiis theorem:
}} }}}
V =
S V
jdV jdS n
This gives the general diffusion equation:
r u c c D
t
c
i i i i
i
v + V V =
c
c
2
Acc.
Diffusive transport
source term
Convective transport
Mass balance general
derivation
The meaning of the Laplace
operator?
2
2
2 2 2
2
2
2
sin
1 ) (sin
sin
1 1 1
0 u u u
u
u c
c
+
c
c
c
c
+
(

c
c
c
c
= V
i i i
i
c
r
c
r r
c
r
r r
c
Spherical coordinates:
2
2
2
2
2
2
2
z
c
y
c
x
c
c
i i i
i
c
c
+
c
c
+
c
c
= V
Cartesian coordinates:
May disappear in symmetric problems!
For the tubular reactor we get
(Diffusion being replaced by dispersion)
r u c c D
i i i i
v + V V =
2
0
Steady-state tubular reactor with dispersion
Steady-state ideal PFR
r u c
i i
v + V = 0
r u c c D
t
c
i i i i
i
v + V V =
c
c
2
Dynamic equation tubular reactor with dispersion
Heat conduction
i
i
p eff p
r H u T c T
t
T
c

A + V V =
c
c

2
Dynamic equation, with heat conduction
i
i
p eff
r H u T c T

A + V V =
2
0
i
i
p
r H u T c

A + V = 0
Steady-state with heat conduction
Steady-state assumed no radial temperature gradient
Partial differential equations
- classification
0
2
2 2
2
2
= + +
c
c
+
c
c
+
c
c
+
c c
c
+
c
c
g fu
y
u
e
x
u
d
y
u
c
y x
u
b
x
u
a
0 4
2
> ac b
0 4
2
= ac b
0 4
2
< ac b
hyperbolic
parabolic
elliptic
4
Partial differential equations
Hyperbolic
Do not approach steady-state
example: the wave equation
Parabolic
Approaches steady-state
example: The diffusion equation
(The steady-state solution can be obtained by
solving the dynamic problem for long times)
Elliptic
Have already reached steady-state
example: the La Place equation, ss solution of
the diffusion equation
0
2
2
2
2
2
=
c
c

c
c
x
u
c
t
u
0
2
2
=
c
c

c
c
x
u
k
t
u
0
2
2
2
2
=
c
c
+
c
c
y
u
t
u
Boundary conditions
Dirichlet-type
The value of the dependent variable
known at the boundary
e.g. C(0) =0; C(rp) =Cs
Neuman type
The value of the derivative of the
dependent variable known at the
boundary
e.g. dC/dr =0 at r=0
Tubular reactors
Two main cases: Packed bed or empty
tube
Principal non-idealities to consider:
Dispersion
axial
radial
Temperature gradients (due to slow
conduction)
axial (normally neglected)
Radial (important)
Pressure drop
Packed beds
Phenomena occur at very different
scales
Macro scale
Micro scale
Molecular scale
Convection, dispersion
Diffusion
Adsorption, reaction
Modeling of tubular reactors
Inter- and intra particle
gradientes negligable?
Pseudohomogenous model Heterogenous model
Radial dispersioneffects
may beneglected?
Axial dispersioneffects
may beneglected?
Radial dispersioneffects
may beneglected?
Axial dispersioneffects
may beneglected?
Radial dispersioneffects
may beneglected?
Radial dispersioneffects
may beneglected?
1-Dpseudohomogenous
model w/o dispersion
1-Dpseudohomogenous
model with
axial dispersion
1-Dheterogen
modell med
axiell dispersion
1-Dheterogen modell
utandispersion
2-Dpseudohomogenous
model with
radial dispersion
2-Dpseudohomogenous
model withaxial and
radial dispersion
2-Dheterogen
modell med
radiell dispersion
2-Dheterogen
modell med
axiell och
radiell dispersion
Yes
Yes
No
No No
No No No
No
Yes
Yes Yes
Yes
Yes
How to estimate necessary
physical parameters x (e.g. D
eff
,

eff
)?
x= f(flow, physical properties)
The exact flow is difficult to obtain
(Navier-Stokes equation), but is
quantified qualitatively way by
Reynolds number
The physical properties of interest can
often be collected in dimensionless
numbers
5
Dimensionless numbers
Table 10.4. Someimportant dimensionlessgroupsfor masstransfer correlations
a
Definition Name Significance
(

=
A
l
D
d k
Sh
Sherwoodnumber masstransfer velocityrelativetodiffusionvelocity
(

=
l A
D
Sc

q
Schmidtnumber momentumdiffusivityrelativetomassdiffusivity
(

=
q

l
ud
Re
Reynoldsnumber inertial forcesrelativetoviscousforces
(
(

=
2
3
) (
q

g l l
g d
Gr
Grashof number bouyancyforcesrelativetoviscousforces
(

=
A
D
du
Pe
Pecletnumber flowvelocityrelativetodiffusionvelocity
a
d isalengthscalecharacteristicof thesystemwhichisstudied, i.e. bubble, cell or cell aggregate. DA is
thediffusioncoefficientfor theconsideredspeciesinthecontinuousphase; u isthelinear velocity of
bubble, cell, etc. relativetothecontinuousphase.
Effective heat conductivity,

eff

eff
=
eff,stat
+
eff,dyn
(static contribution + dynamic contribution)

eff,stat
1. Heat transport through fluid
Conduction
Radiation
2. Heat transport through bed material
(particles)
Conduction through contact points
Conduction through particles
Radiation between particles
Conduction through stagnant films

eff,dyn
Beror av strmningsbilden

eff,dyn
=f(Pr, Re)
Hot-spots
Problems caused by hot-spots
Poor temperature control
Catalyst deactivation
Melting of reactor wall
Explosion!
The appearance of hot-spots depends on
Heat of reaction
Rate of reaction
Heat conductivity within bed and wall cooling
A runaway is an uncontrolled hot-spot
Effective Dispersion,D
eff
Can be obtained from correlations of
1/Pe vs. Re.
Note! Dispersion is typically non-
isotropical, i.e.
D
eff,axiell
= D
eff,radiell
6
Pressure drop
Empty tube:
Friction factor (Fannings friction
factor)
Packed bed:
The Ergun equation
t
d
u
f
dz
dP 4
2
2

=
(
(

=
3
2
3 2
2
) )( 1 ( 75 . 1 ) 1 ( 150 1
c
c
c
c

p p
d
u
d
u
dz
dP
u=gasflow rateinempty tube