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DEMCAMER/CARENA Workshop
January 30th, 2013 @ Eindhoven TU/e
Overview lecture
Modelling membrane permeation
Porous membranes
Dense (supported) membranes for H2
11-2-2013
Page 1
Ni
1
4
K0
RT
3
8 RT
M
B0
p
g
pi ,m
ri
ln
ri
ri
Parameters K0 and B0
depend on the pore
size/structure distributions
11-2-2013
Page 2
Ni
eff
i
p xi
RT r
1
Bosanquet:
Blancks law:
Dieff
1
Dieff,m
Dieff,m
1
1 xi
1
Dieff,K
n
Dieff, j x j
j 1
j i
Dieff, j
Dieff, K
11-2-2013
(harmonic averaging of
molecular and Knudsen diffusion )
Page 3
Di , j
4
8RT
K0
3
Mi
( = porosity)
( = tortuosity)
Film model:
Ji
ci ,0
Di
dci
dz
[mol/m2s]
Diffusivity
[m2/s]
ci ,
Ni
k ci ,0 ci ,
[mol/m2s]
Mass transfer
coefficient [m/s]
z
Film model: k
11-2-2013
Page 4
ctot
c1 c2
constant
Flux of component 1
with respect to the mixture:
J1
dc1
D1
dz
Flux of component 2
with respect to the mixture:
J2
D2
dc2
dz
Jtot
Ji
J1 J2
i 1
Life is nice
and simple?
d
c1 c2
dz
11-2-2013
Page 5
pure He
high flow rate
He
Ar
298 K
105 Pa
298 K
105 Pa
11-2-2013
Page 6
He
Ar
298 K
105 Pa
298 K
105 Pa
Observation:
NHe 3 NAr
Much higher He flux despite identical concentration gradients!
pure Ar
high flow rate
Interaction with
membrane
Explanation:
Movement of mixture with respect to membrane!
Friction He-membrane < Friction Ar-membrane
pressure gradient
Resulting in viscous flow from right to left: retarding He, accelerating Ar
11-2-2013
Page 7
Ni
dArcy:
Ntot
eff
i
p xi
RT r
xi N tot
B0 p
ctot
r
Ni
11-2-2013
B0 p p
RT r
1
xi
eff
Di p
RT
r
Page 8
viscous flow
B0 xi p p
r
Membrane tube
dr
R1
pA(r=R1) = pA,1
pA(r=R2) = pA,2
R1
rm
R2
R1
1 d
rN i
r dr
rNi
11-2-2013
Page 9
constant
R2 N i ,2
Ni ,2
c
R2
c
rm
Ni
c
r
Ni
1
xi
eff
Di p
RT
r
1
xi
eff
Di p
RT
r
c
r
Ni
B0 xi p p
r
dxi
eff
Di p
dr
dr
R1
R2
B0 xi p dp
dr
dr
R1
11-2-2013
Page 10
R2
cRT
dr
r
R1
B0 xi p p
r
R2
dx
Dieff p i dr
dr
R1
diffusion
important when
concentration gradient
is negligible
xi
xi ,2
eff
i
dxi
p xi ,2
xi
B0 xi
xi ,1
eff
i
cRT
dr
r
R1
viscous flow
important when
pressure drop
is negligible
R2
B0 xi p dp
dr
dr
R1
p2
p1
xi ,1
11-2-2013
dr
pdp cRT
r
R1
B0 xi
Page 11
R2
1
2
p22
p12
cRT ln
R2
R1
Note:
p xi ,2
1
2
xi
eff
i
Ni ,2
c
R2
B0 xi
xi ,1
p22
p12
xi
B0 p
N i ,2
2
2
2
1
1
2
1
2
p2
p1
pi ,2
1
Dieff
RT
pi ,1
R2
cRT ln
R1
p2
p1
p pi ,2
R2
cRT ln
R1
pi ,m
B0 p
ri
ln
ri
m
m
11-2-2013
Page 12
pi ,1
N2, CO2
at t=0 connected
by narrow capillary
N2, H2
xH0 2 ,A
xH0 2 ,B
0.50
xN0 2 ,A
0.50
xN0 2 ,B
0.50
0
xCO
2 ,A
0
xCO
2 ,B
0.50
b) from B to A?
c) not at all?
d) or does it do a), b) and c)?
Multiphase Reactors Group, SPI
11-2-2013
Page 13
(isobaric &
isothermal)
N2, CO2
N2, H2
at t=0 connected by
narrow capillary
(isobaric &
isothermal)
Reverse
diffusion
11-2-2013
Page 14
N2, CO2
N2, H2
at t=0 connected by
narrow capillary
Observation:
H2 and CO2 change monotonically to equilibrium
concentrations as expected
N2 initially diffuses first without concentration gradient and
later even against its concentration gradient from A to B,
only later bulbs go gradually back to equal compositions
Explanation:
H2 moves from B to A, and CO2 from A to B
N2 molecules more friction with CO2 than H2
and CO2 seems to drag N2 along from A to B
Multiphase Reactors Group, SPI
11-2-2013
Page 15
(isobaric &
isothermal)
Reverse
diffusion
cannot be explained
with Ficks law!
di
x j Ni
u2
ctot ij
j 1
di
ci
T ,P
ci Fi
c j Fj
i
j 1
xi
with:
RT
n 1
T ,P
ij
xi
ln
j 1
11-2-2013
u1
Page 16
xj
xj
T ,P ,
2
2
Ji
( Ji
Ni
xi Ntot )
i 1
Bii
Bij
B J
ctot B
xi
in
n
j 1
j i
1
xi
ij
xj
ij
B11
B12
...
B1,n
d2
...
B21
...
B22
...
...
...
B2,n 1
...
dn
1
in
11-2-2013
d1
Page 17
[B ]
1
Bn
1,1
Bn
1,2
... Bn
1,n 1
n
j 1
j i
xi N j
x j Ni
eff
i, j
pD
Ni
pDieff, K
1 xi
RT r
xi
pRT
B0 p
Dieff,K
11-2-2013
Page 18
p
r
Mechanism involves
a series of steps:
Low pressure
3
1) adsorption
2) dissociation
3) diffusion
4) re-association
5) desorption
1 2
N H2
Km
ret n
H2
perm n
H2
Pd-membrane
H2
H2O
CO2
HH
HH
H2 ( g )
dcH
DH,Pd
dx
DH,Pd
ret
H
DH,Pd
CH
and
KH
11-2-2013
Page 20
H(ads)
K H pH0.52
is constant
DH,Pd K H,Pd
perm
H
KH
mole ,H 2
N H2
HH
Pd
ret 0.5
H2
perm 0.5
H2
N H2
QH
ret n
H2
perm n
H2
11-2-2013
Page 21
http://www.hysep.com
H
H
H
H H
H H
H
H
H
11-2-2013
Page 22
H
H
H H
H H
concentration
polarisation
Pd
permeation
11-2-2013
Page 23
resistance in support
concentration
polarisation
11-2-2013
Page 24
11-2-2013
Page 25
N2
2O2- + 4e-
O2-
2e-
O2/O2- + ?
N O2
CH4, CO, H2
N O2
Wagner equation:
Dv 0
4Vm m n
ret n
O2
11-2-2013
perm n
O2
Page 26
Dv
4Vm m
ln pOperm
2
( )d ln pO2
ln pOret2
( ) = non-stoichiometry:
n
p
0 O2
11-2-2013
Page 27
11-2-2013
Page 28
N O2
Eact
RT
exp
xO2
ret n
O2
perm n
O2
xCO2
xCO K eq
n = -0.153
Eact = 260 kJ/mol,
C = 2.01108 (cm4/cm2/min, STP)
Zhang et al., J. Membrane Science 291 (2007) 19-32
Multiphase Reactors Group, SPI
11-2-2013
Page 29
11-2-2013
Page 30
11-2-2013 Page 31
Multi-tubular reactor
11-2-2013 Page 32
Example:
multi-tubular module
with sweep gas
Reactants in
Catalyst inside
tubular membranes
Reaction Zone
A
Gas Phase
A, B
Gas Phase
(d)
Products out
Catalytic Membrane
Sweep gas in
11-2-2013 Page 33
Catalytic membrane
11-2-2013 Page 34
Particles suspended
in a gas stream
behaves as a fluidum
11-2-2013 Page 35
11-2-2013 Page 36
Ethylene/propylene
polymerization
11-2-2013 Page 37
Flat membranes
integrated in the walls
Retentate
Retentate
Permeate
Sweep in
Sweep out
Zona de
Reaction
Reaccin
Permeate
zone
Zona de
Regeneracin
Regene500z
Feed
Multiphase Reactors Group, SPI
Feed
11-2-2013 Page 38
ration zone
O2
Fluidized bed
membrane reactor
Gas outlet
Product gas outlet
Cyclone
Selective
O2 dozing
Selective
H2 extraction
Membrane tubes
Heat exchange
surface
P, W
H2 W
H2
11-2-2013 Page 39
Gas inlet
11-2-2013
Modelling catalyst:
simplify
whenever
possible!!!
11-2-2013
Page 40
1
2
r
n
2
r r
g
g
with:
ntot
nreact
Sr
Sr ,i
Mi 1
i, j j
j 1
ntot
C p ,s
T
t
1
2
r
r2 r
Effect of particle
porosity/tortuosity via:
Multiphase Reactors Group, SPI
Deff
11-2-2013
Page 41
eff , s
Di
T
r
Sh
nreact
Sh
rj hr , j
s
j 1
rp
nc 1
r
T
r
nc 1
0
d
g eff ,i , k
0
k 1
eff , s
T
r
r
g
kg
i tot
s ,ik
k ,bulk
k 1
Tbulk
11-2-2013
Page 42
Superficial velocity!
g ug
m , tot am
with am =
4d i
d 02 di2
ug
Dax
ni as
m ,i
ni computed from
particle model
C p,g
T
t
C p,g
ug
T
z
nc
T
z
am
ni as H i
i 1
nc
a Hi
m ,i m
a T Tw
w w
i 1
11-2-2013
Page 43
p
z
150
1
g ug
d
2
p
1.75
3
g
2
1
u
g g
g
3
g
dp
M O2
m ,O2
RT
4
K0
3
8RT
M
B0
pO2 ,m
ri
ri
ln
ri
11-2-2013
Page 44
O O
H
H
CCH
O
C
H HO
O
H
CHOHH
H
H
Catalyst particle
H
C
H
H
Multiphase Reactors Group, SPI
11-2-2013
Page 45
O2
impermeable
O2
CO, CO2,
C2H6, C2H4
CH4 + H2O
O2
O2
O2 concentration
inert
OCM
mole
R
r [m]
SRM
Phenomenological model:
Phenomenological = two-phase model (bubble-emulsion phase)
Use semi-empirical correlations for bubble and solids behaviour
Bubble size (and thus all other key quantities) function of axial position
Extent of gas phase mixing in emulsion phase via number of CSTRs
in series
CFD model:
At what scale: particle scale vs. industrial scale?
Computational resources? Patience?
simplify
whenever
possible!!!
Transfer Q is required to
maintain emulsion phase
at incipient conditions
11-2-2013
Page 51
Effect of internals
not accounted for
(correlations not available)!
Multiphase Reactors Group, SPI
11-2-2013
Page 52
11-2-2013
Page 53
Discrete
Particle
Continuum
Discrete Bubble
Phenomenological
Fluid-particle
interaction
Particleparticle
interaction
11-2-2013
Particle-particle
interaction;
Bubble behavior
Page 54
Large scale
motion
Industrial size
Black box
Industrial size
drag
Fcontact ,a
gravity
gas flow
Intermediate-level model
Eulerian grid size is larger than the particle size
Incorporation of detailed particle interaction models
Computation limitation: 104~106
Multiphase Reactors Group, SPI
11-2-2013
Page 55
ug
0
Sp
+ momentum equation
ug
g
Multiphase Reactors Group, SPI
g
11-2-2013
ug ug
ug
Page 56
ug T
2
3
1
Vcell
Va
a cell
p Sp
r ra
g g
ug I
u g va
dva
ma
dt
Va p
Vp
u g va
ma g Fc ,a
+ rotational momentum
Npart: 104~106
d a
Ia
dt
180
2
g s
2
p g
Ta
18
Computation resource
3
g s
1 1.5
d
2
p
0.31
11-2-2013
Page 57
g s
g
Re s [
d p2
1
g
g s
3 s
1 10
8.4 Re s 0.343 ]
Res 0.5
addition
addition
11-2-2013
Page 58
0%
+40 %
Correlation bubble
behaviour and
emulsion phase
circulation patterns!
0%
11-2-2013
Page 60
+40 %
11-2-2013
Page 61
11-2-2013
Page 62
Concluding remarks
11-2-2013
Page 63