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Chapter 8 PDF
Chapter 8 PDF
Chapter 8 PDF
Heterogeneous reaction
• liquid – gas
Dissolution with chemical reaction
Cl2(s) + 2NaOH(l) NaOCl(l) + NaCl(l) + H2O(l)
3NO2(g) + H2O(l) 2HNO3(l) + NO(g)
• solid – solid
CoO(s) + Al2O3(s) CoAl2O4(s)
Si
Air (O2)
O2
dcO2 [c2 c1 ]
J ( D)
D s
DOs 2
O2 O2
dx
Steady state
NO2 J O( D2 ) O2 rs
[c2 c1 ]
kcO2 [c1 co ] DOs 2 kc2
DOs 2
kcO2 k
c1 a c2 calculation :
c1 co
s
DO2
DOs 2 DOs 2 k .kcO2
(kcO2 k )
kcO2 c1 c2 kcO2 co
s
D
O2
k
c cO2
c
2 s o
D
DOs 2 DOs 2 k .k
(k k )
cO2
O2
cO2
c1 k c2 0
SiO2 layer thickness and Si conversion :
o X Si o=
M SiO2 dt
kcO2 DO2 k
2 M Si SiO2
M SiO2 , M Si , SiO2 , Si Molar weights and densities of SiO2 a Si o Initial thickness of Si slab
3 limiting cases
1. Rate determining step is the external mass transfer of oxygen towards interface (gas - SiO2)
cO2 ( x )
1 1 1 M SiO2
, rs kcO2 co , kcO co t co c1
kcO2 D s
O2 kcO2 k 2
SiO 2
c2
x
2. Rate determining step is the internal mass transfer of oxygen in porous SiO2 layer
1 1 DOs 2 M SiO2 cO2 ( x)
, rs co , 2D c s
t c1
SiO
s s O2 o co
DO2 kcO2 D O2 k 2
c2
x
3. Rate determining step is chemical reaction taking place on the interface (SiO2 - Si)
cO2 ( x)
1 1 1 M SiO2
kco
c1
s , rs kco , t co
k DO2 k kcO2 SiO 2
• heterogeneous catalysis
Adsorbed
products
Reaction pathway
Homogeneous x Heterogeneous Catalysts
Homogeneous Heterogeneous
Active All atoms Surface atoms
sites Concentration Low High (variable)
Diffusion disguises No Important
Reaction conditions 50-200 oC 200-1000 oC
Application Limited Large
Products
Reactants
Desorption
Adsorption
Surface
reaction
Dissociation
Migration
Mechanisms in heterogeneous catalysis
Langmuir-Hinshelwood Rideal-Eley
Desorption
Adsorption
Migration
Surface
reaction
Adsorption x Chemisorption
Adsorption (physical
phenomenon)
Energy of biatomic molecule A2
Chemisorption
(chemical
phenomenon)
0 < Θi < 1
Desorption rate = kd . Θ
Equilibrium
ka . p . (1 - Θ) = kd . Θ
Langmuir adsorption isotherm
Θ = Ns / N = K . p / (1 + K . p) (K = ka/kd)
Asociative chemisorption
KA.pA
Occupancy of A ΘA
1 KA.pA KB.pB
KB.pB
Occupancy of B ΘB
1 KA.pA KB.pB
KA = ka / kd KB = kb / kd
ka
M2(g) + 2 * 2 M-*
kd
Rate of desorption = k d . Θ2
Θ2 K'.p
= K’ . p Θ
(1 - Θ)2
1 K'.p
Isotherms
Langmuir
Θ K.p
n
ads
(chemisorption, adsorption, n* 1 K.p
monolayer, micropores)
Henry n
(chemisorption, adsorption, low occupancy)
ads Θ H p
n*
Freundlich 1
n
(chemisorption, adsorption, non ideal) ads Θ K pn
n*
Assumptions:
adsorption in multilayer s, 1st layer interaction between adsorbent
and adsorbat, in 2nd and further layers condensation-like interaction
p 1 (C 1) p
nads (p p) nmC nmC p
0 0
Mesoporous alumina
15
a (mmol g )
-1 10
0
0,0 0,2 0,4 0,6 0,8 1,0
p/po
Pt surface atoms
Elementary steps of catalytic CO oxidation on Pt
1. CO chemisorption
ri ri ri
Slow step =
Rate determining step
Relation between overall reaction rate and the rate of i-th
elementary step determines the stoichiometric number i
(do not confuse with stoichiometric coefficient !)
ri
r
i
i
CO(g) + [*] CO* 2
O2(g) + 2[*] 2O* 1
CO* + O* *CO2 + * 2
*CO2 CO2(g) + * 2
(k , K1 , K 2 ) X
i 1
exp
1,i X mod
1,i (k , K1 , K 2 )
X1,mod
i (k , K1 , K2 ) calculated from isothermal catalytic PFR
model:
dX1
rM ( X1 ) W / F1o 0, X 1 0
d W / F1
o
2.5
2 ln(KA2) = f(1/T)
y = 7084.1x - 12.075
1.5 R² = 0.8181
0.5
ln(k1) = f(1/T)
y = -5802.3x + 11.056
0 R² = 0.9807
1.80E-03 1.85E-03 1.90E-03 1.95E-03 2.00E-03 2.05E-03
-0.5
-1 y = 1293.1x - 3.2791
R² = 0.7019 ln(KA1) = f(1/T)
-1.5
Models of catalytic reactors
Expanded views of a fixed bed reactor
Models of catalytic reactors
Model equations involve:
• Balance equations for components of reaction mixture in both gas phase
and porous catalytical particle
• Balance of energy (enthalpy)
• Balance of momentum
• Flux constitutive equations for component and energy fluxes
Pseudo homogeneous Heterogeneous
1-D • withou axial dispersion Gradients of concentration
(pure plug flow) and temperature between
• with axial dispersion phases
Boundary conditions
Dimensionless form
2-D pseudo homogeneous model with axial and radial dispersion
OVERVIEW
1. Steady state techniques
1.1 Reactors: Batch, CSTR, PFR
1.2 Transport Disguises at Particle Scale
1.3 Kinetic Analysis : Single Reaction, Complex Reactions, Estimation Methods
2. Transient methods
2.1 Dynamical Changes in catalysts: Reaction Sites, Structure and Morphology,
Surface Composition
2.2 Modes of Operation: Steps and Pulses, Cycled Feed, Self-sustained
Oscillations, TAP, SSITKA
2.3 Modelling and estimation: CO chemisorption on Pt,NO reduction by H2,
Electrocatalytic Ethylene Epoxidation, CO methanation
1. Steady state techniques
1.1 Reactors: Batch, CSTR, PFR
Screening of catalysts – high throughput methods - most
promising formulation investigated in more detail – scale up of
the catalytic reaction towards the industrial application starts
from the knowledge of detailed reaction kinetics rate
equation(s)
Batch reactor, CSTR, PFR
outlet inlet
reactor
catalyst
silica wadding
furnace
700oC
Calculation of reaction rate r [mol/kg/s]
CSTR PFR BATCH
+ direct evaluation of r.r. +simple setup +simple setup
-outlet condition’s control +variation of m/F -isothermicity
-real hydrodynamics -temperature and conc.gradients -
differentiation
-isothermicity
-differentiation in r.r. calculation
F XA o
rM
1 dX A 1 n oA dX A
rM
rM d m / FAo
A
A m A A m dt
FAo FA
XA
FAo
1.2 Transport Disguises at Particle Scale
Ideality at reactor scale (plug flow or ideal mixing), it is not sufficient to obtain
accurate kinetic data
kio L
Shi
Dmi external transfer
Deska
uL Dmi
Re L 10 5
Shi 0,66 Re 1/ 2 1/ 3
Sc Re L Sci
L i
Re L 105 Shi 0,036 Re 0L,8 Sci1 / 3
Koule
Shi 2,0 0,4(Re1L/ 2 0,06 Re 2L/ 3 ) Sci0,4
Packed bed
k cio M 2 / 3
jD Sci
G
m d pG
Sci G Re
Dim So
jD f (Re) C. Re n
h
jH Pr 2 / 3
C pG
C pm m ha(Ts To ) ( H r ) rV ( H r )k xAa ( x oA x As )
Pr
m Ts k xA x oA x As
1 ( H r ) (1 o )
jH f (Re) C Re n To hTo xA
c As rV
o
1 ha(Ts To ) ( H r ) rV ( H r )k xAa ( x oA x As )
cA k cAac oA
Ts k xA x oA x As
x As rV 1 ( H r ) (1 o )
o
1 To hTo xA
xA k xAax oA
c As c oA Ts To
0,02
o
0,95 To
c A
Experimental tests
m / F konst
o
A
XA
FAo
N i k gi ( cio cis )
T ( H r ) Di ci ( ro ) ci ci
i
ci N H h (To Ts ) T ( ro ) i sT ( ro ) ci ( ro ) ci ( ro )
J is Di
x i Prater number
T
J Hs s
x cis ci ( ro ) Ts T ( ro )
d 2 ci a dci
Di 2 vi rV (T , ck ) 0 plate
dx x dx
a= 1 cylinder
d 2T a dT 2 sphere
s 2 ( H r ) rV (T , ck )
dx x dx
x=0 x = ro
dc
dci dT Di i k gi (cio - c si )
0 0 dx
dx dx
dT
s h (To Ts )
dx
Experimental tests (supposing that external gradients are
negligible)
m / F konsto
A
XA
1/ d p
1.3 Kinetic Analysis : Single Reaction, Complex Reactions,
Estimation Methods
The differential or integral method of kinetic analysis
LHHW kinetics
Linearizationlinear
XA regression
Non-linear modelsnon-
linear regression
o
m/F A
Example
Ethanol dehydrogenation (Franckaerts, Froment, 1964)
AR+S
C2H5OH(g) CH3CHO (g) + H2 (g)
r.d.s.
Adsorption of A
k A ( PA PR PS / K )
rM
KA
1 PR PS K R PR K S PS K w Pw
K Surface reaction
kK A ( PA PR PS / K )
rM
1 K A PA K R PR K S PS K w Pw 2 Desorption of R
k R KK R ( PA / PS PR / K )
rM
1 K A PA KK R PA / PS K S PS K w Pw
M 2
( ) X i f i ( )
i 1
Example
Air oxidation of o-xylene on V2O5 (Vanhove, Froment 1975)
r1
o-xylene tolulaldehyde
r2 r3
phtalic anhydrid
CO, CO2
Estimation methods
y f(x, β)
e j β y j f(x j , β) j 1, NEXP
Moment matrix of residuals
NEXP
M(β) e j βe j β
j 1
T
Gradient, Gauss-
Objective functions Newton
(β) detM(β
2. Transient methods
Reaction sites - single crystal surfaces, ultra high vacuum
structure sensitive reaction rate (Dahl et al. 1999: rate of
dissociative adsorption of nitrogen on Ru (0001) surface
was reduced by more than nine orders.