8.

Heterogeneous reaction

• solid – fluid (liquid, gas)

 Dissolution of solids (e.g. MgCO3(s) + HNO3(l))
 Chemical Vapor Deposition (SiH4(g)  Si(s) + 2H2)
 Sublimation (U(s) + 3 F2(g)  UF6(g))
 Reduction of solid oxides (NiO(s) + H2(g)  Ni(s) + H2O(g))
 Metals oxidation (Zn(s) + O2(g)  ZnO(s))
 Catalytic reactions

• 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)

Heat and mass transfer phenomena affect global reaction rate.

 Example

Si(s) + O2(g)  SiO2(s)

cO2  2 cO2 porous

D
s
SiO2
t x 2
O2

Si

Air (O2)
O2

cO2 ( x)  N O2 flux density of O2 in gas phase(mol.m-2.s-1)

co J O( D2 ) flux density of O2 in SiO2 layer (mol.m-2.s-1)

c1
Convection +
k cO2 coefficient of mass transfer of O (m.s-1)
Diffusion 2
rS  kc2
N O2  kcO2 [c1  co ] c2
2 -1
DOs 2 diffusion coefficient of O2 in SiO2 (m .s )
rS rate of chemical reaction (mol. m-2.s-1)
x diffusion

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 :

reaction rate  1 1 1 2 M SiO2

     co t
co  kcO2 k 
s
2 DO2  SiO2
rs 
1  (t ) 1  SiO d
 s  rS 
 o M SiO2  Si
2

   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

Discussion: rS = f(composition), rS = f(temperature) c2

x
External heat and mass transfer

Combustion of the spherical carbon particle

Oxygen molar flux at steady state

Energy flux at steady state

Surface temperature and concentration of oxygen
S
Two balance equations for unknown c1 , TS
Multiple steady state solutions as
in the case of CSTR!
Example
 Catalytic reactions

• homogeneous catalysis O3 + Cl  ClO + O2

 Ozone decomposition in the presence of Cl ClO + O3  Cl + 2O2
 SO2 oxidation by NOx
 Esterification catalyzed by acids or bases 2O3  3O2
 Enzymatic catalysis

• heterogeneous catalysis

 NH3, CH3OH production

 SO2 to SO3 oxidation
 HDS, HDN processes
 Fluid Catalytic Cracking
 Hydrogenation
 Polymerization (Ziegler-Natta catalysts, metallocens)
Catalytic cycle
 Non catalytic x catalytic reaction
Activated
complex of non
catalytic reaction

Encat – energy of activation for non catalytic reaction

Ecat - energy of activation for catalytic reaction
Ei
Encat 
RT
ri e
Ecat

Energy

Reactants The multi-step catalytic reaction

can be faster than one-step
Adsorbed
reactants
reaction
Products

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

Characterization Structure, composition Well defined No clear defintion

Modification Easy Difficult
Temperature stability Low High

Separation Difficult Easy

packed beds

Recycling Feasible Feasible

 Operation
conditions (T, P,…)
Raw materials Reactors -
(impurities, ..,) continuous, batch

Equilibrium Catalytic Hydrodynamics

reaction

Kinetics Heat and mass

Properties of Catalyst, transfer
Preparation procedure
 Steps in a catalytic reaction

1) Mass transfer of reactants to the external surface of catalyst

2) Mass transfer of reactants in porous structure of catalyst
3) Adsorption of reactants
4) Surface reaction (+ migration)
5) Desorption of products
6) Mass transfer of products in porous structure of catalyst
7) Mass transfer of reactants from the external surface of catalyst

The transport steps (1,2,6,7) depend on T, P, composition, flow rates, pore

size, ....
The chemical steps (3,4,5) are
dependent on T, P, composition.
Elementary steps of catalytic reaction
Fluid phase

Products
Reactants

Desorption
Adsorption
Surface
reaction
Dissociation

Migration
 Mechanisms in heterogeneous catalysis

Langmuir-Hinshelwood Rideal-Eley

Desorption

Adsorption

Migration
Surface
reaction
 Adsorption x Chemisorption

2 A  2[*] 2 A* A2  2[*] 2A*

Adsorption (physical
phenomenon)
Energy of biatomic molecule A2

Chemisorption
(chemical
phenomenon)

Distance from catalyst surface

Emc, Emp – activation energy of migration in adsorbed and chemisorbed state
ED – energy of dissociation of molecule A2
Ed – energy of desorption of A2
Ea – energy of activation of transition from adsorbrd to chemisorbed state
 Adsorption x Chemisorption
Adsorption Chemisorption
Principal van der Waals forces covalent or ionic bonds
no electron transfer ! electron transfer
Adsorbent all solids specific sites
Adsorbat gases T < Tc reactive components
Temperature low higher
Enthalpy 10-40 kJ/mol 80-600 kJ/mol
Rate high depends on T
Activation energy low high
Occupancy multilayer monolayer
Reversibility YES YES but …
Use BET method surface concentration
pore size distribution of active sites
 Chemisorption of fluid phase molecule(adsorbat)
Surface occupancy(Θ)
Number of sites occupied by i-th component
Θi =
Total number of sites

0 < Θi < 1

Associative x Dissociative chemisorption

Adsorption (chemisorption) isotherm – Surface occupancy as a function of

partial pressure of given component at constant temperature
Henry isotherm
Θi = Hi . pi
Irving Langmuir
1920 - adsorption isotherm
- kinetics of catalytic reactions
on ideal surfaces
1932 - Nobel Prize
Langmuir adsorption isotherm

Brunauer-Emmett-Teller (BET) adsorption

isotherm
Associative adsorption
ka
M(g) + * M-*
kd

* - active site, ka a kd – kinetic constants for adsorption and desorption

Adsorption rate = ka . p . (1 - Θ) p = partial pressure of adsorbat

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

Langmuir adsorption (chemisorption) isotherm

 Multicomponent asociative chemisorption
ka kb
A(g) + * A-* B(g) + * B-*
kd kd

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

Irreversible chemisorption catalyst poisoning

Dissociative chemisorption

ka
M2(g) + 2 * 2 M-*
kd

Rate of chemisorption = ka . p . (1 - Θ)2

Rate of desorption = k d . Θ2

ka . p . (1 - Θ)2 = kd . Θ2 (K’ = ka/kd)

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*

Temkin Θ  Aln B p 

(chemisorption, non ideal

Brunauer-Emmett-Teller (BET) p  1  (C 1) p

(adsorption, multilayer) nads (p p) nmC nmC p
0 0

Virial p (1 a  a 2  ...)

1 2
(adsorption, multilayer ) R.T
Brunauer-Emmett-Teller (BET)
Extention of Langmuir model

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

Temperature od calcination : 3,3 nm (450 oC) - 4,5 nm (600 oC) -

5,1 nm (800 oC)
Reaction rate per mass
1 1 d 1 1 dni
rM  r   mole.kg 1.s 1
m m dt m  i dt
1 1 dk
rM ,k  rk 
m m dt

Reaction rate per surface

1 1 d 1 1 dni
rS  r   mole.m2 .s 1
S S dt S  i dt
1 1 d k
rS ,k  rk 
S S dt
 Reaction rate per active center (turnover number)
1 1 d 1 1 dni
rRS  r  s 1
nRS nRS dt nRS  i dt
1 1 d k
rRS ,k  rk 
nRS nRS dt

Reaction rate of catalytic reactions

Langmuir-Hishelwood ideal surface
Rate of elementary steps
Rate determining step x steady state hypothesis
CO oxidation on Pt
Overall reaction ( Gr  0 )
o

2CO(g) + O2(g)  2CO2(g)

nebo
2CO(g) + O2(g)  2CO2(g)

Pt surface atoms
 Elementary steps of catalytic CO oxidation on Pt
1. CO chemisorption

CO(g) + [*]  CO* r1  k f ,1 PCO *  kb,1CO

2. O2 dissociative chemisorption * - Pt surface atoms = Catalytic

active centre
O2(g) + 2[*]  2O* r2  k f ,2 PO2 *2  kb,2O2

3. Surface reaction between CO* and O*

CO* + O*  *CO2 + * r3  k f ,3CO O  kb ,3CO2 *

4. CO2 desorption into gas phase

*CO2  CO2(g) + * r4  k f ,4 CO 2  kb ,4 PCO2 *

Pi – partial pressures of gaseous components [Pa]

 i - occupancy (coverage) of the i-th species [-]
k f , j , kb , j - reaction rate constants
rj – rate of the j-th elementary step [mol/kg katalyzátoru/s
mol/molPt/s= 1/s]
Rate determining step in steady state

ri  ri  ri

Forward reaction rate

Fast step

Backward reaction rate ri  ri  step is close to the equilibrium

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

2CO(g) + O2(g)  2CO2(g)

 Rate determining step: surface reaction

Reaction rate as a function of measurable variables

Example

C2H5OH(g) (A1)  CH3CHO(g) (A2) + H(g)

(A3)

catalysts: CuO, CoO a Cr2O3

(Franckaerts J., Froment G.F., Kinetic study of the
dehydrogenation of ethanol, Chem. Eng. Sci. 19 (1964)
807-818).
Kinetics
kK1  P1  P2 P3 / K eq 
rM 
1  K1P1  K 2 P2 
2

rM (mol.g-1.hod-1), Pi (bar), k (mol.g-1.hod-1), Keq (bar), Ki

(bar-1).

Task: to estimate on the basis of experimental data kinetic

and adsorption parameters k , K1 , K 2
EXPERIMENTAL SET-UP
Franckaerts J., Froment G.F., Kinetic study of the dehydrogenation of ethanol, Chem. Eng. Sci. 19
(1964) 807-818
 EXPERIMENTAL DATA

W / F1o P y1o y4o y2o T X1

[ ] [ ] [ ] [ ]
o
[g.hod/mol] [bar] [ C]
1,60 7,0 0,865 0,135 0,0 225,0 0,066
0,80 4,0 0,865 0,135 0,0 225,0 0,083
0,40 3,0 0,865 0,135 0,0 225,0 0,055
1,0 1,0 0,865 0,135 0,0 225,0 0,118
1,0 1,0 0,750 0,130 0,119 225,0 0,052
0,40 1,0 0,865 0,135 0,0 225,0 0,060
1,0 1,0 0,732 0,167 0,101 225,0 0,052
0,40 10,0 0,865 0,135 0,0 225,0 0,038
1,60 7,0 0,865 0,135 0,0 250,0 0,149
0,80 4,0 0,865 0,135 0,0 250,0 0,157
0,40 3,0 0,865 0,135 0,0 250,0 0,108
1,0 1,0 0,865 0,135 0,0 250,0 0,218
1,0 1,0 0,672 0,145 0,183 250,0 0,123
0,60 1,0 0,865 0,135 0,0 250,0 0,152
0,80 1,0 0,672 0,145 0,183 250,0 0,106
0,60 10,0 0,865 0,135 0,0 250,0 0,094
1,60 7,0 0,865 0,135 0,0 275,0 0,254
0,80 4,0 0,865 0,135 0,0 275,0 0,262
0,40 3,0 0,865 0,135 0,0 275,0 0,20
1,0 1,0 0,865 0,135 0,0 275,0 0,362
1,0 1,0 0,672 0,145 0,183 275,0 0,230
0,20 1,0 0,865 0,135 0,0 275,0 0,118
0,40 10,0 0,865 0,135 0,0 275,0 0,148
0,40 1,0 0,865 0,135 0,0 275,0 0,196
Solution:
Minimize the objective function:
NEXP 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

ATHENA Visual Studio.

 225 oC 250 oC 275 oC
k1 5.767986E-01 +- 4.112E-01 8.863130E-01 +- 1.668E-01 1.675828E+00 +- 4.225E-01
KA1 4.839934E-01 +- 3.591E-01 4.876108E-01 +- 9.443E-02 3.803293E-01 +- 1.473E-01
KA2 1.011693E+01 +- 7.376E+00 3.044445E+00 +- 9.054E-01 2.812096E+00 +- 1.078E+00

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

2-D Radial dispersion

1-D pseudo homogeneous model without axial dispersion

dp effective diameter of catalytic particle

f friction coefficient
us mean fluid velocity
K overall heat transfer coefficient
 1-D pseudo homogeneous model with axial dispersion

Boundary conditions

Dimensionless form
 2-D pseudo homogeneous model with axial and radial dispersion

Balance element of volume

Balance equations

Boundary and initial conditions

Fluidized bed catalytic reactor
Experimental determination of kinetics of
heterogeneous catalytic reactions

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

external transfer determ. of mass and heat transfer coefficients

internal transfer determ. of effectiveness factor

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

Criteria for the absence of transport limitations (packed bed)

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
Linearizationlinear
XA regression
Non-linear modelsnon-
linear regression

o
m/F A
Example
Ethanol dehydrogenation (Franckaerts, Froment, 1964)
AR+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 βe j β
j 1
T

Gradient, Gauss-
Objective functions Newton

 (β)  TraceQM(β Marquardt-

Levenberg

 (β)  Trace V 1M(β   Quadratic

expansion

 (β)  detM(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.

Structure and Morphology – CO oxidation on the Pt(110)

surface. Ertl (1994) has shown by photo-emission electron
microscopy that surface concentrations of reacting species
vary with time and 2D-space.
Grunwaldt (2000) found that structure of Cu particles
depend on the reduction potential of gas mixture CO+H2.

Surface composition – surface composition of catalyst may

change with gas composition – redox systems (Mars,
Krevelen, 1953)