Heterogeneous Catalysis and Reactors - Handbook

I. General thermodynamics
nsp

General reaction of nsp species (elements or compounds):  v  ( ps)  0 [Ξ : each

i 1
i i i

different entity in reaction (product or reactant) at physical state ps (gas, liquid, solid)]
Standard heat of reaction: H R ,298 
0
v H i
0
f ,i

At temperature T: H  H    C dT , CP   viCP,i

0 0
R ,T R ,298 P
298
P
 V j 
At pressure P:
H P
R , T0
 H 1
R , T0
  vi 1 
 V j  T0  dP
T  P

Chemical potential: i  i0,T  RT ln ai

(Standard) Gibbs free energy difference: GT   RT ln Keq , K eq 

0
a
i
vi
i

d ln K eq H 0

Van’t Hoff equation:  R

2
dT RT
H R0  1 1 
K eq (T )
If H  f (T ) :
0 ln    
R Keq (T1 ) R  T T1 

If H R  f (T ) and CP ,i  bi  ciT  diT :

0 2

 T  c d
T  T1   T 2  T12 
K eq (T )
R ln  b ln   
K eq (T1 )  T1  2 6
 c d 3   1 1 
  H R0 ,T1  bT1  T12  T1    
 2 3   T T1 
where b  v b ,i i c   vici , d   vi di
fi T , P, yi 
a 
fi T ,1bar ,standard condition 
activity: i 0

Ideal gases: ai  Pi P  yi P P
0 0

Ideal mixtures of non-ideal gases: ai  yi fi f  yi i P P ,

0 0

 P ve 
Chemically pure liquids: ai  1 , high pressure: i
a  exp   RT
 dP 
1 

1
Ideal liquid solutions: ai  xi
Liquid solutions: ai   i xi
Solids: (analogous expressions to the ones for liquids)
 vi  vi
Ideal gas mixtures: K eq   i i
y vi
 vi i gas
P
i
 K
i
K
y  P i gas
,
 vi
i gas

Ideal gases: Keq  K y P

where K y  y
i
vi
i K   ivi
i

General Notation
γi = activity coefficient of species i (liquids)
ΔGT = Gibbs free energy difference
ΔHf0 = standard enthalpy (heat) of formation (T = 298K, P = 1bar)
μi = chemical potential of species i
vi = stoichiometric coefficient of species i
Φi =fugacity coefficient of species i
ai = activity of species i
CP = heat capacity under constant pressure
fi = fugacity of species i
Keq = equilibrium constant
P = pressure (P0: standard pressure)
Pi = partial pressure of species i
R = universal (ideal) gas constant (8.314 5 J/K-mol = 82.057 cm3 atm/K-mol)
T = temperature
ve = molar volume of liquid
yi = molar fraction of species i
--------------------------------------------------------------------------------------------------------

II. Solid catalysts

bP
  b  K A  ka / kd
Langmuir isotherm:
1  bP ,
b   ka / kd 
1/ n
Freundlich isotherm:   bP1/ n , n  1 ,
1
Temkin isotherm:
 ln  b P  , b  k / k
a0 a d

P 1  c  1 P

Brunauer-Emmett-Teller (B.E.T.): V  P  P  V c

0 m cVm P0 ,
c  exp  q1  q2  RT

2
| q1 = heat of adsorption of first layer,
| q2 = heat of liquefaction,
| V = volume (quantity) of adsorbed gas at pressure P,
| P0 = saturation pressure at the temperature of adsorption
| Vm = volume (quantity) of adsorbed gas for the formation of monolayer
| R = universal (ideal) gas constant (8.314 5 J/K-mol = 82.057 cm3 atm/K-mol)
| T = temperature

Henry isotherm:   K P
2
 M 
3
Vm Nav
S  a a  1.09  
 N av  
B.E.T-calculated total surface area: g V ,

 
B.E.T-calculated area (Nitrogen specific): Sg cm /g  4.35 10 Vm cm /g
2 4
 3

| Nav = Avogadro number (6.0231023 molecules/mol)
| M = molecular weight of adsorbed gas
| Vm = volume (quantity) of adsorbed gas for monolayer
| V = gram-molecular volume (STP) = 22400 cm3 /g-mol
| ρ = density of adsorbed gas
| a = projected area of molecule on the surface (2-D, close packing)

Force due to surface tension (cylindrical pore): ft   a  cos

1.19  105
o

Mercury penetration method (all solids): a(A)  P(bar)

| a = pore diameter
|  = contact angle
| σ = surface tension

General Notation
Θ = surface coverage
ka = kinetic coefficient of adsorption
kd = kinetic coefficient of desorption
P = pressure
--------------------------------------------------------------------------------------------------------

III-IV. Chemisorption
Empirical thermodynamic criteria for chemisorption:
4) | S |  10 (cal/mol-K)
5) | S |  12.2  0.0014 H (cal/mol-K)
--------------------------------------------------------------------------------------------------------

3
V. External heat and mass transfer
n 1
kn asCA,b
Damköhler number (nth-order reaction):
Da 
kg am
d pU  f
Reynolds number (Re): f
f
Schmidt number (Sc):  D
f AB

kg d p
Sherwood number (Sh): D
AB

cp f
Prandtl number (Pr): kf
h dp
Nusselt number (Nu): k
f

Pr
Lewis number (Le): Sc

Carberry number (Ca): n Da

E
Arrhenius number (γ): RT
b

kg d p
  2.0  0.6Re 2 Sc 3
1 1

Forced flow around an isolated catalytic particle (mass): Sh

DAB
h dp
  
1 1

Forced flow around an isolated catalytic particle (heat): Nu 2.0 0.6Re 2

Pr 3

kf
kg f 2/3
Mass transfer in fixed-bed reactors: Dj  Sc  f  Re 
G
h
Heat transfer in fixed-bed reactors:
jH  Pr 2/3  f  Re 
cpG
f(Re) can be calculated from the following empirical equations:
Condition Expression
Re < 200 jD  1.66Re0.51
Re > 200 jD  0.98Re0.41
Dwivedi & Upadhay Re > 10  B jD  0.458Re0.407

4
Petrovic & Thodos 3 < Re < 2000 (gases)  B jD  0.357Re0.359
Wilson & Geankoplis 55< Re < 1500 (liquids)  B jD  0.250Re0.31
Wilson & Geankoplis 0.0016< Re < 55 (liquids)  B jD  1.09Re2/3

Fixed bed reactors, in flow regime 15 < Re < 2000: jH = jD

Fixed bed reactors, relation between temperature and concentration differences:
  H    Pr 2/3  jD 
Ts  Tb    CA,b  CA,s       

 f p   Sc   jH 
c
Fixed bed reactors, non-isothermal boundary layer:
  1    1 
n  1  Ca  exp    1   1  n Da  exp    1 
n n

  1   Ca     1   n Da 
 H  CA,b

where f cpTb
d pG
30   5000 , j or j :
Fluidized bed reactors in the range f 1   B  H D

0.44
 d pG 
jH  1.77  
 f 1   B   (same for jD)

Effect of external mass transfer on selectivity (reactions in series, A   B  C ):

1 2 k k

 
 k2 as 
1
k C  
Sp  1  A  
  kg am B 

 1
k 2  CB  b   k a    C    1  

1 s
  A       kg am   k1as  
   g m B   B  b    g m A 
 ka  C  ka   A 
 

| subscript b in concentration ratio denotes bulk stream

General Notation
dp = diameter of catalytic particle
ρf = density of fluid
μf = (dynamic) viscosity of fluid
U∞ = fully developed velocity of fluid
DAB = diffusivity of A in the reaction mixture
kg = mass transport coefficient
h = heat transport coefficient
kf = thermal conductivity of fluid
cp = specific heat of fluid
G = mass velocity of fluid

5
 εB = porosity of bed
E = activation energy of reaction
kn = intrinsic kinetic coefficient per unit of catalyst surface area
CA,b = concentration of A in the bulk stream
CA,s = concentration of A on the catalyst surface
as = surface area of the catalyst per unit volume of catalyst particle
am = external surface area of the catalyst per unit volume of catalyst particle
n = external effectiveness factor
R = universal (ideal) gas constant (8.314 5 J/K-mol = 82.057 cm3 atm/K-mol)
Tb = temperature in the bulk stream
Ts = temperature on the catalyst surface
Sp = observed selectivity
--------------------------------------------------------------------------------------------------------

VI. Internal heat and mass transfer

1 8RT
D  u  u 
 MA
Normal diffusion (kinetic theory of gases): AB A , A
3
| u A = mean velocity of molecules A
| R = universal (ideal) gas constant
| T = temperature (K)
| MA = molecular weight of A (g/mol)
| λ = mean free path

Normal diffusion in gases (Chapman-Enskog equation):

 1 1 
T 3/ 2   
3  MA MB 
DAB  1.8583  10
PT  AB
2
AB
  AB 12   AB 6 
V (r )  4 AB 
LJ
   
12-6 Lennard-Jones energy:
 r   r  
A B
Lorentz-Berthelot mixing rules:  AB  ,  AB   A B
2
If Lennard-Jones parameters are unknown for entity A, they can be approximated by the
A A
following expressions:  A  1.18Vb1/3 or  A  0.841Vc1/3 ,  1.15Tb or  0.77Tc
kB kB
| T = temperature (K)
| MA = molecular weight of A (g/mol)
| MB = molecular weight of B (g/mol)
| DAB = diffusivity of A in the binary mixture A+B (cm2/s)
| PT = total pressure (atm)

6
| σAB = collision diameter of the Lennard-Jones potential between a pair of molecules of
kinds A and B (Å)
| εAB = well depth of the Lennard-Jones potential between a pair of molecules of kinds A
and B (J/mol)
| ΩAB = collision integral (dimensionless)
| kB = Boltzmann constant (1.98710-3 kcal/mol-K = 1.38010-23 J/K)
| Tb = normal boiling temperature (K)
| Tc = critical temperature (K)
| Vb = volume per mole at normal boiling point (cm3/mol)
| Vc = critical volume (cm3/mol)

8 T  M B
D  7.4  10
Normal diffusion in liquids (Wilke-Chang equation): B VA0.6
AB

| DAB = diffusivity of A in the solution A+B (cm2/s)

| μB = viscosity of solution (solvent) (cp)
| T = temperature (K)
| MB = molecular weight of solvent B (g/mol)
| VA = molar volume of A at normal boiling point (cm3/mol)
| χ = empirical parameter of solvent

Normal diffusion in multicomponent systems:

n
1  a 
  yk  y j k  n

1 k 1 D jk  aj 
1 n
1  ak   ak

k j
n
ak
  
1   j y j k 1 D jk 
y k  y j 
| a j |  ,  j  | a |
k 1

1 yj 
D j ,m
k j j
k 1 a j

| aj = stoichiometric coefficient of entity j

| Dj,m = diffusivity of entity j in the multicomponent system
| Djk = diffusivity of entity j in the binary system j+k
| yj = molar fraction of entity j
T  T
D  4.85  103
a  1.94  10 4

a S g
Knudsen diffusion: K ,A
MA MA
| DK,A = (Knudsen) diffusivity of A (cm2/s)
| a = pore diameter (cm)
| MA = molecular weight of A (g/mol)
| ε = porosity of solid
| Sg = total surface area of solid (cm2)
| ρa = apparent density of solid (g/cm3)
| T = temperature (K)

7
Diffusion in porous medium, total diffusivity (simplified):
1
D
1 1

DAB DK ,A
Diffusion in porous medium, total diffusivity (explicit):
1
D JB
1  w yA 1 , w 1
 JA
DAB DK ,A
| JA = molar flux of A, treated as vector.
| JB = molar flux of all entities except A, treated as vectors.

MA
For counter-diffusing, binary (A+B) mixture (no reaction):
w  1 
MB
D
D 
Parallel pore model, effective diffusivity: 
e

| ε = porosity of medium
| δ = tortuosity of medium
 μ2 1  3 M 
D D   2
Dμ
Random pore model, effective diffusivity: e 1 M
M M

1 1
DM  , Dμ 
1 1 1 1
where  
DAB  DKA M DAB  DKA μ
| subscript M corresponds to macropores
| subscript μ corresponds micropores
Total effective diffusivity (including surface contribution): De,t  De   KDs
| Ds = surface diffusivity
| ρ = density of the catalyst
| K = equilibrium constant (linear adsorption isotherm)
1 
 kg 
k e  ks  
Effective thermal conductivity of porous solids:
 ks 
| ks = thermal conductivity of solid phase
| kg = thermal conductivity of gas phase
| ε = porosity of solid catalyst

8
 k1
st
Thiele modulus (plate geometry, 1 -order reaction):
 L  L
De
| L = half thickness of plate catalyst
| k1 = intrinsic reaction rate constant
CA cosh   L z ' z
 z' 
cosh   L 
st
Concentration profile (plate geometry, 1 -order reaction): C , L
A,s

tanh  L
Internal effectiveness factor (plate geometry, 1st-order reaction): n  L
rs k1
Thiele modulus (spherical geometry, 1st-order reaction):
s 
3 De
| rs = radius of spherical catalyst

Internal effectiveness factor (spherical geometry, 1st-order reaction):

1  1 1 
n   
s  tanh  3s  3s 
 r
sinh  3 s 
CA r   rs 
 s 
 r  sinh  3 s 
st
Concentration profile (spherical geometry, 1 -order reaction): C
A,s

n 1
knCA,s Vp
Thiele modulus (general geometry, nth-order reaction):
L , L 
De Sx
| n = integer (order of reaction)
| Vp = volume of particle
| Sx = external surface area of particle
| CA,s = concentration of A on surface

Total effectiveness factor (combined effect of internal and external resistances to mass
transfer) (spherical geometry, 1st order reaction):
1 1 3 2
 
n * n Bi m
kg rs
Biot number for mass transfer (Bim)
Bi m 
De

9
Non-isothermal conditions (spherical geometry, 1st order reaction):
H De
T  Ts 
ke
CA  CA,s 
T CA
  A  , Ts ,
  
*
In dimensionless form:   1   C *
 1 C A
CA,s
De CA,s
Prater number (β):  H 
ke Ts

| Ts = temperature on the surface

rp L2
Weisz-Prater number (Ψ) (general geometry):

De Cs
Criterion for the absence of temperature difference inside the catalyst (general geometry):
| H | rp L2 
1
ke Tb
Criterion for the absence of temperature difference in boundary layer (general geometry):
 H  rp L 
 0.15
hTb
| γ = Arrhenius number
Effect of internal mass transfer on observed selectivity (first order reactions, plate
geometry) (reactions in series, A   B  C ):
1 2 k k

 k    tanh   2   CB,s  2 tanh   2 

Sp   1  1  2 

 1 2  
k k 1 tanh   
1  CA,s 1 tanh  1 
| Sp = observed selectivity
| CB,s = concentration of B on surface
| CA,s = concentration of A on surface
--------------------------------------------------------------------------------------------------------

VII. Catalyst deactivation

Pore mouth poisoning, reaction rate per unit mass (spherical geometry, 1st order reaction):
k1
rp  CA,s rc3
1  1   1/3  1  3
 3 s2  
1 , rs
n 1    1   
1/3

| CA,s = concentration of A on surface

10
| k1 = intrinsic rate constant (first order reaction)
| Φs = Thiele modulus
| n = internal effectiveness factor
| δ = fraction of poisoned (deactivated) sites
| rc = radius of active central core
| rs = total radius of the catalyst
--------------------------------------------------------------------------------------------------------
VIII. Catalytic reactors
Fixed bed reactor, generalized mass and heat balance equations:
CA  2CA   2CA 1 CA    uCA 
  De  z   De r     rp  B
t z 2  r
2
r r  z
T  2T   2T 1 T     cpuT 
 cp   ke  z 2   ke  r  2    rp  BH
t z   r r r   z
| CA = concentration of A
| t = time
| T = temperature
| u = superficial velocity
| ρ = density of fluid
| ρB = density of bed
| rp = global rate of consumption of A per unit mass of catalyst
| (De)z, (De)r = effective diffusivities in axial and radial directions
| (ke)z, (ke)r = effective thermal conductivities in axial and radial directions

dp u dp u
Pe  , Pe 
Axial and radial Peclet numbers (Pe) for mass: z
 De  z r
 De r
dp u dp u
Pe z  , Pe r 
Axial and radial Peclet numbers (Pe) for heat:  ke  z  ke  r
| dp = diameter of catalytic particles

One-dimensional, plug-flow model, mass balance:

rp dW  FA,0 dX A
One-dimensional, plug-flow model, heat exchange term:
U T  Tenv  1 1 d A 1 A
Q4 , U h  k A h A
wall i i

d reactor i m e e
0.9
hi d reactor  dp G   dp 
 0.813   exp  6 
  
Leva formula (heating): kg  d reactor 

11
 0.7
hi d reactor  dp G   dp 
 3.50   exp  4.6 
  
Leva formula (cooling): kg  d reactor 
One-dimensional, plug-flow model, momentum balance:
dP f r u 2  P f r u 2 
 0 →
 
dz d p L d p
 1   B   1  
1.75  150  B
 Re  d p u 
fr  Re  d p  6
volume of particle
B 3 ,  ,
external surface area of particle
FA,0
One-dimensional, adiabatic reactor, temperature vs. conversion:
dT   H  d XA
mc t p

| W = mass of the catalyst

| FA,0 = molar flow of A at reactor entrance
| XA = conversion with respect to reactant A
| hi = heat transfer coefficient – bed side (kcal/m2-h-oC)
| he = heat transfer coefficient – medium side (kcal/m2-h-oC)
| Ai = surface area – bed side (m2)
| Ae = surface area – medium side (m2)
| Am = log mean of Ai and Ae (m2)
| k = thermal conductivity of wall (kcal/m-h-oC)
| dwall = thickness of tube wall (m)
| dreactor = diameter of reactor bed
| G = mass velocity of fluid
| kg = thermal conductivity of mixture
| μ = viscosity of fluid
| P = pressure
| fr = friction coefficient
| εB = porosity of reactor bed
| d p = equivalent diameter of catalytic particles
| u = velocity of fluid
| L = length of reactor bed
| mt = mass flow
| cp = specific heat capacity
| Tenv = temperature of environment
i 1

k j

X A0,i  j 1
i
X A,i 1  i  2,...., N 
Fractional feed stream, conversion:
k
j 1
j

12
 i 1

k j

T0, i  T0  j 1
i Ti 1  T0   i  2,...., N 
Fractional feed stream, temperature:
k
j 1
j

| XA,i-1 = conversion with respect to A at the exit of bed i-1

| XA0,i = conversion with respect to A at the entrance of bed i
| T0 = initial temperature (at the entrance of bed 1)
| T0,i = temperature at the entrance of bed i
| Ti-1 = temperature at the exit of bed i-1
| kj = fraction of inlet stream directed to bed j

Thermal characteristics of non-adiabatic, non-isothermal reactors, design parameters to

identify thermodynamic stability, hot-spots and runaway (1st order reaction):
 H  CA,0 E 2 U
   S   , N 
 cp T0 , RT0 , Rt  cp kv
| Rt = internal bed radius

HYPERBOLIC FUNCTIONS:
e x  e x
sinh x 
2
e x  e x
cosh x 
2
e x  e x
tanh x  x
e  e x
e x  e x
coth x  x
e  e x

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