Chapter 10

Catalysis and Catalytic Reactors

Definitions

• Catalyst
•positive catalysis
– rate (not equilibrium)
•negative catalysis
– yield
– selectivity
• Pathway (mechanism)
Homogeneous catalysis
catalyst is in solution with at least one of the reactants

CHO
CH3 CH i-butyl aldehyde
Co CH3
CH3 CH CH2 + CO + H2
CH3 CH2 CH2 CHO n-butyl aldehyde

Heterogeneous catalysis
involves more than one phase, usually the catalyst is a solid and the
reactants and the products are in liquid or gaseous state

Pt
Al2O3 + 3H2
Catalyst Properties

catalytic reactions occur at the fluid-solid interface

large interfacial area will be useful or even necessary
porous catalysts

e.g. typical silica-alumina cracking catalyst

pore volume : 0.6 cm3/g
average pore radius : 4 nm (40 Å)
surface area :300 m2/g

sometimes the pores are so small that they prevent large molecules
from entering

molecular sieves

e.g. clays, zeolites, microporous carbons

uniform pores of molecular sizes
e.g. 4 Å for zeolite 4A
surface areas of up to 900-1000 m2 or more
 + 6H
2

nonmetal
CH4 +1/2O2 CO + H2 CH3OH zeolite
CH3CH3
when the catalyst is
sufficiently active
monolithic catalysts
(press. drop, heat removal)
e.g. Pt gauze for NH3 ox.
and honeycomb converters
Supported catalyst (e.g. V2O5 / silica, Pt / Al2O3)

Unsupported catalyst (Pt gauze, promoted Fe)

Active site (acid, base, metal)

Deactivation (aging, coking, poisoning)

Turnover frequency

Dispersion, D

Adsorption (physical / chemical)

(chemisorption)
Example CO + 3H2 → CH4 + H2O

The Fisher-Tropsch synthesis was studied using a commercial 0.5 wt

% Ru on γ-Al2O3. The catalyst dispersion percentage of atoms
exposed, determined from hydrogen chemisorption was found to be
49 %. At pressure of 988 kPa and a temperature of 475 K, a turnover
frequency of 0.044 s-1 was reported for methane. What is the rate of
formation of methane in mol/s.g-cat (metal plus support) ?

# 1 & % Ru
− rA" = N CH D % (
4
$ MWRu ' 100
0.044 molecules 1 mol CH 4
− rA" = ×
(surface atom Ru).s 6.02 × 10 23 molecules
0.49 surface atoms 6.02 × 10 23 atoms Ru
× ×
total atoms Ru g atom( mol )Ru
g atoms Ru 0.005 g Ru
× × = 1.07 × 10 −6 mol / s. g − cat
101.1 g Ru g total
Steps in a Heterogeneous Catalytic Reaction
Adsorption Isotherms

A + S 
 A.S

Ct is the total molar concentration of active sites per
unit mass of catalysts, mol/g-cat
Pi partial pressure of species i in the gas phase, atm
Ci-S surface concentration of sites occupied by species
i, mol/g-cat

A B

vacant and occupied sites

For the system shown,

C t = C v + C A.S + C B.S
CO adsorbed as molecules

CO + S  
 CO • S


rate of attachment = kAPCOCv

rate of detachment = k-ACCO.S

net rate of adsorption; rAD = kAPCOCv -k-ACCO.S

K A = k A / k −A

⎛ CCO.S ⎞
rAD = k A ⎜⎜ PCOC v - ⎟⎟
⎝ K A ⎠
 ⎛ CCO.S ⎞
rAD = k A ⎜⎜ PCOC v - ⎟⎟
⎝ K A ⎠

CO is the only adsorbed molecule

C t = C v + CCO .S or C v = C t − CCO .S

at equilibrium net rate = 0

CCO.S = K A PCO C v = K A PCO (C t − CCO.S )

K A PCO C t
rearranging C CO.S = Langmuir Isotherm
1 + K A PCO
PCO 1 PCO
= +
CCO.S K ACt Ct
 C CO.S
mol/g - cat

PCO , kPa

PCO 1
slope =
CCO.S Ct

1
K ACt

PCO
CO adsorbed as atoms

CO + 2S  
C•S+ O•S


rate of attachment = kAPCOC2v

rate of detachment = [Link].S

net rate of adsorption; rAD = kAPCOC2v -[Link].S

K A = k A / k −A

⎛ 2 C [Link] O.S ⎞
rAD = k A ⎜⎜ PCOC v - ⎟⎟
⎝ K A ⎠
 at equilibrium net rate = 0
K A PCOC 2v = [Link].S

for CC.S = CO.S

1/2
( K APCO ) Cv = CO.S

C v = C t − CC.S − CO.S = C t − 2CO.S

rearranging the equations

1/2 1/2

CCO.S =
( K A PCO ) C t P 1/2
CO
=
1 2 ( PCO )
1/2 1/2 +
1 + 2 ( K A PCO ) CCO.S C t ( K A ) Ct
 Adsorption of H2 on Cu powder at 25°C
PH 2 C H 2S × 10 2 PH 2 C H 2S × 10 2
torr g mol/g Cu torr g mol/g Cu
3.25 0.559 45.1 1.160
8.90 0.761 21.5 0.995
17.65 0.941 10.65 0.800
36.2 1.212 5.40 0.659
74.5 1.281 2.95 0.564
204.8 1.471 1.70 0.464

80 12

70
10
60
PH 2 50
PH 2
8

C H 2 ⋅S 40

30 C H 2 ⋅S
6

4
20
2
10

0 0
0 20 40 60 80 100 0 5 10 15 20

PH 2 PH2
1/2

CH2 .S =
K A PH2 C t P 1/2
H2
=
1
+
( )
2 PH2
1 + K A PH2 CH2 .S Ct ( K A )
1/2
Ct
when more than one substance is present

adsorption isotherm of A in the presence of adsorbate B

K A PA C t
C A⋅S =
1 + K A PA + K B PB

adsorption isotherm of B in the presence of adsorbate A

K B PBC t
C B⋅S =
1 + K A PA + K B PB
Surface Reactions
A+S A •S
⎛ C A.S ⎞
rAD = k A ⎜⎜ PA C v - ⎟⎟
⎝ K A ⎠

Single-site mechanism
A •S B•S
A B
⎛ CB⋅S ⎞
rS = k S ⎜⎜ CA⋅S - ⎟⎟
⎝ K S ⎠

Dual-site mechanism
A ⋅S + S B⋅S + S
A B ⎛ C B⋅SC v ⎞
rS = k S ⎜⎜ C A⋅SC v - ⎟⎟
⎝ K S ⎠
 Dual-site mechanism
A ⋅S + B⋅S C ⋅S + D ⋅S
A B C D ⎛ CC⋅SC D⋅S ⎞
rS = k S ⎜⎜ C A⋅SC B⋅S - ⎟⎟
⎝ K S ⎠

Species adsorbed on different types of sites S and S´

B A C D
A ⋅ S + B ⋅ Sʹ′ C ⋅ Sʹ′ + D ⋅ S
⎛ CC⋅Sʹ′C D⋅S ⎞
rS = k S ⎜⎜ CA⋅SCB⋅Sʹ′ - ⎟⎟
⎝ K S ⎠

Single or dual-site mechanisms are sometimes referred to as

following Langmuir-Hinshelwood Kinetics
Reaction between an adsorbed molecule and a molecule in the
gas phase

B A C

A ⋅ S + B(g ) C⋅S

" CC ⋅S %
rS = kS $ C A⋅S PB - '
# K S &

Eley-Rideal Mechanism
Desorption
C ⋅S C+S

the desorption rate law

⎛ Cv PC ⎞
rDC = k D ⎜⎜ CC⋅S - ⎟⎟
⎝ K DC ⎠

rDC = - rAC

1
K DC =
KC

rDC = k D (CC⋅S - K C PC Cv )
The Rate-limiting Step

− rAʹ′ = rAD = rS = rD

One particular step is rate-limiting or rate-controlling

Current I in the case of resistance in series

E E
I= =
R tot R AD + R S + R D

The approach in determining catalytic and heterogeneous

mechanism is called Langmuir-Hinshelwood approach
 NH3 Synthesis from H2 and N2 over Fe catalyst

3 H2 + N2 2 NH3

H 2 + 2S 2H ⋅ S Rapid

N2 + S N2 ⋅ S
Rate-Limiting
N 2S + S 2N ⋅ S

N ⋅S + H ⋅S HN ⋅ S + S
NH ⋅ S + H ⋅ S H2 N ⋅ S + S
Rapid
H2N ⋅ S + H ⋅ S NH 3 ⋅ S + S
NH 3 ⋅ S NH 3 + S
 Reaction of CO and NO over Cu catalyst
1
CO + NO CO 2 + N 2
2
CO + S CO ⋅ S
Rapid
NO + S NO ⋅ S

NO ⋅ S + CO ⋅ S CO 2 + N ⋅ S + S Rate-Limiting

N ⋅S + N ⋅S N2 ⋅ S
Rapid
N2 ⋅ S N2 + S
Synthesizing a Rate Law, Mechanism and Rate-Limiting Step
Cumene decomposition to yield benzene and propylene

C6 H 5CH(CH 3 ) 2 → C6 H 6 + C3H 6
Reaction sequence

kA
C+S k −A
C ⋅S adsorption of cumene on the
surface
kS surface reaction to form adsorbed
C ⋅S k −S
B⋅S + P benzene and propylene in the gas
phase
kD
B⋅ S k −D
B+S desorption of benzene from the
surface

CC → PC
 kA
C+S k −A
C ⋅S rAD = k A PCCv − k −A CC⋅S

C C ⎛ CC⋅S ⎞
Adsorption : rAD = k A ⎜ PCC v −
⎜ ⎟⎟
⎝ K C ⎠

C ⋅S
kS
k −S
B⋅S + P rS = k SCC⋅S − k −SPP CB⋅S

C B +P ⎛ PP CB⋅S ⎞
Surface reaction : rS = k S ⎜ CC⋅S −
⎜ ⎟⎟
⎝ K S ⎠

kD
B⋅S k −D
B+S rD = k DCB⋅S − k −D PBCv

B B ⎛ PBC v ⎞
Desorption : rD = k D ⎜⎜ CB⋅S − ⎟⎟
⎝ K DB ⎠
 ⎛ PBC v ⎞
Desorption : rD = k D ⎜ CB⋅S −
⎜ ⎟⎟
⎝ K DB ⎠

1
KB =
K DB

Desorption : rD = k D (CB⋅S − K BPBCv )

There is no accumulation of reacting species on the surface

− rCʹ′ = rAD = rS = rD
Is the adsorption of cumene rate-limiting?
assume that adsorption step is rate-limiting

⎛ CC⋅S ⎞
− rCʹ′ = rAD = k A ⎜⎜ PCC v − ⎟⎟
⎝ K C ⎠

Steady-state − rCʹ′ = rAD = rS = rD

For adsorption limited reactions, kA is small, kS and kD are large

⇒ rS / k S and rD / k D are very small

rAD / k A is relatively large
⎛ PP CB⋅S ⎞
Surface reaction : rS = k S ⎜⎜ CC⋅S − ⎟⎟
⎝ K S ⎠
Desorption rD = k D (CB⋅S − K BPBCv )
For adsorption limited reaction kS is large
⎛ PP CB⋅S ⎞
Surface reaction : rS = k S ⎜⎜ CC⋅S − ⎟⎟
⎝ K S ⎠

rS C B⋅S PP
≈0 C C⋅S =
kS KS

For adsorption limited reaction kD is large

rD = k D (CB⋅S − K BPBCv )

rD
≈0 CB⋅S = K BCv PB
kD

PB PP
C C⋅S = KB Cv
KS
 ⎛ CC⋅S ⎞
rAD = k A ⎜⎜ PC C v − ⎟⎟
⎝ K C ⎠

⎛ K B PB PP ⎞ ⎛ PB PP ⎞
rAD = k A ⎜⎜ PC − ⎟⎟C v = k A ⎜⎜ PC − ⎟⎟C v
⎝ K SK C ⎠ ⎝ K P ⎠

For the reaction

C B+P
K SK C
rAD = 0 KP =
KB
Equilibrium constant is related with the change in the Gibbs free energy

RT ln K = −ΔG o
The concentration of vacant sites, Cv

Ct = Cv + CC.S + CB.S

PB PP
Ct = Cv + K B C v + K BC v PB
KS
Ct
Cv =
PB PP
1+ KB + K B PB
KS

C t k A (PC − PP PB / K p )
− rCʹ′ = rAD =
1 + K B PB PP / K S + K B PB
 C t k A (PC − PP PB / K p )
− rCʹ′ = rAD =
1 + K B PB PP / K S + K B PB

initially initial rate, -rʹ′C0

PP = PB = 0 − rCʹ′ 0 = Ct k A PC 0 = kPC 0

initial partial pressure of cumene, PC0

Is the surface reaction rate-limiting?
⎛ PP CB⋅S ⎞
Surface reaction : rS = k S ⎜⎜ CC⋅S − ⎟⎟
⎝ K S ⎠
rAD
≈0 CC⋅S = K C PCCv
k AD
rD CB⋅S = K BCv PB
≈0
kD
⎛ PP K B PB ⎞ ⎛ PP PB ⎞
rS = k S ⎜⎜ K C PC − ⎟⎟C v = k SK C ⎜⎜ PC − ⎟⎟C v
⎝ K S ⎠ ⎝ K P ⎠

Ct
Ct = Cv + CC.S + CB.S Cv =
1 + K B PB + K C PC
k s C t K C (PC − PP PB / K P )
− rCʹ′ = rS =
1 + K B PB + K C PC
initial rate is
kPC 0
− rCʹ′ 0 =
1 + K C PC 0
where k = k sCt K C

at low PC0 1 〉〉 K C PC0

− rCʹ′ 0 ≈ kPC0

initial rate, -rʹ′C0

at high PC0 K C PC0 〉〉 1

kPC 0 k
− rCʹ′ 0 = = initial partial pressure of cumene, PC0
K C PC 0 K C
Is the desorption of benzene rate-limiting?
Desorption : rD = k D (CB⋅S − K BPBCv )
rS
≈0 CB⋅S = KSCC⋅S / PP
kS

rAD
≈0 CC⋅S = K CCv PC
k AD

⎛ PC PB ⎞
CB⋅S = KSK CCv PC / PP rD = k D K C K S ⎜⎜ − ⎟⎟C v
⎝ PP K P ⎠
Ct
Ct = Cv + CC.S + CB.S Cv =
1 + K C K S PC / PP + K C PC
k D C t K S K C (PC − PP PB / K P )
− rCʹ′ = rS =
PP + K C PC K S + K C PC PP
 initially PP = PB = 0

− rCʹ′ 0 = k D C t

initial rate, -rʹ′C0

initial partial pressure of cumene, PC0

Summary of the cumene decomposition

Rate-law derived by assuming surface reaction is rate-limiting

agrees with the experimental data
Initial rate, -rʹ′C0

Initial partial pressure of cumene,

PC0

k (PC − PB PP / K P )
− rCʹ′ =
1 + K B PB + K C PC
 Inerts in the feed

I+S I ⋅S

Ct = Cv + CC⋅S + CB⋅S + CI⋅S

CI⋅S = K I PI CV

k (PC − PB PP / K P )
− rCʹ′ =
1 + K B PB + K C PC + K I PI
Octane Number

Fuels with low octane numbers can produce spontaneous combustion

in the cylinder before the air/fuel mixture is compressed to its desired
value and ignited by the spark plug.

K.I.

100% heptane 100% i-octane

Octane Number


n − pentane 
0.75wt %Pt
 
 i − pentane
Al O 2 3

−H +H

n − pentane 
2

 n − pentene 

2 3

 i
Al O
− pentene 

2

 i − pentane
Pt Pt
Octane number and the dual site mechanism
Al2O3
N I
1. Select a mechanism (Mechanism I)

Adsorption N +S N ⋅S

Surface reaction N ⋅S + S I ⋅S + S

Desorption I ⋅S I+S
2. Assume a rate limiting step: The rate law for the surface reaction step

⎛ C I⋅SC v ⎞
− rNʹ′ = rS = k S ⎜⎜ C N⋅SC v − ⎟⎟
⎝ K S ⎠
3. Find the expression for concentration of the adsorbed species Ci. S

C N⋅S = PN K N C v
PI C v
C I⋅S = = K I PI C v
KD
4. Write a site balance
C t = CI⋅S + C N⋅S + C v

5. Derive the rate law

kS Ct2 K N ( PN − PI / K P )
− rN" = rS = 2
(1 + K N PN + K I PI )
6. Compare with data
If the derived rate law does not agree with the data
a)Assume a different rate limiting step and repeat steps 2-6.
b)If, after assuming that each step is rate limiting, none of the derived rate
laws agree with the experimental data, select a different mechanism (e.g., a
single site mechanism):


N + S
 NiS

NiS 
 IiS

IiS 
I +S
and then proceed through steps 2-6.

The single site mechanism, with the following rate law, turns out to be the
correct one.
k ( PN − PI / K P )
− rN′ =
1 + K N PN + K I PI
c) If two or more models agree, statistical tests should be used to
discriminate between them.
Single site

kPA
A ⋅S → B ⋅S - rAʹ′ =
1 + K A PA + K B PB
Dual site
kPA
A ⋅S + S → B⋅S + S - rAʹ′ =
(1 + K A PA + K B PB )2
kPA PB
A ⋅S + B ⋅S → C ⋅S + S - rAʹ′ =
(1 + K A PA + K B PB + K C PC )2
Eley-Rideal
kPA PB
A ⋅ S + B(g) → C ⋅ S - rAʹ′ =
1 + K A PA + K C PC
Rate laws derived from the pseudo-steady state
*
An alternative way to derive rate law −r =0
i⋅S

Ex: isomerization of n-pentene to i-pentene

N +S ⎯⎯
← ⎯kN

k− N
→
⎯ N ⋅S
N ⋅S ⎯k⎯
S
→ I ⋅S

I ⋅S 

kI
k− I

 I+S

The rate law for the surface reaction

− rNʹ′ = rS = k SC N⋅S
The net rates of generation of N•S and S•I sites are

rN* ⋅S = k N PN C v − k − N C N⋅S − k SC N⋅S = 0

*
r = k SC N⋅S − k I C I⋅S + k − I PI C v = 0
I⋅S

Solving for CN•S and CS•I

k N PN C v
C N⋅S =
k −N + kS

k SC N⋅S + k −I PI C v ⎛ k Sk N PN k −I PI ⎞
CI⋅S = = ⎜⎜ + ⎟⎟C v
kI ⎝ k I (k − N + k S ) k I ⎠
The rate law
k N PN Cv
− rN′ = kS
k− N + kS

A site balance

C t = CI⋅S + C N⋅S + C v

k N k SC t PN
− rNʹ′ =
k −N + kS k N ⎛ k S ⎞ k −I
1+ ⎜⎜1 + ⎟⎟PN + PI
k − N + k S ⎝ k I ⎠ kI
 k −I kN
KI = and KN =
kI k −N

k
⎛ K N k S Ct ⎞ PN
− rN′ = ⎜
⎝ 1 + kS / k− N ⎟⎠ 1 + 1
K N PN + K I PI
1 + kS / k− N

Surface reaction limiting k S is much smaller compared to k - N

kS
1〉〉
k -N

kPN
− rNʹ′ =
1 + K N PN + K I PI
Temperature dependence of the rate law

For a surface reaction limited irreversible isomerization

A B
in which both A and B are adsorbed on the surface, the rate law is

kPA
− rAʹ′ =
1 + K A PA + K B PB
at high temperatures (low coverages)

1 〉〉 KA PA + KBPB
− rAʹ′ ≈ kPA
for a reversible izomerization

− rAʹ′ ≈ k(PA − PB / K P )
Design of Reactors for Gas-Solid Reactions

Design Equations
dX
Batch reactor N A0 = −rAʹ′ W
dt
dX
Packed-bed reactor FA 0 = −rAʹ′
dW
FA 0 X
CSTR V=
− rAʹ′

FA 0 X
W=
− rAʹ′
Heterogeneous Data Analysis for Reactor Design C6 H5CH 3 + H 2 → C6 H 6 + CH 4
rTʹ′ × 1010 Partial Pressure (atm)
Run g mol toluene Toluene Hydrogen Methane Benzene
g cat.s -1 PT PH2 PM PB
Set A
1 71.0 1 1 1 0
2 71.3 1 1 4 0
Set B
3 41.6 1 1 0 1
4 19.7 1 1 0 4
5 42.0 1 1 1 1
6 17.1 1 1 0 5
Set C
7 71.8 1 1 0 0
8 142.0 1 2 0 0
9 284.0 1 4 0 0
Set D
10 47.0 0.5 1 0 0
11 71.3 1 1 0 0
12 117.0 5 1 0 0
13 127.0 10 1 0 0
14 131.0 15 1 0 0
15 133.0 20 1 0 0
16 41.8 1 1 1 1
Deducing a rate law from the experimental data
1. Dependence on the product methane
If methane adsorbed → partial pressure of methane in the denominator
and the rate inversely proportional with methane conc.

− rTʹ′ ≈
[]⋅
1 + K M PM + ⋅ ⋅

However from Run1 and Run2, fourfold increase in the PM has little effect
on the rate. Methane is weakly adsorbed or goes directly to gas phase
(KMPM<<1)
2. Dependence on the product benzene
From Run3 and Run4 for fixed conc. H and T , the rate is decreased with
increasing conc. B. Partial pressure of B appears in the denominator.

1
− rTʹ′ ≈
1 + K B PB + ⋅ ⋅
3. Dependence on toluene
At low conc. T (Run10 and Run11), the rate increases with increasing PT,
the rate is independent of PT
PT
− rTʹ′ ≈
1 + K T PT + ⋅ ⋅

4. Dependence on hydrogen
From Run7, 8 and 9, rate increases linearly with increasing PH2.. H2 is not
adsorbed or its coverage is extremely low (KH2PH2<<1)

− rTʹ′ ≈ PH 2
Combining

kPH 2 PT
− rTʹ′ =
1 + K T PT + K B PB
Finding a mechanism consistent with experimental observations

T (g ) + S T ⋅S
⎛ CT⋅S ⎞
Adsorption : rAD = k A ⎜⎜ PT C v − ⎟⎟
⎝ K T ⎠

H2 (g) + T ⋅ S B ⋅ S + M (g )
⎛ PM CB⋅S ⎞
Surface reaction : rS = k S ⎜⎜ PH 2 CT⋅S − ⎟⎟
⎝ K S ⎠

B⋅ S B (g) + S

Desorption : rD = k D (CB⋅S − K BPBCv )

surface reaction rate-limiting
⎛ PM CB⋅S ⎞
rS = k S ⎜⎜ PH 2 CT⋅S − ⎟⎟
⎝ K S ⎠
rAD
From adsorption rate ≈0 CT⋅S = K T PT Cv
k AD

rD
From desorption rate ≈0 CB⋅S = K BCv PB
kD

Ct
Ct = Cv + CT.S + CB.S Cv =
1 + K B PB + K T PT

− rTʹ′ =
(
k s C t K T PH 2 PT − PM PB / K P )
1 + K B PB + K T PT

kPH 2 PT
Neglecting the reverse reaction − rTʹ′ =
1 + K B PB + K T PT
Evaluation of the rate law parameters
kPH 2 PT
− rTʹ′ =
1 + K B PB + K T PT

PH 2 PT 1 K B PB K T PT
= + + Yj = a 0 + a1X1 j + a 2 X 2 j
− rTʹ′ k k k

8.7 × 10 −4 PH 2 PT g mol T
− rTʹ′ =
1 + 1.39 PB + 1.038PT kg [Link]

With known KT and KB, ratio of sites occupied by the various adsorbed species can be
calculated

CT⋅S K T PT C v K T PT K T PA 0 (1 − X) K T (1 − X) 1.038(1 − 0.4)

= = = = = = 1.12
C B⋅S K BC v PB K B PB K B PA 0 X K BX 1.39(0.4)

At 40% conversion ~12 % more sites occupied by toluene than by benzene

 dX − rAʹ′
Reactor Design =
dW FA 0
The hydrodemethylation of toluene is to be carried out in a packed bed
reactor. Plot the conversion, pressure ratio (y), and the partial pressures of
toluene, hydrogen and benzene as a function of W. The molar feed rate of
toluene to the reactor is 50 mol/min and the reactor is operated at 40 atm
and 640oC. The feed consists of 30% toluene, 45% H2 and 25% inerts. H2
is used in excess to help prevent coking. The pressure drop parameter α is
9.8x10-5 kg-1. Also determine the catalyst weight in a CSTR with a bulk
density of 400 kg/m3.
C6 H5CH 3 + H 2 → C6 H 6 + CH 4
Design equation: dFT
= rT!
dW
dX − rTʹ′
=
dW FT 0
Rate law:
kPH 2 PT k = 0.00087 mol / atm 2 / kg cat / min
− rTʹ′ =
1 + K B PB + K T PT K B = 1.39 atm −1 , K T = 1.038 atm −1
Stoichiometry:
# 1− X & # 1− X &
PT = CT RT = CT 0 RT0 % y = P y
$ 1 + ε X (' T0 %
$ 1 + ε X ('

ε = yT 0δ = 0.3(0) = 0
PT = PT 0 (1 − X ) y
(
PH 2 = PT 0 θ H 2 − X y)
PB = PT 0 Xy
0.45
θ H2 = = 1.5
0.30
because ε = 0
P 1/2
y= = (1 − αW ) → α = 9.8 × 10 −5 kg −1
P0

PT 0 = 0.3(40) = 12 atm

1 1/2

40
(
= 1 − 9.8 × 10 −5 W ) → W = 10197 kg
 Example 10.3 Example 10.3
1 18

0.9 16

0.8 y H2
14
0.7
12
0.6

PT,PH2,PB
10
T
X,y

0.5
x 8
0.4
6
0.3

0.2 4

0.1 2
B
0 0
0 1000 2000 3000 4000 5000 6000 7000 8000 9000 10000 0 1000 2000 3000 4000 5000 6000 7000 8000 9000 10000
w w

FA 0 X g mol T
W= At X = 0.65 − rAʹ′ = 2.39 ×10 −3
− rAʹ′ kg cat. min

50(0.65) 4 1.36 ×10 4 kg 3

W= −3
= 1.36 × 10 kg V= = 34 m
2.39 ×10 400 kg / m3
Chemical Vapor Deposition

Gas-phase dissociation GeCl 4(g) GeCl 2(g) + Cl 2 (g)

Adsorption GeCl 2(g) + S GeCl 2⋅ S

Adsorption H 2+ 2S 2H ⋅ S

Surface-reaction GeCl 2⋅ S + 2H ⋅ S Ge (s) + 2HCl (g) + 2S

Ge
Cl2 HCl (g)
H H

Ge
Ge Ge Ge Ge Ge Ge Ge Ge Ge Ge
Surface-reaction is the rate limiting step

ʹ′ʹ′ = k Sf GeCl2 f H2
− rDep
− rDep
ʹ′ʹ′ = deposition rate, nm/s
k S = surface specific reaction rate, nm/s
f GeCl2 = fraction on the surface occupied by germanium chloride
f H2 = fraction on the surface covered by molecular H 2

Fractional area balance 1 = f v + f GeCl2 + f H

⎛ f GeCl2 ⎞
rAD = k A ⎜⎜ PGeCl2 f v − ⎟⎟
⎝ KA ⎠
 rAD
Surface-reaction is rate limiting step ≈0
k AD

f GeCl2 = f v K A PGeCl2

⎛ f 2
⎞
= kH ⎜ PH 2 fv −
2 H2
Dissociative adsorption of H2 on surface rH2
⎝ K H ⎟⎠

rH 2
Surface-reaction is rate limiting step ≈0
k H2

fH = fv K H PH 2

ʹ′ʹ′ = k Sf GeCl2 f H2
− rDep ʹ′ʹ′ = f v3k SK A PGeCl2 K H PH2
− rDep
1 = f v + f v K A PGeCl2 + f v K H PH 2

1
fv =
1 + K A PGeCl2 + K H PH 2

kS K A PGeCl K H PH
rDep
!! = 2 2

( 1 + K A PGeCl + K H PH
2 2
) 3

k ! PGeCl PH
rDep
!! = 2 2

( 1 + K A PGeCl + K H PH
2 2
) 3
If we assume that the gas phase reaction

GeCl 4(g) GeCl 2(g) + Cl 2 (g)

is in equilibrium, we have
PGeCl PCl
KP = 2 2

PGeCl
4

PGeCl
PGeCl = 4
Kp
2
PCl
2

if hydrogen weakly adsorbed K H PH < 1

2

kPGeCl PH PCl2
rDep
!! = 4 2 2
3
(P Cl2
+ K PGeCl
4
)
Catalyst Deactivation
The reactions are considered in two categories: separable
kinetics and nonseparable kinetics

Separable kinetics; rate law and catalyst’s activity are

separated

Separable kinetics : −rAʹ′ = a(past history) × −rAʹ′ (fresh catalyst)

Nonseparable kinetics : −rAʹ′ = −rAʹ′ (past history, fresh catalyst)

1

− rAʹ′ ( t ) a(t)
a (t) =
− rAʹ′ ( t = 0)
0
t
 − rAʹ′ = a(t)k(T)fn(CA , CB ,...., CP )
a(t) = catalytic activity, t dependent
k(T) = specific reaction rate, T dependent
Ci = gas-phase concentration of reactants, products or contaminant

the rate of catalyst decay

da
rd = − = p[a ( t )] k d (T) h(CA , C B ,...., C P )
dt
kd is the specific decay constant
h(Ci) is the functionality of rd on the reacting species concentration
p[a(t)] is the functionality of rd on the activity
p[a(t)] can take a variety of forms

For a first order decay

p (a ) = a
For a second order decay

p (a ) = a 2
Types of Catalyst Deactivation

Deactivation by sintering (aging)

decay by sintering: pore

closure

decay by sintering: agglomeration of deposited metal

sites (T >40 % of the melting temp. of the metal)
 One of the most commonly used decay laws is second order with
respect to the present activity
2 da
rd = k d a = −
dt

a =1 @ t = 0
1 Sa 0
a(t) = Sa =
1+ kdt 1+ kdt
Sintering decay constant
⎛ E d ⎛ 1 1 ⎞ ⎞
k d = k d (T0 ) exp⎜⎜ ⎜⎜ − ⎟⎟ ⎟⎟
⎝ R ⎝ T0 T ⎠ ⎠

Algorithm for the reactor design for a fluid-solid system with decaying
catalyst
mole balance → reaction rate law → decay rate law
stoichiometry → combine and solve → numerical techniques
Example: The first order isomerization AèB is being carried out isothermally
in a batch reactor on a catalyst that is decaying as a result of aging. Derive
an equation for conversion as a function of time.
Solution
Design equation: dX
N A0 = −rAʹ′ W
dt

Reaction rate law − rAʹ′ = kʹ′a(t )CA

Decay law
1
a(t) =
1+ kdt

N A0
Stoichiometry C A = C A 0 (1 − X) = (1 − X)
V

Combining dX W
= kʹ′a ( t )(1 − X)
dt V
 dX W
= kʹ′a ( t )(1 − X)
dt V

W dX
k= kʹ′ = k a ( t )(1 − X)
V dt

1 dX dt
a(t) = =k
1+ kdt (1 − X) 1+ kdt

Solving

1
X = 1−
(1 + k d t )k / kd
Deactivation by coking or fouling

Decay by coking
the amount of coke on the surface at a time t C C = At n
Representative values of A and n for East Texas % coke = 0.47 t(min)
light gas oil yield

Relation between the activity and amount of coke on the surface is

represented with variety of forms.
1
One commonly used form is a=
1 + kCk CCp

1 1
in terms of time a= =
1 + kCk A pt np 1 + k !t m
Decay law for East Texas light gas oil being cracked at 750oF over a
catalyst is 1
a=
1 + 7.6t 1/ 2
Other forms are
− α1C C
1
a=e a=
1 + α 2 CC
Deactivation by poisoning

Poison in the feed

A +S A ⋅S
main kC A
A ⋅S B ⋅ S + C (g ) − rAʹ′ = a ( t )
reaction 1 + K A C A + K BC B
B⋅ S B+S

poisoning da
P+S P ⋅S rD = − = kʹ′d Cmp a q
reaction dt
If it is assumed that the rate is proportional to the number of the
unpoisoned sites (Ct0-CP.S) and the conc. of poison in the gas phase Cp

rP⋅S = kd (Ct 0 − CP⋅S )CP

dCt dCP⋅S
− = = rP⋅S = kd (Ct 0 − CP⋅S )CP
dt dt

Dividing by Ct0 and letting f be the fraction of the total number of sites
that have been poisoned

df
= k d (1 − f )C P
dt

da
− = a ( t )k d C P
dt
 Packed bed reactors

1.0
t1 < t2 < t3 < t4
a(t)
t1 t2 t3 t4

Wexit
W

Movement of activity front in a packed bed

1.0

0.8

0 t4 t

Exit conversion as a function of time

Poisoning by either reactants or products

Main reaction : A +S → B+S - rAʹ′ = k A CnA

Poisoning reaction : A + S → A ⋅S rd = kʹ′d CmA a q
An example where one of the reactants acts as a poison
Ru
CO + 2H 2 ⎯⎯→ CH 4 + 1 / 2O2

da
− rCO = ka ( t )CCO − = rd = kʹ′d a ( t )CCO
dt
For separable deactivation kinetics resulting from contacting a poison
at a constant conc. Cpo and no spatial variation
da
− = rd = kʹ′d a q ( t )C nP0 = k d a q
dt
For the case of first order decay
da
− = k da → a = e -k d t
dt
 Decay rate laws

Functional Decay Reaction Differential Integral Examples

Form of Activity Order Form Form
Linear 0 da a = 1 − β0 t Conversion of para-H on tungsten when poisoned
− = β0 with O2
dt
Exponential 1 da a = e −β1t Ethylene hydrogenation on Cu poisoned with CO
− = β1 a
dt Cracking of gas oil
Vinyl chloride monomer formation
Paraffin dehydrogenation on Cr.Al2O3
Hyperbolic 2 da 1 Vinyl chloride monomer formation
− = β2a 2 = 1 + β2 t
dt a Cyclohexane dehydrogenation on Pt/Al2O3
Isobutylene hydrogenation on Ni
Reciprocal power β3 + 1 da a = A 0 t − β3 Cracking of gas oil and gasoline on clay
=γ − = β 3 a n A 10/ 5
β3 dt
β4 + 1 da a = A 0 t −β4 Cyclohexane aromatization on Pt/Al2O3
=η − = β 4 a n A 10/ 5
β4 dt
 Example: Catalyst Decay in Fluidized Bed modeled as a CSTR

Gas-phase cracking reaction

gas oil (g) → products (g)

A→ B+C
Fluidized CSTR
feed stream 80% gas oil (A, contains sulfur compounds) and 20% inert (I)
Assumptions;
- the cracking reaction is first order
- the rate of catalyst decay is first-order in the present activity and first-
order in the reactant concentration
- the bed can be modeled as a well-mixed CSTR
Determine the reactant concentration, activity, and conversion as a function of
time.
Additional information
v0=5000 m3/h W=50000 kg ρb=500 kg/m3
CA0=0.8 mol/dm3 k= ρbk’=45 h-1
CT0=1.0 mol/dm3 kd= 9 dm3/mol.h

1. Mole balance on reactant

' dN A
v 0C A 0 − vC A + r W =
A
dt
N A = CA V and rA V = rA' W
dC A
v 0C A 0 − vC A + rA V = V
dt

2. Rate law − rA = kaCA

3. Decay law
da
− = k d aC A
dt

4. Stoichiometry (gas-phase, P=P0, T=T0)

FT v 0 (FA + FB + FC + FI 0 )
v = v0 =
FT0 FA 0 + FI 0

FB = FC = FA0 - FA
v FI 0 + 2FA 0 − FA
=
v0 FT0
v FA 0 FA CA v
= 1+ − = 1 + y A0 −
v0 FT0 FT0 CT0 v 0

Solving for v
 1 + y A0 CA 0
v = v0 y A0 =
1 + CA / CT0 CT0
5. Combining
v 0 (1 + y A0 ) dC A
v0CA 0 − CA -kaCA V = V
1 + CA / CT0 dt
Dividing both sides by V and using τ = V / v0

dC A CA 0 (1 + y A0 ) /(1 + CA / CT0 ) + aτk

= − CA
dt τ τ

FA0 − FA vCA ⎛ 1 + yA0 ⎞ ⎛ CA ⎞

X= = 1− = 1− ⎜ ⎟⎜C ⎟
FA0 v0CA0 ⎝ 1 + C A / CT0 ⎠ ⎝ 0⎠
A
 W 50000 3
V= = = 100 m
ρ b 500 kg/m 3

V 100 m3
τ= = 3
= 0.02 h
v 0 5000 m /h
Variation of CA, a, and X with time in a CSTR
Matching the reactor type with speed of catalyst decay

Slow decay Temperature-Time trajectories

Moderate decay Moving-Bed Reactors
Rapid decay Straight-Through Transport reactors