L17 Basic Catalysis and Mechanisms

L17-1
Review: Unsteady State

Nonisothermal Reactor Design
Goal: develop EB for unsteady state reactor Q
Fin Fout
An open system (for example, CSTR)
Hin Hout
W
dEsys n n
 Q  W   FE
i i in   FE
i i out
dt i1 i1
Rate of rate of heat Rate of work Rate of energy Rate of energy
accumulation flow from done by added to leaving system
of energy in
= surroundings
- system on
+ system by
- by mass flow
system to system surroundings mass flow in out
dEsys dEsys
 0 steady state  0 unsteady state
dt dt
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
L17-2
Review: Simplified EB for Well-Mixed
Reactors
n n n dHi n dNi d
Q  WS   FH
i i   FH
i i   Ni   Hi  PV 
i1 in i1 out i1 dt i1 dt dt
Total Energy Balance for unsteady state

Made following Constant PV variation
substitutions & dHi  Cpi dT dNi
 Fi0  F i  irA V d
solved for dT/dt: dt dt dt PV   0
dt
n
Energy balance for Q  WS   Fi0 Hi  Hi0   H RX  T rA V 
i1 dT
unsteady state reactor n

dt
with phase change:  NiCpi
i1
n
Energy balance for Q  WS   Fi0Cpi  T  Ti0   H RX  T rA V 
i1 dT
unsteady state reactor n

dt
without phase change:  NiCpi
i1
L17-3
Review: Unsteady State EB,
Liquid-Phase Reactions
n
Q  WS   Fi0 Cpi  T  Ti0   H RX  T rA V 
i1 dT

n dt
 NiCpi
i1
For liquid-phase reactions, often Cp = SiCpi is so small it can be neglected
When Cp can be neglected, then:
n
 NiCpi  NA0Cps where Cps  SiCpi is the heat capacity of the solution
i1
If the feed is well-mixed, it is convenient to use:
SFi0Cpi  FA0Cps
Plug these equations Q  WS  FA 0 Cps  T  Ti0   H RX  T  rA V  dT


& Ti0 = T0 into the EB: NA0 Cps dt
This equation for the EB is simultaneously solved with the mass

balance (design eq) for unsteady state, nonisothermal reactor design
L17-4
Review: Nonisothermal Batch
Reactor Design
n
Q  WS   Fi0Cpi  T  Ti0   H RX  T rA V 
i1 dT
n
0 
dt
 NiCpi
i1
Q  WS  H RX  T  rA V 
No flow, so: 
n
 NiCpi
i1
Put the energy balance N  N     X  where   Ni0 &  C  C
i A0 i i A i i pi P
in terms of conversion: NA 0
Q  WS  H RX  T  rA V  dT
 
n  dt
NA0   iCpi  Cp X A 
i1 
Solve with the batch reactor design dX A
equation using an ODE solver (Polymath): A0 dt  rA V
N
L17-5
Review: Adiabatic Nonisothermal
Batch Reactor Design
0 0
For negligible Q  WS  H RX  T rA V  dT Substitute:  iCpi  Cps
stirring work:  
 n  dt Rearrange
NA0   iCpi  Cp XA 
i1 
XA dX A T dT
   
C
X 0 pS A0
 C X
p A T H RX  TR   Cp  T  TR 
0
Integrate &  X  CpS  T  T0  CpS  T  T0 

 XA 
solve for XA: A

 H RX  TR   Cp  T  TR  HRX  T  
 H RX  T0   X A  H RX  T0   X A
Solve for T: T  T0     T  T0  n 
Cps  X A Cp
 iCpi  X A Cp
i1
XA
Solve with the batch reactor design dXA
t  NA0 
0 rA V
equation using an ODE solver (Polymath)
L17-6
L17 Basic Catalysis & Reaction

Mechanisms
• Though we have discussed the use of catalyst in a PBR, we have not
discussed the process of catalysis itself
• An understanding of catalysis, the mechanisms, and catalytic reactor design
are the subject of the next few lectures
• Catalyst properties
• Steps involved in a catalytic reaction
• Development of a rate law using steps in catalytic reaction
• Different types of catalyst mechanisms
• Design of catalytic reactors
L17-7
Catalysts & Catalysis

• ~1/3 of the GNP of materials produced in the US involve a catalytic process
• A Catalyst is a substance that speeds up the rate of reaction but is not
changed by the reaction
• A catalyst lowers the energy barrier by promoting a different molecular
pathway (mechanism) for the reaction
• Homogeneous catalysis: catalyst is in solution with at least 1 reactant
• Heterogeneous catalysis: more than 1 phase, usually solid and fluid or
solid and gas is present. Reaction occurs at solid/liquid or gas interface.
Many catalyst are porous (high surface area)
catalyst
L17-8
Steps in a Heterogeneous Catalytic
Reaction
7. Diffusion of B
from external
1. Mass transfer
surface to the bulk
of A to surface
fluid (external
diffusion)
2. Diffusion of A
from pore mouth to 6. Diffusion of B
internal catalytic 3. Adsorption of from pellet interior
surface A onto catalytic to pore mouth
surface
5. Desorption of product
B from surface
4. Reaction on surface
Ch 10 assumes steps 1,2,6 & 7 are fast, so only steps 3, 4, and 5 need to be considered
L17-9
Adsorption Step
The adsorption of A (gas phase) on an active site S is represented by:
A A
A(g) + S ⇌ A·S I
-S-S-S- -S-S-S-
S: open (vacant) surface site A·S: A bound to a surface site
Rate of adsorption = rate of attachment – rate of detachment
rAD  k APACv  k ACAS Conc of sites occupied by A
partial pressure of A Molar conc of vacant sites on surface
• Rate is proportional to # of collisions with surface, which is a function of PA
• Rate is proportional to # of vacant (active) sites, Cv, on the surface
• Active site: site on surface that can form a strong bond with adsorbed species
k
In terms of the adsorption equilibrium constant KA where K A  A
kA
 kA 
rAD  k APACv  k ACAS  rAD  k A A v
P C  C A S 
 k A 
 C 
 rAD  k A  PA Cv  AS  Equation I
 KA 
L17-10
Site Balance
Ct: Total number of active sites per unit mass of catalyst divided by
Avogadro’s # (mol/g cat)
Cv: Number of vacant sites per unit mass of catalyst divided by Avogadro’s #
Active site Active site

Vacant
occupied by A occupied by B
active site
A B
Surface
Cv is not measurable, but the total number of sites Ct can be measured
In the absence of catalyst deactivation, assume the total number of

active sites remains constant:
Site balance:
Ct = Cv + CA·S + CB·S
We will use the site balance equation to put Cv in terms of measurable species
L17-11
Langmuir Isotherm Adsorption

Adsorption of carbon monoxide onto a surface: CO + S ⇌ CO·S
 CCOS  kA
rAD  k APCOCv  k ACCOS  rAD  k A  CO v
P C   KA 
 K A  kA
Determine the concentration of CO adsorbed on the surface at equilibrium
 C 
At equilibrium, rAD = 0: rAD  0  k A  PCOCv  COS 
 KA 
Rearrange & CCOS
  PCOCv  CCOS  K APCOCv
solve for CCO·S KA
Put Cv in terms of Ct using the site balance; only CO can absorb on the surface:
Ct  Cv  CCOS  Ct  CCOS  Cv Insert into eq for CCO·S from rxn rate
CCOS  K APCOCv  CCOS  K APCO  Ct  CCOS  Solve for CCO·S
 CCOS  K APCOCt  K APCOCCOS  CCOS  K APCOCCOS  K APCOCt

K APCOCt Concentration of CO adsorbed on
 CCOS 
1  K APCO surface vs PCO→ Langmuir Isotherm
L17-12
Surface Reaction Step

After the molecule is adsorbed onto the surface, it can react by a few different
mechanisms
1. Singe site mechanism: Only the site to which the reactant is absorbed is
involved in the reaction
 CBS  kS
A B A·S ⇌ B·S rS  k C
S  AS   where K S 
I I  K S  k S
⇌
-S- -S- Equation IIa
2. Dual site mechanism: Adsorbed reactant interacts with another vacant
site to form the product A·S + S ⇌ S + B·S
A B  CBSCv 
I I rS  k S CASCv   Equation IIb
⇌  K S 
-S-S-S -S-S-S-
3. Eley-Rideal mechanism: reaction between adsorbed reactant and a
molecule in the gas phase A·S + B(g) ⇌ C·S
B A C  C 
I I rS  k S CASPB  CS  Equation IIc
⇌  KS 
-S-S-S -S-S-S-
L17-13
Desorption Step
Products are desorbed into the gas phase
C·S ⇌ C + S
C C  PCCv  kD
I ⇌ rD,C  kD CCS   where KD,C 
 K D,C  k D
-S-S-S- -S-S-S-
Equation III
Note that the desorption of C is the reverse of the adsorption of C
rD,C  rAD,C
Also the desorption equilibrium constant KD,C is the reciprocal of the
adsorption equilibrium constant KC
1
KD,C 
KC
Substituting 1/KC for KD,C in the rate equation for product desorption gives:
rD,C  kD CCS  KCPCCv 
L17-14
Derive a Rate Law for Catalytic Rxn

• Postulate catalytic mechanism, and then derive the rate law for that
mechanism
• Assume pseudo-steady state hypothesis (rate of adsorption = rate of
surface reaction = rate of desorption)
• No accumulation of species on the surface or near interface
• Each species adsorbed on the surface is a reactive intermediate
• Net rate of formation of species i adsorbed on the surface is 0, ri·S=0
• One step is usually rate-limiting
• If the rate-limiting step could be sped up, the entire rxn would be faster
• Although reactions involve all 7 steps, (for chapter 10) only adsorption,
surface reaction, or desorption will be rate limiting
• The surface reaction step is rate limiting ~70% of the time!
• Steps to derive the rate law
• Select among types of adsorption, surface reaction, and desorption
• Write rate laws for each individual step, assuming all are reversible
• Postulate which step is rate limiting
• Use non-rate-limiting steps to eliminate the surface concentration
terms that cannot be measured
L17-15
Consider A ⇌ B and assume the following mechanism is correct:
 CAS 
1. Adsorption: A(g) + S ⇌ A·S rAD  k A  PA Cv  
 K A 
 CBSCv 
r  k C
S  AS vC 
K S 
2. Surface reaction: A·S + S ⇌ S + B·S S

 PBCv 
3. Desorption: B·S ⇌ B + S rD  kD CBS  
 K D 
We need to select one of these 3 reactions as the rate limiting step, then
derive the corresponding rate equation, and see if this rate eq matches
experimental data. Which step is the most logical to start with?
a) Adsorption
b) Surface reaction
c) Desorption
d) None of the above
e) Any of these would be “logical” - they all have equal probability of being
the rate limiting step
The surface reaction step as is rate limiting ~70% of the time

L17-16
 CAS 
1. Adsorption: A(g) + S ⇌ A·S rAD  k A  PA Cv  
 K A 
 CBSCv 
r  k C
S  AS vC 
K S 
2. Surface reaction: A·S + S ⇌ S + B·S S

 PBCv 
3. Desorption: B·S ⇌ B + S rD  kD CBS  
 K D 
Derive the rate equation for when the surface reaction is rate limiting (true
~70% of the time)
 C C 
r 'A  rS  k S CASCv  BS v 
 KS 
1. CA·S, Cv, and CB·S need to be expressed in terms of measurable quantities
• For surface reaction-limited mechanisms, kS is small and kA and kD are
relatively large
• Therefore rAD/kA and rD/kD are very small, and can be approximated as
equal to zero
2. Use this relationship to eliminate CA·S and CB·S from their respective rate
equations and the site balance to eliminate CV
L17-17
1. Adsorption 2. Surface reaction 3. Desorption
 C   CBSCv   PC 
rAD  k A  PA Cv  AS  rS  k S CASCv   rD  kD CBS  B v 
 KA   K S   KD 
Derive the rate equation for when  CBSCv 

r 'A  rS  k S CASCv  
the surface reaction is rate limiting  K S 
Use rAD/kA =0 and rD/kD =0 to eliminate CA·S and CB·S from their respective
rate equations and the site balance to eliminate CV
Use rAD/kA =0 & rAD  CAS 
rAD  k A PA Cv  
equation to solve for CA·S:  K D 
rAD CAS CAS
  0  PA Cv    PA Cv  CAS  K APACv
kA KA KA
Use rD/kD =0 & rD equation  PC 

rD  kD CBS  B v 
to solve for CB·S:  KD 
r PC PC
 D  0  CBS  B v  B v  CBS
kD KD KD
L17-18
 C   C C   PC 
rAD  k A  PA Cv  AS  rS  k S CASCv  BS v  rD  kD CBS  B v 
 KA   KS   KD 
Derive the rate equation for when the surface reaction is rate limiting
 CBSCv 
r 'A  rS  k S CASCv  
 K S 
PBCv
rAD/kA =0 & rD/kD =0 CAS  K APACv  CBS
KD
Use site balance to solve for CV: Ct  Cv  CAS  CBS
 Cv  Ct  CAS  CBS Make substitutions for CA·S & CB·S, solve for Cv
PBCv PC
 Cv  Ct  K APA Cv   Cv  K APA Cv  B v  Ct
KD KD
 PB  Ct
 Cv  1  K APA    Ct  Cv 
 KD  PB
1  K APA 
KD
L17-19
 C   CBSCv   PC 
 KA   K S   KD 
Derive the rate equation for when the surface reaction is rate limiting
PBCv Ct
CAS  K APACv  CBS C v 
KD 1  K APA  PB KD
 CBSCv 
r 'A  rS  k S CASCv   Substitute in CA·S, CB·S, &Cv
 KS 
  Ct 
2
PB  Ct  
2
 r 'A  rS  k S K APA      
  1  K APA  PB KD  K SKD  1  K APA  PB KD  
2
 Ct   PB 
 r 'A  rS  k S  
  A A K K 
K P
 1  K P
A A  PB D 
K S D
This is the rate equation in terms of measurable species and rate

constants for the mechanism given in the problem statement
L17-20
Evaluating a Catalytic Reaction
Mechanism
• Collect experimental data from test reactor
• See if rate law is consistent with data
• If not, then try other surface mechanism (i.e., dual-site
adsorption or Eley-Rideal) or choose a different rate-limiting
step (adsorption or desorption)
L17-21
 C   CBSCv   PC 
 KA   K S   KD 
Now derive the rate equation for  C 

r ' A  rAD  k A  PA Cv  AS 
when adsorption is rate limiting:  KA 
Conc of vacant and occupied sites must be eliminated from the rate equation
If adsorption is rate limiting, kS>>kAD, so rS/kS can be approximated as 0. Then:
 CBS Cv  r C C
rS  k S CAS Cv    S  0  CAS Cv  BS v
 K S  kS KS
C C C Need to put CB·S in
 BS v  CAS Cv  BS  CAS measureable terms
KS KS
If adsorption is rate limiting, kD>>kAD, so rD/kD can be approximated as 0. Then:
 P C  rD P C PB Cv
rD  kD CBS  B v    0  CBS  B v   CBS
 KD  kD KD KD
L17-22
 C   CBSCv   PBCv 
rAD  k A  PA Cv  AS  rS  k S CASCv   rD  k C
D  BS  
 KA   K S   K D 
Now derive the rate equation for  C 
r 'A  rAD  k A  PA Cv  AS 
when adsorption is rate limiting:  KA 
Conc of vacant and occupied sites must be eliminated from the rate eq
CBS PB Cv
 CAS  CBS Solve for Cv using the site balance equation
KS KD
Make substitutions  C  C  CBS  PB Cv
Ct  Cv  CAS  CBS t v
for CA·S & CB·S KS KD
 PB   Ct
 Ct  Cv 
PB Cv PB Cv
  Ct  Cv  1 
PB
  Cv
 PB PB
K SK D KD  K K
S D K D 1  
K SKD KD
Substitute
PB Ct Substitute PB Ct
Cv into the CBS  CAS 
expression  PB PB  CB·S into  PB PB 
KD  1    CA·S: K SK D  1   
for CB·S:  K K
S D K D  K K
S D K D
L17-23
 C   C C   PC 
rAD  k A  PA Cv  AS  rS  k S CASCv  BS v  rD  kD CBS  B v 
 KA   KS   KD 
Now derive the rate equation for  CAS 
when adsorption is rate limiting: r ' A  rAD  k A A v
P C  
 K A 
PB Ct PB Ct Ct
CAS  CBS   Cv
 P P   P P  P P
K SKD  1  B  B  KD  1  B  B  1  B  B
 K SKD KD   K SKD KD  K SKD KD
 
Use these eqs  
 P C P C 
to replace CA·S  rAD  k A  
A t B t

PB

PB  PB PB  
& Cv in rAD: 1
 K K K A K SK D  1   
 S D K D  K K
S D K D 
k  
 
Factor  r  k C  P P 
A  B
out Ct: AD A t
 PB PB  PB PB  
1 
 K K  K A K SKD  1   
 S D K D  K K
S D K D 
L17-24
The gas phase hydromethylation of toluene: C6H5CH3 + H2 → C6H6 + CH4 is
to be carried out in a PBR. Plot the conversion and the partial pressures of
toluene, hydrogen and benzene as a function of catalyst weight.
FA0 = 50 mol toluene/min, P0 = 40 atm, T= 913K, a= 9.8 x 10-5 kg-1, Feed is
30% toluene (species tol), 45% hydrogen (species H) and 25% inerts (I)
kPHPtol k= 0.00087 mol/atm2·kg cat·min
Rate law:rT' 
1  K tolPtol  KBPB KB = 1.39 atm-1 Ktol= 1.038 atm-1
'
dXtol rtol  '

kPHPtol
Mole balance:  Rate law: rT
dW FA0 1  K tolPtol  KBPB
 1  Xtol  P   T0   1  Xtol  P 
Stoichiometry:Ctol  Ctol,0      CT  CT0  1   X  P 
 1   Xtol  P0   T   tol  0 
Need concentrations in terms of pressure 1
Ptol Ptol,0
Ptol Vtol  ntolRT  Ptol  C tolRT   Ctol  Ctol,0
RT RT
Total P
Ptol Ptol,0  1  Xtol  P   1  Xtol  P
      P  Ptol,0   y where y=  
RT RT  1   Xtol  P0  Total P tol
at inlet  1   Xtol   P0 
Ftol,0 0.3
  y tol,0   1  1  1  1  0 y Tol,0    0.3    0.3  0   0
FT0 1
L17-25
kPHPtol k= 0.00087 mol/atm 2·kg cat·min
Rate law:rT' 
1  K tolPtol  KBPB KB = 1.39 atm-1 Ktol= 1.038 atm-1
'
dXtol rtol kPHPtol
Mole balance:  Rate law:rT' 
 0
P y tol,0  0.3
Stoichiometry:  Ptol  Ptol,0 1  Xtol  y where y=  
 P0   0
Ptol,0  y tol,0P0  Ptol,0  0.3  40atm  12atm
Use the Ergun equation to evaluate y:
Isothermal rxn & =0, so: y  1  a W 1 2  Ptol  Ptol,0 1  Xtol  1  a W 
12
Need an equation for PB & PH

 
FH2 0.45
PB  Ptol,0  Xtol  y PH2  Ptol,0 H2  Xtol y H2    1.5
Ftol 0.3
L17-26

kPHPtol k= 0.00087 mol/atm2·kg cat·min

Rate law:rT'
 K = 1.39 atm -1 K = 1.038 atm-1
1  K tolPtol  KBPB B tol
dXtol rtol '

kPHPtol  0
Mole balance:  '
Rate law:rT  y tol,0  0.3
 0
Ptol  Ptol,0 1  Xtol  1  a W  Ptol,0  12atm
12
Stoichiometry:
PH2  Ptol,0 1.5  Xtol  y y  1  a W 
12
PB  Ptol,0  Xtol  y
  
Finally, calculate the kg P 1atm 5 1
12
cat where P0 = 1atm:  1  a W 12
  1  9.8  10 kg W
P0 40atm

 0.000625  1  9.8  105 kg1W   Wfinal  10197.7kg
Plug equation in boxes into Polymath to solve
L17-27
L17-28
L17-29

L17 Basic Catalysis and Mechanisms

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L17 Basic Catalysis and Mechanisms

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L17-1

Review: Unsteady State

Total Energy Balance for unsteady state

Plug these equations Q  WS  FA 0 Cps  T  Ti0   H RX  T  rA V  dT

This equation for the EB is simultaneously solved with the mass

Integrate &  X  CpS  T  T0  CpS  T  T0 

L17 Basic Catalysis & Reaction

Catalysts & Catalysis

Many catalyst are porous (high surface area)

Active site Active site

Cv is not measurable, but the total number of sites Ct can be measured

In the absence of catalyst deactivation, assume the total number of

Langmuir Isotherm Adsorption

 CCOS  K APCOCt  K APCOCCOS  CCOS  K APCOCCOS  K APCOCt

Surface Reaction Step

Derive a Rate Law for Catalytic Rxn

The surface reaction step as is rate limiting ~70% of the time

Derive the rate equation for when  CBSCv 

Use rD/kD =0 & rD equation  PC 

This is the rate equation in terms of measurable species and rate

Now derive the rate equation for  C 

Need an equation for PB & PH

FA0 = 50 mol toluene/min, P0 = 40 atm, T= 913K, a= 9.8 x 10-5 kg-1, Feed is

kPHPtol k= 0.00087 mol/atm2·kg cat·min

dXtol rtol '

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