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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

dEsys n n
Q W FE
i i in FE
i i out
dt i1 i1
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
i1 in i1 out i1 dt i1 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
i1 dT
unsteady state reactor n

dt
with phase change: NiCpi
i1
n
Energy balance for Q WS Fi0Cpi T Ti0 H RX T rA V
i1 dT
unsteady state reactor n

dt
without phase change: NiCpi
i1
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
L17-3
Review: Unsteady State EB,
Liquid-Phase Reactions
n
Q WS Fi0 Cpi T Ti0 H RX T rA V
i1 dT

n dt
NiCpi
i1
For liquid-phase reactions, often Cp = SiCpi is so small it can be neglected
When Cp can be neglected, then:
n
NiCpi NA0Cps where Cps SiCpi is the heat capacity of the solution
i1
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
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
L17-4
Review: Nonisothermal Batch
Reactor Design
n
Q WS Fi0Cpi T Ti0 H RX T rA V
i1 dT
n
0
dt
NiCpi
i1

Q WS H RX T rA V
No flow, so:
n
NiCpi
i1
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
i1
Solve with the batch reactor design dX A
equation using an ODE solver (Polymath): A0 dt rA V
N

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
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
i1
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
i1
XA
Solve with the batch reactor design dXA
t NA0
0 rA V
equation using an ODE solver (Polymath)
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
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

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
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

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
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
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
L17-9

Adsorption Step
The adsorption of A (gas phase) on an active site S is represented by:
A A
A(g) + S AS I
-S-S-S- -S-S-S-
S: open (vacant) surface site AS: A bound to a surface site
Rate of adsorption = rate of attachment rate of detachment
rAD k APACv k ACAS 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
kA
kA
rAD k APACv k ACAS rAD k A A v
P C C A S
k A
C
rAD k A PA Cv AS Equation I
KA
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
L17-10

Site Balance
Ct: Total number of active sites per unit mass of catalyst divided by
Avogadros # (mol/g cat)
Cv: Number of vacant sites per unit mass of catalyst divided by Avogadros #

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 + CAS + CBS
We will use the site balance equation to put Cv in terms of measurable species
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
L17-11

Langmuir Isotherm Adsorption


Adsorption of carbon monoxide onto a surface: CO + S COS
CCOS kA
rAD k APCOCv k ACCOS rAD k A CO v
P C KA
K A kA
Determine the concentration of CO adsorbed on the surface at equilibrium
C
At equilibrium, rAD = 0: rAD 0 k A PCOCv COS
KA
Rearrange & CCOS
PCOCv CCOS K APCOCv
solve for CCOS KA
Put Cv in terms of Ct using the site balance; only CO can absorb on the surface:
Ct Cv CCOS Ct CCOS Cv Insert into eq for CCOS from rxn rate
CCOS K APCOCv CCOS K APCO Ct CCOS Solve for CCOS

CCOS K APCOCt K APCOCCOS CCOS K APCOCCOS K APCOCt


K APCOCt Concentration of CO adsorbed on
CCOS
1 K APCO surface vs PCO Langmuir Isotherm
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
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
CBS kS
A B AS BS rS k C
S AS 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 AS + S S + BS
A B CBSCv
I I rS k S CASCv 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 AS + B(g) CS
B A C C
I I rS k S CASPB CS Equation IIc
KS
-S-S-S -S-S-S-
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
L17-13

Desorption Step
Products are desorbed into the gas phase

CS C + S
C C PCCv kD
I rD,C kD CCS 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 CCS KCPCCv
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
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, riS=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
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
L17-15
Consider A B and assume the following mechanism is correct:
CAS
1. Adsorption: A(g) + S AS rAD k A PA Cv
K A

CBSCv
r k C
S AS vC
K S
2. Surface reaction: AS + S S + BS S

PBCv
3. Desorption: BS B + S rD kD CBS
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


Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
L17-16
Consider A B and assume the following mechanism is correct:
CAS
1. Adsorption: A(g) + S AS rAD k A PA Cv
K A

CBSCv
r k C
S AS vC
K S
2. Surface reaction: AS + S S + BS S

PBCv
3. Desorption: BS B + S rD kD CBS
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 CASCv BS v
KS
1. CAS, Cv, and CBS 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 CAS and CBS from their respective rate
equations and the site balance to eliminate CV
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
L17-17
Consider A B and assume the following mechanism is correct:
1. Adsorption 2. Surface reaction 3. Desorption
C CBSCv PC
rAD k A PA Cv AS rS k S CASCv rD kD CBS B v
KA K S KD

Derive the rate equation for when CBSCv


r 'A rS k S CASCv
the surface reaction is rate limiting K S

Use rAD/kA =0 and rD/kD =0 to eliminate CAS and CBS from their respective
rate equations and the site balance to eliminate CV
Use rAD/kA =0 & rAD CAS
rAD k A PA Cv
equation to solve for CAS: K D
rAD CAS CAS
0 PA Cv PA Cv CAS K APACv
kA KA KA

Use rD/kD =0 & rD equation PC


rD kD CBS B v
to solve for CBS: KD
r PC PC
D 0 CBS B v B v CBS
kD KD KD
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
L17-18
Consider A B and assume the following mechanism is correct:
1. Adsorption 2. Surface reaction 3. Desorption
C C C PC
rAD k A PA Cv AS rS k S CASCv BS v rD kD CBS B v
KA KS KD
Derive the rate equation for when the surface reaction is rate limiting
CBSCv
r 'A rS k S CASCv
K S
PBCv
rAD/kA =0 & rD/kD =0 CAS K APACv CBS
KD
Use site balance to solve for CV: Ct Cv CAS CBS

Cv Ct CAS CBS Make substitutions for CAS & CBS, 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
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
L17-19
Consider A B and assume the following mechanism is correct:
1. Adsorption 2. Surface reaction 3. Desorption
C CBSCv PC
rAD k A PA Cv AS rS k S CASCv rD kD CBS B v
KA K S KD

Derive the rate equation for when the surface reaction is rate limiting
PBCv Ct
CAS K APACv CBS C v
KD 1 K APA PB KD

CBSCv
r 'A rS k S CASCv Substitute in CAS, CBS, &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
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
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)

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
L17-21
Consider A B and assume the following mechanism is correct:
1. Adsorption 2. Surface reaction 3. Desorption
C CBSCv PC
rAD k A PA Cv AS rS k S CASCv rD kD CBS B v
KA K S KD

Now derive the rate equation for C


r ' A rAD k A PA Cv AS
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:
CBS Cv r C C
rS k S CAS Cv S 0 CAS Cv BS v
K S kS KS
C C C Need to put CBS in
BS v CAS Cv BS CAS 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 CBS B v 0 CBS B v CBS
KD kD KD KD

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
L17-22
Consider A B and assume the following mechanism is correct:
1. Adsorption 2. Surface reaction 3. Desorption
C CBSCv PBCv
rAD k A PA Cv AS rS k S CASCv rD k C
D BS
KA K S K D
Now derive the rate equation for C
r 'A rAD k A PA Cv AS
when adsorption is rate limiting: KA
Conc of vacant and occupied sites must be eliminated from the rate eq
CBS PB Cv
CAS CBS Solve for Cv using the site balance equation
KS KD
Make substitutions C C CBS PB Cv
Ct Cv CAS CBS t v
for CAS & CBS 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 CBS CAS
expression PB PB CBS into PB PB
KD 1 CAS: K SK D 1
for CBS: K K
S D K D K K
S D K D
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
L17-23
Consider A B and assume the following mechanism is correct:
1. Adsorption 2. Surface reaction 3. Desorption
C C C PC
rAD k A PA Cv AS rS k S CASCv BS v rD kD CBS B v
KA KS KD
Now derive the rate equation for CAS
when adsorption is rate limiting: r ' A rAD k A A v
P C
K A
PB Ct PB Ct Ct
CAS CBS 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 CAS 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
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
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/atm2kg catmin
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
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
L17-25
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/atm 2kg catmin
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
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
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
L17-26
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/atm2kg catmin


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
dW FA0 1 K tolPtol KBPB
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 9.8 105 kg1W Wfinal 10197.7kg
Plug equation in boxes into Polymath to solve
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
L17-27

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
L17-28

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
L17-29

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.