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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
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
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
L17-7
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 #
Surface
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
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
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
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
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
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
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
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.