Multiple Steady States in CSTR Review

L16-1
Review: Multiple Steady States in CSTR

XA,EB
XA,MB
Plot of XA,EB vs T and XA,MB vs T

Intersections are the T and XA that satisfy both mass balance (MB) &
energy balance (EB) equations
Each intersection is a steady state (temperature & conversion)
Multiple sets of conditions are possible for the same reaction in the same
reactor with the same inlet conditions!
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
L16-2
Review: Heat Removal Term R(T) & T0

Heat removed: R(T)
Heat generated G(T)
rA V
FA0
Cp0 1 T TC HRXo
R(T) line has slope of CP0(1+)
UA Cp0FA0 Tc Ta T0
1
R(T)
=0
R(T)
Increase
Increase T0
T
When T0 increases, slope stays

same & line shifts to right
For Ta < T0
Ta
T0
When increases from lowering

FA0 or increasing heat exchange,
slope and x-intercept moves
Ta<T0: x-intercept shifts left as
Ta>T0: x-intercept shifts right as
=0, then TC=T0 =, then TC=Ta
L16-3
Review: CSTR Stability

G(T)
Tc
R(T)
Ta T0 UA Cp0FA0
1
R(T) > G(T) T

falls to T=SS1
G(T) > R(T)

T rises to
T=SS1
G(T) > R(T)

T rises to
T=SS3
2
Heat removed: R(T)
R(T) > G(T)

T falls to T=SS3
Heat generated G(T)
rA V
FA0
Cp0 1 T TC HRXo
Magnitude of G(T) to R(T) curve determines if reactor T will rise or fall

G(T) = R(T) intersection, equal rate of heat generation & removal, no
change in T
G(T) > R(T) (G(T) line above R(T) on graph): rate of heat generation > heat
removal, so reactor heats up until a steady state is reached
R(T) > G(T) (R(T) line above G(T) on graph): rate of heat generation < heat
removal, so reactor cools off until a steady state is reached
L16: Unsteady State Nonisothermal

Reactor Design
Goal: develop EB for unsteady state reactor
An open system (for example, CSTR)
L16-4
Fin
Fout
Hin
Hout
W
dEsys
dt
&
Q
Rate of
rate of heat
accumulation
flow from
=
of energy in
surroundings
system
to system
dEsys
dt
&
W
FE
i i
i1
in
Rate of work
Rate of energy
done by
added to
+
system on
system by
surroundings
mass flow in
0 steady state
dEsys
dt
FE
i i
i1
out
Rate of energy
leaving system
by mass flow
out
0 unsteady state
L16-5
Change in System Energy with Time

dEsys
dt
& W
& FE
Q
i i
i1
in
FE
i i
i1
out
n
Energy of system is the sum of products of each species E
sys NiEi
specific energy Ei & the moles of each species:
i1
n
Ei Ui & Ui Hi PVi so: Esys Ni Hi PVi Differentiate wrt time

i1
dEsys
dt
dEsys n dHi n dNi d n
d n
P
N
V
i
i
Ni Hi PVi
i i
dt
dt
dt
dt
dt i1
i1
i1
i1
dEsys
dt
Total V
n
dHi n dNi d
Ni
Hi
PV
dt i1 dt dt
i1
n
& W
& FH
Q
S
i i
i1
in
FH
i i
i1
For well-mixed reactor

with constant PV- variation
out
dHi n dNi
Ni
Hi
dt i1 dt
i1
Total Energy Balance for unsteady state, constant PV

L16-6
Well-Mixed Reactors, Constant PV

Total Energy Balance for unsteady state
n
n
n
dHi n dNi d
&
&
Q WS FH
Ni
Hi
PV = 0
i i FH
i i
dt i1 dt dt
i1
in i1
out i1
Special case: well-mixed reactors (e.g., batch, CSTR or semibatch) with
constant PV- variation in total P or V can be neglected
n
& W
& FH
Q
S
i i
i1
in
FH
i i
i1
out
dHi n dNi
Ni
Hi
dt i1 dt
i1
Total Energy Balance for unsteady state, constant PV

T
dHi
dHi
dT
o
Evaluate
recalling that Hi H RX TR CpidT so
Cpi
dt
dt
dt
T
R
& W
& FH
Q
S
i i
i1
in
FH
i i
i1
out
dT n dNi
NiCpi
Hi
dt i1 dt
i1
Need to put dNi/dt into terms that can be measured

L16-7
EB for Well-Mixed Reactors, PV=0

n
& W
& FH
Q
S
i i
i1
in
FH
i i
i1
out
dT n dNi
NiCpi
Hi
dt i1 dt
i1
From the mass balance:

Accumulation = In - Out + Gen
dNi
dNi
Fi0 F i irA V Substitute
Fi0 F i i rA V
d
t
dt
n
n
n
dT n
&
&
Q WS FH
NiCpi
Hi Fi0 F i irA V
i i FH
i i
dt i1
i1
i1
in i1
out
n
& W
& F H FH N C dT H F H F H r V
Q
S
i0 i0
i i
i pi
i i0
i i
i i
A
dt
i1
i1
i1
i1
i1
i1
Add FiHi to both sides of equation:
n
n
n
dT n
&
&
Q WS Fi0Hi0 NiCpi
HiFi0 iHi rA V
dt i1
i1
i1
i1
Substitute iHi =HRX(T):
n
HRX(T)
& W
& F H N C dT H F Ho T r V
Q
S
i0 i0
i pi
i i0
RX
A
dt
i1
i1
i1
L16-8
Simplified EB for Well-Mixed Reactors

n
dT
o
&
&
Q
F
H
N
C
HF
Solve for dT/dt:

S
i0 i0
i pi
i i0 H RX T rA V
dt i1
i1
i1
Bring Fi0Hi and HRX(T) terms to other side of equation:
n
dT
o
&
&
Q WS Fi0Hi0 HF
i i0 H RX T rA V NiCpi
dt
i1
i1
i1
Factor Fi0Hi0 and Fi0Hi terms and divide by NiCpi :
n
Energy balance for

unsteady state reactor
with phase change:
& W
& F H H Ho T r V
Q
S
i0
i
i0
RX
A
i1
NiCpi
dT
dt
i1
n
& W
& F C T T Ho T r V
Q
S
i0 pi
i0
RX
A
Energy balance for
dT
i1
unsteady state reactor

n
dt
NiCpi
without phase change:
i1
L16-9
Unsteady State EB, Liquid-Phase Rxns

n
& W
& F C T T Ho T r V
Q
S
i0 pi
i0
RX
A
i1
NiCpi
dT
dt
i1
For liquid-phase reactions, often Cp = iCpi is so small it can be neglected

When Cp can be neglected, then:
n
NiCpi NA0 Cps where Cps iCpi is the heat capacity of the solution
i1
If the feed is well-mixed, it is convenient to use:

Fi0 Cpi FA0Cps
Plug these equations and Ti0 = T0 into the EB gives:
& W
& F C T T Ho T r V
Q
S
A 0 ps
i0
RX
A
NA0 Cps
dT
dt
This equation for the EB is simultaneously solved with the mass

balance (design eq) for unsteady state, nonisothermal reactor design
L16-10
Nonisothermal Batch Reactor Design

n
& W
& F C T T Ho T r V
Q
S
i0 pi
i0
RX
A
i1
NiCpi
dT
dt
i1
No flow, so:
& W
& Ho T r V
Q
S
RX
A
n
NiCpi
dT
dt
i1
Put the energy balance

in terms of XA:
Ni NA0 i i X A
Ni0
where i
& iCpi CP
NA 0
& W
& Ho T r V
Q
S
RX
A
NA0 iCpi Cp X A
i1
dT
dt
Solve with the batch reactor design equation using an ODE solver (Polymath)
dX A
NA0
rA V
dt
Adiabatic Nonisothermal Batch

Reactor Design
L16-11
0 0
& W
& Ho T r V dT
Q
S
RX
A
n
dt
NA0 iCpi Cp X A
i1
& 0
& =0 & Q
In the case of no stirring work and adiabatic operation, W
S
HoRX T rA V
NA0 iCpi Cp X A
i1
o
dT Substitute:
H
dT
RX T rA V
dt iCpi Cps
dt
NA0 Cps Cp X A
dT
Rearrange:
dt
dX A
o
o
H
T
H
T
C
T
T
an
d
-N
rA V
Substitute:
RX
RX R
p
R
A0
dt
dX A
dT
HoRX TR Cp T TR NA 0
NA0 CpS Cp X A
dt
dt
dX A
dT
HoRX TR Cp T TR
CpS Cp X A
dt
dt
HoRX
T rA V NA0 CpS Cp X A
Solve for how XA Ho T C T T dX A C C X dTL16-12

RX R
p
R
p A
pS
dt
dt
changes with T
HoRX TR Cp T TR dX A CpS Cp X A dT
Get like terms together:
XA
X A0 0 CpS
Integrate & solve for XA:

XA
T
dX A
dT

Cp X A T HoRX TR Cp T TR
0
CpS T T0
HoRX
TR Cp T TR
XA
CpS T T0
HRX T
Solving for T:
HoRX T0 X A
HoRX T 0 X A
T T0
T T0
n
Cps X A Cp
iCpi X A Cp
i1
Heat capacity of soln (calculate Cps if not given)
Solve with the batch reactor design equation using an ODE solver (Polymath)
XA
t NA0
dX A
rA V
L16-13
A 1st order, liquid-phase, exothermic reaction AB is run in a batch reactor.

The reactor is well-insulated, so no heat is lost to the surroundings. To control
the temperature, an inert liquid C is added to the reaction. The flow rate of C
is adjusted to keep T constant at 100 F. What is the flow rate of C after 2h?
TC0 = 80 F V0= 50 ft3 HRX=-25000 Btu/lb mol
k(100 F)= 1.2 x 10-4 s-1
Cp, (all components)= 0.5 Btu/lb mol F
CA0= 0.5 lb mol/ft3
1. Solve design eq for comp as function of t
2. Solve EB for FC0 using that info & T=100 F
This is essentially a semi-batch reactor since only C is fed into the reactor
dX A
dNA
rA V would complicate
Design eq:
rA V Note, using NA0
d
t
dt
the calculation because V depends on t
Rate eq: -rA = kCA
dNA
dNA
kC
V
kNA Rearrange and integrate for NA

Combine:
A
dt
dt
NA
dNA t
ln

kdt
kt NA NA0 exp kt
NA0
NA0 NA
0
NA
L16-14

Use EB to find how the flow rate of C depends on the rxn (solve EB for F C0)
0 0 n
& W
& F C T T Ho T r V
Q
S
i0 pi
i0
RX
A
dT
i1
n
dt
NiCpi
0
i1
Fi0Cpi T Ti0 HoRX

i1
F
C
T
T
r
V
A
i0 pi
i0
RX T rA V
i1
F
C
T
C is the only species that flows, so:

C0 pC
i0
RX T rA V
rAV = -kCAV = -kNA where NA NA0 exp kt
FC0 CpC T Ti0 HoRX T kNA0 ekt

Isolate FC0: FC0
HoRX T kNA0 e kt
CpC T Ti0
L16-15

TC0 = 80 F V0= 50 ft3 HRX=-25000 Btu/lb mol
k(100 F)= 1.2 x 10-4 s-1
Cp, (all components)= 0.5 Btu/lb mol F
CA0= 0.5 lb mol/ft3
FC0
HoRX T kNA 0 ekt

CpC T Ti0
NA0 CA0 V0 0.5
At 2h (7200s):
FC0
lb mol
ft 3
1.210
Btu
1
1.2 10 s 25 lb mol e
25,000
lb mol
Btu
0.5
100oF 80oF
lb mol F
FC0 3.16
50ft 3 25 lb mol
4 s1 7200s
lb mol
s
L16-16
Instead of feeding coolant to the reactor, a solvent with a low boiling point is
added (component D). The solvent has a heat of vaporization of 1000 Btu/lb
mol, and initially 25 lb mol of A are placed in the tank. The reactor is wellinsulated. What is the rate of solvent evaporation after 2 h if T is constant at
100 F?Additional info: k(100 F)= 1.2 x 10-4 s-1 HRX=-25000 Btu/lb mol
Still a semibatch reactor, where D is removed from the reactor
Use EB that accounts for a phase change:
0 0 n
&
& F H H Ho T r V
QW
Q =0
S
i0
i0
i
RX
A
dT
i
S=0
n
dt
NiCpi
0
i1
Clicker Question: Does dT/dt = 0?

a) Yes
b) No
L16-17
Instead of feeding coolant to the reactor, a solvent with a low boiling point is
added (component D). The solvent has a heat of vaporization of 1000 Btu/lb
mol, and initially 25 lb mol of A are placed in the tank. What is the rate of
solvent evaporation after 2 h?
Additional info: k(100 F)= 1.2 x 10-4 s-1
HRX=-25000 Btu/lb mol
Still a semibatch reactor, where D is removed from the reactor
Use EB that accounts for a phase change:
0 0 n
&
& F H H Ho T r V
QW
Q =0
S
i0
i0
i
RX
A
dT
i
S=0
n
dt
NiCpi
dT/dt = 0
0
i1
Fi0 Hi0 Hi HoRX T rA V

i1
D is the only species that flows,

and rAV = -kNA0(exp[-kt]), so:
FD0 Hi0 Hi HoRX T kNA 0 e kt F

D0
Hi0-Hi = heat of vap
25,000
FD0
HoRX T kNA0 ekt
Hi0 Hi
Btu 0.00012
25 lb mol e 0.00012 s 7200s F 0.0316 lb mol

lbmol
s
D0
s
1000Btu lb mol
A liquid phase exothermic reaction A B is carried out at 358K in a 0.2 m3 CSTR.L16-18

The
coolant temperature is 273K and the heat transfer coefficient (U) is 7200 J/minm2K.
What is the heat exchange area required for steady state operation? Using this heat
exchange area, plot T vs t for reactor start-up.
CPA =CPS=20 J/gK S=0 CA0= 180 g/dm3 0= 500 dm3/min
T0= 313 K
= 900 g/dm3 HRX(T) = -2500 J/g E=94852 J/molK
k(313K)= 1.1 min-1
a) Heat exchange area for steady state operation:

SS operation
means that T is
constant, so:
dT
dt
& W
& F C T T Ho T r V
Q
S
i0 pi
i0
RX
A
i1
NiCpi
i1
& W
& F C T T Ho T r V
Q
S
i0 pi
i0
RX
A
i1
Q =UA(Ta-T), S=0, and A is only species that flows
UA Ta T FA0 CpA T TA0 HoRX T rA V
Plug in rA = -kCA and solve for A
UA Ta T FA0 CpA T TA0 HoRX T kCA V

A
HoRX T kC A V FA0CpA T TA0

U Ta T

The
T0= 313 K
k(313K)= 1.1 min-1
Use material balance to determine steady state value of C A

FA0 FA rA V 0 CA00 CA0 kCA V 0 CA00 C A0 kCA V
1.1
1
94852J mol 1
CA00
107.4
exp
CA k 358K =
k 358K
min
8.314 J mol K 313 358
0 kV
min
CA
C A 4.1g dm3
HoRX T kCA V FA0 CpA T TA0
g
dm3
180
500
90000 g min
min
dm
500 dm3 min 107.4min1 200dm3
Solve EB for A:
FA0
180 g dm3 500 dm3 min
U Ta T
1000dm3
V=0.2m
200dm3
m3

The
T0= 313 K
k(313K)= 1.1 min-1
Solve for heat exchange area at SS:

A
HoRX T kCA V FA 0 CpA T TA 0

U Ta T
FA0=90,000 g/min
HRX(T) = -2500 J/g
U= 7200 J/minm2K
2500
g
A
V=200 dm3
k= 107.4 min-1 CA= 4.1 g/dm3 CPA =20 J/gK

TA0= 313 K T= 358K
Ta=273K
107.4
g
g
J
4.1
200dm
90000
20
358K 313K
3
min
min
g K
dm
7
200
273K 358K
minm K
A=227.4 m2
L16-21
Will use Polymath to plot T vs t for CSTR start-up (unsteady-state). Need

equations for dCA/dt, dT/dt, and k.
dCA CA0 C A
dNA
rA
FA0 FA rA V
Mass balance:
dt
dt
o
dT UA Ta T FA0CpA T Ti0 H RX rA V
n
dt
Ni0Cps
i1
CPs is in terms of mass (J/gK), so FA0 & Ni0 must also be in terms of mass
FA0=90,000 g/min
Substitute i0 for Ni0, & use for the solution to calculate:
g
3
&
&
&i0 180,000g
200d
m
9
0
0
mi0 V
m
i0
dm
rA=-kCA
Amount of gas leaving reactor (L7)
k=
1.1
1
94852 J mol 1
exp
min
8.314
J
mol
K
313
T
1.1
1
11408.7 1
k=
exp

min
K
313
T
U= 7200 J/minm2K
A=227.4m2 CA0=180g/dm3 =V/0 Ta=273K
HRX=-2500 J/g Ni0=mi0 V=200 dm3 CPs=20 J/gK 0=500 dm3 T0=313
L16-22
Will use Polymath to plot T vs t for CSTR start-up (unsteady-state). Need

equations for dCA/dt, dT/dt, and k.
1.1
1
11408.7 1
dCA CA0 CA
k=
exp
rA
rA=-kCA
min
K
313
T
dt
o
dT UA Ta T FA0CpA T Ti0 H RX rA V
&i0 180,000g
m
n
dt
Ni0Cps
FA0=90,000 g/min
i1
U= 7200 J/minm2K
A=227.4m2 CA0=180g/dm3 =V/0 Ta=273K
HRX=-2500 J/g Ni0=mi0 V=200 dm3 CPs=20 J/gK 0=500 dm3 T0=313
T (K)
L16-23
t (min)
Reaches steady state at ~12 minutes
The elementary, liquid phase, exothermic reaction A B is carried out in a 2 m3 L16-24

CSTR that is equipped with a heat jacket. Pure A enters the reactor at 60 mol/min and
a temperature of 310K. The coolant in the heat jacket is kept at 280 K. Provide all
equations, all constants, the initial time, and the final time that must be entered into
Polymath in order to plot temperature vs time for the first 20 min of reactor start-up.
HRX(TR) = -10,000 cal/mol CPA = CPS =15 cal/molK
CpB=15 cal/molK S=0
E = 20,000 cal/mol k = 1 min-1 at 400 K
UA= 3200 cal/minK
0= 300 L/min
Need equations for how T changes with time, CA changes with time, & k changes with T.
n
dT
dt
& W
& F C T T Ho T r V
Q
S
i0 pi
i0
RX
A
i1
& UA T - T
Q
a
& 0
W
S
NiCpi
i1
b
a
HRX T HoRX TR CP T TR CP CPB CPA Cp 15 15
cal
0
mol K
cal
o
o
o
H
T
10,000
H RX T H RX TR 0
RX
mol
n
F C
i 1
i0
pi
FA 0 Cp,A FB0 Cp,B FB0 0 Fi0 Cpi FA0 Cp,A
i 1
NiCpi NA0 Cps
i1
o
UA
T
T
F
C
T
H
T r V
A
0
p,A
i
0
a
RX R A
Combine with EB: dT
dt
NA0 Cps
The elementary, liquid phase, exothermic reaction A B is carried out in a 2 m3 L16-25

CSTR that is equipped with a heat jacket. Pure A enters the reactor at 60 mol/min and
a temperature of 310K. The coolant in the heat jacket is kept at 280 K. Provide all
equations, all constants, the initial time, and the final time that must be entered into
Polymath in order to plot temperature vs time for the first 20 min of reactor start-up.
HRX(TR) = -10,000 cal/mol CPA = CPS =15 cal/molK
CpB=15 cal/molK S=0
E = 20,000 cal/mol k = 1 min-1 at 400 K
UA= 3200 cal/minK
0= 300 L/min
Need equations for how T changes with time, CA changes with time, & k changes with T.
cal
o
UA
T
T
F
C
T
H
T r V
HoRX T 10,000
A 0 p,A
i0
a
RX R A
mol dT
UA 3200
FA0 60
FA0
Ta 280
CPA 15
dt
t f 20
NA0 Cps
Ti0 310
FA 0 V
NA 0
0 NA0
0
V
t 0 0
rA kCA
0 300
CPS 15
20,000 1
1
1.987 400 T
k 1 exp
V 2m3 1000L 1m3 V 2000
Use the mass balance to get eq for CA(t)
dCA CA0 C A
dNA
dNA
kC A
k
C
V
FA0 FA rA V
A0 0
A 0
A
dt
dt
dt
V 0 C A0 FA 0 0

Multiple Steady States in CSTR Review

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L16-1

Review: Multiple Steady States in CSTR

Plot of XA,EB vs T and XA,MB vs T

Review: Heat Removal Term R(T) & T0

Heat generated G(T)

R(T) line has slope of CP0(1+)

When T0 increases, slope stays

When increases from lowering

Review: CSTR Stability

R(T) > G(T) T

G(T) > R(T)

G(T) > R(T)

R(T) > G(T)

Magnitude of G(T) to R(T) curve determines if reactor T will rise or fall

L16: Unsteady State Nonisothermal

Change in System Energy with Time

Ei Ui & Ui Hi PVi so: Esys Ni Hi PVi Differentiate wrt time

dEsys n dHi n dNi d n

For well-mixed reactor

Total Energy Balance for unsteady state, constant PV

Well-Mixed Reactors, Constant PV

Total Energy Balance for unsteady state, constant PV

Need to put dNi/dt into terms that can be measured

EB for Well-Mixed Reactors, PV=0

From the mass balance:

Simplified EB for Well-Mixed Reactors

Solve for dT/dt:

Energy balance for

unsteady state reactor

Unsteady State EB, Liquid-Phase Rxns

For liquid-phase reactions, often Cp = iCpi is so small it can be neglected

If the feed is well-mixed, it is convenient to use:

This equation for the EB is simultaneously solved with the mass

Nonisothermal Batch Reactor Design

Put the energy balance

Adiabatic Nonisothermal Batch

Solve for how XA Ho T C T T dX A C C X dTL16-12

Get like terms together:

Integrate & solve for XA:

Heat capacity of soln (calculate Cps if not given)

A 1st order, liquid-phase, exothermic reaction AB is run in a batch reactor.

kNA Rearrange and integrate for NA

A 1st order, liquid-phase, exothermic reaction AB is run in a batch reactor.

Fi0Cpi T Ti0 HoRX

C is the only species that flows, so:

rAV = -kCAV = -kNA where NA NA0 exp kt

FC0 CpC T Ti0 HoRX T kNA0 ekt

A 1st order, liquid-phase, exothermic reaction AB is run in a batch reactor.

HoRX T kNA 0 ekt

NA0 CA0 V0 0.5

Clicker Question: Does dT/dt = 0?

Fi0 Hi0 Hi HoRX T rA V

D is the only species that flows,

FD0 Hi0 Hi HoRX T kNA 0 e kt F

HoRX T kNA0 ekt

A liquid phase exothermic reaction A B is carried out at 358K in a 0.2 m3 CSTR.L16-18

a) Heat exchange area for steady state operation:

Q =UA(Ta-T), S=0, and A is only species that flows

UA Ta T FA0 CpA T TA0 HoRX T rA V

Plug in rA = -kCA and solve for A

UA Ta T FA0 CpA T TA0 HoRX T kCA V

HoRX T kC A V FA0CpA T TA0