2.

3 Non-isothermal Non-adiabatic
Reactor Design
 Review: Application to a SS PFR

FA0 FA

XA
T

distance
 Review: Application to a SS PFR

FA0 FA

XA
T

For negligible shaft work (Ẇ S=0) and adiabatic (Q=0)

distance a) Use TEB to construct a table of T as a function of XA
b) Use k = Ae-E/RT to obtain k as a function of XA
c) Use stoichiometry to obtain –rA as a function of XA
d) Calculate: XA
dX A may use numerical
V  FA0 
X rA  X A ,T  methods
A0
 Review: Application to a SS PFR

FA0 FA

XA
T

For negligible shaft work (Ẇ S=0) and non adiabatic (Q≠0)

distance
• In non adiabatic flow reactors, the heat that is retired or
added to the reactor changes with distance down reactor
• Differential form of EB must be used taking into account
geometry
 NINA Steady-State PFR/PBR
Heat is added or removed through the cylindrical walls of the reactor
Q  UA  Ta  T   Ua  Ta  T  V
Ta
FA0 FAe
 FH
i i T  FH
i i
T0 Te
V V+V

A
a Heat exchange area per volume of reactor
V

A  DL 4
a  
V  D2L D
4
 NINA Steady-State PFR/PBR
Heat is added or removed through the cylindrical walls of the reactor
Q  UA  Ta  T   Ua  Ta  T  V
Ta
FA0 FAe
 FH
i i T  FH
i i
T0 Te
V V+V
n n dEˆ sys
Energy balance on small volume of PFR: Q -W   Fi E i -  Fi E i =
i=1 in i=1 out dt

Steady state, kinetic, potential and “other” energy are negligible compared to
enthalpy, heat transfer and work.

Q  Ws   FH
i i V   FH
i i V V  0
0
 NINA Steady-State PFR/PBR
Heat is added or removed through the cylindrical walls of the reactor
Q  UA  Ta  T   Ua  Ta  T  V
Ta
FA0 FAe
 FH
i i T  FH
i i
T0 Te
V V+V

Energy balance on small volume of SS PFR: Q  Ws   FH

i i V   FH
i i V V  0
0
Plug in Q:  Ua  Ta  T  V   FH
i i V   FH
i i V V  0

i i V   FiHi V V
 FH
Dividing by V:  Ua  Ta  T   0
V
 NINA Steady-State PFR/PBR
Heat is added or removed through the cylindrical walls of the reactor
Q  UA  Ta  T   Ua  Ta  T  V
Ta
FA0 FAe
 FH
i i T  FH
i i
T0 Te
V V+V

i i V   FiHi V V
 FH
Energy balance on small volume of SS PFR:  Ua  Ta  T   0
V

d FiHi 
Take limit as V→∞:  Ua  Ta  T   0
dV
 NINA Steady-State PFR/PBR

Ta
FA0 FAe d FiHi 
 FH
i i T  FH
i i  Ua  Ta  T   0
T0 dV
Te
V V+V

 dFi dH
Product rule: Ua  Ta  T   Hi   Fi i  0
dV dV

dFi
But:  ri   i  rA 
dV

dHi dT
and  Cpi
dV dV
 NINA Steady-State PFR/PBR

Ta
FA0 FAe
 dFi dH
 FH
i i T  FH
i i Ua  Ta  T   Hi   Fi i  0
T0 Te dV dV
V V+V

dT
Substitute the differentials:  Ua  Ta  T    Hi i  rA    FiCPi 0
dV

But:  iHi  HRX

dT
 Ua  Ta  T   HRX  rA    FC
i Pi 0
dV
 NINA Steady-State PFR/PBR

Ta
FA0 FAe dT
 FH
i i T  FH
i i
 Ua  Ta  T   HRX  rA    FC
i Pi 0
dV
T0 Te
V V+V

dT
Solve for dT/dV:    FC
i Pi  HRX  rA   Ua  Ta  T 
dV

dT HRX  rA   Ua  Ta  T 
 
dV  FCi Pi
 NINA Steady-State PFR/PBR

Heat Heat
generated removed

dT HRX  rA   Ua  Ta  T 

dV  FiCPi

Heat Heat
generated removed

Multiply Ua and (Ta-T) dT HRX  rA   Ua  T  Ta 

 
by -1 (-1 x -1 = 1) dV  FiCPi
Switched
sign & order
in bracket
 NINA Steady-State PFR/PBR
Heat Heat
generated removed

dT HRX  rA   Ua  T  Ta 
 
dV  FiCPi

HRX  H RX (TR )  CP  T  TR 

Substitute and multiply out the denominator
Fi  FA0  i   i XA 

dT  H RX (TR )  CP  T  TR    rA   Ua  Ta  T 
   iCPi  CP

dV FA0   iCPi  CPi i X A 

dT  H RX (TR )  CP  T  TR   rA   Ua  Ta  T 

 
  Energy balance for SS PFR, Ẇ s=0
dV FA0   iCPi  CP X A 
 NINA Steady-State PFR/PBR
Useful for
SS
dT  H RX (TR )  CP  T  TR   rA   Ua  Ta  T 
 
  PFR
dV FA0   iCPi  CP X A  PBR
Membrane

PFR energy balance is coupled to the PFR design eq, and

PFR design eq is coupled to Arrhenius eq for k or Kequil

(these are the 3 equations that must be simultaneously solved)

 For a PBR
0
dT UA Ta -T +r'A ∆Hrxn (TR )+∆Cp (T-TR )
PBR energy balance: =
dV FA0 ( Θi Cpi +ΔCp X )

PBR design : dW=ρb dV

UA r'A
Ta -T + ∆H0rxn (TR )+∆Cp (T-TR )
Combining:
dT ρb ρb
=
dW FA0 ( Θi Cpi +ΔCp X )

UA
Ta -T +r'A ∆H0rxn
dT ρb Compressed form
=
dW Fi Cpi
 Liquid Phase Reaction in PFR
A B liquid phase rxn carried out in PFR; WS  0 & pure A enters the PFR
dX A rA
• Mole balance 
dV FA0
 C   H RX  TR   1 1  
• Rate law rA  k  CA  B  with K C  T   K C  T2  exp    
 KC   R  T2 T  
 E  1 1 
k  k1 exp     
 R  T1 T  
• Stoichiometry CA  CA0 (1  XA ) CB  CA0 XA

dX A k 1  X A  X A K C  Solve these equations

• Combine  simultaneously with an
dV 0
ODE solver (Polymath)
If this were a gas phase
 H RX (TR )  CP  T  TR   rA   Ua  Ta  T  rxn w/ pressure drop,
• Energy balance dT   
FA0   iCPi  CP X A 
change stoichiometry
dV
accordingly & include an
equation for dP/dW
 Flow Reactor with Heat Transfer Fluid
Let us remember that Ta is the surroundings temperature, which can be constant or variable

Case 1: Flow heat transfer sufficiently high

with respect to heat released or absorbed
mc Hc mc Hc

FA , T FA , T

Ta ≈ Constant along the reactor

V V+ΔV
 Flow Reactor with Heat Transfer Fluid
Let us remember that Ta is the surroundings temperature, which can be constant or variable

Case 2: Reactant flow and heat transfer fluid

in the same direction
mc Hc mc Hc

FA , T FA , T

mc Hc mc Hc dE
Einlet -Eout +Q-Ws =
dt
V V+ΔV
mc Hc V -mc Hc V+∆V +Ua T-Ta ∆V=0
 mc Hc V -mc Hc V+∆V +Ua T-Ta ∆V=0

Dividing by ΔV and applying Lim ΔV 0

dHc
-mc +Ua T-Ta =0
dV
dHc dT
Let’s remember that: =Cpc
dV dV

dT Ua T-Ta
Combining: =
dV mc Cpc
 Flow Reactor with Heat Transfer Fluid
Let us remember that Ta is the surroundings temperature, which can be constant or variable

Case 3: Reactant flow and heat transfer fluid

in opposite direction
mc Hc mc Hc

FA , T FA , T

mc Hc mc Hc dE
Einlet -Eout +Q-Ws =
dt
V V+ΔV
mc Hc V+∆V - mc Hc V + Ua T-Ta ∆V=0
 mc Hc V+∆V - mc Hc V + Ua T-Ta ∆V=0

Dividing by ΔV and applying Lim ΔV 0

dHc
mc +Ua T-Ta =0
dV
dHc dT
Let’s remember that: =Cpc
dV dV

dT Ua T − Ta Ua Ta − T
Combining: =− =
dV mc Cpc mc Cpc
 NINA Steady-State CSTR
CSTR with a heat exchanger, perfectly mixed inside and outside of reactor

Ta1  Ta2 FA0

Q  UA
 T  Ta1  Ta1
T, X Ta2
ln  
 T  Ta2 
T, X
The heat flow to the reactor is in terms of:
• Overall heat-transfer coefficient, U
• Heat-exchange area, A
• Difference between the ambient temperature of inlet and outlet in the heat jacket, Ta1,
Ta2 and rxn temperature, T
 NINA Steady-State CSTR
Case 1: Low coolant flow rate
Rate of energy transferred between the reactor and the coolant:

Q=mc Cpc Ta1 -Ta2 n

WsFA0i C~pi (T Ti0)FA0 HX oRx(TR  p   TTĈ) R0
i1

Ta1 -Ta2
Combining: Q=mc Cpc Ta1 -Ta2 =UA
T -T
Ln a1
Ta2 -T

Ta1 -T UA Ta1 -Ta2 UA

Ln = =
Ta2 -T mc Cpc Ta1 -Ta2 mc Cpc

Ta1 -T UA
=exp
Ta2 -T mc Cpc
 NINA Steady-State CSTR
Case 1: Low coolant flow rate
UA
(Ta1 -T) exp - =(Ta2 -T)
mc Cpc n
WsFA0i C~pi (T Ti0)FA0 HX oRx(TR  p   TTĈ) R0
i1

UA
Solve for Ta2: Ta2 =T+(Ta1 -T) exp -
mc Cpc

Replacing in coolant heat transfer term:

UA
Q=mc Cpc Ta1 -Ta2 =mc Cpc Ta1 -T-(Ta1 -T)exp -
mc Cpc
 NINA Steady-State CSTR
Case 1: Low coolant flow rate

UA
Q=mc Cpc (Ta1 -T)-(Ta1 -T)exp - n
WsFA0i C~pi (T Ti0)FA0 HX oRx(TR  p   TTĈ) R0
i1

mc Cpc

UA
Q=mc Cpc (Ta1 -T) 1-exp -
mc Cpc
 NINA Steady-State CSTR
Case 2: High coolant flow rate
At high coolant flow rates the exponential term will be small.

At high flows of coolant, the exponential term is low, so we can expand the
n
WsFA0i C~pi (T Ti0)FA0 HX oRx(TR  p   TTĈ) R0
i1

exponential term as a Taylor Series, where the terms of second order or

greater are neglected:
e-X ≈1-X

UA UA
Then: Q= mc Cpc (Ta1 -T) 1- 1- =mc Cpc (Ta1 -T)
mCpc mCpc

Q=UA(Ta1 -T)
 NINA Steady-State CSTR

n
Energy balance: Q  Ws  FA0  iCpi (T  Ti0 )  FA0 X  HRX (TR )  C
ˆ (T  T )   0
i1
 p R 

With the exception of processes involving highly viscous materials, the work done by the
stirrer can be neglected (i.e. W s  0 )

With heat exchanger (high coolant flow rate): Q  UA(Ta  T)

n
UA(Ta  T)  0  FA0  iCpi (T  Ti0 )  FA0 X  HRX (TR )  C
ˆ (T  T )  0
i1
 p R 
 NINA Steady-State CSTR

UA(Ta  T) n
   iCpi (T  Ti0 )  X  HRX (TR )  C
ˆ (T  T )
FA0 i1
 p R 

UA(Ta  T)  ˆ 
n
  X HRX (TR )  Cp ( T  TR )   iCpi (T  Ti0 )
FA0   i1

UA(Ta  T) n
  iCpi (T  Ti0 )
FA0 i1
Solving for X: X
  HRX (TR )  C
ˆ (T  T )
 p R 
 NINA Steady-State CSTR

Simplification of energy balance for NINA CSTR operation:

UA(Ta  T) n
  iCpi (T  Ti0 )  X  HRX (TR )  C
ˆ (T  T )
FA0 i1
 p R 

n
Let`s define:  iCpi Cp0
i1

 UA(Ta  T) 
Combining: Cp0    Cp0 (T  Ti0 )  X  HRX (TR )  C
ˆ (T  T )
p R 
 FA0Cp0 
 UA   UA 
Cp0   Ta  Cp0   T  Cp0 T  Cp0 Ti0  X  HRX (TR )  C
ˆ (T  T )
p R 
 A0 p0 
F C  A0 p0 
F C
 NINA Steady-State CSTR

Simplification of energy balance for NINA CSTR operation:

 UA    UA  
Cp0   Ta  Cp0 T     1  Cp0 Ti0  X  HRX (TR )  C
ˆ (T  T ) 
p R 
 A0 p0 
F C   A0 p0  
F C

 UA    T  Ti0 
Let`s define:    Tc   a
 A0 p0 
F C  1   

Combining: Cp0 Ta  Cp0T   1  Cp0Ti0  X  HRX (TR )  C

ˆ (T  T )
 p R 

Cp0  Ta  Ti0   Cp0T   1  X  HRX (TR )  C

ˆ (T  T )
 p R 
 NINA Steady-State CSTR

Simplification of energy balance for NINA CSTR operation:

Cp0  Ta  Ti0   Cp0T   1  X  HRX (TR )  C

ˆ (T  T )
 p R 

 Ta  Ti0   C T   1  X H (T )  Cˆ (T  T )

  1 Cp0 p0    RX R R 
 
  1 p

  1 Cp0Tc  Cp0T   1  X HRX (TR )  Cˆ p (T  TR )

  1 Cp0 (Tc  T)  X HRX (TR )  Cˆ p (T  TR )

 NINA Steady-State CSTR

Simplification of energy balance for NINA CSTR operation:

  1 Cp0 (Tc  T)  X HRX (TR )  Cˆ p (T  TR )

  1 Cp0 (Tc  T)
Solving for X: X
 HRX (TR )  C
ˆ (T  T )
 p R 

 HRX (TR )  Cˆ (T  T ) X

Solving for T:  p R 
 Tc  T
  1 Cp0
 NINA Steady-State CSTR

Case 1: Given FA0, CA0, A, E, Cpi, H°I, and XA, calculate T & V
a) Solve TEB for T at the exit (Texit = Tinside reactor)

 HRX (TR )  Cˆ (T  T ) X

 p R 
 Tc  T
  1 Cp0

b) Calculate k = Ae-E/RT where T was calculated in step a

c) Find -rA with k and XA

d) Plug the k calculated in step b into the design equation to calculate V CSTR
FA0 X A
V
rA
 NINA Steady-State CSTR

Case 2: Given FA0, CA0, A, E, Cpi, H°I, and T, calculate XA & V

a) Solve TEB for X

  1 Cp0 (Tc  T)
X
 HRX (TR )  C
ˆ (T  T )
 p R 

b) Calculate k = Ae-E/RT where T was given

c) Find –rA with k and XA

d) Plug the k calculated in step b into the design equation to calculate V CSTR
FA0 X A
V
rA
 NINA Steady-State CSTR
Case 3: Given FA0, CA0, A, E, Cpi, H°I, and V, calculate T & XA
  1 Cp0 (Tc  T)
a) Solve TEB for T as a function of XA X
 HRX (TR )  C
ˆ (T  T )
 p R 

b) Solve CSTR design equation for XA as a function of T (plug in k = Ae-E/RT )

c) Plot XA,EB vs T & XA,MB vs T on the same graph. The intersection of these 2 lines is the
conditions (T and XA) that satisfies the energy & mass balance

XA,exit
XA,MB XA,EB = conversion determined from the TEB equation
XA XA,MB = conversion determined using the design
equation
XA,EB Intersection is T and XA that satisfies both equations
T Texit
 NINA Steady-State CSTR

To Do:

Read and understand examples 8.8 and 8.9 from Fogler’s book.