CHEE 321: Chemical Reaction Engineering

Module 6: Non-Isothermal Reactors (Chapter 8, Fogler)

Topics to be covered in this Module

Module 6a (Sections 8.2, 8.3, 8.4, 8.6.1 Fogler, 4th Edition)
Develop Energy Balance equations for flow reactors.

Enthalpy, Heat Capacity, and Heat of Reaction and relationship between them

Heat transfer rates for CSTR and PFR/PBR

Algorithms for Non-isothermal CSTR and PFR

Module 6b (Sections 8.5 and 8.7)

Equilibrium Conversion (Reversible Reactions) in Reactors
Conversion attainable during adiabatic operation of endothermic and
exothermic reactors
Increasing Conversion by inter-stage cooling and heating

Why Do We Need Energy Balance ?

Every reaction proceeds with release or absorption of
heat.
The amount of heat released or absorbed depends on
the nature of reacting system
the amount of material reacting
temperature and pressure of reacting system

and can be calculated from heat of reaction (HRxn)

Most industrial reactors will require heat input or heat
removal, hence, we need energy balance.

Energy Balance for Single Reaction

An exothermic reaction is carried out
in an adiabatic plug flow reactor.
How would you calculate the reactor
volume required to achieve a certain
amount of conversion, X ?

We need to relate X and T ----> Energy Balance Equation

User-Friendly Design Equations

User-Friendly Design Equations

We would like to understand how these design equations were developed

General Form of Energy Balance

Rate of flow
of heat to the
system from
the
surrounding

Rate of work
done by the
system on
the
surroundings

Rate of energy
added to the
system by
mass flow into
the system

Rate of energy
leaving the
system by
mass flow out
of the system

W s

Fin Ein

Control Volume
Q
dE

Q W Fin Ein Fout Eout

dt

Fout Eout

Rate of
accumulation
of the energy
within the
system

General Form of Energy Balance

(for multi component system)
W s

F1 , E1

F1 , E1
F2 , E2

F2 , E2
...
Fn , En

Q W

...
Fn , En

F E
i 1

i in

F E
i 1

i out

dE

dt

Next, we will evaluate the W and E terms

Understanding Work and Energy

Terms in the EB equation

Evaluation of the Work (W) term

W s

F1 , E1

F1 , E1
F2 , E2

F2 , E2
...
Fn , En

...
Fn , En

In a chemically reacting systems, there are usually two types of work that
need to be accounted for (i) Shaft Work (e.g. work done by impellers in a
CSTR and batch reactor) and (ii) Flow Work
Rate of flow work is rate of work to
get mass into and out of the system

W W s Rate of Flow Work

Rate of Flow Work

F PV
i 1

i in

F PV
i 1

out

Evaluation of the E term

W s

F1 , E1

F2 , E2

F2 , E2
...
Fn , En
u 2i
Ei U i
g z ...
2

...
Fn , En

Energy Ei is the sum of internal, kinetic, potential

and any other type of energies.

For a majority of reactors, only internal energy is important

Ei U i

F1 , E1

General Form of Energy Balance

(for multi component system)
W s

F1 , E1

F1 , E1
F2 , E2

F2 , E2
...
Fn , En

Q W

...
Fn , En

F E
i 1

i in

F E
i 1

i out

dE

dt

Energy Balance Equation in terms of Enthalpy

Q W

F E
i 1

i in

dE

dt

F E
i

i 1

i out

Substituting appropriate values of Ei and Rate of Work

Q W s

Now,

F PV
i 1

i in

F PV
i 1

i out

FU
i 1

i in

FU
i 1

i out

dE

dt

H U PV

We now have, Energy Balance Equation in terms of Enthalpy

Q W s

F H
i 1

Next, we will focus on the enthalpy

terms

i in

FH
i 1

i out

dE

dt

Heres what well do with Enthalpy terms

Express Hi in terms of Enthalpy of Formation (Hio )
and Heat Capacity (Cpi)
Express Fi in terms of conversion (for single
reaction) or rates of reaction
Define Heat of Reaction (HRxn)
Define Cp

Enthalpy Relationships: Single Reaction System

FA , H A

FA0 , H A0

T0

FB 0 , H B 0
...
FI 0 , H I 0

b
c
d
A B C D
a
a
a

FB , H B
...
FI , H I

If A is the limiting reactant

In

H
i 1

i0

Fi 0

Out

H F
i 1

H A0 FA0

H A FA

H B 0 FB 0

H B FB

H C 0 FC 0

H C FC

H D 0 FD 0

H D FD

H I 0 FI 0

H I FI

FA FA 0 (1 X )
b
X)
a
c
FC FA 0 ( C
X)
a
d
Fd FA 0 ( D
X)
a
FI FA 0 ( I ) FI 0
FB FA 0 ( B

Fi in terms of FA0 and X

from stoichiometry

Enthalpy Relationships: Single Reaction System

n

F
i 1

i0

F H (T )

H i 0 (T0 )

i 1

FA0 {[ H A0 (T0 ) H A (T )] B [ H B 0 (T0 ) H B (T )]

C [ H C 0 (T0 ) H C (T )] D [ H D 0 (T0 ) H D (T )] I [ H I 0 (T0 ) H I (T )]}
[

d
c
b
H D (T ) H C (T ) H B (T ) H A (T )]FA0 X
a
a
a

HRxn
n

Fi 0 H i 0 (T0 )
i 1

[
H
(
T
)

H
(
T
)]

i
i0
0
i
FA0 X [ H Rxn ]
i 1

Fi H i (T ) FA0

i 1

Next, we will evaluate the different terms of RHS

Expressing Hi(T) in terms of Hio and Cpi

n

Fi 0 H i 0 (T0 )
i 1

[
H
(
T
)

H
(
T
)]

i
i0
0
i
FA0 X [ H Rxn ]
i 1

Fi H i (T ) FA0
i 1

Enthalpy at any given temperature is related to enthalpy at a reference

temperature and heat capacity
T

H i (T ) H (Tref )
o
i

pi

dT

T Tref

H io (Tref ) Heat of formation of species " i" at Tref

For no phase change

Hi is available from
Chemical Engg handbook

H i 0 (T0 ) H i (T )

Therefore,

T0

Cpi dT
T

And,

T0

H
i 1

i0

(T0 ) H i (T ) i Cpi dT
T

Heat of Reaction (HRxn)

n

Fi 0 H i 0 (T0 )
i 1

[
H
(
T
)

H
(
T
)]

i
i0
0
i
FA0 X [ H Rxn ]
i 1

Fi H i (T ) FA0
i 1

Heat of reaction is defined as:

H Rxn (T ) [

d
c
b
H D (T ) H C (T ) H B (T ) H A (T )]
a
a
a

Enthalpy at any given temperature is:

T

H i (T ) H io (Tref )

pi

dT

T Tref

H Rxn (T ) H

where,

Cp

o
Rxn

(Tref )

T Tref

Cp dT

d
c
b
Cp D CpC Cp B Cp A
a
a
a

General Form of Energy Balance

W s

F1 , E1

F1 , E1
F2 , E2

F2 , E2
...
Fn , En

...
Fn , En

Q W

F E
i 1

i in

F E
i 1

i out

dE

dt

Energy Balance Equation in terms of Enthalpy

n
n

d
E
Q W s Fi H i in Fi H i out
dt
i 1
i 1
Energy Balance Equation in terms of Conversion

Q W s FA0

i 1

dE
T i Cpi dT ] FA0 X H Rxn (T ) dt
0

Heat Transfer (Q) to/from

Reactors

Heat Transfer (Q) to a CSTR

Heat transferred between coolant and reactor
(from energy balance on the coolant)
c Cpc (Ta1 Ta 2 )
Q m

UA(Ta1 Ta 2 )
ln[ (T Ta1 ) /(T Ta 2 )]

Assuming CSTR temperature,T, is spatially uniform

UA

Q mc Cpc (Ta1 T ) 1 exp

c Cpc )

(m

For high coolant flow rates (Ta1 Ta2=Ta):

Q UA(Ta T )

Heat Transfer (Q) to a PFR

Remember, in PFR/PBR the concentration and reaction rates vary
along the reactor length. Q will likely vary too.
Total heat transferred to the reactor
A

Q U (Ta T ) dA

U a (Ta T ) dV

a = heat exchange area/volume

Heat transfer rate at a given location in a PFR

dQ
Ua (Ta T )
dV

dQ

Ta
T

Non-Isothermal Reactors

Non-isothermal Flow Reactor

Application-1 Special Case: Adiabatic Reactor with No Shaft Work

Q W s H Rxn (Tref ) C p (T Tref ) FA0 X FA0

iCpi (T T0 )
n

i 1

i 1

H Rxn (Tref ) C p(T Tref )

XEB

Q 0
W 0

C
p
(
T

T
)
0
i i

te
rm
<<

If
Cp

X EB

Rx
n

Applying Q = 0 and Ws=0 in the above equation, we get

Non-isothermal Flow Reactor

Application-2: CSTR with Heat Exchange; no shaft work

Q W s H Rxn (Tref ) C p (T Tref ) FA0 X FA0

C
p
(
T

T
)
i i
0
n

i 1

Applying Ws=0 in the above equation, we get

n
UA(Ta T )
~

H Rxn (Tref ) Cp(T Tref ) X i Cpi (T T0 )

FA0
i 1

Let us see if we can apply these concepts to solve a CSTR problem.

Class Problem #6
The following liquid-phase reaction is carried out in a CSTR with heat
exchange:
A B

The feed stream contains A and B in equimolar ratio. The total molar
flow rate is 20 mol/s. The inlet temperature is 325 K, the inlet
concentration of A is 1.5 molar, and the ambient temperature in the
heat exchanger is 300 K.
Calculate the reactor volume necessary to achieve 80% conversion.
Additional information
U= 80 J/m2 s K
A=2 m2
HRxn(298) = -10,000 J/mol
CpA = CpB= 100 J/mol K

CpC = 150 J/mol K

E=25,000 J/mol
k298 = 0.014 L/mol-s

Non-isothermal Flow Reactor

Application-3: PFR with Heat Exchange
Q W s

F
i 1

i0

H i0

FH
i 1

FA0
T0

dQ
dV

FAe
Te

V V+V

Differentiating the Energy Balance equation with respect to V, we get

n
n
dFi
dH i
dQ dW s

0
H i Fi
0
dV dV
dV
i 1 dV
i 1

Non-isothermal Flow Reactor

Application-3: PFR with Heat Exchange (cont.)
Let us evaluate the differential terms of the EB equation
n
n
dFi
dH i
dQ dW s

0
H i Fi
0
dV dV
dV
i 1 dV
i 1

The first term on LHS can be written as

dQ
Ua(Ta T )
dV

dQ
dV

Ta
T
V V+V

a = specific surface area for heat transfer = area/volume

U = overall heat transfer coefficient
Ta = Temperature of heat transfer fluid (outside of the reactor)

Non-isothermal Flow Reactor

Application-3: PFR with Heat Exchange (cont.)
Let us evaluate the differential terms of the EB equation
n
n
dFi
dH i
dQ dW s

0
H i Fi
0
dV dV
dV
i 1 dV
i 1

The derivative in the third term on LHS can be written as

dFi
(ri )
dV

i (rA )

Recall, that for a reaction: aA + bB cC + dD, the reaction rates

are related by the stoichiometric coefficients
(rA ) (rB ) (rC ) (rD )

a b c d

Non-isothermal Flow Reactor

Application-3: PFR with Heat Exchange (cont.)
Let us evaluate the differential terms of the EB equation
n
n
dFi
dH i
dQ dW s

0
H i Fi
0
dV dV
dV
i 1 dV
i 1

The derivative in the fifth term on LHS can be written as

dH i
dT
Cpi
dV
dV

H i (T ) H (Tref )

The fifth term on LHS can be written as

dH i
F

i
dV
i 1
n

dT
dV

FiCpi
i 1

o
i

T Tref

pi

dT

Non-isothermal Flow Reactor

Application-3: PFR with Heat Exchange (cont.)
Substituting, the derivative terms into the Energy Balance Equation
we get
n

dT
Ua(Ta T ) 0 0 i (rA ) H i Fi Cpi
0
dV
i 1
i 1

Rearranging the above equation in terms of dT/dV, we get

n

dT

dV

U a (Ta T ) i ( rA ) H i (T )
i 1

F Cp (T )
i 1

Non-isothermal Flow Reactor

Application-3: PFR with Heat Exchange (cont.)
How do we solve non-isothermal PFR problems?
n

dT

dV

U a (Ta T ) i (rA ) H i (T )
i 1

F Cp (T )
i 1

dFi
i ( rA )
dV

or

g( X ,T )

dX
FA0
(rA )
dV

f ( X ,T )

We MUST solve the two differential equations, g(X,T) and f(X,T),

simultaneously.
We will need Ordinary Differential Equation (ODE) solver -- MATLAB

Other forms of EB equation for PFRs

n

dT

dV

U a (Ta T ) i ( rA ) H i (T )
i 1

F Cp (T )
i 1

For single reaction systems

dT U a (Ta T ) (rA ) [H Rxn (T )]

n
dV
Fi Cpi (T )

You may note

that for
exothermic
i 1
reaction, this
For single reaction systems in term of conversion
term will
dT U a (Ta T ) (rA ) [H Rxn (T )]
result in an

n
increase in T
dV
FA0 [ i Cpi (T ) X Cp ]
i 1

Class Problem #7
It is proposed to design pilot plant for the production of Allyl
Chloride. The feed stream comprises 4 moles propylene/mole
chlorine. The reactor will be vertical tube of 2 inch ID. The
combined feed molar flow rate is 0.6 g-mol/h. The inlet pressure is
2 atmospheres. The feed stream temperature is 275 C. Calculate
Allyl Chloride production as a function of tube length for the
following 2 cases:
Case-1: PFR jacketed with heat exchange fluid circulated at 275 C
Case-2: Adiabatic operation of PFR

Class Problem #7 (cont.)

MAIN REACTION: Cl2 + C3H6 CH2=CH-CH2Cl + HCl
63310
( rCl2 )1 3.3 10 exp[
] [ pCl2 pC3 H 6 ]; in moles/m3 hr atm 2
RT
6

SIDE REACTION: Cl2 + C3H6 CH2Cl-CHCl-CH3

15970
(rCl2 ) 2 187 exp[
] [ pCl2 pC3 H 6 ] ; in moles/m3 hr atm 2
RT
T is in Kelvin and p is in atm
U = 28 W/m2-K
-HRxn1(298)=110,000 J/mol
-HRxn2(298)=181,500 J/mol

(cP )Cl2

36 J / mol K

(c P ) C3 H 6

107 J / mol K

(cP ) AllylChloride

117 J / mol K

(cP ) HCl

30 J / mol K

(cP ) Dichloroporpane 128 J / mol K