08 Energy Balance

Energy balance for chemical reactors
Gabriele Pannocchia
First Year course, MS in Chemical Engineering, University of Pisa

Academic Year 20132014
Department of Civil and Industrial Engineering (DICI)

University of PisaItaly
Email: g.pannocchia@diccism.unipi.it
Gabriele Pannocchia Energy balance for chemical reactors 1 / 45
Outline
1
Introduction and general balance
2
Batch reactor
3
CSTR
Dynamic operation
Steady-state operation
Steady-state multiplicity and stability
4
PFR
Energy balance in transient conditions
Steady-state energy balance
PFR hot spot and runaway
5
Optimized reactor arrangements
6
Summary of balance equations
General energy balance
Q
R
j E
m
1
,

E
1
, c
j 1
m
0
,

E
0
, c
j 0
W
Arbitrary reactor volume V
Inlet: m
0
(mass rate), c
j 0
(concentration of species j ),

E
0
(per-mass energy)
Outlet: m
1
(mass rate), c
j 1
(concentration of species j ),

E
1
(per-mass energy)
General energy balance (continued)
Conservation of energy for system
_
rate of energy
accumulation
_
=
_
rate of energy
entering by inow
_
_
rate of energy
entering by outow
_
+
_
rate of heat
added to system
_
+
_
rate of work
added to system
_
Balance rewritten in terms of dened variables
dE
dt
=m
0

E
0
m
1

E
1
+

Q+

W
The total energy E is composed by several contributions, e.g. internal energy,
kinetic energy, potential energy, and other types of energy:
E =U +K ++
In most chemical reactors, only changes in internal energy are relevant
Work terms
Work terms: overview
The total work

W can be split into three parts:

W
f
: the work done by ow streams while moving material into and out of the
reactor volume

W
s
: the shaft work done by stirrers, compressors, etc.

W
b
: the work done by the reactor volume boundaries
Flow streams work term
If we assume that the ow streams enter (or leave) the reactor volume at
uniform velocity, we can express

W
f
as follows:
W
f
=v
0
A
0
p
0
v
1
A
1
p
1
where v
0
and p
0
are the inlet ow velocity and pressure, A
0
is the bounding
area; likewise for v
1
, p
1
, A
1
Let
0
and
1
be the densities of inlet and outlet ows respectively
We obtain:
W
f
=Q
0
p
0
Q
1
p
1
=m
0
p
0
0
m
1
p
1
1
General energy balance in nal form
Enthalpy
Recall the enthalpy denition H =U +pV or per-mass basis

H =

U +
p
Overall balance
Assume that E =U +K +, we obtain:
d
dt
(U +K +) =m
0
(

H
0
+

K
0
+

0
) m
1
(

H
1
+

K
1
+

1
) +

Q+

W
s
+

W
b
Neglecting kinetic and potential energy terms leads to
dU
dt
=m
0

H
0
m
1

H
1
+

Q+

W
s
+

W
b
Batch reactor: energy balance and derivations
The general balance
The energy balance for the batch reactor is obtained from the general balance
written over the entire reaction volume (V =V
R
)
Deleting the terms associated with ow streams (not present in the batch
reactor) leads to:
d
dt
(U +K +) =

Q+

W
s
+

W
b
The rate of work done by the boundaries is given by:

W
b
=p
dV
R
dt
Minor simplications
Usually kinetic and potential energy terms can be neglected
Moreover, unless the reactor is treating a highly viscous mixture the rate of
shaft work can be also neglected
Recall that H =U +pV
R
, and hence dH =dU +pdV
R
+V
R
dp, to obtain:
dU
dt
+p
dV
R
dt
=

Q
dH
dt
V
R
dp
dt
=

Q (1)
Manipulating the change of enthalpy
The change of enthalpy for single phase reactor
We express the change of enthalpy using (T, p, n
j
) as independent variables:
dH =
_
H
T
_
p,n
j
dT +
_
H
p
_
T,n
j
dp +
j
_
H
n
j
_
T,p,n
k=j
dn
j
(2)
The simple terms
The rst term is by denition the total heat capacity at constant pressure:
_
H
T
_
p,n
j
=C
p
=V
R

C
p
(3)
with c
P
the specic heat capacity of the mixture at constant pressure
The third term is also simple because
_
H
n
j
_
T,p,n
k=j
is the molar enthalpy of
species j , denoted by

H
j
Manipulating the change of enthalpy (cont.)
Useful thermodynamic relations
dG =SdT +V
R
dp +
j
dn
j
(4)
dH =dG +TdS +SdT =TdS +V
R
dp +
j
dn
j
(5)
_
S
p
_
T,n
j
=
_

p
_
T,n
j
_
G
T
_
p,n
j
=
_

T
_
p,n
j
_
G
p
_
T,n
j
=
_
V
R
T
_
p,n
j
(6)
Partial derivative of enthalpy w.r.t. pressure
From (5) and (6) we can write:
_
H
p
_
T,n
j
=T
_
S
p
_
T,n
j
+V
R
=T
_
V
R
T
_
p,n
j
+V
R
=V
R
(1T) (7)
=
1
V
R
_
V
R
T
_
p,n
j
is the isobaric coefcient of expansion of the mixture
Manipulating the change of enthalpy (cont.)
Collecting the three terms of (2)
dH
dt
=V
R

C
p
dT
dt
+V
R
(1)
dp
dt
+
H
j
dn
j
dt
(8)
The reaction term
The reaction term appearing in (8) can be further simplied by recalling the
material balance:
dn
j
dt
=R
j
V
R
=
i j
r
i
V
R
(9)
We then can write:
H
j
dn
j
dt
=
H
j
i j
r
i
V
R
=
i j

H
j
r
i
V
R
=
i
H
Ri
r
i
V
R
(10)
with H
Ri
=
j

i j

H
j
the molar heat of reaction i
Final energy balances for the batch reactor
General energy balance for a batch reactor
From (1), (10) and (8) we obtain:
V
R

C
p
dT
dt
TV
R
dp
dt
=
i
(H
Ri
)r
i
V
R
+

Q (11)
Incompressible uid or constant pressure reactor
If the mixture is incompressible, i.e. =0, or the reactor operates at constant
pressure, the balance becomes:
V
R

C
p
dT
dt
=
i
(H
Ri
)r
i
V
R
+

Q (12)
Energy balance for compressible mixtures
Constant volume reactor with compressible mixture: introduction
For gas-phase mixtures, in constant volume batch reactors, it is possible to
relate
dp
dt
to the change of temperature and moles due to reaction
Derivation
Express the term
dp
dt
as follows (assuming constant V
R
):
dp
dt
=
_
p
T
_
V
R
,n
j
dT
dt
+
j
_
p
n
j
_
T,V
R
,n
k=j
dn
j
dt
(13)
Inserting (13) into (11), recalling the material balance (9), we obtain:
_
V
R

C
p
TV
R
_
p
T
_
V
R
,n
j
_
dT
dt
=
i
[(H
Ri
)+
T
i j
_
p
n
j
_
T,V
R
,n
k=j
_
r
i
V
R
+

Q
Energy balance for compressible mixtures (cont.)
Final result
Observe that
_
V
R

C
p
TV
R
_
p
T
_
V
R
,n
j
_
is the constant volume heat capacity,
which can be written as V
R
c
V
, and obtain:
V
R

C
V
dT
dt
=
i
_
(H
Ri
) +TV
R
i j
_
p
n
j
_
T,V
R
,n
k=j
_
r
i
V
R
+

Q (14)
Ideal gas mixture
Observe that
T =1,
_
p
n
j
_
T,V
R
,n
k=j
=
RT
V
R
Obtain:
V
R

C
V
dT
dt
=
i
(H
Ri
+RT
i
)r
i
V
R
+

Q (15)
Simple reaction in adiabatic conditions
Single reaction
Consider a single reaction:
A
k
B, with r =k(T)c
n
A
and k(T) =k
0
exp(E
a
/(RT))
Dene x
A
=
n
A0
n
A
n
A0
, and write material and energy balance (12):
_
_
n
A0
dx
A
dt
=r V
R
V
R

C
p
dT
dt
=(H
R
)r V
R
Obtain a relation between T and x
A
:
dT
dx
A
=
(H
R
)n
A0
V
R

C
p
When V
R
is constant =
(H
R
)c
A0

C
p
is the adiabatic temperature rise, to obtain:
T =x
A
T =T
0
+x
A
CSTR in dynamic operation: energy balance
Denitions and general balance
Q
0
,
0
,

H
0
: inlet ow rate, density and enthalpy
Q, ,

H: outlet ow rate, density and enthalpy
Q external heat ow,

W
s
rate of shaft work,

W
b
rate of boundary work
General balance applied to V =V
R
:
dU
dt
=Q
0
0

H
0
Q

H +

Q+

W
s
+

W
b
W
s
V
R
R
j
Q
Q
0
, c
j 0
,

H
0
Q, c
j
,

H
Neglect shaft work
dU
dt
+p
dV
R
dt
=Q
0
0

H
0
Q

H +

Q
dH
dt
V
R
dp
dt
=Q
0
0

H
0
Q

H +

Q (16)
CSTR in dynamic operation: single phase system
Expanding the enthalpy change term
As in the batch reactor we can write [see (8)]
dH
dt
=V
R

C
p
dT
dt
+V
R
(1T)
dp
dt
+
H
j
dn
j
dt
(17)
Recall the material balance:
dn
j
dt
=Q
0
c
j 0
Qc
j
+
i j
r
i
V
R
(18)
Combining (16), (17) and (18)
V
R

C
p
dT
dt
+V
R
(1T)
dp
dt
+
j

H
j
[Q
0
c
j 0
Qc
j
+
i

i j
r
i
V
R
] V
R
dp
dt
=Q
0
0

H
0
Q

H +

Q
CSTR in dynamic operation: single phase system (cont.)
Useful observations
Recall that:

j
i j

H
j
=
i j

H
j
=
i
H
Ri
Notice that:
Q
0
0

H
0
=
j
Q
0
c
j 0

H
j 0
j
Qc
j

H
j
=Q

H
Final balance
V
R

C
p
dT
dt
V
R
T
dp
dt
=
i
(H
Ri
)r
i
V
R
+Q
0
j
c
j 0
(

H
j 0

H
j
) +

Q (19)
Reasonable approximation for liquid mixtures
The heat capacity is reasonably constant with temperature and =0. Hence:
H
j 0

H
j
=

C
p j
(T
0
T)
j
c
j 0
(

H
j 0

H
j
) =
0

C
p
(T
0
T):
V
R

C
p
dT
dt
=
i
(H
Ri
)r
i
V
R
+Q
0
0

C
p
(T
0
T) +

Q (20)
Steady-state operation
General steady-state material and energy balances
The steady-state energy balance comes from (19) by setting
dT
dt
=0 and
dp
dt
=0
In general material and energy balances must be solved together:
Q
0
c
j 0
Qc
j
+
i j
r
i
V
R
=0 j =1, . . . , n
s
(21)
i
(H
Ri
)r
i
V
R
+Q
0
j
c
j 0
(

H
j 0

H
j
) +

Q =0 (22)
Steady-state material and energy balances for liquid mixtures
Q
0
(c
j 0
c
j
) +
i j
r
i
V
R
=0 j =1, . . . , n
s
(23)
i
(H
Ri
)r
i
V
R
+Q
0
0

C
p
(T
0
T) +

Q =0 (24)
Simple reaction in adiabatic conditions
Single reaction
Consider a single reaction:
A
k
B, with r =k(T)c
n
A
and k(T) =k
0
exp(E
a
/(RT))
Dene x
A
=
N
A0
N
A
N
A0
, and write material and energy balance (12):
_
Q
0
c
A0
x
A
=r V
R
Q
0

C
p
(T T
0
) =(H
R
)r V
R
Obtain a relation between T and x
A
:
T T
0
=
(H
R
)c
A0

C
p
x
A
Let =
(H
R
)c
A0

C
p
, observe that in general:
T =x
A
Steady-state multiplicity
Introduction
The coupling of energy and material balances can result in a surprisingly
complex behavior even for simple kinetic schemes
This is true even in steady-state operation, in particular because there may
exist multiple steady states
Example
Consider a rst order reaction:
A
k
B, r =k(T)c
A
, k(T) =k
0
exp(E
a
/(RT))
Adiabatic conditions in liquid phase. Recall that =V
R
/Q
0
and x
A
=
c
A0
c
A
c
A0
:
x
A
=
k
1+k
(25)

C
p
(T T
0
) =k(1x
A
)c
A0
(H
R
) (26)
Examine (x
A
, T) vs. for different H
R
Steady-state multiplicity: example
Temperature vs. residence time
260
280
300
320
340
360
380
400
420
440
460
1 10 100 1000 10000 100000
T
(
K
)
(min)
H
R
=300
H
R
=200
H
R
=100
H
R
=50
H
R
=0
H
R
=50
Steady-state multiplicity: example (cont.)
Conversion vs. residence time
0
0.2
0.4
0.6
0.8
1
1 10 100 1000 10000 100000
x
A
(min)
H
R
=300
H
R
=200
H
R
=100
H
R
=50
H
R
=0
H
R
=50
Steady-state multiplicity: ignition and extinction points
Temperature vs. residence time for H
R
=300kJ/mol
280
300
320
340
360
380
400
420
440
460
0 5 10 15 20 25 30 35 40
T
(
K
)
(min)
A
E
B
D
F
C
G
Steady-state stability: heat generation and removal
Heat generation and removal
In the energy balance (26), we replace x
A
from (25) to obtain:

C
p
(T T
0
)
. .
Q
r
=
k
1+k
c
A0
(H
R
)
. .
Q
g
Q
r
is the heat removal rate, associated to the different between output and
input stream enthalpies
Q
g
is the heat generation rate, associated with the reaction rate
Necessary condition for stability
An equilibrium is said to be stable if the system returns to that steady state
after any sufciently small perturbation
A necessary condition for stability is:
d

Q
r
dT
>
d

Q
g
dT
Steady-state stability: heat generation and removal (cont.)
Heat generation and removal for =1.79 min
-100
0
100
200
300
400
500
300 350 400 450 500
H
e
a
t
(
M
J
/
m
3
m
i
n
)
T (K)
A
E (extinction)
Removal
Generation
Heat generation and removal for =15 min
-10
0
10
20
30
40
50
60
300 350 400 450 500
H
e
a
t
(
M
J
/
m
3
m
i
n
)
T (K)
B
D (unstable)
F
Removal
Generation
Heat generation and removal for =30.9 min
-5
0
5
10
15
20
25
30
300 350 400 450 500
H
e
a
t
(
M
J
/
m
3
m
i
n
)
T (K)
C (ignition)
G
Removal
Generation
PFR: energy balance in transient conditions
PFR scheme and thin disk volume element
q(z)zD
Q(z +z)
c
j
(z +z)
V R
j
Q(z)
c
j
(z)
Q, c
j
,

H Q
0
, c
j 0
,

H
0
H(z) H(z +dz)
q(z)
Energy balance: transient conditions in V = A
c
z
(

UV )
t
= (m

H)
z
(m

H)
z+z
+ qDz
PFR: energy balance in transient and steady state
conditions
Obtaining the nal balance
Divide by V and take the limit as V 0:
(

U)
t
=
(Q

H)
V
+
4
D
q
Rewrite

H =
j
c
i

H
j
and obtain:
(

U)
t
=
(Q
j
c
j

H
j
)
V
+
4
D
q
q is the heat ux (i.e. heat ow per unit of transfer area), usually expressed as:
q =U
0
(T
a
T) where T
a
is the external temperature (e.g. jacket temperature)
Steady-state balance
d(Q
j
c
j

H
j
)
dV
=
4
D
q (27)
PFR: steady-state balance rearrangement
Expand the l.h.s. term
Recall the material balances:
d(Qc
j
)
dV
=
i j
r
i
Expand the
d(Q
j
c
j

H
j
)
dV
as follows:
d(Q
j
c
j

H
j
)
dV
=
j
_
Qc
j
d

H
j
dV
+

H
j
d(Qc
j
)
dV
_
d(Q
j
c
j

H
j
)
dV
=Q
j
c
j
d

H
j
dV
+
i
H
Ri
r
i
(28)
PFR: steady-state balance rearrangement (cont.)
Expanding the enthalpy change term

j
c
j
d

H
j
Let

H =
j
c
j

H
j
be the enthalpy per volume of reacting mixture. We have:
d

H =
j
_

H
j
dc
j
+c
j
d

H
j
_
(29)
As in previous cases, its change can be expressed as:
d

H =
_

H
T
_
p,n
j
dT +
_

H
p
_
T,n
j
dp +
j
_

H
n
j
_
T,p,n
k=j
dn
j
(30)
From previous derivations, (30) is re-written as:
d

H =

C
p
dT +(1T)dp +
H
j
dc
j
(31)
Finally, by comparison of (29) and (31) we obtain:
j
c
j
d

H
j
=

C
p
dT +(1T)dp (32)
PFR: steady-state nal balance
General balance
From (27), (28) and (32) we obtain:
Q

C
p
dT
dV
+Q(1T)
dp
dV
=
i
(H
Ri
)r
i
+
4
D
q (33)
Ideal gas or neglect pressure drop
Q

C
p
dT
dV
=
i
(H
Ri
)r
i
+
4
D
q (34)
Incompressible uid
Q

C
p
dT
dV
+Q
dp
dV
=
i
(H
Ri
)r
i
+
4
D
q (35)
PFR hot spot and runaway
Introduction
For exothermic (gas-phase) reactions in a PFR, the heat release can lead to the
formation of a hot spot
When reactions are highly exothermic, small changes in operating parameters
(e.g., inlet concentration, owrate, temperature) can result in very changes of
the temperature prole
This is known as the PFR parametric sensitivity, and a sudden increase in
temperature prole in known as run away
Example: exothermic reaction in a jacketed PFR
Irreversible rst order reaction in gas phase: A
k
B
Observe (N
A
, T) as function of z for different inlet stream temperatures T
0
PFR parametric sensitivity
Reactant molar ow
0
0.0002
0.0004
0.0006
0.0008
0.001
0.0012
0.0014
0.0016
0 0.2 0.4 0.6 0.8 1 1.2 1.4
N
A
(
k
m
o
l
/
s
)
z (m)
T
0
=615 K
T
0
=625 K
T
0
=631 K
T
0
=635 K
PFR parametric sensitivity
Temperature
600
620
640
660
680
700
720
740
0 0.2 0.4 0.6 0.8 1 1.2 1.4
T
(
K
)
z (m)
T
0
=615 K
T
0
=625 K
T
0
=631 K
T
0
=635 K
Optimized reactor arrangements: introduction
Motivations and rationale
In reactor design, it is often desirable to minimize the overall reaction volume
This goal is made possible by arranging a number of reactors (e.g. in series) to
follow a path at maximum reaction rate
To follow such optimized paths, heat transfers are required between reactors
A number of typical arrangements are described and analyzed next
A reversible reaction: kinetic data analysis
Single reversible reaction:
A
k
1
k
1
B
Kinetic data can be conveniently expressed graphically in the plane (T, x
A
)
Dene x
A
=
c
A0
c
A
c
A0
and recall:
r (T, x
A
) =k
1
(T)c
A0
(1x
A
) k
1
(T)c
A0
x
A
Optimized reactor arrangements: kinetic data
Kinetic data
Kinetic data report, in (T, x
A
), a number lines of constant reaction rate
Each line is dened by the implicit relation:
a =k
1
(T)c
A0
(1x
A
) k
1
(T)c
A0
x
A
where a >0 species the reaction rate
The line at a =0 denes the (implicit) equilibrium relation x
Ae
(T)
Locus of maximum rates
For each given conversion, there exists a temperature at which the reaction
rate is at maximum
This is formally dened as:
_
r (T, x
A
)
T
_
x
A
=
dk
1
dT
c
A0
(1x
A
)
dk
1
dT
c
A0
x
A
=0
Kinetic data for an exothermic reaction
Parametric plot of normalized reaction rate r /c
A0
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
60 80 100 120 140
x
A
T (
o
C)
0.002
0.004
0.01
0.02
0.04
0.1
0.2
0.4
1.0
Equilibrium
Isokinetic
Maximum rate
Kinetic data for an endothermic reaction
Parametric plot of normalized reaction rate r /c
A0
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
60 70 80 90 100 110 120 130 140
x
A
T (
o
C)
0.002
0.004
0.01
0.02
0.04
0.1
0.2
0.4
1.0
Equilibrium
Isokinetic
Optimized CSTR arrangements
Scheme 1: Preheating and inter-cooling
Cooler
x
A2
T
2
T
2
T
3
x
A3
T
0
T
0
T
1
T
1
x
A1
Cooler Heater
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
50 60 70 80 90 100 110 120 130 140 150
x
A
T (
o
C)
Equilibrium
Isokinetic
Maximum rate
Optimized CSTR arrangements (cont.)
Scheme 2: Auto-thermal preheating
x
A1
T
0
T
1
T
1
T
2
T
0
x
A2
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
50 60 70 80 90 100 110 120 130 140 150
x
A
T (
o
C)
Equilibrium
Isokinetic
Maximum rate
Optimized CSTR arrangements (cont.)
Scheme 3: Preheating and feed quenching
x
A3
T
3 T
0
T
0
T
1
x
A1
Heater
T
1
T
2
x
A2
T
2
x
A2
x
A1
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
50 60 70 80 90 100 110 120 130 140 150
x
A
T (
o
C)
Equilibrium
Isokinetic
Maximum rate
Optimized reactor arrangements: auto-thermal PFR
T
r
(z)
T
0
T
0
Heater
T
a
(z)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
50 60 70 80 90 100 110 120 130 140 150
x
A
T (
o
C)
Equilibrium
Isokinetic
Maximum rate
Summary of material and energy balances
Balance equations for the batch reactor
Case Material balances Energy balance
Single phase
d(V
R
c
j
)
dt
=
i j
r
i
V
R
V
R

C
p
dT
dt
TV
R
dp
dt
=
i
(H
Ri
)r
i
V
R
+

Q
Constant pressure
d(V
R
c
j
)
dt
=
i j
r
i
V
R
V
R

C
p
dT
dt
=
i
(H
Ri
)r
i
V
R
+

Q
Constant volume
(ideal gas)
dc
j
dt
=
i j
r
i
V
R

C
v
dT
dt
=
i
(H
Ri
+RT
i
)r
i
V
R
+

Q
Liquid phase
dc
j
dt
=
i j
r
i
V
R

C
p
dT
dt
=
i
(H
Ri
)r
i
V
R
+

Q
Steady-state balance equations for the CSTR
Single phase Q
0
c
j 0
Qc
j
+
i j
r
i
V
R
=0
j
Q
0
c
j 0
(

H
j 0

H
j
) +
i
(H
Ri
)r
i
V
R
+

Q =0
Liquid phase Q
0
(c
j
c
j 0
) +
i j
r
i
V
R
=0 Q
0
0

C
p
(T
0
T) +
i
(H
Ri
)r
i
V
R
+

Q =0
Summary of material and energy balances (cont.)
Steady-state balance equations for the PFR
Single phase
d(Qc
j
)
dV
=
i j
r
i
Q

C
p
dT
dV
+Q(1T)
dp
dV
=
i
(H
Ri
)r
i
+
4
D
q
Constant pressure
or ideal gas
d(Qc
j
)
dV
=
i j
r
i
Q

C
p
dT
dV
=
i
(H
Ri
)r
i
+
4
D
q
Liquid phase Q
dc
j
dV
=
i j
r
i
Q

C
p
dT
dV
+Q
dp
dV
=
i
(H
Ri
)r
i
+
4
D
q
Liquid phase,
constant pressure
Q
dc
j
dV
=
i j
r
i
Q

C
p
dT
dV
=
i
(H
Ri
)r
i
+
4
D
q

08 Energy Balance

Uploaded by

Document Information

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

08 Energy Balance

Uploaded by

Copyright:

Available Formats

Energy balance for chemical reactors

First Year course, MS in Chemical Engineering, University of Pisa

Department of Civil and Industrial Engineering (DICI)

Q external heat ow,

You might also like