Steady-State Non-Isothermal Reactor Design Complete

Steady-State Nonisothermal
Reactor Design
Energy Balance Fundamentals
1
Energy Balance, Rationale and Overview
Let’s calculate the volume necessary to achieve a
conversion, X, in a PFR for a first-order, exothermic and
adiabatic reaction.
The temperature profile might look something like this:
T k X
V V V
2
dX - rA
Mole Balance: =
dV FA0
 E  1 1 
rA = -k1 exp   -  CA
Rate Law:  R  T1 T 
CA = CA0 (1- X)
Stoichiometry:
 E  1 1 
k1 exp   -  
dX  R  T1 T  
Combine: = C A 0 (1 - X )
dV FA 0
3
 E  1 1 
ki exp  - 
dX  R  T1 T 
= C A0 (1 - X )
dV FA0
We cannot solve this equation because we don’t

have T either as a function of V or X.
We need another equation. That equation is:

The Energy Balance
4
Heat effects: definition of ΔHRx and ΔCp
aA + bB  cC + dD
or, considering A (limiting reactant) the basis for our calculations:
b c d
A+ B  C + D
a a a
d c b
DH Rx = H D + HC - H B - H A
a a a
d c b
D C P = C PD + C PC - C PB - C PA
a a a 5
Energy Balance: different cases
1. Adiabatic CSTR, PFR, PBR or Batch
WS = 0 DCˆ P = 0
EB: Energy Balance
X EB =
  C (T - T )
i Pi 0
=
  C (T - T )
i Pi 0
- DH o Rx (TR ) + DCˆ p (T - TR )  -DH o Rx
T = T0 +
( Rx )XEB
-DH o
 C i Pi
Ni 0 Fi 0 Ci 0 yi 0
Definition: i = = = =
N A0 FA0 CA0 yA0 6
Adiabatic
Exothermic Endothermic
T0
T T
T0
0 XEB 0 XEB
7
2. CSTR with heat exchange: UA(Τ-Ta) and a
large coolant flow rate (WS = 0 DCˆ P = 0)
UA 
 (T -T a )+ iCPi (T -T 0 )
FA 0 
X EB = o
-DH Rx
C
m
T
Ta
8
2. CSTR with heat exchange (cont’d)
UA 
 (T -T a )+ iCPi (T -T 0 )
FA 0  FA0 X
X EB = and V=
-DH oRx -rA
[ ] [ ]
[ : Calculate V and T] [ : Calculate X and T]
[ : Calculate X and ]
9
3. PFR/PBR with heat exchange
Ta Coolant
FA0
T0
3A. PFR in terms of conversion

=A/V: area of heat exchange per
Qg
  Qr unit volume of reactor (m-1)
dT rADH Rx (T ) - Ua (T - Ta ) Qg - Qr
= =
dV FA0 (  iCPi + DC p X ) FA0 (  iCPi + DC p X )
10
User Friendly Equations Relate T and X or Fi
3B. PBR in terms of conversion
 Ua
rA DHRx (T ) - (T - Ta ) : bulk density of catalyst
(g/cm3 of reactor bed)
dT b
=
dW FA 0 ( Ci Pi + DCp X ) = : bulk density of
catalyst (g/cm3 of reactor bed)
3C. PBR in terms of molar flow rates
 Ua
rA DHRx (T ) - (T - Ta ) DCP = i CPi 
dT b
=
dW F C i Pi
 Fi = FA0 ( i + i X ) 
11
User Friendly Equations Relate T and X or Fi
3D. PFR in terms of molar flow rates
dT rA DHRx (T ) -Ua(T - Ta ) Qg - Qr
= =
dV  FiCP  FiCP
i i
4. For multiple reactions in a PFR (q reactions and m species)

q
dT
 r DHij Rxij -Ua(T - Ta )
i=1
= m
dV
F C i Pj
j =1
Let’s look where these Equations came from. 12
Energy Balance (Derivation)
Reactor with no Spatial Variations
Reactor
13
Energy Balance
Q
Reactor
Rate of flow
of heat to
the system
from the
surroundings
Q
(J/s)
Energy Balance
Q W
Reactor
Rate of flow
Rate of work
of heat to
the system - done by the
system on the
from the
surroundings
surroundings
Q - W
(J/s) (J/s)
Energy Balance
Q W
Fin
Reactor
Ein
Rate of flow Rate of energy

Rate of work
of heat to added to the
system on the
+ system by
from the mass flow into
surroundings
surroundings the system
Q - W + Fin Ein
(J/s) (J/s) (J/s)
Energy Balance
Q W
Fin Fout
Reactor
Ein Eout
Rate of flow Rate of energy Rate of energy

Rate of work
of heat to added to the leaving
system on the
+ system by - system by
from the mass flow into mass flow out
surroundings
surroundings the system of the system
Q - W + Fin Ein - Fout Eout

(J/s) (J/s) (J/s) (J/s)
Energy Balance
Q W
Fin Fout
Reactor
Ein Eout
Rate of Rate of flow Rate of energy Rate of energy

Rate of work
accumulation of heat to added to the leaving
of energy = the system - done by the
system on the
+ system by - system by
within the from the mass flow into mass flow out
surroundings
system surroundings the system of the system
dEˆ sys
dt = Q - W + Fin Ein - Fout Eout
(J/s) (J/s) (J/s) (J/s) (J/s)
Energy Balance

Q
Fi in   Fi out
 
( e.g., FA0 )  ( e.g., FA )
 
Ei in   Ei out
 
W  e.g., E
( e.g., EA0 )  S
( A)
Energy Balance on an open system: schematic.
  dEsystem
Q - W +  Fi 0 Ei 0 in -  Fi Ei out =
dt
19
Intro to Heat Effects
Assumptions:
=0 =0
E i = U i + PE i + KE i Other energies small compared to internal
W = flow work + shaft work
~ ~  ~ m3 
flow work = -  Fi 0 P0 Vi 0 +  Fi PVi  V = 
 mol 
Recall:
H i = U i + PV˜i
20
Substituting for W
    dEsys
 Fi 0Ui 0 -  FU  -  Fi 0 PV
i i +Q -  0 i 0 +  Fi PVi + WS 
 = dt
 Hi 0
  Hi

    dEsys
 Fi 0 U i 0 + PV  -  Fi U i + PVi  + Q - WS = dt
0 i0 
 - W = dEsys
F H
i0 i0 -  Fi H i + Q S
dt
Steady State:  -W
Q  +  F H - F H = 0
S i0 i0 i i
21
F H i0 i0 = FA 0 i Hi0

D 
H Rx
 Fi Hi = FA0 ( i + i X )Hi = FA0 i Hi + FA0 X i Hi

 Fi = FA0 ( i + i X ) 
Q - WS + FA0 (  i ( Hi 0 - Hi ) - X DH Rx ) = 0
22
For No Phase Changes
T
Hi (T) = H (TR )+
0
i TR
CPidT
Enthalpy of formation at temperature TR
Constant Heat Capacities
H i (T ) = H i0 (TR )+ CPi (T - TR )
0
 i i  i i + iCPi (T - TR )
 H =  H
Heat of reaction at temperature T
23
 H =  H +  C (T - T )
i i i
0
i i Pi R
d ˆ c ˆ b ˆ
iCPi = DCP = a CPD + a CPC - a CPB - Cˆ PA
ˆ ˆ
DH R (T ) = DHR (TR )+ DCˆ P (T - TR )
also, between inlet and outlet:

H i 0 - H i = CPi (T0 - T ) = -CPi (T - T0 )
24
Substituting the equations in circle (previous slide)
back into the Energy Balance below
Q - WS + FA0 (  i ( Hi 0 - Hi ) - X DH Rx ) = 0
yields:
Q -WS - FA0 iC Pi (T - Ti 0 ) - FA0 X DHR (TR ) + DCˆ P (T - TR )  = 0
25
Adiabatic Energy Balance

Adiabatic (Q=0) and no Work (WS = 0)
 (T - T )
X=
 i Pi
 C i0
- DH R (TR ) + DCˆ P (T - TR ) 
In many instances, the ΔCp term in the denominator is negligible

with respect to the ΔHR term, so that a plot of X vs. T will usually
be linear
Exothermic
CSTR
PFR
~ PBR
XEB Batch
T0
0 T 26
Adiabatic Energy Balance

Adiabatic (Q=0), no Work (WS = 0) and DCˆ P = 0
X DH R (T ) 
T = T0 -
  Ci Pi
Exothermic
T0
X 27
Example: Adiabatic PFR
A ↔ B*
1) Mole Balance: dX rA
=-
dV FA 0
   E  1 1 
2) Rate Laws: rA = -k C A - CB  k = k1 exp   -  
 KC   R  T1 T  
0
 DH RX  1 1 
DCP = 0 K C = K C 2 exp   - 
 R  T2 T  
Kc: equilibrium constant

* The subject of reversible reactions will be revisited later 28
A↔B
3) Stoichiometry:
C A = C A 0 (1 - X ) At equilibrium rA=0. Then
from from rate law and
CB = CA0X stoichiometry: Xeq=Kc/(1+Kc)
4) Energy Balance
 iC Pi (T - T0 )
X=
- DH R (TR ) 
First need to calculate the maximum conversion
which is at the adiabatic equilibrium conversion. 29
30
A↔B
  C (T - T )
i Pi 0
X=
- DH R (TR ) 
Xe Adiabatic equilibrium conversion

and temperature
T
T0
KC
X eq =
1 + KC 31
We can now form a table. Set X, then calculate T and
FA0/-rA, increment X, then plot FA0/-rA vs. X:
FA0/-rA FA0
dV = dX (reactor dimensionalization)
- rA
X
32
Reactor Design
Reactors with Heat Exchange

• Adiabatic
• Heat Exchange Constant Ta
• Heat Exchange Variable Ta Co-current
• Heat Exchange Variable Ta Counter Current
33
CSTR: Adiabatic Operation
FA0
FI
A B
Elementary liquid phase reaction carried out in a CSTR
The feed consists of both - Inerts I and Species A with

the ratio of inerts I to the species A being 2 to 1.
34
CSTR: Adiabatic Operation
 Assuming the reaction is irreversible for CSTR,

A  B, (KC = ∞) what reactor volume is
necessary to achieve 80% conversion?
[Specify X  Find T and V]
 If the exiting temperature to the reactor is 360K,
what is the corresponding reactor volume?
[Specify T  Find X and V]
 Make a Levenspiel Plot and then determine the
PFR reactor volume for 60% conversion and
95% conversion. Compare with the CSTR
volumes at these conversions.
35
CSTR: Adiabatic Example (solution)
=5 Δ = −20000 (exothermic)
= 300
= 10 A B =?
=?
Additional data
= = 164 = 1.989
= 18 @298 = 0.1 -1
= 10000 =2
36
CSTR: Adiabatic Example (solution)
FA0 X
1) Mole Balances: V=
- rA exit
 CB 
2) Rate Laws: - rA = k  C A -  = kC A
 KC 
E 1 1 
 - 
R  T1 T 
k = k1e
3) Stoichiometry: C A = C A 0 (1 - X )
C B = CA0X
37
CSTR: Adiabatic Example
4) Energy Balance
Adiabatic, ∆Cp=0
T = T0 +
(- DH Rx )X
=T +
(- DH Rx )X
0
  i C Pi C PA +  I C PI
 - (- 20,000)  20,000
T = 300 +   X = 300 + X
164 + (2)(18) 164 + 36
T = 300 + 100 X
38
Irreversible for Parts (a) through (c)
- rA = kC A 0 (1 - X ) (i.e., K C = )
(a) Given X = 0.8, find T and V
Calc Calc Calc Calc

Given X T k -rA V
Calc KC
(if reversible)
39
Given X, Calculate T and V
FA0 X FA0 X
V= =
-rA exit kC A0 (1 - X )
T = 300 + 100 ( 0.8 ) = 380 K
10, 000  1 1  -1
k = 0.1exp - = 3.81min
1.989  298 380 
V=
FA0 X
=
( 5 )( 0.8 )
= 2.82 dm3
- rA ( 3.81)( 2 )(1 - 0.8)
40
Given T, Calculate X and V

Calc Calc Calc Calc
(b) Given T 
 X 
 k 
 -rA 
V
Calc K C
(if reversible)
- rA = kC A 0 (1 - X ) (Irreversi ble)
T = 360 K
T - 300
X = = 0 .6
100
k = 1 .83 min -1
V =
(5 )(0 .6 )
= 2 .05 dm 3
(1.83 )(2 )(0 .4 ) 41
(c) Levenspiel Plot

FA 0 FA 0
=
- rA kC A 0 (1 - X )
T = 300 + 100X
Calc Calc Calc FA 0

Calc
Choose X T k -rA 
-rA
42
(c) Levenspiel Plot
43
CSTR X = 0.6 T = 360 K
CSTR 60%
CSTR X = 0.95 T = 395 K
CSTR 95%
44
30
PFR X = 0.6
25
20
-Fa0/Ra
15
10
PFR 60%
5
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
PFR X = 0.95
PFR 95%
45
CSTR: Adiabatic Example - Summary
CSTR X = 0.6 T = 360 V = 2.05 dm3

PFR X = 0.6 Texit = 360 V = 5.28 dm3
CSTR X = 0.95 T = 395 V = 7.59 dm3
PFR X = 0.95 Texit = 395 V = 6.62 dm3
46
Example: Production of propylene glycol in an
adiabatic CSTR (exothermic reaction)
[Specify V, Find X and T]
Propylene glycol is produced by the hydrolysis of propylene oxide:
You are the engineer in charge of an adiabatic CSTR producing propylene glycol by
this method. Unfortunately, the reactor is beginning to leak, and you must replace it.
There is another CSTR of 300-gal capacity standing idle; it is glass-lined, and you
would like to use it.
 A 0 = 46.62 ft 3 /h
 M 0 = 46.62 ft 3 /h
 B 0 = 233.1 ft 3 /h
FA 0 = 43.0 lb-mol/h
FM 0 = 71.87 lb-mol/h
FB 0 = 802.8 lb-mol/h 47
 A 0 = 46.62 ft 3 /h
 M 0 = 46.62 ft 3 /h
 B 0 = 233.1 ft 3 /h
FM 0 = 71.87 lb-mol/h
FB 0 = 802.8 lb-mol/h
The reaction is first-order in propylene oxide concentration with the specific reaction rate
The units of E are Btu/lb-mol and T is in °R.
There is an important constraint on your operation. Propylene oxide is a rather low

boiling-point substance. With the mixture you are using, you feel that you cannot
exceed an operating temperature of 125 F, or you will lose too much oxide by
vaporization through the vent system.
48
 A 0 = 46.62 ft 3 /h
 M 0 = 46.62 ft 3 /h
 B 0 = 233.1 ft 3 /h
FM 0 = 71.87 lb-mol/h
FB 0 = 802.8 lb-mol/h
(a) Can you use the idle CSTR as a replacement for the leaking one if it will
be operated adiabatically?
(b) If so, what will be the conversion of propylene oxide to glycol?

1 [m] = 3.2808 [ft]
1 [kg] = 2.2046 [1bm]
Conversion
[K] = (5/9) [°R]; [°R] = [°F] + 459.67
Factors
1 [m3] = 35.315 [ft3] = 264.17 [gal] (U.S.) 49
1 [J] = 9.4781 × 10-4[BTU]
adiabatic CSTR (Solution)
Let the reaction be represented by
where
In this problem, neither the exit conversion nor the temperature of the adiabatic
reactor is given. By application of the mole and energy balances, we can solve
two equations with two unknowns (X and T). Solving these coupled equations, we
determine the exit conversion and temperature for the glass-lined reactor to see if it
can be used to replace the present reactor.
50
1. Mole Balance and Design Equation:
The design equation in terms of X is
2. Rate Law:
51
3. Stoichiometry (liquid phase, υ=υ0):
4. Combining yields
Solving for X as a function of T and recalling that τ=V/υ0 gives
This equation relates temperature and conversion through the mole

balance.
52
5. The energy balance for this adiabatic reaction in which there is negligible
energy input provided by the stirrer is
This equation relates X and T through the energy balance.
We see that two equations, the Equation of this slide and the last Equation of the
previous slide, and two unknowns, X and T, must be solved (with XEB = XMB = X).
Before solving the two equations, we need to replace some variables in the mole
and energy balances by their values.
53
6. Calculations:
(a) Evaluate the terms (τ, CA0, Θi):

The total liquid volumetric flow rate υ0 entering the reactor is
54
6. Calculations:
(a) Evaluate the terms (τ, CA0, Θi):
After numerical substitutions, the conversion calculated from the mole balance is:
55
6. Calculations:
(b) Evaluating the energy balance terms
(1) Heat of reaction at temperature T
H Ao ( 68 o F ) = -66600 Btu/lb mol

H Bo ( 68 o F ) = -123000 Btu/lb mol
H Co ( 68 o F ) = -226000 Btu/lb mol
o
DH Rx ( 68 o F ) = H Co ( 68 o F ) - H Bo ( 68 o F ) - H Ao ( 68 o F ) =
-226000 Btu/lb mol - ( -123000 Btu/lb mol - 66600 Btu/lb mol )
= -36400 Btu/lb mol 56
6. Calculations:
(1) Heat of reaction at temperature T
DH Rx = -36400 - 7 (T - TR )
(2) Heat capacity term
57
6. Calculations:
The conversion calculated from the energy balance, XEB, for an adiabatic reaction is
given by Equation
Substituting all the known quantities into the energy balance gives us
58
7. Solution:
We have to solve two non-linear algebraic equations together. A graphical solution
is one option. Here, X is plotted as a function of T for both the mole and energy
balances, and the intersection of the two curves gives the solution where both the
mole and energy balance solutions are satisfied, i.e., XEB = XMB.
T (oR) XMB XEB
59
7. Solution:
We observe from this plot that the only intersection point is at 83% conversion and
613°R. At this point, both the energy balance and mole balance are satisfied. Because
the temperature must remain below 125F (585°R), we cannot use the 300-gal reactor
as it is now. 60
CSTR with heat exchange
Steady-state energy balance:
[Usually Ws is neglected unless, the mixture stirred is very viscous]

Using the mole balance: FA0X=-rAV , and neglecting ΔCp, the energy balance
is rearranged
61
The Q term in the CSTR
The rate of heat transfer from the exchanger to the reactor fluid at temperature
T is
A steady-state energy balance on the heat-exchanger fluid entering and leaving the
exchanger is
62
where Cpc is the heat capacity of the heat exchanger fluid and TR is the reference
temperature. Simplifying gives us
63
Solving for the exit temperature of the heat exchanger fluid:
Ta2 is also equal to (previous slide): Ta 2 = ( m cC pcTa1 - Q ) / m cC pc

Combining the two equations gives:
64
For large values of the heat-exchanger fluid flow rate, mc, the exponent will be
small and can be expanded in a Taylor series (e-x= 1 – x + . . .) where second
order terms are neglected in order to give
65
Then:
where
[Valid only for large heat-transfer fluid flow rates!]
Using the energy balance in conversion terms, neglecting the work of the stirrer and
ΔCp , and substituting Q from the equation above yields
66
Solving for X:
which is coupled to the mole balance equation (below) to dimensionalize

the CSTR.
67
(Some alternative formulations)
Letting the energy balance can be rearranged as
We set the CSTR heat exchange parameters, κ and Tc.
Then the energy balance is formulated as
68
(Some alternative formulations)
The parameters κ and Tc are used to simplify the equations for non-adiabatic
operation.
A. Solving for conversion
A. Solving for temperature
69
PFR with heat exchange
FH i i V -  Fi H i V + DV
+ Ua (T a - T )D V = 0
=A/V: area of heat exchange per
unit volume of reactor (m-1)
- d  Fi H i
+ Ua (T a - T ) = 0
dV
- d  Fi H i  dH i dF i 
= -   Fi +  Hi
dV  dV dV  70
dFi
= ri = i (- rA )
dV
H i = H i0 + C Pi (T - TR )
dH i dT
= CPi
dV dV
- d  Fi H i  dT 
= -  Fi C Pi +  H ii (- rA )
dV  dV 
i H i = DH R x
71
 dT 
-  C Pi Fi + DH R (- rA ) + Ua(Ta - T ) = 0
 dV 
dT
 FiCPi dV = DH R rA - Ua(T - Ta )
dT ( DH R )( rA ) - Ua (T - Ta )
=
dV  FiCPi
Need to determine Ta
72
PFR with heat exchange in terms of conversion
dT (- rA )(- DH Rx ) - Ua (T - Ta )
=
dV  Fi C Pi
Using  Fi = FA0 ( i + i X ) 
 Fi CPi = FA0 (   C +  C X ) = F (   C
i Pi i Pi A0 i Pi + DCPi X )
If DC Pi = 0, then
dT ( -rA )( -DH Rx ) - Ua (T - Ta )
=
dV FA0  i CPi
Need to determine Ta 73
Heat Exchanger Energy Balance
• Ta determination
A. Constant Ta e.g., Ta = 300K
[Holds in the case of high flow rates of heat transfer fluid]
B. Variable Ta Co-Current
dTa Ua (T - Ta )
= ,V = 0 Ta = Tao
dV  Pcool
mC
C. Variable Ta Counter Current

dTa Ua(Ta - T )
= V =0 Ta = ? Guess
dV m C Pcool
Guess Ta at V = 0 to match Ta0 = Ta0 at exit, i.e., V = Vf
74
Variable Ta Co-Current
Coolant Balance:
In - Out + Heat Added = 0
m C H C V
- m C H C V + DV
+ UaDV (T - Ta ) = 0
dH C
- m C + Ua (T - Ta ) = 0
dV
H C = H 0C + C PC (Ta - Tr )
dH C dTa
= C PC
dV dV
dTa Ua (T - Ta )
= , V = 0 Ta = Ta 0
dV m C C PC 75
Variable Ta Counter-Current
Coolant Balance:
In - Out + Heat Added = 0
m C H C V + DV
- m C H C V
+ UaDV (T - Ta ) = 0
dH C
m C + Ua(T - Ta ) = 0
dV
dTa Ua(Ta - T ) [The only difference in this equation and

= the one in the previous slide is a ”-”,
dV m C C PC namey Ta-T vs. T-Ta]
76
Example: Production of acetic
anhydride (endothermic reaction)
Jeffreys, in a treatment of the design of an acetic anhydride manufacturing facility,
states that one of the key steps is the endothermic vapor-phase cracking of acetone to
ketene and methane
He states further that this reaction is first-order with respect to acetone and that the
specific reaction rate can be expressed by
where k is in reciprocal seconds and T is in Kelvin. In this design it is desired to

feed 7850 kg of acetone per hour to a tubular reactor. The reactor consists of a bank
of 1000 one-inch tubes. We shall consider four cases of heat exchanger operation.
The inlet temperature and pressure are the same for all cases at 1035 K and 162 kPa
(1.6 atm) and the entering heating-fluid temperature available is 1250 K.
77
anhydride (cont’d)
A bank of 1000 one-in. 1.79 m in length corresponds to 1.0 m3 (0.001 m3/tube
= 1.0 dm3/tube) and gives 20% conversion. Ketene is unstable and tends to
explode, which is a good reason to keep the conversion low. However, the pipe
material and schedule size should be checked to learn if they are suitable for
these temperatures and pressures. The heat-exchange fluid has a flow rate, of
0.111 mol/s, with a heat capacity of 34.5 J/mol·K.
Plot conversion and temperature along the reactor length for each of the following
cases
Case 1 The reactor is operated adiabatically.
Case 2 Constant heat-exchange fluid temperature Ta = 1250 K
Case 3 Co-current heat exchange with Ta0 = 1250 K
Case 4 Countercurrent heat exchange with Ta0 = 1250 K
2 78
U = 110 J/m  s  K
anhydride (solution)
Let A = CH3COCH3, B = CH2CO, and C = CH4. Rewriting the reaction
symbolically gives us
AB+C
Algorithm for a PFR with Heat Effects
The value of k at 1035 K
aA + bB  cC + dD
d c b
 = + - -1
a a a
79
Before combining the Mole Balance with the Rate Equation, it is first
necessary to use the Energy Balance to determine T as a function of X.
b. Heat Exchanger
80
Example: Production of acetic anhydride
(solution)
81
82
CASE 1: Adiabatic
83
CASE 1: Adiabatic (cont’d)
As temperature drops, so does k and hence the rate, –rA, drops to an insignificant
value. Note that for this adiabatic endothermic reaction, the reaction virtually dies out
after 3.5 dm3, owing to the large drop in temperature, and very little conversion is
achieved beyond this point.
84
CASE 2: Constant heat-exchange fluid temperature, Ta= 1250 K
85
CASE 2: Constant heat-exchange fluid temperature, Ta
Just after the reactor entrance, the reaction temperature drops as the sensible heat from the
reacting fluid supplies the energy for the endothermic reaction. This temperature drop in the
reactor also causes the rate of reaction to drop. As we move farther down the reactor, the
reaction rate drops further as the reactants are consumed. Beyond V = 0.08 dm3, the heat
supplied by the constant Ta heat exchanger becomes greater than that “consumed” by the
endothermic reaction and the reactor temperature rises.
86
CASE 3: Co-current Heat Exchange
The energy balance on a co-current heat exchanger is
with Ta0 = 1250 K at V = 0
87
CASE 3: Co-current Heat Exchange
In co-current heat exchange, we see that the heat-exchanger fluid temperature, Ta, drops
rapidly initially and then continues to drop along the length of the reactor as it supplies
the energy to the heat drawn by the endothermic reaction. Eventually Ta decreases to the
point where it approaches T and the rate of heat exchange is small; as a result, the
temperature of the reactor, T, continues to decrease, as does the rate, resulting in a small
conversion.
88
CASE 4: Countercurrent Heat Exchange
89
CASE 4: Countercurrent Heat Exchange
At the front of the reactor, V = 0, the reaction takes place very rapidly, drawing energy from
the sensible heat of the gas and causing the gas temperature to drop because the heat
exchanger cannot supply energy at an equal or greater rate to that being drawn by the
endothermic reaction. Additional “heat” is lost at the entrance in the case of countercurrent
exchange because the temperature of the exchange fluid, Ta, is below the entering reactor
temperature, T.
90
PBR with heat exchange
FH i i V -  Fi H i V + DV
+ Ua (Ta - T ) D V = 0
W
Ua
FH i i V -  Fi H i +  (Ta - T ) dW =0
V + DV
0
b
Differentiating with respect to W
- d  Fi H i Ua
+ ( Ta - T ) = 0
dW b 91
Ua dFi dHi
(Ta - T ) -  Hi -  Fi =0
B dW dW
dFi
dW
( )
= ri = i -rA
T
Hi = Hi (TR ) +  CPi dT = Hi (TR ) + CPi (T - TR )
TR
dH i dT
= CPi
dW dW
- d  Fi H i  dT 
= -   Fi CPi +  H ii ( - rA ) 
dW  dW  92
Ua  dT
(Ta - T ) + rA i Hi -  FC
i Pi =0
B dW
 H i i = DH R x
Final form of the differential equation of the Energy Balance in

terms of flow rates:
Ua
(Ta - T ) + rADH Rx
dT B
=
dW  FC i Pi
93
Final form of the differential equation of the Energy Balance
in terms of conversion:
Ua
(Ta - T ) + rADH Rx
dT B
= = f ( X ,T )
dW FA0  iCPi + DCPi X 
The mole balance in differential form can be written as:
dX -rA
= = g ( X ,T )
dW FA0
The two coupled differential equations can be solved simultaneously

to calculate how X and T evolve along the reactor bed. 94
Reactor Design
Reversible reactions
Reactors with interstage heat transfer
Multiple steady states
95
Reversible Reactions
A+B  C+D
The rate law for this reaction will follow an elementary rate law.
 CC C D 
-rA = k  CACB - 
 Ke 
Where Ke is the concentration equilibrium constant. We know from Le

Chaltlier’s law that if the reaction is exothermic, Ke will decrease as
the temperature is increased and the reaction will be shifted back to
the left. If the reaction is endothermic and the temperature is
increased, Ke will increase and the reaction will shift to the right.
96
K, which is defined as follows:
- ( Dg Rx
o
)
ln K  = f (T )
RT
To calculate the temperature dependence of K, we take advantage
of the thermodynamic web to give us a relationship among the
desired properties. We wish to find dlnK/dT.
d ln K d ( Dg / RT ) Dg Rx
o
Rx
o o
1 d Dg Rx o
Dg Rx o
DsRx
=- = 2
- = 2
+
dT dT RT RT dT RT RT
 g 
  = -s
 T P
97
o o o
By definition: Dg Rx = DhRx - T DsRx
For exothermic reactions (Δhrx<0), the
o
so
d ln K Dh Rx
equilibrium constant decreases as temperature
= 2 increases, since RT2 is always greater than zero.
dT RT For endothermic reactions (Δhrx>0), the
equilibrium constant increases as temperature
increases.
For small temperature ranges or approximate calculations, we can assume Δhrx

independent of temperature. After variable separation, we get:
o
DhRx
d ln K = 2
dT
RT
Integration yields:
o
K2 DhRx 1 1
ln =-  -  [Often there’s data for K available at 298 K]
K1 R  T2 T1  98
Xe K
endothermic endothermic
reaction reaction
exothermic exothermic
reaction reaction
T T
99
Types of Catalytic Reactors
100
Industrial example: Naphtha reforming
Representative feed
composition of naphtha
75% straight chains

15% naphthenes
10% aromatics
101
Industrial example: Naphtha reforming
The more compact the molecule for a given number of

carbon atoms, the higher the octane rating
Representative feed
composition of naphtha
75% straight chains

15% naphthenes
10% aromatics
Octane number ~ 70 • Each step is highly endothermic
(commercial gasoline > 90)
• Narrow temperature operating
window (430 oC - 530 oC)
102
Industrial example: Increase octane rating of gasoline
Interstage heating
for gasoline
production in
moving-bed
reactors
Temperature
conversion trajectory
for interstage heating
of the endotherming
reforming reaction
103
Problem
For the elementary solid-catalyzed liquid-phase reaction A  B make a plot

of equilibrium conversion as a function of temperature. Determine the
adiabatic equilibrium conversion and temperature when pure A is fed to the
reactor at a temperature of 300 K
Additional information:
HAo ( 298 K) = -40000 cal/mol CPA = 50 cal/mol/K Ke = 100000 at 298 K
HBo ( 298 K) = -60000 cal/mol CPB = 50 cal/mol/K R = 1.987 cal/mol/K
104
Problem-part 1: Calculating equilibrium conversion
A B (elementary reaction)
1. Rate law:
kf  C 
-rA = k f C A - kbCb = k f C A - CB = k f  C A - B 
Ke  Ke 
2. Equilibrium:
CBe
- rA = 0 ; so C Ae =
Ke
3. Stoichiometry:
C A0 X e
 A =  B yields C A0 (1 - X e ) =
Ke
Solving for X e gives X e = K e (T ) (1)

1 + K e (T )
105
4. Equilibrium constant:
d ln K e (T ) DH Rx (T )
Van’t Hoff equation: =
d (T ) RT 2
T
DH Rx (T ) = DH Rx (T0 ) +  DC p dT = DH Rx (T0 ) = constant
T0
Integration of Van’t Hoff equation gives
Ke (T ) -DH Rx  1 1   -DH Rx  1 1  
ln =  -   K e (T ) = K (T
e 0 )exp   -   
Ke (T0 ) R  T T0   R  T T0  
 20000  1 1    298 - T  
K e (T ) = 100000 exp   -  = 100000 exp  33.78   (2)
 1.987  T 298     T 
106
  298 - T  
100000 exp  33.78  
  T  
From (1) and (2) : X e = (3)
  298 - T  
1 + 100000 exp  33.78  
  T 
T(K) Xe 1
298 1
0.8
350 1
400 0.95 0.6
X
425 0.81
0.4
450 0.53
475 0.25 0.2
500 0.11 0
550 0.02 300 400 500 600
T (K)
107
Problem-part 2: Calculating the adiabatic equilibrium
conversion and temperature
Energy balance:
DH = Q = 0  nA0 X DH Rx + nAC pA (T - 300) + nBC pB (T - 300) =0
( )
nA0 XDH Rx + nA + nB Cp (T - 300) =0
XDH Rx + C p (T - 300) =0
Cp
X= (T - 300) = 2.5 10-3 (T - 300) (4)
-DH Rx
108
Problem-part 2: Calculating the adiabatic equilibrium
conversion and temperature
K e (T )
1
Xe =
1 + K e (T )
0.8
X 0.6
0.4
X =2.5  10-3 (T - 300)
0.2
0
300 400 500 600
T (K)
For a feed temperature of 300 K, the adiabatic equilibrium temperature is 465
K and the corresponding adiabatic equilibrium conversion is 0.41.
109
Problem-part 3: Interstage cooling
What conversion could be achieved if two interstage coolers were available
that had the capacity to cool the exit stream to 350 K? Also determine the
heat duty, the coolant flow rate and the size of each countercurrent
exchanger for a molar feed rate of A of 40 mol/s. Assume that 95% of
equilibrium conversion is achieved in each reactor. The feed temperature to
the first reactor is 300 K. The coolant is available at 270 K but cannot be
heated above 400 K.
Additional information:
Cp,c =18 cal/mol/K

U =1000 cal/m2/K
110
Problem-part 3: Interstage cooling (Reactor
1 and Heat exchanger 1)
We saw that for an entering temperature of 300 K the adiabatic equilibrium
conversion was 0.41. For 95% equilibrium conversion, the conversion exiting
the first reactor is 0.4. The exit temperature is found from rearrangement of
the energy balance Eq. (4).
X =2.5 10-3 (T - 300)  T = 400 X + 300
T1 = 400  (0.4) + 300 = 460 K
In the first heat exchanger, the exit (hot) stream from the first reactor is
cooled from 460 K down to 350 K. The heat removal rate is
40 mol 50 cal kcal

Q = nh c p , h (Th ,in - Th ,out ) =  ( 460 K - 350 K ) = 220
s mol  K s
111
Problem-part 3: Interstage cooling (Heat exchanger 1
cont’d)
We see that 220 kcal/s is removed from the reaction system mixture. The rate
at which energy must be absorbed by the coolant stream in the exchanger is
Q = nccp,c Tc,out - Tc,in

( )
We consider the case where the coolant is available at 270 K but cannot be
heated above 400 K and calculate the coolant flow rate necessary to remove
220 kcal/s from the reaction mixture.
Q 220000 cal/s
nc = = = 94 mol/s
c p ,c (Tc ,out - Tc ,in ) cal
18 ( 400 K - 270 K )
mol  K
112
Problem-part 3: Interstage cooling (Heat exchanger 1
cont’d)
Th ,in 460 K Th , out 350 K

Heat Exchanger
Tc , out 400 K Tc ,in 270 K
D T1 = 460 - 400 = 60 K D T2 = 350 - 270 = 80 K
Logarithmic mean D Tmax - D Tmin 80 K - 60 K

temperature D Tlm = = = 69.52 K
ln ( D Tmax / D Tmin ) ln ( 80 / 60 )
difference
Sizing the heat Q 220000 cal/s

A= = = 3.16 m 2
exchanger U  DTlm 1000 cal  69.52 K
m2  K
113
Problem-part 3: Interstage cooling (Reactor 2)
K e (T )
Xe =
1 + K e (T )
1
0,8 The adiabatic equilibrium conversion in

reactor 2 is 0.63. Ninety-five percent of
0,6 the conversion is 0.6 and the
corresponding exit temperature,
X
0,4 calculated from the energy balance, is

T=400(0.6-0.4)+350=430 K
0,2
0
300 350 400 450 500 550 600
T (K)
114
Problem-part 3: Interstage cooling (Heat exchanger 2)
Summary
Th ,in 430 K Th , out 350 K
Heat Exchanger
Tc , out 400 K Tc ,in 270 K
40 mol 50 cal kcal

Q = nh c p , h (Th ,in - Th ,out ) =  ( 430 K - 350 K ) = 160
s mol  K s
Q 160000 cal/s
nc = = = 68.37 mol/s
c p ,c (Tc ,out - Tc ,in ) cal
18 ( 400 K - 270 K )
mol  K
Q 160000 cal/s
A= = = 3.14 m 2
U  DTlm 1000 cal  50.98 K
m2  K
115
Problem-part 3: Interstage cooling (Reactor 3)
K e (T )
Xe =
1 + K e (T )
1
For the final reactor we begin at
0,8 T0=350 K and follow the line
representing the equation for the
0,6 energy balance along to the point of
X
intersection with the equilibrium

0,4 conversion, which is X=0.8.
Consequently, the final conversion
0,2 achieved with three reactors and two
interstage coolers is (0.95)(0.8)=0.76.
0
300 350 400 450 500 550 600
T (K)
116
Optimum Feed Temperature
We now consider an adiabatic reactor of fixed size or catalyst weight and
investigate what happens as the feed temperature is varied. The reaction is first-
order reversible and exothermic. ( A  B )
we can construct the equilibrium conversion, Xe, as a function of temperature
graph and also plot the energy balances for three different entering temperatures
T0.
X EB = 0.075 (T - T0 )
117
Optimum Feed Temperature
We next plot the corresponding conversion profiles down the length of the
reactor for entering temperatures 350 K, 500 K and 600 K
Both high and low feed temperatures lead

to very low reactor exit conversions; there
must be an optimum feed temperature that
maximizes conversion.
As the feed temperature is increased from a very low

value, the specific reaction rate will increase, as will the
conversion. The conversion will continue to increase
with increasing feed temperature until the equilibrium
conversion is approached in the reaction. Further
increases in feed temperature for this exothermic
reaction will only decrease the conversion due to the
decreasing equilibrium conversion.
118
Multiple Steady States (MSS)
We consider the example of hydrolysis of propylene oxide in a CSTR.
If a parameter were changed slightly, there might be more than one intersection
of the energy and mole balance curves. When more than one intersection occurs,
there is more than one set of conditions that satisfy both the energy balance
and mole balance, and consequently there will be multiple steady states (MSS)
at which the reactor may operate. 119
Analysis
We start from the following energy balance formulation which holds when Ws and
ΔCp are neglected.
where
Using the CSTR mole balance , the energy balance may be rewritten as
120
Analysis
The left-hand side is referred to as the heat-generated term
The right-hand side is referred to as the heat-removed term (by flow and heat
exchange) R(T)
To study the multiplicity of steady states, we shall plot both R(T) and G(T) as a
function of temperature on the same graph and analyze the circumstances under which
we will obtain multiple intersections of R(T) and G(T).
121
Heat-Removed Term, R(T)
R(T) increases linearly with temperature, with slope CP0(1+κ) and

intercept Tc. As the entering temperature T0 is increased, the line retains
the same slope but shifts to the right as the intercept Tc increases
122
Heat-Removed Term, R(T)
Ta<T0
FA0 is decreased
A is increased
On the other hand, if Ta>T0, the intercept will move to the right as κ increases.
123
Heat-Generated Term, G(T)
The heat-generated term, G(T), can be written in terms of conversion [X=-rAV/FA0]
To obtain a plot of heat generated, G(T), as a function of temperature, we must

solve for X as a function of T using the CSTR mole balance, the rate law, and
stoichiometry.
For example, for a first-order liquid-phase reaction, the CSTR mole balance becomes

124
First-order liquid-phase reaction in a CSTR
Substituting for k in terms of the Arrhenius equation, we obtain
125
Note that analogous Equations for G(T) can be derived for other reaction orders and
for reversible reactions simply by solving the CSTR mole balance for X. For
example, for the second-order liquid-phase reaction:
the corresponding heat generated term is
126
Heat-Generated Term, G(T): Analysis of behavior of
G(T) curve (first-order reaction)
At very low temperatures, the second term in the denominator for the first-order
reaction can be neglected:
At very high temperatures, the second term in the denominator dominates, and
G(T) is reduced to
127
Heat-Generated Term, G(T): Analysis of behavior of
G(T) curve (first-order reaction)
For a given T, G(T) increases with decreasing activation energy (E) and increasing
space time (τ).
128
Plotting R(T) and G(T) curves together
129
Ignition-Extinction Curve
Ignition point
Extinction point
130

Steady-State Non-Isothermal Reactor Design Complete

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Steady-State Nonisothermal

Energy Balance Fundamentals

We cannot solve this equation because we don’t

We need another equation. That equation is:

1. Adiabatic CSTR, PFR, PBR or Batch

- DH o Rx (TR ) + DCˆ p (T - TR )  -DH o Rx

[ : Calculate V and T] [ : Calculate X and T]

3A. PFR in terms of conversion

3B. PBR in terms of conversion

3C. PBR in terms of molar flow rates

3D. PFR in terms of molar flow rates

4. For multiple reactions in a PFR (q reactions and m species)

Rate of flow Rate of energy

Rate of flow Rate of energy Rate of energy

Q - W + Fin Ein - Fout Eout

Rate of Rate of flow Rate of energy Rate of energy

Energy Balance on an open system: schematic.

 Fi Hi = FA0 ( i + i X )Hi = FA0 i Hi + FA0 X i Hi

Heat of reaction at temperature T

DH R (T ) = DHR (TR )+ DCˆ P (T - TR )

also, between inlet and outlet:

Q -WS - FA0 iC Pi (T - Ti 0 ) - FA0 X DHR (TR ) + DCˆ P (T - TR )  = 0

- DH R (TR ) + DCˆ P (T - TR ) 

In many instances, the ΔCp term in the denominator is negligible

Kc: equilibrium constant

Xe Adiabatic equilibrium conversion

Reactors with Heat Exchange

Elementary liquid phase reaction carried out in a CSTR

The feed consists of both - Inerts I and Species A with

 Assuming the reaction is irreversible for CSTR,

Irreversible for Parts (a) through (c)

(a) Given X = 0.8, find T and V

Calc Calc Calc Calc

Given X, Calculate T and V

Given T, Calculate X and V

(c) Levenspiel Plot

Calc Calc Calc FA 0

(c) Levenspiel Plot

CSTR X = 0.6 T = 360 K

CSTR X = 0.95 T = 395 K

CSTR X = 0.6 T = 360 V = 2.05 dm3

The units of E are Btu/lb-mol and T is in °R.

There is an important constraint on your operation. Propylene oxide is a rather low

The design equation in terms of X is

Solving for X as a function of T and recalling that τ=V/υ0 gives

This equation relates temperature and conversion through the mole

This equation relates X and T through the energy balance.

(a) Evaluate the terms (τ, CA0, Θi):

(a) Evaluate the terms (τ, CA0, Θi):

(1) Heat of reaction at temperature T

H Ao ( 68 o F ) = -66600 Btu/lb mol

(1) Heat of reaction at temperature T

T (oR) XMB XEB

Steady-state energy balance:

[Usually Ws is neglected unless, the mixture stirred is very viscous]

Solving for the exit temperature of the heat exchanger fluid:

Ta2 is also equal to (previous slide): Ta 2 = ( m cC pcTa1 - Q ) / m cC pc

[Valid only for large heat-transfer fluid flow rates!]

which is coupled to the mole balance equation (below) to dimensionalize

Letting the energy balance can be rearranged as

We set the CSTR heat exchange parameters, κ and Tc.

Then the energy balance is formulated as

A. Solving for conversion