CHENG 323 Chap 8 PDF

Dr.
Shaker Haji, University of Bahrain 3/29/2012
CHEMICAL REACTOR DESIGN

CHENG 323 Dr Shaker Haji
8 Steady-State Nonisothermal Reactor Design
CHENG 322 1
Dr. Shaker Haji, University of Bahrain 3/29/2012
In this Chapter
We will focus our attention on heat effects in chemical reactors,

because most rxns are not carried out isothermally.
We will derive user friendly Energy Balance Equation & apply it to
the following cases:
Adiabatic
Heat Exchange with Constant Ta (ambient/coolant T)
Heat Exchange with Variable Ta Co-current Flow
Heat Exchange with Variable Ta Counter Current Flow
8.1 Rationale
For an adiabatic, exothermic rxn:

CA
How does T change with V? How does k change with V?
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8.1 Rationale
Consider an adiabatic, exothermic rxn carried out in a PBR.

Through mole balance, rate law, stoichiometry:
dX dP
F1 (X , P ,T ) F2 (X , P )
dW dW
dT
What else is needed? F3 (X ,T )
dW
How is it obtained?
By carrying out an Energy Balance on the reactor
8.2 The Energy Balance:

The Law of Conservation of Energy
The law of conservation of energy is an empirical law of

physics.
What does is state?
Energy can neither be created nor destroyed, it can only be
transformed from one form to another.
Because energy is conserved:
Accumulation = Input Output
Is this equation valid for system involving rxns?

This eq. is valid whether the system involves a chemical rxn
or not!
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8.2.1 The First Law of Thermodynamics
For a closed system, the energy balance is:
The 's signify that Q & W are not exact differentials of a state function.
E is the total energy of the system
For an open system, the energy balance for the case of one
species entering and leaving (e.g. J/s):
8.2.1 The First Law of Thermodynamics
The unsteady-state energy balance for an open well-mixed

system that has n species, each entering and leaving the
system at their respective Fi & Ei, is
We will now discuss each of the terms in the above

Equation
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8.2.2 Evaluating the Work Term
It is customary to separate the work term, W , into flow work

and other work, W s.
W s , shaft work, include stirring (CSTR), rotation (gas
turbine), and also electrical heating.
Flow work is work that is necessary to get the mass into and
out of the system.
For example, when shear stresses are absent, we write
8.2.2 Evaluating the Work Term
The energy balance equation can be rewritten as:
What does Ei consist of?

Ei = Ui + PEi + KEi
Therefore, Ei + PVi = Ui + PEi + KEi + PVi or?
= Hi + PEi + KEi
In almost all chemical reactor situations, the KE & PE terms
are negligible in comparison with the other terms.
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8.2.4 Dissecting the Steady-State Molar Flow Rates

to Obtain the Heat of Reaction
For a steady-state flow system:
Consider the generalized rxn:
Evaluate the terms:
Recall that , or:
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By substitution:
What is this term called?

Its called the Heat of Reaction at temperature T, Hrxn
Therefore,
8.2.4 Dissecting the Steady-State Molar Flow Rates

to Obtain the Heat of Reaction
Does this Eq. account for the phase change within the reactor?
Yes, through (Hi0 Hi).
Thus, If a phase change takes place during the course of a
reaction, this form of the energy balance must be used
n
FA0 i H i H i 0 (FA0 X ) H rxn (T ) Q W
i 1
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8.2.5 Dissecting the Enthalpies
Are the above equation applicable to all kind of solutions (i.e.

ideal & nonideal)?
No, because we are neglecting any enthalpy changes resulting
from mixing.
We simply assumed that the partial molar enthalpies are equal to
the molar enthalpies of the pure components.
8.2.5 Dissecting the Enthalpies
n
i 1
Evaluate the above term, (Hi Hi0).

For the extreme case, where the reactants are at the solid phase
@ T0 and the products are the gaseous phase @ T:
(Hi Hi 0) = CPl
T0 i
If no phase change is involved:

T

(Hi Hi 0) = C Pi dT ; If CPi is constant, then: (Hi Hi 0) = CPi (TT0)
T0
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8.2.6 Evaluating Hrxn
n
i 1
What is the definition of Hrxn?
Hrxn(T ) i.Hi(T ) or
In general:
Upon substitution & rearrangement:
H rxn
o
(T R )
C P (Heat capacity change of reaction)
This Eq. gives the heat of rxn at any T in terms of the standard heat
of rxn (1 bar) at a reference T (usually 298 K) & the CP term.
Techniques for determining Hrxn at P above 1 bar can be found
elsewhere.
However, for the rxn of H2 & N2 at 400oC, it was shown that Hrxn
increased by only 6% as P was raised from 1 atm to 200 atm!
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8.2.7 After Dissecting
n
FA0 i H i H i 0 (FA0 X ) H rxn (T ) Q W s
i 1
n
FA0 i C P i T i T i 0 (FA0 X ) H rxn
o
(T R ) C P T T R Q W s
i 1
This is the energy balance in terms of mean or constant heat capacities.

In most systems:
Work is neglected
All reactants enter at the same temperature (T0 ), so is the case for the
leaving products (T ).
FA0 i C P i T T 0 (FA0 X ) H rxn

o
(T R ) C P T T R Q
This is the energy balance equation in terms of mean or constant heat

capacities.
This Eq. can be used to relate T to X and then proceed with the CRE
algorithm.
However, unless the rxn is carried out adiabatically, this Eq. is still
difficult to evaluate! Why?
Because in nonadiabatic reactors, the heat exchanged with the system
varies along the length of the reactor.
This problem does not occur in adiabatic reactors, which are
frequently found in industry.
Therefore, the adiabatic reactors will be analyzed first.
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Example 8-2 Calculating Heat of Reaction
Calculate the heat of reaction for the synthesis of NH3 from H2 & N2 at
150oC in kcal/mol of N2 reacted and also in kcal/mol of H2 reacted.
Additional information:
CP of gases: NH3: 8.92, N2: 6.984, and H2: 6.992 cal/mol.K.
CP of liquid NH3: 30.0 cal/mol.K.
Hvap of NH3: 5.581 kcal/mol at Tn = 33.4oC.
Hof (25oC) of NH3: 11,020 cal/mol.
Solution
N2 + 3H2 2NH3 H rxn (T ) H rxn
o
(TR ) CP T TR
Horxn (150oC) = 22,040 + (10.12)(125K) = 22,040 1,265
=23.31 kcal/mol N2 = 7.77 kcal/mol H2
8.3 Adiabatic Operation
How realistic is the assumption of adiabatic operation of

reactors?
Reactions in industry are frequently carried out
adiabatically with heating or cooling provided either
upstream or downstream.
Consequently, analyzing and sizing adiabatic reactors is
an important task.
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8.3.1 Adiabatic Energy Balance

o
(T R ) C P T T R Q W
Develop a method to determine the conversion at the exit

of an adiabatic PFR using a thermocouple!
This Eq. applies to a CSTR, PFR, PBR, and also to a batch

reactor.
N2 + 3H2 2NH3 Horxn (25oC) = 22,040 cal/mol

Feed in stoichiometric ratio, T0=500oC CP = 10.12 cal/mol
0.2
XEB = X 0.15
calculated
through energy 0.1
XEB
balance
0.05
Almost linear
relationship 0
500 550 600 650 700
T (oC) @ adiabatic PFR exit
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Time out: Insight into the Energy Balance Equation
What is the relationship between the following Energy

Balance Eq. and the one in Thermo I & II textbook?
n
FA0 i H i H i 0 (FA0 X ) H rxn (T ) Q W s
i 1
8.3.2 Adiabatic Tubular Reactor

o
We can rearrange the above eq. to solve for T = f(X):
This Eq. will be coupled with the differential mole balance
to obtain T, X, & Cj profiles along the length of the reactor.
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8.3.2 Adiabatic Tubular Reactor
A numerical solution is also possible through dV = FA0/rA dX:
Example 8-3 Liquid-Phase Isomerization of n-Butane
Normal butane, C4H10, is to be isomerized to isobutane in a plug-flow reactor.

Isobutane is a valuable product that is used in the manufacture of gasoline
additives. For example, isobutane can be further reacted to form iso-
octane. The 2004 selling price of n-butane was 72 cents per gallon, while
the price of isobutane was 89 cents per gallon.
The rxn is to be carried out adiabatically in the liquid phase under high
pressure using essentially trace amounts of a liquid catalyst which gives a
specific reaction rate of 31.1 h1 at 360 K.
Calculate the PFR and CSTR volumes necessary to process 100,000 gal/day
(163 kmol/h) of a feedstock containing 90 mol% n-butane & 10 mol%
i-pentane (inert). Also calculate the equilibrium conversion in the reactor.
The feed enters at 330 K.
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Example 8-3 Liquid-Phase Isomerization of n-Butane
Information:
liquid phase rxn, Q = 0, k = 31.1 h1 at 360 K, T0 = 330 K
FA0 = 0.9X163 = 146.7 kmol/h Feed: 90% A, 10 % inert (mol)
Additional Information:
Solution
Solution
The algorithm for the CRE design problem is:

1. Mole balance: PFR: CSTR:
2. Rate law: ,
I have introduced T here; I should also introduce an equation for it!

From energy balance:
o
Therefore, T T 0 H rxn
o
X C i Pi
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3. Stoichiometry:
4. Combine:
5. Evaluate: PFR: CSTR:
Can we solve it with hand calculation?

Yes, then evaluate as much parameters as possible.
How do you find equilibrium conversion?
CBe CA0 X e
From K C KC
C Ae CA0 (1 X e )
Hand Calculation
T T 0 H rxn
o
X C
i Pi
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Hand Calculation
Do you remember this Levenspiel plot from Example 2-7?

Make sure that the requested X is not greater than Xe.
Its better to ask for X in relative to Xe, such as 0.95Xe.
For 40% X, VCSTR < VPFR (VCSTR = 1, VPFR = 1.15 m3)
Computer Calculation
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8.4 Steady-State Tubular Reactor with Heat Exchange
In this section, we consider a tubular reactor in which heat is either

added or removed through the cylindrical walls of the reactor.
Again, we shall assume that there are no radial gradients in the
reactor.
The heat flux through the wall
of the reactor is:
Q U A (T a T )
U a (T a T )V
SI Units:
U [J/(s m 2 K)], U A [J/(s K)]
U a [J/(s m3 K)]
8.4.1 Deriving the Energy Balance for a PFR
For the shown system, carry out an energy balance on the volume V.
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When this form of energy balance is used?

For membrane reactors and multiple reactions (Non-isothermal
reactor with heat exchange).
Rewrite the above Eq. in terms of X for PFR.
Also rewrite it in terms of X for PBR.

recall that W = b.V
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Example 8-4 Liquid-Phase Isomerization of n-Butanecontinued
Assume that 70% conversion is to be achieved in the adiabatic

isomerization of n-butane process discussed in Example 8-3.
The T in thiss case will raise to 360 K at the reactor exit. At this T, a P
of 1.5 MPa is generated (Vapor Pressure) which is greater than the
rupture pressure of the glass vessel being used.
So what do you suggest?
To lower the P and, consequently, the T inside the reactor, it is

suggested to:
1. Use partially insulated tubular reactors instead of the insulated ones
2. Lower the Feed T
Fortunately, there is a bank of ten partially insulated (U.a = 5000
kJ/h.m3.K) tubular reactors each 6 m3 over in the storage shed
available for use. We are also going to lower the entering
temperature to 310 K.
The reactors are cooled by natural convection where average ambient
T in this tropical location is assumed to be 37C. The T in any of the
reactors cannot rise above 325 K. Plot X, Xe, T, and the reaction
rate along the length of the reactor. Does the temperature rise
above 325 K?
Solution
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Does the
temperature rise
above 325 K?
8.4.2 Balance on the Heat Transfer Fluid
What is the heat transfer fluid

usually called?
coolant for exothermic rxns
heating medium for endothermic rxns.
When the heat transfer fluid maintains a constant T & when it does not?
If the flow rate of the heat transfer fluid is sufficiently high with
respect to the heat exchanged with the reacting mixture, then the heat
transfer fluid temperature will be constant.
Otherwise, T of heat transfer fluid (Ta) will vary along the
length of the reactor.
Derive a differential equation for Ta wrt to V.
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Recall: Q U A(Ta T ) U a (Ta T )V
Derive a differential equation for Ta wrt to V.

Case A: Co-Current Flow:
Assume cooling case:
, from CP definition:
Case B: Counter-Current Flow:
Example 8-5 production of Acetic Anhydride
Jeffreys, in a treatment of the design of an acetic anhydride

manufacturing facility, states that one of the key steps is the
vapor-phase cracking of acetone to ketene and methane:
He states further that this reaction is first-order w.r.t. acetone and

that specific reaction rate can be expressed by
34222

k 8.19733 10 e 14 T
where k is in s1 and T is in K.
In this design it is desired to process 7850 kg of acetone per hour

(37.6 mol/s) in a tubular reactor. The reactor consists of a bank of
1000 1-inch schedule 40 tubes (ID=2.66 cm) arranged in parallel
where each tube is 90 cm long (V = 5x104 m3).
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We will consider five cases:

CASE 1: The reactor is operated isothermally (calculate the Q required
to maintain this operation).
CASE 2: The reactor is operated adiabatically.
CASE 3: The reactor is surrounded by a heat exchanger where the heat-
transfer coefficient is 110 J/m2.s.K, and the T of the heating medium, Ta,
is constant at 1250 K.
CASE 4: The heat exchanger in Case 3 now has a variable Ta. The
reactant and the heating medium flow in the same direction.
CASE 5: Same as Case 4, but the reactant and the heating medium flow
in opposite directions.
In the last two cases, air (CPair = 34.5 J/mol.K) at a rate of 0.11 mol/s
with Ta0 = 1250 K is available for heating.
The inlet T & P are the same for all cases at 1035 K & 162 kPa,
respectively.
Horxn(298K)= 80.77 kJ/mol; CPA= 163, CPB= 83, & CPC= 71 J/mol.K.
Plot X, rA, T, & Ta along the length of the reactor.
Case 1:
Isothermal Operation
Conversion
(Xexit=0.50)
Rate of Reaction
Temperature
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Case 2:
Adiabatic Operation
Conversion
(Xexit=0.16)
Rate of Reaction
Temperature
Case 3:
With Heat Exchange
Constant Ta
Conversion
(Xexit=0.57)
Rate of Reaction
Temperatures
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Case 4:
With Heat Exchange
Variable Ta, Co-Current Flow
Conversion
(Xexit=0.35)
Rate of Reaction
Temperatures
Case 5:
With Heat Exchange
Variable Ta
Counter Current Flow
Conversion
(Xexit=0.30)
Rate of Reaction
Temperatures
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8.5 Equilibrium Conversion
What is the highest X that can be achieved in reversible reactions?

The highest is the equilibrium conversion.
In terms of reaction Temperature & heat exchange:
How Xe can be increased for endothermic reactions?
How Xe can be increased for exothermic reactions?
8.5.1 Adiabatic Temperature and Equilibrium Conversion
Exothermic Reaction
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8.5.1 Adiabatic Temperature and Equilibrium Conversion
How can we calculate Xe for a given rxn taking place in a reactor?

Through the equilibrium constant & stoichiometry.
E.g., consider the 1st-order liquid phase rxn carried out in a PFR:
where KC =CBe/CAe & Cie = CA0(i + i.Xe)

K C (T )
Therefore, X e
1 K C (T )
But whats the value of T inside the reactor? How do I calculate it?
T is obtained from the energy balance on an adiabatic reactor:

or
K C (T )
Equilibrium Constant Definition: Xe
1 K C (T )
Energy Balance:
You solve these two Eqs. simultaneously to find the adiabatic T &
adiabatic Xe.
It can be solved:
analytically
using a solver
graphically
CHENG 322 27
Example 8-6 Calculating the Adiabatic Equilibrium Temperature & Conversion
For the elementary solid-catalyzed liquid-phase rxn: A B

1. make a plot of equilibrium conversion as a function of temperature.
2. Determine the adiabatic equilibrium temperature and conversion
when pure A is fed to the reactor at a temperature of 300 K.
Solution:
Solution: From Thermodynamics
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Solution: From Energy Balance
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Consultation time!
Case: being limited by equilibrium conversion. rxn: A B
Assuming that the reaction kinetics is

very fast, how can the max. achievable
conversion (Xe) be increased?
By:
1. Changing the reactor type/operation mode (e.g. reactive
distillation).
2. Adding heat exchanger to the reactor (cooling in this case).
3. Changing the feed temperature (lower T0 in this case).
Consultation time!
Case: being limited by equilibrium conversion.
The max. achievable conversion (Xe) can be increased by:

Changing the reactor type/operation mode.
What if other reactor types are not suitable!
Adding heat exchanger to the reactor.

But rxns in industry are frequently carried out adiabatically!!
Changing the feed temperature.
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Reactor Staging with Interstage Cooling or Heating
Would the Xe(KC(T)) curve change for the shown setup?

Any guess how the XEB(T ) plot would look like?
Exothermic Reaction Carried out in Reactors with

Interstage Cooling
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Endothermic Reaction
How the Xe(T ) curve would look like?
Endothermic Reaction Carried out in Reactors with

Interstage Heating
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Consultation time!
Case: being limited by equilibrium conversion.
The max. achievable conversion (Xe) can be increased by:

Changing the reactor type/operation mode.
What if other reactor types are not suitable!!
Adding heat exchanger to the reactor.
But rxns in industry are frequently carried out adiabatically!!
Changing the feed temperature (e.g. for exothermic rxn, use low T0)
But lower feed temperatures will result in lower kinetics & therfore lower X !!
8.5.2 Optimum Feed Temperature
Consider an adiabatic reactor of fixed size or catalyst weigh.

Investigate what happens as the feed temperature is varied for a
reversible and exothermic rxn.
Example:
AB
A
= 0

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(e.g. reversible exothermic rxn)

(e.g. reversible exothermic rxn)
As T0 , is increased, k will increase, as well the X.

X will continue to increase with increasing T0 until Xe is approached.
Further increases in T0 for this exothermic rxn will only decrease the X
due to the decreasing Xe.
This optimum T0 is shown here:
CHENG 322 34
Example 8-3 Revisited Finding the Optimum Feed Temperature

(page 490)
For the isomerization of n-butane rxn:

what is the optimum T0 that lead to the highest X in a 2.6 m3-PFR?
Solution:
Optimum T0 = 333 K
Exit conditions @
optimum T0:
T = 364 K
X = 0.7085
What is limiting the conversion in either sides of Xmax?
Notes:
X is the conversion at the exit.
Xe is calculated based on
the exit T.
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How does the X varies along the reactor for the optimum T0 case ?
Notes:
X is the local conversion
Xe is calculated based on the local temperature.
How does the X varies along the reactor for the optimum T0 case ?
K C (T )
Xe
Which equations 1 K C (T )
were used to
plot these
two curves?
dX rA

dV FA0
Notes:
X is the local conversion
Xe is calculated based on the local temperature.
CHENG 322 36
Exercises on adiabatic T, adiabatic equilibrium T, optimum T0, X, & Xe:

For the adiabatic isomerization of n-butane, n-C4H10 i-C4H10 , in a 2.6 m3 PFR:
1. Plot the equilibrium conversion as a function of temperature.
K C (T )
Xe
1 K C (T )

For the isomerization of n-butane rxn, n-C4H10 i-C4H10 ,
Zoom in (100 600 K).
CHENG 322 37

Zoomed in (100 600 K).

2. On the same Fig, show the effect of X on the adiabatic temperature, for different T0.
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3. On the same Fig, show the effect of X on the adiabatic temperature, for different T0.
A
= 0


Zoom in more (200 400 K) and use closer values of T0.
CHENG 322 39

3. Use thermodynamics & kinetics to obtain all of the above for the 3 chosen T0.
Xe=0.8
X=Xe=0.71
X=0.07

X=Xe=0.69
Exercises on adiabatic T, adiabatic equilibrium T, optimum T0, X, & Xe.

4. Conclusion Using Thermodynamics & Kinetics Using Only
Together Thermodynamics
Adiabatic PFR, V = 2.6 m3 Adiabatic Equilibrium
Xe=0.8
@ T=303 K T & X Calculations
T0 T X Xe Te Xe
Feed T Exit T X @ Exit Xe @ Exit T Adiabatic Adiabatic
X=0.07
T=303 K
Equilib. T Equilib. X
300 K 303 K 0.07 0.8 332.7 K 0.75
333 K 364 K 0.71 0.71 364 K 0.71
X=Xe=0.71
T= 364 K 350 K 380 K 0.69 0.69 380 K 0.69
Te=332.7 K, Xe=0.75
Te=364 K, Xe=0.71
Te=380 K, Xe=0.69
X=Xe=0.69
T=380 K
CHENG 322 40
8.6 CSTR with Heat Effects
Ideal CSTRs are operated isothermally, so why do we need to worry

about energy balance?
To calculate Q required to maintain the reactor at the desired T.
To calculate T that will be reached within the reactor in case it
was operated with a known Q (e.g. adiabatically).
In conclusion, to calculate two variables out of X, V, & T should
one is specified.
8.6 CSTR with Heat Effects
The general EB for steady state operation:

o
CHENG 322 41

o
For CSTR, can you replace FA0X with another term?

FA0X = rAV
How do we calculate Q exchanged with the reactor? (Hint: heat
transfer course)
How do you calculate the heat transferred to the coolant?

Q mcC Pc T a 2 T a1
In case of high coolant flow rate
(Ta2 Ta1= Ta), Q is calculated by:
Q UA T a T
Q transferred from the reactor:
Q transferred to the coolant: Q mcC Pc T a 2 T a1

To calculate Ta2:
Qreactor = Qcoolant , therefore,
Q transferred to the reactor, where Ta1 = Ta2 = Ta : Q UA T a T
CHENG 322 42
Ways to specify the sizing of a CSTR
Timeout: Design of CSTR with Heat Effects
Case 1. X is specified; Calculate T & V: (Sequential Calculation)

X (E.B.) T, T k, k rA, rA & X (M.B.) V
Case 2. T is specified; Calculate X & V: (Sequential Calculation)

T (E.B.) X, T k, k rA, rA & X (M.B.) V
Case 3. V is specified; Calculate X & T: (Simultaneous Calculation)

Solve E.B. & M.B. Equations X&T
CHENG 322 43
Example 8-8 Production of Propylene Glycol in an Adiabatic CSTR
Propylene glycol is produced by the hydrolysis of propylene oxide:
Over 800 million pounds of propylene glycol were produced in 2004 and the
selling price was approximately $0.68 per pound. Propylene glycol makes up
about 25% of the major derivatives of propylene oxide. The reaction takes
place readily at room temperature when catalyzed by sulfuric acid.
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; you told your boss several times that sulfuric acid was
corrosive and that mild steel was a poor material for construction. There is a
nice-looking overflow CSTR of 300-gal capacity standing idle; it is glass-
lined; and you would like to use it.
Feed process variables are as follows:
C A01 1 lbmol/ft 3 C A02 0 lbmol/ft 3

01 02 01
CHENG 322 44
Feed process variables are as follows: conditions You are feeding 2500
lbm/h (43.04 Ibmol/h) of propylene oxide (P.O.) to the reactor. The feed
stream consists of (1) an equivolumetric mixture of P.O. (46.62 ft3/h) and
methanol (46.62 ft3/h), and (2) water containig 0.1 wt % H2S04. The
volumetric flow rate of waterRON
rate of water is 233.1 ftqlh, uhich is 2.5 times the methanol-PO. Row rate. The
cornspanding
moIar feed rates of methanol and water are 71.87 and 802.8 Ib mol/h,
respectively. The
water-propylene oxide-methanol mixture undergoes a slight decrease in
volume upon mixing
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; you told your boss several times that sulfuric acid was
corrosive and that mild steel was a poor material for construction. There is a
nice-looking
Solution: overflow CSTR of 300-gal capacity standing idle; it is glass-
lined; and you would like to use it.
T(oF) T(oR) k H
o
rxn(T) X MB X EB
75 535 0.97 -36449 0.11 0.00
83 542 1.47 -36501.5 0.15 0.08
90 550 2.22 -36554 0.21 0.17
87 546.9 1.91 -36534.63 0.19 0.14
95 554 2.86 -36587.13 0.26 0.22
102 562 4.24 -36639.63 0.34 0.30
112 572.1 7.09 -36710.66 0.47 0.41
120 580 10.25 -36763.16 0.56 0.49
127 587 14.68 -36815.66 0.64 0.57
135 595 20.84 -36868.16 0.72 0.65
142 602 29.33 -36920.66 0.78 0.74
140 599.3 25.92 -36901.5 0.76 0.71
147 607 36.28 -36954 0.82 0.79
153 613 47.65 -36997.54 0.85 0.85
165 625 79.23 -37081.17 0.91 0.98
CHENG 322 45
Example 8-9 CSTR with a Cooling Coil
A cooling coil is available for use in the hydration of propylene

oxide discussed in Example 8-8. The cooling coil has 40 ft2 of
cooling surface and the cooling water flow rate inside the coil is
sufficiently large that a constant coolant temperature of 85F can
be maintained. A typical overall heat-transfer coefficient for such a
coil is 100 Btu/h.ft2.F. Will the reactor satisfy the previous
constraint of 125F maximum temperature if the cooling coil is
used?
Solution:
CHENG 322 46
Example 8-9 CSTR with a Cooling Coil
Solution:
Mole Balance:
Energy Balance:
By solving these two equations simultaneously:
8.7 Multiple Steady States (CSTR)
Example 8-8 Revisited With T0 = 70oF

Production of Propylene Glycol in an Adiabatic CSTR
Solve example 8-8 again, however, this time with T0 = 70oF.

Find the steady-state X & T inside the CSTR.
CHENG 322 47

T(oF) T(oR) k H
o
rxn(T) X MB X EB G (T ) R(T )
70 530 0.72 -36414 0.08 0.00 2977 0
78 537 1.11 -36466.5 0.12 0.08 4390 3024
85 544 1.65 -36515.5 0.17 0.16 6142 5847
87 546.9 1.91 -36534.63 0.19 0.19 6949 6949
95 554 2.86 -36587.13 0.26 0.27 9517 9974
102 562 4.24 -36639.63 0.34 0.35 12544 12998
112 572.1 7.09 -36710.66 0.47 0.47 17090 17090
120 580 10.25 -36763.16 0.56 0.55 20493 20115
127 587 14.68 -36815.66 0.64 0.63 23688 23139
135 595 20.84 -36868.16 0.72 0.71 26516 26164
142 602 29.33 -36920.66 0.78 0.79 28902 29188
140 599.3 25.92 -36901.5 0.76 0.76 28085 28085
147 607 36.28 -36954 0.82 0.84 30184 31109
153 613 47.65 -36997.54 0.85 0.91 31601 33617
165 625 79.23 -37081.17 0.91 1.04 33627 38435
CHENG 322 48
8.7 Multiple Steady States (CSTR-Exothermic Reaction)

o
FA0 i C P i T T 0 (FA0 X ) H rxn (T ) Q
Where
or Q UA T a T when T a1 T a 2
FA0 i C P i T T 0 (FA0 X ) H rxn (T ) Q
Rewrite the above Eq. so that the heat generation term (i.e. the heat
released term) is on the right hand side.
C T
i Pi T 0 Q / FA0 X (H rxn (T ))
or
C T
i Pi T 0 Q / FA0 (rAV / FA0 ) (H rxn (T ))
Which term represents the following:

Heat-Generated Term: G (T ) X MB (H rxn )
Heat-Removed Term: R (T ) i C P i T T 0 Q / FA0
CHENG 322 49
C T
i Pi T 0 Q / FA0 X (H rxn (T ))
Heat-Generated Term: G (T ) X MB (H rxn )
Heat-Removed Term: R (T ) i C P i T T 0 Q / FA0
What is the relationship between G(T) & R(T) at steady state?
G (T ) R (T )

T(oF) T(oR) k H
o
rxn(T) X MB X EB G (T ) R(T )
70 530 0.72 -36414 0.08 0.00 2977 0
78 537 1.11 -36466.5 0.12 0.08 4390 3024
85 544 1.65 -36515.5 0.17 0.16 6142 5847
87 546.9 1.91 -36534.63 0.19 0.19 6949 6949
95 554 2.86 -36587.13 0.26 0.27 9517 9974
102 562 4.24 -36639.63 0.34 0.35 12544 12998
112 572.1 7.09 -36710.66 0.47 0.47 17090 17090
120 580 10.25 -36763.16 0.56 0.55 20493 20115
127 587 14.68 -36815.66 0.64 0.63 23688 23139
135 595 20.84 -36868.16 0.72 0.71 26516 26164
142 602 29.33 -36920.66 0.78 0.79 28902 29188
140 599.3 25.92 -36901.5 0.76 0.76 28085 28085
147 607 36.28 -36954 0.82 0.84 30184 31109
153 613 47.65 -36997.54 0.85 0.91 31601 33617
165 625 79.23 -37081.17 0.91 1.04 33627 38435
CHENG 322 50
8.7 Multiple Steady States
CHENG 322 51
8.7.3 Ignition-Extinction
Vary the feed temperature (T0)

and record the steady states
temperatures (TS).
Both the mole and energy
balances are satisfied at the
points of intersection or
tangency.
Then plot TS vs. T0.
8.7.3 Ignition-Extinction
T05 is called the ignition T

while T02 is called the
extinction T.
We must exceed a
certain T0 to operate at
the upper steady state
where the T & X are
higher.
CHENG 322 52
8.7.3 Runaway Reactions in CSTR
In many reacting systems, T of the upper steady state may be

sufficiently high that it is undesirable or even dangerous to operate
at this condition.
For example, at the higher Ts, secondary rxns can take place, or as
in the case of propylene glycol (Examples 8-8 & 8-9), evaporation
of the reacting materials can occur.
The ignition temperature occurs at the point of tangency of heat
removed curve to the heat-generated curve.
If we move slightly off point of tangency as shown in Figure 8-24,
then runaway is said to occurred
Test Yourself
Which of the curves

represents G(T)? Multiple Steady States in an Adiabatic CSTR
30,000
Calculate Hrxn. 25,000
G(T ) & R(T ) (kJ/mol)
What are the ignition and 20,000
extinction Ts? And what 15,000
are their corresponding 10,000

reactor steady state Ts? 5,000
What are the Xs just 0
before the ignition and 540 550 560 570 580 590 600
T(K)
extinction Ts?
CHENG 322 53
8.8 Nonisothermal Multiple Chemical Reactions
Most reacting systems involve more than one reaction and do not
operate isothermally.
This section is one of the most important sections of the book.
8.8.1 Energy Balance for Multiple Reactions in Plug Flow Reactors
Lets develop an energy balance suitable for multiple reactions

taking place in a PFR.
Lets do that by starting from the energy balance for a single
reaction taking place in a PFR:
or
Which one should I modify?
CHENG 322 54
Energy balance for

single reaction
What shall we change in the above equation?
Consider the following reaction sequence carried out in a PFR:
The PFR energy balance becomes:
CHENG 322 55
Example 8-10 Parallel Reactions in a PFR with Heat Effects
The following gas-phase reactions occur in a PFR:
Pure A is fed at a rate of 100 mol/s, a temprature of 150oC, and a

concentration of 0.1 mol/l. Determine the temperature and flow rate
profiles down the reactor.
8.8.2 Energy Balance for Multiple Reactions in CSTR
The energy balance for a single reaction taking place in a CSTR:
The Energy balance for multiple reactions in CSTR (q rxns & m

species):
CHENG 322 56
8.8.2 Energy Balance for Multiple Reactions in CSTR
Consider the following reactions carried out in a CSTR:
The CSTR energy balance becomes:
=0
Timeout: Design of CSTR with Heat Effects
Case 1. X is specified; Calculate T & V: (Sequential Calculation)

X (E.B.) T, T k, k rA, rA & X (M.B.) V
Case 2. T is specified; Calculate X & V: (Sequential Calculation)

T (E.B.) X, T k, k rA, rA & X (M.B.) V
Case 3. V is specified; Calculate X & T: (Simultaneous Calculation)

Solve E.B. & M.B. Equations X&T
CHENG 322 57
Example 8-11 Multiple Reactions in a CSTR
The elementary liquid-phase reactions:

1 2
A B C
take place in a 10-liter CSTR. What are the effluent concentrations for
a case where: 0 = 1000 L/min, CA0 = 0.3 mol/L, & T0 = 283 K ?
Solution
V is specified
Calculate T & X (CA, CB, CC)
E.B. & M.B. Simultaneous

Calculation
T&X
Graphical Solution
V is specified
Calculate T & X (CA, CB, CC)
E.B. & M.B. Simultaneous

Calculation
T&X
plot the two equations (E.B. & M.B) combine the two equations then
independently plot the two sides (RHS & LHS)
CHENG 322 58
1
A B
2
Example 8-11 Multiple Reactions in a CSTR B C
UA(Ta T ) FA0CP A T T0 V r1A H rxn1A r2B H rxn2B 0
V r1A H rxn1A r2B H rxn2B FA0CP A T T0 UA(Ta T )

Assume T; Calculate k,
G (T ) R (T ) CA, CB, r1A, r2B, G & R
where: CA & CB are

obtained form
mole balance:
1 2
A B C
10
Note: = = = 0.01 , is this a realistic value?
0 1000
CHENG 322 59

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CHEMICAL REACTOR DESIGN

8 Steady-State Nonisothermal Reactor Design

We will focus our attention on heat effects in chemical reactors,

For an adiabatic, exothermic rxn:

How does T change with V? How does k change with V?

Consider an adiabatic, exothermic rxn carried out in a PBR.

By carrying out an Energy Balance on the reactor

8.2 The Energy Balance:

The law of conservation of energy is an empirical law of

Is this equation valid for system involving rxns?

8.2.1 The First Law of Thermodynamics

For a closed system, the energy balance is:

8.2.1 The First Law of Thermodynamics

The unsteady-state energy balance for an open well-mixed

We will now discuss each of the terms in the above

8.2.2 Evaluating the Work Term

It is customary to separate the work term, W , into flow work

8.2.2 Evaluating the Work Term

The energy balance equation can be rewritten as:

What does Ei consist of?

8.2.4 Dissecting the Steady-State Molar Flow Rates

For a steady-state flow system:

Consider the generalized rxn:

Evaluate the terms:

Recall that , or:

What is this term called?

8.2.4 Dissecting the Steady-State Molar Flow Rates

8.2.5 Dissecting the Enthalpies

Are the above equation applicable to all kind of solutions (i.e.

8.2.5 Dissecting the Enthalpies

Evaluate the above term, (Hi Hi0).

If no phase change is involved:

8.2.6 Evaluating Hrxn

What is the definition of Hrxn?

Upon substitution & rearrangement:

C P (Heat capacity change of reaction)

8.2.7 After Dissecting

This is the energy balance in terms of mean or constant heat capacities.

FA0 i C P i T T 0 (FA0 X ) H rxn

This is the energy balance equation in terms of mean or constant heat

Example 8-2 Calculating Heat of Reaction

8.3 Adiabatic Operation

How realistic is the assumption of adiabatic operation of

8.3.1 Adiabatic Energy Balance

FA0 i C P i T T 0 (FA0 X ) H rxn

Develop a method to determine the conversion at the exit

This Eq. applies to a CSTR, PFR, PBR, and also to a batch

N2 + 3H2 2NH3 Horxn (25oC) = 22,040 cal/mol

Time out: Insight into the Energy Balance Equation

What is the relationship between the following Energy

8.3.2 Adiabatic Tubular Reactor

FA0 i C P i T T 0 (FA0 X ) H rxn

We can rearrange the above eq. to solve for T = f(X):

This Eq. will be coupled with the differential mole balance

to obtain T, X, & Cj profiles along the length of the reactor.

8.3.2 Adiabatic Tubular Reactor

A numerical solution is also possible through dV = FA0/rA dX:

Example 8-3 Liquid-Phase Isomerization of n-Butane

Normal butane, C4H10, is to be isomerized to isobutane in a plug-flow reactor.

Example 8-3 Liquid-Phase Isomerization of n-Butane

The algorithm for the CRE design problem is: