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Topics
1. Why Use the Energy Balance?
2. Overview of User Friendly Energy Balance Equations
3. Manipulating the Energy Balance, DHRx
4. Reversible Reactions
5. Adiabatic Reactions
6. Applications of the PFR/PBR User Friendly Energy Balance Equations
7. Interstage Cooling/Heating
8. Evaluating the Heat Exchanger Term
9. Multiple Steady States
10. Multiple Reactions with Heat Effects
Let's calculate the volume necessary to achieve a conversion, X, in a PFR for a first-order,
exothermic reaction carried out adiabatically. For an adiabatic, exothermic reaction the
temperature profile might look something like this:
The combined mole balance, rate law, and stoichiometry yield:
We will use the Energy Balance to relate X and T. For example, for an adiabatic reaction, e.g.,
, in which no inerts the energy balance yields
The user friendly forms of the energy balance we will focus on are outlined in the following
table.
(1.A)
(1.B)
2. CSTR with heat exchanger, UA(Ta-T) and large coolant flow rate.
(2)
(3.A)
3B. In terms of molar flow rates, Fi
(3.B)
(4)
5. Coolant Balance
Co-Current Flow
(5)
These equations are derived in the text. These are the equations that we will use to solve
reaction engineering problems with heat effects.
Energy Balance:
(1)
OK folks, here is what we are going to do to put this above equation into a usable form.
1. Replace Ei by Ei=Hi-PVi
2. Express Hi in terms of enthalpies of formation and heat capacities
3. Express Fi in terms of either conversion or rates of reaction
4. Define HRX
5. Define CP
6. Manipulate so that the overall energy balance is either in terms of the User
Friendly Equations (yellow box) 1.A, 1.B, 2, 3A, 3B, or 4 depending on the
application
Step 1:
Substitute
, , and
into equation (1) to obtain the General Energy Balance Equation.
General Energy Balance:
For steady state operation:
We need to put the above equation into a form that we can easily use to relate X and T in order to
size reactors. To achieve this goal, we write the molar flow rates in terms of conversion and the
enthalpies as a function of temperature. We now will "dissect" both Fi and Hi. [Note: For an
animated derivation of the following equations, see the Interactive Computer Modules (ICMs)
Heat Effects 1 and Heat Effects 2.]
Flow Rates, Fi
In general,
Enthalpies, Hi
The rate law for this gas phase reaction will follow an elementary rate law.
Where Kc is the concentration equilibrium constant. We know from Le Chaltlier's Law that if the
reaction is exothermic, Kc 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, Kcwill
increase and the reaction will shift to the right.
Van't Hoff Equation
Adiabatic Equilibrium
Conversion on Temperature
Exothermic H is negative
Endothermic H is positive
Van't Hoff
1. Choose X
Calculate T
Calculate k
Calculate KC
Calculate To/T
Calculate CA
Calculate CB
Calculate -rA
2. Increment X and then repeat calculations.
We can now use the techniques developed in Chapter 2 to size reactors and reactors in
series to compare and size CSTRs and PFRs.
Consider:
CSTR+PFR
(a) (b)
Looks like the best arrangement is a CSTR with a 40% conversion followed by a PFR up to 70%
conversion.
a = heat exchange area per unit volume of reactor; for a tubular reactor, a = 4/D
A.
B.
If we include pressure drop:
C.
Note: the pressure drop will be greater for exothermic adiabatic reactions than it will be for
isothermal reactions
Balance on Heat Exchanger Coolant
Co-Current Flow
Counter-Current Flow
with Ta = Tao at W = 0
For an exothermic reaction: with counter current heat exchange
A Trial and Error procedure for counter current flow problems is required to find exit conversion
and temperature.
1. Consider an exothermic reaction where the coolant stream enters at the end of the reactor
at a temperature Ta0, say 300 K.
2. Assume a coolant temperature at the entrance (X = 0, V = 0) to the reactor Ta2 =340 K.
3. Calculate X, T, and Ta as a function of V. We can see that our guess of 340 K for Ta2 at
the feed entrance (X = 0) gives a coolant temperature of 310 K, which does not match the
actual entering coolant temperature of 300 K.
4. Now guess a coolant temperature at V = 0 and X = 0 of 330 K. We see that the exit
coolant temperature of Ta2 = 330 K will give a coolant temperature at V = V1 of 300 K.
Interstage Cooling:
1.) Given X
Find T and V
Solution:
Linear progression of calc T cal k calc KC calc -rA calc
V
2.) Given T
Find X and V
Solution:
Linear progression: calc k cal KC calc X calc -rA calc V
3.) Given V
Find X at T
Solution: plot XEB vs. T and XMB vs. T on the same graph:
At high coolant flow rates the exponential term will be small, so we can expand the
exponential term as a Taylor Series, where the terms of second order or greater are
neglected, then:
where
Now we need to find X. We do this by combining the mole balance, rate law, Arrhenius
Equation, and stoichiometry.
where
At steady state:
To account for heat effects in multiple reactions, we simply replace the term (-delta HRX) (-rA) in
equations (8-60) PFR/PBR and (8-62) CSTR by:
PFR/PBR
CSTR
These equations are coupled with the mole balances and rate law equations discussed in Chapter
6.
Complex Reactions