CL 208

Chemical Reaction Engineering-I

 Non-isothermal Reactor Design

 Seldom does reaction occur non-isothermally

 Temperature can vary along a PFR or heat removal from a CSTR
 What changes in our analysis of isothermal reactors?
 Consider this example:
“ For an exothermic reaction A  B being performed adiabatically in a PFR, what size of
reactor would be required to achieve a conversion of 90%?”

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How to go about solving this?

1. Mole balance (PFR)

2. Rate law (temperature dependency?)

3. How do we calculate temperature?

Energy balance
 First law of thermodynamics
 For Closed Systems/control mass e.g. batch reactors
(no mass crosses the boundaries)
 dE = dQ-dW
 Sign convention
 E = U + PE + KE
 In most cases U > PE, KE 3

Joules /s
 The Energy Balance
First Law of Thermodynamics
 For Open Systems/control volume
 mass crosses the boundaries
 Energy exchange also happens by the flow of mass across the system boundaries

 Note the unit (rate of energy flow i.e. J/s and not J)
 Also note that the system is multi-species and they change between in and out

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 The Flow work

 Separate the work term into flow work and other (shaft)work
 Flow work: Work necessary to get the mass into and out of the system
Wflow = Pv (v = specific volume)
(Or in terms of rate)
 H = U + PV

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The Energy Balance
 Consider the reaction aA + bB  cC + dD
 It can be shown that

 where subscript 0 refers to ‘in’ conditions.

 For single phase system, constant Cp, one can write

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The Energy Balance
 The Energy balance can now be written as

 At steady state, term on LHS is zero

 W here refers to the shaft work only and can be neglected often.
 For an adiabatic system Qdot = 0.
 For multiphase system, the equation in terms of H would be valid.
 Heat of reaction can be calculated from TRef to T

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Heat of Reaction
 Evaluate DHR at T2 for known DHR(T1)

 What is ΔCp?

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Equilibrium Conversion


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Equilibrium Conversion
 How is the equilibrium constant related with conversion?

 What is the relation between K and XA?

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Equilibrium Conversion
 How is the equilibrium constant related with conversion?

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Equilibrium Conversion

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 Representing non-isothermal kinetic data
For any single homogeneous reaction, T, C/XA and –rA are uniquely related.

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Typical X vs T plot

Note that this plot is not using energy balance equation.

The plots represents kinetic data with T dependence.

Temperature progression
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 Graphical Design Procedure

X T k -rA FA0/-
rA

Plot FA0/-rA vs XA and obtain the volume.

For a reversible reaction, remember to check if X can be achieved?

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 Optimum Temperature Progression
We define the optimum temperature progression to be that progression which minimizes
VIF,, for a given conversion of reactant. This optimum may be an isothermal or it may be
a changing temperature: in time for a batch reactor, along the length of a plug flow
reactor, or from stage to stage for a series of mixed flow reactors.

Operating lines for minimum reactor size 17

 Adiabatic Operation

Adiabatic operations with large enough heat effect to cause a rise in temperature (exothermic) or
drop in temperature (endothermic) in the reacting fluid.

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Adiabatic Operation
 Qdot = 0; Work (rate) = 0

 If DCP(T-TR) is negligible wrt heat of reaction, a linear relation is obtained

between X and T.
 This relation is from energy balance. The desired conversion would need to
satisfy mass balance too.
 Valid for CSTR, PFR and Batch reactors.
 Let us rearrange and get T = f(X).
 Ratio of Heat needed to raise the temperature to T and heat released by
reaction at T.
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Adiabatic Operation

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Interstage Cooling and Heating
 Exothermic reversible reaction
 Only a certain degree of conversion can be
achieved at a particular temperature
 Multiple reactors in series

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Interstage Cooling

For an exothermic reaction

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Interstage Heating
An example:
Upgrading Octane number of gasoline

Each step is highly endothermic

Allowable temperature range:
Above 530 °C, undesirable side reactions occur
Below 430 °C, the reaction almost does not take place

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Interstage Heating

For an endothermic reaction

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Non-Adiabatic Operations

∑FiHi ∑FiHi

V V+dV

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Non-adiabatic Operations: PFR
 Start with the energy balance below

 At steady state and no shaft work

 Consider an elemental volume dV having area dV
 Note that dFi/dV = ri = ni (-rA)

 The above eqn. needs to be solved together with mole balance eqn.

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PFR with heat exchange
UdA (Ta-T)

∑FiHi ∑FiHi

V V+dV

 Two cases of coolant flow:

 Ta constant
 Ta varying along the length (cocurrent/countercurrent)

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Non-adiabatic Operations: CSTR
 Use the energy balance equation

 Get X = f (T)

 You can also rewrite to get T =f (X)

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 Non-adiabatic Operations: CSTR
 For specified X:
 Calculate T from T = f(X) obtained from energy balance (EB)
 get k get –rA  Plot FA0/(-rA) vs XA  calculate V
 For specified T:
 Calculate X from X = f(T) obtained from energy balance
 get k get –rA  Plot FA0/(-rA) vs XA  calculate V
 For specified V:
 Plot XEB vs T
 Calculate XMB = f(T)
 The intersection of the two will give reactor operating point.

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 Non-adiabatic Operations: CSTR

Irreversible reaction

T1A: insufficient heat liberated by the

reaction to raise T for the reaction to be
self-sustaining

T1B: More than enough heat liberated

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 Non-adiabatic Operations: CSTR

Irreversible reaction

T1C: 3 solutions

M’’: unstable state.

XA

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Non-adiabatic Operations: CSTR

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 Product Distribution and Temperature
If two competing steps in multiple reactions have rate constants k ,
and k,, then the relative rates of these steps are given by

 A high temperaturefavors the reaction of higher activation energy,

 A low temperature favors the reaction of lower activation energy.
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Product Distribution and Temperature

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