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Textbook: Elements of Chemical Reaction Engineering, 4th Edition

CHE 404
Chemical Reaction Engineering

Chapter 8
Steady-State
Nonisothermal Reactor Design
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Contents

PART 1. Steady-State Energy Balance and Adiabatic PFR Applications


 Energy Balance
 User Friendly Energy Balance Equations
 Adiabatic Operation
 Adiabatic Equilibrium Conversion and Reactor Sizing

PART 2. Flow Reactors with Heat Exchange


 Steady-State Tubular Reactor with Heat Exchange
 Balance on the Heat Transfer Fluid
 Algorithm for PFR/PBR Design with Heat Effects
 CSTR with Heat Effects
 Multiple Steady State (MSS)
 Non-isothermal Multiple Chemical Reactions

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8.4.2 Balance on the Heat Transfer Fluid

Case A. Co-current Flow

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Endothermic

Exothermic

Case B. Counter-current Flow

At the entrance V = 0, X = 0, Ta = Ta2


At the exit V = Vf, Ta = Ta0

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Procedure to Solve for the Exit Conditions
for PFRs with Counter-Current Heat Exchange

Trial-and-error method

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Algorithm for PFR/PBR Design with Heat Effects

A+B 2C
A. Conversion as the
reaction variable

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A+B 2C
B. Molar Flow Rates as
the reaction variable

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WHY???
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8.6 CSTR with Heat Effects

Generalized Energy Balance

For CSTR

Energy Balance on Heat Exchanger Fluid

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Heat capacity of heat exchanger fluid

Taylor series
(e-x = 1 - x  +  ·∙  ·∙  ·∙)
For large values of the exchanger fluid flow rate,

whereTa1  Ta2  Ta

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Relationship between conversion and temperature in a CSTR

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Algorithm for Adiabatic CSTR Design

Case A (8-56) (8-55) Case B


Specify X Specify T
Find V and T Find X and V

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Case C (8-55) CSTR Steady State


Specify V when XEB = XMB
Find X and T

(8-53)

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Ex 8-8. Production of PG in an Adiabatic CSTR

Information
1. PO 1st, H2O 0th order
2. k = 16.96x1012 exp(-32400/RT)
3. CpA = 35 Btu/lbmol °F
4. CpB = 18 Btu/lbmol °F
5. CpC = 46 Btu/lbmol °F
6. CpM = 19.5 Btu/lbmol °F
7. vAO = 46.62 ft3/h
8. vM0 = 46.62 ft3/h
9. vB0 = 233.1 ft3/h
10. FA0 = 43.0 lbmol/h

1. Mole Balance and Design Equation 4. Combining and Solving

2. Rate Law 3. Stoichiometry

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5. Energy Balance

6. Calculations
(a) Evaluate the mole balance terms

(b) Evaluate the energy balance terms

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(613 °R=153 °F, 0.83)

Because the temperature must remain below


125 °F (585 °R),
we cannot use the 300-gal reactor as it is now.

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Multiple Steady States (MSS)

If the volumetric flow rate v0 is increased,


(τ decreased) just a little,

XEB(T) remains unchanged,


But XMB(T) moves to the right (solid line).

This shift results in the XEB(T) and XMB(T)


intersecting three times, indicating three possible
conditions at which the reactor can operate.
THIS IS MULTIPLE STEADY STATES!!!

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Heat-Generated Term

Heat-Removed Term
(by flow and heat exchange)

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Heat-Removed Term, R(T)

Heat-Removed Term

Vary Entering Temperature Vary Non-adiabatic Parameter κ

As the entering temperature T0 is increased, As one increases κ, the slope increases


the line has the same slope but shifts to the right. and the intercept moves to the left.

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Heat of Generation, G(T)


Low T : G(T )  HRx AeE / RT

High T : G(T )  HRx
V
 
0 

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Finding Multiple Steady States

Vary Entering Temperature The points of intersection of R(T) and GtT)


give us the temperature which the reactor can
operate at steady state.

We begin to feed our reactor at T01. If we construct


our G(T) and R(T) curves, there will be only one
point of intersection, point 1. From this point of in
section. one can find the steady-state temperature
in the reactor, TS1, by following a vertical line down
to the T-axis.

If one were now to increase the entering


temperature to T02, the G(T) curve would remain
unchanged, but the R(T) curve would move to the
right (line b), and will now intersect the G(T) at
point 2 and be tangent at point 3. Consequently, we
see that there are two steady-state temperatures,
TS2 and TS3, that can be realized in the CSTR for
entering temperature T02.

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Ignition–Extinction Curve

T05 : Ignition Temperature


T02 : Extinction Temperature

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Stability on Multiple Steady State Temperatures

R(T)

G(T)

Point 8 (TS8):
Unstable steady state

Point 7(TS7), Point 9(TS9):


Locally stable, but not necessarily globally stable

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Runaway Reactions in a CSTR
Lower  S.  S.  →  Upper  S.  S.  if  T  >  ignition  temperature
 At upper S. S.: T is sufficiently high that it is undesirable or even dangerous to operate

 Ignition temperature = at the point of tangency of R(T) and G(T) curve

At the tangency point,

1)

(8-65)

2)

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Runaway Reactions in a CSTR
For a 1st order reaction,

 (8-70)

From (8-65)  (8-70)

Above Trc, transition to the upper S. S. (runaway) will occur.


For many industrial reactions,
- E/RT = 16~24, T=300~500K
- Trc = 15~30oC c.f.)

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Nonisothermal Multiple Chemical Reactions

8.8.1 Energy Balance for Multiple Reactions in PFR

For a single reaction,

For q multiple reactions


(m species, q rxns)

Example

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Nonisothermal Multiple Chemical Reactions

8.8.2 Energy Balance for Multiple Reactions in CSTR

Steady-state energy balance for a single reaction

CSTR energy balance for q multiple reactions and m species

CSTR energy balance for two parallel reactions

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Ex 8-11. Series Reactions in a CSTR

k1 k2 Information
A B C 1. Elementary reaction
2. CSTR V = 10 dm3
3. vAO = 1000 dm3/min, CA0 = 0.3 mol/dm3
4. CpA = CpB = CpC = 200 J/mol K
5. k1 = 3.3 min-1 at 300 K, k2 = 4.58 min-1 at 500 K
6. E1 = 9900 cal/mol, E2 = 27,000 cal/mol
7. ΔHRx1A = -55,000 J/mol A, ΔHRx2B = -71,500 J/mol B
8. UA = 40,000 J/min K, Ta = 57 °C

1.A. Mole Balance on Species A 1.B. Mole Balance on Species B

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2. Rate Laws

3. Energy Balances
Eq (8-82)

Derive it!

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Safety – Accidents in scaling-up exothermic chemical rxns

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