8.

STEADY-STATE NONISOTHERMAL
REACTOR DESIGN
Professional Reference Shelf
R8.1-B Runaway Reactions in Plug Flow Reactors*

Phase Plane Plots

We transform the above temperature and concentration

profiles into a phase plane in the following manner.

(1)

(2)

First, we obtain the temperature and concentration profiles

and then use these to obtain the phase plane plot of CA vs.
T.
For example, at volume V2 the temperature is T2 and the
concentration is CA2.

Now increase the entering concentration CA0. Increasing A0

will increase the reaction rate.

Figure 4. Temperature profiles

Note: We observe an inflection point, i, in the curve for CA03 .

Also note the maximum temperature for each of the
concentrations, i.e. Tm1, Tm2 and Tm3. We now look at the
concentration profiles for each of these entering
concentrations.

Figure 5. Concentration profiles for different values of CA0.

Again, forming a phase plane plot of CA vs. T

Now let's plot the maximum temperature for each entering

concentration, CA0, and the corresponding reactor
concentration CAm at this maximum temperature, Tm.
Figure 4 shows the temperature profile for three different
entering concentrations [CA03 > CA02 > CA01]. Figure 5 shows
the concentration profiles for the same set of entering
concentrations. Figure 7 shows a phase plot of CAm as a
function of Tm. This plot (Figure 7) could also have been
obtained directly from the equation

(3)

If Tm is above the TM (the temperature at which CAm is at its

maximum value) then

(4)

The term Q'g increases more rapidly than the heat generated
"prime" (It's "prime" because it does not include CA). In
other words the rate of increase of temperature dependent
part of Qg is greater than the rate of increase of the
temperature dependent part of the heat of removal, Qr.

The following figure shows a plot of CAm vs. Tm for different

ambient temperatures (To≡ Tw)
We note that the concentration CAm goes through a
maximum as the temperature Tm is varied. Different values
of this maximum result for different values of Ta (Tw). The
line CAM is the locus through these maximum values.

We want to see how the concentration of A at the maximum

temperature CAm varies with the maximum temperature Tm.
Specifically we want to find the maximum value of CAm and
the corresponding temperature Tm.

(5)

(6)

Substituting Equation 6 into Equation 5 and simplifying

yields:

(7)

(8)

• Criteria 1 - Criteria Based on the Critical

Trajectory, CM versus TM. The trajectory going
through the maximum of the "maxima curve" is
considered critical and therefore is the locus of the
critical inlet conditions for CA and T corresponding to
a given wall temperature. That is, the trajector whose
 maximum point crosses the CAM verse TM curve will be
considered as runaway. Note this is a conservative
criteria.

To calculate the CAM vs. T Curve

1. Choose Ta
2. Calculate TM
3. Calculate kM
4. Calculate CAM

The critical trajectory goes through Tm. The

locus of the maximum CAM from Figure 8 is
also shown on this figure. What is the inlet
concentration that is related to this critical
trajectory? The safe inlet concentration can be
found by using adiabatic conditions.
 (9)

(10)

(11)

Criteria 2 - Criteria Based on Inflection

Points

We will now derive a second criteria related to

the inflection point on the Temperature
profile. We are going to derive an equation for
the locus of inflection points as a function of
Ta. To simplify manipulations in the derivation,
we are going to set To=Ta.

Starting with Equation 1, Let

Then Equation 1 can be

rewritten as
 (12)

At the inflection point

Differentiating Equation 12

Differential ting (-rA) and the using equation

12, we arrive at

If we have a first order reaction

then we can solve this equation to find CAi as a

function of Ti to find the locus of the inflection
points.

For a first order reaction

• Criteria 2. Runaway will occur when the trajectory

starting at CA0 and To intersects the locus of the
inflection points.
So how far do we back off from the inflection
point conditions 10?C, 0.1 mole/dm3? These
are arbitrarily set numbers (e.g., 10?C) and
we need a criterion based on the intrinsic
properties of the system and not on arbitrarily
limited temperature range. Therefore use
the locus of CAM as a function of TM.

Why use locus of maximum, CAM vs. TM?

 You want to stay away from the intersection of
the CA/T trajectory and the locus of the
inflection points.

Criteria 2A. (Conservative Criteria) Runaway

will occur if the trajectory starting at CA0 and
To intersects the locus of the maxima of CAM
and TM for different values of To (i.e. Tw
because To = Ta = Tw) (See Figure 5)

Oxidation of Naphthalene

• Criteria 3

Runaway reaction figure adapted from Gilbert

F. Froment and Kenneth B. Bischoff, Chemical
Reactor Analysis and Design, John Wiley and
Sons (1990). A number of computer
experiments were carried out to determine
runaway in a PFR. The results were quantified
using two parameters, S and N. The
parameter S is the product of the
dimensionless activation energy, g, and the
dimensionless adiabatic temperature rise, b.

C 3.1

C 3.2

The dimensionless activation energy is

C 3.3

Approximations and errors in

the original article.

Comparing the term multiplying in

Froment and Bischoff (Eqn 11.5.2-2) on page
408 with Fogler (Eqn 8-56)

on page 459 for

ΔCP = 0
 Equating the coefficient of .

C 3.4

therefore equating Froment and Bischoff with

Fogler,

C3.5

Froment and Bischoff

C 3.6

(1)

The other parameter N given in Froment and Bischoff is

C 3.7 (2)

Use equation C3.7 for liquids. For gasses we again equate the
heat capacities:

C 3.8 (3)

C 3.9
 C 3.10 (4)

Note: The equation for (N/S) in Froment and

Bischoff is not correct. If you check the units
you will find (N/S) is not dimensionless.

where

ρg = Gas density (kg/m3)

= Mean molecular weight
Mm
(kg/kmol)
dt = Tube diameter (m)
CT = Total concentration (kmol/m3)
= Entering concentration of A
CA0
(kmol/m3)
= Overall heat transfer
U
coefficient (J/m2 • s • K)
CPi = Heat capacity (kJ/mol•K)
= Mean molecular weight
Mm
(Daltons)
= Mean Heat capacity on a per
CPm
mass basis (J/kg•K)
R = Gas constant (J/mol•K)
E = Activation energy (J/mol)
= Rate of reaction (mol/s• m3) at
-rA0
To,
ΔHRx = Heat of Reaction (J/mol)
To = Temperature (K) (To = Tw = Ta)
no = reaction order

Figure 11. Runaway diagram** (Adapted from

G.F. Froment and K.B. Bischoff, Chemical
Reactor Analysis and Design, 2nd ed. New
York: John Wiley and Sons,1990).

**You will want to use the original graph in

either Froment and Bishoff or in the original
article as this reproduction is only
approximate. Also remember that these
calculations were carried out for Ta=T0.

Using the (N/S) vs. S Plot

*
All chapter references are for the 4th Edition of the text
Elements of Chemical Reaction Engineering.
 Nombre de archivo:  Fogler__7_2 
Directorio:  D:\De Rosa\Cursos_Pregrado\Diseño de Reactores\2013 
Plantilla:
  C:\Users\Rosa\AppData\Roaming\Microsoft\Plantillas\Normal.dot
m 
Título:   
Asunto:   
Autor:  Rosa 
Palabras clave:   
Comentarios:   
Fecha de creación:  12/06/2013 05:37:00 a.m. 
Cambio número:  1 
Guardado el:  12/06/2013 05:37:00 a.m. 
Guardado por:  Rosa 
Tiempo de edición:  0 minutos 
Impreso el:  12/06/2013 05:38:00 a.m. 
Última impresión completa 
  Número de páginas:  14 
  Número de palabras:  1,105 (aprox.) 
  Número de caracteres:  6,080 (aprox.)