Ch 8: Steady – State Non-isothermal Reactor Design

Energy Balances, Rationale and Overview

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:

To solve this equation we need to relate X and T. We will use the Energy
Balance to relate X and T. For example, for an adiabatic reaction, , the
energy balance can be written in the form

set X, then calculate T, -VA, and , increment X, then plot vs. X

1
1. Adiabatic (Q = 0); CSTR, PFR, Batch and PBR:

2. CSTR with heat exchanger, UA(Ta-T) and large coolant flow rate.

3 . PFR/PBR with heat exchange

3A. In terms of conversion, X

3B. In terms of molar flow rates, Fi

2
 4. For Multiple Reactions

5. Coolant Balance

These are eq’ns we will use to solve rxn engineering problems with heat changes.

3. Energy Balance

Typical units for each term are J/s; i.e. Watts

3
Energy Balance
1st Law of Thermodynamics:

dE = dQ – dW (for a closed system)

Energy of the Heat flow to Work done by the

system the system system on the
surroundings

dE • •
= Q− W + Fin E in - Fout E out {for an open system}
dt 123
rate of energy
added to the
system by mass
flow

Evaluation of the Work Term:

•
W = Wf + Ws

flow shaft
n ~ n ~
= −∑ Fi ⋅ P ⋅ V i + ∑ Fi ⋅ P ⋅ V i + Ws
i =1 in i =1 out

~
Combining with Hi = Ui + P Vi

dE sys • • n n
= Q+ W s − ∑ Fi ⋅ H i in + ∑ Fi ⋅ H i out
dt i =1 i =1

4
 (1)

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
Equations above 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:

5
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.

Flow Rates, Fi

For the generalized reaction:

(2)

In general,
Fi0
Fi = FA0 (Θi +ν i X) where Θi = (3)
FA0
b c d
ν A = -1 ν B = - νC = νD =
a a a

Then
n n

∑H i0 ⋅ Fi0 - ∑ H i ⋅ Fi = FA0 [(H A0 - H A ) + (H B0 - H B ) Θ B ] + ...........

i =1 i =1

n n ⎡ ⎤
= FA0 ∑ [(H i0 - H i ) Θ i ] - ∑ ⎢(ν i ⋅ H i ) FA0 ⋅ X ⎥ (4)
i =1 i =1 ⎢
14 2 43 ⎥
⎣ ∆H RX ⎦
d c b (5)
∆H RX = HD + HC - HB - HA
a a a

(6)
∑F i0 H i0 − ∑ Fi H i = FA0 ∑ Θi (H i0 - H i ) - ∆H RX (T) FA0 X

⎧ dE ⎫
for st - st ⎨ = 0⎬; combining (1) and (6) :
⎩ dt ⎭
• • n
(7)
Q - W + FA0 ∑ Θi (H i0 - H i ) - ∆H RX (T) FA0 X = 0
i =1

If a phase change takes place, it will be included in ∆H RX .

6
Assuming no phase change:

H i = H i (TR ) + ∆H Qi
o
(8)

Enthalpy of Change in enthalpy when T

formation at TR is changed from TR to T.
(ref. temp.)

If there is a phase change:

TM T
H i = H i (TR ) + ∫ C ps,i ⋅ dT + ∆H mi (Tm ) + ∫ C pl,i dT
o
(9)
TR TR

T2

∆H Qi = ∫ C pi ⋅ dT (if no phase change) (10)

T1

T
H i = H i (TR ) + ∫ C pi ⋅ dT
o (11)
TR

Cp = α i + βi ⋅ T + γ i ⋅ T 2
T
H i − H i0 = ∫C
Ti0
pi ⋅ dT = C pi ⋅ [T - Ti0 ] (12)

Substitute into (7) :

• • n
Q - W + FA0 ∑Θ i =1
i ⋅ C pi ⋅ [T - Ti0 ] - ∆ H RX (T) FA0 X = 0 (13)

Combine eq’n (11) & (5)

∆H RX = ∆H RX + ∆C p (T - TR ) (14)
o

where
d c b
∆ H RX = H D (TR ) + H C (TR ) - H B (TR ) - H A (TR )
o o o o o
(15)
a a a

d c b (16)
∆C p = C pD + C pC - C pB - C pA
a a a

7
Combine (13) and (14)
• •
[ ]
n
Q - W + FA0 ∑ Θi ⋅ C pi ⋅ [T - Ti0 ] - ∆H RX + ∆C p (T - TR ) ⋅ FA0 X = 0
o
(17)
i =1

Adiabatic Operation:
•
⎫
Ws = 0⎪
X=
∑Θ C (T - Tio )
[ ]
i pi
• ⎬
- ∆HRX + ∆Cp (T - TR )
o
Q = 0 ⎪⎭

for an exothermic, adiabatic rxn

X for an exo. rxn why does X
increase?
This is from E balance, not
mole balance.

∆H RX > ∆C p (T - TR )
o

T so X vs T is linear!!!

Adiabatic Tubular Reactor

Rearrange (18):

T=
[ o
]
X ⋅ - H RX + ∑ Θ i ⋅ C pi To + X ⋅ ∆C p ⋅ TR
(19)
∑Θ ⋅C i pi + X ⋅ ∆C p

Combine with differential mole balance:

dX
FA0 = - rA (X, T) (20)
dV

To obtain T, X and conc’n profiles along the reactor!

Use (19) to construct a table of T vs X.
Obtain k(T) as a function of X Æ -rA as a function of X.
Look at Table 8-2A.

8
Steady – State Tubular Reactor with Heat Exchange:
• •
∆ Q = U ⋅ ∆A (Ta - T) = Ua ⋅ (Ta - T) ⋅ ∆V assume Ws = 0

FA0
∑F ⋅H
i i T ∑F ⋅H
i i FAe
To
Te
V V+∆V

•
∆ Q+ ∑ Fi ⋅ H i V
− ∑ Fi ⋅ H i V + ∆V
=0 (1)
•
The heat flow to the reactor ∆ Q
Overall heat transfer coefficient (U)
Heat exchange area (∆A)
Difference between ambient temperature (Ta) and reactor temperature (T)
•
∆ Q = U ⋅ ∆A (Ta - T) = Ua ⋅ ∆V ⋅ (Ta - T) (2)
A 4
= Diameter of reactor
V D

If ∆V Æ 0

d ∑ (Fi ⋅ H i )
Ua (Ta - T) = (3)
dV
dFi
mole balance : = ri = ν i (-rA ) (4)
dV
diff. Eq' n (3) H i = C pi ⋅ dT

Ua (Ta - T) =
∑ dFi ⋅ H i - ∑ Fi
dH i (5) dH i dT
dV dV = C pi ⋅ (6)
dV dV

Combine (5) & (4) & (6)

dT
Ua (Ta - T) = ∑ν i ⋅ H i ⋅ (-rA ) - ∑ Fi ⋅ C pi (7)
1 4 2 43 dV
∆H RX

9
Æ Rearrange:

6Heat
4 generated
7 48 6 Heat4 7removed
48
dT rA ⋅ ∆H RX − Ua (T - Ta)
= (8)
dV ∑ Fi ⋅ Cpi
Fi = FA0 ⋅ (Θ + ν i X)
Ua (Ta - T) + rA ⋅ ∆H RX
dT
= {for a PFR}
dV FA0 ⋅ (∑ Θ i + ν i X + ∆C p ⋅ X )
Substitute into (8)

⋅ (Ta - T) + (rA ') ⋅ ∆H RX

Ua
dT ρ
for a PBR {dW = ρb dV} = b
dW ∑F ⋅C
i pi

dX - rA
These eq’ns will be coupled with mole balance eq’ns
=
dV FA0

Balance on the Coolant Heat Transfer Fluid:

Heat transfer fluid

Tao

R1
R2
FA0, To
V V + ∆V Reactants

The fluid will keep the rxn temperature constant for endo/exo – thermic rxns
You might have
A. Co – current Flow
B. Counter – current Flow

10
A. Co – Current Flow
The Energy Balance Ta: coolant temperature

mc, Hc mc, Hc
• • •
E in - E out + Q conduction = 0 FA, T FA, T
V V + ∆V
• •
mc Hc - mc Hc + Ua (T - Ta) ∆V = 0 V
V V + ∆V V + ∆V

Divide by ∆V and take limit as ∆V Æ 0

• exothermic
dH c Tao
mc ⋅ + Ua (T - Ta) = 0
dV

dH c dT dTa Ua (T - Ta)
= Cp a ⇒ = • Tao endothermic
dV dV dV mc ⋅ Cp

B. Counter – Current Flow

Ta2 Ta
FAo, To dTa Ua (Ta - T)
T = •
dV m c ⋅ C pc
V V + ∆V
V=0 V = Vf

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

At the exit V = Vf; Ta = Tao
The sol’n to the counter-current flow problem to find {T X} is a trial & error
procedure.
Assume a coolant temp at the entrance (Ta2)
Solve ODEs to calculate X, T and Ta as a function of V:
Find Ta(V = Vo)

If Ta (V = Vo ) - Ta2 < ε → Ta (V = Vo ) = Ta2

Else assume another Ta2

11
Equilibrium Conversion
As T X {For endothermic rxns}
As T X {For exothermic rxns}

Exothermic Rxns:

Kc
Xe = {1st order rxn}
1 + Kc

From Le Chaltlier’s Law Kp

Kc =
(Kc as T if ∆H<0) exothermic (RT )γ

To find the max X in an exothermic rxn carried adiabatically:

Energy balance
To1 >To
Xe =
∑Θ i ⋅ C pi ⋅ (T - To )
Xe − ∆H RXN (T )
Xe1
⎧if To is changed to To1 ⎫
⎨ ⎬
⎩as T Xe ⎭
To To1
Adabatic temperature

⎧ dlnK ~
⎫
⎪ ∆ H (T) ∆H o
RXN (TR ) + ∆ C p (T - TR )
⎪
= =
p RXN
⎪ dT R ⋅ T2 R ⋅ T2 ⎪
⎪⎪ ~ ⎪⎪
⎨ if ∆ C p = 0 ⎬
⎪ ⎪
⎪K (T ) = K (T ) exp⎧ ∆H RXN (TR ) ⎛⎜ 1 − 1 ⎞⎟⎫
o
⎪
⎪ p 2 p 1 ⎨ ⎜ ⎟ ⎬ ⎪
⎪⎩ ⎩ R ⎝ T1 T2 ⎠⎭ ⎪⎭

12
 To increase the conversion in an exothermic rxn, use multiple reactors with
interstate cooling:

Xe

Xeb

For Endothermic Rxn (you need heating)

Xe

Optimum Feed Temperature

∆H rx
Adiabatic Reactor of fixed size T = To - ⋅X
C pA
Reversible & Exothermic Rxn if ∆H rx < 0 as X ;T
X
2

3 1

350 500 600

T, K

As T Xe but the (-rA) decreases!

(so the conversion is achieved at the end of the reactor)
So there must be an optimum temperature to achieve max X.
Curve A: Rxn rate slow, rxn dictated by rate of rxn and reactor volume
As T ,r ,X
Curve B: Rxn rate very rapid. Virtual equilibrium reached in X dictated by equilibrium
conversion

13
Adiabatic Rxn Algorithm

Suppose

1. Choose X

Calculate T

Calculate k

Calculate T/To

Calculate CA

Calculate CB

Calculate KC

Calculate -rA

2. Increment X and then repeat calculations.

3. When finished, plot vs. X or use some numerical technique to find V.

Levenspiel Plot for an

exothermic, adiabatic reaction.

14
Consider:

PFR Shaded area is the volume.

For an exit conversion of 40% For an exit conversion of 70%

CSTR Shaded area is the reactor volume.

For an exit conversion of 40% For an exit conversion of 70%

We see for 40% conversion very little volume is required.

CSTR+PFR

15
For an intermediate conversion of 40% and exit conversion of 70%

Looks like the best arrangement is a CSTR with a 40% conversion followed by
a PFR up to 70% conversion.

Evaluating the Heat Exchanger Term

Energy transferred between the reactor and the coolant:

Assuming the temperature inside the CSTR, T, is spatially uniform:

16
 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:

Since the coolant flow rate is high, Ta1 Ta2 Ta:

Multiple Steady States (MSS)

where Heat generated term

Heat removed term

17
R(T):
Varying Entering Temperature
R(T)
Slope = Cpo (1+κ)

Increase To

T
Vary non-adiabatic parameter κ:
if you increase FA0 (molar flow rate) or decrease heat – exch area then κ will
decrease
⎧⎪ Ua ⎫⎪
R(T) ⎨κ = ⎬
κ=∞ ⎪⎩ FA0 C p0 ⎪⎭
κ= 0
T + κ ⋅ Ta
Tc = 0
κ decrease 1+ κ

Ta To
T

G(T)

G(T) High E increasing T

G(T)

Low E

T T

For a first order rxn:

τ ⋅k
X=
1+τ ⋅ k

18
Ignition – Extinction Curve:
The point of intersection of G(T) and R(T) give Tst-st.
By plotting Tst-st vs To, we obtain ignition – extinction curve.

Upper st-st

As To Tst-st

Lower st-st

Ignition temp

Extinction temp

Runaway Rxns in a CSTR:

R(T),
G(T)

T0 + κ ⋅ Ta
Tc =
1+ κ Tc T*
Tangency point

R ⋅ T *2
∆Trc = T * - Tc =
E
Reactor T

if this diff. is exceeded, transition to the upper st – st will occur.

At this high temp, it is undesirable or even dangerous.

19
PFR

dT Ua (Ta - T) + (-rA )(-∆H Rxn (T))

= m
(for a single rxn)
∑ Fi Cpi
dV
i =1

When q multiple rxns occur with m species:

[ ]
q
Ua (Ta - T) + ∑ (-rij ) - ∆H Rxn,ij (T)
dT i : rxn
= i =1
m

∑F C
dV j : species
j pj
j=1

Ex: Rxn 1 :
A ⎯⎯→
k1
B
B ⎯⎯→
k2
C

dT Ua (Ta - T) + (-r1A )[- ∆H Rxn,1A (T) ] + (-r2B )[- ∆H Rxn,2B (T) ]

=
dV FA C pA + FB C pB + FC C pC

CSTR
• • n
Q - W s + FA0 ∑Θ i ⋅ C pi ⋅ [T - T0 ] - [∆ H RXN (T) ]⋅ [rA V ] = 0 (for a single rxn)
i =1

When q multiple rxns take place

• • 0 n q
Q - W s + FA0 ∑Θ
i =1
i ⋅ C pi ⋅ [T - T0 ] - V ⋅ ∑ rij ∆ H RXN, ij (T) = 0
i =1
n q
UA(T a - T) + FA0 ∑ Θ i ⋅ C pi ⋅ [T - T0 ] - V ⋅ ∑ rij ∆H RXN, ij (T) = 0
i =1 i =1

20
_ _ _ _ _ _ _ _---""C"'--H APT E RL-- 9""'----

Nonisothermal Reactors

9.1 I The Nature of the Problem

In Chapter 3, the isothennal material balances for various ideal reactors were derived
(see Table 3.5.1 for a summary). Although isothermal conditions are most useful for
the measurement of kinetic data, real reactor operation is nonnally nonisothennal.
Within the limits of heat exchange, the reactor can operate isothennally (maximum
heat exchange) or adiabatically (no heat exchange); recall the limits of reactor be-
havior given in Table 3.1.1. Between these bounds of heat transfer lies the most com-
mon fonn of reactor operation-the nonisothermal regime (some extent of heat ex-
change). The three types of reactor operations yield different temperature profiles
within the reactor and are illustrated in Figure 9.1.1 for an exothennic reaction.
If a reactor is operated at nonisothennal or adiabatic conditions then the ma-
terial balance equation must be written with the temperature, T, as a variable. For
example with the PFR, the material balance becomes:

vir(F i,T) (9.1.1)

Since the reaction rate expression now contains the independent variable T, the material
balance cannot be solved alone. The solution of the material balance equation is only
possible by the simult<meous solution of the energy balance. Thus, for nonisothennal re~
actor descriptions, an energy balance must accompany the material balance.

9.2 I Energy Balances

Consider a generalized tlow reactor as illustrated in Figure 9.2.1. Applying the
first law of thennodynamics to the reactor shown in Figure 9.2.1, the following
is obtained:

(9.2.1)
 CHAPTER 9 Nonisotbermal Reactors 287

---·I PF_R ~
... -,
" \ Adiabatic
/ \

~ /
~ / \
S / \ Isothermal
~ I \\

", ,
.... - Nonisothermal

Length

Figure 9.1.1 I
Temperature profiles in a PFR accomplishing an
exothermic reaction.

Q
Tin
-
min
Pin
V in
1 Pout
Vout
U out

uin Reactor

1
- Zout

Figure 9.2.1 I
Schematic of flow reactor and energy terms.

where w" is "shaft work," that is, pump or turbine work, Vi is the internal energy of
stream i, mi is the mass of stream i, Pi is the pressure of stream i, iii is the volume
of mass i, Ui is the velocity of stream i, Zi is the height of stream i above a datum
plane, and gc is the gravitational constant, for i denoting either the outlet or inlet
stream. For most normal circumstances:

(9.2.2)
288 C H A PT E R 9 Nooiso1bBUDaLBaactms _

and

Using these assumptions to simplify Equation (9.2.1) yields:

Q (Uout + Pout Vout ) - (Vin + Pin V in ) (9.2.3)

Recall that the enthalpy, H, is:

H = V + PV (9.2.4)

Thus, Equation (9.2.3) can be written as:

(9.2.5)

However, since it is more typical to deal with rates of energy transfer, Q , rather than
energy, Q, when dealing with reactors, Equation (9.2.5) can be differentiated with
respect to time to give:

(9.2.6)

where Q is the rate of heat transfer, hi is the enthalpy per unit mass of stream i, and
mis the mass flow rate of stream i. Generalizing Equation (9.2.6) to multi-input,
multi-output reactors yields a generalized energy balance subject to the assumptions
stated above:

Q = 2.:
outlet
houtmout - 2.:
inlet
hinm in
COll,servatioll)
( of energy
(9.2.7)
streams streams

0= 2.: m out - 2.: nlin ( con~ervation)

of mass
(9.2.8)
outlet inlet
streams streams

Note that the enthalpy includes sensible heat and heat of reaction effects as will be
illustrated below.
For a closed reactor (e.g., a batch reactor), the potential and kinetic energy terms
in Equation (9.2.1) are not relevant. Additionally, W s ~ 0 for most cases (including the
work input from the stirring impellers). Since most reactions c~ed out in closed re-
actors involve condensed phases, j.(Pl/) is small relative to 6,U, and for this case is:

Q /:;'V Vproducts - Vreactants (9.2.9)

or from Equations (9.2.9) and (9.2.4):

Q /:;. H, PV constant (conservation of energy) (9.2.10)

9.3 I Nonisothermal Batch Reactor

Consider the batch reactor schematically illustrated in Figure 9.3.1. Typically, re-
actants are charged into the reactor from point (1), the temperature of the reactor
 CHAPTER 9 Nonisothermal Reactors 289

(I) _-=- ,

............................. Temperature
sensor

Temperature
controller

Heat transfer
---'-- fluid
'-- --""'--- (II)

Figure 9.3.1 I
Schematic of a batch reactor.

is increased by elevating the temperature in the heat transfer fluid, a temperature

maximum is reached, the reactor is then cooled by decreasing the temperature of
the heat transfer fluid and products discharged via point (II).
To describe this process, material and energy balances are required. Recall
that the mass balance on a batch reactor can be written as [refer to Equation
(3.2.1)]:

(9.3.1)

If in the rare case that the reactor is accomplishing a constant pressure gas-phase
reaction at nonisothermal conditions:

(9.3.2)

To solve the mass balance, it must be accompanied by the simultaneous solution of

the energy balance (i.e., the solution of Equation (9.2.9». To do this, Equation (9.2.9)
can be written in more convenient forms. Consider that the enthalpy contains both
sensible heat and heat of reaction effects. That is to say that Equation (9.2.10) can
be written as:

heat exchange = (change in sensible heat effects)

+ (the energy consumed or released
by reaction) (9.3.3)

or

Q (9.3.4)
290 CHAPTER 9 Nooisotbermal Reactors

i
Tfinal

(III)

Tinitial '-- ---4 (Tinitial' cI>final)

(Tinitial' cI>initial)

<Pinitial
Extent of reaction

Figure 9.3.2 I
Enthalpy pathways.

where <I> is the extent of reaction (s~ Chapter 1), !::..Hr is the heat of reaction, MS
is the total mass of the system, and (Cp ) is an average heat capacity per unit mass for
the system. Since enthalpy is a state variable, the solution of the integral in Equation
(9.3.4) is path independent. Referring to Figure 9.3.2, a simple way to analyze the in-
tegral [pathway (I)] is to allow the reaction to proceed isothermally [pathway (II)] and
then evaluate the sensible heat changes using the product composition [pathway (III)].
That is,
T,;,,,,

Q= <I> . - <I> Illitlal)

!::..Hr ITinitial (fmal .. +
I
Tinitial
MSfinal IC
\ Pfinaj)
dT (9.3.5)

where a positive value for the heat of reaction denotes an endothermic reaction.
Since the reaction-rate expressions normally employ moles of species in their
evaluation:
T,;"",

I Tinitial
MSfinal (C
.
. .)dT =
p tuwl (9.3.6)

where ni is the moles of species i, and CPi is the molar heat capacity of species i. Note
also that the heat exchange is the integral over time of the heat transfer rate, that is,

Q = J Qdt = J
UAH(T* - T)dt (9.3.7)

where U is an overall heat transfer coefficient, AH is the heat transfer area, and
T* is the reference temperature. Combining Equations (9.3.7), (9.3.6), and (9.3.5)
 CHAPTER 9 Nooisothermal Reactors 291

and recalling the definition of the extent of reaction in terms of the fractional
conversion [Equation (1.2.10)] gives:

(9.3.8)

or in differential form:

-6.Hr l r o dIe:L . dT
UAH(T* - T) = n~- + (nC)- (9.3.9)
v e e dt j I P, dt

Notice that [see Equations (1.2.10) and (1.3.2)]:

n~ dIe d<l>
= rV (9.3.10)
-Ve dt dt
Using Equation (9.3.10) in Equation (9.3.9) yields:

UA H (T * - T) = 6.Hr r orV + "

l
d
LJ (nj T
Cp)--;tt (9.3.11)
I

Equations (9.3.11), (9.3.9), and (9.3.8) each define the energy balance for a batch reactor.

EXAMPLE 9.3.1 I
Show that the general energy balance, Equation (9.3.9), can simplify to an appropriate form
for either adiabatic or isothermal reactor operation.

• Answer
For adiabatic operation there is no heat transfer to the surroundings (i.e., U = 0). For this
case, Equation (9.3.9) can be written as:

_ -
0-
~Hr ITO ne-
0 die
+ L (n C .) dT-
Ve dt p, dt
j I

or when integrated as:

(9.3.12)

If the reactor is operated at isothermal conditions, then no sensible heat effects occur and
Equation (9.3.9) becomes:

(9.3.13)

The description of the nonisothermal batch reactor then involves Equation (9.3.1)
and either Equation (9.3.9) or (9.3.11) for nonisothermal operation or Equation (9.3.12)
292 CHAPTER 9 NQoisothe.unalBeacJ:Qr.s....

for adiabatic operation. Notice that for adiabatic conditions, Equation (9.3.12) provides
a relationship between T and Insertion of Equation (9.3.12) into Equation (9.3.1)
allows for direet solution of the mass balance.

EXAMPLE 9.3.2 I
The hydration of 1-hexene to 2-hexanol is accomplished in an adiabatic batch reactor:

OH
~+H20===>~
(A) (8) (C)

The reactor is charged with 1000 kg of a 10 wI. % H2 S0 4 solution and 200 kg of 1-hexene
at 300 K. Assuming that the heat capacities for the reactants and products do not vary with
temperature, the heat of reaction does not vary with temperature, and the presence of H2S04
is ignored in the calculation of the heat capacity, determine the time required to aehieve
50 pereent conversion and the reactor temperature at that point.

Data:

I-hexene 43.8 -10.0

H 20 16.8 -68.0
2-hexanol 54.0 -82.0

reaction rate constant: k 104 exp -IO;(RJ)] (S-I)

• Answer
The material balanee on the batch reactor is:

or

k(l -
dt

since the reaction is first-order (units on k and large excess of water: I-hexene is the limit-
ing reagent). The energy balance is:

where Vi I. In order to calculate the heat of reaction, the standard heats of formation
can be used as follows:

IO = -4 kcal/mol
 CHAPTER 9 Nooisotherma l Reactors 293

Thus, the energy balance equation can be written:

where

The values of n~ and n~ are:

n~ = (2 X 105 g)(l mol/84 g) = 2381 mol

n~ = (9 X 105 g)(l mol1l8 g) = 50000 mol

so that:

nVn~ = 21

By placing the values for n~, Ai, TO, and the Cp into the energy balance, the result is:

4000 fA
T = 300 + 421.8 7.8 fA

The material balance equation is then solved with k(D being first converted to k(j~) by sub-
stitution of the energy balance for T:

-l~

l
-
4
k = 10 exp ( 4000 fA
Rg 300 + )
421.8 - 7.8 fA
The material balance equation must be solved numerically to give t = 1111 s or 18.52 min.
The reactor temperature at this point is obtained directly from the energy balance with fA = 0.5
to give T = 304.8 K.

EXAMPLE 9.3.3 I
Consider accomplishing the reaction A + B ~ C in a nonisothermal batch reactor. The re-
action occurs in the liquid phase. Find the time necessary to reach 80 percent conversion if
the coolant supply is sufficient to maintain the reactor wall at 300 K.
Data:

C~ = 0.5 mol/L 6.Hr -15 kJ/mol

C~ = 0.6 mol/L VA H 50 J/(s-K)
Cp , CPR 65 J/(mol-K) Cpr = 150 J/(mol-K)
n~ 100 mol

k
1
5 X 10-' exp
ll20000 J/mol ( I
Rg
---
300
T1)lJ (Llmol/s)
 • Answer
The material balance for the batch reactor is:
d'j'
~=kCO(I-t·)·(1.2
dt A . A
j"A)

The energy balance can be written as:

lJA H - I..>. H, nA(Jdj~

' (T' - T )_A di +
The material and energy balance equations must be solved simultaneously. A convenient form
for solution by numerical techniques is:

dfA
dt
dT
dt n~(1

with fA 0 and T 300 K at t O. The results are shown in Figure 9.3.3. From the data
given in Figure 9.3.3, it takes 462 s to reach a fractional conversion of 0.8. Additionally, the
final temperature is 332 K. Notice that the final temperature is not the maximum tempera-
ture achieved during the reaction, in contrast to adiabatic operation.

0.8 340
c:
.S
'"'-< 0.6
<l)
g 330
>
c: ~
0
<l)

c;J
'§'"
c 0.4 <l)
0<
320
.S E
t)
~
J: 310

I I I I I I I I ! I I I
100 200 300 400 500 o 100 200 300 400 500
Time (s) Time (s)

Figure 9.3.3\ Fractional conversion and temperature profiles for the reactor described in Example 9.3.3.
 CHAPTER 9 Nonisothermal Re.ac..ul"-'ou;rs'-- -"2..9.....
5

VIGNETTE 9.3.11

M. K1adko [CHEMTECH, 1 (971) 141] presented an case study of per-

isomerization reaction. In a 50 gal steam-heated
1; 1 ratio of A to sol-
with a reactant-to-
out of con-
ffects of the
in this case
is higher
reaction more efficiently
..
2...
9,.;6L.- --"CLlH1A P'-JTLEI:JlRL<l9~NL'<I..lounl"isDlhermal Beaclms
...... " "_ _
9.4 I Nonisothermal Plug Flow Reactor
Consider a PFR operating at nonisothermal conditions (refer to Figure 9.4.1).
To describe the reactor performance, the material balance, Equation (9.1.1),
must be solved simultaneously with the energy balance, Equation (9.2.7). As-
suming that the PFR is a tubular reactor of constant cross-sectional area and
that Tan? C do not vary over the radial direction of the tube, the heat trans-
fer rate Q can be written for a differential section of reactor volume as (see
Figure 9.4.1):

(9.4.1 )

since

dA H 1Td{dz (differential area for heat transfer)

and

(differential reactor volume)

298 CHAPTER 9 Nooisothermal Reactors

dQ

It . fi + dti
Fj=F,:n F; + dF; = F~ut
hi dt hi+dh i
Tin Tout

dz

Figure 9.4.1 I
Schematic of differential fluid volume in a nonisothermal PFR.

where d r is the diameter of the tubular reactor. Recall again that the enthalpy con-
tains both sensible heat and heat of reaction effects. Thus, the energy balance Equa-
tion (9.2.7) can be written for the differential fluid element of the PFR as:

where the heat of reaction is evaluated at a reference temperature TO and CPi is the mo-
lar heat capacity of species i. Normally, TO is taken as the reactor entrance temperature.

EXAMPLE 9.4.1 I
Show that the general energy balance, Equation (9.4.2), can simplify to an appropriate form
for either adiabatic or isothermal reactor operation.

• Answer
For adiabatic operation dQ = O. Thus, Equation (9.4.2) simplifies to:

(9.4.3)

If TO is the temperature at the reactor entrance and the conversion is zero at this point, then
Equation (9.4.3) can be written for any point in the PFR as:

(9.4.4)

Equation (9.4.4) relates the conversion to the temperature for an adiabatic PFR. If the reac-
tor is operated isothermally, then:

t::.H,
dQ = F~df{ (9.4.5)
EXAMPLE 9.4.2 I
(From C. G. Hill, An Introduction to Chemical Engineering Kinetics and Reactor Design,
Wiley, 1977, pp. 362-364.)
Butadiene and ethylene can be reacted together to form cyclohexene as follows:

CHCH = CH c + CH c CHc==>Oi
(B) (E)
(C)

If equimo1ar butadiene and ethylene at 450°C and 1 atm are fed to a PFR operating adiabat-
ically, what is the space time necessary to reach a fractional conversion of 0.1 O?

k 1075 exp[ -27,500/(RgT)] L/mol/s

/::,. H, - 30000 cal/mol
Cpu 36.8 cal/mol/K
CP1 20.2 cal/mol/K
Cpr = 59.5 cal/mol/K

• Answer
Assume that each CPi is not a strong function of temperature over the temperature range obtained
within the PFR (i.e., each is not a function of T). The material and energy balance equations are:
O
-kC~ -k(ci\f [ I i 'B ]2(T
_
)2
1+ sldB T

and

-CO diB
B dT

Thus, the material balance can be written as:

df' r
1- iB
B _ kCo I
dT - B II 0.5 iB T

2l
since £B 0.5 I
, I -0,5. Now for the energy balance,
1!J

dT since
300 CHAPTER 9 Nooisothermal Reactors

Thus,

2: FiC
1
Pi
r
"TO
dT = FZ (1 - IB)(36.S)(T - TO) + F2 (1 fe)(20.2)(T TO)

+ F2!B(59.5)(T TO)

or

2: FiC
l
Pi
f
TO
T dT = (57 + 2.5 fe) F2 (T - TO)

The energy balance then becomes:

° ° _ (-30,000) °
(57 + 2.5Ie)Fs (T - T) - (-1) Fsfs

or

(30,000) Is
T 723 + -'------'--""'-
57 + 2.51e

The solution of the material balance equation:

with T from the energy balance gives a value of 7 = 47.1 s. Additionally, the exit tempera-
ture is 775 K.

VIGNETTE 9.4.1

The energy balance for the PFR can also be written as follows by combining
Equations (9.4.1) and (9.4.2):
 C H A PT E R 9 NonisolhermaLR""e""'8c"'1"-'ow:ts'-- 1
--"3....0LL

U(T* (9.4.6)

or

U(T* - T)i = ' " FC dT _ !:.H,ITo FO die (9.4.7)

dt ~ I
I Pi dV
R
Vo
,
e dVR

Using the fact that:

Equation (9.4.7) can be written as:

dT 4
!:.H,ITo)r - U(T - T *)- (9.4.8)
-7'
'" FCI Pi dVR = dt

Thus, the material and energy balances for the PFR can be written as (Fe = Cev =
C e 7Td;u/4; dVR = 7Td;dz/4):

(9.4.9)
4U (T - T*) }
dt

with Ce = c2 and T = TO at z = 0, ~here u is the superficial linear velocity, p is

the average density of the fluid, and Cp is the average heat capacity per unit mass.
Equation (9.4.9) is on~ applicable when the density of the fluid is not changing in
the reactor and when Cp is not a function of temperature, since the following rela-
tionship is used to obtain Equation (9.4.9):

(9.4.10)

EXAMPLE 9.4.3

A PFR of dimensions L = 2 m and d 1 = 0.2 m is accomplishing a homogeneous reaction. The

inlet concentration of the limiting reactant is c2 0.3 kmol/m 3 and the inlet temperature is
700K. Other data are: - !J.Hr 10 kJ/kmol,C" 1 kJ/(kg-K),E = lOOkJ/mol,p 1.2kg/m3 ,
4

u = 3 mis, and A 5 s -I. Calculate the dimensionless concentration (y = C e/c2) and tem-
perature (8 profiles for adiabatic (U = 0) and nonisothennal (U 70 J/(m 2 -s-K))
operations. (Example adapted from J. Villadsen and M. L. Michelsen, Solution of Differential
Equation Models by Polynomial Approximation, Prentice-Hall, Englewood Cliffs, 1978, p. 59.)

• Answer
From the units on A, it is clear that the reaction rate is first order. Using Equation (9.4.9)
with a first-order reaction rate expression gives:
302 CHAPTER 9 Nonisotbermal Reactors

-u dC, A exp[ -E/(R~T)]C,

dz
- dT -
upCp dz = (-I1H,)A exp[ -E/(RgT)]C,

Let x = z/L, y = c,/c2 and (j = T/To. Using these dimensionless variables in the material
and energy balance relationships yields:

dy
dx

de -
dx = f3T(Da)y exp [y( 1 - e1)] - Hw(e- 1)

with y = 1 at x = 0 and where:

Notice that all the groupings Da, f3T' y, and H w are dimensionless. For adiabatic operation,
H w O. For this case, the mass balance equation can be multiplied by f3T and added to the
energy balance to give:

d -
(e + f3TY) = 0
dx

Integration of this equation with y e = 1 at x = 0 leads to:

(j = 1 + f3T(1 - y) (9.4.11)

Equation (9.4.11) is the adiabatic relationship between temperature and conversion in

dimensionless form. The mass balance can then be written as:

dy
dx

with

y=latx=O

The solution of this differential equation is straightforward and is shown in Figure 9.4.2. For
the nonisothermal case, the material and energy balances must be solved simultaneously by
 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _~C>LLHuA"_P"'_LT_"EiWlR"__"9'____L'LN,illlisQtbBImaLBaaclo~ ...0
~3 ...3
...

1.2 1.35
1.30
1.0
1.25
0.8
1.20
;>-, 0.6 1.15 "'I
1.10
0.4
1.05
0.2
1.00
0.0 0.95
0.0 0.2 0.4 0.6 0.8 1.0
x

Figure 9.4.2 I Dimensionless concentration and

temperature profiles for adiabatic and nonisothermal
operati~. Ya and 8a are for adiabatic conditions while
Yn; and 8n; are for nonisothermal operation.

numerical methods. The nonisothermal results are plotted also in Figure 9.4.2. Notice that
there is a maximum in the value of 8,,; that occurs at x 0.57 and gives T = 860 K. The
maximum in the temperature profile from nonisothermal operation is normally denoted as
the hot spot in the reactor.

9.5 I Temperature Effects in a CSTR

Although the assumption of perfect mixing in the CSTR implies that the reactor
contents will be at uniform temperature (and thus the exit stream will be at this tem-
perature), the reactor inlet may not be at the same temperature as the reactor. If this
is the case and/or it is necessary to determine the heat transferred to or from the re-
actor, then an energy balance is required.
The energy balance for a CSTR can be derived from Equation (9.2.7) by again
carrying out the reaction isothermally at the inlet temperature and then evaluating
sensible heat effects at reactor outlet conditions, that is,

Q (9.5.1)

where.the superscript f denotes the final or outlet conditions. For adiabatic opera-
tion, Q = O.

EXAMPLE 9.5.1 I
The nitration of aromatic compounds is a highly exothermic reaction that generally uses cat-
alysts that tend to be corrosive (e.g., HN0 3 IH 2 S04 ). A less corrosive reaction employs N 20 s
 as the nitrating agent as illustrated below:

NO z

N,o, +U= O+H'O

2 2

(A) (8) (e) (D)

If this reaction is conducted in an adiabatic CSTR, what is the reactor volume and space time
necessary to achieve 35 percent conversion of NzOs? The reaction rate is first order in A and
second order inB.
Data:

I::.Hr = -370.1 kllmol TO = 303 K

Cp , = 84.5 J/(mol-K) F~ = 10 mol/min
Cps = 137 J/(mol-K) F2 = 30 mol/min
Cpc = 170 ll(mol-K) v = 1000 L/min
CPD = 75 J/(mol-K) C~ = 0.01 mol/L

k 0.090 exp lr(40kJ/mOl)(-3031 - -T1)]

R~
(Llmol? (mint]

• Answer
The reaction occurs in the liquid-phase and the concentrations are dilute so that mole change
with reaction does not change the overall density of the reacting fluid. Thus,

CA = C~ (1 fA)' FA = F~ (1 fA)
Cs = C~ (3 2fA)' Fs = F~(3 2fA)
Fe = 2FUA' FD = F~fA

The material balance on the CSTR can be written as:

The energy balance for the adiabatic CSTR is:

0= I::.HrFUA F~ (1 - fA) CPA (T TO) + F~ (3 2fA)CPB (T - TO)

+ 2FUACpc (T - TO) + F~.t~CPD (T - TO)
For fA = 0.35, the energy balance yields T = 554 K. At 554 K, the value of the rate constant
is k = 119.8 L2/(mo1 2-min). Using this value of k in the material balance gives V 8,500 L
and thus T 8.5 min.

EXAMPLE 9.5.2 I
Consider the aromatic nitration reaction illustrated in Example 9.5.1. Calculate the reactor
volume required to reach 35 percent conversion if the reactor is now cooled.
Data:

VAil 9000 J/(min-K)

T~. 323 K (and is constant)
v 100 L/min
c2 O. 10 mol/L

All other data are from Example 9.5. I .

• Answer
The material balance equation remains the same as in Example 9.5.1. The energy balance is
now:

VAIl (T~ - T) 6.HrF~j~ + F~ (I - fA)C p, (T TO) + F~ (3 2j~)CpfJ (T - TO)

+ 2F~fA CfJc (T - TO) + FV~ CPD (T TO)

whenj~ 0.35, the energy balance yields T 407 K. At 407 K, the reaction rate constant
is k 5.20 L 2/(mof-min). Using this value of k and c2 0.10 mol/L in the material bal-
ance equation gives V 196 L.

9.6 I Stability and Sensitivity of Reactors

Accomplishing Exothermic Reactions
Consider the CSTR illustrated in Figure 9.6.1. The reactor is accomplishing an
exothermic reaction and therefore must transfer heat to a cooling fluid in order
to remain at temperature T. Assume that the heat transfer is sufficiently high to
maintain the reactor wall temperature at T e . Therefore,

Q= UAH(T - TJ vcCpc(Tc - T?) (9.6.1)

heat removed sensible heat change
from reactor of coolant

+-TO

Figure 9.6.1 I
Schematic illustration of a CSTR that is maintained at
temperature T by transferring heat to a coolant t1uid
(Tc >
306 CHAPTER 9 Nonisotbermal Reactors

where V c is the volumetric flow rate of the coolant and Cp , is the heat capacity of
the coolant and is not a function of temperature. Solving for Tc and then substitut-
ing the expression back into the heat transfer equation yields:

. UAHvcCp
Q = ' (T T~) = AA (T - T~) (9.6.2)
UA H + veCpc
The energy balance on the CSTR can be written as [from Equation (9.5.1) with a
first-order reaction rate expression]:

or since:

-Ve rV = F~(je f~) (material balance)

as:

(first-order reaction rate) (9.6.3)

where vP is the volumetric flow rate of the product stream and p and Cp are the av-
erage density and heat capacity of the. outlet stream. Rea:ranging Equation (9.6.3)
and substituting Equation (9.6.2) for Q gives (note that Q is heat removed):

(9.6.4)

Let:

AA
(l'Cl'l=--
vPpCp
-kT(t:.HrITo)
pCp

so that Equation (9.6.4) can be written as:

(1 + Cl'Cl'l)T (TO + Cl'Cl'lT~) = Cl'Cl'2Ce (9.6.5)

Since:

Ce = C~/(l + kT)
from the solution of the material balance equation, Equation (9.6.5) can be formu-
lated as:

(l + Cl'Cl'l)T - (T ° + Cl'Cl'lTcJ
°- _ Cl'Cl'2C~
-- (9.6.6)
1 + kT
Qr (heat removed) = Qg (heat generated)
 CHAPTER 9 Nooisothermal Reactors 307

:~O:O:I= 00, T=
I
I
I
I
I
I
I
I
I
I

T T

TO+0:0: 1T2
1+0:0: 1

Figure 9.6.2 I
Schematic illustration of Q,. and Qg as functions of T.

Q,.
(1) (II) Q,. (III)
",--- Qo -Q ,,'" --Qg
/
/ I:'>
3 g /
I I
I I
I I
I I
I I
I I
I I
I I
/ /
" "
T T T

Figure 9.6.3 I
Steady-state solutions to Equation (9.6.3).

If Q,. and Qg are plotted versus the reaction temperature, T, the results are illustrated
in Figure 9.6.2. A solution of Equation (9.6.6) occurs when Q,. equals Qg, and this
can happen as shown in Figure 9.6.3. Notice that for cases (I) and (III) a single
solution exists. However, for case (II) three steady-states are possible. An impor-
tant question of concern with case (II) is whether all three steady-states are sta-
ble. This is easy to rationalize as follows. At steady-state 1, if T is increased then
Q,. > Qg so the reactor will return to point 1. Additionally, if T is decreased,
Qg > Qr so the reactor will also return to point 1 in this case. Thus, steady-state
1 is stable since small perturbations from this position cause the reactor to return
to the steady-state. Likewise steady-state 3 is a stable steady-state. However, for
steady-state 2, if T is increased, Qg > Q,. and the reactor will move to position 3.
If T is decreased below that of point 2, Q,. > Qg and the reactor will move to point
1. Therefore, steady-state 2 is unstable. It is important to determine the stability
of reactor operation since perturbations from steady-state always occur in a real
system. Finally, what determines whether the reactor achieves steady-state 1 or 3
is the start-up of the reactor.
308 CHAPTER 9 Nonisothermal Reactors

EXAMPLE 9.6.1 I
Calculate the steady-states for the following reactor configuration. Is there an unstable steady-state?

Data:
A + B =} 2C in the liquid phase, V = I L, k 33 X 109 exp [-20,000/(R g DJ L/(mol . min),
- tJ.H r = 20 kcal/mol, C~ 20 mol/L, C~ = 3 mol/L, v = 100 cm 3 /min, TO l7°C, T~ =
87°C, pCp = 650 cal/(L' °C), U = 0.1 cal/(cm 2 • min' K), and AH = 250 cm 2 •

• Answer
The reaction rate expression is:

giving the following material balance:

Therefore.

Qr (1 + aal) T - (TO + aal T~)

-k(C~)2 r(tJ.Hr )(1 - fs)(iIi - fs)
Qg = pCp

First, solve the material balance equation for fE (gives two values for fE-one will have phys-
ical meaning) at a particular T and next calculate Qr and Qg- A sampling of results is pro-
vided below (assume vcCPc » UA H for the calculation of Qr):

310 0.049 0.77 4.55

320 0.124 14.62 11.45
330 0.264 28.46 24.40
340 0.461 42.31 42.50
350 0.658 56.20 60.77
360 0.807 70.00 74.78
370 0.898 83.80 82.85

If these data are plotted, they yield:

314.2 340.0 368.8

T
 CHAPTER 9 Nooisothermal ReactoCGrs"--.~~~~~_~~-,,3
...0~9

Thus, there are three steady-states and they are:

1 314.2 41.2 0.079

2 340.0 67.0 0.460
3 368.8 95.8 0.888

Steady-state 2 is unstable. Notice the vast differences in i8 for the three steady-states. Thus,
it is clear that attempts by a naive designer to operate at steady-state 2 would not succeed
since the reactor would not settle into this steady-state at all.

In addition to knowing the existence of multiple steady-states and that some may
be unstable, it is important to assess how stable the reactor operation is to variations
in the processing parameters (i.e., the sensitivity). In the above example for the
CSTR, it is expected that the stable steady-states have low sensitivity to variations
in the processing parameters, while clearly the unstable steady-state would not.
To provide an example of how the sensitivity may be elucidated, consider a tu-
bular reactor accomplishing an exothermic reaction and operating at nonisothermal
conditions. As described in Example 9.4.3, hot spots in the reactor temperature pro-

T~(4)
I
f
f
, I

,,,
I
I
I
I
/
/
/
/
/

T~(3)
/
!
......•......•.•......•..••..•... ,

....... . ... TOe')

...•..• c .:..

Length

Figure 9.6.4 I
Temperature profiles in a tubular reactor operating
nonisothermically and conducting an exothermic
reaction. T? is the temperature of the coolant fluid.
310 CHAPTER 9 Nooisothermal Reactors

file can occur for this situation. Figure 9.6.4 illustrates what a typical reactor tem-
perature profile would look like. Consider what could happen as the temperature of
the coolant fluid, T~, increases. As T~ becomes warmer T~ (i + 1) > T~ (1), i = 1,
2, 3, then less heat is removed from the reactor and the temperature at the reactor
hot spot increases in value. Eventually, heat is generated at a sufficiently high rate
that it cannot be removed [illustrated for T~ (4)] such that the hot spot temperature
exceeds some physical limit (e.g., phase change of fluid, explosions or fire, the cat-
alyst melts, etc.) and this condition is called runaway. Thus, reactor operation close
to a runaway point would not be prudent, and determining the sensitivity towards the
tendency of runaway a critical factor in the reactor analysis. Several criteria have been
developed to assess the sensitivity of reactors; each involves the use of critical as-
sumptions [see, for example, G. F. Froment and K. B. Bischoff, Chemical Reaction
Analysis and Design, Wiley, New York, 1977, Chapter 1]. Here, an example of how
reactor stability can be assessed is illustrated and was provided by J. B. Cropley.

EXAMPLE 9.6.2 I
A tubular reactor packed with a heterogeneous catalyst is accomplishing an oxidation reac-
tion of an alcohol to an aldehyde. The reactions are:

alcohol + air => aldehyde + air => CO 2 + H2 0

In this series reaction pathway, the desired species is the aldehyde. Since both reactions are
exothermic (second reaction is highly exothermic), the reactor is operated nonisothermally.
The reactor is a shell-and-tube heat exchanger consisting of 2500 tubes of I inch diameter.
Should the heat exchanger be operated in a cocurrent or countercurrent fashion in order to
provide a greater stabilization against thermal runaway?

• Answer
Since this example comes from the simulation of a real reactor, the amount of data neces-
sary to completely describe it is very high. Thus, only the trends observed will be illustrated
in order to conserve the length of presentation.
Schematically, the reactor can be viewed as:

(A)
'-'IL- ---,

Alcohol
+ -':;111111:11: llllJJ!lI!1 IJ1!!1! HIH 'Ill Hill!!! lllIIIlJlll!ll11l!lllIIIHIIJ!1!111 lfrTfTI1TIT -+-- Alcohol, aldehyde, N --
J

02' CO 2, H20
Air

I
®
The cooling fluid is fed at point A or at point B for cocurrent and countercurrent opera-
tion, respectively. Next, the reactor temperature profiles from the two modes of operation
 CHAPTER 9 NnnlsDIDBrmal Reacto~ 311

are illustrated. The three profiles in eaeh graph are for different coolant feed temperatures, T;).
Notice that a hot spot occurs with countercurrent operation. In order to access the sensitivity,

Cocunen! Countercurrent

.......
.............................
h
.. - .. -------
.--_ .. ----- t h
......................................

"T? t
Length Length

Cropely suggests plotting the maximum temperature in the reactor as a function of the inlet
coolant temperature. The results look like:

Inlet coolant temperature

The slope of the line would be an indication of the reactor stability to variations in the inlet
coolant temperature. Clearly, cocurrent operation provides better sensitivity and this conclu-
sion is a general one. The reason for this is that by operating in a cocurrent manner the great-
est ability to remove heat [largest D.T Teoolan,)] can occur in the region of highest
heat generation within the reactor.

Exercises for Chapter 9

1. Calculate the final temperature and time required to reach 50 percent
conversion in the batch reactor described in Example 9.3.2 if the heat of
reaction is now -40 kcallmol. Do you think that this time is achievable in a
large reactor system?
2. Find the final temperature and time required to reach 90 percent conversion
in the reactor system of Exercise I.
312 CHAPTER 9 Nonisothermal Reactors

3. Plot the fractional conversion and temperature as a function of time for the
batch reactor system described in Example 9.3.3 if the reactor is now adiabatic
(U = 0). Compare your results to those for the nonisothermal situation given
in Figure 9.3.3. How much energy is removed from the reactor when it is
operated nonisothermally?
4. Consider what happens in the batch reactor given in Example 9.3.3 if the wall
temperature does not remain constant. For comparison to the constant wall
temperature, calculate the fractional conversion and reactor temperature as a
function of time when:

T* = 300 + O.1t
where t is in seconds.
5. Calculate the exit temperature and T for the PFR described in Example 9.4.2
when mole change with reaction is ignored (i.e., Bs = 0). How much error is
introduced by making this change?
6. Calculate the exit temperature and T for the PFR described in Example 9.4.2
when the temperature effects on the concentration are ignored. Is this a
reasonable simplification or not?
7. An adiabatic PFR can be described by the following set of equations:

;: = 18(1
-4y exp [ *) J
~~ O.2y exp [ 18(1
= *)J
y = (J = 1 at x =0
Solve these equations and plot y and (J as a function of x for
o(entrance) :s x :s 1 (exit). What happens if the heat of reaction is doubled?
8. Ascertain whether the following exothermic reaction:
kj
A+A( )P+P
k2

(k 1 and k1 at 80°C) could bc carried out in the reactor shown below:

14 =0.4
T=80°C

CSTR
 CHAPTER 9 Nooisothermal Reactors 313

Calculate the volume and heat removed from the CSTR and the PFR. Do the
magnitudes of the heat being removed appear feasible? Why or why not?
Data:
CPA = 45 cal mol- l K- 1
CPp = 40 cal mol- 1 K- 1
- liHr 10,000 cal mol- l
C~ = 1.5 mol L- 1
F~ = 100 mol min- l

9. The ester of an organic base is hydrolyzed in a CSTR. The rate of this irre-
versible reaction is first-order in each reactant. The liquid volume in the vessel
is 6500 L. A jacket with coolant at 18°C maintains the reactant mixture at
30°C. Additional data:
Ester feed stream-l M, 30°C, 20 Lis
Base feed stream-4 M, 30°C, lOLls
Rate constant = 10 14 exp(-ll,OOO/T) M- 1s- 1, Tin K
Ii H r = -45 kcal/mol ester
The average heat capacity is approximately constant at 1.0 kcal L -1 °c- 1.
(a) What is the conversion of ester in the reactor?
(b) Calculate the rate at which energy must be removed to the jacket to
maintain 30°C in the reactor. If the heat transfer coefficient is 15 kcal
1
S-l m -2 K- , what is the necessary heat transfer area?

(c) If the coolant supply fails, what would be the maximum temperature the
reactor could reach?
10. A reaction is carried out in an adiabatic CSTR with a volume of 10,000 L.
The feed solution with reactant A, at a concentration of 5 M, is supplied at 10
L s -1. The reaction is first-order with rate constant:
k = 10 13 exp( -12500/T) S-1, where T is in K
The density is 1000 kg m- 3 and Cp = 1.0 kcal kg -1 K- 1. The heat of reaction
is Ii H, = -70 kJ mol- 1•
(a) Calculate the reactor temperature and exit concentration for feed
temperatures of 280, 300, and 320 K.
(b) To maintain the reactor temperature below 373 K, a well-mixed cooling
jacket at 290 K is used. Show that it is possible to get 90 percent conversion
in this reactor with a feed temperature of 320 K. Do you anticipate any
start-up problems?
11. The reversible, first-order reaction shown below takes place in a CSTR.

A B
314 CHAPTER 9 Nonisotbermal Reactors

The following data are known:

k1 = 103 exp(-2500/T)s-l, TinK
AHr = -lOkcalmol- 1
K = 8 at 300 K
Cp = 1 kcal kg- 1 K- 1
P = 1 kg L- 1

(a) For a reactor space time of 10 min, what is the conversion for a 300 K
operating temperature? What is the conversion at 500 K? (Remember: the
equilibrium constant depends on temperature.)
(b) If the feed temperature is 330 K and the feed concentration is 5 M, what
is the necessary heat-removal rate per liter of reactor volume to maintain
a 300 K operating temperature?
STEADY-STATE NONISOTHERMAL
REACTOR DESIGN
(5)

Marcel Lacroix
Université de Sherbrooke
STEADY-STATE NONISOTHERMAL REACTOR DESIGN:
OBJECTIVE

• WE NOW EXAMINE THE EFFECTS OF HEAT IN

CHEMICAL REACTORS.
• THE BASIC DESIGN EQUATIONS, RATE LAWS
AND STOICHIOMETRIC RELATIONSHIPS
DERIVED AND USED FOR ISOTHERMAL
REACTORS ARE STILL VALID FOR
NONISOTHERMAL REACTORS.
• THE MAJOR DIFFERENCE IN NONISOTHERMAL
REACTORS IS THAT THE TEMPERATURE
VARIES ALONG THE LENGTH OF THE PFR OR
HEAT IS TRANSFERRED TO OR FROM THE CSTR

M. Lacroix Nonisothermal Reactor Design 2

 NONISOTHERMAL REACTOR: RATIONALE

EXAMPLE No. 0

• LET US CALCULATE THE VOLUME OF A PLUG

FLOW REACTOR NECESSARY TO ACHIEVE 70%
CONVERSION. THE CHEMICAL REACTION IS
EXOTHERMIC AND THE REACTOR IS OPERATED
ADIABATICALLY. AS A RESULT, THE
TEMPERATURE WILL INCREASE WITH
CONVERSION DOWN THE LENGTH OF THE
REACTOR.

M. Lacroix Nonisothermal Reactor Design 3

 NONISOTHERMAL REACTOR: RATIONALE
dX − rA
1. DESIGN EQUATION: =
dV FA 0
2. RATE LAW: − rA = kC A

3. STOICHIOMETRY: v = v0 ; FA = C Av0 ; FA 0 = C A 0 v0 ; C A = C A 0 (1 − X )
dX k (1 − X ) ⎡ E ⎛ 1 1 ⎞⎤
4. COMBINING: = WITH k = k1 exp ⎢ ⎜ − ⎟⎥
dV v0 ⎣ R ⎝ T1 T ⎠⎦

dX ⎡ E ⎛ 1 1 ⎞⎤ 1 − X
⇒ = k1 exp ⎢ ⎜ − ⎟⎥
dV ⎣ R ⎝ T1 T ⎠⎦ v0
WE NEED ANOTHER RELATIONSHIP RELATING X TO T OR T AND
V TO SOLVE THIS EQUATION. THE ENERGY BALANCE WILL
PROVIDE US WITH THIS RELATIONSHIP.
M. Lacroix Nonisothermal Reactor Design 4
 THERMAL ENERGY CONSERVATION

ACCUMULATION = INLET – OUTLET + GENERATION

M. Lacroix Nonisothermal Reactor Design 5

THERMAL ENERGY CONSERVATION: BASIC EQUATION

RATE OF ACCUMULATION OF RATE OF ENERGY CARRIED IN

INTERNAL ENERGY WITHIN AND OUT OF THE SYSTEM BY
SYSTEM (WATTS) THE MOLES OF EACH SPECIES
(Fi:molar flow rate, moles of i per
second; Hi:enthalpy, Joules per mole)

dEsys n n • •
= ∑ Fi 0 H i 0 − ∑ Fi H i + Q − WS (5.1)
dt i =1 i =1

RATE OF FLOW OF RATE OF SHAFT WORK

HEAT TO THE SYSTEM DONE BY THE SYSTEM
FROM SURROUNDINGS ON SURROUNDINGS
(WATTS) (WATTS)

M. Lacroix Nonisothermal Reactor Design 6

 THERMAL ENERGY CONSERVATION: DISSECTING
MOLAR FLOW RATES TO OBTAIN HEAT OF REACTION
b c d
• GENERALIZED EQUATION, A + B → C + D
a a a

• THE INLET AND OUTLET TERMS BECOME:

IN ∑ H i 0 Fi 0 = H A 0 FA 0 +H B 0 FB 0 + H C 0 FC 0 + H D 0 FD 0 + H I 0 FI 0
OUT ∑ H i Fi = H A FA +H B FB + H C FC + H D FD + H I FI
SUBSTITUTING
Fi 0
NOTE: θ i =
b
FA = FA 0 (1 − X ); FB = FA 0 (θ B − X ); FA 0
a
c d
FC = FA 0 (θ C + X ); FD = FA 0 (θ D + X ); FI = FA 0θ I ;
a a
M. Lacroix Nonisothermal Reactor Design 7
 THERMAL ENERGY CONSERVATION: DISSECTING
MOLAR FLOW RATES TO OBTAIN HEAT OF REACTION

⎡( H A 0 − H A ) + ( H B 0 − H B )θ B + ⎤
∑ Fi 0 H i 0 − ∑ Fi H i = FA 0 ⎢⎢( H C 0 − H C )θ C + ( H D 0 − H D )θ D + ⎥⎥
n n

i =1 i =1
⎢⎣( H I 0 − H I )θ I ⎥⎦
⎡d c b ⎤
− ⎢ H D + H C − H B − H A ⎥ FA 0 X
⎣a a a ⎦
n
= FA 0 ∑ θ i ( H i 0 − H i ) − ∆H Rx (T ) FA 0 X (5.2)
i =1

∆H Rx (T ) : HEAT OF REACTION AT TEMPERATURE T (Joules per mole of A

reacted); THE ENTHALPIES HA, HB,etc. ARE EVALUATED AT THE
TEMPERATURE AT THE OUTLET OF THE SYSTEM T.

M. Lacroix Nonisothermal Reactor Design 8

 THERMAL ENERGY CONSERVATION:
DISSECTING THE ENTHALPIES

• FOR A SINGLE-PHASE CHEMICAL REACTION, THE

ENTHALPY OF SPECIES i AT TEMPERATURE T IS
RELATED TO THE ENTHALPY OF FORMATION AT
THE REFERENCE TEMPERATURE TR BY
T
H i = H (TR ) + ∫ C pi dT
i
0

T
R
THEREFORE,
⎡ 0 T ⎤ ⎡ 0 i0
T
⎤
H i − H i 0 = ⎢ H i (TR ) + ∫ C pi dT ⎥ − ⎢ H i (TR ) + ∫ C pi dT ⎥
⎣ T
R ⎦ ⎣ T
R ⎦
T
⇒ H i − H i 0 = ∫ C pi dT (5.3)
Ti 0
M. Lacroix Nonisothermal Reactor Design 9
 THERMAL ENERGY CONSERVATION:
DISSECTING THE ENTHALPIES

• THE HEAT OF REACTION AT ANY

TEMPERATURE T IS ALSO EXPRESSED IN
TERMS OF THE HEAT OF REACTION AT A
REFERENCE TEMPERATURE (298K) AND AN
INTEGRAL INVOLVING ∆C p :
T
∆H Rx (T ) = ∆H (TR ) + ∫ ∆C p dT
0
Rx
(5.4)
TR

d c b
WHERE ∆C p = C pD + C pC − C pB − C pA
a a a

M. Lacroix Nonisothermal Reactor Design 10

 THERMAL ENERGY CONSERVATION:
FINAL FORM OF THE ENERGY BALANCE EQUATION

• SUBSTITUTING (5.3) AND (5.4) IN (5.2) AND

REPLACING (5.2) IN (5.1), THE STEADY-STATE
ENERGY BALANCE EQUATION BECOMES
• • T n ⎡ T ⎤
Q − WS − FA0 ∫ ∑θ i C pi dT − FA0 X ⎢∆H Rx (TR ) + ∫ ∆C p dT ⎥ = 0
0

Ti 0 i =1 ⎣ TR ⎦
(5.5)

ENERGY BALANCE IN TERMS OF WHEN THE REACTANTS ENTER

TEMPERATURE DEPENDENT THE SYSTEM AT THE SAME
HEAT CAPACITIES TEMPERATURE, Ti0=T0

M. Lacroix Nonisothermal Reactor Design 11

 THERMAL ENERGY CONSERVATION:
DISSECTING THE ENTHALPIES

• FOR CONSTANT OR MEAN HEAT CAPACITIES,

EQUATION (5.3) BECOMES
T
H i − H i 0 = ∫ C pi dT = C pi (T − Ti 0 ) (5.3)’
Ti 0
AND EQUATION (5.4) BECOMES
∆H Rx (T ) = ∆H Rx0 (TR ) + ∆C p (T − TR ) (5.4)’
WHERE
T T

∫ C pi dT ∫ ∆C p dT
TR
C pi = Ti 0 AND ∆C p =
T − Ti 0 T − TR

M. Lacroix Nonisothermal Reactor Design 12

 THERMAL ENERGY CONSERVATION:
FINAL FORM OF THE ENERGY BALANCE EQUATION
FOR CONSTANT OR MEAN HEAT CAPACITIES

• SUBSTITUTING (5.3)’ AND (5.4)’ IN (5.2) AND

REPLACING (5.2) IN (5.1), THE STEADY-STATE
ENERGY BALANCE EQUATION BECOMES

Q − WS − FA 0 ∑θ i C pi (T − Ti 0 ) − FA 0 X [∆H Rx0 (TR ) + ∆C p (T − TR )] = 0

• • n

i =1

(5.6)

ENERGY BALANCE IN TERMS OF WHEN THE REACTANTS ENTER

MEAN OR CONSTANT HEAT THE SYSTEM AT THE SAME
CAPACITIES TEMPERATURE, Ti0=T0

M. Lacroix Nonisothermal Reactor Design 13

 EXAMPLE No.1:
HEAT OF REACTION
• THE HEAT OF REACTION IS THE ENERGY CHANGE OF
THE REACTION OVERALL. IT IS THE DIFFERENCE
BETWEEN THE ENTHALPY OF THE PRODUCTS AND THE
ENTHALPY OF THE REACTANTS.
• CALCULATE THE HEAT OF REACTION FOR THE
SYNTHESIS OF AMMONIA FROM HYDROGEN AND
NITROGEN AT 1500C IN kcal/mole AND IN kJoule/mole OF
HYDROGEN REACTED.

N 2 + 3H 2 → 2 NH 3
• THE HEATS OF FORMATION OF ALL THE ELEMENTS ARE
ZERO AT 25 0C. THE HEATS OF FORMATION OF
COMPOUNDS AT 25 0C ARE TABULATED.
• 1 cal = 4.184 Joule

M. Lacroix Nonisothermal Reactor Design 14

 THERMAL ENERGY CONSERVATION:
HEAT ADDED TO A CSTR

•
Q = UA(Ta − T )
RATE OF HEAT T:REACTION
TRANSFER (WATTS) TEMPERATURE (K)

U:OVERALL HEAT Ta=Ta1=Ta2:INLET

TRANSFER A:HEAT-EXCHANGE TEMPERATURE OF
COEFFICIENT (W/m2K) AREA (m2) HIGH FLOW RATE
COOLANT (K)
M. Lacroix Nonisothermal Reactor Design 15
 THERMAL ENERGY CONSERVATION:
HEAT ADDED TO A PFR AND TO A PBR
• WHEN THE HEAT FLOW VARIES ALONG THE
LENGTH OF THE REACTOR, THE HEAT FLUX
EQUATION MUST BE INTEGRATED ALONG THE
LENGTH OF THE REACTOR TO OBTAIN THE TOTAL
HEAT ADDED TO THE REACTOR:
•
a: HEAT- EXCHANGE AREA
dQ
PFR = Ua (Ta − T ) PER UNIT VOLUME OF PFR
= 4/D FOR TUBULAR PFR OF
dV DIAMETER D

•
PBR d Q Ua
= (Ta − T ) BULK DENSITY OF
dW ρ b CATALYST (g/cm3 of
reactor bed)

M. Lacroix Nonisothermal Reactor Design 16

 THERMAL ENERGY CONSERVATION:
NONISOTHERMAL CONTINUOUS-FLOW REACTORS

• CONSIDER
•
A SYSTEM AT STEADY-STATE, •
NO SHAFT
WORK WS = 0 , ADIABATIC OPERATION Q = 0 . IN
MANY INSTANCES, ∆H Rx0 (TR ) >> ∆C p (T − TR ) AND
THE ENERGY BALANCE EQUATION (5.6) GIVES US
THE EXPLICIT RELATIONSHIP BETWEEN X AND T
NEEDED TO BE USED IN CONJUNCTION WITH THE
MOLE BALANCE TO SOLVE THE TYPE OF PROBLEMS
DISCUSSED EARLIER:
n
∑θ i C pi (T − Ti 0 )
X = i =1
− ∆H Rx0 (TR )

M. Lacroix Nonisothermal Reactor Design 17

 THERMAL ENERGY CONSERVATION:
APPLICATION TO CSTRs

• ALTHOUGH THE CSTR IS WELL MIXED AND THE

TEMPERATURE IS UNIFORM THROUGHOUT THE
VESSEL, IT DOES NOT IMPLY THAT THE REACTION
IS CARRIED OUT ISOTHERMALLY.
• THE DESIGN EQUATION FOR THE CSTR (MOLE
BALANCE) IS
FA 0 X
V=
− rA
AND THE X VERSUS T REALTIONSHIP IS PROVIDED
BY THE ENERGY BALANCE EQUATION
• •
Q − WS n
− ∑θ i C pi (T − Ti 0 ) = X [∆H Rx0 (TR ) + ∆C p (T − TR )]
FA 0 i =1
M. Lacroix Nonisothermal Reactor Design 18
19
 EXAMPLE No.2:
DESIGN OF A CSTR
• PROPYLENE GLYCOL IS PRODUCED BY THE HYDROLYSIS OF
PROPYLENE OXIDE:
(CH 2 )(CH )O(CH 3 ) + H 2O ⎯CATALYST
⎯ ⎯⎯→(CH 2 )OH (CH )OH (CH 3 )
THE REACTION TAKES PLACE AT ROOM TEMPERATURE
WHEN CATALYSED WITH SULFURIC ACID. YOU ARE IN
CHARGE OF AN ADIABATIC CSTR PRODUCING PROPYLENE
GLYCOL BY THIS METHOD. UNFORTUNATELY, THE REACTOR
IS BEGINNING TO LEAK AND YOU MUST REPLACE IT
(SULFURIC ACID IS CORROSIVE AND MILD STEEL IS A POOR
MATERIAL FOR CONSTRUCTION). THERE IS A NICE
OVERFLOW CSTR OF 1136-LITER CAPACITY STANDING IDLE.
IT IS GLASS-LINED AND YOU WOULD LIKE TO USE IT. YOU
ARE FEEDING 1136 kg/h (19.6 kmole/h) OF PROPYLENE OXIDE
(P.O.) TO THE REACTOR. THE FEED STREAM CONSISTS OF (1)
AN EQUIVOLUMETRIC MIXTURE OF P.O. (1320 l/h) AND
METHANOL (1320 l/h).
M. Lacroix Nonisothermal Reactor Design 20
 EXAMPLE No.2: DESIGN OF A CSTR
• (2) WATER CONTAINING 0.1% OF SULFURIC ACID. THE
VOLUMETRIC FLOW RATE OF WATER IS 6600 l/h. THE
CORRESPONDING MOLAR FEED RATES OF METHANOL AND
WATER ARE 32.66 kmole/h AND 365 kmole/h, RESPECTIVELY. THE
TEMPERATURE OF BOTH FEED STREAMS IS 14.5 0C PRIOR TO
MIXING, BUT THERE IS AN IMMEDIATE 9.4 0C TEMPERATURE
RISE UPON MIXING OF THE TWOO FEED STREAMS CAUSED BY
THE HEAT OF MIXING. THE ENTERING TEMPERATURE OF ALL
FEED STREAMS IS TAKEN TO BE 24 0C. FOR THE OPERATING
CONDITIONS, IT WAS FOUND THAT THE REACTION IS FIRST-
ORDER IN PROPYLENE OXIDE CONCENTRATION AND
APPARENT ZERO-ORDER IN EXCESS WATER WITH THE
SPECIFIC REACTION RATE k = A exp(− E / RT ) WHERE
A = 16.96 ⋅ 1012 h −1 ; E = 75311kJ / kmole; R = 8.3144 J / moleK ;

M. Lacroix Nonisothermal Reactor Design 21

 EXAMPLE No.2: DESIGN OF A CSTR
• THERE IS AN IMPORTANT CONSTRAINT ON YOUR OPERATION.
PROPYLENE OXIDE IS A RATHER LOW-BOILING SUBSTANCE
(BOILING POINT OF 340C AT 1 atm). WITH THE MIXTURE YOU
ARE USING, YOU FEEL THAT YOU CANNOT EXCEED AN
OPERATING TEMPERATURE OF 520C, OR YOU WILL LOSE TOO
MUCH OXIDE BY VAPORIZATION THROUGH THE VENT
SYSTEM. CAN YOU USE THE IDLE CSTR AS A REPLACEMENT
FOR THE LEAKING ONE IF IT WILL BE OPERATED
ADIABATICALLY? IF SO, WHAT WILL BE THE CONVERSION OF
OXIDE TO GLYCOL?
• NEXT EXAMINE THE EFFECT OF USING A COOLING COIL OF
SURFACE 3.716 m2 WITH THE COOLING WATER FLOW RATE
SUFFICIENTLY LARGE THAT A CONSTANT TEMPERATURE OF
29.5 0C CAN BE MAINTAINED. THE OVERALL HEAT-TRANSFER
COEFFICIENT IS U = 568W / m 2 K . WILL THE REACTOR
SATISFY THE CONSTRAINT OF 520C MAXIMUM TEMPERATURE
IF THE COOLING COIL IS USED?
M. Lacroix Nonisothermal Reactor Design 22
 EXAMPLE No.2: EFFECT OF COOLING COIL

• NLES Solution

• Variable Value f(x) Ini Guess

• X 0,3326428 2,874E-10 0
• T 311,68313 -8,842E-09 0 X = 33%;
• A 2,084E+12
• B 2,392E-13 T = 312 K
• NLES Report (safenewt)

• Nonlinear equations as entered by the user

• [1] f(X) = X-(16867e-01*(T-297)+3877e-01*(T-3025E-01))/(84608+293E-01*(T-293)) = 0
• [2] f(T) = X-A*B/(1+A*B) = 0

• Explicit equations as entered by the user

• [1] A = 2084E09
• [2] B = exp(-9058/T)

23
 THERMAL ENERGY CONSERVATION:
APPLICATION TO ADIABATIC TUBULAR REACTORS

• •
• ENERGY BALANCE WITH Q = 0 AND WS = 0 :

− ∑θ i C pi (T − Ti 0 ) = X [∆H Rx0 (TR ) + ∆C p (T − TR )]

n

i =1

• MOLE BALANCE:
dX
FA 0 = − rA ( X , T )
dV

• SOLUTION OF THESE EQUATIONS YIELDS THE

TEMPERATURE, CONVERSION AND CONCENTRATION
PROFILES ALONG THE LENGTH OF THE REACTOR.
M. Lacroix Nonisothermal Reactor Design 24
 NOTE ON FIRST-ORDER REVERSIBLE REACTIONS

k1
• BASIC REACTION: A⇔
k
B
2

dC A
• RATE EQUATION FOR A: − rA = − = k1C A − k 2C B
dt

• STOICHIOMETRY: C A = C A 0 (1 − X A ); C B = C A 0 (θ B + X A )
WITH θ B = C B 0 / C A 0

• AT EQUILIBRIUM,
RATE OF DISAPPEARANCE OF A= RATE OF FORMATION OF B

dC A k1 CB (θ B + X A )
= 0 ⇒ k1C A = k 2C B ⇒ K C = = =
dt k 2 C A (1 − X A )
M. Lacroix Nonisothermal Reactor Design 25
26
 EXAMPLE No.3: DESIGN OF A PFR
• NORMAL BUTANE, C4 H10 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 ISOOCTANE. THE
REACTION IS TO BE CARRIED OUT ADIABATICALLY IN THE
LIQUID PHASE UNDE HIGH PRESSURE USING ESSENTIALLY
TRACE AMOUNTS OF A LIQUID CATALYST WHICH GIVES A
SPECIFIC REACTION RATE OF 31.1 h-1 AT 360 K. CALCULATE
THE PFR VOLUME NECESSARY TO PROCESS 163 mole/h OF A
MIXTURE 90 mole% n-BUTANE AND 10 mole% i-PENTANE,
WHICH IS CONSIDERED AN INERT. THE FEED ENTERS AT
330 K. THE REACTION IS n − C4 H10 ⇔ i − C4 H10
• BUTANE: C P ( n − B ) = C P ( i − B ) = 141J / moleK

C P ( i − P ) = 161J / moleK ; E = 65.7 kJ / mole;

• i-PENTANE:
K c = 3.03 _ at _ 600 C ; C A0 = 9.3kmole / m3
M. Lacroix Nonisothermal Reactor Design 27
 EXAMPLE No.3: DESIGN OF A PFR
• ODE Report (RKF45)

• Differential equations as entered by the user

• [1] d(X)/d(v) = -ra/Fa0 POLYMATH PROGRAM
• Explicit equations as entered by the user
• [1] Ca0 = 93e-01
• [2] Fa0 = 9e-01*163
• [3] T = 330+433e-01*X
• [4] Kc = 303e-02*exp(-8303e-01*((T-333)/(T*333)))
• [5] k = 311e-01*exp(7906*(T-360)/(T*360))
• [6] Xe = Kc/(1+Kc)
• [7] ra = -k*Ca0*(1-(1+1/Kc)*X)
• [8] rate = -ra

• Independent variable
• variable name : v
• initial value : 0
• final value : 4

28
EXAMPLE No.3: DESIGN OF A PFR

29
THERMAL ENERGY CONSERVATION: APPLICATION
TO TUBULAR REACTORS WITH HEAT EXCHANGE

Q − FA 0 ∫ ∑θ i C pi dT − FA 0 X ∆H Rx (TR ) + ∫ ∆C p dT ⎤ = 0
⎡
• T n T
0

T i =1
0 ⎣⎢ TR
⎥⎦

M. Lacroix Nonisothermal Reactor Design 30

 THERMAL ENERGY CONSERVATION: APPLICATION
TO TUBULAR REACTORS WITH HEAT EXCHANGE

• DIFFERENTIATING WITH RESPECT •

TO THE VOLUME,
RECALLING − rA = FA 0 dX / dV AND d Q/ dV = Ua(Ta − T ) ,THE
ENERGY BALANCE YIELDS:
dT Ua(Ta − T ) + (−rA )(−∆H Rx (T ))
= n
= g( X ,T )
FA0 (∑ θ i C pi + X∆C p )
dV
i =1

• THE MOLE BALANCE IS 2 EQUATIONS FOR 2

dX − rA UNKNOWNS: X AND T
= = f ( X ,T )
dV FA0
M. Lacroix Nonisothermal Reactor Design 31
EXAMPLE No.4: DESIGN OF A TUBULAR REACTOR
• ONE OF THE KEY STEPS IN THE DESIGN OF AN ACETIC
ANHYDRIDE MANUFACTURING FACILITY IS THE VAPOR-
PHASE CRACKING OF ACETONE TO KETENE AND
METHANE: CH 3COCH 3 → CH 2CO + CH 4
(acetone) → (ketene) + (methane)
A→ B+C
THE REACTION IS FIRST-ORDER WITH RESPECT TO
ACETONE AND THE SPECIFIC REACTION RATE CAN BE
EXPRESSED BY ln(k ) = 34.34 − 34222 / T WHERE k IS IN
RECIPROCAL SECONDS AND T IS IN KELVIN. IN THIS
DESIGN, IT IS DESIRED TO FEED 8000 kg OF ACETONE PER
HOUR TO A TUBULAR REACTOR. THE REACTOR CONSISTS
OF A BANK OF 1000 TUBES (O.D. = 26.6 mm). WE WILL
CONSIDER TWO CASES:
(1) THE REACTOR IS OPERATED ADIABATICALLY;

M. Lacroix Nonisothermal Reactor Design 32

 EXAMPLE No.4: DESIGN OF A TUBULAR REACTOR

(2) THE REACTOR IS SURROUNDED BY A HEAT EXCHANGER

WHERE THE HEAT-TRANSFER COEFFICIENT IS U = 110W / m K
2

AND THE AMBIANT TEMPERATURE IS 1150 K.

• THE INLET TEMPERATURE AND PRESSURE ARE THE SAME

FOR BOTH CASES AT 1035 K AND 162 kPa, RESPECTIVELY.
0
H Rx (TR ) A = −216.67 kJ / mole; HEATS OF FORMATION AT 298 K
0
H Rx (TR ) B = −61.09kJ / mole;
TEMPERATURE-DEPENDENT
0
H Rx (TR )C = −74.81kJ / mole; HEAT CAPACITIES

C PA = 26.63 + 0.183T − 45.86 ⋅ 10 −6 T 2 ( J / moleK );

C PB = 20.04 + 0.0945T − 30.95 ⋅ 10 −6 T 2 ( J / moleK );
C PA = 13.39 + 0.077T − 18.71 ⋅ 10 −6 T 2 ( J / moleK );
M. Lacroix Nonisothermal Reactor Design 33
 EXAMPLE No.4: ADIABATIC CASE
• ODE Report (RKF45)
Differential equations as entered by the user
• [1] d(X)/d(V) = -ra/Fao
• [2] d(T)/d(V) = -ra*(-deltaH)/(Fao*Cpa+X*delCp)

• Explicit equations as entered by the user POLYMATH PROGRAM

• [1] Fao = 383e-01
• [2] Cpa = 2663e-02+183e-03*T-4586e-02*10^(-6)*T^2
• [3] delCp = 68e-01-115e-01*10^(-3)*T-381e-02*10^(-6)*T^2
• [4] k = 82e-01*10^14*exp(-34222/T)
• [5] Cao = 188e-01
• [6] To = 1035
• [7] Tr = 298
• [8] deltaH = 80770+68e-01*(T-Tr)-575e-02*10^(-3)*(T^2-Tr^2)-127e-02*10^(-6)*(T^3-
Tr^3)
• [9] ra = -k*Cao*(1-X)/(1+X)*To/T

• Independent variable
• variable name : V
• initial value : 0
• final value : 5
34
EXAMPLE No.4: ADIABATIC CASE

35
EXAMPLE No.4: CONCLUSION FOR ADIABATIC CASE
• FOR THE ADIABATIC CASE, THE REACTION DIES
OUT AFTER 2.5 m3, OWING TO THE LARGE DROP
IN TEMPERATURE, AND VERY LITTLE
CONVERSION IS ACHIEVED BEYOND THIS POINT.
• ONE WAY TO INCREASE THE CONVERSION
WOULD BE TO ADD A DILUENT SUCH AS N2
WHICH COULD SUPPLY THE SENSIBLE HEAT FOR
THIS ENDOTHERMIC REACTION. HOWEVER, IF
TOO MUCH DILUENT IS ADDED, THE
CONCENTRATION AND RATE WILL BE QUITE
LOW. ON THE OTHER HAND, IF TOO LITTLE
DILUENT IS ADDED, THE TEMPERATURE WILL
DROP AND EXTINGUISH THE REACTION.

M. Lacroix Nonisothermal Reactor Design 36

 EXAMPLE No.4: HEAT EXCHANGER CASE
• ODE Report (RKF45)
Differential equations as entered by the user
• [1] d(x)/d(v) = -ra/fa0
• [2] d(t)/d(v) = (ua*(ta-t)+ra*dh)/(fa0*(cpa+x*dcp))

• Explicit equations as entered by the user POLYMATH PROGRAM

• [1] fa0 = 376e-04
• [2] ua = 16500
• [3] ta = 1150
• [4] cpa = 266e-01+183e-03*t-459e-07*t*t
• [5] dcp = 68e-01-115e-04*t-381e-08*t*t
• [6] ca0 = 188e-01
• [7] t0 = 1035
• [8] term = -127e-08*(t^3-298^3)
• [9] dh = 80770+68e-01*(t-298)-575e-05*(t^2-298^2)+term
• [10] ra = -ca0*358e-02*exp(34222*(1/t0-1/t))*(1-x)*(t0/t)/(1+x)

• Independent variable
• variable name : v
• initial value : 0
• final value : 0,001
37
EXAMPLE No.4: HEAT EXCHANGER CASE

38
 EXAMPLE No.4:
CONCLUSION FOR HEAT EXCHANGER CASE

• THE REACTOR TEMPERATURE GOES THROUGH A MINIMUM

ALONG THE LENGTH OF THE REACTOR. AT THE FRONT OF
THE REACTOR, THE REACTION TAKES PLACE VERY RAPIDLY,
DRAWING ENERGY FROM THE SENSIBLE HEAT OF THE GAS
CAUSING THE GAS TEMPERATURE TO DROP BECAUSE THE
HEAT EXCHANGER CANNOT SUPPLY ENERGY AT THE EQUAL
OR GREATER RATE. THIS DROP IN TEMPERATURE, COUPLED
WITH THE CONSUMPTION OF REACTANTS, SLOWS THE
REACTION RATE AS WE MOVE DOWN THE REACTOR.
BECAUSE OF THIS SLOWER REACTION RATE, THE HEAT
EXCHANGER SUPPLIES ENERGY AT A RATE GREATER THAN
THE REACTION DRAWS ENERGY FROM THE GASES AND, AS A
RESULT, THE TEMPERATURE INCREASES.

M. Lacroix Nonisothermal Reactor Design 39

 EQUILIBRIUM CONVERSION

A⇔ B
• THE HIGHEST CONVERSION THAT CAN BE
ACHIEVED IN REVERSIBLE REACTIONS IS THE
EQUILIBRIUM CONVERSION.
• FOR ENDOTHERMIC REACTIONS, THE
EQUILIBRIUM CONVERSION INCREASES WITH
INCREASING TEMPERATUTE UP TO A MAXIMUM
OF 1.
• FOR EXOTHERMIC REACTIONS, THE
EQUILIBRIUM CONVERSION DECREASES WITH
INCREASING TEMPERATURE.
M. Lacroix Nonisothermal Reactor Design 40
 EQUILIBRIUM CONVERSION:
EXOTHERMIC REACTIONS

TO DETERMINE THE
MAXIMUM CONVERSION
THAT CAN BE ACHIEVED IN
AN EXOTHERMIC REACTION
CARRIED OUT
ADIABATICALLY, WE FIND
THE INTERSECTION OF THE
EQUILIBRIUM CONVERSION
AS A FUNCTION OF
TEMPERATURE WITH
TEMPERATURE-
CONVERSION
RELATIONSHIPS FROM THE
ENERGY BALANCE.

M. Lacroix Nonisothermal Reactor Design 41

 EXAMPLE No.5:
ADIABATIC EQUILIBRIUM TEMPERATURE

• FOR THE ELEMENTARY SOLID-CATALYSED LIQUID-PHASE

REACTION A ⇔ B , DETERMINE THE ADIABATIC
EQUILIBRIUM TEMPERATURE AND CONVERSION WHEN PURE
A IS FED TO THE REACTOR AT A TEMPERATURE OF 300 K.
• ADDITIONAL INFORMATION:
H A0 (298 K ) = −40000cal / mole; H B0 (298 K ) = −60000cal / mole;
C PA = 50cal / moleK ; C PB = 50cal / moleK ; K e = 105 _ at _ 298 K ;
• WHAT CONVERSION COULD BE ACHIEVED IF TWO
INTERSTAGE COOLERS HAVING THE CAPACITY TO COOL THE
EXIT STREAM AT 350 K WERE EMPLOYED? ALSO, DETERMINE
THE HEAT DUTY OF EACH EXCHANGER FOR A MOLAR FEED
RATE OF A OF 40 moles/s. ASSUME THAT 95% OF EQUILIBRIUM
CONVERSION IS ACHIEVED IN EACH REACTOR. THE FEED
TEMPERATURE TO THE FIRST REACTOR IS 300 K.
M. Lacroix Nonisothermal Reactor Design 42
 Example No.6:
Non isothermal Plug Flow Reactor

M. Lacroix Nonisothermal Reactor Design 43

The elementary irreversible gas-phase reaction A → B + C is carried out adiabatically in a PFR
packed with a catalyst. Pure A enters the reactor at a volumetric flow rate of 20dm 3 / s at a
pressure of 10 atm and a temperature of 450K.

dP α⎛T ⎞ P
The pressure drop in the reactor is given by = − ⎜⎜ ⎟⎟ (1 + εX ) . The reactor can be
dW 2 ⎝ T0 ⎠ ( P / P0 )
packed with one of two particle sizes:

α = 0.019 / kg _ cat. for particle diameter D1

α = 0.0075 / kg _ cat. for particle diameter D2

a) Plot the temperature T , conversion X and pressure y = P / P0 along the length of the
reactor that is as a function of the catalyst mass w .
b) Vary the parameters α and P0 to learn the ranges of values in which they dramatically
affect conversion.

Additional information:

CPA = 40 J / mol ⋅ K ; CPB = 25 J / mol ⋅ K ; CPC = 15 J / mol ⋅ K

H A0 = −70kJ / mol ; H B0 = −50kJ / mol ; H C0 = −40kJ / mol . All heats of formation are referenced
to 273 K.

⎡E ⎛ 1 1 ⎞⎤ dm3 44
k = 0.133 ⋅ exp ⎢ ⎜ − ⎟⎥ with E = 31.4kJ / mol ; R = 8.314 J / mol ⋅ K
⎣ ⎝
R 450 T ⎠⎦ kg ⋅ cat ⋅ s
 Example No.6: Plug flow reactor
• ODE Report (RKF45)

• Differential equations as entered by the user

• [1] d(t)/d(w) = ra*dhr/(fao*cpa)
• [2] d(x)/d(w) = -ra/fao
• [3] d(y)/d(w) = -(1+x)*(t/450)*alpha/(2*y)

• Explicit equations as entered by the user

• [1] fao = 542E-02
• [2] dhr = -20000
• [3] cpa = 40
• [4] alpha = 19E-03
• [5] k = 133E-03*exp(37766E-01*(1/450-1/t))
• [6] cao = 271E-03
• [7] ca = cao*(1-x)*(450/t)/(1+x)*y
• [8] ra = -k*ca
• [9] rate = -ra

• Independent variable
• variable name : w
• initial value : 0
• final value : 37

M. Lacroix Nonisothermal Reactor Design 45

 Example No.6: Plug flow reactor

Alpha = 0.019 kg-1 catalyst

M. Lacroix Nonisothermal Reactor Design 46

 Example No.6: Plug flow reactor

Alpha = 0.0075 kg-1 catalyst

M. Lacroix Nonisothermal Reactor Design 47