Reactor Design II-Fourth Year

Dr.Ali N.Khalaf

University of Basrah
College of Engineering
Chemical Engineering Department
Fourth Year
First Semester
Reactor design II

Chapter One
Non-Isothermal Reactors Design

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1- Optimal Temperatures for Isothermal Reactors:

Reaction rates almost always increase with temperature. Thus, the best temperature for a
single, irreversible reaction, whether elementary or complex, is the highest possible
temperature. Practical reactor designs must consider limitations of materials of
construction and economic tradeoffs between heating costs and yield, but there is no
optimal temperature from a strictly kinetic viewpoint.
Reversible reactions, since these are a special form of multiple reactions, usually exhibit
an optimal temperature with respect to the yield of a desired product. One must specify
the temperature at which to operate. Consider the elementary, reversible reaction

Suppose this reaction is occurring in a CSTR of fixed volume and throughput. It is

desired to find the reaction temperature that maximizes the yield of product B. Suppose
Ef > Er, as is normally the case when the forward reaction is endothermic. Then the
forward reaction is favored by increasing temperature. The equilibrium shifts in the
desirable direction and the reaction rate increases. The best temperature is the highest
possible temperature and there is no interior optimum.
For Ef < Er, increasing the temperature shifts the equilibrium in the wrong direction, but
the forward reaction rate still increases with increasing temperature. There is an
optimum temperature for this case. A very low reaction temperature gives a low yield of
B because the forward rate is low. A very high reaction temperature also gives a low
yield of B because the equilibrium is shifted toward the left. The outlet concentration
from the stirred tank, assuming constant physical properties and is given by
&!" ' (#
𝐶!"#$ = …………………….. ……………….. (1)
)* ' (#* ' (%

We assume the forward and reverse reactions have Arrhenius temperature dependences
! 𝐶𝐵𝑜𝑢𝑡
with Ef < Er . Setting = 0 gives
!#

1%
𝑇",$-./0 = *% +(-%.-# …………………….. ………………. (2)
2 03 -#

2- Influence of Temperature on Reactor Operation:

Because most reactions we not carried out isothermally, we now focus our attention on
heat effects in chemical reactors. The basic design equations, rate laws, and
stoichiometric relationships derived and used in Chapter 4 for isothermal reactor design
are still valid for the design of non-isothermal reactors. The major difference lies in the
method of evaluating the design equation when temperature varies along the length of a
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PFR or when heat is removed from a CSTR. Thus, in a batch reactor, the temperature of
the reaction mixture may change with time. In a flow reactor, the temperature may
change with time and position, or the feed and effluent streams may have different
temperatures. To account for these effects, reactor analysis must include the energy
balance.
The material and energy balance equations are a coupled set of equations that together
describe the performance of an ideal reactor. Typically, the energy balance is expressed
in terms of the reactor temperature, which may vary with space and time. The nature of
the variations depends on the reactor type and mode of operation.
In perfectly mixed batch reactors, the temperature is the same at all locations in the
reactor, but changes with time as the reaction proceeds.

Sometimes the reactor is operated with heat transfer through the reactor walls, or via
heating or cooling coils inserted into the reactor. Adiabatic operation is also possible. In
a plug flow reactor, the temperature varies with axial position (i.e., in the direction of
flow) in the reactor. There may or may not be heat transfer through the reactor walls. In
a CSTR, the temperature is uniform everywhere in the reactor and is equal to the outlet
temperature. However, the inlet and outlet temperatures are different. There may or may
not be heat transfer with the surroundings, either through the vessel walls or by heating
or cooling coils within the reactor.

There are three types of operation:

- Isothermal Operation.
- Adiabatic Operation.
- Non-isothermal Operation (with heat exchange).

Let’s calculate the volume necessary to achieve a conversion, X, in a PFR for a first-
order, exothermic and adiabatic reaction.

!" $ !$
Material Balance: = ∫&
#!" %!
#
(
Rate Law: 𝑟' = 𝐴 𝑒 𝐶' $%

Stoichiometry: 𝐶' = 𝐶'* (1 − 𝑥 )

!" $ !$
Combine: = ∫& #
#!" '$%
+!" (-($) ' /

We cannot solve this equation because we don’t have x as a function of V or T. We

need another equation. That equation is Energy Balance Equation.

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3- Energy Balance for Batch Reactors:

The batch reactor is internally uniform in both composition and temperature. The flow
and mixing patterns that are assumed to eliminate concentration gradients will eliminate
temperature gradients as well. Homogeneity on a scale approaching molecular
dimensions requires diffusion. Both heat and mass diffuse, but thermal diffusivities tend
to be orders-of-magnitude higher than molecular diffusivities. Thus, if one is willing to
assume compositional uniformity, it is reasonable to assume thermal uniformity as well.
For a perfectly mixed batch reactor, the energy balance is

𝐻𝑒𝑎𝑡 𝑔𝑒𝑛𝑒𝑟𝑎𝑡𝑒𝑑 𝐻𝑒𝑎𝑡 𝑎𝑑𝑑𝑡𝑖𝑜𝑛 𝑜𝑟 𝑅𝑒𝑚𝑜𝑣𝑒𝑑

$ 2+$ 2 = (𝐴𝑐𝑐𝑢𝑚𝑢𝑙𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝐻𝑒𝑎𝑡)
𝑏𝑦 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑏𝑦 𝐸𝑥𝑡𝑒𝑟𝑛𝑎𝑙 𝐹𝑙𝑢𝑖𝑑

……. (3)

T = reaction temperature K
Ta= External heating or cooling fluid or wall temperature K
A = heat transfer area m2
Cpi = specific heat kJ/Kmol.K
U = overall heat transfer kJ/s.m2.K
∆Hr=Heat of reaction per mole of A reacting

……………………… (4)

3.1 Isothermal operation:

Isothermal operation means dT/dt =0 and therefore T=T0 and

− 𝑉 𝑟$ ∆𝐻% = 𝑈𝐴 (𝑇 − 𝑇& ) …………………………………. (5)

Heat generation = Heat removed

3.2 Adiabatic Operation:

For constant heat of reaction ∆Hr and constant volume

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………….…………………... (.6)

………….…………………... (7)

3.3 Non-isothermal batch reactor:

The general design material balance equation is still valid and may also be expressed in
terms of fractional conversion, x.

………….…………………... (.8)

This equation is solved with the energy balance equation

𝑁𝐶4 = ∑ 𝜃- 𝐶4-

Note for constant Volume batch reactor use Cp, and for constant pressure batch
reactor use Cv.

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Example 1:
Consider the reaction A → B, (–rA) = kCA, k350 = 0.65 min–1, (ΔHr) = 30(kcal/mol) in a
10 liter batch reactor with initial concentration of A = 2 mol/l and temperature To = 350
K. Determine the heat transfer rate required to maintain the temperature at 350 K at
95% conversion
Isothermal operation means dT/dt=0 T = To=350 K

Then: Qg =Qr

𝑄( = − 𝑉 𝑟)∆𝐻*
𝑄+ = −𝑉 𝑘 𝐶)∆𝐻* = −𝑉𝑘 ∆𝐻* 𝐶), 𝑒 -./
Qr = –0.65 × 2.0 e–0.65t × 10 × 30
Qr = –390 e–0.65t (kcal/min). Since Q < 0, it shows that heat is removed from
the system, which is undergoing exothermic reaction.
The time corresponding to a 95% conversion for the first order reaction is determined
by

The heat transfer rate (Qt≡95%) at 95% conversion is

Q = –390e–0.65 × 4.608
Q= –19.51 kcal/min

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Example 2:
Consider the oxidation of carbon monoxide in an adiabatic constant-volume batch
reactor. If the reaction is assumed to be essentially irreversible, it is described by the
'
overall stoichiometry: 𝐶𝑂 + ( 𝑂( → 𝐶𝑂(
The rate of reaction in the presence of water is given by a power law rate expression:

A mixture consisting of 1% CO, 1% O2, 1% H2O, and 97% N2 (mole percentages) is

placed in a constant-volume batch reactor of 0.1 m3 volume at an initial pressure of 1
bar and an initial temperature of 700 K. Calculate the time required to achieve 99%
conversion of the CO, and calculate the pressure and temperature in the reactor at that
time.
∆Hr = - 4.513x103 J/molA
The table of Cv ( J/mol.K) data is presented below

Cv

Solution
The oxidation of CO is a highly exothermic chemical reaction, and, as the reactor is
adiabatic, the energy balance will be quite important. It is thus necessary to solve both
the mole and energy balance equations. We start the solution by considering the mole
balance equation. The mole balance equation for CO can be written in terms of the
concentration because the volume of the reactor is constant. The mole balance is

First note that the number of moles of water, and hence the concentration, is constant
during the reaction, as water does not react and the reactor volume is constant. The
water concentration is given by

The initial concentrations of CO and oxygen can be easily calculated:

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,
𝑂𝑟 ∶ 𝐶)! = (𝐶*) ))+ (𝛳)! − ( )
With these substitutions and resulting simplification, the rate equation becomes

…………….... (A)

We first develop a stoichiometric table:

Substituting for XCO = 0.99, we calculate the total number of moles present to be 1.711
mol. The volume is unchanged; therefore, the pressure in the reactor is

• If we want to find the temperature at the end of reaction and the reaction time
only.

𝑁𝐶4 = ( 𝜃- 𝐶4-
At inlet 𝜃&5 = 1 ∶ 𝜃56 = 1 ∶ 𝜃&56 = 0 ∶
0
𝑁𝐶- = ∑ 𝜃. 𝐶/. = 19.8 ∗ 1 + 17.13 ∗ 1 = 36.93 123$.5

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𝟒.𝟓𝟏𝟑∗𝟏𝟎𝟑
𝑻 = 𝟕𝟎𝟎 + 𝟑𝟔.𝟗𝟑 𝒙
𝑻 = 𝟕𝟎𝟎 + 𝟏𝟐𝟐. 𝟐 ∗ 𝒙
𝑻 = 𝟖𝟐𝟏 𝑲

0.172 :.77 𝑑𝑥
𝑡= 1 96:);)
3.37x107 : (<::*)66.6∗?
e (1 − 𝑥)(1 − 0.5𝑥):.6@
The above equation solved by Simpson Rule to find the reaction time.
𝑡 = 318 𝑠𝑒𝑐
• If we want to find the temperature and conversion as a function of time

The general energy balance equation is

For adiabatic operation Q= QRemoved =0. Then:

.

…………….... (B)

For batch reactor

…………….... (C)

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Substitute Eq. (C) in Eq. (B) gives

AB A? C!/ .∆E% .F! IJ (B9B2 )

= −
A$ A$ (∑ C0 &10 ) (∑ C0 &10 )

&!/ A?
𝑟J = A$
The resulting equations (A, B and C) must be solved simultaneously with the mole
balance, to give the fractional conversion and reactor temperature as a function of time.
The solution of this system of coupled nonlinear ordinary differential equations is
performed numerically, using the Runge–Kutta method.

Or the above equation may written in the finite form as below

∆𝑇 = 𝐶) ∆𝑥 − 𝐶6 ∆𝑡 ( 𝑇 − 𝑇/ ) Energy Balance ……………… (11)

∆𝑥 = 𝐶; 𝑟;J ∆𝑡 𝑀𝑎𝑡𝑒𝑟𝑖𝑎𝑙 𝐵𝑎𝑙𝑎𝑛𝑐𝑒 ....…..….. (12)

𝑟J = 𝑓 (𝑥, 𝑇) 𝑅𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑅𝑎𝑡𝑒 ………….. .. (13)

C .∆EF IJ )
𝐶) = ∑ C!/& 𝐶6 = (∑ C 𝐶; = &
0 10 0 &10 ) !/

A plot of the fractional conversion of CO as a function of time is shown in Figure 1.

The temperature increases as the conversion increases, which are the expected result,
because the reaction is exothermic and the reactor is adiabatic. The fractional
conversion reaches 99% after 318 s, at which point the temperature is 821 K.

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Figure 1: temperature and conversion profile.

4- Energy Balance for Flow Reactors (PFR and CSTR):

Since the reaction is non-isothermal, the temperature will vary along the reaction length
the temperature is related to conversion through energy balance equation:
For a flow reactor:

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.... (14)

This is the general energy balance equation for flow system.

5- Adiabatic Reactors (PFR and CSTR) with constant CP:

The starting equation at steady state is

.... (15)

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….............. (16)

And the conversion is:

…………………….............. (17)

………………………….............. (18)

#
(
𝑟' = 𝐴 𝑒 $% 𝐶'* ( 1 − 𝑥 )

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Or we can find the volume by integrating the design equation numerically

𝑉 ? 𝑑𝑥
⎛ ⎞
=1 ⎜ 91 ⎟
𝐹J" : ∆E
2( B/*∑ % ?
⎝𝐶J: (1 − 𝑥)𝐴𝑒 &10K0
⎠

L!/ ? A?
𝑉=& ∫ R .- S ………………..…(19)
!" J : ∆7%
3( 4/5 ;
M ∑ 910:0 ()9N)

Example 3:
The elementary irreversible organic liquid phase reaction is carried out adiabatically in a
flow reactor. An equimolar feed in A and B enters at 27° C, and the volumetric flow
rate is 2 dm3/s and CA0=0.1 kmol/m3.
a) Calculate the PFR and CSTR volume necessary to achieve 85% conversion.
b) What is the maximum inlet temperature one could have so that the boiling point of
the liquid (550° K) would not be exceeded even for complete conversion?
c) Plot the conversion and temperature as function of PFR volume.
d) Calculate the concentration achieved in one 500 dm3 and in two 250-dm3 CSTRs in
series.
HA°(273)= -20 kcal/mol, HB°(273)= -15 kcal/mol, HC°(273)= -41 kcal/mol
CPA=CPB=15 cal/mol.K, CPC=30 cal/mol.K
k = 0.01 dm3/mol.s at 300° K, E =10000 cal/mol

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Solution Part a:

A+B→C

-
9
𝑘 =𝐴𝑒 34

<""""
9
0.01 = 𝐴 𝑒 <.>?@∗B""

𝐴 = 4.27 ∗ 10@ dm3 /mol. s

. CD@<.E><
@
Then 𝑘 = 4.27 ∗ 10 𝑒 4

Volume of CSTR equals the area of rectangle VCSTR = 0.85 x 206 = 175 dm3
Volume of PFR equals the entire Area under the curve VPFR ~ 305 dm3

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Solution: Part b
What is the maximum inlet temperature one could have so that the boiling point of the
liquid (550 K) would not be exceeded even for complete conversion?

Solution: Part C
Plot the conversion and temperature as function of PFR volume.

Solution: Part D
O ?9:
=
L!/ F!

For one CSTR:

O ?9:
= . CD@<.E><
L!/
&!/D()9?)DP.6<∗):C M B""5D"";

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𝑥 = 0.92

For two CSTR

𝑥) . 𝐹J"
𝑉&QB2 ) = 9 @6<).PR) = 500
𝐶J" 6 (1 − 𝑥) )6 4.27 ∗ 10@ 𝑒 ;::*6::?)

𝑥) = 0.881
(?D9?<) .L!/()9?<)
𝑉&QB2 6 = . CD@<.E>< = 250
&!/D()9?D)DP.6<∗):C M B""5D"";D

𝑥6 = 0.97

Example: 4
The reversible first-order gas reaction A⇋R is to be carried out in a CSTR. For
operations at 300 K the volume of reactor required is 100 liters for 60% conversion of
A. What should be the volume of the reactor for the same feed rate and conversion but
with operations at 400 K?
Data: kl = 1x103 exp [-2416/T] min -1
∆Hr = -8000 cal/mol at 300 K
K = 10 at 300 K : Feed consists of pure A : Total pressure stays constant
Solution:

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Example 5:
The gas-phase reaction A +B→ C is carried out in a pilot plant tubular reactor at about
2 atm and 300oC. The feed rate is 0.120 m3/sec and feed is 40% A, what reactor volume
is needed for 95% conversion under adiabatic operation?
k=1.4x107exp (-7700/T) m3/mol.sec : ∆Hr = -14000 J/mol : CPA = CPB= 15 J/mol.K
Solution:

∑ 𝛳. 𝐶-. =1*15+1.5*15=37.5 J/mol.K

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14000
𝑇 = 573 + 𝑥 = 573 + 373.3 𝑥
37.5
9<<::
𝑟J = 1.4 ∗ 10< 𝑒𝑥𝑝 𝐶J" ( 1 − 𝑥 ) 𝐶J" (1.5 − 𝑥 )
B
0.4 ∗ 2
𝐶$2 = = 0.017 𝐾𝑚𝑜𝑙/𝑚?
0.082 ∗ 573
𝐹$2 = 0.017*0.12 =0.00204 Kmol/sec

+.KL ⎛
𝑉 𝑑𝑥 ⎞
=i ⎜ AB ⎟
𝐹$2 + ∆G$
( @ C( ## E ∑ *%& I& J
⎝𝐶$+ (1 − 𝑥)(1.5 − 𝑥) ∗ 1.4 ∗ 10 𝑒 ⎠
#!" &.73 !$
𝑉= 2 ∫& ( '0011 )
-.1∗-&0 +!1 (-($)(-.3($) 4563045404.4 7

After the integration by Simpson Rule we can find the volume.

-------------------------------------------------------------

6- Flow Reactors with Heat Exchange:

The general energy balance for continuous flow reactors is given by

6.1- PFR with Heat Exchange:

A nonadiabatic PFR exchanges heat with the surroundings. Several different designs are
used industrially. One possibility would be to impose a constant heat flux at the wall of
the reactor. Such a reactor may be constructed in different ways but the simplest
scenario is illustrated in Figure 2.
This design is very similar to a double pipe heat exchanger, consisting of two concentric
tubes with the central tube acting as the reactor and the surrounding jacket containing
the heat transfer fluid.

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Fig.2: Jacket PFR -double pipe heat exchanger.

When reactors are operated in the nonisothermal mode, the diameter of the reactor is
usually relatively small so that an effective rate of heat transfer can be achieved. Use of
a small reactor diameter can lead to a requirement of very long reactor length if a large
volume is required. Rather than have a single very long tube, a common design uses
multiple reactor tubes surrounded by a large shell containing the heat transfer fluid,
resembling a shell and tube heat exchanger. This type of arrangement is shown in
Figure 3.

Fig. 3: Multi-tubular reactor used for nonadiabatic operation.

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Where (a) is heat exchange area per unit volume of the reactor,
J STU P
𝑎=O= FGD
=T
E
U

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……... (20)

……... (21)

- Solving CRE Problem for Reactors with Heat Exchange:

.. (22)

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…(23)

If the coolant temperature varies down the reactor we must add coolant balance:

Heat Exchanger Energy Balance- Variable Ta Co-current

Coolant Balance:

….(24)

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……………. (25)

….……………. (26)

The above Equations (Eq. 20 to Eq. 24) are the general form of the energy balance for a
PFR with external heat exchange. It may be written explicitly in terms of in terms of the
reactor length to give the temperature and conversion profile along reactor length

𝑑𝑉 = 𝐴$#VM 𝑑𝑧 𝐹𝑜𝑟 𝑀𝑢𝑙𝑡𝑖𝑡𝑢𝑏𝑒 𝑅𝑒𝑎𝑐𝑡𝑜𝑟 …………………….. (27)

𝑑𝑉 = 𝐴2M/W$"F 𝑑𝑧 𝐹𝑜𝑟 𝐷𝑜𝑢𝑝𝑙𝑒 𝑃𝑖𝑝𝑒 𝑅𝑒𝑎𝑐𝑡𝑜𝑟 ………………... (28)

STD
𝑑𝑉 = 𝑑𝑧
P
𝒅𝑻 𝑨 .∆𝑯𝒓 .𝒓𝑨 𝑼𝒂 (𝑻(𝑻𝒂 )
= −
𝒅𝒛 𝑭𝑨𝒐 (∑ 𝜽𝒊 𝑪𝑷𝒊 ) 𝑭𝑨𝒐 (∑ 𝜽𝒊 𝑪𝑷𝒊 )

𝑭𝑨𝒐 𝒅𝒙
𝒓𝑨 = 𝑨 𝒅𝒛
𝒅𝑻 ∆𝑯𝒓 𝒅𝒙 𝑨∗𝑼𝒂 (𝑻(𝑻𝒂 )
= −
𝒅𝒛 (∑ 𝜽𝒊 𝑪𝑷𝒊 ) 𝒅𝒛 𝑭𝑨𝒐 (∑ 𝜽𝒊 𝑪𝑷𝒊 )

The above equation may be written in the finite element form as

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∆𝑇 = 𝐶) ∆𝑥 − 𝐶6 ∆𝑧 ( 𝑇 − 𝑇/ ) Energy Balance …………….. (29)

∆𝑥 = 𝐶; 𝑟;J ∆𝑧 𝑀𝑎𝑡𝑒𝑟𝑖𝑎𝑙 𝐵𝑎𝑙𝑎𝑛𝑐𝑒 ....…..… (30)

𝑟J = 𝑓 (𝑥, 𝑇) 𝑅𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑅𝑎𝑡𝑒 …………….. (31)

∆EF J∗I/ J
𝐶) = ∑ K 𝐶6 = L 𝐶; = L
0 &10 !/( ∑ K0 &10 ) !/

The three types of reactor operations yield different temperature profiles within the
reactor and are shown in Figure 4 for an exothermic reaction.

Figure 4: temperature profiles for PFR in three different mode of operation.

6.2- CSTR with Heat Exchange:

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Figure 5: CSTR with heat exchange.

̇ =0 and 𝑸̇ = 𝑼𝑨(𝑻 − 𝑻𝒂 )
If 𝑾𝒔

Solving for x:

.………… (32)

Solving for T:

.… (33)

Example 6:
A second order, liquid phase reaction, A + B → C, is to be performed in a single-stage
CSTR. Given the following data:
1. Determine the size of the reactor required to achieve 85% conversion of A.

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Answer: V = 7.56 m3
2. Estimate the heat-transfer area needed to maintain the reactor temperature at 27oC.
Answer: A=3 m2
3. Calculate what the feed temperature must be if the reactor is to be operated
adiabatically at 27oC.
Answer: To = 8.8°C

Example 7: Consider the reaction A → B, rA = k CA, k300 = 0.05 min-1 , ∆Hr = -20
kcal/mole in a 10 liter reactor with CA0 = 2 moles/liter and To =300 K. At what rate
must heat be removed to maintain the reactor isothermal at 300 K for (a) a batch reactor
at 90% conversion?
This is an isothermal reactor with r = 0.05CA. If batch, then

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Note, however, that the significance of heat removal or addition (Q positive or negative)
is quite different with the batch reactor, requiring a heat removal that varies in time, the
CSTR requiring a constant heat removal rate, and the PFTR requiring a heat removal
rate that varies with position z in the reactor. These are sketched in Figure 6.

Figure 6: heat removal rate that varies with position z or t.

7- Multiple Steady States in a CSTR:

One of the interesting operating features of a nonisothermal CSTR is the existence of
multiple steady states under certain operating conditions. In a reactor with multiple
steady states, there is more than one set of steady-state operating conditions possible.
From a mathematical perspective, the existence of multiple steady states implies that
there is more than one solution (temperature and conversion) that satisfies the mole and
energy balance equations.
In the following, we use some graphical analysis to illustrate how multiple steady states
arise and the implications for reactor operation. A simple first order reaction with a
constant-density fluid is chosen for simplicity, but the principles may be extended to
more complex cases, with a concomitant increase in mathematical complexity.
For illustration purposes, consider a first-order reaction occurring in a nonisothermal
CSTR. The material balance equation is:
O ?
=
L!/ ( &!/ ( )9? )

This equation can be rearranged to give an expression for conversion of A:

('
𝑥X! = )*('
The steady-state energy balance written in terms of conversion and constant heat
capacity is given by Equation.

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Note that 𝑄̇ = 𝑈𝐴(𝑇 − 𝑇& ) is positive if heat is added to the reactor, that is, when (Ta >
T). The above equation can be rearranged as follows:

.… (34)

……………………………………………… (35)

… (39)

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Equation 39 is a nonlinear equation. For a given set of operating conditions, the reactor
temperature is the only unknown value in the equation. However, owing to the nature of
the equation, it is possible that under some sets of operating conditions there will be
more than one solution to Equation 39.
The function G(T) represents the rate of heat generation in the reactor. The second
function is R(T) represents the rate of heat removal by heat transfer with the
surroundings and the rate of fluid removal from the reactor. Note that R(T) is a linear
function of temperature in this case because CP and ∆Hr are assumed to be constant. The
intercept of the straight line depends on, for example, the value of the reactor inlet
temperature. A typical behavior of the function R(T) at different inlet temperatures is
shown in Figure 7.

Fig. 7: Variation of heat removal line with inlet temperature.

An increase in the value of the reactor inlet temperature simply shifts the line to the
right, while maintaining the value of the slope. The slope of the curve can be adjusted
by changing the value of (CP0 (1+ κ). Also the linear energy line depends on the value of
κ as shown in Figure 8.

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Fig. 8: Variation of heat removal line with κ (κ=UA/CP0FA0 ).

A plot of the generation function, G(T), verses T gives a sigmoidal curve because of the
exponential temperature dependence of the rate constant. The shape of the curve
depends in large part on the value of the activation energy. A typical plot is shown in
Figure 9.

.
Fig. 9: Shape of the heat generation function at different reactor temperatures.

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The shape of the curve depends also on the value of space time τ. A typical plot is
shown in Figure 10.

Fig. 10: Variation of heat generation curve with space-time.

All possible reactor operating temperatures must satisfy both functions, G(T) and R(T),
such that the two functions have equal values. If both of the functions are plotted on the
same graph, the points of intersection of the two lines represent permissible solutions to
the reactor energy and mole balance equations. Figure 11 illustrates such a graph. In this
figure, a single G(T) curve is shown, which would correspond to specific values of the
kinetic parameters and enthalpy of reaction. Multiple R(T) curves are shown, each of
which corresponds to a different reactor inlet temperature, with all other parameters the
same.

Fig. 11: Plot of a single heat generation curve and multiple heats removal curves

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Consider first the R(T) line that corresponds to the lowest value of the inlet temperature.
This line is at the extreme left of Figure 10. This line intersects the G(T) at a single
point, labeled 1 in Figure 11. This point of intersection corresponds to the only solution
to the mole and energy balance equations; thus this point represents the reactor
operating temperature. If the reactor inlet temperature is increased, with all other
conditions held constant, the R(T) line moves to the right. The sigmoidal G(T) curve is
not affected by the change in the inlet temperature because T0 does not appear in the
expression for G(T). The second R(T) curve from the left intersects the G(T) curve at
two points, marked with points 2 and 6, respectively. Both these points represent
possible operating temperatures for the reactor, the low- and high-temperature stable
operating conditions for this reactor. The next R(T) line in Figure 10 intersects the G(T)
curve at three points, labeled 3, 5, and 7 respectively. Points 3 and 7 represent stable-
steady states. Point 5 is an unstable steady state which cannot be achieved in practice.
Continuing to increase the inlet temperature, the next R(T) curve illustrated has two
stable steady states at 4 and 8, the final curve has a single steady state at point 9.
The steady state that is realized in the reactor depends on either the initial conditions or
the history of the reactor as shown in Figue 12.

Fig. 12: Plot of CSTR stability diagram.

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Example 8:
Consider a first order adiabatic reaction in a CSTR with the following characteristics:

The rate constant k is expressed as k = exp (15.32 – 7550/T), sec–1.

Determine the operating points for both the mass and heat balance equations.
Solution:
The first order reaction is represented by (–rA) = kCA, and applying the material balance
and the energy balance Equations gives
./
𝑥,- = 01./

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τ= V/Qo = 15.0/0.05 = 300.0 sec.

0331
H&& I H&& /$K(-3.HL – %
)
𝑥FG = = 0331
-JH&& I -JH&& /$K(-3.HL – )
%
O(L7P
𝑥NG = L-&
The figure shows that the steady state values are (XA, T) = (0.02, 300), (0.5, 362), and
(0.95, 410). The middle point is unstable and the last point is the most desirable because
of the high conversion

Example 9:
Determine the operating conditions in a CSTR for a first order exothermic reaction with
heat transfer under the following conditions:
Feed temperature, TO, = 350 K
Initial concentration, CAO = 1.0 mol/L
Temperature of the cooling medium, Ta = K 350 K
Mean residence time, τ =1.0 min
OP
(ΔHR)= - 200 kJ/mol. 𝐶N2 = 1.0 QRS.T : UA/FA.Cp = 1.0
Reaction rate constant, k= exp (25 – 10000/T) min–1
Solution:

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𝟏𝟎𝟎𝟎𝟎
9𝟐𝟎𝟎∗𝟏∗𝟏∗𝐞𝐱𝐩 (𝟐𝟓 – 𝐓 )
𝑮(𝑻) = 𝟏𝟎𝟎𝟎𝟎 𝐤𝐉/𝐦𝐨𝐥
𝟏*𝟏∗𝟏∗𝐞𝐱𝐩 (𝟐𝟓 – )
𝐓

𝑘𝜏
𝑥X! =
1 + 𝑘𝜏
10000
1 ∗ exp (25 – )
T
𝑥X! = 10000
1 + 1 ∗ exp (25 – )
T
V$
𝑅(𝑇) = 𝐶N2 (1 + 𝜅)(𝑇 − 𝑇U ) 𝜅=*
%# W'#

𝑹(𝑻) = 𝟏(𝟏 + 𝟏)(𝑻 − 𝟑𝟓𝟎) = 𝟐(𝑻 − 𝟑𝟓𝟎) 𝐤𝐉/𝐦𝐨𝐥

Both G(T) and R(T) at varying effluent temperature. Figure below shows the profiles of
the heat generation and heat removal terms, and the intersections give the operating
conditions. The values of the fractional conversion XA corresponding to the
temperatures at these points are given in the table below.

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Example 10:
The first order irreversible reaction A(l) → B(l) is carried out in a jacketed CSTR. The
feed contains A and an inert liquid in equimolar amounts, where FA0 = 80 mol/min.
What is the reactor temp when the inlet temp T0 is 450K?
UA= 8000 cal/min·K : Ta= 300K ∆HR=-7500 cal/mol : CpA = CpB =20 cal/mol·K
Cpi =30 cal/mol·K τ=100 min : E=40,000 cal/mol : k=6.6 x 10-3 min-1 at 350K

Solution:

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Plug rate law into G(T) and simplify

Steady state temp G (T) =R (T) for T0 = 450K

Use design equation to get XA as an explicit equation:

The steady state temperature for T0 = 450K is 400 K

Then x=

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8-Adiabatic Equilibrium Conversion:

In an exothermic reaction, the value of ∆Hr is negative. Therefore, an increase in the
temperature decreases the value of K, with a concomitant decrease in the equilibrium
yield. A conflict arises between the need for a high temperature to maximize the
reaction rate, and a low temperature to maximize the conversion. For endothermic
reaction, equilibrium conversion increases with increasing temperature. A typical
equilibrium curve and temperature conversion trajectory for the reactor sequence is
shown in Figure 13.

•For exothermic Reactions: As T increases, the equilibrium shifts to the left. i.e. both
K and Xe decreases
•For endothermic Reactions: As T increases, the equilibrium shifts to the right. i.e.
both K and Xe increases

Fig. 13: equilibrium conversion and equilibrium constant for exothermic

and endothermic reactions.

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Figure 14 shows a typical equilibrium composition line that might be obtained for an
exothermic reaction. The line has an equilibrium conversion near one at low
temperature but the conversion decreases as the temperature increases. Now consider
the performance of two types of reactor, the adiabatic reactor and the isothermal reactor.
For a given set of operating conditions, the adiabatic reaction line governs the
relationship between the temperature and the fractional conversion. Assuming constant
∆Hr and CP, the energy balance equation is:

Fig. 14: The equilibrium line shows the relationship between the temperature and conversion at
equilibrium for a specified starting composition. The adiabatic reaction line shows the maximum
conversion that can be obtained for adiabatic operation for a given inlet temperature. The isothermal
reaction line shows the best conversion for isothermal operation.

A typical adiabatic reaction line is shown in Figure 15 for an arbitrary value of T0. In the
reactor, both the temperature and conversion will increase along this line until the
equilibrium line is encountered at X2 and T2.

At this point, the rate is zero, and the temperature and composition of the process stream
remain constant for any additional reactor volume.

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Fig. 15: The equilibrium conversion for adiabatic operation.

If the same reactor was operated isothermally, the vertical operating line shown in
Figure 14 would be obtained. As the temperature is constant, the fractional conversion
finally attained, equal to X1, and is higher than that achieved in the adiabatic reactor.
Isothermal operation may not be practical, and does not result in a minimum reactor
volume. It is possible to determine an optimal temperature progression along the reactor
so as to maximize the conversion for the minimum possible reactor volume.

Consider the diagram shown in Figure 15. This diagram shows lines of constant
reaction rate corresponding to set values of temperature and conversion. Each solid line
represents a locus of the set of temperature and conversion that give a specified value of
the rate. The top line corresponds to a rate of zero; in other words, the equilibrium line.
We have already seen that the equilibrium conversion drops as the temperature rises. As
we move from the top to the bottom of the figure, the value of the reaction rate
increases. Note, however, that as the value of the reaction rate increases, the maximum
conversion achievable at that rate decreases.
This observation suggests a route for minimizing the reactor volume. One could start
the reaction at a high temperature to take advantage of the high rate at that temperature,
and then progressively lower the temperature to increase the equilibrium yield.
The dashed line in Figure 16 illustrates the type of temperature and conversion pathway
that must be followed to achieve this optimal design. This reactor design would require
a complex cooling pattern along the reactor length, which might not be practical.

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Fig 16: Each solid line in this diagram represents a constant value of reaction rate.

Higher conversions than those shown in Figure 16 can be achieved for adiabatic
operations by connecting reactors in series with interstate cooling. Inter-stage cooling
system consists of a series of reactors or catalyst chambers. In each of the reactor stages,
the temperature rises from inlet to outlet. Heat-exchangers (inter-stage coolers) are
placed between the reactor stages as shown in Figure 17, where the temperature is
reduced without affecting the composition of the process stream. The operating line of a
single-reactor does not naturally follow a trajectory that shadows the locus of maximum
reaction rates. By subdividing the reactor into a number of stages and removing heat
from the reaction mixture after each reactor stage, the temperature is forced lower
before the stream enters the next vessel. This allows working closer to the locus of
maximum rates (see Figure 16). Clearly the larger the number of steps, the closer the
trajectory of the system would approach the theoretical optimum. An inordinately large
increase in the number of inter-stage coolers, however, would tend to increase
construction costs. We would need to determine the optimum number of reactor stages.

Fig. 17: Schematic diagrams of two reactors in series.

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8.1-Multibed Adiabatic Reactors for Equilibrium Limited Reactions:

For relatively fast reactions that are equilibrium limited, the adiabatic reactor is
commonly used in industry. As seen above, the adiabatic reactor experiences a
temperature rise that limits the conversion. Therefore, in applications where very high
conversions are desired, it is common to use multiple reactors in series, with cooling
between each reactor.

Consider, for example, an exothermic reaction that occurs in a series of adiabatic fixed
bed catalytic reactors. The operating path would be similar to the one shown in Figure
18. This plot shows the equilibrium line as a function of temperature and conversion.
For adiabatic operation, the temperature and conversion in the first reactor follow the
adiabatic reaction line denoted Bed 1. When the fraction conversion reaches a value of
X1, which is approaching the equilibrium line, the process stream is cooled by passing it
through a heat exchanger. As this is a catalytic reaction, no further conversion occurs in
this stage, as shown by the flat line. When the process stream is cooled by a
predetermined amount, the stream enters reactor number two, in which it undergoes a
further adiabatic reaction until the conversion is X2.

The stream is cooled as before, and then fed into the last bed, in which the conversion is
brought to X3. Using this strategy, a high level of conversion can be achieved using
adiabatic reactors.A diagram of the reactor that corresponds to Figure 18 and Figure 19.
The exact number of beds and the degree of cooling between the beds depends on the
reaction involved and operating and capital costs.

Fig. 18: Multiple adiabatic reactors in series.

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Fig. 19: Multiple bed adiabatic catalytic reactor with interstage cooling.

The most classic application of the multibed adiabatic fixed bed reactor is the oxidation
'
of sulfur dioxide 𝑆𝑂( + ( 𝑂( ⇋ 𝑆0? , equilibrium limited reversible reaction. This
reaction is used to make sulfur trioxide, which, when added to water, makes sulfuric
acid. Very high yields are desired (in excess of 99%), but the reaction is highly
exothermic and equilibrium limited. As a result the multibed approach has been
adopted, with typical industrial units having three or four beds.
Example 11:
For the elementary solid-catalyzed liquid-phase reaction: A ⇋ B .Make a plot of
equilibrium conversion as a function of temperature. Determine the adiabatic
equilibrium temperature and conversion when pure A is fed to the reactor at a
temperature of 300 K.
Additional information: CPA = CPB = 50 cal/mol.K : ∆Hr = -20000 cal/molA
Keq (298 K) =100000

Solution:

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What conversion could be achieved in Example 11 if two interstage coolers were

available that had the capacity to cool the exit stream to 350 K? Also determine the heat
duty of each exchanger for a molar feed rate of A of 40 moles. Assume that 95% of
equilibrium conversion is achieved in each reactor. The feed temperature to the first
reactor is 300 K.
For an entering temperature of 300 K the adiabatic equilibrium conversion was 0.40.
For 95% of equilibrium conversion, the conversion exiting the first reactor is 0.38.

The first reactor:

The exit temperature from the first reactor is found from a rearrangement of Equation
(e):
𝑋1! = 0.0025(𝑇 − 300)+0
𝑇 = 400 (𝑋 − 0) + 300 = 400 ∗ 0.38 + 300 = 452 𝐾
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We now cool the gas stream exiting the reactor at 460 K down to 350 K in a heat
exchanger. The gas stream is then sent to the second reactor.

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Example 12:
The reversible conversion of A+B ⇋ C+D is carried out in liquid phase in a series of
staged PFR's with interstage cooling. The lowest temperature to which the stream may
be cooled is 300K. The feed is equal molar in A and B and contains no C or D. The
PFR's have a sufficient residence time to achieve 99.9% of the equilibrium conversion
in each stage. The feed enters at 300K and the reaction is carried out adiabatically. If
two reactors and one interstage cooler are used, what is the maximum conversion
(±O.05) that may be achieved after the second PFR?

Data: ∆Hr = -40000cal/molA: CPA = CPB = CPC =CPD =53.3 cal/mol.K

Keq (300K) = 3.22x108 FAo = 5 mol A /min

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