Reactor design Chapter Two

Chapter Two
Design of Isothermal Reactors

Factor affecting the performance of reactor:

1- Variation of temperature and concentration of reacting fluid with position as well
as time.
2- Rate of heat addition or removal from system
3- Type of mixing in the vessel.

1-Batch System (Batch Reactor)

The Batch reactor is the generic term for a type of vessel widely used in the process
industries. Its name is something of a misnomer since vessels of this type are used for a
variety of process operations such as solids dissolution, product mixing, chemical
reactions, batch distillation, crystallization, liquid/liquid extraction and polymerization.
In some cases, they are not referred to as reactors but have a name which reflects the
role they perform (such as crystallizer, or bio reactor).

A typical batch reactor consists of a tank with an agitator and integral heating/cooling
system. These vessels may vary in size from less than 1 litre to more than 15,000 litres.
They are usually fabricated in steel, stainless steel, glass lined steel, glass or exotic
alloy. Liquids and solids are usually charged via connections in the top cover of the
reactor. Vapors and gases also discharge through connections in the top. Liquids are
usually discharged out of the bottom.

The advantages of the batch reactor lie with its versatility. This reactor is simple, need
little supporting equipment, and is therefore, ideal for small scale experimental studies
on reaction kinetics. Industrially, A single vessel can carry out a sequence of different
operations without the need to break containment. This is particularly useful when
processing, toxic or highly potent compounds.

Batch reactors are excellent at handling difficult materials like slurries or products with
a tendency to foul.

Batch reactors represent an effective and economic solution for many types of slow
reactions.

27
Reactor design Chapter Two

The composition changes with time but it is uniform into reactor.

Feed

Agitation Product

The usual agitator arrangement is a centrally mounted driveshaft with an overhead drive
unit. Impeller blades are mounted on the shaft. A wide variety of blade designs are used
and typically the blades cover about two thirds of the diameter of the reactor. Where
viscous products are handled, anchor shaped paddles are often used which have a close
clearance between the blade and the vessel walls.

Most batch reactors also use baffles. These are stationary blades which break up flow
caused by the rotating agitator. These may be fixed to the vessel cover or mounted on
the side walls.

Despite significant improvements in agitator blade and baffle design, mixing in large
batch reactors is ultimately constrained by the amount of energy that can be applied. On
large vessels, mixing energies of more than 5 Watts per litre can put an unacceptable
burden on the cooling system. High agitator loads can also create shaft stability
problems. Where mixing is a critical parameter, the batch reactor is not the ideal
solution. Much higher mixing rates can be achieved by using smaller flowing systems
with high speed agitators, ultrasonic mixing or static mixers.

28
Reactor design Chapter Two

Mass Balance on Batch Reactor

For limiting reactant A

consumption = - accumulation
dN A
(  rA .V )   ….. 1
dt
dN A dx
N A  N A0 (1  x A )    N A0 By subs. In eq. 1
dt dt
dx
(rA .V )  N A0 t/CA0
dt
x x
dx dx
t  N A0  t  C A0 

1/- rA
0
 rA .V 0
 rA
xA
Design equation for Batch reactor

for constant volume t

CA
dC A
t C  rA
1/- rA

A0
CA CA0

2-Continuous Reactors
The continuous reactors will have both inlet and outlet streams. These reactors require
smaller and less expensive equipments and give more uniform operating conditions and
products than batch processes. The process requires quality instrumentation for process
control. These are suitable and economical for large-scale productions. The continuous
reactors are of two types, tubular and stirred tank. Tubular reactors are also known as
plug-flow type.

29
Reactor design Chapter Two

Plug-Flow Reactor(Tubular Reactor) PFR

Input output
flow flow

PFRs are also sometimes called as Continuous Tubular Reactors (CTRs).

Fluid going through a PFR may be modeled as flowing through the reactor as a series of
infinitely thin coherent "plugs", each with a uniform composition, traveling in the axial
direction of the reactor, with each plug having a different composition from the ones
before and after it. The key assumption is that as a plug flows through a PFR, the fluid
is perfectly mixed in the radial direction but not in the axial direction (forwards or
backwards). Each plug of differential volume is considered as a separate entity, and
effectively. As it flows down the tubular PFR, the residence time (τ) of the plug is a
function of its position in the reactor.

Applications

Plug flow reactors are used for some of the following applications:

 Large-scale reactions especially for gaseous reactions

 Fast reactions

 Homogeneous or heterogeneous reactions

 Continuous production

 High-pressure reactions

Production of LDPE in Tubular Reactor

30
Reactor design Chapter Two

Mass Balance on Tubular Reactor

FA Z  FA Z  dZ  (rA dV )  0

 dFA  FA  FA  dFA
  rA
 rA dV …… 1
dV
dFA dx
FA  FA0 (1  x)    FA 0
dV dV
By subs in eq. 1
dx
FA 0  rA By integration
dV
x
dx
V  FA0 
0
 rA Design equation for PFR

 /CA0
FA0  Q0 C A0
V
x x

1/- rA
V dx dx
 C A0     C A0  Q0
Q0 0
 rA 0
 rA
xA

 :Space time 
1
Spacevelocity

For constant volume

CA
dC A 
    rA
1/- rA

C A0

CA CA0

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Reactor design Chapter Two

Continuous Stirred Tank Reactor(Mixed flow Reactor) CSTR

These reactors are also known as autoclave. In a CSTR, one or more fluid reagents are
introduced into a tank reactor equipped with an impeller while the reactor effluent is
removed. The impeller stirs the reagents to ensure proper mixing.. Some important
aspects of the CSTR:

 At steady-state, the flow rate in must equal the mass flow rate out, otherwise the
tank will overflow or go empty (transient state). While the reactor is in a transient
state the model equation must be derived from the differential mass and energy
balances.
 The reaction proceeds at the reaction rate associated with the final (output)
concentration.
 Often, it is economically beneficial to operate several CSTRs in series. This allows,
for example, the first CSTR to operate at a higher reagent concentration and
therefore a higher reaction rate. In these cases, the sizes of the reactors may be
varied in order to minimize the total capital investment required to implement the
process.
 It can be seen that an infinite number of infinitely small CSTRs operating in series
would be equivalent to a PFR.

32
Reactor design Chapter Two

Mass Balance on CSTR

FA0  FA  (rA .V )  0
FA0  FA  rA .V ……… 1

FA  FA0 (1  x) By subs in eq. 1

FA0  FA0 (1  x)  rA.V
V x

FA0  rA Design equation for CSTR

F A 0  Q0 C A 0
x
  C A0
 rA

 : Residence time

For constant volume


C  CA
1/- rA

  A0
 rA
CA CA0

Applications

 Suitable for liquid reactions

 Sensitive reactions (Have high activation energy) because of mixing

 Perfable for slow reaction

 Suitable for explosive reactions

33
Reactor design Chapter Two

Mixing
Mixing is another important classifying feature for continuous reactors. Good mixing
improves the efficiency of heat and mass transfer.

Mixing by diffusion

Diffusion mixing relies on concentration or temperature gradients within the product.

This approach is common with micro reactors where the channel thicknesses are very
small and heat can be transmitted to and from the heat transfer surface by conduction. In
larger channels and for some types of reaction mixture (especially immiscible fluids),
mixing by diffusion is not practical.

A simple tube can be used as a reactor.

Small-bore systems usually rely on mixing by diffusion

Mixing with the product transfer pump

In a continuous reactor, the product is continuously pumped through the reactor. This
pump can also be used to promote mixing. If the fluid velocity is sufficiently high,
turbulent flow conditions exist (which promotes mixing). The disadvantage with this
approach is that it leads to long reactors with high pressure drops and high minimum
flow rates. This is particularly true where the reaction is slow or the product has high
viscosity. This problem can be reduced with the use of static mixers. Static mixers are
baffles in the flow channel which are used to promote mixing. They are able to work
with or without turbulent conditions. Static mixers can be effective but still require
relatively long flow channels and generate relatively high pressure drops. The
oscillatory baffled reactor is specialized form of static mixer where the direction of
process flow is cycled. This permits static mixing with low net flow through the reactor.
This has the benefit of allowing the reactor to be kept comparatively short.

The oscillatory baffled reactor uses a combination of static

The static mixer permits mixing with or mixing and cycling of flow direction.

34
Reactor design Chapter Two
without turbulent conditions
Mixing with a mechanical agitator
Some continuous reactors use mechanical agitation for mixing (rather than the product
transfer pump). Whilst this adds complexity to the reactor design, it offers significant
advantages in terms of versatility and performance. With independent agitation,
efficient mixing can be maintained irrespective of product throughput or viscosity. It
also eliminates the need for long flow channels and high pressure drops.

One less desirable feature associated with mechanical agitators is the strong axial
mixing they generate. This problem can be managed by breaking up the reactor into a
series of mixed stages separated by small plug flow channels.

35
Reactor design Chapter Two

Examples
1- A second order gas phase reaction A B + C , carried out in a batch reactor at
0
100 C and 3 atm. Calculate the conversion ratio after a half of hour from reaction
starting if you know that k= 0.04 m3/kmol.sec for pure A.
Solution
x
dx
t  C A0 
0
 rA
2 1 x 2
 rA  kC A  rA  kC A 0 (
2
)
1  x
2 1
  y A0    1 *   1
1
y P 1 * 3atm
C A0  A0 T 0  3
 0.098kmol / m 3
RT atm.m
0.082 * 373K
mol.K

1  x 2
x x
dx 1
t  C A0 
0 kC
2 1 x 2
t  (
kCA0 0 1  x
) dx
A0 ( )
1  x

1  x 1   1  x 2 (1   ) 2 2 (1   )
  ( )    2
1 x 1 x
,
1 x (1  x) 2
1 x

(1   ) 2 2 (1   )
x
1
t 
kCA0 0 (1  x) 2

1 x
  2 dx
x
4 4 4
tkCA0   (   1)dx  tkCA0  [  4 ln(1  x)  x]
0
(1  x) 1  x
2
1 x
4
(30 * 60) * 0.04 * 0.098   4  4 ln(1  x)  x
1 x
4
11.056   4  4 ln(1  x)  x
1 x
x  0.75
36
Reactor design Chapter Two

2- For the elementary reaction A B with reaction rate constant k=0.5 min-1, and
initial concentration 2 mol/liter, volumetric rate = 4 liter/min. If the reaction is carried
out in mixed flow reactor to reach to conversion ratio 0f 90%, find the volume of
reactor and the resistance time.
Solution

V x

FA0  rA

 rA  kC A  kCA0 (1  x) Elementary (n =1)

FA0  C A0Q0
V x

C A0 * Q0 kC A0 (1  x)
V x V 0 .9
  
Q0 k (1  x) 4 0.5(1  0.9)

V=72 liter
V 72
   18 min
Q0 4

3- For the liquid reaction, A 3B, the volume of CSTR is 2m3, find the outlet
concentration if you know that the initial concentration is 1 koml/m3 and Q0=3m3/sec at
60 0C.(k= 0.002 m3/kmol.sec at 300 K, k=0.01 m3/kmol.sec at 400 K)
Solution

Temperature K T1=300 T =333 T2=400

Reaction constant k k1=0.002 k= k2 =0.01
m3/kmol.sec

ln(k1/k2) = E/R [1/T2 - 1/T1]

37
Reactor design Chapter Two

k 2 E T2  T1 E
ln  [ ]   1931.325
k1 R T2 * T1 R
k2 400  333
ln  1931.325[ ]  k  0.00378m 3 / kmol.sec
k 400 * 333

n= 2  rA  kCA 2
C  CA V C A0  C A
  A0 
 rA Q0 kCA2
2 1  CA

3 0.00378CA2

4- The homogeneous gas decomposition of phosophorine:

10
4 PH3 (g) P4 (g) + 6 H2 (g)  rA  C PH 3
hr
What the size of plug flow reactor operating at 649 0C and 460 kPa can produce 80%
conversion of a feed consisting of 40 mol of pure phosphorine per hour?
Solution
x
dx
V  FA0 
0
 rA
y A0 * PT 0 1 * 460
C A0    0.06kmol / m3  60mol / m3
RT 8.314 * (649  273)

38
Reactor design Chapter Two

1 x
 rA  10C A  10C A0
1  x
74
  1*  0.75
4
1  x
x x
dx 40
V  40 V   dx
0 10C
1  x 10 * 0 . 06 0
1  x
1  x
A0

1  x
x
1
0 1  x dx  (1   ) ln
1 x
 x

40 1
V [(1   ) ln  x]
10 * 0.06 1 x
V  147.78liter

5- A homogeneous gas reaction A 3R, has a reported rate at 215 0C

(-rA=10-2CA1/2) mol/liter .sec.
Find the space time needed for 80%conversion of 50% inert feed to a plug flow reactor
operating at 215 0C and 5 atm, CA0= 0,0625 mol/liter.
Solution

1  x 1/ 2
 rA  10 2 C A0
1/ 2
( )
1  x
x
dx
  C A0 
0
 rA
x
dx
  C A0 
1  x 1/ 2
10 2 C A 0
1/ 2
0 )(
1  x
1  x 1 / 2
x
  100C A 0 0 1  x ) dx
1 / 2
(

3 1
  0 .5 * 1
1

39
Reactor design Chapter Two
x
1  x 1/ 2 C 1/ 2

A  ( ) dx  A0  CA01/2/100
0
1 x 100
h
A  [ y 0  y n  4 y odd  2 y even ] [(1+x)/(1_x)]1/2
3
xA
h=0.2

x [(1+x)/(1_x)]1/2
0 1
0.2 1.227
0.4 1.528
0.6 2
0.8 3
0.2
A [1  3  4(1.227  2)  2(1.528)]
3
C A01 / 2
A  1.331 
100
  33.28 sec

40
Reactor design Chapter Two

6- One lit/min of liquid containing A and B where CA0=0.1 mol/lit, CB0= 0.1 mol/lit
flow into mixed flow reactor of volume 1 lit. The material reacts in complex manner for
which the stochiometry is unknown. The outlet stream from the reactor contains A,B
and C(CA=0.02 mol/lit, CB=0,03 mol/lit and CC=0.04 mlo/lit). Find the rate of the
reaction of A, B and C for the conditions within the reaction

Solution
C  CA C A0  C A
  A0  rA 
 rA 
V 1lit
   1 min
Q0 1lit / min
C  CA 0.1  0.02
 rA  A0  rA   0.08mol / lit
 1
C  CB 0.1  0.03
 rB  B 0  rB   0.07mol / lit
 1
C  CC 0 0.04  0
rC  C rC   0.04mol / lit
 1

7- Pure gaseous reactant A (CA0=100 mmol/lit)is fed to mixed flow reactor(V=0.1 lit),
where it dimerzes 2A R . For the different gas feed rate, the following data
where obtained:
Run No. 1 2 3 4
Q0 (lit/hr) 30 9 3.6 1.5
CA (mmol/lit) 85.7 66.7 50 33.3
Find the rate equation for this reaction.

Solution

1 2 1
  y A0    1*   
2 2
CA
1
1 x
C A0
C A  C A0 x 
1  x
C A
1
C A0
41
Reactor design Chapter Two

C A0 x C x C A0 x
   rA  A0 
 rA  V / Q0
Q0 CA x -rA Log(-rA) logCA
30 85.7 0.25 7500 3.875 1.933
9 66.7 0.5 4500 3.653 1.824
3.6 50 0.667 2401 3.38 1.699
1.5 33.3 0.8 1200 3.08 1.522

 rA  kCAn
log( rA )  log k  n log C A
We Choose the 1st. And 4th. points to calculate the above equation
 rA1 7500
log log
 rA 4 1200  n  1.939
n n
C 1 85.7
log A log
CA 4 33.3
Log(7500)=log k +(1.939)log 85.7 k= 1.3397

 rA  1.3397 C A
1.939

You can solute this example another way:

Q0 CA x
30 85.7 0.25
9 66.7 0.5
3.6 50 0.667
1.5 33.3 0.8

C A0 x C A0 x
 rA  
 V / Q0
C A0 x C xQ
kC A   k  A0 n 0
n

V / Q0 VCA

42
Reactor design Chapter Two

Let n=2
Q0 CA x k (n=2) k (n=1) k (n=0)
30 85.7 0.25 1.02 7.5*103
9 66.7 0.5 1.014 4.5*103
3.6 50 0.667 0.96 2.401*103
1.5 33.3 0.8 1.082 1.2*103

kav = 1.019 m3 / kmol. sec

-rA=1.019CA2

8- From the following data find a satisfactory rate equation for the gas phase
decomposition of pure A, A R +S in a mixed flow reactor, CA0=0.002 mol/llit
Run No. 1 2 3 4 5
 sec 0.423 5.1 13.5 44 192
x 0.22 0.63 0.75 0.88 0.96
Ans: n=1.4
k=11.8

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Reactor design Chapter Two

Sheet No. 2
1- A stream of aqueous monomer a( 1mol/lit), 4 lit/min enters a 2- lit mixed flow
reactor is radiated therein, and polymerizes as follows:

In the exit stream CA=0.01 mol/lit, and for a particular, and for a particular reaction
product w, Cw=0.002 mol/lit, find the rate of reaction A and the rate of formation of w.
Ans; rw=4*10-3 mol/lit.min

2- In an isothermal batch reactor 70% of a liquid reactant is converted in 13 min, what is

the space time and space velocity are needed to effect this conversion in a plug flow
reactor . Ans: space velocity = 0.077 min-1

3- We plan to replace our present mixed flow reactor with one having double the
volume. For the same aqueous feed (10 mol A/lit) and the same feed rate, find the new
conversion, the reaction kinetics are represented by A R [-rA=k CA1.5] and present
conversion is 70% Ans: x =0.8

4- An aqueous feed of A and B (400 lit/min, 100 A mmol/lit, 200mmol B/lit), is to be

converted to product in a plug flow reactor. The kinetics of reaction is represented by:
A+B R [-rA= 200 CACB]
Find the volume of reactor for 99.9% conversion of A.
Ans: V =126.2 lit

5- A mixed flow reactor (2 m3) processes an aqueous feed (100 lit/min) containing
reactant A (CA0= 100 mmol/lit).The reaction is reversible and represented by A R
[-rA=0.04 CA-0.01 CR]. What is the equilibrium conversion and actual conversion in
reactor in both CSTR, PFR.

6- A specific enzyme acts as catalyst in the formation of reactant A. At a given enzyme

concentration in the aqueous feed stream (25 lit/min). Find the volume of plug flow
reactor needed for 95% conversion of reactant A(CA0= 2 mol/lit).The kinetics of the
fermentation at this enzyme concentration is given by : A R
[-rA=(0.1 CA)/(1+0.5 CA)]. Find the volume of CSTR, PFR
Ans: VPFR =426.5 lit, VCSTR =4987.5 lit
44
Reactor design Chapter Two

7- A gaseous feed of a pure A (2 mol/lit, 100 mol/min) decomposes to give a variety of

products in PFR. The kinetics of the conversion is : A 2.5R
-
[-rA=(10 min 1) CA]. Find the expected conversion in a 22 lit of reactor.
Ans: x =0.3
0
8- 1 lit/sec of a 20% ozone -80% air mixture at 1.5 atm and 93 C passes through a plug
flow reactor. Under these conditions Ozone decomposes according elementary reaction:
2O3 3O2 [k=0.05 lit/mol.sec].What the size of reactor is needed for 50%
conversion.

9- An aqueous feed containing A(1 mol/lit)enters a 2- lit PFR and reacts away
(2A R), [-rA= 0.05 CA2 mol/lit.sec]. Find the outlet concentration of A for a feed
rate of 0.5 lit/min.

10- Pure gaseous A at 3 atm and 30 0C (120 mmol/lit)is fed into a 1 llit of CSTR at
various flow rates. There it composes, the exit concentration of A is measured for each
flow rate. From the following data , find the rate equation to represent the kinetics of
decomposition of A.

Q0 (lit/min) 0.06 0.48 1.5 8.1

CA (mmol/lit) 30 60 80 105
Ans: n=1.5, k=1.8

10- The liquid reaction A R and the rate of reaction is given in below, How long
must we react each batch reactor for the concentration to drop from CA0 =1.3 mol/lit to
CAf = 0.3 mol/lit?
CA (mmol/lit) 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
-rA mol/lit.min 0.1 0.3 0.5 0.6 0.5 0.25 0.1 0.06

What is the size of the tubular reactor needed for 80% conversion of feed stream of
1000 mol A/hr at CA0 = 1.5 mol/lit.

11- Acetaldehyde is to decomposed in a plug flow reactor to CO and methane at 791 K

and 1 atm with a 50% conversion of pure feed . The specific reaction rate constant at

45
Reactor design Chapter Two

this temp. is k= 0.33 lit/mol.sec and the reaction is second order irreversible with
respect to acetaldehyde. Find the space time for this reactor.
Ans:  =349 sec

12- Determine the PFR volume necessary to produce 300*106 lb ethylene/year from
cracking a feed stream of pure ethylene. The reaction is irreversible and elementary. It is
desired to achieve 80% conversion of ethane operating with isothermal reactor at 1100K
and 6 atm. k(1000 k)= 0.027 sec-1, E=82 kCal/gmol

C2H6 C2H4 + H2

13- A second irreversible gas phase reaction 2A R, [-rA= k CA2] is carried out in
PFR at constant temperature and pressure. Determine an expression for the length of
reactor L as a function of (Q0, k, x, CA0,  ).

14- A homogenous liquid phase A R, at a rate equation [-rA= k CA2], with 50%
conversion in CSTR. What will this conversion be if the reactor is replaced by PFR of
equal size if the other condition is un changed?.
Ans: x= 0.67

46