Continuous Stirred Tank Reactor Design

CHEMICAL REACTION RATE

The rate of a chemical reaction is the rate of formation or transformation of a

participant in a chemical reaction. It is expressed as the number of mass or mole of material
converted per unit volume of reactor per unit time. Thus, the rate of appearance or
disappearance of a chemical species i in a homogeneous reaction is (Levenspiel, 2003):

d ( ni / V )
ri = eq 5-1
dt

If i is a reactant, the negative sign is used to signify depletion with time. Whereas, the
positive sign is used if its a product. Where ni is the number of moles of component i, V
is the reactor volume and t is the reaction time.

For a constant volume reaction,

1 dni dCi
ri = eq 5-2
V dt dt
As expressed in the Law of Mass Action, the rate of a chemical reaction is proportional
to the active masses of participating reactants. Therefore, the rate is dependent on the
concentration of the participating reactants. In elementary reaction, the stoichiometric
coefficient of the reactants is equal to the order of the reactions. This order becomes the
power to which the reactant is raised.
If the given chemical reaction is

aA bB cC dD eE eq 5-3

then, the rate of reaction for the disappearance of reactant A is

dC A
rA kC A CB CC eq 5-4
dt

Again, except in elementary reactions, the order of the reaction is not equal to the
stoichiometric coefficients as in a, b , and c . k is the rate constant of the
reaction.
 CSTR DESIGN 2

Elementary and Non-Elementary Reactions

Elementary Reaction

Elementary reaction occurs only in a single step.

Example: 1. A Product eq 5-5

2. A+B Product eq 5-6

Non-elementary Reaction

Non-elementary reaction occurs in two or more steps of reactions and there is no

direct correspondence between the stoichiometric coefficient and the rate expression of the
reaction.
Mechanism of Non-Elementary Reaction (Levenspiel, 2003)

Non-chain reaction mechanism

Reactants (intermediates)* eq 5-7

(intermediates)* Products eq 5-8

Chain Reaction Mechanism

Reactants (intermediates)* eq 5-9

(intermediates)* + Reactant (intermediates)*
+ Product eq 5-10
( intermediates)* Product eq 5-11

REACTION RATES OF DIFFERENT MECHNISMS

Reversible Reactions

First Order Reversible Reactions

k1
A R eq 5-12
k2

The rate expression for substance A and R are written as

-dCA
rA net
=k1CA -k 2 C R eq 5-13
dt net
 CSTR DESIGN 3

dCR
rR net
=k1C A -k 2 C R eq 5-14
dt net

At equilibrium rnet = 0. Therefore,

k1CAe =k 2 CRe eq 5-15

k1 C Re
kC = = eq 5-15
k 2 C Ae

After establishing the material balance and upon integration, the final working
equation in terms of fractional conversion is:

XA
ln 1- =- k 2 k C +1 t eq 5-16
XAe

Irreversible Reactions in Parallel

k1
A R assumed desired product eq 5-17
k2
A T unwanted product eq 5-18
k3
A S unwanted product eq 5-19
The rate equation is for reactant A

-dC A
rA = = (k1 k2 k 3 )C A eq 5-20
dt
Integration gives

CA = CAo e-(k1 +k2 +k3 )t eq 5-21

Irreversible Reactions in Series (Consecutive Reactions)

Consider the unimolecular first order reaction

k1 k2
A B R eq 5-22

The rate equation for component A

-dC A
=k1C A eq 5-23
dt
 CSTR DESIGN 4

Rearranging and integrating :

CA = CAo e-k1t eq 5-24

dC B
=k1C A -k 2 C B eq 5-25
dt

Homogeneous Catalyzed Reactions

In the homogeneous catalyzed type of reactions, the overall rate is the sum of rates of
both the uncatalyzed and catalyzed reactions.

The uncatalyzed reaction is

k1
A R eq 5-26

and the catalyzed reaction is

k2
A+C R C eq 5-27

The rate expression of component A is

-dC A
= k 1C A + k 2 C A C C eq 5-28
dt

The concentration of the catalyst (CC) is assumed to be constant.

-dC A
= (k1 +k 2 C C )C A eq 5-29
dt

Integration gives
CA
ln = (k1 +k 2 CC ) t eq 5-30
CAo

Autocatalytic Reactions

An autocatalytic reaction is a reaction in which one of the products of reaction acts as

a catalyst.
For an uncatalyzed reaction:
k1
A R eq 5-31

For which the equation rate is:

-dC A
rA = =k C A C R eq 5-32
dt
 CSTR DESIGN 5

The corresponding catalyzed reaction where product R acts as a catalyts is

k1
A + R R + R eq 5-33

the rate equation is

-dC A
rA = =k C A C R eq 5-34
dt
Establishing the material balance and upon integration, the final rate expression is

Co -CA CAo
ln =Co kt eq 5-35
Co -CAo CA

CLASSIFICATION OF REACTORS

Although the purpose of this chapter is to present the determination of CSTR

specifications, Batch and Plug flow reactors will be briefly described

Batch Reactor

Batch reactors are usually simple in design with minimum auxiliary and
instrumentation requirements. It is commonly employed for small scale production, testing of
new productions, manufactured of expensive and easily contaminated system. High
conversion could be easily obtained by increasing the reaction time, although production
output is reduced correspondingly. It is usually not applicable for large industrial scale
production where labor cost would be high and production output is low compared to
continuous flow reactors. In batch reactor there is neither inflow nor outflow of both
reactants and products while the reaction is in progress.

Plug Flow Reactors (PFR)

In Plug flow reactor, reactant continually flows through a cylindrical vessel or pipe.
The reactant diminished along the length, and there is no radial variation in concentration.
This type of continuous flow reactors are simple in design and practically has no power
requirement.

reactat product

Figure 5-1. Plug Flow Reactor.

 CSTR DESIGN 6

Continuous-Stirred Tank Reactor (CSTR)

CSTR is commonly used for industrial production. It is assumed of having no spatial

variation in concentration and temperature. As name implies the reactor is well mixed,
allowing the assumption of same concentration at any point within the reactor and the
product. It is also called Backmix Reactor (Fogler, 1999). Even a well designed and
operated CSTR will produce lower conversion per unit reactor volume against Plug Flow
type reactors. In this chapter, design of Continuous Stirred Tank Reactor will be discussed.
Most homogeneous liquid phase reactions employs CSTR.

reacta product
n ow

Figure 5-2. Continuous Stirred Tank Reactor.

CSTR DESIGN EQUATIONS

Space Time and Space Velocity concept

The space time, , is the time required to process one reactor volume of feed and is
given by the following equation:

C AoV V
eq 5-36
FAo vo
where

CAo is the initial concentration

V is the volume of the reactor,

FAo is the molal flowrate of component A and,

vo is the volumetric flow rate.

 CSTR DESIGN 7

Whereas, space velocity (S) refers to the number of reactor volumes of reactant fed
into the reactor per unit time and is given by the following equation:

1 FAo vo
S eq 5-37
C AoV V

Overall Material Balance

reactant leaves
Reactant enters Volume element

Reactant accumulates

Reactant disappears by reaction

Figure 5-3. Over-all Material Balance.

rate of reactant rate of reactant rate of disappearance due rate of accumulation of

flow into element = flow out of element + to chemical rxn within + reactant in element of volume
of volume of volume the element of volume

eq 5-38

Input = output + rate of disappearance + rate of accumulation of A

At steady- state process, rate of accumulation of reactant = 0

FAo = FA + (-rA) V eq 5-39

However,

FA = FAo FAo XA eq 5-40

Then,

XA V
eq 5-41
-rA FAo
 CSTR DESIGN 8

Where XA is the fractional conversion of reactant A

In terms of space time
C Ao X A
eq 5-42
-rA

REACTION RATES AND SPACE TIME

Zero Order irreversible chemical reaction

A-----------Product eq 5-43

(-rA) = k eq 5-44

substituting ( rA) into space time equation,

C Ao X A
eq 5-45
k

First Order irreversible chemical reaction

A-----------Product eq 5-46

(-rA ) k CA eq 5-47

substituting ( rA) into space time equation,

C Ao X A
eq 5-48
kC A
Second order irreversible chemical reaction

2A------------Product eq 5-49

(-rA ) k C A2 eq 5-50

substituting ( rA) into space time equation,

C Ao X A C Ao X A
2 eq 5-51
k C A2 2
k C Ao 1- X A
 CSTR DESIGN 9

Nth order irreversible chemical reaction

nA------------Product eq 5-52

(-rA ) k C An eq 5-53

substituting ( rA) into space time equation,

C Ao X A C Ao X A
n eq 5-54
k C An n
k C Ao 1- X A

CSTR SIZING

CSTR sizing is dictated by residence time requirement. The longer the residence time,
the bigger the reactor volume at constant volumetric flow rate. This is expressed below:

= V / vo eq 5-55

where:
= Space time or Residence time, sec [hr]
V = Volume of Reactor, m [ft 3]
vo = Volumetric flowrate, m/sec [ft 3/s]

Overall chemical kinetics which includes, chemical specie, amount of specie, reaction
temperature, presence of catalyst, agitation etc determines the degree of residence time as
shown in Table 5-1.

Table 5-1. Residence Time and/or Space Velocities in Industrial Chemical Reactors.
Residence
Reactor
Product Time or
Phase Catalyst T, C P, atm
(raw materials) Space
(CSTR)
Velocity
Alkylate (i-C4, butanes) L H2SO4 5-10 2-3 5-40 min
Alkylate (i-C4, butanes) L HF 25-38 8-11 5-25 min
Butadiene sulfone (butadiene, SO2) L t-Butyl catechol 34 12 0.2 LHSV
Caprolactam (cyclohexane oxime) L Polyphosphoric acid 80-110 1 0.25-2 h
Chloral (Cl2, acetaldehyde) LG None 20-90 1 140 h
Cumene hydroperoxide (cumene, air) L Metal porphyrins 95-120 2-15 1-3 h
Cyclohexanone (cyclohexanol) L N. A. 107 1 0.75 h
Dextrose (starch) L H2SO4 165 1 20 min
Dextrose (starch) L Enzyme 60 1 100 min
Dodecylbenzene (benzene, propylene L AlCl3 15-20 1 1-30 min
tetramer)
Ethyl acetate (ethanol, acetic acid) L H2SO4 100 1 0.5-0.8 LHSV
Ethylene, propylene chlorohydrins (Cl 2, H2O) LG None 30-40 3-10 0.5-5 min
 CSTR DESIGN 10

Table 5-1 continued...

Residence
Reactor
Product Time or
Phase Catalyst T, C P, atm
(raw materials) Space
(CSTR)
Velocity
Glycerol (allyl alcohol, H2O2) L H2WO4 40-60 1 3h
o-Methyl benzoic acid (xylene, air) L None 160 14 0.32 h
3.1 LHSV
Nitrobenzene (benzene, HNO3) L H2SO4 45-95 1 3-40 min
Phenol (cumene hydroperoxide) L SO2 45-65 2-3 15 min
t-Butyl methacrylate (methacrylic acid, L H2SO4 25 3 0.3 LHSV
i-butene)
Aldehydes (diisobutene, CO) LG Co Carbonyl 150 200 1.7 h
LHSV Space velocity (hourly) liquid
N. A. Not Available
Adapted from Table 23 - 1 Section 23 - 7 Perrys Chemical Engineers Handbook 7th ed.

Standard Stirred Tank Configuration

Stirred tank configuration for a six flat blade turbine Trambouze et. al., (1988),
provide for the standard type agitation system. As shown below, the following are standard
configuration:

D
T
W

H Dd
T
ZL
I

DI
ZI

Figure 5-4. Dimensions for CSTR Design.

 CSTR DESIGN 11

ZL DI 1
1 eq 5-56 eq 5-57
DT DT 3

W 1 ZI
eq 5-58 1 eq 5-59
DT 10 DI

Dd 3 I 1
eq 5-60 eq 5-61
DI 4 DI 4

b 1 m 1
eq 5-62 eq 5-63
DI 5 DT 5

where:
ZL = Static liquid depth
DT = Tank diameter
DI = Impeller diameter
ZI = Impeller distance from tank bottom
W = Baffle width
Dd = Impeller disc diameter
I = Impeller blade length
b = Impeller blade width
HT = Tank height
m = Baffle tip distance from tank bottom

Mixing Time

To estimate the mixing time, Norwood and Metzner correlation provides for the
equation applicable for six flat blade turbine:

2 0.5
1
DI ZL
N tm 5 N Fr 6 eq 5-64
DT DT

where:
tm = Mixing time
N = Impeller revolutions per unit time
DI = Impeller diameter
DT = Tank diameter
ZL = Static liquid depth
N Fr = Froude Number
 CSTR DESIGN 12

N 2 DI
N Fr eq 5-65
g
where g = acceleration due to gravity

Impeller Selection

Agitation is designed to increase fluid turbulence, and is often employed in the

following (Mc Cabe, 2001):
1. homogenization of a fluid phase
2. increased heat transfer between a solid surface and a fluid phase
3. creation of interfacial area between two immiscible fluid phases.
4. maintenance of a divided solid in suspension in a fluid phase

Agitation as used in the process industries is the production of irregular disturbances

or turbulent motion within a fluid by means of mechanical devices acting on that fluid
(Brown, 1950). Most of the fluids handled in the process industry are low viscosity
Newtonian fluids.

Several references classify impellers according to their form, functions and uses in the
mixing operations (Brown, 1950; Foust et. al, 1980 and McCabe, 2001) as shown in Figure 5-
5. Figure 56 may be used I n the selection of appropriate impeller type.

Anchor Propeller 6 flat blade disc-turbine

Paddle Gate anchor Helical screw

Figure 5-5. Types of Impeller. Adapted from Doran, Pauline M. 1995

Bioprocess Engineering Principles.
 CSTR DESIGN 13

A graphical method of impeller selection is presented on Figure 5-6.

107

106

Helical Screws

Ribbons
105

Helical
Viscosity (centipoise)

Gate anchors
104

Paddles
Flat-blade turbines
Anchors

103
Propellers

102

10

1
Impeller Type

Figure 5-6. Viscosity Ranges for Different Impellers. Adapted from F.A Holland and
F.S. Chapman, 1966, Liquid Mixing and Processing in Stirred Tanks
as cited by Doran, Pauline M. (1995) Bioprocess Engineering
Principles.

Baffles

Baffles are flat vertical strips set radially along the tank inner wall. They are mounted
inside the tank to produce higher mixing and horizontal liquid surface (Perry and Green,
1997). In the absence of baffles in a stirred tank, vortex are formed because of the centrifugal
force acting on the liquid and could reach deep to the impeller which is undesirable (Mc Cabe,
2001). Due to the motion of the impeller in the fluid and the resultant movement of the liquid
past the baffles and wall, the skin friction and the drop form have to be considered in relation
to the speed of rotation and design of blade and tank.

Figure 5-7 provides for baffle inclination and attachment selection guide.
 CSTR DESIGN 14

Figure 5-7. Baffle Arrangements (a) Baffles are attached to the wall for low-viscosity
liquids. (b) Baffles set away from the wall for moderate-viscosity
liquids. (c) Baffles set away from the wall and at an angle for high-
viscosity liquids. Adapted from F.A Holland and F.S. Chapman, 1966,
Liquid Mixing and Processing in Stirred Tanks as cited by Doran, Pauline
M. 1995. Bioprocess Engineering Principles)

Power Dissipation

Power dissipated by the agitator maybe computed by:

5
Pa N P N 3 DI eq 5-66

where
Pa = Power dissipated by an agitator
N = RPM of the impeller
= Density of the mixture
DI = Impeller diameter
NP = Power number
 CSTR DESIGN 15

An estimation of typical horsepower for agitators is given below (Parker, 1964; Schlegel,
1972): This maybe used to approximate power requirement due to mixing of CSTR.

Fluid Approximate Horsepower

Blending vegetable oil 1.0 hp per 100,000 lb

Blending gasoline 0.019 hp per m3
Clay dispersion 10 12 hp per 1,000 gal
Fermentation (pharmaceutical) 3 10 hp per 1,000 gal
Suspension polymerization 6 7 hp per 1,000 gal
Emulsion polymerization 3 10 hp per 1,000 gal
Solution polymerization 15 40 hp per 1,000 gal

Radius of Action of an Agitator

Radius of action of an agitator should be checked after reactor, blade and baffle sizes
have been calculated to ensure there is enough intensity of mixing inside the reactor, as this
will affect reaction conversion. Radius of Action RA may be calculated as:

2 P 2
RA 9 10 eq 5-67

Horizontal radius of action Ra H and vertical radius of action RaV are 50% and 20%
respectively of the computed radius of action.

where
P = Power, watts
= Viscosity, Pa . s
Ra = Radius of action, m
Ra H = Half major axis ellipsoidal
RaV = Half minor axis ellipsoidal

To ensure high degree of agitation a linear speed at blade tip should be greater than 4. Where
tip speed is given by:

Vp = NDI (m/s) eq 5-68

Another indicator of high degree of agitation is Power dissipated per unit volume of fluid
W
which should have at least 1,500 3 value.
m

Below is the summary of degree of agitation against tip blade speed and Power per unit
volume (Trambouze et. al, 1988):
 CSTR DESIGN 16

Degree of Agitation Tip Speed m watt

s Power
Volume m 3
Low 3.25 750
Medium 3.25 to 4 750 to 1500
High 4 up 1500 up

For an initial condition, a 50% on blade tip speed of 4 m

s and Power per unit volume of
watt
1500 could be a good choice. On the other hand, a good compromise should be
m3
reached, so that just enough mixing is provided for certain required residence time for power
requirement to be justifiable. An acceptable criteria used is:

tm
< 0.1
eq 5-69