UNIT II

IDEAL REACTORS
• The mathematical expression called the rate equation describes the
progress of a homogeneous reaction.
• The rate equation for a reacting component ‘i’ is an intensive
measure, and it explains how rapidly component ‘i’ forms or
disappears in a given environment as a function of the conditions.

• In reactor design, what size, type of reactor and method of operation

are best for a given job.
• Because this may require that the conditions in the reactor vary
with position as well as time - proper integration of the rate
equation for the operation.
• Temperature and composition of the reacting fluid may vary from point
to point within the reactor, depending on the endothermic or exothermic
character of the reaction, the rate of heat addition or removal from the
system, and the flow pattern of fluid through the vessel.
• In effect, then, many factors must be accounted for in predicting the
performance of a reactor.
• Equipment in which homogeneous reactions are effected can be one of 3
general types; the batch, the steady-state flow, and the unsteady-flow or
semibatch reactor.
• The batch reactor is simple, needs little supporting equipment, and is therefore
ideal for small-scale experimental studies on reaction kinetics. Industrially it
is used when relatively small amounts of material are to be treated.
• The steady-state flow reactor is ideal for industrial purposes when large
quantities of material are to be processed and when the rate of reaction is
fairly high to extremely high. Supporting equipment needs are great; however,
extremely good product quality control can be obtained. As may be expected,
this is the reactor that is widely used in the oil industry.
• The semibatch reactor is a flexible system but is more difficult to analyze than
the other reactor types. It offers good control of reaction speed because the
reaction proceeds as reactants are added. Such reactors are used in a variety of
applications from the calorimetric titrations in the laboratory to the large open
hearth furnaces for steel production.
 IDEAL REACTORS FOR A SINGLE REACTION
• The performance equations for a single fluid (homogeneous reactions)
reacting in the three ideal reactors.
• This performance equation involves reaction rate which is used to
determine the size of reactor. So Kinetics of reaction is very important for
designing reactor.
• The economics of the process is determined by chemical step – reactant to
product conversion.
• For this conversion we need a chemical reactor – heart of the chemical
process
• Reactors vary based on size & shape and mode of operation.
• Shape: Continuous Stirred Tank Reactors, Plug Flow Reactor
• Mode of Operation: Batch, Continuous, Semi Batch
Batch Reactor:
• In the batch reactor, or BR, the reactants are initially charged into a container,
well mixed, and are left to react for a certain period.
• The resultant mixture is then discharged.
• This is an unsteady-state operation where composition changes with time;
however, at any instant the composition throughout the reactor is uniform.
• Batch Reactor consists of cylindrical vessel equipped with agitator for stirring
the contents.
• It is provided with either external jacket or cooling coil for both heating or
cooling the reactor contents.
• Advantages: Simple in construction; Simple to operate; Flexibility in operation;
Low cost, Small instrumentation; High conversion
• Disadvantages: High labour cost; requires considerable time for cleaning, Poor
quality – Difficulty to maintain the same quality in different batches (Large)
Applications of Batch Reactor:
• Used for liquid phase reactions when the productions rates are low
• Test the new process which have not fully developed, also expensive products
manufacture such as dyes, pharmaceuticals, dye intermediates.
• They are in tank or tubular in structure
• In Tank type reactors are contents are agitated by a mechanical stirrer
• Tubular reactors are consists of one or more tubes in parallel in which the
reaction progresses as the reactants move through the tubes. These tubes
may be packed with catalyst pellets or inert solids. Single tube may be
provided with heat jacket for heat transfer and multitubes construction is
more or less as heat exchanger.
• Advantages
• They are used for high production rates comparatively short reaction time for
reducing the operating cost and facilitating the control of product quality.
• Well suited for automatic control
• Initial cost is quite high but operating cost is low
• It offers greater constancy in the operating conditions and hence offer greater
constancy in product quality
• Tank Reactors
• The other ideal steady-state flow reactor is called the mixed reactor,
• The backmix reactor, the ideal stirred tank reactor, the C* (meaning C-star),
CSTR, or the CFSTR (constant flow stirred tank reactor), and, as its names
suggest, it is a reactor in which the contents are well stirred and uniform
throughout.
• It has provisions for continuous inflow and outflow of reactants and products
respectively
• Certain pool of reaction mixture is maintained consistently inside the reactor
• Thus, the exit stream from this reactor has the same composition as the fluid
within the reactor. Also there is no variation for temperature and
concentration throughout the reactor
• This type of flow as mixed flow, and the corresponding reactor the mixed flow
reactor, or MFR.
• Advantages of Tank Reactors
• Easy to maintain good temperature control and also possible to operate at
isothermal condition even heat of reaction is high
• It provide long residence time
• It may be used in single or in series
• Disadvantages of Tank Reactors
• Large reactors are needed for higher conversion
• Not recommended for high pressure reactions because of cost consideration
(large wall thickness, complex sealing arrangements required for agitator)
• Not suited for high heat of reaction due to low heat transfer area available per
unit volume and low heat transfer coefficients
• Plug Flow Reactor
• The ideal steady-state flow reactors is variously known as the plug flow, slug
flow, piston flow, ideal tubular, and unmixed flow reactor,
• Plug flow reactor, or PFR, - this pattern of flow as plug flow.
• It is characterized by the fact that the flow of fluid through the reactor is
orderly with no element of fluid overtaking or mixing with any other element
ahead or behind.
• Actually, there may be lateral mixing of fluid in a plug flow reactor; however,
there must be no mixing or diffusion along the flow path.
• The necessary and sufficient condition for plug flow is for the residence time
in the reactor to be the same for all elements of fluid.'
• The reactant enters at one end and the product leaves at other end with
continuous variation in concentration of reaction mixture along with flow
path
• Advantages: Easy to maintain as there are no moving parts and gives high
conversion per unit volume of reactor
• Well suited for high pressure reaction & for reactions with high heat of
reaction
• Eg: Catalytic cracking of petroleum, ammonia synthesis
• Disadvantages: It is difficult to control the temperature with the reactor and
hot spots can occur in case of exothermic reaction system
• Most of the homogeneous liquid phase reactions uses CSTR and
homogeneous gas phase reaction uses PFR
• Fixed Bed Reactor:
• Understood that the term V, called the reactor volume, really refers to
the volume of fluid in the reactor.
• When this differs from the internal volume of reactor, then Vr
designates the internal volume of reactor while V designates the
volume of reacting fluid.
• For example, in solid catalyzed reactors with voidage ε we have

• For homogeneous systems, however, we usually use the term V alone

PERFORMANCE EQUATION

FOR

IDEAL BATCH REACTOR

• In a batch reactor, since the composition is uniform throughout at
any instant of time, so mass balance is taken into account the
whole reactor.
• Noting that no fluid enters or leaves the reaction mixture during
reaction, Eq. 1, which was written for component A, becomes
• Moles of A fed initially = NAO

• Conversion of A at any time t = XA

• Moles of A reacted / Moles of A fed initially = XA

• Moles of A reacted = NAO XA

• Moles of A unreacted NA = NAO - NAO XA = NAO (1- XA) (Moles of A

accumulated inside the reactor)

• Sub in Eq.1
• Rearranging and integrating gives
(3)
• Integrating with the limits
At time t = 0, XA = 0

At time t = t, XA = XA

(4)

(5)

• This is the general equation showing the time required to achieve a conversion
XA for either isothermal or nonisothermal operation
• The volume of reacting fluid and the reaction rate remain under the integral
sign, for in general they both change as reaction proceeds.
• If the density of the fluid remains constant

• Rearranging Eq.5 (6)

(7)

• For all reactions in which the volume of reacting mixture changes

proportionately with conversion, such as in single gas-phase reactions with
significant density changes, Eq. 5 becomes

• (8)

• This is the general performance equation for batch reactor with variable
density. Above Eqn is applicable for both Const. & Variable V
• For non isothermal operation, variation of rate with temperature and
variation of temperature with conversion should be known before
arriving the solution.
Space-Time and Space-Velocity

• The reaction time t is the natural performance measure for a

batch reactor, so are the space-time and space-velocity the
proper performance measures of flow reactors
• Thus, a space-velocity of 5 hr-l means that five reactor volumes of feed
at specified conditions are being fed into the reactor per hour.
• A space-time of 2 min means that every 2 min one reactor volume of
feed at specified conditions is being treated by the reactor.
• If the stream entering the reactor, the relation between s and τ and the
other pertinent variables is
• STEADY-STATE MIXED FLOW REACTOR
• The performance equation for the mixed flow reactor is obtained from
Eq. 1 which makes an accounting of a given component within an
element of volume of the system
• Since the composition is uniform throughout, the accounting may be
made about the reactor as a whole.
Input = Output + disappearance of reactant A + accumulation (1)
• if FA0 = VoCA0 is the molar feed rate of component A to reactor, then
considering the reactor as a whole we have
• Molar flow rate of ‘A’ inside the reactor (input) = FA0 (2)

• Molar flow rate of ‘A’ leaving the reactor (output) FA = FA0 (1-XA) (3)

• (4)
• Substituting these 3 terms in Eq (1)
• (5)

• (6)

(7)
• where XA and rA are measured at exit stream conditions, which are
the same as the conditions within the reactor
• If the feed on which conversion is based, subscript 0, enters the
reactor partially converted, subscript i, and leaves at conditions given
by subscript f, we have
• (8)

• (9)
• For the special case of constant-density systems X A = 1 - CA/CAo in,
which case the performance equation for mixed reactors can also be
written in terms of concentrations
•
(10)

(11)
• Note that it is a rectangular area for the case of mixed flow
reactor
• For constant density systems CA/CA0 = 1-XA thus the performance
expression for first-order reaction becomes Eqn 11.

(12)

(13)

(14)

(15)
 (16)

(17)

(18)

(19)

• On the other hand, for linear expansion

(20)
 (21)

(22)

(23)

(24)

(25)

• thus for first-order reaction the performance

expression of Eq. 25 becomes
(26)
• For second-order reaction,

• The performance Eqn 7 becomes

• Similar expressions can be written for any other form of rate

equation.
• These expressions can be written either in terms of concentrations or
conversions.
• Using conversions is simpler for systems of changing density, while
either form can be used for systems of constant density.
• Conversion in terms of Damkohler number
(i) First order reaction in CSTR with fractional conversion = 0
The performance equation for CSTR for constant density reaction
system is (1)

For first order reaction rate equation is (2)

Combining above 2 equations

(3)

If the change in volume is zero during the course of reaction, the

conversion is given by (4)
 (5)

(6)

(8)

(9)
(10)

(11)

(12)
• The Damkohler number is the dimensionless number that helps
us to make quick estimates of conversion that can be achieved in
flow reactors.
• High values of Damkohler number indicates high value of
conversion and low value of Damkohler number indicates low
value of conversion
• Conversion in terms of Damkohler number
(ii) Second order reaction in CSTR with fractional conversion = 0
The performance equation for CSTR for constant density reaction
system is

For second order reaction rate equation is

Combining above 2 equations

If the change in volume is zero during the course of reaction, the

conversion is given by
STEADY STATE PLUG FLOW REACTOR
• In a plug flow reactor the composition of the fluid varies from
point to point along a flow path;
• Consequently, the material balance for a reaction component
must be made for a differential element of volume dV.
• Thus for reactant A,
(1)
 (2)
(3)

(4)

• Substituting the above terms in Eqn 1.

(5)

(6)
• We know that
• Rearranging Eqn 5. (7)
• The equation which accounts for A is in the differential section of
reactor of volume dV.
• For the reactor as a whole the expression must be integrated.
• Now FA0 the feed rate, is constant, but rA is certainly dependent on the
concentration or conversion of materials

(8)

(9)

(10)

• Eq 10 allows the determination of reactor size for a given feed rate &
required conversion.
• Compare performance Eqs. of MFR & PFR. The difference is that in plug
flow rA varies, whereas in mixed flow rA is constant.
• As a more general expression for plug flow reactors, if the feed
on which conversion is based, subscript 0, enters the reactor
partially converted, subscript i, and leaves at a conversion
designated by subscript f, we have

(11)

• For the special case of constant-density systems

(12)

• in which case the performance equation can be expressed in

terms of concentrations,
 (13)

(14)
• Performance equations are given either in terms of conversion
or concentration
• The performance equations interrelate the rate of reaction, the
extent of reaction, the reactor volume, and the feed rate, and if
any one of these quantities is unknown it can be found from the
other three.
• Performance equation in case of constant density systems for
first order reaction

(15)

(16)
 (17)

• Performance equation in case of constant density systems for

first order reaction
(18)

(19)

(20)

(21)
(22)

(23)

(24)

(25)
 (29)

(30)
 (31)

(32)

(33)

(34)
• (1) For systems of constant density (constant-volume batch and
constant-density plug flow) the performance equations are
identical, T for plug flow is equivalent to t for the batch reactor,
and the equations can be used interchangeably.
• (2) For systems of changing density there is no direct
correspondence between the batch and the plug flow equations
and the correct equation must be used for each particular
situation. In this case the performance equations cannot be
used interchangeably.
Space time & Holding time

• For constant density systems (all liquids and constant density

gases)
• For changing density systems V/V0
• depends on what happens in the reactor, while the value of is
independent of what happens in the reactor.
• Special case of constant fluid density the space-time is
equivalent to the holding time - all liquid phase reactions
• However, for fluids of changing density, e.g., nonisothermal gas
reactions or gas reactions with changing number of moles, a
distinction should be made between and and the correct
measure should be used.