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Retrospective Theses and Dissertations

1970

Variable-volume operation of a stirred tank reactor


Monty Marvin Lund
Iowa State University

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Lund, Monty Marvin, "Variable-volume operation of a stirred tank reactor " (1970). Retrospective Theses and Dissertations. Paper 4246.

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70-25,803
LUND, Monty Marvin, 1943VARIABLE-VOLUME OPERATION OF A STIRRED
TANK REACTOR.
Iowa State University, Ph.D., 1970
Engineering, chemical

University Microfilms, A XEROK Company, Ann Arbor, Michigan

THIS DISSERTATION HAS BEEN MICROFILMED EXACTLY AS RECEIVED

VARIABLE-VOLUME OPERATION OF A
STIRRED TANK REACTOR

by

Monty Marvi n Lund


A Dissertation Submitted to the
Graduate Faculty in Partial Fulfillment
The R e q u i r e m e n t s f o r t h e D e g - e e o f
DOCTOR OF PHILOSOPHY

Major Subject;

Chemical Engineering

Approved:

Signature was redacted for privacy.


I n C h a r g e o f M a j o r Work

Signature was redacted for privacy.


Head o f M a j o r D e p a r ' n ^ e n t

Signature was redacted for privacy.

lovia State Univers i ty


Of S c i e n c e a n d T e c h n o l o g y
Ames, I o w a
1970

TABLE OF CONTENTS

Page
NOMENCLATURE

iv

INTRODUCTION

'

The S t i r r e d Tank Reactor

Variable-Volume Operation

Purpose

Types of Variable-Volume Operation

Reaction Systems Studied

Solutions to the Mathematical Models

LITERATURE REVIEW

The Dynamics of Thermally Sensitive Reactors

Reactor Models for Finite Mixing

Yield and Selectivity for Complex Chemical Reactions

12

Periodic Operation of Chemical Reactors

15

THE GENERAL EQUATIONS

19

CONSTANT VOLUME OPERATION

29

Isothermal

29

Adi abat i c

29

Single reaction of arbitrary order


First order reactions
Steady state operation
Transient operation
VARIABLE-VOLUME OPERATION

3'
3&
3&
43
51

Reactor F i l l i n g and Emptying

52

Semi c o n t i n u o u s V a r i a b l e - V o l u m e O p e r a t i o n

54

III

Isothermal

70

First order reactions


Effect of relative rate constant
Effect of flow average reactant conversion
Effect of semibatch cycle parameters
The optimal semibatch cycle
General characteristics of semibatch operation
Reversible f i r s t order reactions
Second order reactions
Single reactions of arbitrary positive order
Van De V u s s e r e a c t i o n s

72
81
86
87
89
9'
92
93
9^
99

Adiabatic

108

Continuous Variable-Volume Operation

130

CONCLUSIONS

137

General

137

Isothermal

137

First order reactions


Single reactions with arbitrary positive order
V a n De V u s s e r e a c t i o n s
Adiabatic

137
139
139
139

RECOMMENDATIONS

141

LITERATURE CITED

142

ACKNOWLEDGMENTS

^^5

iV

NOMENCLATURE

Lat in

Heat transfer area in Equation 3

Proportionality constant in Equation 1 la

Cj

Concentration of component j

C^^

Concentration of component A in the feed

Cj

Dimensionless concentration of component } , Cj/C^^

C".'

Dimensionless flow average concentration of component j


the discharge stream

Cp

Heat capacity of reactor contents

Cpg

Heat capacity of coolant

Activation energy in Equation l i b

in

g(9j9') Residence time frequency function


(-AH.)

Heat of reaction f o r i t h reaction

(-6H?)

Dimensionless heat of reaction for i t h reaction, ( - A H j ) / ( )

Reaction rate constant


Reaction rate constant at feed temperature

Dimensionless reaction rate constant, K/K^

Dimensionless linear reaction rate parameter

L'

Dimensionless Arrhenius reaction rate parameter

Dimensionless rcnctor heat transfer parameter

Dimensionless couler heat transfer parameter

Dimensionless re t at i ve rate constant

Discharge flow rate

Q,^

Feed flow rate

Q,
K
/V
0,

Feed and discharge flow rate for the reference reactor

Q.^

Dimensionless feed flow rate,

Q.|^

Dimensionless discharge flow rate during k fraction of the


semicontinuous cycle

0,^1^

Dimensionless feed flow r a t e during k f r a c t i o n o f the semi


continuous cycle

Dimensionless relative thermal energy

Dimensionless discharge flow rate,

Ideal gas law constant

Reaction rate

Dimensionless reaction rate

S(8, 0') Residence time distribution function


T

Temperature
Feed temperature

Dimensionless temperature, T/T^

Tj.

Cooler temperature
Cooler feed temperature

T i me

Heat transfer coefficient

VoIume

v.,

Maximum v o l u m e

Vj,

Cooler volume

Minimum volume

Dimensionless volume

vi

Conversion o f component A
Flow average conversion o f component A i n the discharge stream
Ampli tude

Stoichiometric coefficient for the j t h species i n the


ith reaction
Relative y i e l d o f product when only one product
Relative yield of product j
Dimensionless time, t Q^/V^
Dimensonless time at end of k fraction of the semicontinuous
c y c l e , t k 0%/%%
Dimensionless time at beginning of semicontinuous cycle.

Dens i t y
Coolant density
The k f r a c t i o n of
Equation 46

the semicontinuous cycle defined by

Dimensionless average re si ce ice time defined by Equation 51


Dimensionless flow average residence time defined by
Equation 55
Dimensionless time interval defined by Equation 46
Phase lag
Relative yield
Frequency

vii

Subscripts
i

Refers to i

reaction: i = i , 2, 3j

Refers to j

component;

Refers t o k f r a c t i o n o f the semi continuous cycle


k = F, B, E, D
F - Filling
B - Batch
E - Emptying
D - Down

j = A , B , C, D

INTRODUCTION

The S t i r r e d Tank Reactor


The s t i r r e d tank reactor i s a device used t o process raw materials,
u s u a l l y i n l i q u i d f o r m , t o d e s i r e d p r o d u c t m a t e r i a l s b y means o f a c h e m i
cal reaction.

Generally, the stirred tank reactor is a cylindrical vessel

with a diameter approximately equal to i t s length and an impeller to pro


vide stirring actiono

The major distinguishing characteristic o f the

stirred tank reactor i s the level of mixing caused by the s t i r r i n g action.


At one conceptual extreme the reactor i s " p e r f e c t l y mixed" which means
that the reactor contents are uniform i n temperature and concentration
and that feed material, upon entering the reactor i s immediately dis
persed throughout the reactor, and the feed concentration and temperature
drop instantaneously to the concentration and temperature of the reactor
contents.

Consequently, product material discharged from the perfectly

m i x e d r e a c t o r h a s t h e same c o n c e n t r a t i o n a n d t e m p e r a t u r e a s t h e r e a c t o r
contents.

At the other extreme, the reactor i s not stirred and there

exists a zero level of mixing.

This means that there i s no mixing o f r e -

actants of different levels of concentrations in the reactor.


The batch reactor i s a tank reactor that has a zero level of mixing.
The b a t c h r e a c t o r i s a s s u m e d t o b e i n i t i a l l y c h a r g e d w i t h r e a c t a n t o f
uniform concentration and temperature.

Fresh feed is not introduced into

the batch reactor during the reaction time, and thus there i s no mixing
of reactants with different levels of concentration.

The batch reactor

is mathematically equivalent to a steady state operated plug flow re


a c t o r w i t h t h e same r e s i d e n c e t i m e .

The p l u g f l o w r e a c t o r i s a t u b u l a r

reactor i n which material flows through the reactor as a plug with no


backmixing or dispersion along the length of the reactor.
I n t h i s t h e s i s t h e a c r o n y m STR i s u s e d t o d e n o t e t h e s t i r r e d t a n k
reactor.

I n g e n e r a l , t h e STR may b e o p e r a t e d w i t h f e e d a n d d i s c h a r g e

streams that are continuous or discontinuous periodic functions of time.


T h e a c r o n y m CSTR i s u s e d t h r o u g h o u t t o d e n o t e t h e c o n t i n u o u s s t i r r e d t a n k
reactor for which the feed and discharge streams are constant at the
identical volumetric flow rate.

When u s e d w i t h o u t a n y m o d i f i e r s t h e

a c r o n y m CSTR d e n o t e s s t e a d y s t a t e o p e r a t i o n o f t h e c o n t i n u o u s s t i r r e d
tank reactor.

Variable-Volume Operation
V a r i a b l e - v o l u m e o p e r a t i o n o f t h e STR i s a p r o c e s s w h i c h u s e s p e r i o d i c
feed and discharge flow rates as the driving force to cause a periodically
varying volume and i n turn, a periodic residence time.
concentration

The r e s u l t i n g

and temperature variations i n the reactor are also periodic

functions of time.

T h u s , t h e v a r i a b l e - v o l u m e o p e r a t i o n o f t h e STR i s a

special case of periodic operation of

t h e STR.

In general, periodic operation of


reactor which are periodic functions of

t h e STR i m p l i e s o u t p u t s f r o m t h e
time.

T h e STR may b e f o r c e d t o

generate periodic outputs by forcing the reactor with periodic inputs such
a s f e e d r a t e , f e e d c o n c e n t r a t i o n , o r c o o l a n t f l o w r a t e , o r t h e STR m a y
generate periodic outputs when the inputs are constant, i f the parameters
are such that a stable l i m i t cycle exists about an unstable steady state
poi nt.
T h e s t u d y o f p e r i o d i c o p e r a t i o n o f t h e STR i s a r e c e n t d e v e l o p m e n t i n

the f i e l d of chemical reactor design.

In the past, steady state operation

o f t h e CSTR h a s b e e n c o n s i d e r e d t o b e t h e m o s t d e s i r a b l e .

However, i t

h a s b e e n f o u n d t h a t some t y p e s o f p e r i o d i c o p e r a t i o n o f t h e STR may r e


sult i n improved performance from the standpoint of increasing p r o f i t ,
production rate, or yield

Purpose
T h e p u r p o s e o f t h i s r e s e a r c h i s t o show t h a t v a r i a b l e - v o l u m e

opera

t i o n o f t h e STR c a n b e u s e d t o i n c r e a s e t h e p r o d u c t i o n r a t e o f t h e STR
r e l a t i v e t o t h e p r o d u c t i o n r a t e o f t h e CSTR.

Relative production rate

i s measured by relative yield or relative throughput.

Relative yield is

defined as the r a t i o of average yield by variable-volume operation of

the

STR t o y i e l d b y t h e CSTR w h e r e b o t h r e a c t o r s h a v e t h e same a v e r a g e t h r o u g h


p u t o f m a t e r i a l a n d t h e same m a x i m u m v o l u m e .

Relative throughput is de

fined as the r a t i o of the average throughput by variable-volume operation


o f t h e STR t o t h e c o n s t a n t t h r o u g h p u t o f t h e CSTR w h e r e b o t h r e a c t o r s
h a v e t h e same a v e r a g e y i e l d a n d t h e same maximum v o l u m e .
and relative throughput are not independent.

Relative yield

They are simply two d i f f e r

ent methods for measuring relative production rate.

When t h e r e l a t i v e

yield and the relative throughput are greater than unity, the variablevolume operation i s considered an improvement over the performance o f the
CSTR.

Types o f Variable-Volume Operation


In this work two general types of variable-volume operation of the
STR a r e s t u d i e d .

These are semi continuous variable-volume operation and

continuous variable-volume operation.

Semibatch operation i s a special

case of semi continuous variable-volume operation that i s studied i n detai 1.


Semi c o n t i n u o u s v a r i a b l e - v o l u m e o p e r a t i o n e m p l o y s f e e d a n d d i s c h a r g e
flow rates that are periodic functions of time and are discontinuous a t
different points during the semicontinuous cycle.

Semibatch operation i s

a simple special case o f semi continuous variable-volume operation i n that


semibatch operation employs a feed flow rate only during the f i l l i n g
fraction of the semibatch cycle, and a discharge flow rate only during
the emptying fraction o f the semibatch cycle, whereas feed and discharge
flow rates may be present throughout the semi continuous cycle.
The continuous variable-volume operation employs feed and discharge
flow rates that are continuous periodic functions of time.

Reaction Systems Studied


V a r i a b l e - v o l u m e o p e r a t i o n o f t h e STR was s t u d i e d f o r v a r i o u s r e a c t i o n
schemes.

These are the single reaction of positive order i n the i s o

t h e r m a l STR,

the f i r s t order irreversible and exothermic reaction i n the

a d i a b a t i c STR, a n d t h e Van De V u s s e r e a c t i o n s i n t h e i s o t h e r m a l STR.

The

V a n De V u s s e r e a c t i o n s a r e a n e x a m p l e o f a r e a c t i o n s y s t e m c o m p o s e d o f
consecutive reactions with higher order side reactions.

Most of the

analysis o f the d i f f e r e n t reaction schemes i s presented f o r the case o f


s e m i b a t c h o p e r a t i o n o f t h e STR.

Solutions to the Mathematical Models


This thesis presents a theoretical analysis of variable-volume

o p e r a t i o n o f t h e STR.

Mathematical models are presented for the various

cases of variable-volume operation of

t h e STR

For many cases where an

a n a l y t i c a l s o l u t i o n i s n o t t r a c t a b l e , e x t e n s i v e u s e i s made o f t h e a n a l o g
and d i g i t a l computer to solve the systems of equations which describe
the mathematical models.

LITERATURE REVIEW

In recent years interest i n the periodic operation of a chemical re


actor as a means t o improve y i e l d over the optimum steady state has been
increasing rapidly.

Periodic operation refers to the situation i n which

some o f t h e o u t p u t o r i n p u t v a r i a b l e s o f a r e a c t o r a r e p e r i o d i c f u n c t i o n s
of tim.

T h e v a r i a b l e - v o l u m e STR i s a s p e c i a l c a s e o f t h e p e r i o d i c o p e r a

tion of a chemical reactor.


Theoretical analysis of the periodic operation of a reactor has been
a p p l i e d t o t h e CSTR a n d t o t h e p l u g f l o w r e a c t o r p r o c e s s i n g a l i q u i d w h i c h
undergoes a homogeneous l i q u i d phase reaction.
nonisothermal cases have been considered.

Both the isothermal and

The chemical kinetics con

sidered have been limited mainly to f i r s t or second order isothermal or


exothermic reactions
This research work is concerned i n general, with the non:sothermal
v a r i a b l e - v o l u m e STR w h e r e i n a h o m o g e n e o u s l i q u i d p h a s e e x o t h e r m i c r e a c t i o n
is occurring

T h e v a r i a b l e - v o l u m e STR g i v e s r e s u l t s f o r r e a c t a n t c o n

v e r s i o n w h i c h u s u a l l y f a l l b e t w e e n t h e s t e a d y s t a t e CSTR c o n v e r s i o n a n d
t h e b a t c h r c a c t o r o r p l u g f l o w r e a c t o r c o n v e r s i o n w i t h t h e same r e s i d e n c e
time and thus might be modeled by a reactor with a f i n i t e mixing level.
Results are obtained for various types of reaction kinetics.
publications are reviewed which concern:

Therefore,

1) the dynamics of thermally

sensitive reactors, 2) reactor models for f i n i t e mixing, 3) yield and


selectivity for complex chemical reactions, and 4) periodic operation of
chemical reactors.

The Dynamics o f Thermally Sensitive Reactors


Van H e e r d e n ( 3 3 ) p r o b a b l y g a v e t h e f i r s t t r e a t m e n t o f a u t o t h e r m i c
p r o c e s s e s i n t h e CSTR.

He s h o w s t h a t t h e s e p r o c e s s e s may b e c h a r a c t e r i z e d

by a heat versus temperature diagram on which the inLersection of the heat


generation curve and the heat consumption curve give the steady state
operating points.

Van Heerden shows that f o r the single exothermic r e

action there are from one to three steady state operating points.

In the

case of three steady states, the low and high temperature steady states
satisfy the necessary conditions for stability, while the intermediate
steady state is necessarily unstable

Van H e e r d e n c a l l e d t h i s u n s t a b l e

steady state the ignition point, since a slight increase i n temperature


w i l l cause the reaction to proceed to the higher temperature steady state.
I n a l a t e r paper, Van Heerden (34) explains that the p o s s i b i l i t y o f more
than one steady state can be ascribed t o the backmixing o f heat along the
reaction path.

In order to gain insight into the conditions under which

a n e x o t h e r m i c p r o c e s s may h a v e m o r e t h a n o n e s t e a d y s t a t e . V a n H e e r d e n p e r
f o r m e d c a l c u l a t i o n s t o sh o w t h e r e g i o n s o f t h r e e p o s s i b l e s t e a d y s t a t e s f o r
t h e c a s e s o f a f i r s t o r d e r e x o t h e r m i c r e a c t i o n i n I ) a n a d i a b a t i c CSTR,
2) an adiabatic plug flow reactor with heat exchange between i n l e t and out
l e t , and 3) an adiabatic plug flow reactor with axial conduction of heat.
A f t e r V a n H e e r d e n ' s ( 3 3 ) f i r s t p a p e r , B i l o u s a n d A mundson ( 5 ) e x
tended his work.

They determined the shape o f the heat generation curve

i n t h e ( h e a t , t e m p e r a t u r e ) p l a n e f o r some c o m p l e x t y p e s o f c h e m i c a l r e
actions and showed that sometimes more than three steady states are possible,
some o f w h i c h a r e n e c e s s a r i l y u n s t a b l e .

The transient equations were

linearized and used t o obtain necessary and sufficient conditions f o r the


s t a b i l i t y of a steady state i n terms of the steady state conditions.
( C o n v e r s i o n , t e m p e r a t u r e ) p h a s e p l a n e p l o t s w e r e made b y s i m u l a t i n g t h e
nonlinear transient equations on the analog computer.

These p l o t s show

the path of approach to the stable states i n the (conversion-temperature)


plane.

Bilous and Amundson (6) also developed an a n a l y t i c a l method f o r

predicting regions of parametric sensitivity in a tubular reactor.

Para

metric sensitivity refers to the fact that under the proper conditions the
thermal behavior of a tubular reactor is extremely sensitive to small
changes i n the operating variables

The tubular reactor does not e x h i b i t

t h e t y p e o f u n s t a b l e b e h a v i o r f o u n d i n t h e CSTR.
The work o f Bilous and Amundson (5) i s extended by A r i s and Amundson
(3) who give an analysis of

the s t a b i l i t y and control of the nonisothermal

CSTR i n w h i c h a s i n g l e e x o t h e r m i c r e a c t i o n i s o c c u r r i n g -

The a n a l y s i s i s

limited to local control, since the transient equations are linearized


about a steady state operating point and are therefore valid for only small
perturbations in the inputs.

Control of a steady state by the three ideal

modes o f c o n t r o l a n d w i t h t e m p e r a t u r e o r c o n c e n t r a t i o n a s t h e c o n t r o l
variable i s discussed.

I t i s established that an uncontrolled unstable

s t e a d y s t a t e c a n a l w a y s b e made s t a b l e b y t h e u s e o f i d e a l p r o p o r t i o n a l
control, i f temperature is the control variable.

Calculations and (con

v e r s i o n , t e m p e r a t u r e ) p h a s e p l a n e p l o t s a r e p r e s e n t e d w h i c h show t h e e v o l u
tion of an uncontrolled unstable steady state to a controlled stable steady
state by the application of increasing amounts of ideal proportional control.
Kermode and Stevens (22) used the root locus method t o determine the amount

o f t h e i d e a l modes o f c o n t r o l n e c e s s a r y t o make a n u n c o n t r o l l e d s t e a d y
s t a t e become s t a b l e .

The root locus method was applied t o the linearized

e q u a t i o n s f o r t h e n o n i s o t h e r m a l CSTR w i t h a f i r s t o r d e r e x o t h e r m i c r e
action

The results from t h e root locus method agreed well with results

obtained by simulation of the nonlinear equations on the analog computer


Luus and Lapidus (28) developed an averaging technique which could
be used t o determine the s t a b i l i t y of second order nonlinear systems
The technique can also be used to prove the existence or nonexistence of
l i m i t c y c l e s a n d t o s h o w how f a s t a p h a s e p o i n t i n t h e ( c o n c e n t r a t i o n ,
temperature) phase plane approaches a singular point or a l i m i t cycle
The technique was successfully applied t o the analysis and control o f a
CSTR w h i c h w a s d i s t u r b e d b y some o s c i l l a t i n g I n p u t v a r i a b l e .

Reactor Models for Finite Mixing


Levenspiel and Bischoff (25) discuss the effect of backmixing on the
molecular scale on conversion I n an isothermal chemical reactor.

Plots

are presented which show the r a t i o o f the residence time i n the p e r f e c t l y


m i x e d o r CSTR t o t h e r e s i d e n c e t i m e I n t h e u n m i x e d o r p l u g f l o w r e a c t o r
versus conversion

E x c e p t f o r z e r o o r d e r r e a c t i o n s , t h e CSTR a l w a y s r e

quires a larger residence time than the plug flow reactor

The e f f e c t of

backmixing becomes Increasingly Important f o r higher order reactions.

The

r e a c t o r l o n g i t u d i n a l d i s p e r s i o n n u m b e r , D u / L , i s p r e s e n t e d a s a means o f
determining conversion at Intermediate or f i n i t e levels of mixing
Denbigh (11) shows that the decrease I n conversion caused by backmixing
i n an isothermal reactor I s due to a decrease I n the average reaction
ratec

10

Levenspiel and Bischoff

(2b) describe t h e o r e t i c a l l y the phenomenon o f

f i n i t e mixing or nonideal flow by such mathematical models as dispersion


models, tanks i n series models, and combined reactor types models.

The

residence time distribution and the internal age distribution are defined
and experimental methods for their determination are presented.

Nauman

(30) develops a theory for residence time distribution functions i n an

unsteady state perfectly mixed reactor.

In the unsteady state reactor

there i s a different residence time distribution for each point i n time.


Danckwerts (10)

shows that a knowledge o f the residence time d i s t r i

bution is not sufficient to determine reactor conversion i n a nonlinear


reacting system.

In addition to the residence time of a molecule, a

knowledge of the behavior of the molecule and i t s neighbors while they


reside in the reactor is required.

T h i s b e h a v i o r o f t h e m o l e c u l e s may b e

d e s c r i b e d b y t h e i r mode o f d i s p e r s i o n .
of segregation

Danckwerts introduced the concept

t o c h a r a c t e r i z e t h e mode o f d i s p e r s i o n .

In a completely

segregated f l u i d the molecules are assumed t o pass through the reactor i n


f i n i t e packets of small volume compered to the reactor, but large enough to
contain many molecules.

Each l i t t l e packet passes through the reactor as

a minute batch reactor.

In the nonsegregated f l u i d the molecules are dis

persed on a molecular scale.

F l u i d i n a CSTR i s u s u a l l y t h o u g h t o f a s

being nonsegregated unless specified otherwise.

F l u i d s w h o s e mode o f d i s

persion is between the completely segregated and nonsegregated f l u i d are


said to be p a r t i a l l y segregated.

Levenspiel

{2k, p. 310) c a l l s the com

pletely segregated f l u i d a macrofluid and the nonsegregated f l u i d a microf l u i d . Danckwerts (10) showed that the average reaction r a t e , and thus
c o n v e r s i o n , was h i g h e r I n a c o m p l e t e l y s e g r e g a t e d s y s t e m i f t h e r e a c t i o n

11

o r d e r w a s g r e a t e r t h a n 1 , l o w e r i f l e s s t h a n 1 , a n d e q u a l i f t h e o r d e r was
one

Z w i e t e r i n g ( 3 6 ) e x p r e s s e d m a t h e m a t i c a l l y t h e c o n d i t i o n o f maximum

mixedness or nonsegregation of f l u i d i n a flow system with an arbitrary


residence time distribution.

Zwietering showed that the conversion i n a

chemical reactor w i t h a known residence time d i s t r i b u t i o n must be between


t h e c o n v e r s i o n s c o r r e s p o n d i n g t o c o m p l e t e s e g r e g a t i o n a n d maximum m i x e d
ness of the reacting fluid
Under adiabatic operating conditions, the conversion i n a plug flow
r e a c t o r i s n o t a l w a y s g r e a t e r t h a n t h e c o n v e r s i o n i n a CSTR w i t h t h e same
residence time

D e p e n d i n g o n t h e d e g r e e o f c o n v e r s i o n d e s i r e d , a CSTR o r

a CSTR f o l l o w e d b y a p l u g f l o w r e a c t o r w i l l r e q u i r e t h e l e a s t r e s i d e n c e
time for the desired conversion.

Cholette and Blanchet (9) were probably

the f i r s t to study series reactor combinations under adiabatic operating


conditions.

They found that for isothermal and endothermic reactions the

plug flow reactor always gives a greater conversion than a series combina
t i o n o f t h e CSTR a n d p l u g f l o w r e a c t o r .

However, for exothermic reactions,

a s e r i e s c o m b i n a t i o n o f a CSTR f o l l o w e d b y a p l u g f l o w r e a c t o r was f o u n d
t o g i v e a h i g h e r c o n v e r s i o n t h a n t h e CSTR o r p l u g f l o w r e a c t o r a l o n e f o r
high enough levels of conversion.

M o r e o v e r , i t was e s t a b l i s h e d t h a t t h e r e

existed an optimal level of mixing, that i s , an optimal proportion of com


b i n e d r e a c t o r v o l u m e d e v o t e d t o t h e CSTR, w h i c h w o u l d m a x i m i z e c o n v e r s i o n .
No e x p l a n a t i o n was g i v e n f o r t h e o c c u r r e n c e o f t h e o p t i m u m m i x i n g l e v e l .
Aris (2) gave the general analytical and graphical conditions for which
t h e CSTR f o l l o w e d i n s e r i e s b y a p l u g f l o w r e a c t o r o p t i m a l a n d a l s o a n
analytical expression for the optimum mixing level

i t was shown that the

12

optimum level of mixing for the reactor combination always afforded a


stable steady state operation.
Most reactor models to determine conversion at f i n i t e mixing levels
h a v e b e e n f o r m u l a t e d i n t e r m s o f s e r i e s o f CSTRs, c o m b i n a t i o n s o f CSTRs
and plug flow reactors, and plug flow reactors with axial dispersion.
Gillespie and Carberry (20) have presented yet another model whereby f i n i t e
mixing levels are simulated by a plug flow reactor with a recycle stream.
With no recycle, plug flow reactor conversion i s achieved.

At a recycle

r a t e o f 2 0 o r m o r e t i m e s t h e f l o w r a t e o f f r e s h f e e d , CSTR c o n v e r s i o n i s
achieved.

Intermediate levels of mixing are simulated by recycle rates

between 0 and 20.

The unique advantage of

the recycle model i s that the

recycle i s contained in the boundary condition for the reactor.

Whenever

the design equation for the plug flow reactor can be integrated, the
e f f e c t o f f i n i t e mixing can be determined.

Gillespie and Carberry (20)

s how t h e r e l a t i o n s h i p b e t w e e n t h e r e c y c l e r a t i o i n t h e i r p l u g f l o w r e a c t o r
w i t h r e c y c l e f i n i t e m i x i n g m o d e l a n d t h e n u m b e r o f CSTRs i n s e r i e s w h i c h
give equivalent mixing.

Gillespie and Carberry (20) also apply their

f i n i t e m i x i n g m o d e l t o t h e a d i a b a t i c c a s e t o show t h a t f i n i t e m i x i n g l e v e l s
afford the optimum conversion for sufficiently exothermic reactions.

An

analytical solution i s possible whenever an analytical solution i s possible


for the adiabatic plug flow reactor.

Douglas and Eagleton (14) give an

analytical solution to the adiabatic plug flow reactor design equation i n


terms of exponential integral functions.

Yield and S e l e c t i v i t y for Complex Chemical Reactioii


A complex reaction i s considered here to be a mixture of high order

13

reactions, consecutive reactions, and competing reactions.


For systems of complex chemical reactions Carberry (7) defines yield
at a point as the rate of generation of a desired product relative to the
rate of consumption of a key reactant and selectivity at a point as the
rate of generation of a desired product relative to the rate of generation
o f some u n d e s i r e d p r o d u c t .

Denbigh (12) defines instantaneous yield i n a

similar way and also defines an overall reactor y i e l d .

Denbigh (12)

demonstrates the application of these definitions to the determination of


yield i n tubular and mixed tank reactors by experimental and analytical
methods.
Levenspiel

(24, Chapter 7) discusses the effect of mixing on the

yield and selectivity obtainable from systems of complex reactions.

Plots

showing yield versus conversion for a mixed system of f i r s t order consecu


tive and competing reaction are giveno

I t i s shown that f o r such a mixed

system o f reactions the maximum amount o f desired intermediate or the


maximum s e l e c t i v i t y a t a g i v e n c o n v e r s i o n i s o b t a i n e d w h e n r e a c t i o n m a t e r i
als are not mixed at different levels of conversion.

I t is also determined

that backmixing or mixing at different levels of conversion is detrimental


to the yield of higher order reactions.
Van de Vusse (32) defined y i e l d as B produced t o A fed and s e l e c t i v i t y
as B produced t o A consumed and compared y i e l d and s e l e c t i v i t y i n the
i s o t h e r m a l p l u g f l o w r e a c t o r a n d CSTR f o r t h e f o l l o w i n g c o m p l e x r e a c t i o n
scheme.
A !

> 3

>C

>D

14

For t h i s scheme, degredation o f B t o C i s suppressed by using a plug flow


reactor with a short residence time.

Formation of byproduct D is kept low

i f t h e c o n c e n t r a t i o n o f A i s l o w ; h e n c e , a CSTR w i t h a l o n g r e s i d e n c e t i m e
is appropriate.

The choice of reactor type and residence time i s governed

by the relative values of the rate constants.

If

v a l u e f o r t h e s e l e c t i v i t y i s a l w a y s i n t h e CSTR.

> K^,

the maximum

T h e maximum v a l u e f o r t h e

yield is obtained i n the plug flow reactor i f Kg/K^ s 0.04(K^C^^/K^^


o t h e r w i s e t h e maximum y i e l d i s o b t a i n e d i n t h e CSTR.

Gillespie and Car-

b e r r y ( 1 9 ) show t h a t a n i n t e r m e d i a t e l e v e l o f m i x i n g b e t w e e n t h e CSTR a n d
p l u g f l o w r e a c t o r may p r o d u c e a maximum y i e l d o f B f o r Van d e V u s s e ' s ( 3 2 )
reaction scheme.

They showed that when K^C^^<: K2, a l l backmixing has a

detrimental effect on y i e l d and when

some I n t e r m e d i a t e l e v e l o f

mixing w i l l maximize yield.


Gillespie and Carberry (20) use the plug flow reactor with recycle
model f o r f i n i t e backmixing to determine the e f f e c t of f i n i t e backmixing
on s e l e c t i v i t y and y i e l d f o r a number of linear and nonlinear y i e l d sensi
tive isothermal reaction schemes.

Carberry (7) extends his previous

analysis to the rdiabatic reactor t o shvw the e f f e c t of complete heat


backmixing as well as complete mass backmixing on y i e l d f o r complex r e
action types with different levels of exothermicity.
Wei

(35) states that when a reactor design equation can be solved f o r

a single f i r s t order irreversible reaction, i t can be solved for a system


o f c o u p l e d f i r s t o r d e r r e a c t i o n s o f a n y number o f s p e c i e s a n d a r b i t r a r y
coiiiplexi ty

Wei p r e s e n t s a m a t r i x m e t h o d t o u n c o u p l e t h e c o u p l e d s y s t e m

o f l i n e a r equacions for complex rt;dctioii schemes i n t o an equivalent set o f

15

independent f i r s t order irreversible reactions.

Wei s o l v e s t h e u n c o u p l e d

system of equations to give produce distributions for different ideal


reactor models.

Periodic Operation o f Chemical Reactors


A chemical reactor system that i s described by a nonlinear system of
differential equations or a linear system of differential equations with
variable coefficients w i l l in general give different time average values
f o r periodic output variables when forced by periodic inputs than the
steady state values obtained by using constant inputs equal to the average
of the oscillating inputs.

S u c h a c h e m i c a l r e a c t o r s y s t e m may a l s o a c t a s

a c h e m i c a l o s c i l l a t o r ; t h a t i s t h e r e a c t o r may s h o w s t a b l e c y c l i c b e h a v i o r
under the proper conditions when the inputs are constant, i n which case the
time average values of the o s c i l l a t i n g variables w i l l be different from the
corresponding steady state values

Much o f t h e b a s i c t h e o r y o f t h e p e r i o d

i c behavior of nonlinear systems i s contained i n a book by Minorsky (29)


Minorsky's book i s used as a source work by v i r t u a l l y a l l the authors who
have published material about the behavior of the periodically operated
chemical reactor.
Douglas and Rippen (16) show a s h i f t i n the time average value o f the
o u t p u t r e l a t i v e t o t h e s t e a d y s t a t e o u t p u t f o r a n i s o t h e r m a l CSTR w i t h
second order kinetics where the inputs are sinusoidal functions of time.
I t was found that a sinusoidal input concentration would increase the time
average conversion s l i g h t l y for a l l frequencies and amplitudes.

A combined

sinusoidal input flow and sinusoidal input concentration showed an increase


or a decrease i n time average conversion, depending on the amplitude, the

16

frequency, and the phase angle between the input flow and concentration,
A large amplitude, low frequency, and 180 phase angle gave the largest
increase i n time average conversion.

Results for the lower l i m i t of zero

frequency were obtained analytically and results at frequencies greater


than zero were obtained with the aid of an analog computer.

The authors

a l s o s h o w t h a t t h e t h e r m a l l y s e n s i t i v e n o n i s o t h e r m a l CSTR w h i c h g e n e r a t e s
stable oscillating outputs from constant inputs w i l l have a different
time average conversion than the corresponding steady state value.

De

p e n d i n g o n t h e p a r a m e t e r v a l u e s , t h e t i m e a v e r a g e c o n v e r s i o n may b e g r e a t e r
or less than the steady state conversion

This result can be deduced from

t h e r e s u l t s o f A r i s a n d Amundson ( 3 ) , b u t t h e s e a u t h o r s a r e i n t e r e s t e d i n
the stability of the steady state.

Douglas (13) gives an analytical method

for determining the frequency response to sinusoidal input? for the iso
t h e r m a l CSTR w i t h s e c o n d o r d e r k i n e t i c s .

The a n a l y t i c a l method i s to

a p p r o x i m a t e t h e n o n l i n e a r d y n a m i c s o f t h e CSTR b y u s i n g a p e r t u r b a t i o n
technique given by Minorsky ( 29. pp. 217-23!).

T h i s m e t h o d was f o u n d t o

agree well with results obtained from the analog computer at low f r e
quencies.
D o u g l a s a n d G a i t o n d e ( 1 5 ) sh ow t h a t a n o n i s o t h e r m a l CSTR w i t h a f i r s t
order chemical reaction and one singular point or steady state can be
forced to generate stable l i m i t cycles,

the size of which are determined by

the addition of ideal proportional control on the temperature


feedback tends to stabilize the reactor and decrease the size of

Negative
the limit

cycles and positive feedback tends to induce i n s t a b i l i t y i n the reactor


and increase the size of the l i m i t cycle.

A perturbation technique

17

(Minnrsky, 1962) of nonlinear mechanics i s used to evaluate the o s c i l l a t i n g


CSTR r e l a t i v e l - ih-. o p t u n a J s t e a d y s t a t e o p e r a t i o n .

Gai tonde and Douglas

(18) -xtenJ i.l.Cii u.r'iurh'.i'iun technique t o apply to any system o f 2 f i r s t


o r d e r n o n ) i nco.- i ; r : r , .r.t i ;;i ! e q u a t i o n s .
successful In n

I tciti ve -cnse

However, their work I s only

The d i r e c t i o n o f t h e s h i f t i n t h e

Vu i LiL . i f c!;i u i i . i i l a ; l ;)f| Vcir I a b l e c a n b e d e t e r m i n e d , b u t n o t t h e


f i i a g n i t u d e of- tf;;.

.luecaro. GaI tonde, and Douglas (4) obtained ex-

perimental ro..ui

i n r e a., l o r t e m p e r a t u r e o s c i l l a t i o n s I n a CSTR w h i c h

w a s d e s i g n e d c.. g. ,1^ , . j l c a s t a b l e l i m i t c y c l e .
expcr ii.ivni! 1

v ^ 11

The reaction used f o r the

tho hydrolysis of acetyl chlori de.

The

authors fou;sJ i;.uL ihoi ; e.eer 1 inencal results compared closely with the
iiuiiKM'I cc.i

In: I' ,

H o r i i ....i.i I :
lio.. e r pel i V

-/leni equations.

i : .

soHie g e n e r a l r e s u l t s c o n c e r n i n g t h e o p t i m i
, ...

lu..;.-'

cur

y i terns b y u s i n g a v a r i a t i o n a l a p p r o a c h .

C o n d i l i o n s i \ , i ..i.ich .-sr. v)f t i n,u:n s t e a d y s t a t e c a n b e i m p r o v e d b y p e r i o d i c


iiijcruiiuii
t i liii

I :, i : !..

u ori

t h e iii..A I ni ,1, t ;

..

. .

i':,,.
r

:uerc,: res . I t s i r c applied to the opu i e o p t i m u c i ceriipera t u r e c y c l e t o p r o d u c e

; i :> i i i s u'c l e r m i n e d .

Chang and Bankoff (8)

d e v e l o p e d cun.i" i t a t i v n -clier.ie b a i l e d o n t h e m e t h o d o f c h a r a c t e r i s t i c s t o
optii.iize a per i uei ou i i y ope rated jacketed tubular reactor i n which conu c c u t l v c r e a d i e r . : , e r e Ue ' n g c a r r i e d o u t .
r. I t / r i d t-h,.
,, '

i,,

f ; !' i !

y il.I il of
Vie 1 d.

The input i s perturbed sinusoid-

r.;i.'eer.x ui e input to maximize the time average y i e l d

.I':-:!:!

/" ^ l i o h t i n c r e a s e i n t h e t i m e a v e r a g e

i l i t e r - . ..".ii ti Ce I s I ..--ill / l u l l r c l a t i v e t o t h e o p t i m u m s t e a d y s t a t e

18

Larsen (23) introduces a special case of the semi batch operation cycle
used in this research work.

Larsen shows that the average y i e l d f o r semi-

b a t c h o p e r a t i o n r e l a t i v e t o t h e s t e a d y s t a t e y i e l d f o r t h e same a v e r a g e
r e s i d e n c e t i m e may b e i n c r e a s e d i n t h e i s o t h e r m a l CSTR w i t h f i r s t o r d e r
kinetics.

Lund and Seagrave (27) extend this work to show y i e l d increases

r e l a t i v e t o the steady state y i e l d f o r adiabatic semi batch operation with


a f i r s t order exothermic reaction

Fang and Engel

(17) also showed an

average y i e l d increase by semi batch operation r e l a t i v e t o the steady


s t a t e CSTR f o r i s o t h e r m a l f i r s t a n d s e c o n d o r d e r r e a c t i o n s .

Fang and

Engel verified their result- experimentally using the hydrolysis of acetic


anhydride i n water as the reaction system.

19

THE GENERAL EQUATIONS

The general equations are derived below f o r the variable-volume opera


t i o n o f a STR i n w h i c h a n e x o t h e r m i c r e a c t i o n w i t h a r b i t r a r y r e a c t i o n
k i n e t i c s i s occurring I n the horogeneous l i q u i d phase.
provided with a cooling jacket.

The reactor i s

The system i s depicted i n Figure 1.

T h e g e n e r a l e q u a t i o n s f o r t h e v a r i a b l e - v o l u m e STR a r e t h e n w r i t t e n i n
dimensionless form i n such a way t h a t the system variables are defined
w i t h r e s p e c t t o a r e f e r e n c e CSTR.

Finally, two performance c r i t e r i a are

d e f i n e d w h i c h e v a l u a t e t h e p e r f o r m a n c e o f t h e v a r i a b l e - v o l u m e STR w i t h
r e s p e c t t o t h e r e f e r e n c e CSTR.

These performance c r i t e r i a are called r e l a

tive y i e l d and relative throughput.

The general equations i n dimensionless

form provide the basis for computation of relative yield and relative
t h r o u g h p u t f o r d i f f e r e n t t y p e s o f v a r i a b l e - v o l u m e o p e r a t i o n o f t h e STR
discussed later in this thesis.
A m a t e r i a l a n d e n e r g y b a l a n c e a r o u n d t h e v a r i a b l e - v o l u m e STR y i e l d s
the following independent equations:
1-

overall volumetric balance


\J = V

2o

+ r ^ (Q. - d) dt
. ^
T
o

reactant j balance

dC.
dt
1, 2,

n independent reactions

(Eq. 1)

20

2-Qc(t)

Q:M.

T,(0
(V

v(0
A

A;

"Q(t)
Tcf

C^(t)
T(t)

Figure 1.

Schematic diagram of the


stirred tank reactor

21

3.

reactor thermal energy balance

dr

^
dt

(T, - T) +
f

n
Z

(-AH.)r

V q

pCp

pCp

(Eq. 3)

where q = ( - ^ ) (T-T^)

4.

Cooler thermal energy balance

dT^

Qp

Vq
' f q - 4)

The assumptions used in these equations are


1.

the reactor is well stirred, that is the reactor contents are


uniform i n concentration and temperature, and product is dis
c h a r g e d f r o m t h e r e a c t o r a t t h e same c o n c e n t r a t i o n a n d t e m p e r a
ture as the reactor contents

2.

the cooler is well stirred

3.

there i s no volume change due to reaction

4.

(-AH.) p,

Cp, Cp_, Qj,, V ^ , ( U A / V ) a r e c o n s t a n t .

(UA/V) i s

constant i f U is constant and A and V are both d i r e c t l y pro


portional to the liquid level in the reactor.

^ a n d T^. a r e

constant.
For s species and n independent reactions Equation 2 represents a
set of s reactant balances.

However, only n reactant balances are inde

pendent provided that the feed composition i s constant and that the i n i t
composition and i n i t i a l extent o f each reaction i n the reactor are conipat i b1e.
I n t h i s work computations v;erc performed using a reaction rate

22

c o n s t a n t t h a t was e i t h e r a l i n e a r f u n c t i o n o f t e m p e r a t u r e o r a n A r r h e n i u s
function of temperature.

Only irreversible reactions for which the rate

constant for the reverse reaction is zero are considered for the nonisothermal case.

The rate constant is expressed below as a linear func

tion of temperature and Arrhenius function of temperature respectively.


K =

+ b(T - T^)

(Eq. 5a)

K =

exp[- I "
g

(Eq. 5b)

(I- Y " ) ]
f

These equations may conveniently be put i n dimensionless form by


introducing the following dimensionless variables.

Cj = Cj/Caf

9 = t 0*/%^

T"' = T/T^

a"' = d/Qp

= K/Kf

(-AH.)'=
'

(Eq. 6)

Gf = 0^/0%

(-AH.)
:
(-AH,)

= V/V

The subscript R refers to the reference reactor.

The reference re

actor i s the (STR w i t h the same maximum volume, feed composition, and
feed temperature as the variable-volume STR.

The dimensionless concen

tration is determined with respect to the concentration of reactant A in


the feed stream.

The isothermal and adiabatic cases for the variable-

v o l u m e STR a r e s t u d i e d i n d e t a i l .

The reference reactor i s isothermal

f o r t h e c a s e o f t h e i s o t h e r m a l v a r i a b l e - v o l u m e STR a n d a d i a b a t i c f o r
the case of the adiabatic variable-volume STR.
When t h e d i m e n b i o n i e b b v a r i a b l e y a r e s u b s t i L u t e d i n t o E q u a t i o n s 1

23

through S, the following dimensionless equations result.

= V" + r (d* - Q ")de


o
J 9^
r

dCj'

Q:'
~

d0

(c"

- CV) + P

= ], 1,

dT

Q.r
=

7.

de

M"

G = - i L
de

(Eq. 7)

n
s

a,, r.

i=l

'

(Eq. 8)

n independent reactions
n
(1-T") + RP Z
;=i

Q_'- ( T
_ T P + NV
c
cf
c

.1.
(-AH;)" r " - M(T - T . " )
'
'
^

(T'-T )

(Eq, 9)

(Eq. 10)

K" = 1 + L (t"-1)

(Eq. 11a)

(Eq. l i b )

= exp[-L' ("^ -1)]


""'

The dimensionless parameters which appear i n the dimensionless equa


tions are defined below.
Relative Rate Constant

P = (see Table 1 )

Relative Thermal Energy

R = ("AH^^C^^/pCpT^

Reactor Heat Transfer


Parameter

^
"

, UA \
.
V ^ V^R^V

Srl^etr'
Linear Reaction Rate
Parameter

L = b T /K
f f

Arrhenius Reaction Rate


Parameter

L ' = E/PL T,
9 f

24

T h e e x p r e s s i o n s f o r r e a c t i o n r a t e , r'.', for the different types of re


action systems studied are given i n Table 1.
T h e g e n e r a l n o n i s o t h e r m a l o p e r a t i o n o f t h e v a r i a b l e - v o l u m e STR is n o t
considered i n the remainder of this work

Only the special cases of iso

thermal and adiabatic operation are considered

For the isothermal case

only Equations 7 and 8 are required to determine product concentrations.


Further, the feed temperature i s a r b i t r a r i l y assumed equal to the tempera
ture of the reactor contents, so that the reaction rate constant, K , i s
unity.

For the adiabatic case Equations 1, 8, 3, and 11 with M set equal

to zero must be solved simultaneously to determine concentration and


temperature profiles
The two performance c r i t e r i a , namely, r e l a t i v e y i e l d and r e l a t i v e
throughput, are defined below.

For a particular type of variable-volume

o p e r a t i o n e i t h e r c r i t e r i a may b e u s e d .

The two c r i t e r i a merely represent

different ways of evaluating the production rate of the variable-volume


STR w i t l ' i r e s p e c t t o t h e r e f e r c n c c CSTR.

The two c r i t e r i a are not inde

pendent and a method for determining r e l a t i v e throughput when the r e l a t i v e


y i e l d i s known i s presented.
Definition of relative yield

relative yield i s defined as the

r a t i o of the flow average product concentration from the variablei / o l u m e STR t o t h e c o n s t a n t p r o d u c t c o n c e n t r a t i o n f r o m t h e r e f e r e n c e


CSTR.

T h e v a r i a b l e - v o l u m e STR a n d t h e r e f e r e n c e CSTR h a v e t h e s a m e

maximum volume,

t h e same f e e d c o m p o s i t i o n a n d t e m p e r a t u r e , a n d t h e

same t i m e a v e r a g e t h r o u g h p u t o f p r o c e s s m a t e r i a l .
of product j is expressed mathematically by

The r e l a t i v e y i e l d

25

Table 1.

Rate expressions for reaction systems studied

Reaction

Dmensonless rate
expression,

system

Relative rate
constant, P

vH

K
A
i-B
isothermal

KfVM/Q%

K
A
>B
adi abati c

K C,

k
a;=B

''A " ^Ae

Kt

isothermal
K
2a
>b
i sothermal

-A-

-C
a

-.2

K"C;

KfCAfVM/%R

adi abati c
kj
a

k,

>b

>c

K
2A

r = C A Kp

i sothermal

kT

^2
[[

26

flow average concentration of j in product from


v a r i a b l e - v o l u m e STR
"i -

'

c o n c e n t r a t i o n o f j i n r e f e r e n c e CSTR

Cj / ([])%

(Eq. ]2)

J;

where C. =

da

-1
g

(Eq. 13)

P
r

d9

and 0p - 0p I i s the time interval f o r one variable-volume period


for which the concentration is a steady periodic function of time.

Definition of relative throughput

relative throughput is defined

as the r a t i o o f the time average throughput i n the variable-volume


STR t o t h e c o n s t a n t t h r o u g h p u t i n t h e r e f e r e n c e CSTR.

The variable-

v o l u m e STR a n d t h e r e f e r e n c e CSTR h a v e t h e s a m e m a x i m u m v o l u m e , t h e
same feed composition and temperature, and the same f l o w average
concentration of product from the reactor.

The relative throughput

is defined mathematically by

V -

time average throughput of


p r o c e s s m a t e r i a l i n v a r i a b l e - v o l u m e STR
constant throughput of process material
i p. r e f e r e n c e CSTR.

27

a/(Cl)^

(Eqo 14)

, 8p

9p
r

de
8p_,

where 0p - 9p_^ i s the length o f one variable-volume period.


I m p l i c i t i n the above definitions of relative yield and relative
throughput is the fact that the relative throughput is equal to unity i n
the definitions of r e l a t i v e y i e l d and vice versa.
Consider the r e l a t i v e y i e l d of product j t o be known as a function of
t h e r e l a t i v e r a t e c o n s t a n t , P

The concentration o f component j i n the

r e f e r e n c e CSTR i s d e t e r m i n e d b y s o l u t i o n o f t h e s t e a d y s t a t e f o r m o f t h e
general dimsnsiofiless equations.

The flow average concentration o f

c o m p o n e n t j i n t h e r e f e r e n c e CSTR a n d i n t h e v a r i a b l e - v o l u m e STR i s t h e n
given respectively by

( C I = c j f + f (,%, " i j r i ' R

f q -

' 5 )

Cj' = "ij ( c j ) ^

(Eq. 16)

Now t h e r e l a t i v e t h r o u g h p u t , v , m a y b e d e t e r m i n e d w i t h r e s p e c t t o a s e c o n d
r e f e r e n c e CSTR w h i c h h a s a c o n c e n t r a t i o n o f c o m p o n e n t j g i v e n b y

(c:),
J^R'

C:
J

w h e r e t h e s u b s c r i p t R ' d e n o t e s t h e s e c o n d r e f e r e n c e CSTR.

(Eq. 17)
The r e l a t i v e

28

t h r o u g h p u t w i t h r e s p e c t t o t h e s e c o n d r e f e r e n c e CSTR i s d e t e r m i n e d b y
solution of the steady state form of the general dimensionless equations
w i t h P replaced by PY.

Relative throughput with respect to the second

r e f e r e n c e CSTR i s t h e n g i v e n b y

Y =

'

-P ( Z

(Eq. 18)

. r.)^,

1 =1

After Y has been determined i n Equation 18^

the corresponding conversion

of component A is given by

(.%, "iA
1 =1

'9'

Equations 15; 16; 18; and 19 determine r e l a t i v e throughput as a function


o f flow average conversion of component A from a knowledge of r e l a t i v e
y i e l d versus r e l a t i v e rate constant and the steady state solutions t o
the general dimensionless equations.

29

CONSTANT VOLUME OPERATION

Solutions to the general equations i n dimensionless form for tran


s i e n t a n d s t e a d y s t a t e o p e r a t i o n o f t h e CSTR a r e g i v e n h e r e .

The steady

state solutions yield the dimensionless concentration, temperature, and


r e l a t i v e r a t e c o n s t a n t f o r t h e r e f e r e n c e CSTR a n d m a y b e u s e d l a t e r i n
the determination of relative yield and relative throughput for variablevolume operation.

T h e t r a n s i e n t a n d s t e a d y s t a t e s o l u t i o n s f o r t h e CSTR

aid in understanding the conditions for which variable-volume operation


o f t h e STR m a y r e s u l t i n a r e l a t i v e y i e l d o r r e l a t i v e t h r o u g h p u t g r ^ a t A r
than unity.
The dimensionless equations for constant volume operation are ob
tained from the dimensionless form of the general equations by setting
Q^/V

equal to unity.

Isothermal
T h e s t e a d y s t a t e c o n c e n t r a t i o n i n t h e CSTR i s e a s i l y d e t e r m i n e d f o r
the reaction schemes considered i n t h i s work.

The transient concentration

p r o f i l e in time can be determined analytically for the case of f i r s t


o r d e r r e a c t i o n s i n t h e CSTR.

These solutions are given i n Table 2.

Adi abatic
I n t h e a d i a b a t i c CSTR a l l o f t h e h e a t g e n e r a t e d b y t h e e x o t h e r m i c
reaction i s used to heat the incoming feed to the adiabatic operating
temperature.

T h e a d i a b a t i c CSTR a n d t h e i s o t h e r m a l CSTR a r e o p p o s i t e

e x t r e m e s o f t h e m o r e g e n e r a l n o n i s o t h e r m a l CSTR.

30

Table le

Solutions to isothermal constant volume equations

Reaction
scheme

Steady state
concentration, C

A^B

C ^ ' = l / ( 1 + P)

Transient concentration
profile, C"(9)

C^' = ~

(l-exp[-(l+P)0])

+ C^'(O) e x p [ - ( l + P ) e ]

I+PC"

1+ P C "
" "T+p (i-exp[-(i+p)e])

k'
+

2a _ ! L , r

K,

2A

K,
40

r"

(2P

(0) exp[-(l+p)e]

+n - s/ ( 2 P + ] ) ^ - 4P^

- d + P ) +i
(1+ P ) ^ + 4 P K ,C

Cg = P C ^ / C I + P K ^ / K ^ )

/K

31

Single reacti on of arbi trary order


The reaction rate for a single reaction i n which each species con
centration can be r e l a t e d t o the extent o f reaction may be expressed as a
function of the concentration of species A and temperature
r* = r"(C*

T*).

Figure 2 shows the form o f curves of constant reaction rate f o r the exo
t h e r m i c i r r e v e r s i b l e r e a c t i o n i n t h e (1 -

T ) plane.

At steady state

t h e d i m e n s i o n l e s s f o r m o f t h e g e n e r a l e q u a t i o n s f o r t h e CSTR b e c o m e
1 - C^' - P r ' " ' ( T " ' ) = 0

(Eqo 2 0 )

1 - t " + RP r ' ' ( C ^ ; T " ) = 0

(Eq, 21 )

Equations 20 and 21 may be combined t o eliminate r

and give the energy

balance line
I - C^' =

^ T

-i

(Eq. 22)

Equation 22 also holds for the adiabatic plug flow reactor.


i s p l o t t e d a s l i n e FG i n F i g u r e ^ .
d u c t s t a t e s f r o m t h e a d i a b a t i c CSTR.
point (Oj I)o

Equation 22

FG g i v e s t h e l o c i o f a l l p o s s i b l e p r o
FG a l w a y s c r o s s e s t h e T

axis at the

T h e s l o p e o f FG i s d e t e r m i n e d b y t h e f e e d c o n d i t i o n s f o r a

particular reaction.

This i s apparent from the definition of R.

R.

(Eq. 23)
p Cp T ^

K is the

dimensionless adiabatic temperature rises

At complete con

version
K = t " - lo

(Eq. 24)

32.

TEMPERATURE, T "
Figure 2.

Loci of constant reactic# rate for an exothermic


irreversible reaction
The curves are lines of constant reaction rate

33

I f t h e v a l u e s o f r e a c t i o n r a t e a l o n g FG a r e p l o t t e d a g a i n s t c o n
version, 1 -

the reaction r a t e w i l l go through a maximum a t (1 -

corresponding t o p o i n t A on FG.

The slope of this curve i s called the

a d i a b a t i c d e r i v a t i v e o f r e a c t i o n r a t e b y A r i s (1^ C h a p t e r 8 ) a n d i s
given by
r " ( C T*) =
d(l-C^)

A t a p o i n t A o n FG
d (l-C^)/dT

= 1/R

production rate,
p o i n t Ao

+ R

(Eq. 25)
ST"

d ^ r / d ( l - C ^ ) = 0^ a n d i t f o l l o w s t h a t
a t p o i n t A

From Equation 20 i t i s seen that the

( l " C ^ ' ) / P j i n t h e a d i a b a t i c CSTR i s a l s o a m a x i m u m a t

Aris (1, Chapter 8) also shows that i f the energy balance l i n e

f o r a d i a b a t i c o p e r a t i o n i s g i v e n b y l i n e FG i n F i g u r e 2 , t h e n t h e l e a s t
residence time is achieved under the following conditions:
1.

I f a conversion less than (1-C^)^ is desired,

then the least

r e s i d e n c e t i m e i s a c h i e v e d i n t h e a d i a b a t i c CSTR
2.

I f a conversion greater than (1-C^)^ is desired,

then the

l e a s t t o t a l r e s i d e n c e t i m e i s a c h i e v e d b y a n a d i a b a t i c CSTR
with conversion

followed i n series by an adiabatic

plug flow reactor to increase the conversion to the desired


value.

T h i s i s c a l l e d t h e o p t i m a l a d i a b a t i c CSTR a n d p l u g f l o w

reactor combination
The average reaction rate i s a maximum i n the optimal reactor combina
tion.

In general,

the reactor type w i t h the maximum average reaction

rate w i l l require the least residence time to operate at a specified


convui siOil.

34

T h e s t a b i l i t y o f t h e s t e a d y s t a t e i n a n a d i a b a t i c CSTR i s a l s o a n
important consideration.

A knowledge of the s t a b i l i t y of the steady

state w i l l give insight into the stability problems to be expected with


the adiabatic variable-volume
a d i a b a t i c CSTR.

5TR.

Consider Equations 20 and 22 for the

The l o c i o f Equations 20 and 22 i n the (1-C^,T ) plane

a r e d e n o t e d b y l i n e s a n d l i n e FG r e s p e c t i v e l y i n F i g u r e 3^

The i n t e r

s e c t i o n o f l i n e s w i t h FG r e p r e s e n t s t e a d y s t a t e s o l u t i o n s t o E q u a t i o n s
20 and 22.

I f a n a d i a b a t i c CSTR i s o p e r a t i n g a t s t e a d y s t a t e C , a

slight increase i n residence time w i l l ignite the reaction and the steady
state w i l l shift to steady state I .

Similarly a slight decrease i n

r e s i d e n c e t i m e i n a n a d i a b a t i c CSTR w i t h s t e a d y s t a t e E w i l l c a u s e t h e
reaction to be blown out, and the steady state w i l l s h i f t to A.

I f the

r e f e r e n c e a d i a b a t i c CSTR h a s t h e s t e a d y s t a t e c o r r e s p o n d i n g t o p o i n t E ,
t h e r e a c t i o n m a y b e b l o w n o u t i n t h e a d i a b a t i c v a r i a b l e - v o l u m e STR,
since the instantaneous residence time i n the adiabatic variable-volume
STR may d e c r e a s e b e l o w t h e r e s i d e n c e t i m e i n t h e r e f e r e n c e a d i a b a t i c
CSTR.

Also the r e a c t i o n may be r e i g n i t e d as the instantaneous residence

t i m e i s i n c r e a s i n g i n t h e a d i a b a t i c v a r i a b l e - v o l u m e STR.

The possi

b i l i t y of such a blowing out and reigniting of the reaction i s

much

l e s s w h e n t h e r e f e r e n c e a d i a b a t i c CSTR h a s s t e a d y s t a t e J a n d d e v i a t i o n s
of the instantaneous residence time in the adiabatic variable-volume
STR a r e s u f f i c i e n t l y s m a l l a b o u t t h e a v e r a g e r e s i d e n c e t i m e w h i c h
c o r r e s p o n d s t o t h e r e s i d e n c e t i m e i n t h e r e f e r e n c e a d i a b a t i c CSTR.

Of

course, t h i s analysis does not apply accurately to the variable-volume


STR s i n c e i t o p e r a t e s i n a t r a n s i e n t m a n n e r .

However, the possibility

35

increasing residence
time

TEMPERATURE, T

Figure 3.

Loci of material and energy balance lines for


the adiabatic continuous stirred tank reactor

36

of this very undesirable type of operation is s t i l l present.

Only i f the

r e s i d e n c e t i m e i n t h e v a r i a b l e - v o l u m e STR c h a n g e s v e r y s l o w l y s o t h a t
steady state conditions are always present, w i l l the above analysis be
correct,

Fi rst order reactions


S t e a d y s t a t e a n d t r a n s i e n t o p e r a t i o n o f t h e a d i a b a t i c CSTR a r e c o n
sidered
reaction.

here for the case of an exothermic and irreversible f i r s t order


The rate constant, K , i s assumed to be a linear function of

temperature as given by Equation 11a.


Stead, state operation

At steady s t a t e che dimensionless form;

of the general equations become


1 - C* - PK" C ^ = 0

(Eq. 26)

1 - T

(Eq. 2?)

+ RPK"C^' = 0

K" = 1 + L (T" - 1 )

(Eq. 1 l a )

The i n t e r s e c t i o n of the material balance 1 i tie ueLermined by Equation


26 and the energy balance l i n e determined by Equation 22 i n the (1-C^,T )
plane gives the steady state operating point.

Since the rate constant,

K , i s a linear function of temperature, there can be only one possible


steady s t a t e operating point f o r fixed values o f R, L, and P.

(If the

rate constant, K , were given by the Arrhenius equation, then as many as


3 steady states would be possible.)

The steady state operating p o i n t

always satisfies the necessary condition for stability

There i s no

i g n i t i o n p o i n t o r b l o w o u t p o i n t f o r t h e r e a c t i o n i n t h e a d i a b a t i c CSTR-

37

E q u a t i o n s 26, 21, a n d H a m a y b e s o l v e d s i m u l t a n e o u s l y t o g i v e c o n
centration as a function of R, Lj and P.

The r e s u l t i s

The rate constant, K , the temperature, T , and the reaction r a t e , r ,


may also be w r i t t e n as a function o f Rj L, and Po
T ; K j and r
eters.

plotted against

Figures 4 and 5 show

log^gClOO P) with R and L as param

The analog computer was used to generate these plots using

log^Q (100 P) as the independent variable.

The p l o t of reaction rate

versus conversion of reactar,t A i n Figure 6 i s a plot of the values of


reaction rate along the energy balance line.

The slope of the curve f o r

reaction rate versus conversion in Figure 6 i s the adiabatic derivative


d e f i n e d b y E q u a t i o n 25

For values of conversion for which the adiabatic

d e r i v a t i v e i s p o s i t i v e , a n a d i a b a t i c CSTR w i l l a c h i e v e t h e g r e a t e s t c o n
version.

For values of conversion for which the adiabatic derivative i s

n e g a t i v e , t h e o p t i m a l a d i a b a t i c CSTR a n d p l u g f l o w r e a c t o r c o m b i n a t i o n
w i l l achieve the greatest conversion
From Equation 28 i t i s seen that R and L always appear as the pro
d u c t RLo

Therefore
= C^tRL, P).

(Eqo 2 9 )

B y c o n s i d e r i n g E q u a t i o n s 1 1 a , 2 2 , 26, a n d 2 8 i t i s s e e n t h a t
K' = K'(RL,P)

(Eq. 30)

(Eqo 31)

= r

(RL, P)

T " = T " ' ( R , L , P ) .

(Eq. 32)

R a n d L m p p p A r A s t h e p r o d u c t RL i n t h e s e e x p r e s s i o n s b e c a u s e t h e

Figure h.

Concentration and temperature versus the logarithm


of the relative rate constant

DI MENS IONLESS CONCENTRAT I ON,

DIMENSIONLESS TEMPERATURE,

T"

VD

Figure 5.

Reaction rate and rate constant versus


the logarithm of the relative rate constant

0 1 MENS IONLESS RATE

DI MENS IONLESS REACTION RATf,K

5 \

,o

CONSTATN,K"

o
o

CO

CO

42

RL = 80

RL = 60

RL = 40

.4

CONVERSION, ( I - C

Figure 6.

Reaction rate vs. conversion for an exothermic


reaction under adiabatic conditions

43

rate constant, K , i s a linear function of temperature.

If K

were given

by the Arrhenius expression, a l l the variables would depend on the i n


d i v i d u a l v a l u e s o f R , L , a n d P
The maximum production r a t e , given by (1-C^)/P, occurs when the r e
action r a t e i s a maximum and the adiabatic derivative i s zero.

The maxi

mum r e a c t i o n r a t e a n d c o r r e s p o n d i n g v a l u e s o f t h e o t h e r v a r i a b l e s m a y b e
determined as a function of

RLo

The r e s u l t i n g expressions are given

below.

(i<)
P

= r - =
-Amax
max

4RL

(Eq. 33)

max

(Eq. 3 5)
max

T'V"

(RL+1)

= I + ^ - jj-

(Eq. 36)

max

(Eq. 37)

max

I t ' i s i n t e r e s t i n g t o n o t e t h a t ( 1 - C ^ ) ...
approaches . 5 as RL becomes
r
max
1argeo
Transient operation

Some t r a n s i e n t s o l u t i o n s o f t h e c o n s t a n t

v o l u m e a d i a b a t i c CSTR e q u a t i o n s w e r e d e t e r m i n e d .

The analog computer

was used t o solve the system o f equations, since analytical solutions o f


these coupled and nonlinear f i r s t order differential equations are not

44

known.

P l o t s o f t h e r e s u l t s a r e s h o w n i n F i g u r e s 7^ 8 ^ a n d 9 .

The e f f e c t

o f the product RL i s shown i n Figure 1 , and the e f f e c t o f the r e l a t i v e


r a t e constant, P, i s shown i n Figure 8 .

During the transient operation,

the concentration and the rate constant and thus the reaction velocity
depend on the product RL, as has also been shown for steady state opera
tion.

This i s shown by combining the transient equations and thereby

obtaining one second order d i f f e r e n t i a l equation i n which R and L always


occur i n combinationo

For a given RL,

the reaction rate attains larger

values during the transient operation than the steady state reaction rate
only f o r values of the r e l a t i v e rate constant, P, greater than P *
max
Figure 9 shows the e f f e c t o f the i n i t i a l concentration o f reactant,
C ^ ( 0 ) , i n t h e r e a c t o r o n t h e t r a n s i e n t b e h a v i o r f o r f i x e d P a n d RLo I t
i s interesting to note that the transient reaction rate goes through the
only for the
maximum value, r ^ ^ ^ f o r values o f P greater than P max
unrealizeable case where the i n i t i a l dimensionless concentration is equal
to unity.

Figure 7.

Effect of heat sensitivity on the transient


behavior of the adiabatic continuous stirred
tank reactor

DIMENSIONLESS TEMPERATURE,

N3

(jy

DIMENSIONLESS REACTION RATE,

T"

K C

O
o
3:

o
m

es
o
ro
O

00

I
O

m
<D

w
o

o
DIMENSIONLESS CONCENTRATION,

Figure 8.

Effect of the relative rate constant on the


transient behavior of the adiabatic continuous
stirred tank reactor

DIMENSIONLESS TEMPERATURE,

Ln

ro
o

DIMENSIONLESS RUCTION RATE,^

K C

O
O

n 7\

o
oo
CO
H
3:

W
o

o
o

o
o

o
o

DIMENSIONLESS CONCENTRATION,:

Figure 9.

Effect of i n i t i a l concentration in the reactor


on the transient behavior of the adiabatic
continuous stirred tank reactor

DIMENSIONLESS

CONCENTRATION.

DIMENSIONLESS REACTION RATE.

C
A

cn
O
m

CO
CO

II

II

K C^

31

VARIABLE-VOLUME OPERATION

The p h r a s e " v a r i a b l e - v o l u m e o p e r a t i o n " o f a STR i s u s e d t o d e n o t e a


p e r i o d i c o p e r a t i o n o f t h e STR f o r w h i c h t h e d r i v i n g f o r c e i s a p e r i o d i c
r e s i d e n c e t i m e f u n c t i o n , V/Q,^.

I n g e n e r a l t h e p e r i o d i c f e e d and d i s c h a r g e

rates for the reactor which determine the volume and residence time w i l l
generate a variable volume which i s a periodic function of time.
Two v a r i a b l e - v o l u m e o p e r a t i o n s a r e c o n s i d e r e d .

They a r e semi c o n t i n u

ous variable-volume operation and continuous variable-volume operation.


Semi b a t c h o p e r a t i o n , w h i c h i s a s p e c i a l c a s e o f s e m i c o n t i n u o u s v a r i a b l e volume operation, i s considered i n detail, since fewer parameters are i n
volved in the analysis.

Furthermore, sem:batch operation results i n a

relative yield or relative throughput greater than that obtained by the


more general semicontinuous variable-volume operation for the case of a
single reaction

in the isothermal reactor.

I n o r d e r f o r v a r i a b l e - v o l u m e o p e r a t i o n o f t h e STR t o o c c u r t h e f e e d
flow rate must be alternately greater and less than the discharge flow rate
during the variable-volume cycle-

Tha p a r a m e t e r s u s e d t o d e t e r m i n e t h e

variable=volumc cycle are, i n general, a measure of the amplitude and


frequency o f the feed and discharge flow rates and the phase angle between
the feed and discharge flow rates.

An i n c r e a s e i n r e l a t i v e y i e l d a n d

r e l a t i v e t h r o u g h p u t i s o b t a i n e d when t h e d i s c h a r g e f l o w r a t e i s s u c h t h a t
p r o d u c t i s d i s c h a r g e d a t a l o w r a t e when t h e p r o d u c t c o n c e n t r a t i o n i s l o w
i n the reactor and product i s discharged from the reactor at a high rate
when t h e p r o d u c t c o n c e n t r a t i o n i s h i g h i n t h e r e a c t o r .

52

Reactor F i l l i n g and Emptying


The semi c o n t i n u o u s c y c l e f o r s e m i c o n t i n u o u s v a r i a b l e - v o l u m e o p e r a
t i o n o f t h e STR a l w a y s h a s some p o r t i o n s o f t h e c y c l e d e v o t e d t o f i l l i n g
and emptying the reactor.

The s o l u t i o n s t o t h e d i m e n s i o n l e s s f o r m o f t h e

general equations for the case of a f i r s t order reaction i n an isothermal


STR a r e g i v e n b e l o w

These solutions are used i n the determination of

analytical expressions for relative yield and relative throughput for


t h i s c a s e b y semi b a t c h o p e r a t i o n

loO

R e a c t o r f i l l i n g (Q.^ = 1 , Q =0^

ci; =
A

2o0

V (0) = V^) :

[1 - (PV*C*(0)-1) e x p ( - P 9 ) ] o

P(V^+8 )

(Eq. 38)

R e a c t o r E m p t y i n g (Q.

= 1^ Q.^ = 0 , V (O) = 1 ) ;

Ca = 0 ^ ( 0 ) e x p ( - P 0 ) o

3.0

(Eq. 39)

R e a c t o r F i l l i n g {Q.'^ > Q." > 0, \l" (0) =

Consider only the

time interval required to f i l l the reactor.

No l o s s i n

g e n e r a l i t y o c c u r s i f i t i s s p e c i f i e d t h a t Q.r = 1 .

An a n a

l y t i c a l s o l u t i o n c a n b e d e t e r m i n e d i f Q.^ i s a n i n t e g e r m u l t i p l e
of

(Qj! - Q. ) o

df
;
(Of-

This condition i s expressed mathematically by

I
=

= n (an integer)

I - 0"
n 1J

I f n = 2 and v" = 0,
by

(Eq. 40)

3^

o Q

the concentration of rcactant A i s given

53

[*=

2rP9-l +exp(-P9)l

(Eq. 4,)

(p^r

F o r t h e g e n e r a l c a s e t h e s o l u t i o n becomes

fl, + [(Pnv;)" t - ( 0 ) -

exp(-P9)

C =

[Pn(/ + e /n ) l "
where
Aj = n[Pn(Vg + 0/n) ] " ^-n(n-1) [Pn(\/^+0/n)l" ^...+ (-1)" 'n(n-l).'

Ag = n [ P n V g ] " ' - n ( n - 1 ) [ P n V ^ ] " ^

4.0

'n(n-l).'

R e a c t o r E m p t y i n g (Q," > Q." > 0 , V " ( 0 ) = 1 ) ;

Consider only the

time interval required to empty the reactor.


a n a l y t i c a l s o l u t i o n c a n b e d e t e r m i n e d i f Q.
p l e (Q.'^ - Q. ) .

= I.

is an integer multi

This condition is expressed mathematically by

r% =

G-Of

Set

= m (an integer)

' - Of

(Eq. 43)

m= ^ 3, 4, . . .

For the special case where n = 2, the concentration of reactanc


A is given by
= ( 1 - f l / m ) [Pm- (Pm-C^(O) ) e x p ( - P 0 ) - B P m e x p r P n i ( l + 0 / m ) 3 ] ( E q . 4 4 )
where

1/
(-t)
B =

L
k=l

k
(Pm) [ 1 - ( t - 8 / m ) ^ l
- 1n(}-0/m).
K.KJ

F o r t h e g e n e r a l c a s e t h e s o l u t i o n becomes
.

m-2

" li&yy

(-I)J (Pm)J(m-2-j).'Kl-9/m)J-(l-e/m)"- 'exp(-PO)l

j=0

(Eq. 45)
4- C%(0)

( l - 0 / m ) ^ ^ ' c x p ( - P 9 ) + ( - l ) ^ ^ r p m ( l - 8 / m l ^ ' e x p r P m ( l - 0 / m ) ]B

54

I t can be seen that the expressions for the concentration of rea c t a n t A a r e much m o r e c o m p l i c a t e d i f t h e r e i s a p o s i t i v e d i s c h a r g e
f l o w r a t e w h e n f i l l i n g t h e r e a c t o r o r a p o s i t i v e f e e d r a t e when e m p t y i n g
the reactor.

Semi c o n t i n u o u s V a r i a b l e - V o l u m e O p e r a t i o n
The c y c l e f o r semi c o n t i n u o u s o p e r a t i o n o f t h e STR i s shown i n F i g u r e

10 a n d t h e c y c l e f o r semi b a t c h o p e r a t i o n o f t h e STR i s shown i n F i g u r e


]].

The e q u a t i o n s w h i c h d e s c r i b e t h e semi c o n t i n u o u s c y c l e a n d t h e s e m i -

batch cycle are given i n Table 3 and Table 4 respectively.

These cycles

are divided into fractions i n which a different residence time function,


V'/Q,^, i s used for each fractiono
the input flow,

There results a flow pattern i n which

i s alternately greater and less than the output flow.

The semi c o n t i n u o u s c y c l e i s m o r e g e n e r a l t h a n t h e semi b a t c h c y c l e


i n t h a t a n i n p u t a n d o u t p u t f l o w r a t e may b e p r e s e n t d u r i n g t h e f i l l i n g ,
b a t c h , a n d e m p t y i n g f r a c t i o n o f t h e semi c o n t i n u o u s c y c l e o

F o r t h e semi =

batch cycle, feed i s introduced into the reactor only during the f i l l i n g
fraction- and product is discharged only during the emptying fraction of
t h e semi b a t c h c y c l e .
The f o l l o w i n g e q u a t i o n s m e r e l y d e f i n e p a r a m e t e r s w h i c h a r e c o n
v e n i e n t c o l l e c t i o n s o f o t h e r p a r a m e t e r s f o r t h e semi c o n t i n u o u s c y c l e .
These parameters are used t o simplify equations given l a t e r .
= 0 - 9
F
r
O

(Eq. 46a)

(Eq* 4 6 b )

= 0

- 9

Figure 10.

T h e semi c o n t i n u o u s c y c l e

DIMENSIONLESS DISCHARGE,

(D
a
"1

DIMENSIONLESS FEED, Q

DIMENSIONLESS

VOLUME, V

F i g u r e 11

T h e semi b a t c h c y c l e

DIMEN5IONLESS FEED,

DIMEN5IONLESS DISCHARGE, Q
o
o

o
o

DIMENSION LESS VOLUME, V

1;

3:
m

%
z.

r*
m
U")

CD

a>

59

(Eq. 46c)

'D

(EQo 46d)

- P = 0 "

(Eq. 46e)

%-

(Eq. 46f)

S'

(Eq. 46g)

^0 "f

T a b l e 3

Batch

(Eq. 46i)

*P
"B " "E

(Eq. 46j)

"D = '

Equations for the semicontinuous cycle

Operation/
fraction of
cycle

Filling

(Eq. 46h)

"C '

T i me

Feed Rate
n"

eo< 9 < Gp
.< 8 <

Empty!ng

8 o < 9 < 9r

Down

8E< 8 < *0

'fB

-fE

+1^1, ( f)

f ^ p ' 4 (Sp) - 4 (?) + Qj (5,)

(<F - 'IP

V o l ume
V*

^fP

Cons t r a l n i n q E q u a t i o n s
5p = V ( ?p) +

Discharge
: Rate

'fB
Q."

1.0

i+(Q.f^-Q.) (9-9g)

6o

Table 4.

E q u a t i o n s f o r t h e semi b a t c h c y c l e

Feed
Rate

Time

Operation/
fraction of
Cycle

Di s c h a r g e
Rate

Volume
v"'

-,v

8^<8

Batch

0p < 0

Emptyi ng

OC
DC

Down

UL
DC

CD

OC
DC

CD

Of F

DC

Filling

CD
m

%f

Cl""'

\* < F (

<
0

1 - Qp

S -V

(e -

0g)

v"
0

Constraining Equations
Y

"

Y ^ = 1 - V"
0
II

The v o l u m e o f r e a c t i n g f l u i d i n t h e r e a c t o r a n d t h e f e e d and d i s
charge flow rates are determined as a function of time f o r the general
semicontinuous cycle by fixing eight parameters

The i n s t a n t a n e o u s r e s i

d e n c e t i m e f u n c t i o n , V / Q ^ , may t h e n b e d e t e r m i n e d b y f i x i n g t h e f o l l o w
ing eight parameters.
V /Q.^ -

(V / Q ^ )

T p , T g , Tp}

''7)

F o r t h e semi b a t c h c y c l e t h e v o l u m e o f r e a c t i n g f l u i d a n d t h e f e e d a n d
discharge flow rates are determined as functions of
parametersc

The p a r a m e t e i ' b may b e f i x e d a s f o l l o w s .

time by fixing five

61

=(V"/Q.'^)

(Vg, Op, Pg,

(Eq. 48)

Y)

I n t h e STR i n w h i c h t h e m i x i n g o c c u r s o n t h e m o l e c u l a r s c a l e , t h e
conversion of reactant depends on the reaction kinetics and the residence
time distribution of material leaving the reactor.

Therefore, a knowledge

o f t h e r e s i d e n c e t i m e d i s t r i b u t i o n o f m a t e r i a l l e a v i n g t h e STR d u r i n g s e m i c o n t i n u o u s o p e r a t i o n becomes

important.

The average residence time of

m a t e r i a l l e a v i n g t h e STR d u r i n g s e m i c o n t i n u o u s o p e r a t i o n i s a p e r i o d i c
function of time.

There w i l l be a different residence time distribution

f o r each point i n time during the semi continuous cycle.

This is unlike

the steady state operated reactor i n which there is one residence time
distribution which applies for a l l values of time.
An equation f o r the residence time distribution function and the
r e s i d e n c e t i m e f r e q u e n c y f u n c t i o n f o r a n u n s t e a d y s t a t e STR h a v e b e e n
d e v e l o p e d b y Nauman

(30) and are given respectively by

r
9
) = exp - r
"9-8'

,v

,v

(dr/V

)d0

(Eq. 49)

(Eq. 50)

where S(9,9') = fraction of material leaving the reactor at time 0 which


remained in the reactor for a duration of time greater
than 9 ' , i.e. fraction of material leaving at 0 ' which
entered before 9 - 9 ' .

Note that the symbol 9 denotes

dimensionless real time while 9' denotes dimensionless


residence time.
The average dimensionless residence time tor material leaving the

62

u n s t e a d y r e a c t o r a t t i m e 0 i s g i v e n b y Nauman ( 3 0 ) a s
03
t( 0 ) = r

9 'g ( 9 , 9 ')d8' .

(Eq. 5 0

T h e a v e r a g e r e s i d e n c e t i m e as g i v e n b y E q u a t i o n 51 a p p l i e s f o r b o t h t h e
m a t e r i a l l e a v i n g t h e STR a n d t h e m a t e r i a l i n t h e S I R d u e t o t h e a s s u m p t i o n
o f p e r f e c t m i x i n g i n t h e STR.
E q u a t i o n s 4 9 ; 5 0 ; and 51 w e r e u s e d t o d e t e r m i n e t h e r e s i d e n c e t i m e
d i s t r i b u t i o n f u n c t i o n , t h e r e s i d e n c e t i m e f r e q u e n c y f u n c t i o n , and t h e
a v e r a g e r e s i d e n c e t i m e f o r m a t e r i a l l e a v i n g t h e STR d u r i n g semi b a t c h
operation.
Table 5 gives expressions for the residence time distribution func
tion and the residence time frequency function for any real time during
the f i l l i n g fraction of the semibatch cycle.

Table 6 gives expressions

f o r t h e r e s i d e n c e t i m e d i s t r i b u t i o n and t h e r e s i d e n c e t i m e f r e q u e n c y
d u r i n g t h e b a t c h , e m p t y i n g , a n d down f r a c t i o n s o f t h e s e m i b a t c h c y c l e .
These residence time functions are discontinuous at values of residence
Vv* "J:
t i m e ; 9 ' ^ f o r w h i c h t h e f u n c t i o n Q,^/\/ i s d i s c o n t i n u o u s .
F i g u r e 1 2 shows a p l o t o f t h e r e s i d e n c e t i m e f r e q u e n c y f u n c t i o n f o r
an absolute time, 8^, which corresponds to the end of a semibaich cycle.
The t i m e , 9 ^ , i s assumed l a r g e e n o u g h s o t h a t t h e a v e r a g e r e s i d e n c e t i m e
is a steady periodic function of real time.
curve is unity.

The total area under the

i f t h e maximum r e s i d e n c e t i m e i s f i n i t e , t h e f r e q u e n c y

function at the point where residence time is equal to real time is given
by the Dirac delta function, defined by

Table 5*

Equations for residence time distribution and frequency functions for any real time
during the f i l l i n g f r a c t i o n of the semi batch cycle

Residence Time

Residence Time
Distribution Function

S(8,9')

A I

Cycle

"o + SfF(-o-e')

R e s i d e n c e T i me
Frequency Function
g(0,8')
fF

O S S ' ^ 3 - 0

\ " %'fF

g 9'

6 9-9

+ $ -
F F
"o + 1'fF ("-o'

n- I
(S-^o)

$p ^ 0 '

"o^"o

+ tp-g'))

+ ifF

^ ( G - G g ) + 5p

9^+(j-l )

0'

-0 + jSf -

G'-O

fF

^ 9-2o + J ^

^f- < G '


r

"o + <F

{\iy ( v ; + o - f F ^ Q - y j S p - 8 ' ) )
V'o +

(G-Go)

(<>"' I f F
+ OfF (G-^o)

6(9-8 )

a' = 0
\ * fF ' " " ' c '

ON
V-O

Table 6.

Equations for the residence time d i s t r i b u t i o n and frequency functions for any real time
during the batch, emptying, or down fractions o f the semi batch cycle
R e s i d e n c e T i me
Distribution Function
S(9,0')

Res i dence Time


Cycl e

0 ^ 9 '
"

n - 1 "<v

g(0,0-)

^ -

9-9^ < G'

g 0-0p +

Sp,

+ Q., ( 0 - 0
Tr

+ $

- 9 ' )

fF

0 - 0 + $ <; 0 ' <" Q"Q +


F
"P
F
T
9-0 +c

s 0' < 0-0 +6 +5

9-0p +(j-1)
n-j

Residence Time
Frequency Function

^ 9-0

*p +

"o ^fF

Sp 3 9 '

+ j5

9-0 P+ j $p & 9 ' < 0 - 0 | _ + j ? p + 5 j .

9' = 0

(Vg^j (V^+'i^j-(0-0p+j 5p+$p-0'))

(v;)

OfF

6(8' - 8)

Figure 12.

R e s i d e n c e t i m e f r e q u e n c y f u n c t i o n f o r semi b a t c h
operation of the stirred tank reactor
this figure gives the residence time frequency
function at a real time corresponding t o the end
of the
semi b a t c h c y c l e w h e r e n a p p r o a c n e s i n f i n i t y
semibatch cycle parameters:
,j

=cr
F

=0.25, Y = 1.0
L

= 0.2, a

= 0.5,

bb

s.oor

4.00

3.00

z
o
u

D
u_

>
u 2.00
z
LU
D

1.00

JZL

o.ooL
0.0

0.8

1.6
2.4
DIMENSION LESS RESIDENCE TIME, 0'

3.2

4.0

67

9V 0

0' = a

6(0'-0) =

The a r e a u n d e r

(Eq. 52)

t h e r e s i d e n c e t i m e frequency function curve at residence

time 0' = 0 is given by


CO

6 ( 8 ' - 9 ) K ) " d9' = (V%)"

J g

(Eq. 53)

F i g u r e 13 shows a p l o t o f t h e a v e r a g e residence time of material i n


the SIR during semi batch operation versus real time.

Figure 13 shows that

the average residence time goes through a transient at small values of


real time.

The smooth curve i n Figure 13 gives the average residence

time of tracer material i n a CSTR where real time and residence time are
measured from the instant when tracer material is introduced into the re
actor as a step change i n concentration.

The residence time frequency

f u n c t i o n f o r t h e CSTR i s g i v e n b y
e

-0'

d>^ 9

a{9,9') =

.
0

(Eq. 54)

9'>9

As r e a l t i m e a p p r o a c h e s i n f i n i t y , the average residence time of tracer


material i n the CSTR approaches u n i t y .

As the minimum volume is increased

toward the maximum volume, the average residence time curve shown i n
Figure 13 for semi batch operation of the STR w i l l approach the average
r e s i d e n c e t i m e c u r v e s h o w n f o r t h e CSTR.
An a v e r a g e r e s i d e n c e t i m e f u n c t i o n which is independent of real time
may be defined for semi continuous or semibatch operation of the STR.

This

is called the flow average residence time for material discharged from the
STR during one periodic cycle and is given i n dimensionless form by

68

u 1.00

>0.40
S 0.20

y 0.00

1/1

0.8

2.4

3.2

4.0

4.8

DIMENSIONLESS REALTIME, 9

UJ

Figure 13.

Average residence time of material i n the


semi b a t c h o p e r a t e d s t i r r e d t a n k r e a c t o r
versus real time
semi b a t c h c y c l e p a r a m e t e r s ;

V^" = 0.2,

= 0.5,

= 0.25, i' = 1.0

curve A - average residence time In the reference


continuous stirred tank reactor
c u r v e B - a v e r a g e r e s i d e n c e t i m e d u r i n g semi b a t c h
operation of the stirred tank reactor

5.6

69

Ci'\(o)de

(Eq. 55)
r

oTdo

^p-i

w h e r e t h e r e a l t i m e , 9 , i s l a r g e e n o u g h s o t h a t T( 0 ) i n E q u a t i o n 5 ' i s a
steady periodic function.
The f l o w a v e r a g e r e s i d e n c e t i m e ,

, f r o m E q u a t i o n 5 5 may b e s i m p l y

e x p r e s s e d as a f u n c t i o n o f t h e s e m i b a t c h c y c l e p a r a m e t e r s f o r s e m i b a t c h
operation of the SIR.

The e x p r e s s i o n i s

(-F

_ 1

'^E)

(Eq. 56)

~
E q u a t i o n 56 i s m o s t d i r e c t l y
1)

obtained by the following steps:

Evaluate 7(0) i n Equation 5' at a time 0^ approaching


i n f i n i t y where 7(8) i s a steady periodic function.

The

result is

I P!

2)

;('p) =

In the time interval


T( J ) ,

(Eq. 57)

0^ the average residence time,

i n c r e a s e s a t t h e same r a t e as r e a l t i m e , s i n c e f r e s h

feed is not being introduced into the reactor.


t ( J ) may b e e x p r e s s e d i n t l i e i n t e r v a l J

r(U) - ; l 'p)

3)

Therefore

^ 0 ^ by

(Eq. 58)

S u b s t i t u t i o n o f E q u a t i o n 5 8 i n t o E q u a t i o n 55 and i n t e g r a t i o n

70

over the time interval for emptying the reactor results i n


E q u a t i o n 56 a b o v e .
E v a l u a t i o n o f E q u a t i o n 56 f o r t h e s e m i b a t c h c y c l e o f F i g u r e 1 3 g i v e s
a value for the flow average residence time, T, equal to 0.8.

T h i s means

that the material discharged from the reactor during the emptying fraction
o f t h e s e m i b a t c h c y c l e was i n t h e r e a c t o r f o r a n a v e r a g e t i m e e q u a l t o
8 0 p e r c e n t o f t h e r e s i d e n c e t i m e f o r m a t e r i a l i n t h e r e f e r e n c e CSTR.
As t h e m i n i m u m volume i n c r e a s e s t o w a r d t h e m a x i m u r v o l u m e t h e f l o w
a v e r a g e r e s i d e n c e t i m e , T , f o r semi c o n t i n u o u s o r s e m i b a t c h o p e r a t i o n
approaches unity.

E q u a t i o n 56 shows t h a t t h i s r e l a t i o n s h i p i s l i n e a r f o r

the case of semibatch operation of

t h e STR.

Figure 14 is a plot of the

f l o w a v e r a g e r e s i d e n c e t i m e , T , as a f u n c t i o n o f m i n i m u m v o l u m e f o r s e m i b a t c h o p e r a t i o n o f t h e STR.

T h u s , i t may b e e x p e c t e d t h a t t h e p e r f o r m a n c e

o f t h e s e m i b a t c h o p e r a t e d STR w i l l a p p r o a c h t h e p e r f o r m a n c e o f t h e CSTR
a s t h e m i n i m u m v o l u m e f o r semi c o n t i n u o u s o r s e m i b a t c h o p e r a t i o n a p p r o a c h e s
t h e maximum v o l u m e o f t h e CSTR.
A n o b v i o u s o b s e r v a t i o n f r o m t h e r e s u l t s shown f o r t h e

dimensionless

flow average residence time, T, and the dimensionless average residence


time, T(0), i s that their upper bound is unity.

Intuitively, this must

be the case, since the throughput of material per cycle for semicontlnuous
o p e r a t i o n o f t h e STR i s t h e same as t h e t h r o u g h p u t I n t h e r e f e r e n c e CSTR
a n d t h e a v e r a g e v o l u m e p e r c y c l e f o r semi c o n t i n u o u s o p e r a t i o n o f t h e STR
i s l e s s t h a n t h e v o l u m e o f t h e r e f e r e n c e CSTR.

Isothermal
R e s u l t s f o r r e l a t i v e y i e l d and r e l a t i v e t h r o u g h p u t h a v e b e e n

71

.00

H 0.95

UJ

u
z
LU
Q 0.90
00

LU

cm

0.85

3 0.80

CD

<
en

LU

LL.
00

oo

0.75

LJ
_J

o
00

z 0.70
LU

0.2

0.0

0.4

0.6

0.8

1.0

DIMENSIONLESS M I N I M U M VOLUME, V

Figure ]4.

Flow average residence time of material discharged


from the semi batch operated s t i r r e d tank reactor
during one steady periodic semi batch cycle versus
minimum volume
fixed semi batch cycle parameters;
efj. =

= 0.25, Y = 1.0

O g = 0.5

72

d e t e r m i n e d f o r t h e i s o t h e r m a l c a s e o f s e m i c o n t i n u o u s o p e r a t i o n o f t h e STR
for various reaction kinetics.

These results are discussed below for the

various kinetics.
First order reactions

Concentration profiles were determined for

s e m i c o n t i n u o u s o p e r a t i o n o f t h e STR f o r d i f f e r e n t f e e d f l o w r a t e a n d d i s
charge flow rate functions i n the semi continuous cycle.

The concentra

t i o n p r o f i l e s and the corresponding semi continuous cycles were obtained


by an analog computer simulation of the reactor system and are shown i n
Figures 15; l 6 ; and 17.

Figure 17 shows the special case o f semi continu

ous operation, namely, semi batch operation, that i s studied i n d e t a i l .


The feed and discharge flow rate p r o f i l e s are d i f f e r e n t for each figure
as indicated, and the resulting concentration p r o f i l e s serve t o show the
effect of changing the flow profiles.
F i g u r e 1 5 s h o w s a n e x a m p l e o f a CSTR w i t h a c o n s t a n t f e e d r a t e a n d
a variable discharge rate.

By inspection i t is clear that the flow

average conversion uT itactani: i n the discharge stream is less for semic o n t i n u o u s o p e r a t i o n o f t h e STR t h a n i n t h e r e f e r e n c e CSTR.
relative yield of product is less than unity.

Thus the

I t was found t h a t f o r any

semi batch cycle for which the reactor i s fed or discharged a t a constant
continuous rate, the relative yield is less than unity.
since the average value of

This is expected

the residence time is less than the residence

t i m e i n t h e r e f e r e n c e CSTR.
A compdfison o f Figures l 6 and 17 shows that the presence o f a feed
and discharge stream throughout the semi continuous cycle results i n a
biiidllct

( c l a t l v t yield than that obtained when a l l the feed i s charged t o

Figure 15.

Yield decrease by semi continuous operation o f the


sti rred tank reactor

semicontinuous cycle parameter:


Q.fg =

Qp = CTg = 0 , 0 ^ 2

= 0 . 2 , Cp =

~ I'O, ^ = 1.0

= 0.5,

DIMENSIONLESS VOLUME, V"


o

o
o

r-

D I M E N S I O N L E S S FLOW R A T E S , Q . ^ ' \ Q "


NJ
O

o
o

CTN

._i

4^

rm

VI
VI

O
Z

DIMENSIONLESS CONCENTRATION, C

1
1

I
I
I
t
iO

/O
Mi

QJ
3
TT
-J
a>
0)
o
rf
o
-t

o
o
3
3
C
O
c
cn
rf
n
"1
fO
Q-

"O
II
vn

Figure 16.

Yield decrease by semi continuous operation


of the stirred tank reactor
semi continuous cycle parameters:
(tj- =
Y = 1.0

= 0.5, og = o-fb " = 0.0,

= 0.2,
= op

= 0.5,

DIMENSIONLESS VOLUME,
o

oo
O

V"

DIMENSIONLESS FLOW RATES,

o
o

N5
O

DIMENSIONLESS CONCENTRATION,

ro

'-t-

C,

CTN

c/>
c/>

m
CD

-P-

Figure 17.

Yield increase by semi batch operation o f the


stirred tank reactor
semi batch cycle parameters:
a

= 0.0, Y = 1.0

= 0 . 2 , CTp =

= 0.5,

DIMENSIONLESS
VOLUME, V"

o
o

m
z
CO
O

UT

DIMENSIONLESS CONCENTRATION,

DIMENSIONLESS
FLOW RATE, a/%

c
C

N>
O

o
o

ro

-P-

ro

CO

c/o

uu

CD

0 in

C^'^

79

the reactor during the f i l l i n g fraction and a l l the product is discharged


from the reactor during the emptying f r a c t i o n of the semi continuous cycle.
The r e l a t i v e y i e l d i s greater for the semi continuous cycle of Figure 17
than f o r the semi continuous cycle o f Figure 16.

In fact, relative yield

i s greater than unity for the case shown i n Figure I 7 .


S i n c e t h e r e l a t i v e y i e l d i s g r e a t e r i n t h e STR u s i n g t h e s p e c i a l
case o f semi continuous operation called semi batch operation, the r e l a t i v e
yield and r e l a t i v e throughput by semi batch operation are studied i n d e t a i l .
An analytical expression can be determined f o r r e l a t i v e y i e l d and r e l a t i v e
throughput for semi batch operation of the STR.
consist of

The system of equations

the dimensionless general equation for concentration in the

STR g i v e n b y E q u a t i o n 8 , t h e e q u a t i o n s d e s c r i b i n g t h e s e m i b a t c h c y c l e
given i n Table 4 , and the d e f i n i t i o n s o f r e l a t i v e y i e l d and r e l a t i v e
throughput given by Equation 12 and Equation 14 respectively.
Relative y i e l d o f product may be expressed as a function o f the f i v e
parameters shown i n Equation 59 below.

T1 = T1(V^, O p , G g , C g , P )

(Eq. 59)

Equation 59 's arrived at by considering the following.


1)

t h e f u n c t i o n \i /Q,^ i s d e t e r m i n e d a s a f u n c t i o n o f t h e p a r a m
eters

2)

shown i n Equation 48

the relative throughput i n Equation 48 is set equal to unity


due to the d e f i n i t i o n of relative yield

3)

the concentration p r o f i l e f o r a given semi batch operation


can be determined by specifying the relative rate constant,
P, i n Equation 8.

80

R e l a t i v e throughput may be expressed as a f u n c t i o n o f the f i v e param


eters

shown i n Equation 60 below.

Y = Y ( V * , O p , O g , G g , "Xa)

( E q - GO)

Equation 60 is arrived at by considering the following;


1)

when

is specified, P is determined i n Equation 8

2)

the relative yield must be equal to unity by the definition


of relative throughput.

3)

the relative throughput is determined by solving simul


taneously Equation 8 , Equation 12 with r e l a t i v e yield set
equal to unity, and Equation 48.

The solutions to the system of equations for r e l a t i v e yield and


relative throughput are given respectively by

1+p
H=

exp[-Pgg(l-Vg)] (l-exp[-Pgj-(1-V^) ])

(1-expT-Pg^ (1-V^) ]

1 ~

P^Op

(1-Vg) (l-V^ expr-P(l-V^)])


(Eq. 61)

1/2
Op

(l-V^) (l-V^ exp

^0^
(1-X^) Y

Y =
(1-a.p

exp
(I-\)Y

-Ve"-"o'
(i-Xa) Y

(I-X^) Y

J
(Eq. 62)

Equation 6l gives relative yield explicitly.


implicit in Equation 62.

Relative throughput is

Equation 62 i s a transcendental equation and

cannot be solved e x p l i c i t l y for relative throughput.

Relative y i e l d and

81

r e l a t i v e t h r o u g h p u t i n E q u a t i o n s 6l a n d 62 a r e g i v e n w i t h r e s p e c t t o t h e
s a m e r e f e r e n c e CSTR i n w h i c h t h e r e l a t i v e r a t e c o n s t a n t , P , a n d t h e f l o w
average conversion of A,

are related by

X^=P/(1+P).

(Eq. 63)

When the r e l a t i v e y i e l d i s known as a f u n c t i o n o f the r e l a t i v e r a t e con


s t a n t i n Equation 6 l , then the r e l a t i v e throughput f o r the same semi batch
cycle i s also determined as a function o f the flow average conversion of
A given by
\

(Eq. 64)

The r e l a t i v e throughput at the conversion of A given by Equation 64 is


determined as a function o f r e l a t i v e y i e l d by the application o f Equations
16 and 18.

The r e s u l t is

Figure 18 shows p l o t s o f r e l a t i v e y i e l d versus


stant for d i f f e r e n t semi batch cycles.
lated from Equation 6 l ,

the relative rate con

The results i n Figure 18 were calcu

Figure 19 shows p l o t s of r e l a t i v e throughput

versus flow average conversion of reactant A as determined by Equations


64

and 65 .
Effect of relative rate constant

an i

The r e l a t i v e rate constant i s

lependent parameter i n Equation 59 for relative yield.

I t is impor

tant to note that the parameters for the semi batch cycle alone do not
d e t e r m i n e h o w t h e s e m i b a t c h o p e r a t e d STR w i l l p e r f o r m w i t h r e s p e c t l u t h e
r e f e r e n c e CSTR.

The value of the r e l a t i v e r a t e constant i s equally

F i g u r e J8o

Effect of relative rate constant and batch fraction on


r e l a t i v e y i e l d by semi batch operation o f the isothermal
stirred tank reactor

CO

CONSTANT

F i g u r e 19=

Effect o f flow average concentration and batch


f r a c t i o n on r e l a t i v e throughput by semi batch
operation of the isothermal stirred tank reactor

30.0
20.0

10.0

0.01

0.02

0.05

0.10

0.20

DIMENSIONLESS FLOW AVERAGE CONCENTRATION/]

0.50

- y )

1.00

86

important-

At low values of the relative rate constant, which correspond

to a small conversion of reactant, the relative yield is less than unity


and steady s t a t e operation i s preferred t o semi batch operation o f the STR.
As t h e r e l a t i v e r a t e c o n s t a n t i s i n c r e a s e d t h e r e l a t i v e y i e l d g o e s t h r o u g h
a maximum value greater than u n i t y as shown i n Figure 18.

The maximum

value o f relative yield and the corresponding reactant conversions i n


Figure 18 for the semibatch cycle with c^= 1.0 and

= 0 are

T| = 1 . 3 a t P = 1 . 8
= 0 . 6 4 4 i n t h e r e f e r e n c e CSTR
= 0 . 8 3 4 i n t h e s e m i b a t c h o p e r a t e d STR
Thus the maximum increase i n y i e l d f o r t h i s case of semibatch operation
is thi rty percent.
From Equation 6 l i t can be shown that

pTco

= 1.0

pi^O ^ = "o - 3 "7 * i

(Eq. 66)

+ 'E + 'f)

67)

For the semibatch cycles shown i n Figure 18, Equation 67 reduces to

pITo ^

+ Cp

Effect of flow average reactant conversion

(Eq. 68)

The flow average

r e actant conversion is an independent parameter i n Equation 60 for rela


tive throughput.

The relative throughput i s a monotonie increasing

function o f the flow average conversion o f reactant as shown i n Figure 19At high values of flow average reactant conversion the relative throughput

87

i s g r e a t e r t h a n u n i t y a n d s e m i b a t c h o p e r a t i o n o f t h e STR i s p r e f e r r e d t o
t h e CSTR.
T h e v a l u e s o f r e l a t i v e t h r o u g h p u t a t z e r o a n d 100% c o n v e r s i o n a r e
given by

VZ 1
Aa I

(Eq. 69)

/2 0 ' ' "o - 3

"i H-v'o) (2% + 'E + "F'

7)

For the semi batch cycles shown i n Figure 19; Equation 70 reduces t o
2'"^

Y = !j

+ Cfp

(Eq. 71 )

V "
These l i m i t i n g values of relative throughput are evaluated using Equation
65 and noti ng that
1 im

Y
1

2'" '
X
0

= 1 im

(Eq. 72)

P- ^

(Eq. 73)
P- 0

Effect of semibatch cycle parameters

The e f f e c t on r e l a t i v e

yield of the parameters which determine the semibatch cycle are discussed
below.

I t can be deduced from Equation 65 that a change i n the r e l a t i v e

y i e l d w i l l change the r e l a t i v e throughput i n t h e same d i r e c t i o n .

There

f o r e , the d i r e c t i o n o f the change i n r e l a t i v e throughput is known f o r a


change i n a semibatch cycle parameter.

88

Effect of batch fraction

Figure 18 shows that the upper

bound of relative yield with respect to the batch fraction, ag, is achieved
w h e n Og i s e q u a l

to unity.

This corresponds to instantaneous f i l l i n g and

e m p t y i n g o f t h e r e a c t o r , a n d t h e s e m i b a t c h - o p e r a t e d STR b e c o m e s s i m p l y a
batch reactor for each semibatch cycle.

The i n i t i a l concentration i n the

batch reactor is equal to the volumentric average of the fresh feed


charged t o the reactor and the concentration of the material remaining i n
the reactor from the previous cycle.
perfect mixing.

This i s due to the assumption of

An expression f o r the upper bound of r e l a t i v e y i e l d w i t h

respect to the batch fraction is obtained by taking the limit in Equation


6 ] as shown below.

(l-VQ)exp[-P(]-VQ)]
(Eq. 74)

1 im T] = [ -^ ]
1-Vg exp[-P {] - \ l ]

Effect of minimum volume

From Equation 61 i t is found

[exp(-Pog) [l-exp(-Pop) ] r i -exp(-Pa^) 1

that
n ( v ; = 0) = [

]
P

Op Gp
(Eq, 75)

and

(Eq. 76)

1 i m T| = 1
V

- 1

As t h e m i n i m u m v o l u m e , V ^ , a p p r o a c h e s u n i t y , t h e t i m e p e r i o d f o r a s e m i batch cycle decreases until at

= 1, the semibatch cycle has disappeared

a n d t f i e p e r f o r m a n c e o f t h e CSTR i s r e a l i z e d .
D i f f e r e n t i a t i o n o f E q u a t i o n 6 1 s h o w s t h a t T, ( V ^ - 1 ) - 1 as g i v e n b y

89

Equation 76 i s e i t h e r a maximum or minimum, since the equation

(11(0 ) = 0
dV"
o

(Eq. 77)

-J;
is satisfied only at V

= 1 in the interval 0 ^ V

^1.

Therefore, rela-

tive yield is either a monotonie increasing or monotonie decreasing


function o f the minimum volume i n the interval 0 i \ l

^ 1.

This leads to

the following two results;


1)

i f Tl(\/^) > 1 f o r some semi batch operations, then the r e l a t i v e


y i e l d w i l l be a maximum w i t h respect t o minimum volume a t
V

2)

yV
o

= 0.

I f TlfV^) < 1 f o r some semi batch operation, then the r e l a *


t i v e y i e l d w i l l have the maximum value o f u n i t y a t V = 1
'

'

f o r which the semi batch cycle has disappeared and the


p e r f o r m a n c e o f t h e CSTR i s r e a l i z e d .
Effect of unequal f i l l i n g and emptyi ng times
o f the f i l l i n g and emptying fractions o f the semi batch cycle,

I f the sum
+ a^, is

held constant, then i t is readily seen i n Equation 61 that the relative


y i e l d is symmetric w i t h respect to the f i l l i n g and emptying fractions.
Furthermore, the r e l a t i v e y i e l d i s a maximum w i t h respect t o the f i l l i n g
and emptying fractions o f the semi batch cycle when the f i l l i n g f r a c t i o n is
equal to the emptying fraction.
The optimal semi batch cycle

The optimal semibatch cycle i s

defined as the semibatch cycle which affords a maximum r e l a t i v e y i e l d or


relative throughput with respect to the semibatch cycle parameters.
above discussion on the effects of the semibatch cycle parameters on

The

90

r e l a t i v e y i e l d and r e l a t i v e throughput lead t o the following specifications


for the optimal semi batch cycle.
1)

the minimum volume,

is equal to zero.

2)

the batch fraction,

i s as l a r g e a s p o s s i b l e .

A batch

fraction equal to unity requires instantaneous f i l l i n g and


emptying and cannot be achieved i n any real reactor.
3)

the f i l l i n g fraction, jp, is equal

to the emptying

fraction,
4)

the down time i s zero.

The respective equations f o r the optimal r e l L i i v e y i e l d as a function


o f r e l a t i v e r a t e constant and the optimal r e l a t i v e throughput as a function
of flow average conversion of reactant are

(I-exp[-P9p])

1+ P

(Tl)

exp[-P9g]
(Eq. 78)

1 -

OPTIMAL

OPTIMAL

(Y)
1-

, 1
exp
.( I - X j ) * .
(Eq. 79)

exp

The upper bounds for the relative yield and relative throughput with
respect t o the optimal semi batch cycle occur when the batch f r a c t i o n , a^,
of the semi batch cycle i s equal

to unity.

The equations for the upper

bound o f r e l a t i v e y i e l d as a function of the r e l a t i v e r a t e constant and


the upper bound of r e l a t i v e throughput as a f u n c t i o n o f f l o w average

91

conversion of reactant are given respectively by

(11) UPPER

" exp[-P]

(Eq. 80)

BOUND
x/(i-x.)

c/c-V)

When t h e b a t c h f r a c t i o n o f t h e s e m i b a t c h c y c l e i s u n i t y a n d t h e m i n i
mum v o l u m e ,

is equal

t o zero, the reactor i s operating as a batch r e

actor w i t h instantaneous f i l l i n g and emptying or equivalently as a continu


ous plug flow reactor w i t h the same residence time.

The upper bound of

relative yield expressed by Equation 80 gives the ratio of plug flow re


a c t o r c o n v e r s i o n t o s t e a d y s t a t e CSTR c o n v e r s i o n f o r t h e s a m e r e s i d e n c e
time and feed conditions.

The upper bound of r e l a t i v e throughput ex

p r e s s e d b y E q u a t i o n 8 1 g i v e s t h e r a t i o o f t h e s t e a d y s t a t e CSTR r e s i d e n c e
time t o the plug flow reactor residence time f o r the same conversion and
feed condi tions.
General characteris t i cs of semi batch operati on

The general

c h a r a c t e r i s t i c s o f t h e s e m i b a t c h o p e r a t i o n o f t h e STR w h i c h m a y b e u s e d t o
explain why i t i s possible to obtain a r e l a t i v e y i e l d and a r e l a t i v e
throughput greater than unity are determined by

considering

c h a r a c t e r i s t i c s o f t h e CSTR a n d t h e p l u g f l o w r e a c t o r .

the

In the plug flow

reactor there is no mixing of material with different levels of concen


tration.

I n t h e CSTR t h e c o n t e n t s a r e c o m p l e t e l y m i x e d s o t h a t t h e c o n

centration in the reactor is uniform.

U p o n e n t e r i n g t h e CSTR t h e f e e d c o n

centration drops immediately to the concentration of

the rcactor contents.

92

T h e s e m i x i n g c h a r a c t e r i s t i c s o f t h e p l u g f l o w r e a c t o r a n d t h e CSTR a r e
combined i n the semibatch operation o f the STR.

Therefore, the semi batch

o p e r a t i o n o f t h e STR m a y b e v i s u a l i z e d a s s i m u l a t i n g a l e v e l o f m i / . ' , n g
b e t w e e n t h e m i x i n g l e v e l s i n t h e p l u g f l o w r e a c t o r a n d t h e CSTR.

Further

more, the average r e a c t i o n r a t e f o r a s i n g l e r e a c t i o n i s a maximum i n the


p l u g f l o w r e a c t o r a n d a m i n i m u m i n t h e CSTR f o r t h e i s o t h e r m a l c a s e .

Thus

the decrease i n mixing has the e f f e c t of increasing the average reaction


r a t e f o r s e m i b a t c h o p e r a t i o n o f t h e STR r e l a t i v e t o t h e CSTR a n d a r e l a
t i v e y i e l d and r e l a t i v e throughput greater than u n i t y may be obtained.
I t i s also seen t h a t f o r some cases of semibatch operation the r e l a
t i v e y i e l d and r e l a t i v e throughput may be less than u n i t y .

This may be

explained by the fact that the flow average residence time of material
discharged from the reactor per semibatch cycle is less than the residence
t i m e o f m a t e r i a ] l e a v i n g t h e CSTR.

When t h e d e c r e a s e i n f l o w a v e r a g e

residence time more than compensates for the increase i n average reaction
rate by semibatch operation, the relative yield and relative throughput
o b t a i n e d b y s e m i b a t c h o p e r a t i o n o f t h e STR a r e l e s s t h a n u n i t y .
Revers ible f i r s t order reactions
completion.

No chemical reaction goes t o

The irreversible reaction is merely a l i m i t of the rever

s i b l e reaction as the equilibrium constant becomes i n f i n i t e l y large.

The

isothermal reversible reaction can be treated as an i r r e v e r s i b l e reaction


i f concentration is measured I n excess of the equilibrium concentration.
Relative yield and relative throughput were determined analytically
for this case for semibatch operation or

the STR.

Tlie system of equations

93

i s the same as f o r the case o f the f i r s t order i r r e v e ; - i b l e reaction ex


cept that the reaction rate term and the relative rate constant are modi
f i e d as given by Table 1.

The resulting expression for relative yield of

t h e p r o d u c t B i s g i v e n b y E q u a t i o n 6 l , w i t h P as d e f i n e d i n T a b l e 1 .

The

resulting expression for relative throughput is given by Equation 62 with


replaced by
A.

where

is the equilibrium conversion of reactant

Thus the form o f the analytical expressions f o r r e l a t i v e yield and

r e l a t i v e throughput i s the same f o r the r e v e r s i b l e and i r r e v e r s i b l e case


o f the f i r s t order reaction i n the semi batch operated STR.

Figure 18 for

r e l a t i v e y i e l d with P defined i n Table 1 and Figure 19 for r e l a t i v e


throughput with

replaced by X^/X^^ are correct for the reversible f i r s t

order reaction.
i t follows t h a t the same semi batch cycle i s optimal f o r both the
reversible and i r r e v e r s i b l e f i r s t order reaction i n the isothermal STR.
Second order reactions

Larger values of r e l a t i v e y i e l d and rela

t i v e throughput are attained when the reaction i s second order than when
the reaction is f i r s t order.

I t i s well known that f o r a given reactor

volume and conversion the r a t i o of throughput i n the plug flow reactor


t o t h r o u g h p u t i n t h e CSTR i s a l w a y s g r e a t e r t h a n u n i t y f o r r e a c t i o n s o f
order greater than zero, and that this r a t i o increases w i t h increasing
reaction order.

Therefore, since the plug flow reactor gives the upper

bounds of r e l a t i v e y i e l d and r e l a t i v e throughput by semi batch operation


f o r the f i r s t order r e a c t i o n , i t i s reasonable t o assume the same t o be
true for second order reactions, or more generally for reactions of
arbitrary positive order.

The expressions for the upper bounds of r e l a t i v e

94

y i e l d and relative throughput for the second order reaction of Table 1 are
then given respectively by

2p2
(TL)

=
UPPER
BOUND

;
(l+P) r (2P+l)- V 4P+1 ]

(Eq. 82)

WuppER=

(Eq.83)

BOUND

T h e g e n e r a l e q u a t i o n f o r c o n c e n t r a t i o n i n t h e STR i s n o n l i n e a r a n d
probably cannot be solved analytically.

Therefore, an analytical ex

pression f o r r e l a t i v e yield and r e l a t i v e throughput f o r semibatch opera


tion cannot be obtained.

An analog computer simulation of semibatch opera

t i o n o f t h e STR w a s u s e d t o d e t e r m i n e r e l a t i v e y i e l d a n d r e l a t i v e t h r o u g h
put.
Figure 20 and Figure 21 show results obtained f o r r e l a t i v e y i e l d and
r e l a t i v e t h r o u g h p u t r e s p e c t i v e l y f o r s e m i b a t c h o p e r a t i o n o f t h e STR f o r
second order reactions.

Any semibatch operation which has the batch

f r a c t i o n equal t o the f i l l i n g f r a c t i o n , the minimum volume equal t o 10


percent o f the maximum volume, and the down time equal

to zero, will give

values of r e l a t i v e y i e l d and r e l a t i v e throughput between the upper and


lower curves i n Figures 20 and 21 r e s p e c t i v e l y .

comparison of the re

s u l t s f o r f i r s t order reactions and for second order reactions shows that


larger values of relative yield and relative throughput are obtainable by
semibatch operation for the case of second order reactions.
Single reactions of arbitrary positive order

Similar to the

statement f o r second order reactions, i t i s reasonable to assume that

F i g u r e 20

Limiting cases of relative yield by semibatch operation of


tank reactor with second order kinetics
Curve A - plug flow reactor
Curve B - sgmibatch operation of the stirred tank reactor,
=

Oo 1 J

'jg

Od Oj

gp =

Oo 5

the stirred

1.4

RELATIVE RATE CONSTANT,

Figure 21.

Limiting cases o f relative throughput by


semi batch operation o f the s t i r r e d tank reactor
with second order kinetics
Curve A - plug flow reactor
Curve B - semi batch operation o f the s t i r r e d
tank reactor.
= 0.1,
= 0.0,
Cp = Cg = 0.5

98

50.0

20.0

10.0

0.01

0.02

0.05

0.1

0.2

0.5

DIMENSIONLESS FLOW AVERAGE CONCENTRATION, ( 1 - X )

1 . 0

99

relative yield and relative throughput w i l l increase with increasing re


action order and that the plug flow reactor, which i s a l i m i t i n g case of
semi batch operation of the STR, w i l l give the upper bounds for r e l a t i v e
y i e l d a n d r e l a t i v e t h r o u g h p u t b y s e m i b a t c h o p e r a t i o n o f t h e STR f o r r e
actions of arbitrary positive order.

Furthermore, i t is reasonable to

assume t h a t two semi batch cycle parameters, namely, minimum volume, V^,
and batch f r a c t i o n , a^, w i l l have q u a l i t a t i v e l y the same e f f e c t s on r e l a
t i v e y i e l d and r e l a t i v e throughput for a l l reactions of positive order.
These assumptions are based on knowledge of the performance of the plug
f l o w r e a c t o r r e l a t i v e t o t h e CSTR.

However, these jssumptions have not

been verified.
For the case of f i r s t order reactions the r e l a t i v e yield and rela
tive throughput are maximized with respect to the f i l l i n g and emptying
f r a c t i o n o f the semibatch cycle when the f i l l i n g f r a c t i o n i s equal to the
emptying fraction.

However, i t i s not reasonable to expect this to be

true for reactions of order other than unity, since the general equalion
for concentration, Equation 8, is nonlinear for reactions of order
different from unity.
Van De Vusse reactions
Table I .

The Van De Vusse reactions are shown i n

They form a simple example o f a reaction system composed of

both consecutive and higher order side reactions

(32).

When c o n s e c u t i v e r e a c t i o n s w i t h h i g h e r o r d e r s i d e r e a c t i o n s o c c u r i n
a reactor, the yield of the desired intermediate product is greatly in
fluenced by the mixing level in the reactor.

I n the case of consecutive

reactions the plug flow reactor, i n which there is no mixing or reacLants

100

of different concentrations, w i l l produce a greater yield of intermediate


p r o d u c t t h a n w i l l t h e CSTR, i n w h i c h t h e m a x i m u m m i x i n g o f r e a c t a n t s
o c c u r s i n o r d e r t o p r o d u c e a u n i f o r m c o n c e n t r a t i o n w i t h i n t h e CSTR.

In

the case of parallel reactions where the undesired side reactions are of
h i g h e r o r d e r , t h e CSTR w i l l p r o d u c e a g r e a t e r y i e l d o f t h e d e s i r e d p r o d u c t .
When b o t h c o n s e c u t i v e a n d h i g h e r o r d e r s i d e r e a c t i o n s a r e o c c u r r i n g , t h e
choice of a reactor type is governed by the relative values of the re
action r a t e constants and reactant concentrations, and i n some cases a
l e v e l o f m i x i n g b e t w e e n t h e CSTR a n d t h e p l u g f l o w r e a c t o r w i l l g i v e t h e
maximum y i e l d o f the desired intermediate product.
S e m i b a t c h o p e r a t i o n o f t h e STR m a y b e v i s u a l i z e d a s a s i m u l a t i o n o f
a l e v e l o f m i x i n g b e t w e e n t h e CSTR a n d t h e p l u g f l o w r e a c t o r .

Thus, semi-

b a t c h o p e r a t i o n o f a STR m a y r e s u l t i n a y i e l d o f d e s i r e d i n t e r m e d i a t e
p r o d u c t w h i c h i s g r e a t e r t h a n t h e CSTR y i e l d .

Furthermore, the yield by

s e m i b a t c h o p e r a t i o n m a y b e g r e a t e r t h a n t h e y i e l d o f e i t h e r t h e CSTR o r
plug flow reactor f o r some values o f the reaction parameters f o r systems
of consecutive reactions with higher order side reactions.
For the Van De Vusse r e a c t i o n scheme i t was therefore investigated
whether, i n f a c t , the yield, (C'g), of the desired intermediate could be i n
c r e a s e d b y s e m i b a t c h o p e r a t i o n o f t h e STR o v e r t h e y i e l d o b t a i n e d i n t h e
CSTR o r i n t h e p l u g f l o w r e a c t o r .

Yield of the desired intermediate is

defined as the f l o w average dimensionless concentration o f the i n t e r


mediate product B i n the discharge from the reactor, C^.

Once the y i e l d ,

(Cg), i s known, r e l a t i v e y i e l d i s simply calculated fnom Equation 12.


However, results are presented here simply as y i e l d i n such a way that

101

t h e r e l a t i v e y i e l d w i t h r e s p e c t t o t h e CSTR o r t h e p l u g f l o w r e a c t o r i s
readi1y apparent.
The general equations i n dimensionless form cannot be solved ana
l y t i c a l l y to determine the concentration profiles during semi batch opera
t i o n of the STR.

The concentration profiles during the semi batch cycle

and y i e l d o f intermediate B were determined by numerical solution of the


equations using the d i g i t a l computer and by simulation of the process on
the analog computer.
are given in Table 2.

A n a l y t i c a l s o l u t i o n s f o r c o n c e n t r a t i o n s i n t h e CSTR
Van De Vusse (32) gives analytical solutions f o r

concentrations in the plug flow reactor.


An analysis o f the system o f equations f o r semi batch operation of the
STR s h o w s t h a t t h e f l o w a v e r a g e c o n c e n t r a t i o n o f t h e r e a c t i o n s p e c i e s m a y
be given as a function o f the parameters shown i n the following equations.

(P; Og)

"B

"B

VK^/K^)

"B' "F' "E' "o'

C q = Cg ( P ; Og^ Op;

(P, Og, Op,

(Eq. 84a)

"3 'Af/*i'

Kg/K,, Kg C^f/K,)

. 84c)

(Eq. 84d)

S o m e r e s u l t s f o r y i e l d o f B , ( C g ) , b y s e m i b a t c h o p e r a t i o n o f t h e STR
are shown i n Figures 22 and 23.

Figure 22 shows a case where the reaction

r a t e constant (K^ C^^) f o r the higher order side reaction i s small com
pared to the reaction rate constant (Kg) for the degradation of B.

The

r e s u l t i s that the y i e l d o f B,(Cg), may be greater f o r see:batch operation


of the STR, as i s seen for the semibatch cycles of Figure 22, than the

102

K^/K

0.40

0.30

0.20

UJ

0.10

v.u

0.0

0.2

0.4

0.6

0.8

FLOW AVERAGE CONVERSION, X


Figure 22.

Yield of intermediate B in different reactor


systems w i t h Van De Vusse reactions versus
conversion of feed component
Curve A - plug flow reactor
C u r v e B a n d C - s e m i b a t c h o p e r a t i o n o f t_b,e
s t i r r e d t a n k r e a c t o r . \ Iq" = 0 . 2
Curve B - Og = 0.75, Cp =
= 0.125
Curve C - Og = 0 . 0 ,

= 0.5

Curve D - continuous stirred tank reactor

Figure 23.

Yield of intermediate B in different reactor


systems w i t h Van De Vusse reactions versus
conversion o f feed component
Curve A - plug flow reactor
Curve B - semi batch operation o f a s t i r r e d tank
reactor: V^" = 0.2, o = 0.75,
CTp = 0 - ^ = 0 . 1 2 5
Curve C - continuous stirred tank reactor

104

0.14

10.0

0.12

0.10

0.08

C
O
Q

_l

LU
>-

0.06

0.04

0.02

0.00

0.0

0,2

0.4

0.6

FLOW AVERAGE CONVERSION, x

0.8

1.0

105

y i e l d o f B i n t h e CSTR=
limit of yield of B.
constant

However, the plug flow reactor gives the upper

Figure 23 shows a case where the reaction r a t e

is large compared to Kg.

I t is seen i n Figure 23 that

the maximum y i e l d o f B i s obtained by semi batch operation o f the STR.


A region i n the plane of the dimensionless parameter,
versus the dimensionless parameter, K ^ / K j , was determined f o r which the
yield of B is greater by a particular semibatch operation than in either
t h e CSTR o r t h e p l u g f l o w r e a c t o r .

The particular semibatch cycle i s de

fined by f i x i n g the semibatch cycle parameters as given below.

ag = 0 . 7 5

= 0.2

d p = O-j:

Y = 1 .0

*0 = O'O

The r e s u l t is shown i n Figure 24.

The upper

curve i n Figure 2k is the

locus o f points f o r which the maximum y i e l d o f 6 i s thp. same i n the plug


flow reactor and i n the semibatch operated STR.

The lower curve i n Fig

ure 2k i s the locus o f points f o r which the maximum y i e l d i s the same i n


t h e CSTR a n d i n t h e s e m i b a t c h o p e r a t e d S T R .

For a l l points between the

upper and lower curves the maximum y i e l d o f B i s greater i n the semibatch


o p e r a t e d STR t h a n i n e i t h e r t h e p l u g f l o w r e a c t o r o r i n t h e CSTR.
r e g i o n i s d e n o t e d as R e g i o n I I i n F i g u r e 2 k .

This

The middle curve i n Figure

2k was obtained by Van De Vusse (32) and i s the locus of points For which
t h e m a x i m u m y i e l d o f B i s e q u a l i n t h e p l u g f l o w r e a c t o r a n d i n t h e CSTR.
The upper and lower curves i n Figure 2k were determined from plots of
the maximum y i e l d o f B i n the CSTR, the plug flow r e a c t o r , and the

Figure 24.

Region o f maximum y i e l d o f B f o r Van De Vusse reactions


by semi batch operation o f the s t i r r e d tank reactor i n
the (K
Kg/Kj) plane
Semi batch c y c l e parameters:

= 0.75, a^. =

= 0.125,

V " = 0.2
o
Region I - maximum y i e l d greatest i n the plug flow
reactor
R e g i o n 11 - m a x i m u m y i e l d g r e a t e s t i n t h e s e m i b a t c h
operated stirred tank reactor
Region I I I - maximum y i e l d greatest i n the
continuous stirred tank reactor
Region IV - maximum y i e l d greater i n the plug flow
reactor than in the continuous stirred
tank reactor
Region V - maximum y i e l d greater i n the cont i nuous
stirred tank reactor than in the plug
flow reactor

10.00

Region

Rg i on I I
CN

ce

LU

Req i on

Region IV

LU
ce

Region V

o
tn

Van De Vusse's Curve

O.Oll / / I
0.3
0.5

2.0

5.0

10.0

DIMENSIONLESS REACTION PARAMETER,

20.0

K C

50.0

./H

108

s e m i b a t c h o p e r a t e d STR v e r s u s t h e r e a c t i o n p a r a m e t e r K ^ C ^ ^ / K j .

A p l o t was

made f o r each of three d i f f e r e n t values o f the r e a c t i o n parameter K^/K^.


Figure 25 shows the p l o t f o r K^/K^ equal t o u n i t y .

I n Figure 25 the

intersection point o f the curve for the plug flow reactor and the curve
f o r s e m i b a t c h o p e r a t i o n o f t h e STR g i v e s o n e p o i n t f o r t h e u p p e r c u r v e i n
Figure 24 where the maximum y i e l d o f B i s the same f o r the plug flow r e
actor and f o r semi batch operation o f the STR.

S i m i l a r l y , points for Van

De Vusse's curve and the lower curve i n Figure 24 are obtained from Fig
ure 25.
R e g i o n 11 i n t h e ( K ^ C ^ ^ / K j , K ^ / K j ) p l a n e f o r w h i c h t h e m a x i m u m y i e l d
i s g r e a t e r i n t h e s e m i b a t c h o p e r a t e d STR t h a n i n t h e p l u g f l o w r e a c t o r o r
i n t h e CSTR w i l l b e d i f f e r e n t f o r e a c h s e m i b a t c h c y c l e a s d e f i n e d b y t h e
semibatch cycle parameters.

I t should be possible to determine the semi-

batch cycle which w i l l maximize the area of Region I I .


not been done.

However, this has

A second problem which has not been solved i s the dtermi

na Li on of the semibatch cycle which maximizes the yield of R for values of


the reaction parameters

and K^/Kj f o r which the maximum y i e l d of

B may be obtained by semibatch operation o f the STR.

Ad i abat i c
T h e s e m i b a t c h o p e r a t i o n o f a n a d i a b a t i c STR w a s s t u d i e d u s i n g t h e
k i n e t i c scheme of a s i n g l e i r r e v e r s i b l e and exothermic f i r s t order r e
action.

Some e f f e c t s o f h e a t s e n s i t i v i t y o n r e l a t i v e y i e l d a n d r e l a t i v e

throughput were determined by comparing results from systems with d i f f e r


ent amounts of heat s e n s i t i v i t y .

The relative yield and relative through

put used for this comparison correspond to a limiting case of semibatch

109

0.35

0.30
K/K| = 1.0

0.20
Q
_J

LU
>

z:
3

IS*.

;o.io
<
z:

0.00
0.5

1.0

5.0

2.0

D I M E N S I O N ! E S S REACTION PARAMETER. K . C . V K .
'

Figure 25.

j At

Maximum y i e l d o f intermediate B in d i f f e r e n t
r e a c t o r s y s t e m s w i t h V a n De V u s s e r e a c t i o n s
versus the dimension!ess reaction parameter
for the side reaction
Curve A - plug flow reactor
Curve B - semi batch operation o f the s t i r r e d
tank reactor.
'= 0.2. a = 0.75
G

= cr

= 0.125

Curve C - continuous s t i r r e d tank reactor

10.0

110

o p e r a t i o n , n a m e l y , t h e o p t i m a l a d i a b a t i c CSTR a n d p l u g f l o w r e a c t o r
combi nation.
The assumption that the rate constant, K , could be approxiiiuit- il as
a linear function o f temperature was used f o r most of the results pre
sented here.

This i s a good approximation to the Arrhenius equation lor

the r a t e constant as a function o f temperature o n l y f o r a teniperaLnic


i n t e r v a l i n w h i c h t h e r a n g e o f v a l u e s f o r t h e r a t e c o n s t a n t i s bii.t l
However, i t was determined that the Arrhenius temperature function and
the linear temperature function for the rate constant give qualitatively
the same r e s u l t f o r the e f f e c t o f heat s e n s i t i v i t y on r e l a t i v e y i e l d and
relative throughput.
The system of equations f o r semi batch operation o f t h e a d i a b a t i c STR
a lso cannot be solved analytically.

T h e r e f o r e , t h e process was s i n.ul a t c i i

on the analog computer.


An analysis o f the system o f equations shows t h a t t h e r e l a t i v e y i e l d
of product and r e l a t i v e throughput for semi batch operation are determined
as a function of the parameters shown i n Equations 85 and 86 respectively,
when the rate constant i s a linear function of temperature.

1 ] = T l ( R L , P , \ I ^ , O g , O p , Og)

(Eq. 85)

Y = Y(RL, X^, V^, CTg, CTp, Op)

(Eq. 8() )

When the r a t e constant i s given by the Arrhenius e q u a t i o n t h e r e l a i i v c


y i e l d and r e l a t i v e throughput are also functions of the individual

values

of the parameters R and L.


Some r e p r e s e n t a t i v e p l o t s o b t a i n e d f r o m t h e a n a l o g c o i i i | ) u t e r w h i c h

Ill

show p r o f i l e s of

the reactor variables for both the semi batch operation

o f t h e a d i a b a t i c STR a n d t h e r e f e r e n c e a d i a b a t i c CSTR a r e s h o w n i n F i g u r e s
26 t o 31'

I n F i g u r e s 2 6 t o 31 t h e r a t e c o n s t a n t i s a l i n e a r f u n c t i o n o f

temperature is defined by Equation 11a.

The flow average concentration of

reactant A in the product stream during steady periodic operation,(0^1,


may be determined g r a p h i c a l l y from these f i g u r e s , since the concentration
p r o f i l e is nearly linear during the emptying f r a c t i o n of the semi batch
cycle.

The r e l a t i v e yield of product is then calculated by


1
11 -

(Eq. 87)

Once the r e l a t i v e y i e l d i s known, r e l a t i v e throughput is calculated by


solution of Equation 18.
Some e f f e c t s o n t h e c o n c e n t r a t i o n p r o f i l e s f o r s e m i b a t c h o p e r a t i o n
r e l a t i v e t o t h e r e f e r e n c e a d i a b a t i c CSTR c o n c e n t r a t i o n d u e t o c h a n g i n g
the system parameters may be determined by comparing Figures 26 t o 31.
However, the interaction effects of the different parameters on relative
y i e l d c a n n o t b e s e e n i n F i g u r e s 2 6 t o 31 -

The adiabatic case i s much

more complicated than the isothermal case, and the relationships between
the semi batch cycle parameters, namely, V^,, Op,

and Og, foi' r e l a t i v e

yield or relative throughput for a given adiabatic system are not the
same as f o r the isothermal case.

Aris (2) has shown that f o r adiabatic

steady state operation the reactor system which maximizes the average re
action rate w i l l require the least residence time to obtain a given con
version for fixed feed conditions.

Figure 6 shows the shape of the r e

a c t i o n r a t e curve as a f u n c t i o n o f conversion f o r an adiabatic system.

Figure 26.

Y i e l d increase by semi batch operation o f the adiabatic


St i rred tank reactor
semi batch cycle parameters:
Op =

= 0.125,

relative yield;

= 0 . 5 , cTg = 0 . 7 5 ,

Y = 1.0

1] = 1 . 1 1 4

transient and steady state p r o f i l e s f o r the


reference adiabatic continuous stirred tank
reactor

transient and periodic p r o f i l e s f o r semi batch


operation of the adiabatic s t i r r e d tank reactor

DIMENSIONLESS REACTION RATE, K C ^

DIMENSION LESS CONCENTRATION, C


O
o

o
ro

o
-U

o
o

O
o

to
<-n

en
o

O
O

Figure 27.

Yield increase by semi batch operation o f t h e


adiabatic stirred tank reactor
semi batch cycle parameters:
a^. =

= 0.125

= 0 . 5 , ag = 0.75,

^ = 1.0

r e l a t i v e y i e l d ; Tj = 1 . 1
transient and steady state profiles f o r
the reference adiabatic continuous stirred
tank reactor
transient and periodic profiles for the
semi batch operation of the a d i a b a t e s t i r r e d
tank reactor

DIMENSIONLESS

VOLUME,

V"

DI MENS IONLESS REACT I ON


RATE,

oo
oo

' o

vn

DIMENSIONLESS CONCENTRATION,

Figure 28.

Yield increase by semi batch operation o f t h e


adiabatic stirred tank reactor
semi batch cycle parameters;
C T = CTp = 0 . 1 2 5

= 0.2,

= 0.75,

Y = 1.0

r e l a t i v e y i e l d ; Tl = 1 . 1
transient and steady state p r o f i l e f o r the
reference adiabatic continuous s t i r r e d tank reactor
transient and periodic p r o f i l e f o r the ?emibatch
operation of the adiabatic s t i r r e d tank reactor

Figure 29.

Yield decrease by semi batch operation o f t h e


adiabatic stirred tank reactor
semi batch cycle parameters:
Op =

= 0.125

= 0 . 2 , .:Tg= 0 . 7 5 ,

^ = i.O

r e l a t i v e y i e l d ; T] < 1 . 0
transient and steady state p r o f i l e for the
reference adiabatic continuous s t i r r e d tank reactor
transient and periodic p r o f i l e for the
semi batch operation o f the a d i a b a t i c s t i r r e d
tank reactor

DIMENSIONLESS CONCENTRATION,

C^

DIMENSIONLESS CONCENTRATION,

Jo

C^"

cn

00

o
o

Figure 30.

Yield increase by semibatch operation of the adiabatic


stirred tank reactor
semibatch cycle parameters: M^
CTp =

= 0,5, o

= 0.60,

= 0.125

r e l - a t i v e y i e l d ; T| = 1 . 0 7
transient and steady state p r o f i l e for t h e
reference adiabatic continuous s t i r r e d tank reactor
transient and steady state p r o f i l e f o r the
semibatch operation of the adiabatic s t i r r e d
tank reactor

Figure 31.

Yield decrease by semibatch operation of the adiabatic


St i rred tank reactor
semibatch cycle parameters: V

= 0.5. r 0 . 7 5 .

= Oj- = 0 . 1 2 5
r e l a t i v e y i e l d : Ti < 1 . 0
transient and steady state p r o f i l e f o r t h e
reference adiabatic continuon'- s t ; rred tank reactor
t r a n s i e n t and p e r i o d i c p r o f i l e f o r t h e semi batch
operation of adiabatic stirred tank reactor

DIMENSIONLESS CONCENTRATION,

.o

Q\

oo

DIMENSIONLESS CONCENTRATION,

C^'^
o

o
o

CO

N3

C^'"'

z
I

ro

CD

-p-

o
o

120

The slope of this curve is the adiabatic derivative d e f i n e d by EquaLion


25.

Thus, for a conversion corresponding to a positive adiabatic deriva

t i v e the r e a c t i o n r a t e i s a maximum i n the adiabatic CSTR, and the adia


b a t i c CSTR r e q u i r e s t h e l e a s t residence t i m e .

For a conversion correspond

ing to a negative adiabatic derivative the average reaction rate is a


maximum, and the residence time i s a minimum i n the optimal adiabatic
CSTR a n d p l u g f l o w r e a c t o r c o m b i n a t i o n a s d e f i n e d o n p a g e 3 3 -

For iso

thermal steady s t a t e operation the plug flow reactor always has a higlier
average r e a c t i o n r a t e t h a n t h e CSTR and always r e q u i r e s a s m a l l e r r e s i
dence time to attain a specified conversion.
Since the plug flow reactor, i n which the average r e a c t i o n r a t e i s a
maximum, gives the upper bounds o f r e l a t i v e y i e l d and r e l a t i v e throughput
f o r semi batch operation i n the isothermal case, i t i s reasonable t o assume
that the steady state reactor system which maximizes

the average reaction

r a t e w i l l provide the upper bounds f o r r e l a t i v e throughput for semi batch


operation of the adiabatic STR.

Based on t h i s assump Li un the rollov/ing

two conclusions may be reached:


1)

when the adiabatic derivative i s p o s i t i v e at the conversion


i n the reference adiabatic CSTR, the r e l a t i v e y i e l d and
relative throughput w i l l always be less than unity.

This

is due to the fact that the average reaction rate by seinibatch operation must be less than the reaction rate i n the
r e f e r e n c e a d i a b a t i c CSTR.
2)

when the adiabatic derivative i s n e g a t i v e i n the rclcrcrxc


a d i a b a t i c CSTR, there e x i s t an optimal adiabatic CLIR end

121

s e m i b a t c h o p e r a t e d STR c o m b i n a t i o n .

I n this optimal combina

t i o n t h e a d i a b a t i c CSTR i s o p e r a t e d a t t h e m a x i m u m r e a c t i o n
rate and i s followed i n series by the semi batch operated
adiabatic STR.

As t h e b a t c h f r a c t i o n , O g , a p p r o a c h e s u n i t y

and the minimum volume, M a p p r o a c h e s zero for the semibatch cycle the relative yield and r e l a t i v e throughput
approach their upper bounds, which are obtained i n the
o p t i m a l a d i a b a t i c CSTR a n d p l u g f l o w r e a c t o r c o m b i n a t i o n .
The upper bounds of r e l a t i v e y i e l d and r e l a t i v e throughput obtained
b y t h e o p t i m a l a d i a b a t i c CSTR a n d p l u g f l o w r e a c t o r c o m b i n a t i o n m a y b e
expressed analytically.

The expressions are given below for the case

where the rate constant, K , is a linear function of temperature.

2RLP

RL exp('v)-l

(Tl)
UPPER
BOUND

(RLP-P-I) - [(RLP+P+1) -4RLP?

RL(exp(\)+I)

(Eq. 88)
where y = (RL+l)P

^
RL+l
2(RL-1)

and P z (P)^"

(RL+1)'

MAX

%&/

(RLX^ + I ) ]

(Y)

(Eq. 89)
RLX^ +

UPPER
BOUND
RL+1

RL(l-X^)

2(RL-1)
(RL+1)2

122

where X. ^ (X.)_*
A
A ' r MAX

'
2RL

W h e n t h e v a l u e s o f P a n d X ^ i n E q u a t i o n s 8 8 i i n d o Q 11,

i;

!i . ^

respective values corresponding t o the maximum r e a c t i o n r a l j ,

bounds for both relative yield and relative throughput arc oquai

'

. . v .

T h e o p t i m a l a d i a b a t i c CSTR a n d p l u g f l o w r e a c t o r c o n i b i . l a i '

be t h o u g h t o f as t h e o p t i m a l a d i a b a t i c CSTR and batch i-cacivi' _

by the semi batch operated STR, an adiabatic accumuiato/ w.-.s.: I

c
' ii

ii m;

T ! r : .< , i

im

actor i n t h i s combination may be thought of as the l i i n i t i m i


s e m i b a t c h o p e r a t e d STR a s t h e b a t c h f r a c t i o n ,

.ilvi

! '

Of course, when the continuous reactor is followed by Lh.? bu I'/.!i

reaction occurs would be required between the two ruacLorb.

- !

i.lir:

approaclios un , iv

if

minimum volume of contents i n the batch reactor i s (jroaii i


t h e b a t c h r e a c t o r i s n o t c o m p l e t e l y e m p t i e d a t t l i e e n d I! I
the additional parameter

I 'cM. 1 I

is introduced in the a n a l y t i i a l u . p i c b ' ( i u \

f o r r e l a t i v e y i e l d and r e l a t i v e throughput.

The presence nl

th,- ix i i

volume of material in the batch reactor at the end of a cycle n j . liii


e f f e c t o f r e d u c i n g t h e i n i t i a l c o n c e n t r a t i o n a n d t e m p e r a t u r e e.l U i ^
o f the next c y c l e .

The assumption o f p e r f e c t mixing ri,c|u i iu;, ;h..i

f r e s h feed be completely mixed w i t h t h e material already prr^^vn t


reactor.

ri.-

i n t n,

T h e i n i t i a l c o n c e n t r a t i o n a n d t e m p e r a t u r c a i l l i ' . ' : ic; ;

new cycle then become the volumetric average of these i :Sj;. ^ ;


erties

Mjrt

m.i
,

in the fresh feed charged to the reactor and the

i ng in the reactor from the previous cycle.


obtained i n the l i m i t as

approaches zero.

, e i e -

Equations WW and :/! aie


For the

jii

123

approaches the volume of the batch reactor the resulting expressions


correspond to the r e l a t i v e y i e l d and r e l a t i v e throughput of two adiabacic
CSTRs

in series.

T h e f i r s t a d i a b a t i c CSTR o p e r a t e s a t t h e c o n v e r s i o n

corresponding to the maximum reaction r a t e , and the second adiabatic


CSTR b r i n g s t h e c o n v e r s i o n t o t h e d e s i r e d l e v e l .
Curves A, B and C o f Figure 32 show p l o t s o f Equation 88 f o r the
r e l a t i v e y i e l d i n systems w i t h d i f f e r e n t amounts of heat s e n s i t i v i t y as
measured by the parameter RL.
t h a t the maximum value o f

By comparing curves A, B, and C i t is seen

the r e l a t i v e y i e l d decreases as the heat sensi

t i v i t y of the reaction system increases.

However, f o r highly heat, sensi

tive reactions there is a range of values of the relative rate constant


for which the r e l a t i v e y i e l d i n the adiabatic reactor is greater Llian i n
the isothermal reactor.

Furthermore, the maximum value of r e l a t i v e y i e l d

occurs at smaller values of the relative rate constant for highly heat
sensitive reactions

than for reactions of lesser heat sensitivity.

Curves k , B, and C o f Figure 33 show p i o t s o f EquaLion 83 fur l e l a t i v e throughput i n systems with different values of the product RL.

By

comparing these curves i t is seen that the relative throughput decreases


as RL increases.
Curves D and E i n Figure 32 show plots of r e l a t i v e y i e l d obtained by
a single adiabatic plug flow reactor and by a p a r t i c u l a r semi batch opera
t i o n o f a s i n g l e a d i a b a t i c STR r e s p e c t i v e l y .

Curve D s hows Lhr w u i I - known

f a c t that the y i e l d may be greater i n an adiabatic CSiR than i n -m adia


b a t i c p l u g f l o w r e a c t o r w i t h t h e s a m e r e s i d e n c e t i lue a n d f e e d c o n d i t i o n s .
The p o i n t where the r e l a t i v e y i e l d i s equal l o uni l.y on curve D ccrrc:nonds

124

qO.8

0.03

0.10

0.20I

0.50

1.00

2.00

RELATIVE RATE CONSTANT, P

Figure 32.

Limiting cases of relative yield by semibatcii


of the adiabatic stirred tank reactor

. rnti m

t h e r a t e c o n s t a n t , K , u s e d i n d e t e r m i n i n g l i u " .
a linear function of temperature

cu rvi"

i-

c u r v e A - i s o t h e r m a l p l u g f l o w r e a c t o r : RL
curve B - optimal adiabatic continuous s l i r i ' d i iv rc.icior
and plug flow reactor combi nai ion : -I ~ 7.;'
curve C - optimal adiabatic continuous scirr.-.i i.tn: r,,.ci.)r
and p l u g f l o w r e a c t o r comb i n a l i .,ri ; ili
i.n
c u r v e D - a d i a b a t i c p l u g f l o w r e a c t o r : RL

= 'rJ.n

c u r v e E - s e m i b a t c h o p e r a t i o n o f t h e a d i dfiuC i c - r i i - :
tank r e a c t o r : RL = 40.0. V

Figure 33.

Limiting cases of relative throughput by


semi batch operation o f the adiabatic s t i r r e d
tank reactor
the rate constant, K , used i n determining
the curves i n t h i s f i g u r e was a linear
function of temperature
c u r v e A - i s o t h e r m a l p l u g f l o w r e a c t o r : RL = 0 . 0
curve B - optimal adiabatic continuous stirred
tank reactor and plug flow reactor
combination; RL = 2.0
curve C - optimal adiabatic continuous stirred
tank reactor and plug flow reactor
combination; RL = 40.0

curve D - a d i a b a t i c p l u g f l o w r e a c t o r : RL = ^ 0 . 0
curve E - semi batch operation of the adiabatic
s t i r r e d tank reactor: RL= 40.0,
V ^ ' " = 0 . 1 , cTg = 0 . 0 , 0 ^ = 0 ^ = 0 . 5

]26
100.0

0.11
0.01

I
0.10

DiriEMSIOMLESS FLOW a v e r a g e c o n c e n t r a t i o n , ( i - % !

l.W

127

to the conversion for which the average reaction rate i n the adiabatic
p l u g f l o w r e a c t o r i s t h e same as the r e a c t i o n r a t e i n t h e a d i a b a t i c CSTR.
T h e o p t i m a l a d i a b a t i c CSTR a n d p l u g f l o w r e a c t o r c o m b i n a t i o n m a y b e
thought o f as s i m u l a t i n g a l e v e l o f mixing between complete mixing i n t h e
CSTR and no m i x i n g i n t h e p l u g f l o w r e a c t o r .

Thus, i t may be concluded

that an intermediate level of mixing w i l l maximize the yield o f product


i n an adiabatic reactor system with fixed feed conditions and a residence
time greater than that corresponding to an adiabatic derivative equal
zero.

to

S i n c e semi b a t c h o p e r a t i o n o f t h e STR s i m u l a t e s an i n t e r m e d i a t e

mixing l e v e l , i t may be expected that f o r s u f f i c i e n t l y heat s e n s i t i v e r e


actions there exist values of the semi batch cycle parameters f o r which
semi b a t c h o p e r a t i o n o f a s i n g l e a d i a b a t i c STR w i l l r e s u l t i n a r e l a t i v e
yield between the relative yields obtained i n the adiabatic plug flow re
actor and i n the optimal adiabatic CSTR and plug flov/ reactui" combi nat i on.
That i s , a r e a c t i o n f o r which RL i s equal t o 40 may prove t o be s u f f i
ciently heat sensitive to result in a plot of relative y i e l d by seinibdLcfi
operation versus relative rate constant that i s between curves C and D in
Figure 32.

Furthermore, i t may be expected t h a t t h e r e e x i s t s an optima]

semi batch cycle at each value o f the r e l a t i v e r a t e constant which maxi


mizes the r e l a t i v e y i e l d for semi batch operation o f a single a d i a b a t i c
STR.

One of these optimal semibatch cycles w i l l r e s u l t i n the maximum

r e l a t i v e y i e l d obtainable by semi batch operation o f a single adiabatic SIR


a t some value o f the r e l a t i v e r a t e constant.
Curves D end E i n Figure 3 3 show plots of r e l a t i v e throuuhpu L o b
t a i n e d b y a s i n g l e a d i a b a t i c p l u g f l o w r e a c t o r a n d b y s e m i b a t c h i x i c t n i i u ii

128

o f a s i n g l e a d i a b a t i c STR r e s p e c t i v e l y .

As i n the case f o r r e l a t i v e y i e l d ,

i t may be expected that f o r s u f f i c i e n t l y heat sensitive reactions there


exists an optimal semibatch cycle at each value of conversion which maxi
mizes the relative throughput for semibatch operation of a single adia
b a t i c STR.

At low values of conversion the optimal semibatch operation of

t h e s i n g l e a d i a b a t i c STR w o u l d c o r r e s p o n d t o t h e a d i a b a t i c CSTR a n d t h e
r e l a t i v e throughput would be equal t o unity.

At high values of conversion

t h e o p t i m a ] s e m i b a t c h o p e r a t i o n o f t h e s i n g l e a d i a b a t i c STR a n d t h e r e l a
tive throughput would correspond to that of adiabatic plug flow reactor.
The results shown i n Figures 32 and 33 are v a l i d i n a quantitative
sense only f o r reactor systems i n which the r a t e constant may be approxi
mated as a l i n e a r f u n c t i o n o f temperature.

The dependency of the rate

constant on temperature is more accurately given by the Arrhenius equation,


(Equation lib).

Figure 34 shows plots of r e l a t i v e y i e l d versus the rela

tive rate constant i n reactor systems for which the rate constant i s
determined by the Arrhenius equation.
mated by curve B of Figure 32.

Curve A i n Figure 34 i s approxi

For reactions with a greater heat sensi

t i v i t y the plots for relative yield versus relative rate constant and
relative throughput versus conversion obtained when the rate constant i s
given by the Arrhenius equation w i l l be less accurately approximated by
plots obtained when the rate constant i s given as a linear function o f
temperature.

However, i t is expected that the same q u a l i t a t i v e r e s u l t s

will be obtained.

That i s , heat sensitivity w i l l tend to decrease the

r e l a t i v e throughput and the maximum value of

the relative vield.

1 he

discussion on the upper bounds of relative yield and r e l a t i v e throughput


a n d t h e o p t i m a l s e m i b a t c h c y c l e i s e q u a l l y v a l i d f o r b o lh i h u l i n e a r

129

a
_j
LU
>
LU
>

_I
q:

LU

0.2

0.5

1.0

2.0

10.0

RELATIVE RATE CONSTANT, P

Figure 34.

Limiting cases o f r e l a t i v e y i e l d by semi b a t c h o p e r a t i o n


of the adiabatic stirred tank reactor
The rate constant, K , used in determining t h e s e c u r v e s
was a linear function o f temperature.
Curve A optimal adiabatlc continuous stirred t a n k
reactor and plug flow reactor combination:
R = 0.1, L' = 20.0
Curve B adiabatic plug flow reactor: R = 0 . 1 , L ' = 2 0 . 0

130

equation and the Arrhenius equation f o r the rate constant as a l'unci

ol

temperature.

Continuous Variable-Volume Operation


The continuous variable-volume operation o f t h e STR ernploy;;. k

' . lii

discharge flow rates that are continuous periodic functions of li.ic.

i!;i

i s i n contrast t o the semi continuous operation o f t h e STR d i scu. :,:.j


previously which employs feed and discharge f l o w rates i h o i ancontinuous periodic functions of time.

The study of

i i -

the conti nuc-us

/ n i

a b l e -volume o p e r a t i o n o f t h e STR was undertaken t o s h w ' h c t i l '-possible to obtain a relative yield greater than unity by u vai i ^ '
v o l u m e o p e r a t i o n w h i c h e m p l o y s c o n t i n u o u s p e r i o d i c f e e d a11J d l - . i

i:

streams.
The continuous variable-volume cycle w h i c h was D U i J i e J rxl '..i i
a r e l a t i v e y i e l d greater than u n i t y was obtained employs
charge flow rates that are sinusoidal functions of tinie.

i'uLci

'

c i i .~

Tlie ki nuli ^

scheme i s t h a t o f a f i r s t o r d e r i r r e v e r s i b l e r e a c t i o n I n an I >oilter.-<c:l
STR.
Douglas and Rippen (16) studied the periodic o p e r a t i o n oP ! l u i o thermal STR w i t h second order k i n e t i c s i n w h i c h the feed and di - J i n :'
streams were sinusoidal

functions of time which were in phase

same amplitude and frequency.

h:-:

T h u s t h e v o l u m e o f t h e STR w a ^ c u n i : i ; i .

D o u g l a s a n d R i p p e n f o u n d t h a t t h e a v e r a g e c o n v e r s i o n w a s d a c i L u v d ' v i d!
type o f operation for all values of the amplitude and , rcqucricy

il . . .

t h e r e s u l t s o b t a i n e d b y s e m i b a t c h o p e r a t i o n o f t h e S T R l o a d l o II n c k i elusion that a relative yield greater than unity may be nbuiincd by

131

continuous variable-volume operation i n which the feed and d i s c h a r g e f l o w


rates are sinusoidal functions o f time w i t h the same a m p l i t u d e pnd f r e
quency but out of phase.

This occurs because the product i s withdrawn

from the reactor a t a low rate during t h a t p o r t i o n of t h e cycle when the


product concentration is low and a t a high rate during t h a t p o r t i o n o f
the cycle when the product concentration i s high.
The feed r a t e and discharge r a t e are given i n d i m e n s i o n l e s s Form as
sinusoidal functions of time by

Q,'^ = Z s i n CO 0 + 1

(Eq. 90)

Q,

(Eq.

= Z s i n ( 0 - 0 ) + 1

91)

where Z = ampli tude


m" = Z n f

radians per residence time

= f / (

cycles per residence time

MAX
0 = phase lag of output flow behind input f l o w i n r a d i a n s .

The average feed and discharge flow rates a r e t h e same as i n t h e


reference CSTR.

The amplitude, Z, is restricted such that


0 ^ Z < 1 ,

(Eq.

92)

since an amplitude greater than unity would r e s u l t i n a n e g a t i v e flov/


r a t e during some p o r t i o n o f the cycle.
The volume i s determined as a p e r i o d i c f u n c t i o n o f t i m e I w c v a l u a ! i n - i
the integral i n Equation 7-

The result i s

[ 1 - c o s ) 9 + c o s ( c D 9- 0 ) - c o s 0 ] + V
O)

(''"O)]

(Eq.

93)

132

The volume i n Equation 93 is restricted such that


0 < V"

(Eq. 94)

With t h i s r e s t r i c t i o n the volume i s determined as a function o f time and


fixed values o f the amplitude, Z, the frequency, m , and the phase lag,
0, i n Equation 95 below.

V" = I -

[ cos ca'd - cos

- 0)-2 cos

^ 2 ^

(Eq. 95)

m"
where m" ^

and m = 4Z cos (

(Eq. 96)

The concentration p r o f i l e i s determined as a function of time by


integration of Epuation 8.

Finally, application of the definition for

r e l a t i v e y i e l d w i l l determine the r e l a t i v e y i e l d as a function o f the


parameters shown below
T1 = T ^ P , z , c o " , 0 )

(Eq. 97)

The system o f equations was solved using the analog computer.

Some

of the effects of the parameters i n Equation 97 on r e l a t i v e yield were


determined.

These effects are discussed below.

As the amplitude, Z, approaches z e r o , t h e s i n u s o i d a l o p e r a t i o n o f


t h e STR approaches t h e o p e r a t i o n o f t h e steady s t a t e CSTR, and t h u s , t h e
r e l a t i v e y i e l d is equal t o u n i t y when the amplitude i s equal

to zero.

It

has not been proven, but i t i s reasonable t o assume t h a t the r e l a t i v e


yield is a monotonie function of the amplitude.

This means t h a t i f the

r e l a t i v e y i e l d i s greater than u n i t y f o r some p a r t i c u l a r values o f the

133

parameters P, Z, m , and 0, then the maximum r e l a t i v e y i e l d i s o b t a i n e d


when the amplitude i s equal
P; m'\ and 0.

t o u n i t y f o r the same values o f the parameters

The minimum volume during sinusoidal operation o f Llm STR

is an inverse function of the amplitude.

T h u s t h e m i n i m u m v o l u m e ciiii i n n

s i n u s o i d a l o p e r a t i o n o f the STR has an e f f e c t o n r e l a t i v e y i e l d s i n i l a r

to

the e f f e c t o f minimum volume on r e l a t i v e y i e l d f o r the case o f semi botch


operation o f the STR.

Since i t was expected t h a t an aniplitLidc criuuI

to

u n i t y w o u l d g i v e t h e m a x i m u m v a l u e o f r e l a t i v e y i e l d g r e a t e r Liiaii u n i L y ,
the value o f amplitude was f i x e d a t u n i t y f o r t h i s study.
Figure 35 shows that the r e l a t i v e y i e l d goes

t h r o u g h a iriaxicuiiM i / i t h

respect to both the relative rate constant and the frequency for lIio f i x e d
values of amplitude and phase lag given i n the figure.
Figure 36 shows the r e l a t i v e y i e l d as a f u n c t i o n o f

t h e phase l a g for

specified fixed values of the amplitude, frequency, and relative rate con
stant.

The maximum r e l a t i v e y i e l d i n Figure 36 i s equal t o 1.018 and

occurs at a phase lag of

radians=

For different values of

the fixed

parameters, the maximum r e l a t i v e y i e l d would be e x p e c t e d t o o c c u r a t a


different phase lag.

i n Figure 36 i t i s seen t h a t t h e r e l a t i v e y i e l d i b

less than u n i t y when the feed and discharge flow r a t e s are i n pha>e and
the reactor volume is constant at i t s maximum value.

This result agrees

with the r e s u l t obtained by Douglas and Rippen ( | 6 ) .


I t would bo an interesting problem to d e t e r m i n e the r.nixi

v.,! ue u f

the r e l a t i v e yield i n the four dimensional space spanned by 1 1 i i ar,.i:,eters


P , Z , CO , a n d 0 .

However, i t is doubtful for

this case th<it

yield greater than about 1.03 could be obtained.

r-l.-tive

T h i s c o n c I u s i e n i -,

Figure 35.

Effect o f the relative rate constant and frequency


on relative yield for sinusoidal operation of the
continuous stirred tank reactor

Figure 36.

Effect of the phase lag of the discharge s t r e a m


behind the feed stream for sinusoidal operation
of the continuous stirred tank reactor

RELATIVE YIELD.

136

reached by observing that the values of r e l a t i v e y i e l d near the maximum


i n Figures 35 and 36 are a f f e c t e d t o a small degree by changes i n the
parameters.

These results demonstrate that the average yield relative to

the steady s t a t e y i e l d may be increased by a continuous variable-volume


operation of the SIR i n which the feed and discharge flow rates are con
tinuous periodic functions of time.

137

CONCLUSIONS

General

1)

S e m i b a t c h o p e r a t i o n o f t h e STR c o m b i n e s t h e m i x i n g c h a r a c t e r i s t i c s o f
t h e CSTR a n d t h e p l u g f l o w r e a c t o r a n d t h u s s i m u l a t e s a l e v e l o f
mixing between these two l i m i t s .

2)

T h e a v e r a g e r e s i d e n c e t i m e o f m a t e r i a l l e a v i n g t h e STR d u r i n g v a r i a b l e volume operation i s a periodic function of real time as the real

time

becomes large.
3)

T h e f l o w a v e r a g e r e s i d e n c e t i m e o f m a t e r i a l l e a v i n g t h e STR d u r i n g
one variable-volume cycle is less than the average residence time of
m a t e r i a l l e a v i n g t h e CSTR w h e r e b o t h r e a c t o r s h a v e t h e s a m e m a x i m u m
volume and average throughput.

Isothermal

First order reactions


1)

A r e l a t i v e y i e l d and r e l a t i v e throughput greater than u n i t y may be


obtained by variable-volume operation of

2)

the STR.

The upper bounds of r e l a t i v e y i e l d and r e l a t i v e throughput by variablevolume operation are obtained by the plug flow reactor, or equiva
lent! y, the batch reactor.

3)

Larger values of r e l a t i v e yield and r e l a t i v e throughput are obtainable


by semi batch operation of
the STR.

t h e STR t h a n b y s e m i c o n t i n u o u s o p e r a t i o n o f

The presence of feed and discharge flow rates

ihroughouL

the semi continuous cycle has the e f f e c t of reducing the r e l a t i v e


yield and relative throughput.

138

k)

The optimal semi continuous operation which maximizes r e l a t i v e y i e l d


and r e l a t i v e throughput i s obtained by the semi batch cycle with the
minimum volume set equal

to zero, the f i l l i n g fraction set equal to

the emptying f r a c t i o n , and the batch f r a c t i o n s e t as

l a r g e as p o s s i b l e .

The upper bounds of r e l a t i v e y i e l d and r e l a t i v e throughput are then


obtained by the batch reactor w i t h instantaneous f i l l i n g and
emptyi ng.
5)

A relative yield and relative throughput greater than unity cannot be


obtained by a variable-volume operation i n which either

the feed flow

rate or the discharge flow rate has a constant value.


6)

T h e r e l a t i v e y i e l d f o r v a r i a b l e - v o l u m e o p e r a t i o n o f t h e STR g o e s
through a maximum a t a f i x e d value o f the r e l a t i v e r a t e constant.

7)

T h e r e l a t i v e t h r o u g h p u t f o r v a r i a b l e - v o l u m e o p e r a t i o n o f t h e STR
approaches i n f i n i t y as the flow average conversion o f reactant
approaches unity.

8)

A variable-volume operation i n which the feed and discharge flow rates


are continuous functions o f time may r e s u l t i n a r e l a t i v e y i e l d and
relative throughput greater than unity.

To achieve this in the case

of sinusoidal variable-volume operation where the feed and discharge


f l o w r a t e have the same amplitude and frequency, i t i s necessary that
the feed flow rate and discharge flow rate be out of phase.
9)

The form of the analytical solutions f o r r e l a t i v e y i e l d and r e l a t i v e


t h r o u g h p u t b y s e m i b a t c h o p e r a t i o n o f t h e STR a r e t h e s a m e f o r b o t h
the reversible and irreversible f i r s t order reaction schemes.

139

Single reactions wi th arbi t r a r y pos i t i v e order


1)

A r e l a t i v e y i e l d and r e l a t i v e throughput greater than u n i t y may be


obtained for any reaction of order greater than zero.

2)

The maximum values of r e l a t i v e y i e l d and r e l a t i v e throughput f o r


v a r i a b l e - v o l u m e o p e r a t i o n o f t h e STR i n c r e a s e w i t h i n c r e a s i n g r e a c t i o n
order.

3)

The variable-volume cycle parameters affect the r e l a t i v e yield and


r e l a t i v e throughput i n the same d i r e c t i o n f o r a l l s i n g l e reactions o f
pos i t i v e order.

Van De Vusse reactions


1)

The yield of desired intermediate is dependent on the values of the


dimensionless reaction parameters,

C^^/Kj and K^/Kp

There exist

values of these dimensionless reaction parameters for which the maxi


mum y i e l d i s o b t a i n e d r e s p e c t i v e l y i n t h e p l u g f l o w r e a c t o r , t h e
semi b a t c h operated STR, and the CSTR.

Adi abati c
The following conclusions apply for the case of the single f i r s t
order i r r e v e r s i b l e and exothermic reaction.
1)

Thermal s e n s i t i v i t y of the reaction rate constant has the e f f e c t of


decreasing the relative yield and relative throughput obtainable by
variable-volume operation o f the STR.
A.

As thermal s e n s i t i v i t y increases, the maximum value o f


r e l a t i v e y i e l d o b t a i n a b l e b y s e m i b a t c h o p e r a t i o n o f t h e STR
decreases.

140

B.

As thermal s e n s i t i v i t y increases, t h e maximum value o f


relative yield occurs at smaller values of the relative
rate constant.

C.

As thermal s e n s i t i v i t y increases, the maximum value o f


relative throughput at any level of flow average conversion
decreases.

2)

The upper bounds of r e l a t i v e yield and relative throughput are attained


b y t h e o p t i m a l a d i a b a t i c CSTR a n d p l u g f l o w r e a c t o r c o m b i n a t i o n .

3)

There exists a range of values for the relative rate constant for
which values of relative yield and relative throughput obtained by
semibatch operation o f the SIR w i l l be both greater than u n i t y and
greater than the relative yield and relative throughput obtained in
the plug flow reactor.

4)

I f the temperature dependency of the reaction rate constant is a


linear function of temperature, then the conversion of reactant in
the adiabatic system is a function of the product of the lieal of re
action and the linear proportionality constant which relates the
reaction rate constant and temperature.

I f the rate constant is

given as a function o f temperature by the Arrhenius equation, then


the conversion of reactant i n the adiabatic system is a function of
the individual values of the heat of reaction and the activation
energy in the Arrhenius equation.

14]

RECOMMENDATIONS

An analytical scheme should be developed which w i l l determine the


emibatch cycle parameters and the conversion of reactant which w i l l
maximize the y i e l d o f intermediate f o r the Van De Vusse r e a c t i o n
scheme.

The theory developed by Horn and L i n (21),

which makes use

of methods of variational calculus to optimize a periodic process, may


be applied to this problem.
An analytical scheme should be developed which w i l l determine the
semi batch cycle parameters and the conversion of reactant which w i l l
maximize the yield of product from a single f i r s t order exothermic
reaction in the adiabatic stirred tank reactor.
by Horn and L i n (21)

The theory developed

may also be applied t o t h i s problem.

The adiabatic case of semi batch operation of the s t i r r e d tank reactor


should be investigated more f u l l y using a reaction rate constant
which is 6" Arrhcnius function of temperature,
The adiabatic case of semi batch operation of the s t i r r e d tank reactor
should be studied for the case of single reversible reactions of
different positive orders.

]k2

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145

ACKNOWLEDGMENTS

The author wishes to express his gratitude t o Professor R. C.


Seagrave f o r his guidance, suggestions, and encouragement during t h i s
proj ecto
The author wishes to acknowledge the financial support he received
f o r t h i s project by fellowships from the National Aeronautics and Space
Administration, the National Defense Education Act, Monsanto Company, and
Minnesota Mining and Manufacturing Company and by a research a s s i s t a n t ship with the Engineering Research Institute at Iowa State University.
In addition, the author wishes to thank his wife, Lorraine, for her
encouragement and moral

support.