Iowa State University Capstones, Theses and

Retrospective Theses and Dissertations

Dissertations

1970

Variable-volume operation of a stirred tank reactor

Monty Marvin Lund
Iowa State University

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Recommended Citation
Lund, Monty Marvin, "Variable-volume operation of a stirred tank reactor " (1970). Retrospective Theses and Dissertations. 4246.
https://lib.dr.iastate.edu/rtd/4246

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 70-25,803

LUND, Monty Marvin, 1943-

VARIABLE-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 1

Variable-Volume Operation 2

Purpose 3

Types of Variable-Volume Operation 3

Reaction Systems Studied 4

Solutions to the Mathematical Models k

LITERATURE REVIEW 6

The Dynamics of Thermally Sensitive Reactors 7

Reactor Models for Finite Mixing 9

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 3'

First order reactions 3&

Steady state operation 3&

Transient operation 43

VARIABLE-VOLUME OPERATION 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 72

Effect of relative rate constant 81

Effect of flow average reactant conversion 86
Effect of semibatch cycle parameters 87
The optimal semibatch cycle 89
General characteristics of semibatch operation 9'

Reversible f i r s t order reactions 92

Second order reactions 93
Single reactions of arbitrary positive order 9^
Van De V u s s e r e a c t i o n s 99

Adiabatic 108

Continuous Variable-Volume Operation 130

CONCLUSIONS 137

General 137

Isothermal 137

First order reactions 137

Single reactions with arbitrary positive order 139
V a n De V u s s e r e a c t i o n s 139

Adiabatic 139

RECOMMENDATIONS 141

LITERATURE CITED 142

ACKNOWLEDGMENTS ^^5
 iV

NOMENCLATURE

Lat in

A Heat transfer area in Equation 3

b 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 in

the discharge stream

Cp Heat capacity of reactor contents

Cpg Heat capacity of coolant

E Activation energy in Equation l i b

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 ) / ( )

K Reaction rate constant

Reaction rate constant at feed temperature

K Dimensionless reaction rate constant, K/K^

L Dimensionless linear reaction rate parameter

L' Dimensionless Arrhenius reaction rate parameter

M Dimensionless rcnctor heat transfer parameter

N Dimensionless couler heat transfer parameter

P Dimensionless re t at i ve rate constant

0 Discharge flow rate

Q,^ Feed flow rate

Q, Feed and discharge flow rate for the reference reactor

K
/V
0, Dimensionless discharge flow rate,

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

R Dimensionless relative thermal energy

R Ideal gas law constant

g

r Reaction rate

r Dimensionless reaction rate

S(8, 0') Residence time distribution function

T Temperature

Feed temperature

T Dimensionless temperature, T/T^

Tj. Cooler temperature

Cooler feed temperature

t T i me

U Heat transfer coefficient

V VoIume

v., Maximum v o l u m e

Vj, Cooler volume

V Minimum volume
o
V 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^

Dimensîonless 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 the semicontinuous cycle defined by

Equation 46

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

j Refers to j component; j = A , B , C, D

k 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
 1

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
 2

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. The r e s u l t i n g

concentration 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 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

reactor which are periodic functions of 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
 3

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 . Relative yield

and relative throughput are not independent. 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 variable-

volume 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

\
 k

continuous variable-volume operation. Semibatch operation i s a special

case of semi continuous variable-volume operation that i s studied i n de-

tai 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

 5

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.

 6

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. Both the isothermal and

nonisothermal cases have been considered. 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. Therefore,

publications are reviewed which concern: 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.
 7

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

 8

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
 9

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 . Danckwerts introduced the concept

of segregation 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 micro-

f 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 Reactioiià

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

S
A + A >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 > K^, the maximum

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. 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» Negative

feedback tends to stabilize the reactor and decrease the size of 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 . However, their work I s only

successful In n I tciti ve -cnse» 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 . The reaction used f o r the

expcr ii.ivniû! 1 v ^ 11 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' , I -/leni equations.

H o r i i ....i.i 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

lio.. e r pel i V i : •. lu..;.-' , ... cur a 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 I :, i : !.. i':,,. :uùerc,: res . I t s i r c applied to the op-

t i liii u ori .. . . , r h u 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

t h e iii..A I ni ,1, t ; _ ; 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 à 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 con-

u 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 . The input i s perturbed sinusoid-

r. I t / r i d t-h,. r.;i.'eer.x ui e input to maximize the time average y i e l d

,, ' i,, f ; !'• i ! • .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

y il.I il of 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

Vie 1 d.
 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 hor„ogeneous l i q u i d phase. The reactor i s

provided with a cooling jacket. 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 + r ^ (Q. - d) dt (Eq. 1)
o . ^ T
o

2o reactant j balance

dC.

dt

1, 2, n independent reactions
 20

Q:M. 2—»-Qc(t)
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 n (-AH.)r V q
^ ^ (T, - T) + Z — (Eq. 3)
dt V f pCp pCp

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 coni-

pat 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 non-

isothermal 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 " (I- Y " ) ] (Eq. 5b)

g 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 (Eq. 6)

= K/Kf Gf = 0^/0%

(-AH.)
(-AH.)'= :— V = V/V
M
' (-AH,)

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.

r = V" + r ® (d* - Q ")de

o J 9^ r
(Eq. 7)

dCj' Q:' n
—— = —~ (c" - CV) + P s a,, r. (Eq. 8)
d0 M i=l '

i = ], 1, n independent reactions

dT Q.r n .1.
= 7. (1-T") + RP Z (-AH;)" r " - M(T - T . " ) (Eq, 9)
de M" ;=i ' ' ^

G— = - i L Q_'- ( T _ T P + NV (T'-T ) (Eq. 10)

de c cf c

K" = 1 + L (t"-1) (Eq. 11a)

K = exp[-L' ("^ -1)] (Eq. l i b )

ï""'

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 ^ , UA \ .

Parameter " V ^ V^R^V

Srl^etër'

Linear Reaction Rate L = b T /K

Parameter f f

Arrhenius Reaction Rate

L ' = E/PL T,
Parameter 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 variable-

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

of product j is expressed mathematically by

 25

Table 1. Rate expressions for reaction systems studied

Reaction Dîmensîonless rate Relative rate

expression,

I
system constant, P

vH

K
A i-B KfVM/Q%
isothermal

K
A >B •K C,
adi abati c

k
a;=±B
Kt ''A " ^Ae

isothermal

K -A- 2
2a >b -C
a
i sothermal

-.2
•K"C; KfCAfVM/%R
adi abati c

kj k,
a >b >c

K ^2
2A r„ = C A - [[

Kp
i sothermal
kT
 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; da
— P -1
where C. = 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

time average throughput of

V - 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:), C: (Eq. 17)

J^R' 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. 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 = ' ^ ^ (Eq. 18)

-P ( Z . r.)^,
1 =1 J

After Y has been determined i n Equation 18^ the corresponding conversion

of component A is given by

\ (.%, "iA '9'

1 =1

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 variable-

volume 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 Steady state Transient concentration

scheme concentration, C profile, C"(9)

A^B C ^ ' = l / ( 1 + P) C^' = ~ (l-exp[-(l+P)0])

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

K I+PC" 1+ P C "
" "T+p— (i-exp[-(i+p)e])
k'

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

2a _ ! L , r r" - (2P +n - s/ ( 2 P + ] ) ^ - 4P^

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

K,
2A 40 Cg = P C ^ / C I + P 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 ' " ' ( Ç 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. Equation 22

i s p l o t t e d a s l i n e FG i n F i g u r e ^ . 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 ­

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. FG a l w a y s c r o s s e s t h e T axis at the

point (Oj I)o 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*) = - + R (Eq. 25)

d(l-C^) ST"

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

d (l-C^)/dT = 1/R a t p o i n t A» From Equation 20 i t i s seen that the

production rate, ( 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

p o i n t Ao 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 5TR. Consider Equations 20 and 22 for the

a d i a b a t i c CSTR. 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 ç 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 Ç 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 t

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

reaction. 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 + RPK"C^' = 0 (Eq. 2?)

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 Figures 4 and 5 show

T ; K j and r plotted against log^gClOO P) with R and L as param­

eters. 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)

r = r (RL, P) (Eqo 31)

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
DI MENS IONLESS REACTION RATf,K 0 1 MENS IONLESS RATE CONSTATN,K"

o CO
o o o

CO
5 \ë ,o
 42

RL = 80

RL = 60

RL = 40

0 .4 6 8

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<)
= r - = (Eq. 33)
P -A- max 4RL
r
max

max

P (Eq. 3 5)
max (RL+1)

T'V" = I + ^ - jj- (Eq. 36)

max

K (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

maximum value, r ^ ^ ^ f o r values o f P greater than P - only for the

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, T" DIMENSIONLESS REACTION RATE, K C
— — N3
O (jy O ^

o
3:
m
es
o
o
ro
00
m O o

—I
m O
<D

O
w
o

DIMENSIONLESS CONCENTRATION,
Figure 8. Effect of the relative rate constant on the
transient behavior of the adiabatic continuous
stirred tank reactor
 DIMENSIONLESS TEMPERATURE, DIMENSIONLESS RUCTION RATE,^ K C
— — ro
O Ln o
O
O

n 7\
1
O

oo
CO
H
3:
m
D

W
o
o o o
o o
o œ
o

DIMENSIONLESS CONCENTRATION,:
A
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. C DIMENSIONLESS REACTION RATE. K C^
A

cn
O
m
CO
CO

O II II
 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^ V (0) = V^) :

ci; = % [1 - (PV*C*(0)-1) e x p ( - P 9 ) ] o (Eq. 38)

A P(V^+8 ) ° *

2o0 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 (Eq. 39)

3.0 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 This condition i s expressed mathematically by

df I
; — = — = n (an integer) (Eq. 40)
(Of- I - 0"
n — 1J 3^ •o Q

I f n = 2 and v" = 0, the concentration of rcactant A i s given

by
 53

[*= 2rP9-l +exp(-P9)l (Eq. 4,)

A (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 ^ ] " ^ 'n(n-l).'

4.0 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. Set = I.

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. is an integer multi­

p l e (Q.'^ - Q. ) . This condition is expressed mathematically by

—r—% = — = m (an integer) (Eq. 43)

G-Of ' - Of 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/ k
(-t) (Pm) [ 1 - ( t - 8 / m ) ^ l
B = L - 1n(}-0/m).
k=l 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 . 1
" li&yy Z (-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 re-

a 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 There results a flow pattern i n which

the input flow, 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 .

Ç = 0 - 9 (Eq. 46a)
F r O

$ = 0 - 9 (Eq* 4 6 b )
Figure 10. T h e semi c o n t i n u o u s c y c l e
 DIMENSIONLESS DISCHARGE, DIMENSIONLESS FEED, Q DIMENSIONLESS VOLUME, V

(D
a
"1
F i g u r e 11 T h e semi b a t c h c y c l e
 DIMEN5IONLESS DISCHARGE, Q DIMEN5IONLESS FEED, DIMENSION LESS VOLUME, V
o
o
o
o S
1—;—

a
3:
m
z
%
z.
r*
m
U")

CD
m

a>
 59

(Eq. 46c)

(EQo 46d)
D 'D °E

- P = «0 " (Eq. 46e)

(Eq. 46f)
%- S'

(Eq. 46g)

(Eq. 46h)
"C ' V

(Eq. 46i)
^0 - *P

(Eq. 46j)
"f "B •" "E "D = '

T a b l e 3» Equations for the semicontinuous cycle

Operation/ T i me Feed Rate Discharge V o l ume

fraction of n" : Rate
V*
cycle

Filling eo< 9 < Gp ^fP

Batch .< 8 < 1.0

'fB 'fB

Empty!ng 8 o < 9 < 9r Q." i+(Q.f^-Q.£) (9-9g)

-fE

Down 8E< 8 < *0

Cons t r a l n i n q E q u a t i o n s

Ï 5p = V ( ?p) + +1^1, ( îf)

f ^ p ' 4 (Sp) - 4 (?„) + Qj (5,)

(<F - 'IP
 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

Operation/ Time Feed Di s c h a r g e Volume

fraction of Rate Rate
v"'
Cycle -,v
Cl""'
%f

Filling 8^<8
DC Of F
0 \* < F ( S -V
Batch 0 0 1
V

0p < 0
OC

<
DC
DC

DC

Emptyi ng 0
V

V
OC

UL

1 - Qp (e - 0g)
CD

CD

CD

Down 0 0
A

v"
m

Constraining Equations

Y
" V
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 time by fixing five

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 .

 61

=(V"/Q.'^) (Vg, Op, Pg, Y) (Eq. 48)

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 ,v ,v
) = exp - r (dr/V )d0 (Eq. 49)
"9-8' ^

(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
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. The total area under the

curve is unity. 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 R e s i d e n c e T i me
Residence Time Distribution Function Frequency Function
Cycle A I S(8,9') g(0,8')

"o + SfF(»-«o-e') fF
O S S ' ^ 3 - 0
\ " %'fF

•9 g 9' 6 9-9 + $ - £
o o F F
"o + 1'fF ("-«o'
n- I

"o^"o + tp-g')) »fF

(S-^o) - $p ^ 0 ' ON
V-O
^ ( G - G g ) + 5p + ifF

9^+(j-l ) £0'

®-®0 + jSf - "o + <F

G'-O + - ^f- < G ' {\iy ( v ; + o - f F ^ Q - y j S p - 8 ' ) ) (<>"' I f F

o r r

^ 9-2o + J ^ V'o + (G-Go) + OfF (G-^o)

a' = 0 6(9-8 )
\ * ®fF ' " " ' c '
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 Residence Time
Res i dence Time Distribution Function Frequency Function
Cycl e S(9,0') g(0,0-)

0 ^ 9 ' ^ -

"
9-9^ < G' g 0-0p + Sp, V + Q., ( 0 - 0 + $ - 9 ' )
o Tr r r fF

0 - 0 + $ <; 0 ' <" Q"Q + §

n - 1 "<v F T F "P

9-0 +c s 0' < 0-0 +6 +5 V

"o ^fF

9-0p +(j-1) *p + Sp 3 9 '

n-j ^ 9-0 + j5

9-0 P+ j $p & 9 ' < 0 - 0 | _ + j ? p + 5 j . (Vg^j (V^+'i^j-(0-0p+j 5p+$p-0')) (v;) OfF

9' = 0 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: V = 0.2, a = 0.5,

O D
,j =cr =0.25, Y = 1.0
F L
 bb

s.oor

4.00

3.00
z
o
u
z
D
u_
>
u 2.00
z
LU
D
o

1.00

o.ooL JZL
0.0 0.8 1.6 2.4 3.2 4.0
DIMENSION LESS RESIDENCE TIME, 0'
 67

o 9V 0
6(0'-0) = (Eq. 52)
m 0' = a

The a r e a u n d e r 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

r 6 ( 8 ' - 9 ) K ) " d9' = (V%)" . (Eq. 53)

J g O O

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

-0'
e d>^ 9
a{9,9') = . (Eq. 54)
0 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 5.6
Z
UJ DIMENSIONLESS REALTIME, 9
Q

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
 69

r 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

— _ 1 (-F '^E)
(Eq. 56)
~ ï

E q u a t i o n 56 i s m o s t d i r e c t l y obtained by the following steps:

1) 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!
;('p) = (Eq. 57)

2) In the time interval J 0^ the average residence time,

T( J ) , 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. Therefore

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 ^ 0 ^ by

r(U) - ; l 'p) (Eq. 58)

• F

3) 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

CD 0.85 _
<
en
LU

3 0.80 _
O
LL.

00
oo 0.75
LJ
_J
z
o
00
z 0.70
LU

0.0 0.2 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; O g = 0.5

efj. = = 0.25, Y = 1.0
 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 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 t h a n i n t h e r e f e r e n c e CSTR. Thus the

relative yield of product is less than unity. 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. This is expected

since the average value of 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: = 0 . 2 , Cp = = 0.5,

Q.fg = Qp = CTg = 0 , 0 ^ 2 ~ I'O, ^ = 1.0

 DIMENSIONLESS VOLUME, V" D I M E N S I O N L E S S FLOW R A T E S , Q . ^ ' \ Q " DIMENSIONLESS CONCENTRATION, C
A
o NJ o o
o o O o CTN

._i
r-

O 4^
Z
r-
m
VI
VI

3 J
m 1 "O
I 1
I II
I vn
t o
QJ o
iO /O 3 3
Mi TT
-J 3
a> C
0) O
o c
rf
o
-t cn
rf
n
"1
fO
Q-
Figure 16. Yield decrease by semi continuous operation
of the stirred tank reactor

semi continuous cycle parameters: = 0.2,

(tj- = = 0.5, og = o-fb " = 0.0, = op = 0.5,

Y = 1.0
 DIMENSIONLESS VOLUME, V" DIMENSIONLESS FLOW RATES, Q DIMENSIONLESS CONCENTRATION, C,
o o o N5 O o o o
o o O o ro '-t-

oo CTN
O
m
c/>
c/>

CD

-P- —
 I

Figure 17. Yield increase by semi batch operation o f the

stirred tank reactor

semi batch cycle parameters: = 0 . 2 , CTp = = 0.5,

a = 0.0, Y = 1.0
D
 DIMENSIONLESS DIMENSIONLESS DIMENSIONLESS CONCENTRATION, C^'^
VOLUME, V" FLOW RATE, a/%

o o — c N> o o o o
o UT O C» O o ro -P-

m
z
CO ro
O

CO
c/o

m uu
CD

0» in
n
 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. The system of equations

consist of 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 shown i n Equation 48

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

H= 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 =

exp (1-a.p -Ve"-"o'

(I-\)Y (I-X^) Y (i-Xa) Y J

(Eq. 62)

Equation 6l gives relative yield explicitly. Relative throughput is

implicit in Equation 62. 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 the relative rate con­

stant for d i f f e r e n t semi batch cycles. The results i n Figure 18 were calcu­

lated from Equation 6 l , 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 The r e l a t i v e rate constant i s

an i 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 0.50 1.00

DIMENSIONLESS FLOW AVERAGE CONCENTRATION/] - y )

 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 (Eq. 66)

pi^O ^ = "o - 3 "7 * i + 'E + 'f) 67)

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

pITo ^ + Cp (Eq. 68)

Effect of flow average reactant conversion 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 19-

At 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 (Eq. 69)
Aa I

J /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 im Y
(Eq. 72)
1 P- ^

2'" ' = (Eq. 73)

X 0 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. This i s due to the assumption of

perfect mixing. 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)]
1 im T] = [ -^ ] (Eq. 74)
1-Vg exp[-P {] - \ l ]

Effect of minimum volume From Equation 61 i t is found

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

n ( v ; = 0) = [ ]
P Op Gp
(Eq, 75)
and

1 i m T| = 1 (Eq. 76)

V - 1
o

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 (Eq. 77)

dV" °
o

-J;
is satisfied only at V = 1 in the interval 0 ^ V ^1. Therefore, rela-
o 0

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

o

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

yV
V = 0.
o

2) 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
' ' 0

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 I f the sum

o f the f i l l i n g and emptying fractions o f the semi batch cycle, + 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. The

above discussion on the effects of the semibatch cycle parameters on

 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]) exp[-P9g]
1+ P
(Tl) 1 - (Eq. 78)
OPTIMAL

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

OPTIMAL
1- 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 the

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 . 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 No chemical reaction goes t o

completion. 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 where is the equilibrium conversion of reactant

A. 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) = ; (Eq. 82)
UPPER (l+P) r (2P+l)- V 4P+1 ]
BOUND

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 . A 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 the stirred
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
1.4

RELATIVE RATE CONSTANT, P

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 1 . 0

DIMENSIONLESS FLOW AVERAGE CONCENTRATION, ( 1 - X )

 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 The Van De Vusse reactions are shown i n

Table I . 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. 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

are given in Table 2. 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) VK^/K^) (Eq. 84a)

"B "B "B' "F' "E' "o' "3 'Af/*i'

C q = Cg ( P ; Og^ Op; y ( E q . 84c)

(P, Og, Op, Kg/K,, Kg C^f/K,) (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

CÛ
o

Û 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

CÛ
O

Q
_l
LU

>-
0.06

0.04

0.02

0.00
0.0 0,2 0.4 0.6 0.8 1.0

FLOW AVERAGE CONVERSION, x

 105

y i e l d o f B i n t h e CSTR= However, the plug flow reactor gives the upper

limit of yield of B. Figure 23 shows a case where the reaction r a t e

constant 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. This

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 . 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

Rëg i on I I

CN

ce
LU
Req i on

Region IV

LU
ce
Region V

o
tn

Q Van De Vusse's Curve

O.Oll / / I
0.3 0.5 2.0 5.0 10.0 20.0 50.0

DIMENSIONLESS REACTION PARAMETER, K C ./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 . However, this has

not been done. A second problem which has not been solved i s the détermi­

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 2.0 5.0 10.0

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

Figure 25. 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
r L

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

 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 î

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

Op = = 0.125, Y = 1.0

relative yield; 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
 DIMENSION LESS CONCENTRATION, C DIMENSIONLESS REACTION RATE, K C ^
O o o o O to en O
o ro -U o o <-n o O
Figure 27. Yield increase by semi batch operation o f t h e
adiabatic stirred tank reactor

semi batch cycle parameters: = 0 . 5 , ag = 0.75,

a^. = = 0.125 ^ = 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 DIMENSIONLESS CONCENTRATION, C
RATE,
o o o o o
o vn ô o o

m
oo
oo

' o
Figure 28. Yield increase by semi batch operation o f t h e
adiabatic stirred tank reactor
semi batch cycle parameters; = 0.2, = 0.75,

C T = CTp = 0 . 1 2 5 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: = 0 . 2 , .•:Tg= 0 . 7 5 ,

Op = = 0.125 ^ = 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, C^"

o o o o
Jo cn 00

o
o
Figure 30. Yield increase by semibatch operation of the adiabatic
stirred tank reactor

semibatch cycle parameters: M^ = 0,5, o = 0.60,

CTp = = 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, C^'^ DIMENSIONLESS CONCENTRATION, C^'"'

.o
^
o
Q\
o
oo o
o o o o

o o N3
o
o o

o o
m

o
z
I—
ro

o o

CD

o o

-p-
CO
o

o
o o
o
o o
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 seini-

batch 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 semi-

batch 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.

RL exp('v)-l 2RLP
(Tl)
UPPER RL(exp(\)+I) (RLP-P-I) - [(RLP+P+1) -4RLP?
BOUND
(Eq. 88)

where y = (RL+l)P ^
RL+l

2(RL-1)
and P z (P)^"
MAX (RL+1)'

%&/ (RLX^ + I ) ]
(Y) (Eq. 89)
UPPER RLX^ + 2(RL-1)
BOUND
RL+1 RL(l-X^) (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 ù 11, • • i;

respective values corresponding t o the maximum r e a c t i o n r a l j , l!i . ^ - !

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 ' • ; .ilvi

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' _ ! '

Of course, when the continuous reactor is followed by Lh.? bu I'/.!i c

by the semi batch operated STR, an adiabatic accumuiato/ w.-.s.: I ' ii ; ii m;

reaction occurs would be required between the two ruacLorb. T ! r : •.< , i

actor i n t h i s combination may be thought of as the l i i n i t i m i im i.lir:

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 , 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 I 'cM. 1 I

the additional parameter 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 ^ Mjrt

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 ri.-

f r e s h feed be completely mixed w i t h t h e material already prr^^vn t i n t n,

reactor. 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; ; m.i

new cycle then become the volumetric average of these i :Sj;. ^ ; • , , -

erties in the fresh feed charged to the reactor and the e i e -

i ng in the reactor from the previous cycle. Equations WW and î:/! aie

obtained i n the l i m i t as approaches zero. 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. By comparing curves A, B, and C i t is seen

t h a t the maximum value o f 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 . rnti m

of the adiabatic stirred tank reactor

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 " •. cu rvi" i-
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

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 I
0.01 0.10 l.W

DiriEMSIOMLESS FLOW a v e r a g e c o n c e n t r a t i o n , ( i - % !
 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 to

zero. 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. Curve A i n Figure 34 i s approxi­

mated by curve B of Figure 32. 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
LU
q:

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 an- i i -

continuous periodic functions of time. The study of 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 ûrxl '..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 i'uLci c i i .~

charge flow rates that are sinusoidal functions of tinie. 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 h:-:

same amplitude and frequency. 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, = Z s i n (œ 0 - 0 ) + 1 (Eq. 91)

where Z = ampli tude

m" = Z n f radians per residence time

f = 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

V = — [ 1 - c o s Œ ) 9 + c o s ( c D 9- 0 ) - c o s 0 ] + V (''"O)] (Eq. 93)

O)
 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 ^ 1 (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 t o u n i t y f o r the same values o f the parameters

P; m'\ and 0. 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 • r-l.-tive

yield greater than about 1.03 could be obtained. 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 the STR.

2) 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 variable-

volume 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 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 STR. 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

àemibatch 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. The theory developed

by Horn and L i n (21) 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.