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1970
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70-25,803
LUND, Monty Marvin, 1943VARIABLE-VOLUME OPERATION OF A STIRRED
TANK REACTOR.
Iowa State University, Ph.D., 1970
Engineering, chemical
VARIABLE-VOLUME OPERATION OF A
STIRRED TANK REACTOR
by
Major Subject;
Chemical Engineering
Approved:
TABLE OF CONTENTS
Page
NOMENCLATURE
iv
INTRODUCTION
'
Variable-Volume Operation
Purpose
LITERATURE REVIEW
12
15
19
29
Isothermal
29
Adi abat i c
29
3'
3&
3&
43
51
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
72
81
86
87
89
9'
92
93
9^
99
Adiabatic
108
130
CONCLUSIONS
137
General
137
Isothermal
137
137
139
139
139
RECOMMENDATIONS
141
LITERATURE CITED
142
ACKNOWLEDGMENTS
^^5
iV
NOMENCLATURE
Lat in
Cj
Concentration of component j
C^^
Cj
C".'
Cp
Cpg
in
(-6H?)
L'
Q,^
Q,
K
/V
0,
Q.^
Q.|^
0,^1^
Reaction rate
Temperature
Feed temperature
Tj.
Cooler temperature
Cooler feed temperature
T i me
VoIume
v.,
Maximum v o l u m e
Vj,
Cooler volume
Minimum volume
Dimensionless volume
vi
Conversion o f component A
Flow average conversion o f component A i n the discharge stream
Ampli tude
Dens i t y
Coolant density
The k f r a c t i o n of
Equation 46
vii
Subscripts
i
Refers to i
reaction: i = i , 2, 3j
Refers to j
component;
j = A , B , C, D
INTRODUCTION
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.
the batch reactor during the reaction time, and thus there i s no mixing
of reactants with different levels of concentration.
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
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
When u s e d w i t h o u t a n y m o d i f i e r s t h e
a c r o n y m CSTR d e n o t e s s t e a d y s t a t e o p e r a t i o n o f t h e c o n t i n u o u s s t i r r e d
tank reactor.
Variable-Volume Operation
V a r i a b l e - v o l u m e o p e r a t i o n o f t h e STR i s a p r o c e s s w h i c h u s e s p e r i o d i c
feed and discharge flow rates as the driving force to cause a periodically
varying volume and i n turn, a periodic residence time.
concentration
The r e s u l t i n g
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
t h e STR.
t h e STR i m p l i e s o u t p u t s f r o m t h e
time.
T h e STR may b e f o r c e d t o
generate periodic outputs by forcing the reactor with periodic inputs such
a s f e e d r a t e , f e e d c o n c e n t r a t i o n , o r c o o l a n t f l o w r a t e , o r t h e STR m a y
generate periodic outputs when the inputs are constant, i f the parameters
are such that a stable l i m i t cycle exists about an unstable steady state
poi nt.
T h e s t u d y o f p e r i o d i c o p e r a t i o n o f t h e STR i s a r e c e n t d e v e l o p m e n t i n
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
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 yield is
the
Relative throughput is de
Relative yield
When t h e r e l a t i v e
yield and the relative throughput are greater than unity, the variablevolume operation i s considered an improvement over the performance o f the
CSTR.
Semibatch operation i s
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
o p e r a t i o n o f t h e STR.
t h e STR
a n a l y t i c a l s o l u t i o n i s n o t t r a c t a b l e , e x t e n s i v e u s e i s made o f t h e a n a l o g
and d i g i t a l computer to solve the systems of equations which describe
the mathematical models.
LITERATURE REVIEW
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
T h e v a r i a b l e - v o l u m e STR g i v e s r e s u l t s f o r r e a c t a n t c o n
v e r s i o n w h i c h u s u a l l y f a l l b e t w e e n t h e s t e a d y s t a t e CSTR c o n v e r s i o n a n d
t h e b a t c h r c a c t o r o r p l u g f l o w r e a c t o r c o n v e r s i o n w i t h t h e same r e s i d e n c e
time and thus might be modeled by a reactor with a f i n i t e mixing level.
Results are obtained for various types of reaction kinetics.
publications are reviewed which concern:
Therefore,
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
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
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.
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 .
These p l o t s show
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
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
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
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.
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.
v e r s i o n , t e m p e r a t u r e ) p h a s e p l a n e p l o t s a r e p r e s e n t e d w h i c h show t h e e v o l u
tion of an uncontrolled unstable steady state to a controlled stable steady
state by the application of increasing amounts of ideal proportional control.
Kermode and Stevens (22) used the root locus method t o determine the amount
o f t h e i d e a l modes o f c o n t r o l n e c e s s a r y t o make a n u n c o n t r o l l e d s t e a d y
s t a t e become s t a b l e .
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
Plots
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
The e f f e c t of
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
The
residence time distribution and the internal age distribution are defined
and experimental methods for their determination are presented.
Nauman
T h i s b e h a v i o r o f t h e m o l e c u l e s may b e
d e s c r i b e d b y t h e i r mode o f d i s p e r s i o n .
of segregation
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
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
F l u i d s w h o s e mode o f d i s
Levenspiel
pletely segregated f l u i d a macrofluid and the nonsegregated f l u i d a microf l u i d . Danckwerts (10) showed that the average reaction r a t e , and thus
c o n v e r s i o n , was h i g h e r I n a c o m p l e t e l y s e g r e g a t e d s y s t e m i f t h e r e a c t i o n
11
o r d e r w a s g r e a t e r t h a n 1 , l o w e r i f l e s s t h a n 1 , a n d e q u a l i f t h e o r d e r was
one
Z w i e t e r i n g ( 3 6 ) e x p r e s s e d m a t h e m a t i c a l l y t h e c o n d i t i o n o f maximum
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.
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 .
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
12
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.
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.
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.
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
13
Denbigh (12)
Plots
I t is also determined
> 3
>C
>D
14
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.
If
v a l u e f o r t h e s e l e c t i v i t y i s a l w a y s i n t h e CSTR.
> K^,
the maximum
T h e maximum v a l u e f o r t h e
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.
some I n t e r m e d i a t e l e v e l o f
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
15
Wei s o l v e s t h e u n c o u p l e d
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
A combined
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.
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
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.
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,
Negative
the limit
A perturbation technique
17
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
perimental ro..ui
i n r e a., l o r t e m p e r a t u r e o s c i l l a t i o n s I n a CSTR w h i c h
w a s d e s i g n e d c.. g. ,1^ , . j l c a s t a b l e l i m i t c y c l e .
expcr ii.ivni! 1
v ^ 11
The
authors fou;sJ i;.uL ihoi ; e.eer 1 inencal results compared closely with the
iiuiiKM'I cc.i
In: I' ,
H o r i i ....i.i I :
lio.. e r pel i V
-/leni equations.
i : .
soHie g e n e r a l r e s u l t s c o n c e r n i n g t h e o p t i m i
, ...
lu..;.-'
cur
y i terns b y u s i n g a v a r i a t i o n a l a p p r o a c h .
I :, i : !..
u ori
t h e iii..A I ni ,1, t ;
..
. .
i':,,.
r
; i :> i i i s u'c l e r m i n e d .
d e v e l o p e d cun.i" i t a t i v n -clier.ie b a i l e d o n t h e m e t h o d o f c h a r a c t e r i s t i c s t o
optii.iize a per i uei ou i i y ope rated jacketed tubular reactor i n which conu c c u t l v c r e a d i e r . : , e r e Ue ' n g c a r r i e d o u t .
r. I t / r i d t-h,.
,, '
i,,
f ; !' i !
y il.I il of
Vie 1 d.
.I':-:!:!
/" ^ l i o h t i n c r e a s e i n t h e t i m e a v e r a g e
i l i t e r - . ..".ii ti Ce I s I ..--ill / l u l l r c l a t i v e t o t h e o p t i m u m s t e a d y s t a t e
18
Larsen (23) introduces a special case of the semi batch operation cycle
used in this research work.
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.
Fang and
19
The reactor i s
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.
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.
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-
2o
+ r ^ (Q. - d) dt
. ^
T
o
reactant j balance
dC.
dt
1, 2,
n independent reactions
(Eq. 1)
20
2-Qc(t)
Q:M.
T,(0
(V
v(0
A
A;
"Q(t)
Tcf
C^(t)
T(t)
Figure 1.
21
3.
dr
^
dt
(T, - T) +
f
n
Z
(-AH.)r
V q
pCp
pCp
(Eq. 3)
where q = ( - ^ ) (T-T^)
4.
dT^
Qp
Vq
' f q - 4)
2.
3.
4.
(-AH.) p,
(UA/V) i s
^ a n d T^. a r e
constant.
For s species and n independent reactions Equation 2 represents a
set of s reactant balances.
pendent provided that the feed composition i s constant and that the i n i t
composition and i n i t i a l extent o f each reaction i n the reactor are conipat i b1e.
I n t h i s work computations v;erc performed using a reaction rate
22
c o n s t a n t t h a t was e i t h e r a l i n e a r f u n c t i o n o f t e m p e r a t u r e o r a n A r r h e n i u s
function of temperature.
constant for the reverse reaction is zero are considered for the nonisothermal case.
+ b(T - T^)
(Eq. 5a)
K =
exp[- I "
g
(Eq. 5b)
(I- Y " ) ]
f
Cj = Cj/Caf
9 = t 0*/%^
T"' = T/T^
a"' = d/Qp
= K/Kf
(-AH.)'=
'
(Eq. 6)
Gf = 0^/0%
(-AH.)
:
(-AH,)
= V/V
The 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.
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 .
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
dCj'
Q:'
~
d0
(c"
- CV) + P
= ], 1,
dT
Q.r
=
7.
de
M"
G = - i L
de
(Eq. 7)
n
s
a,, r.
i=l
'
(Eq. 8)
n independent reactions
n
(1-T") + RP Z
;=i
Q_'- ( T
_ T P + NV
c
cf
c
.1.
(-AH;)" r " - M(T - T . " )
'
'
^
(T'-T )
(Eq, 9)
(Eq. 10)
K" = 1 + L (t"-1)
(Eq. 11a)
(Eq. l i b )
P = (see Table 1 )
R = ("AH^^C^^/pCpT^
^
"
, UA \
.
V ^ V^R^V
Srl^etr'
Linear Reaction Rate
Parameter
L = b T /K
f f
L ' = E/PL T,
9 f
24
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 .
T h e v a r i a b l e - v o l u m e STR a n d t h e r e f e r e n c e CSTR h a v e t h e s a m e
maximum volume,
t h e same f e e d c o m p o s i t i o n a n d t e m p e r a t u r e , a n d t h e
same t i m e a v e r a g e t h r o u g h p u t o f p r o c e s s m a t e r i a l .
of product j is expressed mathematically by
The r e l a t i v e y i e l d
25
Table 1.
Reaction
Dmensonless rate
expression,
system
Relative rate
constant, P
vH
K
A
i-B
isothermal
KfVM/Q%
K
A
>B
adi abati c
K C,
k
a;=B
Kt
isothermal
K
2a
>b
i sothermal
-A-
-C
a
-.2
K"C;
KfCAfVM/%R
adi abati c
kj
a
k,
>b
>c
K
2A
r = C A Kp
i sothermal
kT
^2
[[
26
'
c o n c e n t r a t i o n o f j i n r e f e r e n c e CSTR
Cj / ([])%
(Eq. ]2)
J;
where C. =
da
-1
g
(Eq. 13)
P
r
d9
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.
is defined mathematically by
V -
27
a/(Cl)^
(Eqo 14)
, 8p
9p
r
de
8p_,
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.
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
f q -
' 5 )
Cj' = "ij ( c j ) ^
(Eq. 16)
Now t h e r e l a t i v e t h r o u g h p u t , v , m a y b e d e t e r m i n e d w i t h r e s p e c t t o a s e c o n d
r e f e r e n c e CSTR w h i c h h a s a c o n c e n t r a t i o n o f c o m p o n e n t j g i v e n b y
(c:),
J^R'
C:
J
w h e r e t h e s u b s c r i p t R ' d e n o t e s t h e s e c o n d r e f e r e n c e CSTR.
(Eq. 17)
The r e l a t i v e
28
t h r o u g h p u t w i t h r e s p e c t t o t h e s e c o n d r e f e r e n c e CSTR i s d e t e r m i n e d b y
solution of the steady state form of the general dimensionless equations
w i t h P replaced by PY.
r e f e r e n c e CSTR i s t h e n g i v e n b y
Y =
'
-P ( Z
(Eq. 18)
. r.)^,
1 =1
of component A is given by
(.%, "iA
1 =1
'9'
29
The steady
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
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.
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
Reaction
scheme
Steady state
concentration, C
A^B
C ^ ' = l / ( 1 + P)
Transient concentration
profile, C"(9)
C^' = ~
(l-exp[-(l+P)0])
+ C^'(O) e x p [ - ( l + P ) e ]
I+PC"
1+ P C "
" "T+p (i-exp[-(i+p)e])
k'
+
2a _ ! L , r
K,
2A
K,
40
r"
(2P
(0) exp[-(l+p)e]
+n - s/ ( 2 P + ] ) ^ - 4P^
- d + P ) +i
(1+ P ) ^ + 4 P K ,C
Cg = P C ^ / C I + P K ^ / K ^ )
/K
31
T*).
Figure 2 shows the form o f curves of constant reaction rate f o r the exo
t h e r m i c i r r e v e r s i b l e r e a c t i o n i n t h e (1 -
T ) plane.
At steady state
t h e d i m e n s i o n l e s s f o r m o f t h e g e n e r a l e q u a t i o n s f o r t h e CSTR b e c o m e
1 - C^' - P r ' " ' ( T " ' ) = 0
(Eqo 2 0 )
(Eq, 21 )
balance line
I - C^' =
^ T
-i
(Eq. 22)
Equation 22
FG g i v e s t h e l o c i o f a l l p o s s i b l e p r o
FG a l w a y s c r o s s e s t h e T
axis at the
T h e s l o p e o f FG i s d e t e r m i n e d b y t h e f e e d c o n d i t i o n s f o r a
particular reaction.
R.
(Eq. 23)
p Cp T ^
K is the
At complete con
version
K = t " - lo
(Eq. 24)
32.
TEMPERATURE, T "
Figure 2.
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 -
corresponding t o p o i n t A on FG.
a d i a b a t i c d e r i v a t i v e o f r e a c t i o n r a t e b y A r i s (1^ C h a p t e r 8 ) a n d i s
given by
r " ( C T*) =
d(l-C^)
A t a p o i n t A o n FG
d (l-C^)/dT
= 1/R
production rate,
p o i n t Ao
+ R
(Eq. 25)
ST"
d ^ r / d ( l - C ^ ) = 0^ a n d i t f o l l o w s t h a t
a t p o i n t A
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.
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.
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
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,
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.
5TR.
a r e d e n o t e d b y l i n e s a n d l i n e FG r e s p e c t i v e l y i n F i g u r e 3^
The i n t e r
s e c t i o n o f l i n e s w i t h FG r e p r e s e n t s t e a d y s t a t e s o l u t i o n s t o E q u a t i o n s
20 and 22.
I f a n a d i a b a t i c CSTR i s o p e r a t i n g a t s t e a d y s t a t e C , a
slight increase i n residence time w i l l ignite the reaction and the steady
state w i l l shift to steady state I .
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.
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
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
35
increasing residence
time
TEMPERATURE, T
Figure 3.
36
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,
(Eq. 26)
1 - T
(Eq. 2?)
+ RPK"C^' = 0
K" = 1 + L (T" - 1 )
(Eq. 1 l a )
(If the
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
plotted against
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.
n e g a t i v e , t h e o p t i m a l a d i a b a t i c CSTR a n d p l u g f l o w r e a c t o r c o m b i n a t i o n
w i l l achieve the greatest conversion
From Equation 28 i t i s seen that R and L always appear as the pro
d u c t RLo
Therefore
= C^tRL, P).
(Eqo 2 9 )
B y c o n s i d e r i n g E q u a t i o n s 1 1 a , 2 2 , 26, a n d 2 8 i t i s s e e n t h a t
K' = K'(RL,P)
(Eq. 30)
(Eqo 31)
= r
(RL, P)
(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.
DIMENSIONLESS TEMPERATURE,
T"
VD
Figure 5.
5 \
,o
CONSTATN,K"
o
o
CO
CO
42
RL = 80
RL = 60
RL = 40
.4
CONVERSION, ( I - C
Figure 6.
43
If K
were given
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
below.
(i<)
P
= r - =
-Amax
max
4RL
(Eq. 33)
max
(Eq. 3 5)
max
T'V"
(RL+1)
= I + ^ - jj-
(Eq. 36)
max
(Eq. 37)
max
I t ' i s i n t e r e s t i n g t o n o t e t h a t ( 1 - C ^ ) ...
approaches . 5 as RL becomes
r
max
1argeo
Transient operation
Some t r a n s i e n t s o l u t i o n s o f t h e c o n s t a n t
v o l u m e a d i a b a t i c CSTR e q u a t i o n s w e r e d e t e r m i n e d .
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
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.
values during the transient operation than the steady state reaction rate
only f o r values of the r e l a t i v e rate constant, P, greater than P *
max
Figure 9 shows the e f f e c t o f the i n i t i a l concentration o f reactant,
C ^ ( 0 ) , i n t h e r e a c t o r o n t h e t r a n s i e n t b e h a v i o r f o r f i x e d P a n d RLo I t
i s interesting to note that the transient reaction rate goes through the
only for the
maximum value, r ^ ^ ^ f o r values o f P greater than P max
unrealizeable case where the i n i t i a l dimensionless concentration is equal
to unity.
Figure 7.
DIMENSIONLESS TEMPERATURE,
N3
(jy
T"
K C
O
o
3:
o
m
es
o
ro
O
00
I
O
m
<D
w
o
o
DIMENSIONLESS CONCENTRATION,
Figure 8.
DIMENSIONLESS TEMPERATURE,
Ln
ro
o
K C
O
O
n 7\
o
oo
CO
H
3:
W
o
o
o
o
o
o
o
DIMENSIONLESS CONCENTRATION,:
Figure 9.
DIMENSIONLESS
CONCENTRATION.
C
A
cn
O
m
CO
CO
II
II
K C^
31
VARIABLE-VOLUME OPERATION
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
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
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
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
loO
R e a c t o r f i l l i n g (Q.^ = 1 , Q =0^
ci; =
A
2o0
V (0) = V^) :
[1 - (PV*C*(0)-1) e x p ( - P 9 ) ] o
P(V^+8 )
(Eq. 38)
R e a c t o r E m p t y i n g (Q.
= 1^ Q.^ = 0 , V (O) = 1 ) ;
Ca = 0 ^ ( 0 ) e x p ( - P 0 ) o
3.0
(Eq. 39)
No l o s s i n
g e n e r a l i t y o c c u r s i f i t i s s p e c i f i e d t h a t Q.r = 1 .
An a n a
l y t i c a l s o l u t i o n c a n b e d e t e r m i n e d i f Q.^ i s a n i n t e g e r m u l t i p l e
of
(Qj! - Q. ) o
df
;
(Of-
I
=
= n (an integer)
I - 0"
n 1J
I f n = 2 and v" = 0,
by
(Eq. 40)
3^
o Q
53
[*=
2rP9-l +exp(-P9)l
(Eq. 4,)
(p^r
F o r t h e g e n e r a l c a s e t h e s o l u t i o n becomes
fl, + [(Pnv;)" t - ( 0 ) -
exp(-P9)
C =
[Pn(/ + e /n ) l "
where
Aj = n[Pn(Vg + 0/n) ] " ^-n(n-1) [Pn(\/^+0/n)l" ^...+ (-1)" 'n(n-l).'
4.0
'n(n-l).'
= I.
is an integer multi
r% =
G-Of
Set
= m (an integer)
' - Of
(Eq. 43)
m= ^ 3, 4, . . .
1/
(-t)
B =
L
k=l
k
(Pm) [ 1 - ( t - 8 / m ) ^ l
- 1n(}-0/m).
K.KJ
F o r t h e g e n e r a l c a s e t h e s o l u t i o n becomes
.
m-2
" li&yy
j=0
(Eq. 45)
4- C%(0)
( l - 0 / m ) ^ ^ ' c x p ( - P 9 ) + ( - l ) ^ ^ r p m ( l - 8 / m l ^ ' e x p r P m ( l - 0 / m ) ]B
54
I t can be seen that the expressions for the concentration of rea c t a n t A a r e much m o r e c o m p l i c a t e d i f t h e r e i s a p o s i t i v e d i s c h a r g e
f l o w r a t e w h e n f i l l i n g t h e r e a c t o r o r a p o s i t i v e f e e d r a t e when e m p t y i n g
the reactor.
Semi c o n t i n u o u s V a r i a b l e - V o l u m e O p e r a t i o n
The c y c l e f o r semi c o n t i n u o u s o p e r a t i o n o f t h e STR i s shown i n F i g u r e
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 -
These cycles
F o r t h e semi =
batch cycle, feed i s introduced into the reactor only during the f i l l i n g
fraction- and product is discharged only during the emptying fraction of
t h e semi b a t c h c y c l e .
The f o l l o w i n g e q u a t i o n s m e r e l y d e f i n e p a r a m e t e r s w h i c h a r e c o n
v e n i e n t c o l l e c t i o n s o f o t h e r p a r a m e t e r s f o r t h e semi c o n t i n u o u s c y c l e .
These parameters are used t o simplify equations given l a t e r .
= 0 - 9
F
r
O
(Eq. 46a)
(Eq* 4 6 b )
= 0
- 9
Figure 10.
T h e semi c o n t i n u o u s c y c l e
DIMENSIONLESS DISCHARGE,
(D
a
"1
DIMENSIONLESS FEED, Q
DIMENSIONLESS
VOLUME, V
F i g u r e 11
T h e semi b a t c h c y c l e
DIMEN5IONLESS FEED,
DIMEN5IONLESS DISCHARGE, Q
o
o
o
o
1;
3:
m
%
z.
r*
m
U")
CD
a>
59
(Eq. 46c)
'D
(EQo 46d)
- P = 0 "
(Eq. 46e)
%-
(Eq. 46f)
S'
(Eq. 46g)
^0 "f
T a b l e 3
Batch
(Eq. 46i)
*P
"B " "E
(Eq. 46j)
"D = '
Operation/
fraction of
cycle
Filling
(Eq. 46h)
"C '
T i me
Feed Rate
n"
eo< 9 < Gp
.< 8 <
Empty!ng
8 o < 9 < 9r
Down
8E< 8 < *0
'fB
-fE
+1^1, ( f)
(<F - 'IP
V o l ume
V*
^fP
Cons t r a l n i n q E q u a t i o n s
5p = V ( ?p) +
Discharge
: Rate
'fB
Q."
1.0
i+(Q.f^-Q.) (9-9g)
6o
Table 4.
E q u a t i o n s f o r t h e semi b a t c h c y c l e
Feed
Rate
Time
Operation/
fraction of
Cycle
Di s c h a r g e
Rate
Volume
v"'
-,v
8^<8
Batch
0p < 0
Emptyi ng
OC
DC
Down
UL
DC
CD
OC
DC
CD
Of F
DC
Filling
CD
m
%f
Cl""'
\* < F (
<
0
1 - Qp
S -V
(e -
0g)
v"
0
Constraining Equations
Y
"
Y ^ = 1 - V"
0
II
The v o l u m e o f r e a c t i n g f l u i d i n t h e r e a c t o r a n d t h e f e e d and d i s
charge flow rates are determined as a function of time f o r the general
semicontinuous cycle by fixing eight parameters
The i n s t a n t a n e o u s r e s i
d e n c e t i m e f u n c t i o n , V / Q ^ , may t h e n b e d e t e r m i n e d b y f i x i n g t h e f o l l o w
ing eight parameters.
V /Q.^ -
(V / Q ^ )
T p , T g , Tp}
''7)
F o r t h e semi b a t c h c y c l e t h e v o l u m e o f r e a c t i n g f l u i d a n d t h e f e e d a n d
discharge flow rates are determined as functions of
parametersc
61
=(V"/Q.'^)
(Eq. 48)
Y)
I n t h e STR i n w h i c h t h e m i x i n g o c c u r s o n t h e m o l e c u l a r s c a l e , t h e
conversion of reactant depends on the reaction kinetics and the residence
time distribution of material leaving the reactor.
Therefore, a knowledge
o f t h e r e s i d e n c e t i m e d i s t r i b u t i o n o f m a t e r i a l l e a v i n g t h e STR d u r i n g s e m i c o n t i n u o u s o p e r a t i o n becomes
important.
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.
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
r
9
) = exp - r
"9-8'
,v
,v
(dr/V
)d0
(Eq. 49)
(Eq. 50)
62
u n s t e a d y r e a c t o r a t t i m e 0 i s g i v e n b y Nauman ( 3 0 ) a s
03
t( 0 ) = r
9 'g ( 9 , 9 ')d8' .
(Eq. 5 0
T h e a v e r a g e r e s i d e n c e t i m e as g i v e n b y E q u a t i o n 51 a p p l i e s f o r b o t h t h e
m a t e r i a l l e a v i n g t h e STR a n d t h e m a t e r i a l i n t h e S I R d u e t o t h e a s s u m p t i o n
o f p e r f e c t m i x i n g i n t h e STR.
E q u a t i o n s 4 9 ; 5 0 ; and 51 w e r e u s e d t o d e t e r m i n e t h e r e s i d e n c e t i m e
d i s t r i b u t i o n f u n c t i o n , t h e r e s i d e n c e t i m e f r e q u e n c y f u n c t i o n , and t h e
a v e r a g e r e s i d e n c e t i m e f o r m a t e r i a l l e a v i n g t h e STR d u r i n g semi b a t c h
operation.
Table 5 gives expressions for the residence time distribution func
tion and the residence time frequency function for any real time during
the f i l l i n g fraction of the semibatch cycle.
f o r t h e r e s i d e n c e t i m e d i s t r i b u t i o n and t h e r e s i d e n c e t i m e f r e q u e n c y
d u r i n g t h e b a t c h , e m p t y i n g , a n d down f r a c t i o n s o f t h e s e m i b a t c h c y c l e .
These residence time functions are discontinuous at values of residence
Vv* "J:
t i m e ; 9 ' ^ f o r w h i c h t h e f u n c t i o n Q,^/\/ i s d i s c o n t i n u o u s .
F i g u r e 1 2 shows a p l o t o f t h e r e s i d e n c e t i m e f r e q u e n c y f u n c t i o n f o r
an absolute time, 8^, which corresponds to the end of a semibaich cycle.
The t i m e , 9 ^ , i s assumed l a r g e e n o u g h s o t h a t t h e a v e r a g e r e s i d e n c e t i m e
is a steady periodic function of real time.
curve is unity.
i f t h e maximum r e s i d e n c e t i m e i s f i n i t e , t h e f r e q u e n c y
function at the point where residence time is equal to real time is given
by the Dirac delta function, defined by
Table 5*
Equations for residence time distribution and frequency functions for any real time
during the f i l l i n g f r a c t i o n of the semi batch cycle
Residence Time
Residence Time
Distribution Function
S(8,9')
A I
Cycle
"o + SfF(-o-e')
R e s i d e n c e T i me
Frequency Function
g(0,8')
fF
O S S ' ^ 3 - 0
\ " %'fF
g 9'
6 9-9
+ $ -
F F
"o + 1'fF ("-o'
n- I
(S-^o)
$p ^ 0 '
"o^"o
+ tp-g'))
+ ifF
^ ( G - G g ) + 5p
9^+(j-l )
0'
-0 + jSf -
G'-O
fF
^ 9-2o + J ^
"o + <F
{\iy ( v ; + o - f F ^ Q - y j S p - 8 ' ) )
V'o +
(G-Go)
(<>"' I f F
+ OfF (G-^o)
6(9-8 )
a' = 0
\ * fF ' " " ' c '
ON
V-O
Table 6.
Equations for the residence time d i s t r i b u t i o n and frequency functions for any real time
during the batch, emptying, or down fractions o f the semi batch cycle
R e s i d e n c e T i me
Distribution Function
S(9,0')
0 ^ 9 '
"
n - 1 "<v
g(0,0-)
^ -
g 0-0p +
Sp,
+ Q., ( 0 - 0
Tr
+ $
- 9 ' )
fF
9-0p +(j-1)
n-j
Residence Time
Frequency Function
^ 9-0
*p +
"o ^fF
Sp 3 9 '
+ j5
9' = 0
(v;)
OfF
6(8' - 8)
Figure 12.
R e s i d e n c e t i m e f r e q u e n c y f u n c t i o n f o r semi b a t c h
operation of the stirred tank reactor
this figure gives the residence time frequency
function at a real time corresponding t o the end
of the
semi b a t c h c y c l e w h e r e n a p p r o a c n e s i n f i n i t y
semibatch cycle parameters:
,j
=cr
F
=0.25, Y = 1.0
L
= 0.2, a
= 0.5,
bb
s.oor
4.00
3.00
z
o
u
D
u_
>
u 2.00
z
LU
D
1.00
JZL
o.ooL
0.0
0.8
1.6
2.4
DIMENSION LESS RESIDENCE TIME, 0'
3.2
4.0
67
9V 0
0' = a
6(0'-0) =
The a r e a u n d e r
(Eq. 52)
J g
(Eq. 53)
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.
f u n c t i o n f o r t h e CSTR i s g i v e n b y
e
-0'
d>^ 9
a{9,9') =
.
0
(Eq. 54)
9'>9
toward the maximum volume, the average residence time curve shown i n
Figure 13 for semi batch operation of the STR w i l l approach the average
r e s i d e n c e t i m e c u r v e s h o w n f o r t h e CSTR.
An a v e r a g e r e s i d e n c e t i m e f u n c t i o n which is independent of real time
may be defined for semi continuous or semibatch operation of the STR.
This
is called the flow average residence time for material discharged from the
STR during one periodic cycle and is given i n dimensionless form by
68
u 1.00
>0.40
S 0.20
y 0.00
1/1
0.8
2.4
3.2
4.0
4.8
DIMENSIONLESS REALTIME, 9
UJ
Figure 13.
V^" = 0.2,
= 0.5,
5.6
69
Ci'\(o)de
(Eq. 55)
r
oTdo
^p-i
w h e r e t h e r e a l t i m e , 9 , i s l a r g e e n o u g h s o t h a t T( 0 ) i n E q u a t i o n 5 ' i s a
steady periodic function.
The f l o w a v e r a g e r e s i d e n c e t i m e ,
, f r o m E q u a t i o n 5 5 may b e s i m p l y
e x p r e s s e d as a f u n c t i o n o f t h e s e m i b a t c h c y c l e p a r a m e t e r s f o r s e m i b a t c h
operation of the SIR.
The e x p r e s s i o n i s
(-F
_ 1
'^E)
(Eq. 56)
~
E q u a t i o n 56 i s m o s t d i r e c t l y
1)
The
result is
I P!
2)
;('p) =
(Eq. 57)
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
r(U) - ; l 'p)
3)
Therefore
^ 0 ^ by
(Eq. 58)
S u b s t i t u t i o n o f E q u a t i o n 5 8 i n t o E q u a t i o n 55 and i n t e g r a t i o n
70
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
t h e STR.
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
be the case, since the throughput of material per cycle for semicontlnuous
o p e r a t i o n o f t h e STR i s t h e same as t h e t h r o u g h p u t I n t h e r e f e r e n c e CSTR
a n d t h e a v e r a g e v o l u m e p e r c y c l e f o r semi c o n t i n u o u s o p e r a t i o n o f t h e STR
i s l e s s t h a n t h e v o l u m e o f t h e r e f e r e n c e CSTR.
Isothermal
R e s u l t s f o r r e l a t i v e y i e l d and r e l a t i v e t h r o u g h p u t h a v e b e e n
71
.00
H 0.95
UJ
u
z
LU
Q 0.90
00
LU
cm
0.85
3 0.80
CD
<
en
LU
LL.
00
oo
0.75
LJ
_J
o
00
z 0.70
LU
0.2
0.0
0.4
0.6
0.8
1.0
DIMENSIONLESS M I N I M U M VOLUME, V
Figure ]4.
= 0.25, Y = 1.0
O g = 0.5
72
d e t e r m i n e d f o r t h e i s o t h e r m a l c a s e o f s e m i c o n t i n u o u s o p e r a t i o n o f t h e STR
for various reaction kinetics.
various kinetics.
First order reactions
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
average conversion uT itactani: i n the discharge stream is less for semic o n t i n u o u s o p e r a t i o n o f t h e STR t h a n i n t h e r e f e r e n c e CSTR.
relative yield of product is less than unity.
Thus the
semi batch cycle for which the reactor i s fed or discharged a t a constant
continuous rate, the relative yield is less than unity.
since the average value of
This is expected
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
Figure 15.
Qp = CTg = 0 , 0 ^ 2
= 0 . 2 , Cp =
~ I'O, ^ = 1.0
= 0.5,
o
o
r-
o
o
CTN
._i
4^
rm
VI
VI
O
Z
DIMENSIONLESS CONCENTRATION, C
1
1
I
I
I
t
iO
/O
Mi
QJ
3
TT
-J
a>
0)
o
rf
o
-t
o
o
3
3
C
O
c
cn
rf
n
"1
fO
Q-
"O
II
vn
Figure 16.
= 0.2,
= op
= 0.5,
DIMENSIONLESS VOLUME,
o
oo
O
V"
o
o
N5
O
DIMENSIONLESS CONCENTRATION,
ro
'-t-
C,
CTN
c/>
c/>
m
CD
-P-
Figure 17.
= 0.0, Y = 1.0
= 0 . 2 , CTp =
= 0.5,
DIMENSIONLESS
VOLUME, V"
o
o
m
z
CO
O
UT
DIMENSIONLESS CONCENTRATION,
DIMENSIONLESS
FLOW RATE, a/%
c
C
N>
O
o
o
ro
-P-
ro
CO
c/o
uu
CD
0 in
C^'^
79
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)
t h e f u n c t i o n \i /Q,^ i s d e t e r m i n e d a s a f u n c t i o n o f t h e p a r a m
eters
2)
shown i n Equation 48
3)
80
Y = Y ( V * , O p , O g , G g , "Xa)
( E q - GO)
when
2)
3)
1+p
H=
exp[-Pgg(l-Vg)] (l-exp[-Pgj-(1-V^) ])
(1-expT-Pg^ (1-V^) ]
1 ~
P^Op
1/2
Op
^0^
(1-X^) Y
Y =
(1-a.p
exp
(I-\)Y
-Ve"-"o'
(i-Xa) Y
(I-X^) Y
J
(Eq. 62)
Relative throughput is
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)
(Eq. 64)
The r e s u l t is
and 65 .
Effect of relative rate constant
an i
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.
F i g u r e J8o
CO
CONSTANT
F i g u r e 19=
30.0
20.0
10.0
0.01
0.02
0.05
0.10
0.20
0.50
- y )
1.00
86
important-
The maximum
= 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)
+ 'E + 'f)
67)
pITo ^
+ Cp
(Eq. 68)
function o f the flow average conversion o f reactant as shown i n Figure 19At high values of flow average reactant conversion the relative throughput
87
i s g r e a t e r t h a n u n i t y a n d s e m i b a t c h o p e r a t i o n o f t h e STR i s p r e f e r r e d t o
t h e CSTR.
T h e v a l u e s o f r e l a t i v e t h r o u g h p u t a t z e r o a n d 100% c o n v e r s i o n a r e
given by
VZ 1
Aa I
(Eq. 69)
7)
For the semi batch cycles shown i n Figure 19; Equation 70 reduces t o
2'"^
Y = !j
+ Cfp
(Eq. 71 )
V "
These l i m i t i n g values of relative throughput are evaluated using Equation
65 and noti ng that
1 im
Y
1
2'" '
X
0
= 1 im
(Eq. 72)
P- ^
(Eq. 73)
P- 0
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.
There
88
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.
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.
(l-VQ)exp[-P(]-VQ)]
(Eq. 74)
1 im T] = [ -^ ]
1-Vg exp[-P {] - \ l ]
that
n ( v ; = 0) = [
]
P
Op Gp
(Eq, 75)
and
(Eq. 76)
1 i m T| = 1
V
- 1
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
(11(0 ) = 0
dV"
o
(Eq. 77)
-J;
is satisfied only at V
= 1 in the interval 0 ^ V
^1.
Therefore, rela-
^ 1.
This leads to
2)
yV
o
= 0.
'
I f the sum
+ a^, is
The
90
is equal to zero.
2)
i s as l a r g e a s p o s s i b l e .
A batch
to the emptying
fraction,
4)
(I-exp[-P9p])
1+ P
(Tl)
exp[-P9g]
(Eq. 78)
1 -
OPTIMAL
OPTIMAL
(Y)
1-
, 1
exp
.( I - X j ) * .
(Eq. 79)
exp
The upper bounds for the relative yield and relative throughput with
respect t o the optimal semi batch cycle occur when the batch f r a c t i o n , a^,
of the semi batch cycle i s equal
to unity.
91
(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
p r e s s e d b y E q u a t i o n 8 1 g i v e s t h e r a t i o o f t h e s t e a d y s t a t e CSTR r e s i d e n c e
time t o the plug flow reactor residence time f o r the same conversion and
feed condi tions.
General characteris t i cs of semi batch operati on
The general
c h a r a c t e r i s t i c s o f t h e s e m i b a t c h o p e r a t i o n o f t h e STR w h i c h m a y b e u s e d t o
explain why i t i s possible to obtain a r e l a t i v e y i e l d and a r e l a t i v e
throughput greater than unity are determined by
considering
c h a r a c t e r i s t i c s o f t h e CSTR a n d t h e p l u g f l o w r e a c t o r .
the
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
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
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.
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
Thus
This may be
explained by the fact that the flow average residence time of material
discharged from the reactor per semibatch cycle is less than the residence
t i m e o f m a t e r i a ] l e a v i n g t h e CSTR.
When t h e d e c r e a s e i n f l o w a v e r a g e
residence time more than compensates for the increase i n average reaction
rate by semibatch operation, the relative yield and relative throughput
o b t a i n e d b y s e m i b a t c h o p e r a t i o n o f t h e STR a r e l e s s t h a n u n i t y .
Revers ible f i r s t order reactions
completion.
The
the STR.
93
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
where
Figure 18 for
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
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.
94
y i e l d and relative throughput for the second order reaction of Table 1 are
then given respectively by
2p2
(TL)
=
UPPER
BOUND
;
(l+P) r (2P+l)- V 4P+1 ]
(Eq. 82)
WuppER=
(Eq.83)
BOUND
T h e g e n e r a l e q u a t i o n f o r c o n c e n t r a t i o n i n t h e STR i s n o n l i n e a r a n d
probably cannot be solved analytically.
Therefore, an analytical ex
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.
comparison of the re
Similar to the
F i g u r e 20
Oo 1 J
'jg
Od Oj
gp =
Oo 5
the stirred
1.4
Figure 21.
98
50.0
20.0
10.0
0.01
0.02
0.05
0.1
0.2
0.5
1 . 0
99
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.
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.
true for reactions of order other than unity, since the general equalion
for concentration, Equation 8, is nonlinear for reactions of order
different from unity.
Van De Vusse reactions
Table I .
(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.
100
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 .
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 .
Once the y i e l d ,
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.
A n a l y t i c a l s o l u t i o n s f o r c o n c e n t r a t i o n s i n t h e CSTR
Van De Vusse (32) gives analytical solutions f o r
(P; Og)
"B
"B
VK^/K^)
C q = Cg ( P ; Og^ Op;
(Eq. 84a)
"3 'Af/*i'
Kg/K,, Kg C^f/K,)
. 84c)
(Eq. 84d)
S o m e r e s u l t s f o r y i e l d o f B , ( C g ) , b y s e m i b a t c h o p e r a t i o n o f t h e STR
are shown i n Figures 22 and 23.
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
102
K^/K
0.40
0.30
0.20
UJ
0.10
v.u
0.0
0.2
0.4
0.6
0.8
= 0.5
Figure 23.
104
0.14
10.0
0.12
0.10
0.08
C
O
Q
_l
LU
>-
0.06
0.04
0.02
0.00
0.0
0,2
0.4
0.6
0.8
1.0
105
y i e l d o f B i n t h e CSTR=
limit of yield of B.
constant
ag = 0 . 7 5
= 0.2
d p = O-j:
Y = 1 .0
*0 = O'O
The upper
This
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.
= 0.75, a^. =
= 0.125,
V " = 0.2
o
Region I - maximum y i e l d greatest i n the plug flow
reactor
R e g i o n 11 - m a x i m u m y i e l d g r e a t e s t i n t h e s e m i b a t c h
operated stirred tank reactor
Region I I I - maximum y i e l d greatest i n the
continuous stirred tank reactor
Region IV - maximum y i e l d greater i n the plug flow
reactor than in the continuous stirred
tank reactor
Region V - maximum y i e l d greater i n the cont i nuous
stirred tank reactor than in the plug
flow reactor
10.00
Region
Rg i on I I
CN
ce
LU
Req i on
Region IV
LU
ce
Region V
o
tn
O.Oll / / I
0.3
0.5
2.0
5.0
10.0
20.0
K C
50.0
./H
108
s e m i b a t c h o p e r a t e d STR v e r s u s t h e r e a c t i o n p a r a m e t e r K ^ C ^ ^ / K j .
A p l o t was
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.
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.
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
109
0.35
0.30
K/K| = 1.0
0.20
Q
_J
LU
>
z:
3
IS*.
;o.io
<
z:
0.00
0.5
1.0
5.0
2.0
D I M E N S I O N ! E S S REACTION PARAMETER. K . C . V K .
'
Figure 25.
j At
Maximum y i e l d o f intermediate B in d i f f e r e n t
r e a c t o r s y s t e m s w i t h V a n De V u s s e r e a c t i o n s
versus the dimension!ess reaction parameter
for the side reaction
Curve A - plug flow reactor
Curve B - semi batch operation o f the s t i r r e d
tank reactor.
'= 0.2. a = 0.75
G
= cr
= 0.125
10.0
110
o p e r a t i o n , n a m e l y , t h e o p t i m a l a d i a b a t i c CSTR a n d p l u g f l o w r e a c t o r
combi nation.
The assumption that the rate constant, K , could be approxiiiuit- il as
a linear function o f temperature was used f o r most of the results pre
sented here.
1 ] = T l ( R L , P , \ I ^ , O g , O p , Og)
(Eq. 85)
(Eq. 8() )
values
Ill
show p r o f i l e s of
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
(Eq. 87)
more complicated than the isothermal case, and the relationships between
the semi batch cycle parameters, namely, V^,, Op,
yield or relative throughput for a given adiabatic system are not the
same as f o r the isothermal case.
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 26.
= 0.125,
relative yield;
= 0 . 5 , cTg = 0 . 7 5 ,
Y = 1.0
1] = 1 . 1 1 4
o
ro
o
-U
o
o
O
o
to
<-n
en
o
O
O
Figure 27.
= 0.125
= 0 . 5 , ag = 0.75,
^ = 1.0
r e l a t i v e y i e l d ; Tj = 1 . 1
transient and steady state profiles f o r
the reference adiabatic continuous stirred
tank reactor
transient and periodic profiles for the
semi batch operation of the a d i a b a t e s t i r r e d
tank reactor
DIMENSIONLESS
VOLUME,
V"
oo
oo
' o
vn
DIMENSIONLESS CONCENTRATION,
Figure 28.
= 0.2,
= 0.75,
Y = 1.0
r e l a t i v e y i e l d ; Tl = 1 . 1
transient and steady state p r o f i l e f o r the
reference adiabatic continuous s t i r r e d tank reactor
transient and periodic p r o f i l e f o r the ?emibatch
operation of the adiabatic s t i r r e d tank reactor
Figure 29.
= 0.125
= 0 . 2 , .:Tg= 0 . 7 5 ,
^ = i.O
r e l a t i v e y i e l d ; T] < 1 . 0
transient and steady state p r o f i l e for the
reference adiabatic continuous s t i r r e d tank reactor
transient and periodic p r o f i l e for the
semi batch operation o f the a d i a b a t i c s t i r r e d
tank reactor
DIMENSIONLESS CONCENTRATION,
C^
DIMENSIONLESS CONCENTRATION,
Jo
C^"
cn
00
o
o
Figure 30.
= 0,5, o
= 0.60,
= 0.125
r e l - a t i v e y i e l d ; T| = 1 . 0 7
transient and steady state p r o f i l e for t h e
reference adiabatic continuous s t i r r e d tank reactor
transient and steady state p r o f i l e f o r the
semibatch operation of the adiabatic s t i r r e d
tank reactor
Figure 31.
= 0.5. r 0 . 7 5 .
= Oj- = 0 . 1 2 5
r e l a t i v e y i e l d : Ti < 1 . 0
transient and steady state p r o f i l e f o r t h e
reference adiabatic continuon'- s t ; rred tank reactor
t r a n s i e n t and p e r i o d i c p r o f i l e f o r t h e semi batch
operation of adiabatic stirred tank reactor
DIMENSIONLESS CONCENTRATION,
.o
Q\
oo
DIMENSIONLESS CONCENTRATION,
C^'^
o
o
o
CO
N3
C^'"'
z
I
ro
CD
-p-
o
o
120
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
This
is due to the fact that the average reaction rate by seinibatch operation must be less than the reaction rate i n the
r e f e r e n c e a d i a b a t i c CSTR.
2)
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 .
t i o n t h e a d i a b a t i c CSTR i s o p e r a t e d a t t h e m a x i m u m r e a c t i o n
rate and i s followed i n series by the semi batch operated
adiabatic STR.
As t h e b a t c h f r a c t i o n , O g , a p p r o a c h e s u n i t y
and the minimum volume, M a p p r o a c h e s zero for the semibatch cycle the relative yield and r e l a t i v e throughput
approach their upper bounds, which are obtained i n the
o p t i m a l a d i a b a t i c CSTR a n d p l u g f l o w r e a c t o r c o m b i n a t i o n .
The upper bounds of r e l a t i v e y i e l d and r e l a t i v e throughput obtained
b y t h e o p t i m a l a d i a b a t i c CSTR a n d p l u g f l o w r e a c t o r c o m b i n a t i o n m a y b e
expressed analytically.
2RLP
RL exp('v)-l
(Tl)
UPPER
BOUND
RL(exp(\)+I)
(Eq. 88)
where y = (RL+l)P
^
RL+l
2(RL-1)
and P z (P)^"
(RL+1)'
MAX
%&/
(RLX^ + I ) ]
(Y)
(Eq. 89)
RLX^ +
UPPER
BOUND
RL+1
RL(l-X^)
2(RL-1)
(RL+1)2
122
where X. ^ (X.)_*
A
A ' r MAX
'
2RL
W h e n t h e v a l u e s o f P a n d X ^ i n E q u a t i o n s 8 8 i i n d o Q 11,
i;
!i . ^
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 '
c
' ii
ii m;
T ! r : .< , i
im
.ilvi
! '
- !
i.lir:
approaclios un , iv
if
I 'cM. 1 I
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
ri.-
i n t n,
Mjrt
m.i
,
approaches zero.
, e i e -
jii
123
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
occurs at smaller values of the relative rate constant for highly heat
sensitive reactions
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
124
qO.8
0.03
0.10
0.20I
0.50
1.00
2.00
Figure 32.
. rnti m
t h e r a t e c o n s t a n t , K , u s e d i n d e t e r m i n i n g l i u " .
a linear function of temperature
cu rvi"
i-
c u r v e A - i s o t h e r m a l p l u g f l o w r e a c t o r : RL
curve B - optimal adiabatic continuous s l i r i ' d i iv rc.icior
and plug flow reactor combi nai ion : -I ~ 7.;'
curve C - optimal adiabatic continuous scirr.-.i i.tn: r,,.ci.)r
and p l u g f l o w r e a c t o r comb i n a l i .,ri ; ili
i.n
c u r v e D - a d i a b a t i c p l u g f l o w r e a c t o r : RL
= 'rJ.n
c u r v e E - s e m i b a t c h o p e r a t i o n o f t h e a d i dfiuC i c - r i i - :
tank r e a c t o r : RL = 40.0. V
Figure 33.
curve D - a d i a b a t i c p l u g f l o w r e a c t o r : RL = ^ 0 . 0
curve E - semi batch operation of the adiabatic
s t i r r e d tank reactor: RL= 40.0,
V ^ ' " = 0 . 1 , cTg = 0 . 0 , 0 ^ = 0 ^ = 0 . 5
]26
100.0
0.11
0.01
I
0.10
DiriEMSIOMLESS FLOW a v e r a g e c o n c e n t r a t i o n , ( i - % !
l.W
127
to the conversion for which the average reaction rate i n the adiabatic
p l u g f l o w r e a c t o r i s t h e same as the r e a c t i o n r a t e i n t h e a d i a b a t i c CSTR.
T h e o p t i m a l a d i a b a t i c CSTR a n d p l u g f l o w r e a c t o r c o m b i n a t i o n m a y b e
thought o f as s i m u l a t i n g a l e v e l o f mixing between complete mixing i n t h e
CSTR and no m i x i n g i n t h e p l u g f l o w r e a c t o r .
to
S i n c e semi b a t c h o p e r a t i o n o f t h e STR s i m u l a t e s an i n t e r m e d i a t e
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 ,
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.
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.
tive rate constant i n reactor systems for which the rate constant i s
determined by the Arrhenius equation.
mated by curve B of Figure 32.
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.
will be obtained.
1 he
129
a
_j
LU
>
LU
>
_I
q:
LU
0.2
0.5
1.0
2.0
10.0
Figure 34.
130
ol
temperature.
' . lii
i!;i
The study of
i i -
/ n i
a b l e -volume o p e r a t i o n o f t h e STR was undertaken t o s h w ' h c t i l '-possible to obtain a relative yield greater than unity by u vai i ^ '
v o l u m e o p e r a t i o n w h i c h e m p l o y s c o n t i n u o u s p e r i o d i c f e e d a11J d l - . i
i:
streams.
The continuous variable-volume cycle w h i c h was D U i J i e J rxl '..i i
a r e l a t i v e y i e l d greater than u n i t y was obtained employs
charge flow rates that are sinusoidal functions of tinie.
i'uLci
'
c i i .~
Tlie ki nuli ^
scheme i s t h a t o f a f i r s t o r d e r i r r e v e r s i b l e r e a c t i o n I n an I >oilter.-<c:l
STR.
Douglas and Rippen (16) studied the periodic o p e r a t i o n oP ! l u i o thermal STR w i t h second order k i n e t i c s i n w h i c h the feed and di - J i n :'
streams were sinusoidal
h:-:
T h u s t h e v o l u m e o f t h e STR w a ^ c u n i : i ; i .
D o u g l a s a n d R i p p e n f o u n d t h a t t h e a v e r a g e c o n v e r s i o n w a s d a c i L u v d ' v i d!
type o f operation for all values of the amplitude and , rcqucricy
il . . .
131
Q,'^ = Z s i n CO 0 + 1
(Eq. 90)
Q,
(Eq.
= Z s i n ( 0 - 0 ) + 1
91)
= f / (
MAX
0 = phase lag of output flow behind input f l o w i n r a d i a n s .
(Eq.
92)
The result i s
[ 1 - c o s ) 9 + c o s ( c D 9- 0 ) - c o s 0 ] + V
O)
(''"O)]
(Eq.
93)
132
(Eq. 94)
V" = I -
- 0)-2 cos
^ 2 ^
(Eq. 95)
m"
where m" ^
and m = 4Z cos (
(Eq. 96)
(Eq. 97)
Some
to zero.
It
133
T h u s t h e m i n i m u m v o l u m e ciiii i n n
to
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.
radians=
the fixed
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.
v.,! ue u f
r-l.-tive
T h i s c o n c I u s i e n i -,
Figure 35.
Figure 36.
RELATIVE YIELD.
136
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)
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
2)
the STR.
The upper bounds of r e l a t i v e y i e l d and r e l a t i v e throughput by variablevolume operation are obtained by the plug flow reactor, or equiva
lent! y, the batch reactor.
3)
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
ihroughouL
138
k)
l a r g e as p o s s i b l e .
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)
139
2)
3)
There exist
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)
140
B.
C.
2)
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)
14]
RECOMMENDATIONS
]k2
LITERATURE CITED
1.
Aris. R.
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ACKNOWLEDGMENTS
support.