System details

Figure 1
Column Configuration.
In the two-product reaction system, the column has both bottoms and distillate
products coming from the two ends of the column. The two reactant feed streams are
fed into the middle section of the column. With a one-product reaction system without
inerts, the column has only a bottoms or a distillate product. If the product component
C is heavier than the reactant components and !, there is a bottoms stream but no
distillate. The column operates at total reflu" with all of the overhead vapour
condensed and returned to the column as reflu". There is no need to have a rectifying
section because there is no distillate and no need to maintain any composition at the
top of the column. #o the column configuration in the one-product ternary system
without inerts is $uite different than the two-product configuration. Figure 1 shows
the flowsheet. There are only stripping and reactive sections.
Chemistry and Phase Equilibrium Parameters.
1 gives %inetic and vapor-li$uid phase e$uilibrium parameters used in the numerical
case considered in this paper. The overall reaction rate on the nth tray depends on the
molar holdup M
&'
, the specific forward and bac%ward reaction rates k
F
and k
!
, and
the li$uid mole fractions.

The e$uilibrium constant K
e$
at ()) * is +,. &elative volatilities are constant at +
between ad-acent components.
The product C is the high-boiling component, so it is removed from the bottom of the
column.
Design Parameters and Procedure. The ternary system without inerts has two feed
streams and a bottoms stream, but there is no distillate. In addition, the impurity in the
bottoms product will be mostly the heavier of the two reactants, component !. This
means that the flowrates of the two fresh feed streams F
,
and F
,!
will not be e$ual.
In addition, the reaction is not e$uimolar. Two moles of reactants produce one mole
of product. Therefore, there is a decrease in the molar li$uid flowrates in the reaction
section due to the none$uimolar reaction. The design procedure used for this system is
to fi" the production rate of product C at 1+.) mol s-1 and the purity of the bottoms
product at ,../ mole fraction C. This means that the bottoms flowrate is 1+.)0,../ 1
1+./23 mol s-1. The production rate re$uires that 1+.) mol s-1 of both and ! be
consumed. Therefore, at least this amount must be fed to the column. In addition,
however, there is a loss of reactants in the bottoms to account for the + mol 4
impurity. It is mostly !, but there is also a small amount of . The concentrations of
and ! change with the various designs. Therefore, the flowrates of the fresh feeds
are slightly different in each design. dynamic rela"ation method is used to find
steady-state conditions. t each point in time during the dynamic simulation, the fresh
feed flowrates are calculated from the fi"ed value of the bottoms flowrate B and the
present values of the bottoms compositions xB,j, which change with time until a
steady-state solution is achieved.
#ince ! is heavier than , the fresh feed flowrate of ! is somewhat larger than that of
. The reflu" flowrate is changed to drive the bottoms composition to ./ mol 4 C.
The vapour boilup controls the level in the base. There is no distillate. The reflu"
drum level is not controlled. The base case considered has five stripping trays and
nine reactive trays. The column operates at / bar and has +,,, mol of holdup on
reactive trays. The column diameter is 1.,. m, as calculated from vapor loading
limitations 5e$uation given in a previous paper21. This diameter gives a reasonable
li$uid height 5in terms of hydraulics1 on the reactive trays of ,.,33 m with the +,,,
mol of li$uid holdup. 6nder these conditions, the bottoms composition is ,.+2 mol 4
and 1.32 mol 4 !. The resulting fresh feeds are F
,
1 1+.)( mol s
-1
and F
,!
1 1+./+
mol s-1. The vapor boilup re$uired to achieve this purity of the product is )+.,( mols
-
1
, and the reflu" flowrate is /,.13 mol s-1, which is the overhead vapor rate. Table +
gives conditions for the base case. 7ote that the reflu" composition is mostly the
lightest component , but some of the other two components are also present. Figure
+ gives the composition profiles. 8$uimolal overflow is assumed, so the li$uid and
vapor rates are constant in the nonreactive section of the column. 9owever,
there are changes in the li$uid and vapor flowrates in the reactive section due to two
effects: 511 the reaction is not e$uimolar 51mole of product is produced by the
consumption of + moles of reactants1 and 5+1 the e"othermic reaction causes
vapori;ation of some of the li$uid. Therefore, vapor rates increase up the
column and li$uid rates decrease down the column. &emember the heat of reaction is
negative.
Figure +
Effect of Pressure.
7ow that we have a design procedure and a base case, we are ready to see how
various parameters affect the ternary reactive column without inerts. #ince, vapor
boilup is a direct measure of energy consumption, the optimum economic pressure is
3 bar. There is an optimum pressure because there is an optimum temperature. 9igh
temperatures give low chemical e$uilibrium constants because the activation energy
of the bac%ward reaction is larger than that of the forward reaction in this e"othermic
reaction system. <ow temperatures give small specific reaction rates and reduce
reaction rates. The pressure of 3 bar gives temperatures on the reactive trays that
range from (/) to (3/ *, as shown in Figure =. 9igher pressures give higher
temperatures that decrease the chemical e$uilibrium constant. <ower pressures give
lower temperatures that decrease specific
reaction rates. The lower graphs in Figure ( give the compositions of the reflu" xD,j
and the bottoms product, xB,j. They change very little with pressure. 7otice that the
reflu" has a high concentration of the lightest component while the bottoms
impurity is mostly the heavier reactant !. It should be pointed out that the flowrate of
the vapor boilup by itself is not the only energy issue. What also matters is the cost of
the energy, which depends on its temperature level. 9igher column pressures mean
higher base temperatures and re$uire higher temperature energy sources. >ver the
pressure range )-. bar, Figure = shows that the base temperature varies from =+, to
==, *, which would change the re$uired pressure of the steam significantly.
Holdup on Reactive Trays.
Intuition would lead us to predict that increasing reactive tray holdup M
&'
should
improve performance and decreases energy consumption. This is indeed true. For the
base-case value of M
&'
1 1,,, mol, vapor boilup V# is )+., mol s-1. ?ecreasing M
&'
to /,, and ),, mol raises V# to )=.2 and )..3 mol s
-
, respectively. Increasing M
&'
to
+,,, mol decreases V# to ),.3 mol s
-1
. There are no counterintuitive effects of
reactive tray holdup.
.!. "umber of Reactive Trays. dding more reactive trays improves the steady-
state design of the ternary system because vapor boilup decreases as reactive trays are
added. The composition profiles throughout the column. The sharp li$uid composition
changes that occur between the top of the column on tray N
T
and in the reflu" drum
5stage N
T
@ 11 for the values of N
&'
5+, 1,1 is caused by the total reflu" operation. The
vapor composition on tray N
T
is higher for the lighter component than the li$uid
composition. The reverse is true for the heavier component !. Therefore, the li$uid
leaving the total condenser is richer in than the top tray and leaner in !.
#bout the reactants $ product%
Reactant #% &sobutene
&sobutylene 5or +-methylpropene1 is a hydrocarbon of significant industrial
importance. It is a four-carbon branched al%ene 5olefin1.
'ses% It is reacted with methanol and ethanol in the manufacture of the gasoline
o"ygenates methyl tert-butyl ether 5AT!81 and ethyl tert-butyl ether 58T!81,
respectively. l%ylation with butane produces isooctane, another fuel additive.
Bolymeri;ation of isobutylene produces butyl rubber 5polyisobutylene1. ntio"idants
such as butylated hydro"ytoluene 5!9T1 and butylated hydro"yanisole 5!91 are
produced.
(anufacture% Isobutylene can be isolated from refinery streams by reaction with
sulfuric acid, but the most common industrial method for its production is by catalytic
dehydrogenation of isobutane.
Fig.(
Reactant )*+% (etahnol
(ethanol, also %nown as methyl alcohol, ,ood alcohol, ,ood naphtha or ,ood
spirits, is a chemical with the formula C9
(
>9. Aethanol is produced naturally in the
anaerobic metabolism of many varieties of bacteria.
'ses% Aethanol, a common laboratory solvent, is especially useful for 9B<C,
6C0CI# spectroscopy, and <CA# due to its low 6C cutoff.
Fig.=
Product )C+% (T*E
(ethyl tert-butyl ether, also %nown as methyl tertiary butyl ether and (T*E, is
an organic compound with molecular formula 5C9
(
1
(
C>C9
(
. AT!8 is a volatile,
flammable, and colorless li$uid that is sparingly soluble in water.
AT!8 is manufactured via the chemical reaction of methanol and isobutylene.
'ses% AT!8 is almost e"clusively used as a fuel component in fuel for gasoline
engines. It is one of a group of chemicals commonly %nown as o"ygenates because
they raise the o"ygen content of gasoline.
Fig.2
Result and Discussions%
Wor% ?one:
>b-ective: The effect of %inetic and design parameters on Ternary
&eactive ?istillation Columns and henceforth create a ./4 efficient system. The
system here is without any inert.
Effect of .ariation /f Equilibrium Constant%
Initially we too% a system at / bar pressure D *
e$
E+, with a reactive distillation
column having 1) trays. The feed we too% were isobutene and methanol and we got
AT!8 as our final product. We set ./4 pure product as our target. For that purpose
we calculated the amount of heat re$uired 5Fr1. fter that we varied the *
e$
for same
pressure. 9ere, we observed that the process is feasible only within a certain pressure
range. lso the vapour boilup ratio decreases with increasing the pressure. Thus we
%now that as we increase the *
e$
the reaction is easily possible but the limit of
increasing that is also fi"ed. Too much increase or decrease in the value of *
e$
will
disturb the desired concentration.
Bressure E / bar
*
e$
Capor boilup, mol s
-1
*e$E+, )1.())1
*e$E1+ /).2+)1
*e$E1) 3,.)(+(
*e$E+= 22.2()+
*e$E+/ 21.,2)2
&8#6<T
Case 1
*eeping the pressure to be same
0a1
Initial pressure E / bar
?esired output E ./4 product
*e$ E +,
Terms to be calculated:
Capour boilup
In the sub case we change the value of Fr to obtain the value of the product to be ./
4.
Therefore
Capour boilup in mol s
-1
E )1.())1 by simulation
0b1
Initial pressure E / bar
?esired output E ./4 product
*e$ E 1+
Terms to be calculated:
Capour boilup
Corresponding we change the Fr value so as to obtain the desired product.
In the sub case we change the value of Fr to obtain the value of the product to be ./
4.
Therefore
Capour boilup in mol s
-1
E /).2+)1 by simulation
0c1
Initial pressure E / bar
?esired output E ./4 product
*e$ E 1)
Terms to be calculated:
Capour boilup
Corresponding we change the Fr value so as to obtain the desired product.
In the sub case we change the value of Fr to obtain the value of the product to be ./
4.
Therefore
Capour boilup in mol s
-1
E 3,.)(+( by simulation
0d1
Initial pressure E / bar
?esired output E ./4 product
*e$ E +=
Terms to be calculated:
Capour boilup
Corresponding we change the Fr value so as to obtain the desired product.
In the sub case we change the value of Fr to obtain the value of the product to be ./
4.
Therefore
Capour boilup in mol s
-1
E 22.2()+ by simulation
0e1
Initial pressure E / bar
?esired output E ./4 product
*e$ E +/
Terms to be calculated:
Capour boilup
Corresponding we change the Fr value so as to obtain the desired product.
In the sub case we change the value of Fr to obtain the value of the product to be ./
4.
Therefore
Capour boilup in mol s
-1
E 21.,2)2 by simulation
Result in the tabular form
Table2
*
e$
Capor boilup, mol s
-1
*e$E+, )1.())1
*e$E1+ /).2+)1
*e$E1) 3,.)(+(
*e$E+= 22.2()+
*e$E+/ 21.,2)2
3ith graph as follo,s for the first result
Fig.) It is the corresponding graph of the temperature against tray number for the
given initial condition.
keq v/s Vapor boilup, mol s-1
0
10
20
30
40
50
60
70
80
90
100
0 5 10 15 20 25 30
keq
V
a
p
o
r

b
o
i
l
u
p
,

m
o
l

s
-
1
Fig.3 The above plot represents the variation of Caopr boilup ratio with *
e$
The effect of change of *
e$
as discussed in the theory is clearly reflected from the
graph i.e. with the increase in *
e$
the boilup value decreases. For the
reactor0column0recycle process, optimum temperature of reactor increases with the
increase of K
EQ
value. 9igher temperatures give bigger specific reaction rates, which
results in smaller reactor holdup VR. #ince lower temperatures decrease specific
reaction rates, more zB leaves the reactor with decreasing value of K
EQ.
Therefore,
lower values of K
EQ
result in higher amount of vapor boilup in the column to get the
specified product purity.
Case +
*eeping the *e$ to be the same
0a1
*e$ E +,
?esired output E ./4 product
B E / bar
Terms to be calculated:
Capour boilup
In the sub case we change the value of Fr to obtain the value of the product to be ./
4.
Therefore
Capour boilup in mol s
-1
E )1.())1 by simulation
0b1
*e$ E +,
?esired output E ./4 product
B E 3 bar
Terms to be calculated:
Capour boilup
In the sub case we change the value of Fr to obtain the value of the product to be ./
4.
Therefore
Capour boilup in mol s
-1
E 22.2()+ by simulation
0c1
*e$ E +,
?esired output E ./4 product
B E ) bar
Terms to be calculated:
Capour boilup
In the sub case we change the value of Fr to obtain the value of the product to be ./
4.
Therefore
Capour boilup in mol s
-1
E 2,.,1(( by simulation
0d1
*e$ E +,
?esired output E ./4 product
B E 2 bar
Terms to be calculated:
Capour boilup
In the sub case we change the value of Fr to obtain the value of the product to be ./
4.
Therefore
Capour boilup in mol s
-1
E =2.=1,/ by simulation
Table +
*e$E+, Capor boilup, mol s
-1
BE/ bar )1.())1
BE3 bar 22.2()+
BE) bar 2,.,1((
BE2 bar =2.=1,/
Fig./ It the general case variation of mole fraction in the respective trays vs. the tray
number, for the case 1 part 5a1
Pressure v/s Qr
0
10
20
30
40
50
60
70
0 2 4 6 8 10
Pressure
Q
r
Fig.. The above figure ahows the variation of Fr when we change Bressure for a
given value of *
e$
The above graphs have been plotted between
1. Tray number and temperature
+. tray number and mole fraction
The condenser wor%s at a temperature of (3. *. The bottom product which we are
getting has ./4 purity. In the graph we also see that at two trays the change in
temperature in sudden. Those two trays are where we supply feed. This is because the
input feed ta%es latent heat for phase change or pre-heating before the reaction. These
trays are tray number 1 and .. While simulating the program we actually put up the
feed trays as + and 1,. GH is isobutene which is introduced at tray 1 and G!H is
methanol which is introduced at tray .. The reaction is etherification. We are not
ta%ing any distillate here i.e. this is a situation of & E I.
&E 5<0?1
Where, &E &eflu" ratio
<E reflu"
?E distillate and since here ?E,, so, it becomes infinite. #o, this is a situation
of minimum no. of trays and minimum height of distillation column possible. s we
go high in the column we find more volatile components because the temperature is
high. This is evident from Fig.).
Fig./ is the graph of variation of mole fraction of the ( components of the system with
no. of trays. dding more reactive trays improves the steady-state design of the
ternary system because vapor boilup decreases as reactive trays are added. Fig.3 also
shows the composition profiles throughout the column for + values of N
&'
51 and .1.
7ote. the sharp li$uid composition changes occur between the top of the column on
tray N
T
and in the reflu" drum 5stage N
T
@ 11. This is caused by the total reflu"
operation. The vapor composition on tray N
T
is higher for the lighter component
than the li$uid composition. The reverse is true for the heavier component !.
Therefore, the li$uid leaving the total condenser is richer in than the top tray and
leaner in !. Thus, the li$uid composition profiles -ump up for and drop for ! at the
top of the column.
It is %nown that the e$uilibrium constant K
EQ
decreases with increasing temperature
for an e"othermic reaction, and higher e$uilibrium constant pushes the reaction to the
right. Thus, the column can operate at higher pressures when K
EQ
is larger, and higher
values of K
EQ
re$uire less vapor boilup. The optimum number of stripping trays does
not change significantly, because product purity is specified and relative volatilities
are constant. >n the other hand, since there is a need of e"tra trays to achieve to the
conversion in the reactive ;one, the optimum number of reactive trays increases
dramatically with the decrease of K
EQ
.
The increase of vapor boilup and reactor si;e0number of reactive trays with smaller
K
EQ
increases both the capital and energy costs.
Conclusion%
AT!8 Ternary system having two reactants and one product has been e"plored. The
effects of a number of %inetic and design parameters have been e"plored and found to
change significantly from system to system.