Escolar Documentos
Profissional Documentos
Cultura Documentos
Optimization
Department
of Chemical
and Petroleum
Engineering,
Faculty
of Engineering,
UAE
University,
P.O.
Box
17555, Al-Ah,
United
Arab
Emirates
Abstract
A fundamental fixed-bed catalytic reactor model has beendevelopedfor usein selectingalternative operating strategieson a
commercialmethyl-t-butyl ether (MTBE) unit. The model is basedon generalchemicalengineeringprinciplesand is tuned to
representthe operation of the reactors systemof a given MTBE unit. Constrainedoptimization techniquesare usedto determine
the optimum operating conditions of the reactors systemthat give the maximum net profit. The model will enablethe user to
predict the required bed temperature rises, the required recycle rate for specificsingle-passconversion and the required heat
removal rate in the coolers of an existing unit. For optimization purposes,the model is usedto investigatethe effect on unit
profitability when variablessuchasthe conversionper passor the total conversionweremodified. A computer program, MTBEC,
wasdevelopedfor solving the model equations.Conversionper passwasvaried from 62.3%to 87.3%in incrementsof 5%. Based
on thesecases,conversionper passhigher than the original designvalue of 72.3%is suggested.The optimum conversionper pass
value appearsto be about 75.5% and representsan improvement of about 1.5%on daily net profit for the pricesquoted. These
resultsdemonstratethe useof the modelin selectingmore economicallyattractive operating targets.The modelcan alsobe used
to investigatethe effect of other variablesamenableto optimization, e.g. fresh feed stock quality, feed costsand bed temperature
profiles.
Keywords:
MTBE synthesis;Fixed-bed reactor system; Catalytic reactor model; Constrained optimization techniques;Model
equations
1. Introduction
way of improving productivity per given reactor volume may be accomplished by optimizing
the plant
operating conditions [2]. However, the optimization of
an existing producing unit is a different type of optimization than that made by the original designer of the
unit. The original design is based on a given set of
product prices and capital equipment costs with given
feed and product specifications. All process equipment
are sized and rated to meet the design operation. After
a certain period of operation, the economics may
change significantly from the original design basis.
Certain pieces of equipment, feed and/or product
qualtities may become bottlenecks or constraints to the
most economic operation. In addition, new catalysts are
being developed whose activities and selectivities are
better than that used in the original design [3]. As such,
a process model is needed to predict optimum operations more economically.
In its simplest form this
model may be a heuristic model developed by an operator through first-hand observation of the unit. How-
132
EM.
Elkanzi
/ Chemical
Engineering
and Processing
35 (1996)
131-139
H-C-OH
+ H-C-OH
H
CH,
I
I
+ C=CH, $ H-C-0-C-CH,
(1)
I
I
I
H
CH,
CH,
This reaction is exothermic with 37.7 kJ of heat released
for each mole of isobutylene converted, the maximum
conversion being determined by a thermodynamic equilibrium value [4-61. The reaction is also extremely
selective to isobutylene, i.e. other butenes are not converted [7] other than under conditions of hot spots
when linear butenes can react [8]. Under design conditions and using a sulfonated polystyrene resin (e.g.
polystyrene/divinylbenzene copolymer), essentially the
only hydrocarbon molecule to react is isobutylene. The
remaining hydrocarbons in the feed stream are almost
entirely inert. However, undesirable side-reactionsmay
take place side by side with the main reaction of Eq.
(1). The most important side-reaction is the dimerization of isobutylene to a mixture of the isomers 2,4,4trimethyl-1-pentene (TMP-1) and 2,4,4-trimethyl2-pentene (TMP-2). Interaction of two molecules of
isobutylene produces the dimer [4],
CI-4
CH,
CH,
CH3
I
CH,
I
CH,
CH, H CH,
(2)
(3)
I
CH,
CH,
CH,
H
I
H-C-OH
I
H
CK
2. Process description
+H-C-0-C-H+H1O
I
CH,
(4)
The direct addition of olefins catalyzed by ion-exchange resins to give ethers was investigated by Ancillotti et al. [12]. They confirmed the high reactivity of
isobutylene with methanol compared to other olefins.
Several investigators [4,5,12- 171have studied the kinetics of the reaction of Eq. (1) both in the liquid and
vapor phases, and generally two approaches were followed for the analysis of the kinetic data. In the first
approach the reaction is considered as a homogeneous
catalytic reaction where the reactants are confined
within the gel-like resin. In the second approach, the
resin is treated like a solid catalyst and the reaction is
considered as a heterogeneouscatalytic reaction. In one
study [5], a first-order dependence with respect to
isobutene was found together with a -0.25 order dependence with respect to methanol. In another study
[12], a power law rate expression with a zero-order
dependenceof rate on methanol concentrations of more
than 4 mall- was reported. In the same study, a
133
Pa)
Under industrial conditions the forward reaction goes
almost to completion
(96% conversion of isobutylene). Moreover, the reported [4] ratio of k,/kl at
60 C is about 0.03 and the corresponding activation
energies ratio is about 1.6. Thus the reversible step
may be neglected and Eq. (4a) reduces to a first-order dependence on the isobutylene concentration. In
fact, the analysis of the kinetic data of Subramanian
and Bhatia [13] based on first-order kinetics gives a
better fit of the data than the assumed second-order
forward step and the reversible first-order one. Based
on the above argument and on the results of Ancillotti et al. [12] and on the analysis of industrial data,
a heterogeneous rate expression for the first-order dependence on isobutylene concentration with an activation energy of 17.4 kcal mol- will be used in this
study.
2.3. The seactor system
In the idealized process involving the flow diagram
shown schematically in Fig. 1, the reactor system includes the catalytic reactors, coolers and static mixers. The fresh feed enters a static mixer where
methanol and isobutylene liquids are blended. The
combined fresh feed (FF) then mixes with the first
reactors effluent recycle (R*) and passes through a
Table 1
Normal reactor system operation
Parameter
Reactor I
Reactor II
LHSV, s-
Inlet temp., K
AT, K
2.94 x 1O-3
321
14.2(q)
7.5 x 10-4
314.7
3.2(%)
72.3(X,)
55.5(X,)
91(X,)
87.3
2.88
25
29.3
1.3x103
96(X,)
91.4
25
29.3
8.5 x 10
4.16
0.0072
0.25
0.64
4.9
0.01
0.83
0.2
Table 2
Price assumptions
Feeds:
iC,(mixed butenes)
MeOH
Products:
MTBE
Utilities
Water cooling (11.1 K rise), m3
Electricity, kWh
Power, pumping
14 per kg MTBE
2.2 per kg MTBE
SO.07 per BHP h-
134
EM.
Elkanzi
/ Chemical
Engineering
Table 3
Base case economics
and Processing
35 (1996)
131-139
Product
Quantity
Unit value
MTBE
3780.7 BBL d-
Feeds:
iC4
MeOH
2993.4 BBL d-
1290 BBL d-
CpidT-
S per day
ET
C,i dT-
FiA.H~X=
s298
i=l
(7)
and
52 385
30 828
QR= i
Operating costs:
Pumping
Cooling
Other?
Total cost
Net profit per day
Net profit per BBL
MTBE
2532
7597
34 445
127 787
43 100
11.4
CpidT
(8)
sT
x2 dXi
and
a Others include: operating costs other than reactor system + freight to USA + sales/delivery + fixed costs + import duty +
depreciation.
3. Optimization
RT
i-l
model
(9)
CBri>
x = 0.96 -X,
2
1 -x,
(10)
,I
2 Pi
i=l
TT
Cpi dT-
s
0
where
Cmyi)
(-r,)=k,k,exp
FF
01
Xl
=l+RR(l-XI)
.
*Cy
I>
(6)
EEiAHgX2/=
(11)
s 298
and
QE = i
i=l
EEi
TO Cpi dT
sT
costs)
(13)
E.M.
Elkanzi
/ Chemical
Engineering
and Processing
3.5 (1996)
135
131-139
0.2 /
O.l-
d
2
I
2.2
I
2.4
I
2.6
I
3.0
2.8
RECYCLE
I
3.2
I
3.4
3.6
RATIO
(14)
ATzG%
(15)
136
2.2
2.4
2.6
2.8
3.0
3.2
3.4
3.6
3.8
RECYCLE
RATIO
137
108
0
:
107
":
P
* 106
E-2
8 105
104
103
102
101
100
2
2.2
2.4
2.6
2.8
3.0
3.2
3.4
3.6
3.0
RECYCLE
4.0
RATIO
4. Conclusions
The optimum operating conditions of an adiabatic
reactors system producing MTBE has been evaluated
using a one-dimensional
homogeneous fixed-bed catalytic reactor model. It has been found that the optimal
policy is a function of the recycle ratio and the external
heat removal rates. The convergence of the optimization method depends upon the cost of these parameters
and has been found to be definite for the prices considered. No generalization appears to be possible, since
optimization of other catalytic processes will be admittedly more complicated as compared to the case studied
here. However, the observed easy implementation
of
the model should give the necessary confidence to accept the challenge.
Appendix A: Nomenclature
concentration, km01 mm3
specific heat, kJ kmol- K-
CP
E
acivation energy, kJ kmol-l
E*
reactor I effluent, kmol s-i
EE
reactor II feed, km01 s-l
F
reactor I feed, kmol s-r
FF
fresh feed, km01 s-l
AH
heat of reaction, kJ kmol-
I
isobutylene feed rate, kmol s-l
k,, kz reaction rate constants
frequency factor, ms-
ko
catalyst deactivation constant = 1
kd
A4
methanol feed rate, km01 s-i
n
reaction order = 1
ci
138
300
0.2
0.4
DIMENSIONLESS
AXIAL
0.6
DISTANCE
0.8
LO
Q
R*
p-l,
T, +T
V
x
&
Subscripts
E
effluent
component
i
inlet
ii
recycle
per pass
S
References
[l] Methanol, MTBE suppliers will likely keep up with rising demand, Oil Gas J., (March 19, 1993) 48.
EM.
Elkanzi
/ Chemical
Engineering
49.
and Processing
35 (1996)
131-139
139