Korean J. Chem. Eng.

, 22(3), 387-392 (2005)

Simulation Studies on Reactive Distillation for Synthesis of tert-Amyl Ethyl Ether

Ukrit Sahapatsombud, Amornchai Arpornwichanop*, Suttichai Assabumrungrat , †

Piyasan Praserthdam and Shigeo Goto**

Center of Excellence in Catalysis and Catalytic Reaction Engineering,
*Control and Systems Engineering, Department of Chemical Engineering,
Faculty of Engineering, Chulalongkorn University, Bangkok 10330, Thailand
**Department of Chemical Engineering, Nagoya University, Chikusa, Nagoya 464-8603, Japan
(Received 22 December 2004 • accepted 14 February 2005)

Abstract −In this work, a reactive distillation column in which chemical reactions and separations occur simulta-
neously is applied for the synthesis of tert-amyl ethyl ether (TAEE) from ethanol (EtOH) and tert-amyl alcohol (TAA).
A rate-based kinetic model for liquid-phase etherification and an equilibrium stage model for separation are employed
to study the reactive distillation. The calculation is carried out using the commercial software package, Aspen Plus.
Simulations are performed to examine the effects of design variables, i.e., a number of rectifying, reaction and stripping
stages on the performance of reactive distillation column. It has been found that an optimal column configuration for
the TAEE production under the study is designed with no rectifying, 4 reaction and 8 stripping stages. With such an
appropriate specification of the reactive distillation column, the effects of various operating variables on the TAA con-
version and TAEE selectivity are further investigated and the results have shown that the reflux ratio and operating
pressure are the most important factors to the operation of the reactive distillation.
Key words: tert-Amyl Ethyl Ether, Reactive Distillation, Simulation

INTRODUCTION chaiya and Datta, 1995; Linnekoski et al., 1997]. Tertiary amyl al-
cohol (TAA), a main component in fusel oil which is a byproduct
Reactive distillation, sometimes called “catalytic distillation”, has from the fermentation process for the ethanol production, can be an
drawn considerable attention from both academic and industrial alternative reactant instead of IA. Therefore, the synthesis of TAEE
sectors over the past decades. Reactive distillation combines a cat- from TAA and ethanol should be a promising route as both reac-
alytic reactor and a distillation in one single unit operation. Its four tants are derived from renewable resources [Chang et al., 1998].
potential benefits are: (i) shifting an equilibrium conversion, (ii) Unfortunately, there are still very limited efforts concerning this
reacting away azeotropic mixtures, (iii) improving selectivity and reaction system. Only one work is found in the literature consider-
(iv) saving energy due to the efficient use of reaction heat for sep- ing the synthesis of TAEE via this route in a reactive distillation
aration [Baur et al., 2000]. It has been applied to many esterifica- [Aiouache and Goto, 2003b]. It is, therefore, the aim of this study
tion and hydrolysis processes involving alkyl acetate and glycols, to investigate in more detail the performance of reactive distillation
alkylation for cumene, and the formation of fuel oxygenates in chem- for the production of TAEE from TAA and ethanol. Simulation stud-
ical and petrochemical industries. ies are carried out using the ASPEN PLUS simulator. Emphasis is
A number of publications dealing with a production of oxygen- placed on the determination of an appropriate configuration of the
ates in reactive distillation have been published in the past decades. reactive distillation column for the TAEE production. In addition,
Most of the early works focused on the synthesis of small tertiary an analysis of the effects of key operating parameters such as reflux
ethers (i.e., methyl tertiary butyl ether (MTBE) and ethyl tertiary ratio, operating pressure, and feed stage location, on the conversion
butyl ether (ETBE)) [Hommerich and Rautenbach, 1998; Tang et of TAA and the selectivity of TAEE is performed.
al., 2003; Assabumrungrat et al., 2004]. However, since it has been
reported that MTBE may pollute underground water [Dai, 2000], STUDIES ON THE SYNTHESIS OF TAEE
the production of higher tertiary ethers such as tertiary-amyl methyl IN REACTIVE DISTILLATION
ether (TAME) and tertiary-amyl ethyl ether (TAEE) have been of
present interest to replace MTBE [Thiel et al., 1997; Kitchaiya and 1. Reactive Distillation Model
Datta, 1995]. TAEE is a more favorable choice compared to TAME Simulation of the synthesis of TAEE in a reactive distillation (RD)
in environmental terms as ethanol, one of the reactants, can be de- is carried out by using the Aspen Plus simulation package. The RAD-
rived renewably from agricultural products such as sugar cane, corn FRAC model, which is a rigorous equilibrium-stage distillation mod-
and potatoes. Most previous works considered the production of el to describe a multistage vapor-liquid separation in the distillation
TAEE from isoamylene (IA) and ethanol in reactive distillation [Kit- column, is used in this study. The equilibrium stage model is often
applied with great success for the simulation of distillation col-
To whom correspondence should be addressed.
†
umns [Dirk-Faitakis and Chuang, 2003]. Similar to our previous
E-mail: [email protected] work [Assabumrungrat et al., 2004], the property option set PSRK
387
388 U. Sahapatsombud et al.
ters of the column configuration are needed to be specified for the
simulation of the RADFRAC column [Quitain, et al., 1999]. These
can be chosen from the following parameters: heat duty at the re-
boiler (Q ), condenser temperature (Tc), ratio of total distillate flow
r

to feed (D/F) and reflux ratio (R). Here, the parameters, Q and R, r

are selected in our study as they can be practically manipulated in

real operation.
2. Kinetic Model
In this work, a non-equilibrium kinetic model is used to describe
the reactions occurring in the reaction stages. TAEE is produced
by the direct etherification of TAA with EtOH in the liquid phase
over Amberlyst 15, a commercial acid catalyst, and is inhibited by
two undesired side reactions: the dehydration of TAA to IA and the
etherification of the IA produced to TAEE. Although IA can be rep-
resented by two isomers: 2-methyl-1-butene (2M1B) and 2-methyl-
2-butene (2M2B), they are lumped together with the properties of
the major isomer 2M2B [Rihko and Krause, 1993]. Kinetic and ther-
modynamic studies have shown that the etherification of EtOH with
TAA and IA and the dehydration of TAA are reversible and equi-
Fig. 1. The configuration of a reactive distillation column. librium-limited. The etherifications in Eqs. (1) and (3) are exother-
mic while the dehydration in Eq. (2) is endothermic.
The reaction scheme for the liquid phase synthesis of TAEE from
based on the predictive Soave-Redlich-Kwong equation of state is TAA and EtOH taking place in the reaction section can be sum-
employed. This correlation has been widely used for the prediction marized as follows:
of enthalpy and other thermodynamic properties. Interaction param-
eters for computing multi-component vapor-liquid and liquid-liquid ↔
TAA+EtOH TAEE+H2O (1)
equilibriums are predicted by using the UNIFAC activity coefficient ↔
TAA IA+H2O (2)
model [Sneesby et al., 1997].
Fig. 1 shows a typical configuration of the RD column used in the IA+EtOH TAEE ↔ (3)
simulation studies. The column contains a total of 14 stages counted The kinetic models of the above reactions on Amberlyst 15 are
down from the top. This includes a total condenser and a partial taken from Aiouache and Goto [2003a]. In their work, the rate equa-
reboiler as respectively shown in stage 1 and 14. The RD column tions expressed in activity form are based on the power law model
is divided into three sections: rectifying, reaction and stripping sec- of which the validity was verified with the experimental data. How-
tions. The chemical reactions are assumed to occur in the liquid phase ever, the expressions for the rate equations in mole fraction form
in the reaction section represented by 4 reactive stages (stage 6-9). are required in Aspen Plus. For this reason, the kinetic parameters
The feed is introduced at the top of the reaction section (stage 6). for the liquid phase synthesis of TAEE reported by Aiouache and
To be noted is that such a column configuration is determined as a Goto [2003a] are multiplied with the average activity coefficients
preliminary simulation study; however, it can be adjusted to meet of each component. The new sets of the kinetic parameters and the
optimal performance of the RD column. Table 1 summarizes the equilibrium constants shown in Table 2 are derived from the Arrhe-
column parameters and feed conditions under the standard opera- nius and Van’t Hoff plots for various temperatures. Therefore, the
tion. The mixed TAA-EtOH feed stream enters the RD column at rate equations of the reactions (1) to (3) can be expressed in terms
25 oC. It should be remembered that two additional input parame- of mole fractions as follows.
rEtOH = − mrQ k1⎛⎝xEtOHxTAA − x-------------------
TAEExH O⎞ 2
- + k ⎛x x − x---------- -
TAEE⎞
(4)
Table 1. Feed conditions and specification of reactive distillation Keq1 ⎠ 3⎝ IA EtOH Keq3 ⎠
column under the standard condition rTAA = − mrQ k1⎛⎝xEtOHxTAA − x-------------------
TAEE xH O⎞ 2
- + k ⎛x − x--------------
IAxH O⎞ 2
- (5)
Feed conditions Column specification Keq1 ⎠ 2⎝ TAA Keq2 ⎠
Temperature [K] 298 Rectification stages 4 Table 2. Expressions of the parameters used in the kinetic model
Flow rate [mol/s] 2.71×10− 3
Reaction stages 4
Mole fraction [-] Stripping stages 4 Parameters00000 Activation energy, Ea (kJ/mol)
1) EtOH 0.5 Total stages 14 k =exp (15.189 − 6597.3/T)
1
54.9
2) TAA 0.5 Catalyst weight per stage 0.125 k =exp (14.490 − 6372.9/T)
2
53.0
[kg] k =exp (22.540 − 9184.6/T)
3
76.4
Pressure [kPa] 101.3 Pressure [kPa] 101.3 Keq =exp (− 0.471+524/T)
1

Reflux ratio (R) [-] 2 Keq =exp (5.16 − 1824.3/T)

2

Reboiler duty (Qr) [W] 52 Keq =exp (− 5.64+2349/T)

3

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 Simulation Studies on Reactive Distillation for Synthesis of tert-Amyl Ethyl Ether 389
rIA=rEtOH− rTAA (6) mole fraction profiles of each component with the column stage
rTAEE=− rEtOH (7)
number are shown in Fig.2. It can be seen that 27.93 mol% of TAEE
can be obtained in the liquid residue of the RD while the distillate
rH O=− rTAA
2
(8) comprises mostly IA (87.67 mol%) and a little amount of EtOH
where Q is ion-exchange capacity of Amberlyst 15 (Q=4.9 mol-H+/ and H2O. Fig.2 also presents the temperature profile inside the col-
kg). umn. The temperature at the reboiler and the condenser is 353 and
3. Model Validation 309 K, respectively. It is noticed that the temperature profile is rather
In order to use the RADFRAC model from Aspen Plus for simu- smooth in the reaction section due to a mild reaction heat released.
lating a reactive distillation with confidence, the reliability of the To operate the RD column efficiently, it is important to convert
model is tested by comparing the simulated results obtained in this TAA into the desired product (TAEE) and to obtain TAEE in the
study with the experimental data from Aiouache and Goto [2003b]. liquid residue as high as possible. Thus, the conversion of TAA and
With the same standard experimental conditions from Table 2 in the selectivity of TAEE as defined below are considered to com-
their paper, results of the simulation run in comparison to the ex- pare the performance of the reactive distillation.
perimental data are shown in Table 3. It can be seen that the com- Conversion of TAA
positions in the distillate and the residue, calculated by Aspen Plus, difference in molar flowrate of inlet and outlet of TAA
= -----------------------------------------------------------------------------------------------------------------------------------
are in good agreement with the experimental data. The small dif- feed molar flowrate of TAA
ference may be due to the modified kinetic parameters that are based ×100%
on the mole fraction rate expression.
Selectivity of TAEE
RESULTS AND DISCUSSION molar flowrate of TAEE in residue
= --------------------------------------------------------------------------------------------------------------------------------------------------
total molar flowrate of TAEE and IA in distillate and residue
1. Standard Condition ×100%
The reactive distillation and kinetic model mentioned in the pre- The conversion of TAA and the selectivity of TAEE at the stan-
vious section are used in the simulation of the RD column. Under dard condition are 71.29% and 77.87%, respectively. In the follow-
the standard conditions given in Table 1, the simulated results of ing sections, key design and operating variables are varied to study
their effects on the conversion of TAA and the selectivity of TAEE.
Table 3. Comparison of simulated results and experimental data 2. Effects of Design Variables
from Aiouache and Goto [2003b] As stated earlier, the specification of the reactive distillation col-
Distillate (mole fraction) Residue (mole fraction) umn given in Table 1 for the synthesis of TAEE is a preliminary
Components configuration. To find optimal design variables for the operation of
Experimental Simulation Experimental Simulation
TAEE 0.047 0.040 0.185 0.167 the RD, simulations are carried out to study the effects of these var-
iables on the RD performance. The important design variables con-
TAA 0.046 0.042 0.227 0.231 sidered here include the number of rectifying, reaction and strip-
EtOH 0.139 0.103 0.309 0.345 ping stages.
IA 0.727 0.812 0.000 0.000 2-1. Number of Reaction Stages
HO 2
0.041 0.051 0.279 0.282 The function of a reaction section within the RD column is to
T (K) 313.1 313.6 351.2 355.2 provide a location where the reactions occur. Fig. 3 shows the effect

Fig. 2. Mole fraction and temperature profiles inside the column

at the standard operating condition (Feed molar flowrate=
2.71×10−3 mol/s, Reflux ratio=2, Catalyst=0.5 kg, Feed Fig. 3. Effect of the number of reaction stages on the reactive dis-
TAA : EtOH=1 : 1). tillation performance.
Korean J. Chem. Eng.(Vol. 22, No. 3)
390 U. Sahapatsombud et al.
of the number of reaction stages (1-6 stages) on the RD column
performance. It is noted that all other design and operating vari-
ables such as the number of rectifying and stripping stages, reflux
ratio, reboiler duty and feed conditions are kept at the values of the
standard condition and the feed is still introduced at the top of the
reaction section. The simulated results show that by using more reac-
tion stages the conversion of TAA increases but the selectivity of
TAEE decreases. According to Fig. 3, it can be seen that 4 reaction
stages give a better performance in term of the selectivity. Increas-
ing a number of reaction stages above the optimal value results in
more IA production, leading to a decrease in the selectivity of TAEE.
This is to be expected as an excess number of reaction stages can
promote undesired dehydration of TAA to IA (Eq. (2)). Although
IA can further react with EtOH to form TAEE according to Eq. (3),
most of IA is in gas phase and its solubility in the liquid mixture is
low under the standard operating pressure (0.1 MPa). As a conse- Fig. 5. Effect of the number of stripping stages on the reactive dis-
quence, a slight amount of TAEE is produced from the liquid phase tillation performance.
etherification of IA (Eq. (3)). From this reason, the number of reaction
stages of 4 is used in the column configuration for the next simula-
tions. 2-3. Number of Stripping Stages
2-2. Number of Rectifying Stages In a reactive distillation, the number of stripping stages is adjusted
The purposes of a rectification section are to remove light com- to ensure that a satisfactory separation is achieved. The main func-
ponents from the reaction zone, to prevent loss of TAEE in the dis- tion of the stripping section is to purify the TAEE product in the
tillate and to recycle the unreacted reactants back to the reaction residue. It can be seen from Fig. 5 that the TAA conversion slightly
section in the RD column. The effect of the number of the rectify- decreases as the number of stripping stages is increased from 4 to
ing stages on the selectivity of TAEE and the conversion of TAA 10 stages; however, the selectivity of TAEE shows a contrary trend.
is demonstrated in Fig. 4. It is found that even though the TAA con- Increasing the stripping stages causes more TAA contents removed
version increases with the increase of the number of rectification from the reaction section to the residue and therefore, the TAA con-
stages, the selectivity of TAEE decreases. This can be explained by version is decreased. In addition, the increased stripping stages de-
the fact that with the increased number of the rectifying stages, IA, crease the concentration of TAEE in the reaction zone, shifting the
the lightest component, is more removed from the reaction section, equilibrium of the etherification of TAA in the forward direction.
decreasing the concentration of IA in the reaction zone. This causes As a result, the selectivity of TAEE becomes higher. Fig.5 also shows
the equilibrium equation of Eq. (2) to shift in the forward reaction the mole fraction of TAEE in the residue. The TAEE purity in the
and thus, the conversion of TAA becomes higher whereas the se- residue exhibits a similar response to the change in the selectivity;
lectivity of TAEE becomes lower. From the simulated results shown it gradually increases to 26% mole fraction of TAEE as more stages
in Fig. 4, it seems that the increase of the number of rectifying stages are added. The results for the studied system indicate that both the
has no significant effects on the performance of the reactive dis- two parameters, the selectivity and purity of TAEE, earn benefits
tillation. Therefore, no rectification stage is recommended for this from the increase in the number of stripping stages. Therefore, the
system. optimum configuration would be 8 stripping stages.
At this stage, the optimal design variables for the reactive distil-
lation are no rectifying, 4 reaction and 8 stripping stages. It should
be noted that the location of feed consisting of TAA and EtOH is
still fixed at the top tray of the reaction section. This suitable con-
figuration will be further used in order to examine the effects of op-
erating variables: reflux ratio, catalyst weight, operating pressure
and location of feed. This provides beneficial information for improv-
ing an operation of the reactive distillation.
3. Effects of Operating Variables
3-1. Reflux Ratio
Fig. 6 presents the effect of the reflux ratio on the performance
of the reactive distillation. It can be seen from this figure that an
increase in the reflux ratio from 2 to 16 causes a decrease in the con-
version of TAA; however, it has a positive effect on the selectivity
of the desired TAEE product in residue as the selectivity increases
from 81.59% to 94.22%. This is because the increase of the reflux
Fig. 4. Effect of the number of rectifying stages on the reactive dis- ratio increases the concentration of IA in the reaction section where
tillation performance. it can react with EtOH to produce more TAEE. It is noticed that IA
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 Simulation Studies on Reactive Distillation for Synthesis of tert-Amyl Ethyl Ether 391

Fig. 6. Effect of the reflux ratio on the reactive distillation perfor- Fig. 8. Effect of the column pressure on the reactive distillation per-
mance. formance.

is a major component in the distillate. Moreover, some contents of tillation, other factors, e.g., cost of catalyst and capacity of column
unreacted reactants, EtOH and TAA, in the distillate are recycled should also be considered in selecting the appropriate amounts of
back to the reaction section, leading to higher selectivity of TAEE. catalyst in the reaction section.
However, it should be noted that some extents of the reflux IA can 3-3. Operating Pressure
react with H2O (reverse reaction of Eq. (2)) generating more TAA. The operating pressure is one of the key operating parameters of
This is probably a reason for the slight decrease of the TAA conver- a distillation column. The choice of operating pressure for the reac-
sion. tive distillation column depends on many considerations such as
3-2. Catalyst Weight overhead temperature, bottom temperature and reaction tempera-
Since a catalyst is used to accelerate the reaction rate and to in- ture in the system. Since chemical reactions take place in the liquid
fluence the selectivity, the effect of the amount of total catalyst in phase, the reaction temperature is close to the boiling point of the
the reaction section on the performance of RD column is studied. liquid phase flowing around the catalyst. Fig. 8 shows the influ-
Fig. 7 shows that as the total amount of catalyst in the reaction sec- ence of the column pressure on the TAA conversion and TAEE se-
tion increases, the amount of TAA converted to TAEE as well as lectivity. It is found that as the pressure increases from 0.1 to 0.6
the selectivity of TAEE increase. However, it is observed that when MPa, the reaction stage temperature increases linearly from 48 to
the catalyst weight is more than 0.4 kg, the conversion of TAA and 100 oC (data not shown). From the kinetic parameters given in Table
the selectivity of TAEE are slightly improved. This indicates that 2, one would expect that rate of the dehydration of TAA to IA, Eq.
the reactions are approaching equilibrium-limited conditions. It should (2), is more pronounced when the reaction temperature increases,
be noted that the catalyst is uniformly distributed along the reaction resulting in the lower selectivity of TAEE as can be seen from Fig. 8.
stages in this study, and that although the increase in the amount of However, the conversion of TAA is quite insensitive to the operating
catalyst has a positive effect on the performance of the reactive dis- pressure. This suggests that the operating pressure of 0.1 MPa is suit-
able for the reactive distillation to synthesis TAEE. It should be noted
that operation of the reactive distillation column at lower than the
atmospheric pressure (0.1 MPa) is not attractive due to high operating
cost. In addition, it was found from our preliminary results that a
lower pressure is not beneficial to the performance of this system.
3-4. Feed Stage Location
Since the location of the feed can be adjusted to make the best
separation and the most favorable reaction conditions, simulations
are performed to investigate the effects of the feed location of TAA
and EtOH on the RD performance. The cases where the feed reac-
tants (TAA and EtOH) are separated in two streams on the reac-
tion section are compared with the one that both TAA and EtOH
are mixed in one feed stream as in the standard conditions. The re-
sults are summarized in Table 4. It has been known that when the
feed components are separated in two different locations, the reac-
tant with lower boiling point is normally introduced at the lower
stage of the reaction section, compared to the higher boiling point.
Fig. 7. Effect of the catalyst weight on the reactive distillation per- However, it is found here that feeding TAA and ethanol together at
formance. the top of the reaction section offers the highest conversion of TAA
Korean J. Chem. Eng.(Vol. 22, No. 3)
392 U. Sahapatsombud et al.
Table 4. Effect of feed separation on the TAA conversion and the TAEE selectivity
Feed location Reaction TAA TAEE Residue composition (%mole fraction)
TAA EtOH stage conversion selectivity TAEE TAA EtOH IA HO2

2 2 2-5 69.64 81.71 28.68 15.38 21.3 0 34.63

2 3 2-5 69.52 79.16 27.82 15.17 22.61 0 34.38
2 4 2-5 67.88 74.50 25.57 16.04 24.98 0 33.40
2 5 2-5 61.06 60.53 18.74 19.48 31.96 0 29.71

(69.64%) and selectivity of TAEE (81.71%). It is noticed that sepa- REFERENCES

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