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Journal of the Taiwan Institute of Chemical Engineers 59 (2016) 8690

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Journal of the Taiwan Institute of Chemical Engineers


journal homepage: www.elsevier.com/locate/jtice

Short communication

Dehydration of methanol to dimethyl ether in a dual-catalyst system


catalytic distillation tower
Wei-Bin Su, Jyh-Haur Hwang, Hsun-Yi Huang, Tse-Kuei Chang
Rening and Manufacturing Research Institute, CPC Corporation, Taiwan, No.217, Min-Sheng South Road, Chia-Yi 60051, Taiwan

a r t i c l e i n f o a b s t r a c t

Article history: A novel design of a dimethyl ether (DME) catalytic distillation (CD) tower is explored. Due to the wide boiling
Received 28 January 2015 range among the reaction mixture components: water, methanol and DME, a dual-catalyst system CD tower
Revised 27 July 2015
is designed to minimize the tower temperature and catalyst deactivation rate. A DME CD tower model was
Accepted 28 July 2015
developed and validated with both VLE data and pilot test data, and the model so obtained agrees with the
Available online 17 August 2015
results published by An et al. The dual-catalyst system CD tower, wherein the upper section of bed is loaded
Keywords: with low temperature catalysts and the lower section of bed is loaded with high temperature catalysts, are
Dimethyl ether arranged such that both catalysts are used at optimum dehydration temperatures and the product DME can
Catalytic distillation still be condensed with normally available cooling water.
Dehydration 2015 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
Tower design

1. Introduction CD tower pressure selection has been included in this study because
it was never been explored [35].
Methanol dehydration to DME as shown in Eq. (1) is a reversible Starting with the vaporliquid equilibrium data for H2 OMeOH
reaction [1]. The coproduct water is strongly adsorbed on the cata- DME system [710], the binary parameters for VLE methods were re-
lyst surface and thus inhibits the dehydration rate [2]. The process gressed and validated. Combining available kinetic data [3] and the
is exothermic and the heat of reaction should be removed from the VLE method, a pilot CD model was formulated and validated with pi-
reactor. The CD tower [35] can replace one dehydration reactor and lot test data. The activity and aging tests were performed in a bench-
two distillation towers used in the conventional DME process [6]. Ap- scale xed bed to evaluate the commercial catalysts life. Instead of a
plication of CD technology in DME synthesis offers many advantages, single-catalyst system, a dual-catalyst system CD tower is designed
such as higher conversion, energy saving and capital cost reduction. and a model is setup to explore the relationship between operating
However, only a few reports were published for this process [35]. pressure and catalyst bed locations.

2CH3 OHCH3 OCH3 +H2 O (1) 2. Experimental

The concept to design a CD tower for undergoing methanol de- 2.1. Pilot tower and test procedure
hydration seems clear. The reactant methanol has an intermediate
boiling point among three species in the reaction mixture so that The pilot system consists of a fully instrumented CD column. The
methanol can be concentrated in the middle of the CD tower, where inside diameter of the column was 76.2 mm and the height was
catalyst is located. DME and water can be withdrawn respectively 5.79 m. The reaction section was loaded with 949 g of dry Amberlyst
from the top and bottom of the CD tower. Due to a large difference 35 (A35) (Rohm and Haas). The distillation sections were packed with
in the boiling point between DME and water, the design pressure of 20 mm Raschig rings. The column conguration is shown in Fig. 1.
the tower shall enable the use of the available low cost heat sink and Real-time temperature was monitored via on-line instrumentation.
heat source. For example, the dew point of DME is 40.3 C when the Test data was collected under steady-state conditions.
CD tower pressure is 9 bar and therefore using 30 C cooling water as Before start-up, the system was blanketed with nitrogen at
heat sink to condense DME is impractical. Another consideration for 1.36 bar. After the column reached the steady state at total reux
a CD tower is that higher tower pressure results in higher tempera- for one hour, a 99.5% methanol was continuously fed to the reaction
ture in the reaction zone, thus the catalyst may be deactivated. The zone. The control for reux ratio and liquid level across reboiler was
turned on. After the column was operated for six hours, six samples

Corresponding Author. Tel.: +886 5 2224171, fax: +886 5 2285590. were taken. The sampling points were S-1, S-2, S-3 and S-4, which
E-mail address: 078221@cpc.com.tw (W.-B. Su). corresponded to 5.182, 3.962, 1.524 and 0.305 m height above the

http://dx.doi.org/10.1016/j.jtice.2015.07.037
1876-1070/ 2015 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
W.-B. Su et al. / Journal of the Taiwan Institute of Chemical Engineers 59 (2016) 8690 87

ID=76.2 mm 40

S-top 30

Pressure, bar
overhead
reflux
T1 20
1.524 m

Rectification T2 S-1
zone T3
feed
10
T4 S-2
1.829 m

Reaction
T5
zone 0
T6
0 0.2 0.4 0.6 0.8 1
H2 O mole fraction
T7
feed
Fig. 2. The vaporliquidliquid data of DME-H2 O at 100.11 C. xH2O , o yH2O , ----------
2.438 m

Stripping T8 S-3 PRWS-UNIFAC, UNIFAC.


zone T9

T10 S-4 different. According to Pozo and Streeett [9], there existed VLL equi-
libria for H2 ODME system. Carefully checked with the VLLE data, the
S-btm theoretical UNIFAC method cant give a good prediction. This is shown
in Fig. 2. The regressed interaction parameters ki j for PRWSUNIFAC
bottom method are 0.1113, 0.3654, and 0.0992 for H2 OMeOH, H2 ODME and
Fig. 1. The pilot CD tower conguration.
MeOHDME system, respectively. These results were used in the CD
tower simulation.
It should be noted that the VLE predictions derived from vari-
reboiler shown in Fig. 1. Other two samples, S-top and S-btm, were ous property methods via different commercial software, such as As-
taken at the outlet of the condenser and reboiler. pen Plus, Hysys or ChemCAD, arent always consistent. Even with
the same software, different VLE predictions may result from dif-
2.2. Aging and residual activity test ferent versions. The parameters for PRWSUNIFAC method are only
suitable for use in Aspen V8. It is important that parameters for the
The catalyst aging test was performed with a feed of 50/50% by VLE method should be regressed with VLE data, so that the selected
weight methanol/soften water in a continuousdownow xed-bed method can give a good VLE prediction.
reactor. The experiments with 99.5% methanol feed were performed
to observe the residual catalysts activity after a period of operation. 4. Kinetic model
A gradient packing method was used so that the catalyst bed would
have a nearly uniform temperature and minimum wall effects. Mass The past studies for DME synthesis showed that suitable catalysts
balance was 99% and the loss material can be attributed to the are acidic ion exchange resins, e.g. A35 [35]. The reaction mecha-
fugitive dimethyl ether in the overhead sample. nism was reported to t with either LangmuirHinshelwood (LH) or
EleyRideal (ER) kinetic model, and the LH model was found to be su-
3. VLE method and parameters perior [2]. The coproduct water competes with methanol for adsorp-
tion and inhibits the methanol dehydration rate [2,3,5]. So the water
Generally, a cubic equation of state (EOS) coupling with an activ- concentration plays a key role in rate of reaction. The published ki-
ity model for liquid phase e.g., NRTLRK method can predict reliable netic data were conducted at temperatures in the range of 110135
phase behavior. The WongSandler (WS) mixing rule was developed [2], 70130 [3] C. Because the data from the above references cover
to implement the EOS, allowing VLE data obtained at low pressures the reaction temperature in our column, the kinetic data reported in
to make good VLE predictions for non-ideal mixtures at high pres- [3] were used in this study.
sures [11]. To simplify VLE method, programming parameter regres-
sion was performed on a commercial simulator, Aspen V8. The VLE 5. Results and discussion
data include three sets of T-x-y data at 5, 8, and 11.2 atm for H2 O-
MeOH [7] and fourteen sets of P-x-y data for MeOHDME [8] and 5.1. Pilot CD model validation
H2 ODME [9], measured at temperatures up to 160 C. These pres-
sures and temperatures are within the range of operating conditions The pilot CD tower shown in Fig. 1 comprised ten stainless steel
of the CD tower, as shown later in this paper. The ternary data for VLE sections, three for rectication zone, three for reaction zone, and four
method evaluation are four sets of P-x-y data at 60, 80, 100 and 120 C for stripping zone. The length per section was 0.61 m. A thermocou-
[10]. ple was positioned at the middle of each section. So there are twelve
The recommended PRWSUNIFAC [10], PengRobinson (PR) EOS measurement points, including the condenser and reboiler. The sim-
[8], RKSWSUNIQUAC [12], and NRTLRK [13] methods were evalu- ulated vapor compositions were compared with the four sampling
ated. To understand the differences among various property meth- points located at the middle of each section. Including the condenser
ods, RKSWSUNIFAC and UNIFAC method were included in the eval- and the reboiler, the total stage number was 18. The reactive stages
uation. The average absolute, maximum and minimum relative error were number 7, 8 and 9. Table 1 summarizes the operating conditions
between the calculated and experimental VLE data for the ternary and outlet streams analysis of the pilot tests.
system showed that the PRWSUNIFAC and RKSWSUNIFAC meth- From tower conguration (Fig. 1), operating conditions (Table 1),
ods were comparable and superior to others. The VLE prediction by VLE method and kinetic data, the pilot CD model can be formulated
UNIFAC method was reasonable but its deviation interval was quite as a RadFrac block in Aspen V8. In the model, a parameter overall
88 W.-B. Su et al. / Journal of the Taiwan Institute of Chemical Engineers 59 (2016) 8690

140 1 40

120 0.8

MeOH Conversion, %
vapor weight fraction
30
Temperature, oC

100 0.6

20
80 0.4

60 0.2 10

40 0
1 2 3 4 5 6 7 8 9 10 11 12 0
Measurements 0 100 200 300
Days on Stream
Fig. 3. Temperature and mass concentration proles for pilot CD Run3. Experimental
data: o temperature,  MeOH,  H2 O, simulation data: dashed line and solid line. Fig. 4. Activity and aging test for A35 and A70. 99.5%MeOH-A35, o 50%MeOH-A35,
 99.5%MeOH-A70,  50%MeOH-A70.
column eciency is a needed input such that simulation results can
match the experimental data. The criterion is to minimize the objec-
tive function (OBJ) which can be a function of temperature, compo- possible reason is that the rst run didnt reach steady state. Although
nent concentration, or heat duty. Four temperature points along the the tower temperatures and owrate were stable, the initial charge in
pilot tower as shown in Fig. 1 were used to dene the OBJ in Eq. (5). the reboiler for start-up wasnt replaced completely after 6 hr of con-
The calculated eciency for Run2 and Run3 were 0.275 and 0.4, re- tinuous operation for Run1. The modeling results in Fig. 3 are fairly
spectively. However, the obtained eciency for Run1 was larger than consistent with the pilot test data. This model was then used to ex-
1.5. The reason for this discrepancy is explained later. The average plore the performance of a commercial CD tower.
eciency for the pilot tower, including three CD trays was found to
be 0.3375. The HETP of rectication and stripping zones packed with 5.2. Catalyst aging tests
Raschig rings equals 0.903 m.
Ob jective F unction The methanol conversion is dened as:
 2  2  2 MeOH
T2cal T2exp T3cal T3exp T9cal T9exp XMeOH = 100% (6)
= + + FMeOH
T2exp T3exp T9exp
 2 where MeOH and FMeOH are outlet and inlet methanol molar ow
T10cal T10exp rates. Fig. 4 shows the methanol conversion variation with different
+ (5)
T10exp feed mixtures in the bench test for both catalysts. It is known that
acidic ion exchange resins are made of divinyl-benzene cross-linked
After the eciency of 0.3375 was introduced to the pilot CD
sulfonated polystyrene. These catalysts can be damaged or poisoned
model, a typical recalculated result for Run3 is shown in Fig. 3. Also,
under some conditions such as exposure to excessive temperature
a similar prole for Run2 was obtained and not shown here. Because
or impurities. For example, A35 is recommended to be used below
the tower pressure was at 6.44 bar, the temperatures of reaction zone
150 C. If reaction temperature is close to the limitation, catalyst ac-
fell in the range of 118120 C. The vapor mass fraction proles of
tive sites would be lost and catalyst life shortened.
water and methanol along the CD tower are also shown in Fig. 3. The
For A35, the time on stream totaled 180 days and accumulated
simulated vapor mass fractions agree with the component analysis
aging test was 120 days. The initial conversion for the feed with 99.5%
data.
methanol was about 35.8%. After 50 day aging operation at 120 C the
In Table 1, the mass concentration deviation of tower outlet liq-
conversion decreased to 32.3%. The conversion further decreased to
uid streams, S-top and S-btm seems smaller from Run1 to Run3. The
21% at the end of 120 aging days. These results ensure that the activity
of A35 is sucient to catalyze methanol dehydration at 120 C and the
Table 1 catalyst remained active for more than 120 days.
Operating conditions and outlet streams analysis of the pilot tests. Lower activity but less deactivation rate for Amberlyst 70 (A70)
Run number Run1 Run2 Run3 was observed at the similar conditions (Fig. 4). Although accumulated
aging test in the latter run was only 30 days, the results still indicate
Operating conditions
A70 could replace A35 at reaction temperature higher than 120 C.
Feed rate, kg/hr 1.84 1.103 1.393
Feed stage 6 11 11
The recommended operating temperature for A70 is up to 190 C. Its
Tower pressure, bar 6.44 6.457 6.436 thermal stability has also been reported to be better than that of A35
Tower P, bar 0.0038 0.0065 0.0141 by Siril et al. [14]. Although A70 has lower acid site concentration, its
Reux ratio 3.056 2.437 3.923 activity can be enhanced by increasing reaction temperature so that
Distillate to feed ratio (wt) 0.369 0.548 0.486
methanol conversion is acceptable for industrial applications.
Condenser temp. C 30.0 30.0 29.7

Sample analysis 6. Dual-catalyst system CD tower


Component, wt% Exp. Calc. Exp. Calc. Exp. Calc.

H2 O 0.0 0.8 0.0 2.3 0.0 1.7


Incorporating the PRWSUNIFAC method, the CD tower model
S-top MeOH 67.5 40.0 42.2 53.0 42.6 47.5 proposed by An et al. [3] was rebuilt and simulated with the optimum
DME 32.5 59.1 57.8 44.7 57.4 50.8 input parameters of a CD tower. The calculated DME and water con-
H2 O 56.2 19.0 47.5 26.5 31.7 25.1 tent in overhead and bottom product was 97.2 wt% and 93.2 wt%, re-
S-btm MeOH 43.7 81.0 52.4 73.5 66.6 74.9
spectively. Its slightly different from the original work. If the property
DME 0.0 0.0 0.0 0.0 1.6 0.0
method was changed to the default NRTLRK, the calculated DME and
W.-B. Su et al. / Journal of the Taiwan Institute of Chemical Engineers 59 (2016) 8690 89

Table 2
Comparison of the single-catalyst (A35) and dual-catalyst (A35/A70) systems CD tower at 9 and 11 bar.

Pressure, bar 9 9 9 11 11 11
Single-catalyst Dual-catalyst Dual-catalyst Single-catalyst Dual-catalyst Dual-catalyst

Total stage 30 30 44 30 30 42
Reactive stages 820 820 834 820 820 832
In upper section 812 812 812 811 811 810
Catalyst A35 A35 A35 A35 A35 A35
Temp. C 126130 129133 126130 58124 135139 75128
In lower section 1320 1320 1334 1220 1220 1132
Catalyst A35 A70 A70 A35 A70 A70
Temp. C 131137 133136 131138 133149 140145 133148
DME wt% 97.2 79.8 97.6 99.999 92.3 99.999
H2 O wt% 93.2 60.7 94.1 99.999 82.5 99.999

water content in overhead and bottom product was 99.98 wt% and
99.96 wt%. The different results between them may be caused by the
160
use of different VLE methods. Another reason is that different meth-
ods for molar volume estimation were used to calculate the reaction
rate. The method for computing the molar volume might be different
in the user-supplied subroutine. The third reason is different versions 140
of commercial software were used, because the work by An et al. was
performed in Aspen Plus 10.10.
The temperature proles in the reaction zone fell in the range
120

Temperature, oC
of 126137 C at tower pressure of 9 bar. In this case methanol
concentration below the reaction zone is about 80 wt%, with 20%
water. Fig. 4 indicates that A35 deactivated under the conditions of
120 C. The deactivation rate shall be faster at 130 C. This means 100
that a single catalyst system CD tower loaded with A35 cant provide
a satisfactory operation cycle. However A70 is much stable and has
lower deactivation rate. It could be a catalyst candidate for the CD 80
tower, although it shows lower activity than A35 [2]. The combina-
tion, dual-catalyst system design would optimize the catalyst activity
and result in a superior overall eciency.
60
6.1. Effect of bed design on pressure

Followings are some option conditions for DME production via the 40
dual-catalyst system CD tower. Table 2 shows the modeling results of 0 10 20 30 40 50
the dual-catalyst system CD tower at 9 and 11 bar. Stage Number
It starts at the production of 97.2 wt% DME and 93.2 wt% water Fig. 5. The temperature prole of a CD tower at 9 bar. ---------- Single-catalyst system,
from the overhead and bottom of a CD tower. Total stages are 30 Dual-catalyst system, Low temp reaction, High temp. zone with A35,
and reactive stages are 8 to 20. The temperatures at reaction zone High temp. zone with A70.
are 126.3137.2 C. Then the reaction zone is divided into the upper
section of bed, staged 812 and 126.3130.3 C, for low temperature
dehydration and the lower section of bed, staged 1320 and 131.2 148.6 C (Table 2). No organic catalyst can provide good and stable
137.2 C, for high temperature dehydration. To lower the rate of cata- performance with such a wide range of reaction temperature. One
lyst deactivation, attempts were made to keep the upper bed temper- solution is to use a dual-catalyst system design in the reaction zone.
ature below 130 C and A35 in the lower section of bed was replaced Table 2 shows the temperature across the upper section of bed is in
with A70. The average methanol conversion of A70 during activity the range of 74.8128.1 C so A35 can be used here. On the other hand,
and aging test is 35% of A35, as shown in Fig. 4. The overall dehy- the temperature across the lower section of bed is 133.2147.9 C. The
dration rate of A70 was assumed to be 35% of A35. Since A70 is less use of A70 is required.
active, stage numbers across the lower section of bed are increased in
the dual-catalyst system tower model such that the same methanol 7. Conclusions
conversion could be obtained. In order to compare with the base case
model, other input parameters were not varied. Fig. 5 is the temper- Like all process models, the simulation results are dependent on
ature prole of the nal design of the dual-catalyst system CD tower the kinetic data, VLE method, and physical property calculations. The
for producing 97.2 wt% DME at 9 bar. It requires an extra 14 reactive best VLE method for the systems composed of H2 OMeOHDME was
stages in the lower section to compensate the less active A70 such found to be PRWS or RKSWS property method in Aspen V8. The pi-
that the dual-catalyst system CD tower can give similar performance lot test data showed that methanol dehydration to DME can be car-
as the single-catalyst system CD tower. The temperatures across the ried out in a CD tower equipped with A35 and A70. Therefore, a CD
lower section of bed are 130.7137.6 C, almost the same as that in a tower model coupling with the VLE method and the rate equation
single-catalyst system CD tower. However, its prole is atter. was developed and validated with our test data. The catalyst aging
The dew point of DME is 48.3 C at pressure of 11 bar. In this case, tests demonstrated that ion exchange resins, e.g. A35 and A70, can be
33 C cooling water that is normally available in the industry can be deactivated by sodium ion in the 50/50% methanol/water feed mix-
used. The single-catalyst system temperature is in the range of 57.7 ture. Besides catalyst deactivation, the tower pressure of 11 bar was
90 W.-B. Su et al. / Journal of the Taiwan Institute of Chemical Engineers 59 (2016) 8690

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