Chemical Engineering & Processing: Process Intensification 149 (2020) 107824

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Chemical Engineering & Processing: Process Intensification

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Intensified reactive distillation configurations for production of dimethyl T

ether
Nikhil K. Gor, Nilesh A. Mali*, Sunil S. Joshi
Chemical Engineering and Process Development Division, CSIR - National Chemical Laboratory, Dr. Homi Bhabha Road, Pune, 411008, India

A R T I C LE I N FO A B S T R A C T

Keywords: The combustion properties of dimethyl ether (DME) are similar to the conventional fuels; hence it is being used
Reactive distillation as a promising green energy source. The conventional method of DME production by methanol dehydration is
Reactive divided wall column highly energy consuming due to the use of a series of distillation columns. In the present study, an energy
Energy efficient configuration efficient reactive distillation configuration is proposed for DME production which leads to higher methanol
Total annual cost
conversion with less energy requirement as compared to reported configurations. The reactive distillation (RD)
and dual reaction zone reactive divided wall column (RDWC) were analyzed using steady state ASPEN simu-
lations. Subsequently, all the design parameters were optimized by sensitivity analysis to minimize the Total
Annual Cost (TAC) of the configuration. The results showed that the RD column is more energy efficient than
RDWC as it requires 10.68 % less TAC. The proposed RD and dual reaction zone RDWC configurations were
found to have less specific energy requirements and less cost per kg of DME than any other configuration
reported earlier.

1. Introduction
The world energy consumption is increasing at a steady rate for the
many reasons like population growth, industrialization and transpor-
tation etc. For all these reasons the consumption of fossil fuels like coal,
oil and natural gas is also increasing at an extended rate. In 2017, about
81 % of the global energy demand was fulfilled by fossil fuels only [1].
Being non-renewable sources, high use of these fuels have raised the
problem of shortage in supply, increased prices and CO2 emissions
worldwide. In US in 2016, transportation alone contributed about 28 %
of the total greenhouse gas emission [2]. Increasing emission of CO2
and other greenhouse gases makes necessary the use of green and re-
newable energy sources. Alcohols and their derivatives like dimethyl
ether, diethyl ether and biofuels etc. are the most attractive alternates
which can serve this purpose. Among these, dimethyl ether (DME) is
one of the promising eco-friendly energy alternatives.
DME is the simplest form of all ethers. It is colorless, non-toxic, non-
corrosive, non-carcinogenic and environmental friendly chemical [3].
The properties of DME are similar to liquefied petroleum gas (LPG) [4].
DME can be easily blended with LPG and used for cooking. DME - LPG
blend reduces NOx emission from household combustion [5]. Up to 20
% volume of DME blended with LPG requires no modification in the
current LPG infrastructure [6]. DME also has high cetane number
(> 55) due to which 10–20 % DME by mass can be blended with diesel
to reduce consumption of conventional fuel. Use of DME/diesel blend
can achieve less emission of particulate matter, NOx, and SOx [7,8]. It
can be used as a feedstock for a variety of important chemicals like
methyl acetate, ethylene, propylene, isomers of butene. [9–11].
DME can be produced by two methods, direct and indirect. Direct
method involves the synthesis of DME from syngas. Syngas can be ob-
tained from a variety of feedstocks like natural gas, coal and biomass
etc., which undergoes hydrogenation to form methanol and methanol
dehydrates to form DME [12]. This method requires bi-functional cat-
alyst which can be simultaneously used for hydrogenation as well as
dehydration [13,14]. In indirect method already produced and purified
methanol over acid catalyst undergoes dehydration reaction to form
DME [12].
The indirect method of DME production has been largely studied
and applied industrially as shown in Fig. 1. It is a highly exothermic
reaction and gives near equilibrium conversion of 80–85 % for γ-Al2O3
in the temperature range of 300−350 °C and pressure range of
1−20 bar [15]. Conventionally, reaction of vapor phase methanol takes
place over a solid acid catalyst in a fixed bed reactor as shown by Eq.
(1). The reaction yields DME and water in the gas phase. The product
stream is then passed through a series of distillation columns for pur-
ification. In first distillation column pure DME is obtained as overhead

⁎
Corresponding author.
E-mail address: na.mali@ncl.res.in (N.A. Mali).

https://doi.org/10.1016/j.cep.2020.107824
Received 15 October 2019; Received in revised form 16 January 2020; Accepted 16 January 2020
Available online 24 January 2020
0255-2701/ © 2020 Elsevier B.V. All rights reserved.
N.K. Gor, et al.
Fig. 1. Convention methos for DME production.
product and unreacted methanol and water are sent to the second
distillation column. From the second column methanol is obtained as
top product and recycled back to the reactor and water is taken from
the bottom [16]. This conventional method of DME synthesis is proved
to be highly energy consuming [17–19] as conversion of methanol to
DME is equilibrium limited which requires unreacted methanol to be
recycled back to the reactor and two distillation columns are require for
separation which results in significant energy consumption for opera-
tion.
CH3OH (g)↔CH3OCH3 (g) + H2O (g) (1)
Due to higher energy requirement of conventional DME production
process energy efficient routes for DME synthesis were developed
[20–23]. Iliuta et al. [24] studied the modeling and simulation of in-situ
water removal in fixed bed membrane reactor for direct method of DME
production to drive the equilibrium to right hand side and increase the
production of DME. Vakili et al [25] utilized the exothermic heat of
direct DME synthesis for the dehydrogenation of cyclohexane in a
thermally coupled heat exchanger reactor. Farsi et al. [23] carried out
methanol dehydration reaction in multi-stage spherical reactors and
found higher DME production.
Though many different ways of DME process improvement and
production have been studied, reactive distillation (RD) provides big-
gest advantage that it can shift the equilibrium of the reaction towards
the right hand side by continuous removal of the products from the
reaction zone and gives higher conversions than the conventional re-
actors. In the conventional process, reaction occurs in gas phase which
is reversible in nature and hence, its conversion is thermodynamically
limited. In gas phase reaction, the equilibrium conversion of methanol
achieved is 80–85%. Whereas in RD column, continuous removal of
products shifts the equilibrium towards product side to give complete
methanol conversion. Reactive distillation is the intensified distillation
configuration in which reaction and separation happens in the same
column. The heterogeneous and homogenous catalyst can be used for
the reaction. The RD also reduces the capital investment required as
reactor and separation is merged in a single column.
Reactive divided wall column (RDWC) is another energy efficient
and highly integrated configuration for reaction and separation in a
single column. RDWC is a complex arrangement in which a column is
divided into two sections by introducing a dividing wall in the shell.
The reaction zone is present on the feed side of the column where the
reaction occurs and the lighter component is taken from the top side,
heavy component from the bottom and middle component as a side
draw. RDWC incorporates advantages of both RD as well as Divided
Wall Column (DWC) which makes it cost effective and energy efficient
in many cases [26,27].
An et al. [20] proposed the liquid phase kinetics of the methanol
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Chemical Engineering & Processing: Process Intensification 149 (2020) 107824
dehydration over Amberlyst-35 catalyst and applied that kinetic rate
equation for the simulation of RD. The kinetic model proposed was
based on Eley-Rideal mechanism and he found dehydration of methanol
as first order reaction. For the simulation in Aspen Plus, they modelled
RD column, with sequentially varying the parameters for optimization,
with 30 stages having 13 stages reactive zone with catalyst loading
9.23 kg/stage in the middle of the column and operated in the pressure
range of 0.9–1 MPa with DME purity of 99.97 % with complete me-
thanol conversion but they didn’t consider RDWC for complete con-
version.
Lei et al. [19] proposed liquid phase kinetics of dehydration of
methanol over macroscopic sulphonic acid ion exchange resin. They
found that the kinetic rate equation based on the Eley - Rideal me-
chanism and power law model best fit the experimental kinetic data.
They compared three cases for the DME production, in first case me-
thanol was partially reacted in a fixed bed reactor into DME and water
which was then fed to the RD column for complete conversion; second
case was conventional method where reaction happens in a fixed bed
reactor followed by series of distillation columns for separation and the
third case was of RD column for DME synthesis and separation followed
by a distillation column for methanol and water separation. The opti-
mized parameters of the three processes were determined by Design
Spec function in Aspen Plus keeping the purities of product at their
bound. The first configuration of the reactor and RD column was found
to be better than the other two as it gave a higher quantity of product
with complete methanol conversion. They also proposed that single RD
column could give high DME throughput and complete methanol con-
version but at the cost of higher pressure drops in the reaction zone
with structured packing, hence will have narrow operating range in
terms of liquid and vapor velocities. This indicates that there is need of
alternate configuration for higher throughput.
Su et al. [28] explored dual catalyst system RD column and vali-
dated its simulated model with pilot catalytic distillation model. For
single reaction zone RD column, they used PRWS-UNIFAC thermo-
dynamic method and kinetics for Amberlyst-35 catalyst proposed by
Hosseininejad et al. [29] based on Langmuir-Hinshelwood mechanism.
They found good agreement among experimental and calculated re-
sults. However, they found that temperature in the reactive section of
the RD was high enough to deactivate the catalyst and hence they used
two reactive zones in which upper reactive zone had catalyst (Amber-
lyst-35) that showed good activity at low temperature (< 130 °C) and
lower zone had catalyst (Amberlyst-70) that showed good activity at
high temperature (> 130 °C). However, Amberlyst-70 had lower ac-
tivity than Amberlyst-35 and to get the same conversion as single re-
active zone RD column they had to increase the number of reactive
stages in the lower zone of double reactive zone RD column.
For DME synthesis, Kiss & Suszwalak, [18] compared the
N.K. Gor, et al.
conventional reactor and distillation sequence with the energy efficient
process alternatives, RD and RDWC. To have a fair comparison with the
work of Lei et al. [19], keeping the same feed conditions, catalyst and
kinetic data with rigorous optimization, they proposed that RDWC is
more energy efficient than conventional and RD process. They even
found that RD column followed by a distillation column to separate
methanol and water is more energy consuming than the conventional
process. They found that RDWC could save 11.6 % and 58.6 % energy
as compared to the conventional process and RD column respectively.
The conversion obtained in the case of conventional process was 90 %
while for both reactive distillation columns, it was 50 % only and the
unreacted methanol was separated and recycled.
In another study for 100 ktpy DME production Bildea et al. [17]
compared three configurations. First configuration was the conven-
tional reactor followed by distillation sequence; second was a RD
column and third was reactor followed by reactive distillation column.
He found that total annual cost (TAC) required for the RD process is
least as compared to the other two processes. Rigorous optimization is
performed using Calculator block of Aspen Plus and linking it with ga
(Genetic Algorithm) function of Matlab. For all the three cases complete
conversion of methanol was achieved. He concluded that RD process in
a single column as promising option for new DME plants with lower
capital and operating cost. Whereas for a revamping of the existing
plant, combined process of the reactor and reactive distillation was
more promising as it showed better potential for higher production
capacity by complete methanol conversion without recycle.
From the literature study, it was observed that many people have
studied DME synthesis in RD and RDWC, but the reported conversion
for RDWC column was up to 50 % only. Dual catalytic reaction zone in
RD column has been published but no such study has been published for
RDWC for DME synthesis. Also, there is no clear comparison among RD
and RDWC based on TAC for the 100 % conversion methanol. Hence, in
this study, novel dual catalytic reaction zone RDWC is simulated and
compared with RD on the basis of TAC required for 100 % methanol
conversion. The schematic diagram of RD and dual catalytic reaction
zone RDWC are shown in Fig. 2.
2. Problem statement
DME synthesis by methanol dehydration is a reversible reaction
which occurs over the acidic catalyst. Present study considers macro-
porous sulphonic acid ion exchange resin as catalyst. Many kinetic rate
equations have been proposed for the methanol dehydration in the
vapor phase [30–33], very few rate equations are available for reaction
in the liquid phase. The rate equation developed and proved experi-
mentally by Lei et al. [19], for the same ion exchange resin catalyst was
taken to account for the liquid phase kinetics in the reactive distillation
which is applicable in the temperature range of 118−150 °C and is
Fig. 2. Schematic diagram of (a) RD column and (b) RDWC column. Grey portion indicates catalytic reaction zone.
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Chemical Engineering & Processing: Process Intensification 149 (2020) 107824
Table 1
Feed conditions.
Parameter Value
Temperature (°C) 25
Pressure (bar) 10
Feed flow rate (kmol/hr) 9
Feed composition (mol %)
Methanol 99
DME 00
Water 01
given in Eq. (2).
r = kWcat [CH3 OH ]m [H2 O]n (2)
Where, rate constant k = 5.19 × 109 m3 kg catalyst−1 s−1, activation
energy E =133.8 kJ mol−1, m = 1.51 and n = -0.51.
The feed conditions for all the configurations analyzed in this study
are kept same as that reported by Lie et al. [19] and are given in
Table 1.
The reactive distillation of the methanol for the production of DME
was analyzed using steady state process simulations in Aspen Plus V10
with the rigorous RADFRAC distillation column model. UNIQUAC-
Redlich-Kwong was selected as the thermodynamic method for the si-
mulations with built-in binary interaction parameters for DME-me-
thanol and methanol-water system while parameters for DME-water
system were taken from NIST-RK database. These parameters were
validated against experimental P-x,y data of DME-methanol [34], T-x,y
data of methanol-water [35] and P-x,y data of DME-water [36]. Fig. 3
shows plots of experimental data with the data estimated using UN-
IQUAC-Redlich-Kwong model through Aspen Plus using the interaction
parameters and a good agreement between the experimental and esti-
mated values is observed indicating suitability of the model and its
parameters for the proposed simulation study.
3. Economic analysis
The economic analysis, to determine Total Annual Cost (TAC) of the
process, was performed using the equations and values listed in Table 2
and were taken from Bildea et al., [17]. The TAC of the process is the
summation of the operating cost and capital cost. Operating cost in-
volves the cost towards the utilities required such as steam, cooling
water, electricity etc. In the present study, steam and water were con-
sidered as utilities for the reboiler and condenser of the distillation
column. The column pressure was selected such that cooling water
would be sufficient to condense the overhead vapors. The cost of the
steam and cooling water are taken from Luyben [37], and are given in
Table 2.
N.K. Gor, et al.
Fig. 3. Experimental data vs. simulated data (a) P-x,y data of DME-methanol at T =20 °C; (b) T-x,y data of methanol-water at P =5 atm; (c) P-x,y data of DME-water
at T =100.11 °C.
Table 2
Equations and values for TAC calculations.
Parameter
For heat exchanger (reboiler and condenser)
Chex ($)
Material correction factor Fm
Pressure correction factor Fp
Design factor for condenser Fd
Design factor for reboiler Fd
Heat transfer coefficient for
a
condenser
Heat transfer coefficient for
reboilera
High pressure steam (42 bar
and 254 °C)
Medium pressure steam
(11 bar and 184 °C)
Low pressure steam (6 bar and
160 °C)
Cooling water (32 °C)
For distillation column
Cshell ($)
Height of column (m)
Material correction factor Fm
Pressure correction factor Fp
Cost of Reactive Packing
a
Luyben [37].
Chemical Engineering & Processing: Process Intensification 149 (2020) 107824
Here M&S is Marshall and Swift index which accounts the inflation
in the cost of material and its value in 2018 was 1638.2 [38]; A is the
Equation area of the heat exchanger in m2. The cost of catalyst was not con-
sidered because the same amount of catalyst was used in each config-
uration. The payback period of 3 years was assumed with 8000 op-
(M&S/280)×(474.7 A0.65 )×(2.29+Fm(Fd+Fp)) erational hours per year and TAC was calculated as given in Eq. (3).
1 for carbon steel
0 for P < 20 bar
Capital Cost
0.8 for fixed tube HE TAC= Operating Cost +
1.35 Payback Period (3)
0.852 kW/m2 K
Capital cost involves the cost of materials required for the major
0.568 kW/m2 K process equipments. In this study for the distillation column, cost of
$9.88/GJ
reboiler, condenser, column shell cost and cost of column internals was
taken into account. For the column shell cost, height and diameter of
$8.22/GJ the column are estimated. The ASPEN ‘Packing sizing’ function take
cares of all packing parameters along with pressure drop and flooding
$7.78/GJ
velocities calculations and variation in physical properties like density,
$0.72/GJ viscosity with temperature. Hence, the column diameter was de-
termined using the ‘Packing sizing’ function. Sulzer KATAPAK reactive
(M&S/280)×(957.9D1.066H 0.82 )×(2.18+FmFp) packing was selected with a HETP of 0.5 m. This packing was con-
1.2 × HETP × Number of theoretical stages sidered in the reactive zone of the column. The rest of the column was
1 for carbon steel
considered to be packed with Sulzer MELLAPAKPL packing having
1 + 0.0074 (P-3.48) + 0.00023 (P-3.48)2
10000 $/m3 HETP of 0.4. The total height of the column was taken as 20 % excess
than required for total packed height. Although column size is small, as
the column height is significant multiple packing sections along with
multiple liquid redistributors will be required to avoid channelling.
Hence, as a conventional heuristic of having approximately excess
height of 20 % is followed to accommodate column internals, such as
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N.K. Gor, et al. Chemical Engineering & Processing: Process Intensification 149 (2020) 107824

packing support, feed distributor, liquid redistributors and some height

at top for vapor-liquid disengagement.

4. Simulation methodology

4.1. Reactive distillation

Simulation of the reactive distillation of methanol was performed in

a single distillation column having 30 stages. The separation of me-
thanol-DME and water is quiet easy in RD column as 99.92 % of me-
thanol reacts which leaves only DME and water for the separation in the
column. This is the most significant advantage of reactive distillation
that it shifts the equilibrium to the right by continuous removal product
from the reaction zone to get higher conversions. The initial simulation
was performed taking 35 stages of the column. The configuration was
then optimized on the basis of minimization of TAC to achieve desired
purity of the products. The minimum TAC was obtained for the 30
stages. For the 30 stage RD column, the first stage is the condenser from
which 99.9 % pure DME is obtained. The rectifying section has only
four stage. The reactive zone is present in the middle part of the
column, and it runs from stage 6 to stage 29. The last stage is the re-
boiler from which pure water is obtained. Catalyst loading of 15 kg per
stage (total catalyst loading = 15 × 24 = 360 kg) was used. The cata-
lyst loading and reflux ratio are two parameters that influence the
purity of products and economics of the process. Higher the reflux ratio,
higher amount of methanol will come into the column therefore; con-
centration of methanol will be higher in the reactive section of the
column, higher will be the driving force and less amount of catalyst can
also give the desired purity. It was found that for the desired purity of
99.9 mol% of DME, molar reflux ratio of 0.931 was required for catalyst
loading of 360 kg whereas it increases to 0.986 for catalyst loading of
312 kg. Hence, proper tradeoff between required product purity and
economics must be achieved for the selection of reflux ratio and catalyst
loading. The optimization of RD was performed with an objective of
minimizing the TAC of the process subject to constraint of required
product purities. This exercise involves a number of structural design
and operating parameters. Structural design parameters considered
Fig. 4. Flowchart showing optimization strategy for RD.
involves total number of stages (N), feed stage (NF), and number of
reactive stages (NR) and location of reactive stages (PR). Reflux ratio
(RR) and boilup ratio (BR) are considered as the operating parameters The RDWC has been modeled as a double reactive zone column. The
for the column. The systematic simulation methodology used to get the first reaction zone is present over the complete 19 stages of pre-frac-
optimized configuration of RD column is shown in Fig. 4 in the form of tionator and second reaction zone is present in the main column from
a flowchart. stage 22 to stage 26. The catalyst loading over each stage is 15 kg and
While optimizing the RD column initially total number of stages total 24 reactive stages are taken for the simulation. Greater number of
were fixed, the feed stage, number of reactive stages and location of reactive stages are present in the pre-fractionator to treat fresh feed that
reactive stages were decided by evaluating the configuration for each is coming into the column while unreacted methanol that goes into the
possible extent of reactive stages separately. To get the desired product rectifying section and flows down to the other side of wall undergoes
purity reflux and boilup ratio were varied and corresponding reboiler reaction at the second reaction zone.
duty was checked whether it is minimum or not. The TAC of these The optimization of reboiler duty for the double reaction zone
configurations were calculated and optimum stages was decided which RDWC has many degrees of freedom. The structural design parameters
leads to minimum TAC. The trial and error method was used to get the are the number of stages in main column (N1), number of stages in pre-
initial guess as shortcut column DSTWU doesn’t support the reactions. fractionator (N2), feed stage, number of reactive stages in the first re-
action zone (NR1), number of reactive stages in the second reaction
4.2. Reactive divided wall column zone NR2), position of the first reaction zone (PR1), position of the
second reaction zone (PR2), number of stages across the wall and po-
Aspen Plus have no inbuilt model for the reactive divided wall sition of the wall. The operating parameters are reflux ratio (RR), boilup
column, hence the RDWC is modelled as a thermally coupled Petlyuk ratio (BR), liquid split (LS) and vapor split (VS) (in the simulation
column configuration as shown in Fig. 5. Two RADFRAC models were model of the present work liquid and vapor flow rates to pre-fractio-
used to model both, pre-fractionator and main column of the RDWC. nator). The optimum values of all these variables must be determined to
Starting from 35 stages, all the parameters in the RDWC were optimized get the optimum RDWC configuration. The optimization strategy fol-
for minimization TAC to get the optimum configuration. The optimum lowed to get optimum configuration is shown in the Fig. 6 in the form of
configuration has 28 stages. The first stage being the condenser, the a flowchart.
rectifying section has six stages. The dividing wall runs from stage 8 to While optimizing the parameters initially, number of stages in the
stage 26 accommodating 19 stages on both sides. The stripping section main column and pre-fractionator were kept fix. The position of wall,
has only one stage and reboiler is the final stage. Feed is introduced on number of reactive stages in both columns and their position were
the 8th stage which is the first stage of pre-fractionator. decided by trial and error method and accordingly the values of LS, VS,

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N.K. Gor, et al. Chemical Engineering & Processing: Process Intensification 149 (2020) 107824

Fig. 5. Simulation model for reactive thermally coupled Petlyuk column configuration equivalent to RDWC.

Fig. 7. TAC vs. Number of Stages for the RD column.

5. Results and discussions

5.1. Reactive distillation

The plot of TAC ($/yr) vs. total number of stages is shown in Fig. 7.
This plot shows that for the 30 number of stages, the TAC required is
minimum. The optimum feed stage was also determined on the same
basis of TAC. The Fig. 8 shows that optimum feed stage location for the
RD column is 8 which lead to minimum TAC. Similarly, the position of
the reactive zone in the column was decided which gives minimum
TAC. Since the 29th stage is the penultimate stage, shifting the reaction
zone below will make the reboiler as a reactive stage which drastically
decreases the purity of water as unreacted methanol appears in the

Fig. 6. Flowchart showing optimization strategy for RDWC.

RR and BR were changed to get the desired purity. The reboiler duty
(Qr) for such a configuration was evaluated and checked if its value was
minimum or not. If it wasn’t minimum, then the position of wall,
number of reactive stages and their position were changed. The TAC for
all these configurations was evaluated and then N2 were changed to get
the minimum TAC value for the given N1 stages.
Fig. 8. TAC vs. Feed stage for the RD column.

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N.K. Gor, et al. Chemical Engineering & Processing: Process Intensification 149 (2020) 107824

Table 3
Comparison of TAC for optimum position of reactive stages in RD.
Parameters Position of Reactive Stages

3-26 4-27 5-28 6-29

Diameter (m) 0.188 0.188 0.187 0.187

Condenser area (m2) 3.91 3.88 3.86 3.84
Reboiler area (m2) 1.08 1.08 1.07 1.06
Condenser Duty (kW) 41.96 41.67 41.41 41.22
Reboiler Duty (kW) 45.51 45.23 44.97 44.77
Column shell cost (103 $) 30.18 30.15 29.95 29.93
Condenser cost (103 $) 20.83 20.73 20.65 20.59
Reboiler cost (103 $) 10.64 10.60 10.56 10.53
Packing cost (103 $) 3.334 3.328 3.286 3.282
Total capital cost (103 $) 64.98 64.82 64.44 64.33
Condenser operating cost (103 $/yr) 0.872 0.864 0.859 0.855
Reboiler operating cost (103 $/yr) 12.95 12.87 12.79 12.74
Total operating cost (103 $/yr) 13.82 13.73 13.65 13.59
TAC (103 $/yr) 35.48 35.34 35.13 35.04

Values in bold are optimum values. Fig. 10. Liquid composition profile of the RD column.

bottom stream. Also treating the reboiler as a reactive stage in presence

of heterogeneous catalyst is practically not possible. Whereas shifting
the reaction zone upward i.e. from stage 5–28 or from stage 4–27 re-
duces the effective rectifying zone and decreases the purity of the top
product and hence requires higher reflux ratio to achieve desired purity
of DME. Hence, the optimum position of reaction zone was taken as
from stage 6–29. Table 3 shows the comparison of TAC for the optimum
reaction zone.
Figs. 9 and 10, shows the RD column temperature and liquid com-
position profiles with optimum 30 column stages and feed stage as stage
8. Fig. 11 shows the methanol consumption profile over the reactive
stages. The methanol composition profile shows that in the middle part
of the column where reaction zone is present, the composition of me-
thanol is higher and hence, the methanol consumption rate also shows
increasing trend. At the 26th stage, methanol consumption rate is
maximum because the temperature is sufficiently high although the
composition of methanol is less to give the highest conversion over the
stage. Though reaction zone starts from stage 6 and feed is given on
stage 8, composition of methanol is also sufficiently high over the stages
4–6. This also supports the fact that keeping reaction zone over upper
stages and giving feed on upper stages increases the methanol in the
overhead product and decreases its purity. All the optimum design,
operating and economical parameters of the RD column along with
product purities are given in Table 4.
Fig. 9. Temperature profile of the RD column.
Fig. 11. Methanol consumption profile over the stages of the RD column.
5.2. Reactive divided wall distillation column (RDWC)
The optimum total number of stages in the column was determined
by the minimization of the TAC of the configuration. Fig. 12 shows the
TAC in $/yr against the number of stages, and it shows that minimum
TAC is obtained for the column with 28 stages.
The other parameters for the optimum RDWC configuration were
also determined by minimization of TAC. The plot TAC vs. number of
stages in the pre-fractionator, shown in Fig. 13 indicates for the 19
stages in the pre-fractionator the obtained TAC is minimum. When pre-
fractionator stages are increased; to keep the same number of stages in
main column (i.e. other side of dividing wall) the length of the wall is
also increased. So, for 20 stages in pre-fractionator wall runs from stage
6–27 and for 21 stages it is from stage 5–27 which reduces the stages in
the rectifying section and hence purity of top product decreases. To
compensate decrease in the top purity reflux ratio need to increase and
which ultimately increases the heat requirement and overall TAC. In
these cases, all the stages in the pre-fractionator are taken as reactive
stages, as shown in Fig. 14 of liquid composition profile of the pre-
fractionator, the concentration of methanol is sufficiently high over
many stages to give high reaction rate. Also liquid leaving the pre-
fractionator contains more than 99 % of water, which also supports the
fact that keeping only one stage in stripping section is sufficient.
In RDWC position of wall plays an important role for effective se-
paration, reaction and energy requirement. The Table 5 shows the
shows the data compared on the basis of TAC to determine the optimum
position of the wall. The data indicates that minimum TAC is obtained

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Table 4
Optimum design, operating and economical parameters of the RD column.
Parameters Optimum Values

Design Parameters
Total stages 30
Feed stage 8
Reactive stages 6-29
Diameter (m) 0.187
Height (m) 16.32
Condenser area (m2) 3.84
Reboiler area (m2) 1.06

Operating Parameters
Molar reflux ratio 0.931
Molar boilup ratio 0.977
Condenser duty (kW) −41.22
Operating pressure (bar) 10
Reboiler duty (kW) 46.66
DME purity (mol %) 99.9
Fig. 13. TAC vs. Pre-fractionator stages.
Water purity (mol %) 99.9
DME mass flow rate (kg/hr) 205.15

Economic Parameters
Column shell cost (103$) 29.92
Condenser cost (103$) 20.59
Reboiler cost (103$) 10.53
Packing cost (103$) 3.28
Total capital cost (103$) 64.33

Condenser operating cost (103$/yr) 0.854

Reboiler operating cost (103$/yr) 12.74
Total operating cost (103$/yr) 13.59
TAC (103$/yr) 35.04

Values in bold are optimum values.

Fig. 14. Pre-fractionator liquid composition profile.

Table 5
Comparison on the basis of TAC for optimum position of wall.
Parameters Position of wall

6-24 7-25 8-26

Design Parameters
Main column reactive stages 20-24 21-25 22 – 26
Diameter (m) 0.252 0.249 0.247
Fig. 12. Plot of TAC vs. Total number of stages of RDWC. Condenser area (m2) 4.46 4.33 4.22
Reboiler area (m2) 1.22 1.19 1.16

when a wall is placed from stage 8 to stage 26 and increases when

Operating Parameters
moved up from that position. When wall is moved downwards i.e. from Liquid split flow rate (kmol/hr) 2 1.9 1.9
stage 9–27, that brings the main column reaction zone from stage Vapor split flow rate (kmol/hr) 4.8 4.8 4.7
23–27 with no stripping section. That drastically reduces the purity of Condenser duty (kW) −47.89 −46.48 −45.24
Reboiler duty (kW) 51.44 50.03 48.79
top product to less than 70 % and to get the desired purity it requires
very high reflux ratio and that ultimately increases the cost. Though the Economic Parameters
number of reactive stages was kept constant, moving wall upward re- Column shell cost (103 $) 37.88 37.46 37.10
duces the effective rectifying section and moving wall downward re- Condenser cost (103 $) 22.69 22.26 21.87
duces the stripping section and hence affects the purity of the products. Reboiler cost (103 $) 11.53 11.32 11.14
Packing cost (103 $) 3.20 3.15 3.12
Fixing the position of wall also fixes the position of the second re-
Total capital cost (103 $) 75.29 74.19 73.22
action zone in the main column. For the given configuration, the op-
timum position of the main column reaction zone is from stage 22 to Condenser operating cost (103 $/yr) 0.992 0.963 0.938
stage 26. This reaction zone is present at the bottom of the wall. This is Reboiler operating cost (103 $/yr) 14.64 14.24 13.88
because, as the unreacted methanol from pre-fractionator that flows to Total operating cost (103 $/yr) 15.63 15.20 14.82
TAC (103 $/yr) 40.73 39.93 39.23
the stripping section would vaporized and flow back to the other side of
wall. These vapors attain equilibrium over the stages and condense to

8
N.K. Gor, et al. Chemical Engineering & Processing: Process Intensification 149 (2020) 107824

Fig. 17. Reboiler duty vs. Vapor split flow rate.

Table 6
Fig. 15. Liquid composition profile of the main column. Optimum design, operating and economical parameters for RDWC.
Parameters Optimum Values
the liquid phase. This liquid flows down the stages and undergoes re-
Design Parameters
action at the reactive stages. When the reaction zone is present from
Number of stages 28
stage 22 to stage 26 where the temperature is high, higher methanol Feed stage 8th
conversion is obtained and less methanol goes to the stripping section Stages in pre-fractionator 19
to dilute the bottom product. Fig. 15 shows the liquid composition Reactive stages 1 – 19 in pre-fractionator
profile of main column. 22 – 26 in main column
Location of wall Stage 8 to 26
Figs. 16 and 17 shows the plot of TAC vs. liquid and vapor split flow
Diameter (m) 0.247
rate going to pre-fractionator, respectively. The minimum TAC is ob- Height (m) 14.76
tained for liquid flow rate of 1.9 kmol/hr going to the pre-fractionator Condenser area (m2) 4.22
column shown by stream L21 in Fig. 5. This corresponds to molar Li- Reboiler area (m2) 1.16
Operating Parameters
quid Split Ratio of 0.808. For vapor split flow rate minimum TAC is
Operating pressure (bar) 10
obtained at the 4.7 kmol/hr which is shown by stream V21 and going Molar Reflux ratio 1.119
into pre-fractionator. This corresponds to molar Vapor Split Ratio of Molar Boilup ratio 1.066
0.973. The molar liquid and vapor split ratio are given by Eq. (4) and Liquid split flow rate (kmol/hr) 1.9
(5) respectively. The product purities and hence, the reboiler duty are Vapor split flow rate (kmol/hr) 4.7
DME purity 99.9 %
quite sensitive to the both Liquid and Vapor Split ratios. Hence, are
Water purity 99.9 %
optimized carefully for the desired product purities. These split ratios DME mass flow rate (kg/hr) 205.17
are the key parameters to be maintained in RDWC column hydro- Condenser duty (kW) −45.24
dynamics design as deviation from optimum value during operation Reboiler duty (kW) 48.79
Economic Parameters
will lead to either problem in achieving desired product purities or
Column shell cost (103 $) 37.10
minimum reboiler duty. Condenser cost (103 $) 21.87
Reboiler cost (103 $) 11.14
Molar Liquid Split Ratio Packing cost (103 $) 3.12
Molar flow of liquid flowing to pre − fractionator from the stage Total capital cost (103 $) 73.22
= Condenser operating cost (103 $/yr) 0.938
Molar flow of liquid coming to the stage Reboiler operating cost (103 $/yr) 13.88
(4) Total operating cost (103 $/yr) 14.82
TAC (103 $/yr) 39.23

Molar Vapor Split Ratio

Molar flow of vapor flowing to pre − fractionator from the stage
=
Molar flow of vapor coming to the stage
(5)
Table 6 shows all the optimum design, operating and economical
parameters for RDWC.

5.3. Total annual cost comparison

Table 7 shows the comparison of the RD column and RDWC on the

Fig. 16. Reboiler duty vs. Liquid split flow rate.
basis of TAC. It shows the area of reboiler, condenser, their operating
and capital cost, diameter and height of column, its shell cost and the
cost of packing. The overall diameter of the RDWC is determined such
that it can accommodate the area of both pre-fractionator and main
column. Though the height of RDWC is less than the RD column, due to

9
N.K. Gor, et al. Chemical Engineering & Processing: Process Intensification 149 (2020) 107824

Table 7 the same throughput as RD and RDWC but the cost of reactor have to be
TAC comparison of RD and RDWC. considered.
Parameters RD RDWC
6. Conclusion
Diameter (m) 0.187 0.247
Height (m) 16.32 14.76
The two energy intensified configurations, RD and dual reaction
Condenser duty (kW) 41.22 45.24
Condenser area (m2) 3.84 4.22
zone RDWC, were proposed and studied in detail using ASPEN steady
Reboiler duty (kW) 44.77 48.79 state simulations. All the operating and structural parameters were
Reboiler area (m2) 1.06 1.16 optimized by sensitivity analysis with an objective of minimizing TAC
Column Shell cost (103 $) 29.92 37.10 of the system while meeting the desired DME and water purities. Using
Condenser cost (103 $) 20.59 21.87
these configurations, higher methanol conversion and hence higher
Reboiler cost (103 $) 10.53 11.14
Cost of packing (103 $) 3.28 3.12 DME production rate was obtained as compared to previously reported
Reboiler Operating Cost (103 $/yr) 12.74 13.88 configurations in the literature. The comparison of both the config-
Condenser Operating Cost (103 $/yr) 0.854 0.938 urations on the basis of TAC showed that 10.68 % less TAC is required
Total Capital Cost (103 $) 64.33 73.22
for RD configuration than RDWC. In terms of capital and operating cost
Total Operating Cost (103 $/yr) 13.59 14.82
TAC (103 $/yr) 35.04 39.23
also RD 12.14 % and 8.30 % require less cost respectively, than RDWC.
Proposed configurations also leads to lower specific energy requirement
Values in bold are optimum values. as compared to similar configurations proposed earlier in the literature.
Hence, RD and double reaction zone RDWC could be seen as better
less number of theoretical stages required, but it accommodates two alternatives to conventional DME production process.
columns in a single shell which increases its diameter and which in- For the novel proposed configurations, it is also necessary to analyze
creases the column shell cost. Also the areas required for reboiler and various operating conditions range in which these configurations are
condenser are more in case of RDWC which increases the condenser and suitable for production without any operation issues. For this few more
reboiler cost and overall RDWC requires higher capital cost than the RD simulation analyses are necessary which involves dynamic simulation
column. to analyze effect of various process disturbances and performance of
Comparing the operating cost of both the columns, RD requires less various process control schemes. This will help to envisage any possible
reboiler and condenser duty and hence the operating cost of RD column operational issues and possible conditions in which applicability of the
is less than RDWC. From the values of the TAC it is clear that the RD proposed new configuration is limited. The dual reactive zone RDWC
column is more energy efficient and economic than RDWC. It requires configuration has not been much explored on this front and needs to be
10.68 % less TAC than the RDWC also it saves 12.14 % in capital cost analyzed in detail before going for pilot or commercial applications.
and 8.30 % in operating cost.
Table 8 compares the TAC of RD and RDWC with the results of the Declaration of Competing Interest
literature. Based on the same purity constraints and the same amount of
catalyst used, the specific energy on reboiler duty (reboiler duty re- The authors declare that they have no known competing financial
quired per kg of DME produced) and specific cost of DME (the cost of interests or personal relationships that could have appeared to influ-
one kg of DME) is calculated compared with the work of [18] and [19]. ence the work reported in this paper.
From the data in Table 8, it has been observed that the proposed RD
and RDWC configurations are better in terms of energy required per kg CRediT authorship contribution statement
of DME. Also the cost of per kg DME is less compared to what literature
proposes. These configurations also gives the higher throughput with Nikhil K. Gor: Writing - original draft, Software, Formal analysis,
less energy requirement and with complete conversion of methanol. In Visualization. Nilesh A. Mali: Conceptualization, Methodology,
case of RDC + DC configuration, the capital and operating cost in- Supervision, Writing - review & editing. Sunil S. Joshi: Resources,
creases due to use of two distillation columns for reaction and separa- Funding acquisition.
tion. Hence, the cost of DME per kg is also higher in that case. Though
duel reactive zone RDWC is not as cost effective as compared to RD Acknowledgement
column but it is better than single reaction zone RDWC proposed by
[18] as it gives nearly double DME production with lower energy re- The Authors are thankful to CSIR-National Chemical Laboratory,
quirement. Even if the TAC required for single reaction zone RDWC is Pune (Maharashtra), India for supporting the present work.
less but its throughput is also less and hence gives higher cost of per kg
of DME and nearly double reboiler energy for per kg of DME. Fixed bed Appendix A. Supplementary data
reactor followed by RD column could be the good alternative as it gives
Supplementary material related to this article can be found, in the

Table 8
Comparison of results with literature results.
Parameter This work [18] [19]

RD RDWC RDC + DC RDWC Reactor + RD RD + DC

DME mass flow rate (kg/h) 205.15 205.17 103.65 103.65 206.27 102.96
Conversion (%) 99.90 99.90 50.06 50.40 99.55 49.66
Reboiler duty (kW) 44.77 48.79 141.79 58.70 78.23 316.33
Specific energy on reboiler duty (kW h/kg of DME) 0.218 0.238 1.368 0.566 0.379 3.072
Capital cost (103 $) 64.33 73.22 135.26 96.53 – –
Operating cost (103 $/yr) 13.59 14.82 32.18 13.99 – –
TAC (103 $/yr) 35.04 39.23 45.71 23.64 – –
Specific cost of DME (10−3 $/kg) 19.49 21.82 50.34 26.04 – –

10
N.K. Gor, et al.
online version, at doi:https://doi.org/10.1016/j.cep.2020.107824.
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