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Computers and Chemical Engineering 106 (2017) 17–22

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Computers and Chemical Engineering


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

Short Communication

Improving the conventional reactor/separation/recycle DME process


William L. Luyben
Department of Chemical Engineering, Lehigh University, Bethlehem, PA, 18015, United States of America

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

Article history: The conventional process to produce dimethyl ether (DME) by the dehydration of methanol is a classical
Received 5 March 2017 example of a chemical process with a reaction section, a separation section and recycles of material and
Received in revised form 1 May 2017 energy connecting the two. Alternative processes have been explored in attempts to increase process
Accepted 11 May 2017
intensification. A recent paper claims that reactive distillation can reduce capital investment and energy
Available online 12 May 2017
costs when compared to a conventional reactor/separation/recycle process.
The purpose of this paper is to demonstrate that the conventional process can be significantly improved
Keywords:
to the point that it is much superior to the published conventional process and is even more economical
DME process
Cooled tubular reactor
than the published reactive distillation process. The proposed flowsheet requires more capital investment
Vaporizer (53%) than the reactive distillation process but saves 38% in energy costs, which produces an attractive
61% return on the larger capital investment.
© 2017 Elsevier Ltd. All rights reserved.

1. Introduction tion costs. High conversion means small methanol recycle flowrates
and small separation costs in terms of both capital and energy. But
Turton et al. (Turton et al., 2003) presented the dimethyl ether high conversion requires a large reactor since reactor temperature
(DME) process as a typical example of a chemical process. This must be low to avoid the chemical equilibrium constraint.
widely used design textbook gives a flowsheet and some pre- A recent paper by Bildea et al. (Bildea et al., 2017) compares
liminary design parameters for this process. The chemistry is the the economics of a conventional DME process (reaction, separa-
decomposition of methanol to form DME and water. tion and recycle) with a reactive distillation process that requires
only a single column. The reactive distillation process is claimed
2MeOH ⇔ DME + Water
to have significantly lower capital investment (30%) and slightly
The reaction is exothermic and reversible, so low reactor tem- lower energy cost (6%) than the conventional process.
peratures improve conversion. The Turton flowsheet assumed a The purpose of this paper is to show that the conventional
vapor-phase reaction conducted in an adiabatic tubular. The liq- process developed in the published paper can be significantly
uid fresh feed and recycle streams are first vaporized and then improved. The improvement over the published conventional pro-
preheated in a feed-effluent heat exchanger before entering the cess is achieved by investing slightly more capital (7%) to achieve
reactor operating at 12 bar. Reactor effluent is cooled and fed to the a large decrease in energy cost (38%). The modified conventional
first distillation column operating at 10 bar (so that cooling water process is even more attractive than the published reactive distil-
can be used in the condenser), which produces a DME distillate. lation column. By investing more capital (53%) a large decrease in
The bottoms stream is separated in the second distillation column, energy cost (32%) is achieved. The return on investment is a very
which produces a water bottoms product and a methanol distillate attractive 60%.
for recycle back to the vaporizer. The Bildea flowsheet is described and the basic design parame-
Since the reaction is exothermic, low reactor temperatures ters are discussed in the following section so that the modifications
increase the chemical equilibrium constant and permit higher con- proposed in this work can be clearly understood.
version. But lower temperatures decrease specific reaction rates, so
larger reactors are required to attain the desired conversion. This 2. Conventional process in published paper
classical engineering trade-off between reactor size and reactor
temperature must also consider the effects of conversion on separa- 2.1. Preheat system

Fig. 1 gives the flowsheet of the conventional reac-


E-mail address: WLL0@Lehigh.edu tion/separation/recycle process in the published paper. Fresh

http://dx.doi.org/10.1016/j.compchemeng.2017.05.008
0098-1354/© 2017 Elsevier Ltd. All rights reserved.
18 W.L. Luyben / Computers and Chemical Engineering 106 (2017) 17–22

Fig. 1. – Published paper conventional flowsheet.

methanol feed (546 kmol/h) is combined with 121.3 kmol/h of practice calls for vaporizing a liquid stream first before superheat-
methanol recycle. Both of these streams are liquids. They are fed ing. The most widely applied example of this principle is in a steam
at 33 ◦ C and 12 bar into a feed-effluent heat exchanger (FEHE) that generating power plant in which boiler feed water is fed into the
is heated by a very hot 395.4 ◦ C vapor stream, which is the reactor steam drum and the saturated steam is then superheated in another
effluent. The cold stream entering the FEHE is liquid methanol. section of the furnace.
As this stream is heated to its bubblepoint of 144 ◦ C (at 12 bar), it
begins to vaporize. This two-phase flow can produce serious fluid
mechanic problems with slug flow in the FEHE.
More importantly, the phase change produces flat temperature
profiles on the cold side that lead to temperature pinch points. As 2.2. Reactor
clearly discussed in the published paper (see Fig. 5 in that paper),
there is a limit to the attainable temperature of the cold stream of After heating to 275 ◦ C in a fired furnace, the vapor stream enters
about 140 ◦ C because of temperature cross-over. The heat duty in a tubular reactor that is specified to be an adiabatic vessel with solid
the FEHE is only 2.29 MW. The approach temperature on the hot catalyst. The diameter is 1.89 m and the length is 12 m. The vessel
end of the FEHE is a very large T = 395–140 = 255 ◦ C. This is a clear size and the inlet temperature are determined by imposing several
indication that the feed preheat system proposed in the published limitations.
paper has the potential for significant improvement. The small duty The reactor diameter is set by imposing a fluid velocity of
in the FEHE results in requiring a large 6.89 MW duty in the fur- 0.25 m/s. Higher velocities are said to give too much pressure drop,
nace, which requires the use of an expensive high-temperature heat and lower velocity reduce mass transfer rates between the gas and
source (burning fuel). the solid packing.
Using a heat exchanger to both vaporize and superheat a liquid The reactor length and the inlet temperature affect conversion,
feed stream is a basic weakness in the published paper flowsheet. which affects the cost of the downstream separation section. Higher
As the results presented in the next section demonstrate, energy conversion means less recycle. The optimum conversion, reactor
requirements can be greatly reduce by first vaporizing the liq- length and inlet temperature are found in the published paper by
uid stream at modest temperature in one heat exchanger (kettle minimizing the total annual cost of the entire process. Catalyst
reboiler) using medium pressure steam and then heating the vapor degradation limited reactor temperatures to a maximum of 400 ◦ C,
to the desired reactor inlet temperature in a second heat exchanger which naturally occurs at the exit of the adiabatic reactor. The opti-
(FEHE) using the hot reactor effluent. mum value of inlet temperature is 275 ◦ C with a 12 m reactor vessel,
It should be noted that the Turton design and many other which results in a reactor exit temperature (395.4 ◦ C) near the max-
papers (Luyben, 2010; Reyes and Luyben, 2001) over the last several imum limit. The resulting per pass conversion of methanol is 81.8%,
decades describing processes with liquid feeds and vapor-phase which requires the separation section to have a methanol recycle of
reactor have all used vaporizers. Standard practical engineering 121.3 kmol/h. Fig. 2 shows the monotonically increase temperature
profile down the length of the 12 m tubular reactor.
W.L. Luyben / Computers and Chemical Engineering 106 (2017) 17–22 19

Fig. 2. – Temperature profiles.

If the reactor size could be increased or higher temperatures 2.4. Economics


could be attained inside the reactor, higher conversions could be
achieved. Tables 1, 2 and 3 in the published paper give detailed equipment
As demonstrated in the next section, the modified design uses a and economic results for the optimum design. The total capital
cooled tubular reactor so that a higher conversion can be attained investment is $3,417,600, 29% of which is the expensive furnace.
while staying below the maximum temperature constraint. This The annual energy cost is $2,652,400 per year, taking a credit
results in a smaller methanol recycle of 114.4 kmol/h, which trans- $129,900 per year for the steam generated. Clearly the furnace is
lates into lower energy and capital costs of the separation section. the big-ticket item in the published conventional process.
The modified process described in the next section has a slightly
larger capital investment ($3,664,400) but a much lower energy
cost ($1,615,000 per year).

3. Modified conventional process


2.3. Distillation columns
Fig. 3 shows the flowsheet of the modified process. The changes
The hot vapor leaving the FEHE at 219 ◦ C is cooled to 170 ◦ C from the published paper process include the use of a vaporizer,
and generates low-pressure steam from the 0.576 MW duty. The a cooled tubular reactor and an economizer. The same number of
process stream at 170 ◦ C leaving the steam generator is fed to the stages is used in the two columns, but they are smaller in diameter
first distillation column. and require less reboiler duty because of the smaller recycle flow.
Column C1 operates at 10 bar and produces a 99.99 mol% DME
distillate. Reflux drum temperature is 44 ◦ C so the condenser duty 3.1. Preheat system
of 6.453 MW can be removed using cooling water. The column has
18 stages and is fed on Stage 10. Reflux ratio is 3.94 and reboiler The two liquid streams (fresh feed and recycle) are heated in
duty is 0.625 MW from medium-pressure steam. an economizer from 51 ◦ C to 140 ◦ C by the 204 ◦ C process stream
The bottoms stream from C1 is fed on Stage 21 of a 30-stage coming from a downstream steam-generating heat exchanger
distillation column that produces a 99.9 mol% methanol distillate described later. The methanol is heated to just below its bubble-
and a 99.99 mol% water bottoms. The column operates at 1 bar. point temperature (144 ◦ C) at the system pressure of 12 bar. An
Reflux-drum temperature is 64.2 ◦ C and reflux ratio is 1.37. Reboiler overall heat-transfer coefficient U = 0.28 kW m−2 K−1 is used with
duty is 2.04 MW from low-pressure steam. liquid on the cold side and gas on the hot side. There is a small
20 W.L. Luyben / Computers and Chemical Engineering 106 (2017) 17–22

Fig. 3. – Modified process flowsheet.

amount of liquid formed on the hot side. The minimum approach adiabatic reactor is selected, the maximum temperature naturally
temperature is on the hot end (204–140 = 64 ◦ C) so 2.117 MW of occurs at the reactor exit as shown in Fig. 2. The conversion dictates
heat can be transferred into the cold liquid stream. The required the adiabatic temperature rise, so the reactor inlet temperature
heat-transfer area is 101 m2 . cannot be arbitrarily increased.
The saturated liquid stream from the economizer is fed to a If a cooled tubular reactor is selected, the profile exhibits a peak
vaporizer that is heated by medium-pressure steam (184 ◦ C at $8.22 temperature part way down the length of the reactor. This peak
per GJ). The liquid methanol in the vaporizer boils at 144 ◦ C, giv- must not exceed the temperature limitation. The peak depends on
ing a T for heat transfer of 40 ◦ C. The heat duty is 5.538 MW. the conversion and the heat transfer, both area and the coolant tem-
The capital cost of the vaporizer is calculated from the heat- perature. Small diameter tubes give more heat-transfer area, but
transfer area (244 m2 ) using an overall heat-transfer coefficient mechanical limitations limit tube size. We assume a tube diameter
U = 0.56 kW m−2 K−1 . of 0.05 m.
Saturated methanol vapor at 144 ◦ C and 12 bar leaving the top A peak temperature of 398 ◦ C is achieved by varying the number
of the boiling liquid in the vaporizer is superheated to 290 ◦ C in of tubes and the temperature of the coolant. The reactor tem-
feed-effluent heat exchanger before entering the reactor. The FEHE peratures are above the critical temperature of water (374 ◦ C), so
heat duty is 1.577 MW, and the minimum approach T is on the Dowtherm is selected as the coolant. Liquid Dowtherm is fed into
hot end (360.5–290 = 70.5 ◦ C). Using U = 0.10 kW m−2 K−1 in this the shell side of the reactor to cover the tubes with liquid. The
gas/gas system, the heat-transfer area required is 197 m2 . liquid boils and cools the process flowing inside the tubes. The
The hot stream entering the FEHE is the reactor effluent at Dowtherm temperature is constant over the entire length of the
398 ◦ C. The hot stream leaves the FEHE at 235 ◦ C so it can be used to reactor, so the Aspen Rplug reactor model with a “constant thermal
generate a small amount of medium-pressure steam at 184 ◦ C. If a fluid” heat-transfer option gives a realistic simulation.
T = 20 ◦ C approach is specified on the cold end, the process stream We tentatively select a reasonable reactor length of 10 m (to be
exit temperature is 204 ◦ C, giving a heat duty 0.356 MW, which is checked for pressure drop later). Then the number of tubes and the
an energy credit. Using U = 0.56 kW m−2 K−1 gives a heat-transfer coolant temperature are varied to achieve a peak temperature that
area of 17 m2 . does not exceed the 400 ◦ C limit. Fig. 2 shows the process temper-
ature profile and the coolant temperature profile when 2000 tubes
are used and the coolant temperature is 360 ◦ C. A peak temperature
3.2. Reactor of 398 ◦ C occurs at 2 m from the reactor inlet. A low overall heat-
transfer coefficient U = 0.03 kW m−2 K−1 is used in this packed bed
As is always the case in the design of a chemical process, the gas system. The resulting total heat-transfer area is 3300 m2 and
selection of the reactor type and the determination of the opti- the capital cost is estimated based on area.
mum operating and design parameters are critical issues. In the Now the pressure drop can be checked. The length of the tubes,
DME vapor-phase reaction process, the primary limitation is a max- the number of tubes and the catalyst particle size affect the pressure
imum temperature of 400 ◦ C caused by catalyst degradation. If an
W.L. Luyben / Computers and Chemical Engineering 106 (2017) 17–22 21

Table 1
– Equipment Comparison.

Published Paper Design Modified Design

Recycle (kmol/h) 121.3 114.4


FEHE Area (m2 ) 12.32 197
Duty (MW) 2.29 1.577
Economizer Area (m2 ) – 101
Duty (MW) – 2.117
Vaporizer Area (m2 ) – 244
Duty (MW) – 5.538
Furnace Duty (MW) 6.88 –
Reactor Ty pe Adiabatic Cooled by Dowtherm
Size L = 12m; D = 1.89 m 2000 tubes
Dtube = 0.05 m
L = 10 m
Duty (MW) 0 0.715
Coolant Temp (◦ C) – 360
Steam Generator Duty (MW) 0.576 0.356
Sink LP steam (160 ◦ C) MP steam (184 ◦ C)
Column C1 NT 18 18
NF 10 10
ID (m) 1.68 1.51
QR (MW) 0.625 0.888
AR (m2 ) 44.5 88.8
QC (MW) 6.45 5.045
AC (m2 ) 681.2 742
Reflux ratio 3.94 2.86
Column C2 NT 30 30
NF 21 21
ID (m) 1.16 0.876
QR (MW) 2.044 1.763
AR (m2 ) 77.0 85.4
QC (MW) 2.82 2.533
AC (m2 ) 144.7 180
Reflux ratio 1.37 1.21

Table 2
– Economic Results.

Published Paper Design Modified Design


6
Capital (10 $) FEHE 0.0412 0.2262
Economizer – 0.1465
Vaporizer – 0.2598
Furnace 1.006 –
Reactor 0.5658 (Note 1) 1.412
Catalyst 0.1887 (Note 2) 0.2199
Steam Generator 0.1041 0.0459
Column C1 Shell 0.2216 0.2066
Trays 0.0192 0.0192
Condenser 0.5589 0.5355
Reboiler 0.1117 0.1348
Column C2 Shell 0.2182 0.1775
Trays 0.0189 0.0189
Condenser 0.2042 0.2135
Reboiler 0.1592 0.1313
Total Capital 3.4176 3.6641

Operating Costs (106 $/y)


Vaporizer (LP Steam) – 1.311
Furnace (fuel) 1.9837 –
Column C1 Condenser 0.1339 0.1017
Reboiler 0.1482 0.2102
Column C2 Condenser 0.0585 0.0511
Reboiler 0.4581 0.3950

Energy Credits (106 $/y)


Steam Generator 0.1292 0.09428
(LP or MP steam)
Reactor (Dowtherm) – 0.3460
Net Operating Cost (106 $/y) 2.6524 1.6380
TAC (106 $/y) 3.7916 2.8602

Note 1: Published reactor cost reduced by calculated catalyst cost.


Note 2: Catalyst cost = $10/kg; bulk density = 560 kg/m3.

drop. With a reactor length of 10 m, 2000 tubes and a catalyst par- The fluid mechanics in the reactor show a superficial velocity of
ticle diameter of 4 mm, the Ergun Equation in Aspen Plus predicts 0.95 m/s in the tubes. The volumetric flowrate at the reactor exit
a small pressure drop of only 0.1 bar.
22 W.L. Luyben / Computers and Chemical Engineering 106 (2017) 17–22

(360 ◦ C and 11.7 bar) is 55.7 m3 /min and the cross-sectional area of duty) makes the column diameter smaller (1.51 versus 1.68 m) and
all 2000 tubes is 0.982 m2 . gives a smaller reflux ratio.
The methanol conversion in the reactor under these operating In the second column, the smaller overhead distillate (the
conditions and reactor size is 82.7%. Recall that conversion in the methanol recycle) makes the energy and capital costs of the modi-
published paper design is 81.8%. The increase seems small, but it fied design lower than those of the published paper design. Column
results in a 12.8% decrease in the methanol recycle (114.4 versus diameter, reboiler duty and condenser duty are all smaller. Note
121.3 kmol/h). This is an example of the dominant effect of conver- that the condenser duty is smaller but the required condenser area
sion and yield in chemical process design. is larger (180 versus 145 m2 ), which is due to the lower pressure
(0.6 bar) used in the modified design and the resulting lower reflux-
drum temperature.
3.3. Columns The results show the superior economics of the modified design.
Total capital cost is slightly larger ($3,664,100 versus $3,417,600),
The smaller methanol recycle in the cooled reactor process but the net energy cost is 38% lower ($1,638,000 per year versus
means smaller diameter distillation columns and lower energy $2,652,400 per year). The published paper design has a total annual
requirements. The number of stages in each column is assumed cost of $3,791,600 per year. The modified design has a total annual
to be the same as in the published paper design. Two Aspen Design cost of $2,860,200 per year, which is a significant 20% reduction.
spec/vary function are used in each column to achieve the specified Up to this point we have compared the two conventional reac-
purities of the two product streams and the purity of the recycle tion/separation/recycle designs. The results demonstrate clearly
from the top of the second column. the superiority of the modified process. It is interesting to com-
The published paper design uses 99.9 mol% methanol as the pare the improved conventional process developed in this paper
specification for the recycle purity. A slightly less pure recycle with the reactive distillation process presented by Bildea et al. They
(99.5 mol%) was found to give the minimum total annual cost. report a total capital investment of only $2,394,000. This is 53% less
Another difference is pressure in the second column that is than the capital investment of the modified conventional process.
reduced in the modified design to 0.6 bar to increase the relative However, the energy cost of the reactive distillation process is
volatility between methanol and water. In the published paper pro- reported as $2,414,000 per year. This is 38% more than the energy
cess, the pressure is 1 bar, giving a reflux-drum temperature of cost of the modified conventional process. Using a simple return-
64 ◦ C. At 0.6 bar the reflux-drum temperature is 52 ◦ C so cooling on-investment economic indicator, a very attractive 60% return is
water can still be used in the condenser. indicated.
Energy Saving
ROI =
Incremental Capital Investment
4. Equipment and economic comparison
$2, 414, 000 − $1, 638, 800 per year
Details of equipment sizes and design parameters of the two =
$3, 664, 100 − $2, 394, 000
alternative processes are compared in Table 1. Table 2 give eco-
nomic data for capital investment and energy costs. The numbers $775, 200 per year
= = 0.61
for the published paper design are taken directly from the Bildea $1, 2701, 000
et al paper. Capital costs are installed equipment cost. Total annual
cost uses a 3-year payback period.
Thus the modified conventional process looks more attractive
In the preheat section, the use of a vaporizer cuts the energy
than the reactive distillation process.
consumption significantly. In the published paper design, expen-
sive fuel is burned in a furnace to provide 6.88 MW. In the modified
5. Conclusion
design, less expensive low-pressure steam is used and the heat duty
is only 5.538 MW. The capital cost of the vaporizer is much less than
The design of the DME process has been explored by examining
the furnace ($259,800 versus $1,006,000). The cost of energy is also
alternatives to the conventional design presented in a recent paper.
less ($1,311,000 per year versus $1,983,700 per year).
The advantages of using a vaporizer on the liquid feed streams are
The capital cost of the cooled reactor is calculated from its heat-
demonstrated compared to attempting to vaporize and superheat
transfer area (3300 m2 ) and is significantly larger than the simple
in a single heat exchanger. The advantages of using a cooled reactor
adiabatic vessel ($1,412,000 versus $564,800). The amount of cata-
in this exothermic reaction system with a maximum temperature
lyst in the two reactors is about the same, so the catalyst costs (using
limitation are demonstrated compared to using an adiabatic reac-
$10 per kg) are not much different. The reactor cost shown in the
tor.
published paper ($754,480) is assumed to include the catalyst. The
numbers in Table 2 separate the vessel and catalyst costs.
It is clear that the big-ticket item in the modified process is the References
reactor while the big-ticket item in the published process is the
Bildea, C.S., Gyorgy, R., Bruncy, C.C., Kiss, A.A., 2017. “Optimal design of intensified
furnace. processes for DME synthesis”. Comput. Chem. Eng. (in press).
Since Dowtherm is generated in the cooled reactor to remove Luyben, W.L., 2010. D̈esign and Control of Methanol Reactor/Column Process,¨. Ind.
Eng. Chem. Res. 49, 6150–6163.
0.715 MW, an energy credit of $346,000 per year reduces energy
Reyes, F., Luyben, W.L., 2001. ‘Design and plantwide control of a gas-phase
costs. Both designs have steam generators that provide energy adiabatic tubular reactor process with liquid recycle’. Ind. Eng. Chem. Res. 40,
credits. The published paper design converts 0.576 MW into low- 3762–3774.
pressure steam worth $129,200 per year. The modified design Turton, R., Baille, R.C., Whiting, W.B., Shaelwitz, J.A., 2003. Analysis, Synthesis and
Design of Chemical Processes, 2nd edition. Prentice Hall, page 939.
converts 0.356 MW into medium-pressure steam worth $84,280
per year.
In the separation section, the lower feed temperature to the first
column in the modified design (138 versus 170 ◦ C) results in a larger
reboiler duty (0.888 versus 0.625 MW). But the smaller vapor rate
in the rectifying section (as indicated by the smaller condenser heat