INSTITUTO POLIT

ECNICO NACIONAL
ESCUELA SUPERIOR DE INGENIER

IA QU

IMICA
E INDUSTRIAS EXTRACTIVAS
Optimizacion y Simulacion de Procesos
Final Project
Production of Dimethyl Ether (DME) via the Dehydration of Methanol
1 Process Notes
Dimethyl ether (DME) is used primarily as a propellant. DME is miscible with most organic solvents,
it has a high solubility in water, and it is completely miscible in water and 6% in ethanol.
1
Recently,
the use of DME as a fuel additive for diesel engines has been investigated due to its high volatility
(desirable for cold starting) and high cetane number.The production of DME is via the catalytic
dehydration of methanol over an acid zeolite catalyst. The main reaction is as follows:
2CH
3
OH (CH
3
)
2
O + H
2
O (1)
methanol DME
In the temperature range of normal operation, there are no signicant side reactions.
A preliminary process ow diagram for a DME process is shown in Fig. 1, in which 50,000 metric
tons per year of 99.5wt% purity of DME product is produced. Due to the simplicity of the process,
a stream factor of 0.95 (8375 h/yr) is used. Preliminary equipment summaries and process stream
information are given in Tables 1 and 2, respectively.
2 Process Description
Fresh methanol, Stream 1, is combined with recycled reactant, Stream 13, and vaporized prior to
being sent to a fixed-bed reactor operating between 250

C and 368

C. The single-pass conversion of
methanol in the reactor is 80%. The reactor efuent, Stream 7, is then cooled prior to being sent to
the first of two distillation columns, T-201 and T-202. DME product is taken overhead from the first
column. The second column separates the water from the unused methanol. The methanol is recycled
back to the front end of the process, while the water is sent to waste water treatment to remove trace
amounts of organic compounds.
3 Reaction Kinetics and Reactor Configuration
The reaction taking place is mildly exothermic with a standard heat of reaction, H
reac
(25

C) =
11700 kJ/kmol. The equilibrium constant for this reaction at three different temperatures is given,
by Bondiera andNaccache,
2
below:
T K
p
473 K (200

C) 92.6
573 K (300

C) 52.0
673 K (400

C) 92.6
The corresponding equilibrium conversions for pure methanol feed over the above temperature
range is greater than 92%. The equilibrium constants reported above appear to be higher than those
1
Figure 1: Production of Dimethyl Ether from Methanol.
calculated using standard Gibbs free energy and heat of formation data. The single-pass conversion
of 90% used above may not be attainable due to the equilibrium constraint. A single-pass conversion
of 80% may be more realistic goal for this design.
The reaction takes place on an amorphous alumina catalyst treated with 10.2% silica. There are
no significant side reactions below 400

C. Above 250

C, the rate equation is given by Bondiera and

Naccache
2
as:
r
methanol
= k
0
exp

E
a
R
g
T
r

p
methanol
(2)
where k
0
= 1.21 10
6
kmol/(m
3
catalyst filled reactor h kPa), E
a
= 80.48kJ/mol, and p
methanol
=
partial pressure of methanol (kPa).
Significant catalyst deactivation occurs at temperatures above 400

C, and the reactor should be de-

signed so that this temperature is not exceeded anywhere in the reactor. The design given in Fig. 1
uses a single packed bed of catalyst which operates adiabatically. The temperature exotherm of 118

C,
occurring in the reactor, is probably on the high side and gives an exit temperature of 368

C. However,
the single-pass conversion is quite high (80%), and the low reactant concentration at the exit of the
reactor tends to limit the possibility of a runaway. In practice, the catalyst bed might be split into two
sections with an intercooler between the two beds. This has the overall effect of increasing the volume
(and cost) of the reactor and should be investigated if catalyst damage is expected at temperatures
lower than 400

C. In-reactor cooling (shell and tube design) and cold quenching by splitting the feed
and feeding at different points in the reactor could also be investigated as viable alternative reactor
configurations.
4 Vapor-Liquid Equilibrium (VLE)
The DME-water binary system exhibits two liquid phases when the DME concentration is in the range
34% to 93%. However, upon addition of 7% or more alcohol, the mixture becomes completely miscible
over the complete range of DME concentration. In order to ensure that this nonideal behavior is
simulated correctly, it is recommended that binary VLE data for the three pairs of components be
used in order to regress binary interaction parameters (BIPs) for a UNIQUAC thermodynamics model.
If VLE data for the binary pairs are not used, the UNIFAC can be used to estimate BIPs. The result
shown in Table 2 a were obtained using UNIQUAC/UNIFAC on the Aspen Plus simulator. The SRK
thermodynamics package was used for the enthalpy calculations in this simulation.
2
Table 1: Prelimary Equipment Summary Table for DME Process.
Equipment P-201 A/B P-202 A/B P-203 A/B V-201 V-202 T-201 T-202 R-201
MOC Carbon steel Carbon steel Carbon steel Carbon steel Carbon steel Carbon steel Carbon steel Carbon steel
Power (kW) 7.2 1.0 5.2 - - - - -
Efciency 60% 40% 40% - - - - -
Type/drive Reciprocating/ Centrifugal/ Centrifugal/ - - - - -
Electric Electric Electric
Temperaure (

C) 25.0 46.0 121.0 - - - - -

Pressure in (bar) 1.0 10.3 7.3 - - - - -
Pressure out (bar) 15.5 11.4 16.0 - - - - -
Diameter (m) - - - 0.96 0.85 0.79 0.87 0.72
Height/length (m) - - - 2.89 2.53 15.8 14.9 10.00
Orientation - - - Horizontal Horizontal Vertical Vertical Vertical
Internals - - - - - 22 SS Trays 26 SS Trays Packed bed
24 in spacing 18 in spacing section 7.2 m
high lled
with catalyst
Pressure (barg) - - - 9.3 6.3 9.6 6.3 13.7
Equipment E-201 E-202 E-203 E-204 E-205 E-206 E-207 E-208
Type Float. Head Float. Head Float. Head Float. Head Fixed TS Float. Head Float. Head Float. Head
Vaporizer Partial Cond. Reboiler Condenser Reboiler Condenser
Duty (MJ/h) 14,400 2,030 12,420 2,490 3,140 5,790 5,960 1,200
Area (m
2
) 99.4 171 101.8 22 100.6 83 22.7 22.8
Shell side
Max temp (

C) 154 250 280 153 46 167 121 167

Pressure (barg) 14.2 14.1 12.8 9.5 9.3 6.6 6.3 6.6
MOC Carbon steel Carbon steel Carbon steel Carbon steel Carbon steel Carbon steel Carbon steel Carbon steel
Phase Boiling liq. V Cond. Vapor Boiling liq. Cond. Vapor Boiling liq. Cond. Vapor L
Tube side
Max temp (

C) 184 368 40 184 40 184 40 40

Pressure (barg) 10 12.9 4 10 4 10 4 4
MOC Carbon steel Carbon steel Carbon steel Carbon steel Carbon steel Carbon steel Carbon steel Carbon steel
Phase Cond. Steam V L Cond. Steam L Cond. Steam L L
Table 2: Flow Table for DME Process.
Stream No. 1 2 3 4 5 6 7 8
Temperature (

C) 25 25 45 154 250 364 278 100

Pressure (bar) 1 15.5 15.2 15.1 14.7 13.9 13.8 13.4
Vapor fraction (molar) 0 0 0 1 1 1 1 0.0798
Mass ow (tonne/h) 8.37 8.37 10.49 10.49 10.49 10.49 10.49 10.49
Mole ow (kmol/h) 262.2 262.2 328.3 328.3 328.3 328.3 328.3 328.3
Component mole flow (kmol/h)
Dimethyl ether 0 0 1.5 1.5 1.5 130.5 130.5 130.5
Methanol 259.7 259.7 323 323 323 64.9 64.9 64.9
Water 2.5 2.5 3.8 3.8 3.8 132.9 132.9 132.9
Stream No. 9 10 11 12 13 14 15 16 17
Temperature (

C) 89 46 153 139 121 167 50 46 121

Pressure (bar) 10.4 11.4 10.5 7.4 15.5 7.6 1.2 11.4 7.3
Vapor fraction (molar) 0.148 0 0 0.04 0 0 0 0 0
Mass ow (tonne/h) 10.49 5.97 4.52 4.52 2.13 2.39 2.39 2.17 3.62
Mole ow (kmol/h) 328.3 129.7 198.6 198.6 66.3 132.3 132.3 47.1 113
Component mole flow (kmol/h)
Dimethyl ether 130.5 129.1 1.4 1.4 1.4 0 0 46.9 2.4
Methanol 64.9 0.6 64.3 64.3 63.6 0.7 0.7 0.2 108.4
Water 132.9 0 132.9 132.9 1.3 131.6 131.6 0 2.2
Utility mps cw mps cw mps cw cw
Equipment E-201 E-203 E-204 E-205 E-206 E-207 E-208
Temperature in (

C) 184 30 184 30 184 30 30

Temperature out (

C) 184 40 184 40 184 40 40

Flow (tonne/h) 7.22 297.1 1.25 75.12 2.9 142.6 28.7
3
5 Report
The solution of the problem should be undertaken in groups of no more than three students. A very
important point to success is to break the problem into subtasks and thus divide the labor.
Requirements:
1. Language: Your report MUST be written in the English language, otherwise it will not be
accepted. It is worth remarking that this is a technical report, nonetheless a good command of
your English language is required.
2. Summary: A short summary outlining the calculations undertaken, summary of key results,
and an outline of the rest of the report.
3. Process Description: description of the process flowsheet. Detail any changes to flowsheet
structure or operating parameters required to make the problem feasible.
4. Process Flow Diagram and Stream Tables: give flowrate, composition, pressure, temper-
ature, enthalpy flow, and phase of all streams.
5. Model Formulation: discuss any assumptions and/or simplifications introduced in formulation
of the process model with a justification. Discuss the physical property models employed, with
supporting rational and data.
6. Flowsheeting Calculations: decomposition strategy, initialization and convergence method
used, particular problems encountered. Brief mathematical analysis of results, e.g., check overall
balances, estimate numerical errors, are design specifications satisfied?
7. Appendix: Aspen Plus input file (.inp) and report file (.rep) for your final converged flowsheet.
The submission deadline is May 29th, 2014 at 16.00 hrs. As part of the grade, you will be questioned
concerning to the project you are handing in. Note that no extension in the deadline will be granted
under any circumstances! and, for every hour of delay a 35% of your grade will be deducted.
6 Problem Decomposition
You have to solve this complex modeling task within a very limited period of time. The key of your
success will lie in working as a team and divide the labor. It is vital to build the flowsheet model in
an evolutionary manner. As general guidelines:
Start with a unidirectional flowsheet, and then add in recycle streams one at a time.
Do material balance only calculations, and then material and energy balance calculations (Aspen
Plus allows you to switch off energy balance calculations).
Use simple models (e.g., SEP2), and then more rigorous models (e.g., RADFRAC).
Use the results of earlier calculations as initial guesses for more rigorous calculations, and put
tight bound on manipulated variables. You may want to use different flowsheet decompositions
for simpler models.
Do simulation and/or sensitivity calculations first and then design calculations.
Use ideal physical property models and then more rigorous/appropriate models later.
You can also spend some time on thinking about how the overall task can be split into a series of
subtasks that can be worked on by individuals in parallel. For example, initially the following three
tasks can be done in parallel:
1. Develop and converge material balance only model of the flowsheet (simple models see Fig.2).
2. Start building material and energy balance model for part of flowsheet (see Fig. 3) to provide
initial guesses for later.
4
At the end of this phase, you should have good initial guesses (10%) for the material flows in the
flowsheet and a decision concerning a good physical property model. In the second stage:
1. With a good guess for liquid feed to distillation column train, get rigorous models working for
the distillation train.
2. Continue to add models and recycle streams to the material and energy balance model, each
time using the results of the previous calculation as initial guesses for the next. Add rigorous
distillation models last.
(a) Material Balance 1. (b) Material Balance 2.
Figure 2: Production of DME Material Balance: Simple Models.
Figure 3: DME Process Energy Balances.
References
[1] DuPont, DuPont Talks about its DME Propellant, Aerosol Age, USA, May and June 1976.
[2] Bondiera, J., and C. Naccache, Kinetics of Methanol Dehydration in Dealuminated H-
Mordenite: Model with Acid and Basic Active Centres, Applied Catalysis 69, 139-148, 1991.
[3] McKetta, J. J.; Cunningham. Encyclopedia of Chemical Processing and Design, Marcel-Dekker:
New York, 1976.
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