PRO/IITM Process Engineering

Dimethyl Ether Plant Casebook

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 PRO/II Process Engineering DME Casebook

Contents
Contact Information.................................................................................................................. 3
CASE 7: Catalytic dehydration of Methanol to Dimethyl Ether (DME) ............................ 7
Abstract.................................................................................................................................... 7
Introduction .............................................................................................................................. 7
Manufacturing Routes ......................................................................................................... 7
Process Overview ..................................................................................................................... 7
Process Simulation ................................................................................................................... 9
Component Data ................................................................................................................. 9
Thermodynamic Dat a ........................................................................................................ 10
Stream Data ..................................................................................................................... 13
Feed Stream ............................................................................................................... 13
Recycle Stream ........................................................................................................... 13
Reaction Dat a ................................................................................................................... 14
Unit Operations ....................................................................................................................... 17
Feed Section .................................................................................................................... 17
Reaction Section ............................................................................................................... 18
Separation Section ............................................................................................................ 26
Simulation Results and Discussions ......................................................................................... 36
Conclusion ............................................................................................................................. 47
Referenc es ............................................................................................................................. 49
Appendix A Keyword Input File .............................................................................................. 51

5
 PRO/II Process Engineering DME Casebook

CASE 7: Catalytic dehydration of Methanol

to Dimethyl Ether (DME)
Abstract
This case book demonstrat es the use of PRO/ II Process Engineering in the simulation of a chemic als
processing plant manufacturing 50,000 metric tons per year of Dimethyl Ether (DME ) with a purity of
99.5% from dehydration of Methanol assuming 8,375 hours per year of operation. DME is widely used as
a feedstock for production of methylating agent as well as a refrigerant when mixed wit h propane. The
process plant simulated here includes a reactor, a DME recovery distillation column and a Water
recovery distillation column. SIMSCI’s SRKM databank, along with Methanol/DME/Water solubility data,
provides a good simulation of the system’s liquid-liquid and vapor-liquid equilibria.

Introduction
Dimethyl Ether (DME ), a natural gas derived product, is a useful building block for making important
[1]
chemicals, including dimethyl sulfate and high -value oxygenated c ompounds . Furthermore, it is a clean
st
fuel, as it is non-toxic and burns without particulate emission. Henc e, termed as the fuel of 21 century. It
can be used as an alternative in diesel trucks due to its high cetane number, for power generation, fuel
cells and also as cooking gas. This last application is of ut most importance especially in developing
countries like China, India and Brazil and has the potential to cont ribute to the effective management of
[2]
energy resources in the future .

Manufacturing Routes
DME can be manufactured in two distinct ways: the first called the indirect route us es the produced
Methanol to promote dehydration; the second way is known as the direct route, in which DME is
[3].
produced in single stages using bi-functional catalysts
[4]:
Reaction occurring in the indirect route is as shown below
2CH3OH ↔ CH3OCH3 + H2O
Reaction occurring in the direct route is as shown below:
CO + 2H2 ↔ CH3OH
2CH3OH ↔ CH3OCH3 + H2O
CO + H2O ↔ CO2 + H2

Process Overview
DME is produced via gas-phase dehydration of Methanol over an acid -based zeolite catalyst:
2CH3OH ↔ CH3OCH3 + H2O ΔH298 = -23.4 kJ/mol [5]
The catalytic reaction is quite specific to DME production and there are no significant side reactions.
Typically, a fixed-bed adiabatic reactor is employed to carry out the dehydration reaction. Typical
0
conditions at the inlet to the reactor are 250 C and 15 bar, and the catalytic reactor is designed to have a
single-pass conversion of 80%, since equilibrium limits it from achieving much more than that under
these conditions. A typical catalyst is in shape of cylinders 30 mm long and 8 mm diameter has a packed
3
bed density of 3.8 g/cm and voidage of 0. 4. For this example, the rate of reaction, on the catalyst mass
basis, is assumed to be:

7
PRO/II Process Engineering DME Casebook CASE 7: Catalytic dehydration of Methanol to Dimethyl Ether (DME)

Rate = k0e-Ea/RTC 2MeOH (kmol/kgcat.s)

Where
k 0 – pre-ex ponential factor = 540,
Ea – activation energy = 64 kJ/mol and
3
CMeOH – concentration of Met hanol (kmol/m )
[5]
And the equilibrium reaction data is assumed to be :
ln(Keq) = (86)logT + 3138/T + (1.33*10^-3)T –(1.23*10^-5)T2
where
Keq – equilibrium constant and
T – given temperature

Note: Different catalysts will have different coefficients. Consult with catalyst manufacturer.

For the overall process, liquid Met hanol present at the standard conditions is pressurized first,
pre-heated in a heat exchanger, and then vaporized to the reactor inlet temperat ure by heat exchange
with the reactor product, which contains unreacted Methanol, DME and Water, initially all in gas phase.
After cooling by heat exchange with the reactor feed, the product is further cooled to condense most of
the material. DME, Methanol and Water are separated in a series of distillation columns configured in
direct sequence. Unreacted Met hanol is recycled back to the initial feed stream just downstream of the
0
pressurizing pump. The Water byproduct is cooled to 50 C and discharged to the facility’s effluent
handling system.

Figure: Process Flow Diagram for manufacture of DME from dehydration of Methanol.

8
 PRO/II Process Engineering DME Casebook

Process Simulation
Component Data
All components are available in the PRO/II Process Engineering data bank. We select the components
from DIPPRL2016: DIPPR databank becaus e the properties are up-to-date. We choos e this databank by
selecting the databank Hierarchy and setting the order of dat abank search as shown in Figure: Selecting
DIPPR databank at the top of the order followed by SimSci Databank .

Figure: Depicting Data Window for the entry of required components.

Figure: Selecting DIPPR databank at the top of the order followed by SimSci Databank

9
PRO/II Process Engineering DME Casebook CASE 7: Catalytic dehydration of Methanol to Dimethyl Ether (DME)

Thermodynamic Data
For all of the units in the flowsheet, the Soave-Redlich-K wong-Modified Panagiotopoulos-Reid (S RKM)
equation of state is an excellent predictor for polar-nonpolar systems, where the non -ideality is large or
strongly asymmetric and for systems that employ very high pressures. This method is modification of the
mixing rule for the S RK-P anagiopoulos-Reid by SimSci in which two more adjustable paramet ers, cij and
cji are introduced.
The SRKM met hod in PRO/ II Process Engineering uses an improved alpha correlation developed by
SimSci. The improved correlation provides more accurat e vapor pressure predictions than the original
SRK formulation for a wide variety of components.
In addition to K-values, the SRKM equation may be used to predict the enthalpies, entropies and
densities for the liquid and vapor phases.
The binary interaction parameters of DME-Methanol, DME-Wat er and Methanol-Water are already
present as default and we are using these values for further simulation. Figure illustrates the steps to
[6]
Data Entry Window .

Figure: Selection of suitable thermodynamic package

10
CASE 7: Catalytic dehydration of Methanol to Dimethyl Ether (DME) PRO/II Process Engineering DME Casebook

Figure: Modifying the default data if necessary.

Figure: Verifying the binary interaction parameters

11
PRO/II Process Engineering DME Casebook CASE 7: Catalytic dehydration of Methanol to Dimethyl Ether (DME)

Figure: The binary interaction parameters are non -zero.

Table: SRKM Binary Interaction Parameters.

Component i Methanol Methanol Water

Component j Water DME DME

kija -0.0669093 -0.045767 -0.210727

kjia 0.00482863 -0.000784 0.158649

kijb -9.76208 0 -3.4145

kjib -25.4477 0 -138.441

cij 0.0506094 2.89028 1

cji 1.15893 0.05465 1

Equation UOM K K K

Table note: These values have been provided by SimSci. If user has more accurate data for binary interaction parameters from
new er experiments, the data should be supplied here.

12
CASE 7: Catalytic dehydration of Methanol to Dimethyl Ether (DME) PRO/II Process Engineering DME Casebook

Stream Data
Feed Stream
The main feed stream, Methanol, is defined as usual by entering the rate, composition, temperature, and
pressure as shown in Figure: Data Window f or entry of temperature, pressure, flowrate and composition
for Feed Stream.

Figure: Data Window for entry of temperature, pressure, flowrate and composition for Feed Stream.

Recycle Stream
The unreacted Methanol from the Water recovery distillation column is recycled and mixed with the feed
stream. The ratio of feed stream to the recycle stream is approximately 4. An initial estimate of the rate
and composition of the recycle stream is entered and after running the simulation, the actual data is
reported.

13
PRO/II Process Engineering DME Casebook CASE 7: Catalytic dehydration of Methanol to Dimethyl Ether (DME)

Figure: Data Window for entry of temperature, pressure, flowrate and composition of Recycle Stream.

Reaction Data
The reaction equation of DME synthesis from dehydration of Met hanol is given by:
2CH3OH ↔ CH3OCH3 + H2O ΔH298 = -23.4 kJ/mol
The equilibrium data for the reaction is given by:
ln(Keq) = (86)logT + 3138/T + (1.33*10^-3)T –(1.23*10^-5)T2
The above data is entered in the Reaction Dat a category of Input and is shown in the Figures 10 -14:

Figure: Description of the catalytic reaction.

14
CASE 7: Catalytic dehydration of Methanol to Dimethyl Ether (DME) PRO/II Process Engineering DME Casebook

Figure: Data Window for defining the reaction.

Figure: Data Window for entry of reaction stoichiometry.

15
PRO/II Process Engineering DME Casebook CASE 7: Catalytic dehydration of Methanol to Dimethyl Ether (DME)

Figure: Data Window for the entry of heat of reaction.

Figure: Data Window for the entry of reaction equilibrium data.

16
 PRO/II Process Engineering DME Casebook

Unit Operations
The process flow diagram is divided into three sections:
1. Feed
2. Reaction
3. Separation

Feed Section
Pressurizing the feed stream: Initially, the temperature, pressure, rat e and composition of the
Methanol are ent ered into the data window as shown in the Component Data section. The feed is
pressuriz ed to 16.5 bar by employing a centrifugal pump with pump efficiency of 75% and mec hani cal
efficiency of 75%. The following figure depicts the entry of the data for the centrifugal pump.

Figure: Data Window for the entry of outlet pressure, pump efficiency and mechanical efficiency.

Recycle stream: The unreacted Methanol along with small fraction of Water and DME are recycled back
to be mixed with the feed stream. Initially, before running the simulation, an estimate for flowrate and
composition is entered with the condition that the flowrate ratio of feed and recycle stream is 4:1. This is
already depicted in figure
Mixing of recycle and feed stream: A mixer is employed to mix the feed and recycle stream uniformly
and thoroughly.

17
PRO/II Process Engineering DME Casebook CASE 7: Catalytic dehydration of Methanol to Dimethyl Ether (DME)

Figure: Depicting the Feed Section of the Process Flow Diagram.

Reaction Section
Shell and Tube Heat Exchanger: The mixed feed enters the heat exhanger and is partially vaporized
by the heat obtained from the products of the reactor in the heat exchanger. The required data for the
heat exchanger is entered in the Data Window as depicted in the following figures.

Figure: Data Window for entry of Heat Exchanger data.

Pressure Drop to be considered since the simulation is run under industrial conditions.

18
CASE 7: Catalytic dehydration of Methanol to Dimethyl Ether (DME) PRO/II Process Engineering DME Casebook

Figure: Data Window specifying the Cold Product Outlet Temperature.

Figure: Data Window specifying the configuration depending on the situation.

Figure: Zonal Analysis to be included to account for phase change.

Heating the mixed feed stream

19
PRO/II Process Engineering DME Casebook CASE 7: Catalytic dehydration of Methanol to Dimethyl Ether (DME)

The partially vaporized pre-heated mixed feed from the heat exchanger is vaporized completely by
0
means of a heating utility. Since the reaction takes place at 250 C, the outlet temperature is set to this
value.

Figure: Data Window for entry of Heating specification.

Figure: Data Window specifying Cold Product Outlet Temperature.

Fixed Bed Adiabatic Reactor (PFR)

The vaporized mixed feed ent ers the tubular reactor operated at adiabatic conditions. The temperature is
0
set at 250 C. The dehydration of Methanol occurs in the presence of a acid -based zeolite catalyst. The
catalyst are in a shape of a cylinder having a diameter of 8 mm and length of 30 mm. The packed bed
voidage is 0.4. The kinetics of the reactor are entered as shown in the Process Overview. The Reactor
Data is entered accordingly depending on the requirement. A slight pressure drop is observed as the
reaction proceeds along the length of the reactor. Hence, the lengt h of the reactor, number and diameter
of the tubes have to be chosen appropriately to make sure the pressure drop is not very large.

20
CASE 7: Catalytic dehydration of Methanol to Dimethyl Ether (DME) PRO/II Process Engineering DME Casebook

Figure: Data Window for Plug Flow Reactor.

Figure: Data Window for entry of Kinetic Data.

21
PRO/II Process Engineering DME Casebook CASE 7: Catalytic dehydration of Methanol to Dimethyl Ether (DME)

Figure: Data Window for entry of pre-exponential factor and activation energy.

Figure: Data Window for entry of reactor data.

22
CASE 7: Catalytic dehydration of Methanol to Dimethyl Ether (DME) PRO/II Process Engineering DME Casebook

Figure: Data Window for entry of Pressure specifications.

Figure: Data Window specifying pressure drop method and the dimensions of the catalyst.

23
PRO/II Process Engineering DME Casebook CASE 7: Catalytic dehydration of Methanol to Dimethyl Ether (DME)

Conversion control: The conversion of the reactant to product is controlled by the means of a controller
by specifying the appropriat e variable as shown in the followi ng figure.

Figure: Data Window for controlling the conversion of the reaction.

Cooling the mixed product-feed stream

The mixed product-feed stream ent ers the heat exchanger through the cold side section and the product
–feed mixture condenses and cools down to a lower temperat ure. The mixture is completely condensed
before it enters the distillation column.

Figure: Data Window for entry of Cooling Utility specification.

24
CASE 7: Catalytic dehydration of Methanol to Dimethyl Ether (DME) PRO/II Process Engineering DME Casebook

Figure: Data Window for entry of inlet and outlet temperatures of the cooling utility.

Figure: Data Window for the entry of Hot Product Outlet Temperature.

The complete flow diagram of the reaction section is depicted in the the following figure.

25
PRO/II Process Engineering DME Casebook CASE 7: Catalytic dehydration of Methanol to Dimethyl Ether (DME)

Figure: Depicting the Reaction Section of the Process Flow Diagram.

Separation Section
Two distillation columns in direct sequence are employed in this section for separation. In the first
distillation column, DME is separated from Water and unreacted Methanol. In the second column, the
unreacted Methanol and traces of DME are separated from Water.
DME recovery di stillation column (1st di stillation column): For this example, the design
specifications are chosen according to the requirement. The number stages/trays are chos en to be 7
with a tray efficiency of 75%, flooding factor of 90%, weir height of 5cm and Tray spacing of 40 cm. User
should consult with a column vendor to confirm the proper efficiency and column internals to use. The
actual number of stages/trays can be found by employing the shortcut columns and providing a detailed
specification. The column is maint ained at a pressure of 9.5 bar and pressure drop is observed along the
column. The mixture of product and the unreacted feed enters at the mid-section of the column. The
location can be varied depending on the requirement but in general the location is at the mid-section. For
more accuracy, the location of feed can be found via an x -y diagram or Fenske’s equation. DME
separates out from unreacted Met hanol and Water as a distillate with a purity of 99.5% and the residual
is collected as bottoms which are fed to the next distillation column.

26
CASE 7: Catalytic dehydration of Methanol to Dimethyl Ether (DME) PRO/II Process Engineering DME Casebook

Figure: Data Window for specifying the First Distillation Column.

Figure: Data Window for entry of Tray Pressure and Pressure Drop.

27
PRO/II Process Engineering DME Casebook CASE 7: Catalytic dehydration of Methanol to Dimethyl Ether (DME)

Figure: Data window for the specifying the location of feed and an estimate product rate.

Figure: Data Window for the entry of Tray Hydraulics

28
CASE 7: Catalytic dehydration of Methanol to Dimethyl Ether (DME) PRO/II Process Engineering DME Casebook

Figure: Data Window for the entry of Tray Sizing.

Figure: Data Window for the entry of Tray Efficiency.

Figure: Data Window for entry of tray efficiency for each tray.

29
PRO/II Process Engineering DME Casebook CASE 7: Catalytic dehydration of Methanol to Dimethyl Ether (DME)

Figure: Data Window for entry of specifications and variables.

Water recovery distillation column (2nd Di stillation Column): The effluent from the first distillation
column enters the second distillation as the feed. Now, this feed is composed of unreacted Met hanol,
Water and negligible amounts of DME. The purpose of this distillation column is to separate unreacted
Methanol from Water. For simplicity, the same design specifications are employed for this column as
well. Let’s specify a 99% of Water recovery in the bottoms.

Figure: Data Window for specifying the Second Distillation Column.

30
CASE 7: Catalytic dehydration of Methanol to Dimethyl Ether (DME) PRO/II Process Engineering DME Casebook

Figure: Data Window for entry of Tray Pressure and Pressure Drop.

Figure: Data Window for specifying the location of feed and estimate product rate.

31
PRO/II Process Engineering DME Casebook CASE 7: Catalytic dehydration of Methanol to Dimethyl Ether (DME)

Figure: Data Window for entry of specifications and variables.

0
Cooling the bottom s: The temperature of Water is lowered to 50 C with use of a cooling utility and sent
to the treatment plant for removal organic impurities.

Figure: Data Window for specifying the cooling utility.

32
CASE 7: Catalytic dehydration of Methanol to Dimethyl Ether (DME) PRO/II Process Engineering DME Casebook

Figure: Data Window for the entry of inlet and outlet temperatures for the cooling utility.

Figure: Data Window for the entry of Hot Product Outlet Temperature.

Pressurizing and cooling the recycle stream: The unreacted Methanol, trace amounts of Water and
negligible amount of DME are separated out as distillate and are recycled back, to be mixed with original
feed. . Initially, the recycle is at a low pressure and hig h temperature. So the stream is pressurized to the
0
required value by the use of pump and cooled to lower temperature (50 C) with help of cooling Water.
Now, the recycle stream is mixed uniformly with the feed in a mixer.

33
PRO/II Process Engineering DME Casebook CASE 7: Catalytic dehydration of Methanol to Dimethyl Ether (DME)

Figure: Data Window for the entry of Outlet Pressure, Pump efficiency and mechanical efficiency.

Figure: Data Window for specifying the cooling utility.

Figure: Data Window for the entry of Hot Product Outlet Temperature.

Complete Flow diagram of this section is depicted in the following figure::

34
CASE 7: Catalytic dehydration of Methanol to Dimethyl Ether (DME) PRO/II Process Engineering DME Casebook

Figure: Depicting the Separation Section of the Process Flow Diagram.

35
PRO/II Process Engineering DME Casebook CASE 7: Catalytic dehydration of Methanol to Dimethyl Ether (DME)

Completer Process Flow Diagram

Figure: The complete Process Flow Diagram after running the simulation.

Simulation Results and Discussions

After the physical equilibrium and reaction kinetics are confirmed, t he reaction and separation process is
simulated. To make the simulation closer to reality, which means the parameters model should be
[6]
related directly to the actual, the actual production process is brought to validat e this model .
The design c apacity of the industrial DME production device from a factory is 50, 000 metric tons per y ear
with 8,375 hours of operation per year. The zeolite -acid catalyst is used of this reaction because they
[7]
have a high thermo-stability, great acid strength and adaptability to practically all types of catalysis .
The whole simulation process is performed under actual process conditions. The properties and
components of main stream in the simulation process are given in the following Table.

36
CASE 7: Catalytic dehydration of Methanol to Dimethyl Ether (DME) PRO/II Process Engineering DME Casebook

Table: The properties and components of all streams in simulation proce ss

0
Stream Name Phase T ( C) P (bar) Flowrate Composi tion
(kmol/hr)
CH3OH H2O DME

FEED Liquid 25.0 1.0 265 1.0000 0.0000 0.0000

PRFEED Liquid 25.3 16.5 265 1.0000 0.0000 0.0000
HE XIN Liquid 30.6 18.0 336 0.9797 0.0163 0.0039
HE XOUT Liquid 130.0 16.5 336 0.9797 0.0163 0.0039
REACTINLE T Vapor 250.0 15.0 336 0.9797 0.0163 0.0039
REACTOUTLE Vapor 250.0 15.0 336 0.1960 0.4082 0.3958
COOLERIN Mixed 151.8 13.5 336 0.1960 0.4082 0.3958
COOLOUT Liquid 50. 12.0 336 0.1960 0.4098 0.3958
DIS TILLIN Liquid 147.6 10.0 204 0.3210 0.6725 0.0065
DESIREDP RO Vapor 46.9 10.0 132 0.0037 0.0013 0.9950
WASTEWATE R Liquid 176.2 9.6 133 0.0100 0.9900 0.0000
COOLWWATE R Liquid 50.0 8.1 133 0.0100 0.9900 0.0000
RECY CLE Liquid 131.3 9.5 71 0.9039 0.0773 0.0188
PRESSURE CY Liquid 131.7 18.0 71 0.9039 0.0773 0.0188
COOLRE CY CL Liquid 50.0 16.5 71 0.9039 0.0773 0.0188

The whole process simulation results provide t he outputs of the key units, properties data about the main
streams between equipments or in columns and offer reference for actual process design and operation
[8].

In this manufacture of DME via dehydration of Methanol, a 2 -4 counter-current shell -and-t ube heat
exchanger is employed to pre-heat the mixed feed before heating it to the reactor temperature. The
0
mixed feed enters at the cold side inlet (approx. 30 C) and the outlet temperature of the cold side
0 0
is130 C. The reactor products, at a temperature of 250 C, enter at hot side inlet and the temperat ure is
0
reduced (approx. 147 C) due to the exchange of heat taking place bet ween hot and cold fluid. The
differenc e in temperatures bet ween hot and cold fluid is the driving force. If the t emperatures overlap with
each other, it leads to fatal errors and causes the heat exchanger to fail. In reality, the exchange of heat
doesn’t occur without drop in pressure. A pressure drop of 1.5 bar is assumed as the process proceeds.
Zones Analysis is included to account for the change in phas e occurring at the hot side in the heat
exchanger. A sharp change in the linearity is observed at the hot side indicating change of phase of
majority of Water from vapor to liquid. The temperature v Duty for the heat exchanger is depicted in the
Figure:Temperature vs Duty for 2-4 counter-current shell-and-tube heat exchanger

Note: The generation of plots for heat exchangers is depicted in the following figure.

37
PRO/II Process Engineering DME Casebook CASE 7: Catalytic dehydration of Methanol to Dimethyl Ether (DME)

Figure: Generation of plot for shell-and-tube heat exchanger.

The plot for Zones Analysis is directly generated in PRO/ II Process Engineering. The plot is exported to
an excel spreadsheet by right-clicking and selecting ‘Export to Excel’.

Figure: Temperature vs Duty for 2-4 counter-current shell-and-tube heat exchanger.

0
The reaction in the fixed bed adiabatic reactor occurs at temperat ure of 250 C and pressure of 15 bar in
0
the presence of zeolite-acid catalyst. The pre-heated mixed feed (130 C) from the heat exchanger is
0
heated to 250 C by means of a heating utility before entering the reactor. As the reaction proc eeds in the
forward direction along the length of the reactor, the pressure drops from 15 bar to 14.98 bar. Hence, the
length, tube diameter and number of tubes are chosen appropriately to avoid high pressure drops and
backward flow. The pressure vs distance in fixed bed adiabatic reactor is depicted in Figure: Pressure vs
Distance in Fixed-bed Adiabatic Reactor (PFR). A linear dec reas e in the pressure is observed.

Note: The plots for Fixed-Bed Adiabatic Reactor are generated by accessing the spreadsheet tools in
PRO/II Proc ess Engineering and selecting ‘Plug Flow Reactor’. The graphs are generated in an excel
spreadsheet.

38
CASE 7: Catalytic dehydration of Methanol to Dimethyl Ether (DME) PRO/II Process Engineering DME Casebook

Figure: Pressure vs Distance in Fixed-bed Adiabatic Reactor (PFR).

The controller is set to a conversion of 80% because it’s the maximum attainable conversion as the
equilibrium limits the conversion. In order to attain 80% conversion, the length of the reactor is varied.
Finally, the lengt h of the reactor required for optimum design is 12.44 m.
The molar flowrates of the components vs distance is depicted in Figure: Molar flowrates of all
components vs Distance in Fixed-bed Adiabatic Reactor (PFR). Initially, an exponential decrease in the
flowrate of Methanol is observed, as Methanol rapidly decomposes to DME and Water. As the
conversion proceeds and inches closer to 80%, the decrease becomes more linear, less exponential and
eventually becoming constant.

39
PRO/II Process Engineering DME Casebook CASE 7: Catalytic dehydration of Methanol to Dimethyl Ether (DME)

Figure: Molar flowrates of all components vs Distance in Fixed -bed Adiabatic Reactor (PFR).

Now, the products DME and Water have to be separated from the unreacted Methanol. The reactor
0
products (250 C) enter at the hot side inlet of the heat exchanger and are cooled down to lower
0 0
temperature (approx. 147 C). The temperat ure is further cooled to 50 C and the entire product is
0
condensed to liquid for the separation to occur. Cold Water at a temperature of 30 C is used as the
0
cooling utility and exiting at a temperature of 45 C.
Zones analysis is included to account for the c hange of phase occurring when the hot product condenses
to cold liquid. All the components condens e over the entire range of hot side temperatures. Hence, we
don’t observe a sharp change when all t he components change from vapor to liquid. The Temperature vs
Duty is depicted in Figure: Temperature vs Duty for the first cooling section.
Note: The plot for cooling section is generated as shown in Figure:Generation of plot for shell -and-tube
heat exchanger. The only change would be selecting ‘COOLING1’. The same procedure is used as
shown for heat exchanger.

40
CASE 7: Catalytic dehydration of Methanol to Dimethyl Ether (DME) PRO/II Process Engineering DME Casebook

Figure: Temperature vs Duty for the first cooling section.

DME, Water and unreacted Methanol are separated via a series of distillation columns in direct
sequence. Initially, a DME recovery distillation column is used to rec over DME of highest purity. 99% of
DME is recovered with a purity of 99.5%. The top tray pressure is at 10 bar and t he pressure varies along
the lengt h of the column. The feed is fed at the mid -section of the column. McCabe –Thiele method can
be employed for more accurate and optimized loc ation of feed. The vaporized product (DME) from the
top tray is partially condensed to liquid with a help of a partial condenser. The liquid produced returns to
the column as reflux while the remaining vapor product (DME ) is collected as the distillate. The resulting
reflux ratio was found t o be 0.48. The bottoms from the last tray of column enter t he reboiling section and
the low-boiling components are returned to the column in the form of reboiled vapor. The remaining
product is collected as the bottoms. The vapor fraction of DME vs Tray number is depicted in Figure:
Mole fraction of DME vs Tray number for the first distillation column. The vapor fraction of DME steadily
decreases till Tray Number 5 and then decreases rapidly thereafter with increase in Tray Number,
inferring that the maximum separation occurs bet ween Tray Numbers 4 & 7.

Note: The generation of plot for the first distillation column is shown in the following two figures.

Figure: Selecting the option for generation of plot for the first distillation column.

41
PRO/II Process Engineering DME Casebook CASE 7: Catalytic dehydration of Methanol to Dimethyl Ether (DME)

Figure: Selecting the required Y-axis variable for plot generation.

The plot for column vapor and liquid composition is directly generated in PRO/II Process Engineering.
The plot is exported to an excel spreadsheet by right-clicking and selecting ‘Export to Excel’.

Figure: Mole fraction of DME vs Tray number for the first distillation column.

42
CASE 7: Catalytic dehydration of Methanol to Dimethyl Ether (DME) PRO/II Process Engineering DME Casebook

The bottoms from the first column are fed to the mid -section of the second column which is the Water
recovery distillation column. 96% of Water is recovered with a purity of 99%. The top tray pressure is at
9.5 bar and the pressure varies along the length of the column. The vaporized product from top tray
composed of unreacted Methanol, DME and Water is partially condensed to liquid with the help of a
partial condenser. The liquid is returned to the column as reflux and the remaining vapor product is
collected as the distillate. This distillate containing unreacted Methanol, DME and Water is recycled and
mixed with the original feed. The reflux ratio was found to be 3.94. The bottoms are mainly composed of
Water. Water from last tray of the column enters the reboiling section and any low-boiling components
are returned to the column in form of reboiled vapor. The remaining Water is collected as the bottoms
and sent to the treatment to remove organic impurities. The liquid fraction of Water vs Tray number is
depicted in Figure: Mole fraction of Water vs Tray number for the second distillation column. The liquid
fraction of Water steadily increases with increase in Tray number, inferring that Water separated out
uniformly.

Note: The generation of plot for second distillation column is shown in Figure: Selecting the option for
generation of plot for the first distillation column. The only change would be selecting ‘DIS TILL2’. The
selection of Y -axis variable is depicted in the Figure: Selecting the required Y-axis for plot generation.

Figure: Selecting the required Y-axis for plot generation.

The plot for column vapor and liquid composition is directly generated in PRO/II Process Engineering.
The plot is exported to an excel spreadsheet by right-clicking and selecting ‘Export to Excel’

43
PRO/II Process Engineering DME Casebook CASE 7: Catalytic dehydration of Methanol to Dimethyl Ether (DME)

Figure: Mole fraction of Water vs Tray number for the second distillation column.

0
The Water discharged as bottoms from the second column is at a temperature of 176 C. The Water is
0 0
cooled t o 50 C via a cooling utility. Cold Wat er at a temperature of 30 C is used as the cooling utility. The
0
cold Water is discharged at a temperature of 45 C. The temperature vs Duty is depicted in Figure:
Temperat ure vs Dut y for the second cooling section.

Note: The plot for cooling section is generated as shown in Figure: Generation of plot for shell -and-t ube
heat exchanger. The only change would be selecting ‘COOLING2’. The same procedure is used as
shown for heat exchanger.

Figure: Temperature vs Duty for the second cooling section.

The unreacted Methanol, Water and DME discharged as distillate from the second column are at a
0
temperature and pressure of 131 C and 9.5 bar respectively. Before it can be mixed with the original
feed, the pressure has to be increased and temperature reduced. This recycle stream is pressurized to
0
18 bar with a help of a centrifugal pump and the temperature reduced t o 50 C with help of a cooling utility.
0 0
The cold Water at 30 C is used as the cooling utility and discharges at 45 C. The Temperat ure vs Duty is
depicted in Figure: Temperature vs Duty for the third cooling section.

Note: The plot for cooling section is generated as shown in Figure: Generation of plot for shell -and-t ube
heat exchanger. The only change would be selecting ‘COOLING3’. The same procedure is used as
shown for heat exchanger.

44
CASE 7: Catalytic dehydration of Methanol to Dimethyl Ether (DME) PRO/II Process Engineering DME Casebook

Figure: Temperature vs Duty for the third cooling section.

45
 PRO/II Process Engineering DME Casebook

Conclusion
This simulation proposed a DME production process system, which includes: Methanol dehydration
system, heat transfer system and separation system after the reaction. The whole simulation process
was divided into three sections; Feed section, Reaction section and Separation section. Accordingly, the
whole process for high purity (99.5%) DME synthesis via Methanol dehydration in a fixed-bed adiabatic
reactor was developed.
The target for 50,000 metric ton per year DME yields, the length and volume of the catalytic reactor was
0
calculated. On the inlet operating conditions of temperature 250 C, pressure 15 bar and flow of
335kmol/ hr, the reactor outlet conversion reached 80%, and the DME yield was 50, 771 metric tons per
year. The distillation parameters of the product were also det ermined: column bottom temperature
0
147 C, overhead temperat ure 470C and reflux ratio 0.48. The purity of DME can reach above 99. 5%.
The entire process simulation results provided the outputs of the key units, the properties data for mai n
streams between equipments or in columns, offered useful reference for the actual process design and
operation optimization.

47
 PRO/II Process Engineering DME Casebook

References
1. Mingting Xu, Jack H. Luns ford, D. Wayne Goodman, Alak Bhattacharyya (1997). Synthesis of DME
from Methanol over solid-acid catalyst. Applied Catalysis A: General 149, 289-301.
2. FS. Ramos', A.M. Duarte de Fanas, L.E.P. Borges, J.L. Mont eiro, M.A. Fraga, E.F Sousa-Aguiard,
L.G. Appel (2005). Role of dehydration catalyst acid properties on one-step DME synthesis over
physical mixtures. Catalysis Today, Volume 101, Issue 1, 39-44.
3. Zoha Azizia, Mohsen Rezaeimanesh, Tahere Tohidian, Mohammad Rez a Rahimpour (2014).
Dimethyl ether: A review of technologies and production challenges. Chemic al Engineering and
Processing: Process Int ensification 82, 150 -172.
4. Minh Tri Luu, Dia Milani, Matthew Wake, Ali Abbas (2016). Analysis of di-methyl ether production
routes: Process performance evaluations at various syngas compositions. Chemical Engineering
Science 149, 143-155.
5. M. Farsi, R. Eslamloueyan, A. Jahanmiri (201 1). Modeling, simulation and cont rol of dimet hyl ether
synthesis in an industrial fixed-bed reactor. Chemical Engineering and Proc essing 50, 85–94.
6. Ziyang Bai, Hongfang Ma, Haitao Zhang, Weiyong Ying, Dingye Fang (2013). Process simulation of
dimethyl ether synthesis via Methanol vapor phas e dehydration. Polish Journal of Chemical
Technology, 15, 2, 122-127.
7. G.Perot, M.Guisnet (1990). Advantages and disadvant ages of zeolites as catalysts in organic
chemistry. Journal of Molecular Catalysis, Volume 61, Issue 2, 173-196.
8. Han Yuanyuan, Zhang Haitao, Ying Weiyong, Fang Dingy e (2009). Modeling and Simulation of
Production Process on Dimethyl Ether Synthesized from Coal -based Syngas by One-step Method.
Chinese Journal of Chemical Engineering, 17(1), 108-112.

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 PRO/II Process Engineering DME Casebook

A PPENDIX A
Keyword Input File
$ Generated by PRO/II Keyword Generation System <version 10.2>
$ Generated on: Tue Aug 28 10:12:43 2018
TITLE
PRINT HISTORY=ON
TOLERANCE STREAM =0.001,-0.005555555555556,0.001,0.01, &
TEMPERATURE=-0.0005555555555556, PRESSURE=0.001, &
DUTY=0.0001, MISCELLANEOUS=0.001, FLASH=3e-006, MBAL=1
DIMENSION METRIC, MDUTY=ON, BASIS=MOLE, TEMP=C, PRES=BAR, WT=KG, &
TIME=HR, LENGTH=M, FLENGTH=MM, LIQVOL=M3, VAPVOL=M3, &
LDENSITY=KG/M3, VDENSITY=KG/M3, XDENSITY=DENS, &
SPVOL=M3/KG-MOL, SPVVOL=M3/KG-MOL, ENERGY=KCAL, WORK=KW, &
DUTY=KCAL/HR, CONDUCT=KC/H, HTCOEF=KC/H, FOUL=HMC/K, &
VISCOSITY=CP, KVIS=CST, SURFACE=D/CM, STDTEMP=0, &
STDPRES=1.01325, PBASIS=1.01325
SEQUENCE SIMSCI
CALCULATION TRIALS=50, RECYCLE=ALL, TVPBASIS=37.7777777778, &
RVPBASIS=APIN, COMPCHECK=CALC, MAXOPS=1000000, CDATA=FIX, &
FLASH=DEFAULT, DVARIABLE=ON, PHASE=SIMSCI, TMAX=OLDLIMIT, &
TMIN=OLDLIMIT
COMPONENT DATA
CURRENT SEARCH = DIPPRL2017:DIPPR,SIMSCI
LIBID 1,METHANOL/2,H2O/3,DME, BANK=CURRENT
ASSAY FIT=ALTERNATE, CHARACTERIZE=TWU, MW=TWU, CONVERSION=API94, &
GRAVITY=WATSONK, TBPIP=1, TBPEP=98, NBP=LV, &
CURVEFIT=CURRENT, KVRECONCILE=TAILS, FORMATION=VER91, &
SPIRAL=SHORT
THERMODYNAMIC DATA
TRESET CONSTANT = NOFLASH
METHOD SYSTEM=SRKM, SET=SRKM01, DEFAULT
STREAM DATA
PROPERTY STREAM=FEED, TEMPERATURE=25, PRESSURE=1.01325, PHASE=M, &
COMPOSITION(M,KGM/H)=1,265
PROPERTY STREAM=COOLRECYCL, TEMPERATURE=25, PRESSURE=15, PHASE=M, &
RATE(M)=1000, COMPOSITION(M)=1,0.6/2,0.3/3,0.1
NAME FEED,Feed
OUTPUT FORMAT=COMPMOLAR, SPTPRINT=ON, SPTCALC=ON
RXDATA
RXSET ID=CATALYTIC, NAME=catalytic dehydration of Methanol
REACTION ID=CATALYTIC
STOICHIOMETRY 1,-2/2,1/3,1
HORX HEAT=-5.493455622432, REFCOMP=1, REFTEMP=25, REFPHASE=V
EQUILIBRIUM(K,KG,M3,BAR) B=3138, C=37.34259661311, D=0.00133, &
E=-1.23e-005
EPHASE DEFAULT=V
UNIT OPERATIONS
PUMP UID=PUMP1
FEED FEED
PRODUCT M=PRFEED
OPERATION EFF=75, PRESSURE=16.5, MEFF=75
MIXER UID=MIXER
FEED PRFEED,COOLRECYCL

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PRO/II Process Engineering DME Casebook CASE 7: Catalytic dehydration of Methanol to Dimethyl Ether (DME)

PRODUCT M=HEXIN
OPERATION PRESSURE=18
HX UID=HEATEXCHAN, ZONES(OUTPUT)=5
HOT FEED=REACTOUTLE, M=COOLERIN, DP=1.5
COLD FEED=HEXIN, M=HEXOUT, DP=1.5
CONFIGURE COUNTER, TPASS=4, SPASS=2, XOPTION=STOP
OPER CTEMP=130
HX UID=COOLING1, ZONES(OUTPUT)=5
HOT FEED=COOLERIN, M=COOLOUT, DP=1.5
UTILITY WATER, TIN=30, TEMPERATURE=45
CONFIGURE COUNTER
OPER HTEMP=50
COLUMN UID=DISTILL1
PARAMETER TRAY=7,IO=14
FEED COOLOUT,4,TNOTSEPARATE, NOTSEPARATE
PRODUCT OVHD(WT)=DESIREDPRO,5174.452429843, BTMS(M)=DISTILLIN, &
SUPERSEDE=ON
CONDENSER TYPE=PART
DUTY 1,1,,CONDENSER
DUTY 2,7,,REBOILER
PSPEC PTOP=10, DPCOLUMN=1.5
PRINT COMPOSITION=M, PROPTABLE=ALL, TLOADING, FRIDATA
ESTIMATE MODEL=CHEM, RRATIO=3
SPEC ID=DISTILSPEC1, STREAM=DESIREDPRO,FRACTION, COMP=3,WET, &
VALUE=0.995
SPEC(CHANGE) ID=DISTILSPEC3, RRATIO, VALUE=1
SPEC ID=DISTILSPEC2, STREAM=DESIREDPRO, RATE(KGM/H), COMP=3, &
WET, DIVIDE, STREAM=COOLOUT, RATE(KGM/H), COMP=3,WET, &
VALUE=0.99
VARY DNAME=CONDENSER
VARY DNAME=REBOILER
TSIZE SECTION(COLSECT-1)=2,6,CAP, SPACING(TRAY)=400, DMIN=381, &
FF=90, DPCALC=1, WEIR=50
TEFFICIENCY(EQUILIBRIUM) 2,0.75
EFACTOR 0.75
REBOILER TYPE=KETTLE
COLUMN UID=DISTILL2
PARAMETER TRAY=10,IO=20
FEED DISTILLIN,6,TNOTSEPARATE, NOTSEPARATE
PRODUCT OVHD(M)=RECYCLE, BTMS(M)=WASTEWATER,1300, &
SUPERSEDE=ON
CONDENSER TYPE=BUBB
DUTY 1,1,,CONDENSER
DUTY 2,10,,REBOILER
PSPEC PTOP=9.5, DPCOLUMN=1.5
PRINT COMPOSITION=M, PROPTABLE=ALL, TLOADING, FRIDATA
ESTIMATE MODEL=CHEM, RRATIO=3
SPEC ID=DISTILSPEC6, RRATIO, PHASE=L, VALUE=3
SPEC ID=DISTILSPEC7, STREAM=WASTEWATER, RATE(KGM/H), COMP=2, &
WET, DIVIDE, STREAM=DISTILLIN, RATE(KGM/H), COMP=2, &
WET, VALUE=0.96
SPEC(CHANGE) ID=DISTILSPEC8, STREAM=WASTEWATER,FRACTION, &
COMP=2,WET, VALUE=0.99
VARY DNAME=CONDENSER
VARY DNAME=REBOILER
TSIZE SECTION(COLSECT-1)=2,9,CAP, SPACING(TRAY)=400, DMIN=381, &
FF=90, DPCALC=1, WEIR=50
TEFFICIENCY(EQUILIBRIUM) 2,0.75

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CASE 7: Catalytic dehydration of Methanol to Dimethyl Ether (DME) PRO/II Process Engineering DME Casebook

EFACTOR 0.75
REBOILER TYPE=KETTLE
PUMP UID=PUMP2
FEED RECYCLE
PRODUCT M=PRESSURECY
OPERATION EFF=75, PRESSURE=18, MEFF=75
HX UID=COOLING3, ZONES(OUTPUT)=5
HOT FEED=PRESSURECY, M=COOLRECYCL, DP=1.5
UTILITY WATER, TIN=30, TEMPERATURE=45
CONFIGURE COUNTER, TPASS=1, SPASS=1
OPER HTEMP=50
HX UID=HEATING
COLD FEED=HEXOUT, M=REACTINLET, DP=1.5
OPER CTEMP=250
PLUG UID=PFR
FEED REACTINLET
PRODUCT M=REACTOUTLE
OPERATION LENGTH=15, DIAMETER=100, TUBES=500, PHASE=V, &
POINTS=10, THERMAL, TEMPERATURE=250
RXCALCULATION CONCENTRATION, RUNGEKUTTA, NSTEPS=20
PACK DPCORR=ERGUN
CATALYST PDIAM=8, PORO=0.4, PSHAPE=CYLI, PLEN=30
RXSTOIC RXSET=CATALYTIC
REACTION CATALYTIC
KINETIC PEXP(K,KG,M3,KG/CM2,HR)=540, &
ACTIVATION=0.01528613738416
KORDER 1,2
CONTROLLER UID=CONTROLLER
SPEC PLUGFLOW=PFR, CONVERSION(1), VALUE=0.8
VARY PLUGFLOW=PFR, LENGTH(M)
CPARAMETER IPRINT, CONTINUE
HX UID=COOLING2, ZONES(OUTPUT)=5
HOT FEED=WASTEWATER, M=COOLWWATER, DP=1.5
UTILITY WATER, TIN=30, TEMPERATURE=45
CONFIGURE COUNTER
OPER HTEMP=50
END

53