Subject:

Simulation of Production of Dimethyl Ether from Methanol

From:

Katelyn Pate and Tom Bertalan

To:

Dr. Stephen Ritchie

9 December 2011
Dr. Ritchie,
The goal of this project was to reproduce via simulation in Chemstations CHEMCAD the process
described in appendix B1 of Turton et al. (Turton) (1). In the reaction described for this process, two
equivalents of methanol are combined via dehydration to produce dimethyl ether (DME) and water. The
simulation typically matched Turtons values within 1-2%. Unit operation parameters (page 5), stream
compositions (page 6), and a process flow diagram (PFD) (page 7) are attached.
Katelyn Pate
Tom Bertalan
CHE 481, Chemical Process Design I

CHE 481-1
Katelyn Pate | Tom Bertalan

2011 12 09
Simulation of Production of Dimethyl Ether from Methanol

Approach
We first assembled a PFD visually, while simplifying some combinations of unit operations into single
black-box simulators. In particular, the two combinations of trayed tower, reboiler, condenser, and reflux drum
were each combined into single SCDS Distillation Columns. Some bypass loops were also excluded, such as a
flow control loop around P-201, and a short bypass line beside E-202. Control hardware was also excluded (such
as LICs that manipulated tower product flow rates). However, because pressure in streams 13 and 10 (the two
tower distillate product streams) was higher than that inside the towers, pumps P-202 and P-203 were used
after the reflux tees (not before it, as shown in Turton, Figure B.2 (1)) to achieve this higher pressure.

Model Decisions and Parameters

Thermodynamics
Because the DME-water-methanol system exhibits nonideal behavior (1), we used a UNIFAC global kvalue model, in which UNIQUAC was used to estimate the binary interaction parameters since actual VLE data
was not available. Soave's modification of the Redlich-Kwong equation of state (2) was used as the global
enthalpy model because of its suitability for multicomponent mixtures, and its citation by Turton.
Heat Transfer Coefficients
All heat exchangers were first specified in design mode, in which one emerging stream temperature is
supplied, and then later respecified in rating mode, in which heat transfer area ( , in m2) and heat transfer
coefficient ( , in W/m2K) are supplied. Areas were taken from equipment tables on pages 942-943 of Turton,
while coefficients were initially estimated using the heuristic values on page 345. With input streams per
exchanger then set at the temperature, pressure, and composition specified in Turton's stream tables, we then
manipulated these coefficients until the exiting streams had the desired temperatures.
Reactor
The reactor R-201 was initially specified only through stoichiometry and conversion. However, for the
final simulation, we switched to CHEMCAD's "Kinetic Reactor (KREA)", which makes better use of the kinetics
information supplied by Turton. A possible alternative would be to use CHEMCAD's "Equilibrium Reactor
(EREA)", since Turton also cites some equilibrium constants (3).
Although Turton calls for a simpler packed-bed reactor, we used CHEMCAD's nearest equivalent of a
plug-flow reactor, without specifying any complicating details like number of parallel tubes. We specified

Page 2 of 7

CHE 481-1
Katelyn Pate | Tom Bertalan

2011 12 09
Simulation of Production of Dimethyl Ether from Methanol

adiabatic thermal mode, with a conversion of 0.798 with respect to methanol to achieve the desired
input/output flow stoichiometry.
We used Turton's units of kPa, kmoles, kg, kJ, m3, and hours where possible, but activation energy was
converted to units of 80480 kJ/kmol, from Turton's units of kJ/mol. Literature values for this activation energy
depend on catalyst used, but could be as high as 154 kJ/mol (4) (5). We used exponential factors of 1, 10-6, and
10-6 for methanol, DME, and water respectively (to signify that the reaction was first order in methanol and
zeroeth order in the products, as claimed by Turton).
CHEMCAD calculated a heat of reaction of -3106 MJ/h, which was 20% lower than Turton's suggested
value of -3868 MJ/h, but which achieved the desired output temperature of about 364C while keeping the
maximum temperature within the reactor below Turtons 400C catalyst-denaturation limit, as depicted in
Figure 1.
400

Temperature [C]

350
300
250
200
150
100
50
0
0

0.5

1.5
Position in Reactor [m3]

2.5

Figure 1. Profile of temperature through positions in the simulated plug-flow reactor.

Convergence
By default, CHEMCAD will iterate through recycle calculations 40 times before declaring that the recycle
calculation did or did not converge. We found this to be insufficientin about half of our simulation runs,
CHEMCAD reported this failure of convergence. So, in Run > Convergence > Max recycle iterations, we raised this
number to 150, which seemed to consistently allow enough computation time for CHEMCAD to find a
satisfactory solution.

Page 3 of 7

CHE 481-1
Katelyn Pate | Tom Bertalan

2011 12 09
Simulation of Production of Dimethyl Ether from Methanol

Works Cited
1. Turton, Richard, et al., et al. Analysis, Synthesis, and Design of Chemical Processes. Upper Saddle River, New
Jersey : Pearson Education, Inc., 2003. ISBN 0-13-064792-6.
2. Equilibrium constants from a modified Redkh-Kwong equation of state. Soave, Giorgio. Milan : Pergamon
Press, October 1, 1971, Chemical Engineering Science, Vol. 27, pp. 1197-1203.
3. Kinetics of Methanol Dehydration in Dealuminated H-Mordenite: Model with Acid and Basic Active Centres.
Bondiera, J. and Naccache, C. 1991, Applied Catalysis, Vol. 69, pp. 139-148.
4. Synthesis of dimethyl ether (DME) from methanol over solid-acid catalysts. Xu, Mingting, et al., et al. 1997,
Applied Catalysis A: General, Vol. 149, pp. 289-301.
5. Intrinsic and Global Reaction Rate of Methanol Dehydration over -Al2O3 Pellets. Beri, Gorazd and Levec,
Janez. 1992, Ind. Eng. Chem. Res., Vol. 31, pp. 1035-1040.

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CHE 481-1
Katelyn Pate | Tom Bertalan

2011 12 09
Simulation of Production of Dimethyl Ether from Methanol

Unit Ops Report

Name
Output pressure
Efficiency

P-201 A/B
15.5000
0.6000

P-202 A/B
11.4000
0.4000

P-203 A/B
15.5000
0.4000

Name
2nd Stream T Out C
U W/m2-K
Area/shell m2
Calc Ht Duty MJ/h

E-201
184.0000
580.0000
99.4000
14421.0508

E-202

E-203
40.0000
234.0000
101.8000
-11792.8711

Name
Reactor type
Reaction phase
Thermal mode
Reactor volume m3
Conversion
Molar Flow Unit
Activ. E/H of Rxn Unit
Volume Unit
Overall IG Ht of Rxn
(MJ/h)
Mass unit
Partial P unit
Include holdup flag

R-201
2
1
2
3.0714
0.7989
1
4
1
-3105.8335

bar

27.6000
171.0000
2035.9839

1
6
1

Reaction Stoichiometrics and Parameters

RateConst =
1.2100e+006
Act.E =
8.0480e+004
Hrxn =
Comp
Stoich.
Exp.factor
AdsorbFac.
AdsorbE
1
-2.00e+000
1.0000e+000
0.0000e+000
0.0000e+000
2
1.00e+000
1.0000e-006
0.0000e+000
0.0000e+000
3
1.00e+000
1.0000e-006
0.0000e+000
0.0000e+000
Name
No. of stages
1st feed stage
Condenser mode
Condenser spec
Cond comp i pos.
Reboiler mode
Reboiler spec.
Est. T top C
Est. T bottom C
Est. T 2 C
Calc cond duty MJ/h
Calc rebr duty MJ/h
Calc Reflux ratio

E-208
40.0000
250.0000
22.8000
-1183.5540

T-201
22
12
6
0.9954
2
6
0.0070
45.9657
148.8026
45.9699
-3505.9812
2135.5090
0.5290

T-202
26
14
6
0.9593
1
6
0.0053
118.1277
166.1348
124.5812
-5676.3052
5567.3657
1.5605

Page 5 of 7

0.0000e+000
AdsorbExp.
0.0000e+000
0.0000e+000
0.0000e+000

CHE 481-1
Katelyn Pate | Tom Bertalan

2011 12 09
Simulation of Production of Dimethyl Ether from Methanol

Stream Compositions
Stream No.
Temp C
Pres bar
Vapor mole fraction
Total kmol/h
Methanol
Dimethyl Ether
Water

1
25.0000*
1.0000*
0.00000
262.2000
259.7000
0.0000
2.5000

2
25.3936
15.5000
0.00000
262.2000
259.7000
0.0000
2.5000

3
45.2647
15.2000
0.00000
328.6240
323.4192
1.4011
3.8036

4
155.7232
15.1000
1.0000
328.6240
323.4192
1.4011
3.8036

Stream No.
Temp C
Pres bar
Vapor mole fraction
Total kmol/h
Methanol
Dimethyl Ether
Water

5
251.7531
14.7000
1.0000
328.6240
323.4192
1.4011
3.8036

6
367.1346*
13.9000*
1.0000
328.6241
65.0305
130.5956
132.9980

7
280.1164
13.8000
1.0000
328.6377
65.0370
130.5994
133.0013

8
99.3156
13.4000
0.23317
328.6377
65.0370
130.5994
133.0013

Stream No.
Temp C
Pres bar
Vapor mole fraction
Total kmol/h
Methanol
Dimethyl Ether
Water

9
91.2244
10.4000
0.27670
328.6377
65.0370
130.5994
133.0013

10
46.2951
11.4000
0.00000
129.7984
0.6004
129.1977
0.0000

11
148.8344
10.5000
0.00000
198.8395
64.4366
1.4017
133.0013

12
137.5024
7.4000
0.035898
198.8395
64.4366
1.4017
133.0013

Stream No.
Temp C
Pres bar
Vapor mole fraction
Total kmol/h
Methanol
Dimethyl Ether
Water

13
119.2164
15.5000
0.00000
66.4244
63.7192
1.4011
1.3036

14
166.1362
7.6000
0.00000
132.3980
0.7005
0.0000
131.6974

15
50.0237
1.2000
0.00000
132.3979
0.7005
0.0000
131.6974

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CHE 481-1
Katelyn Pate | Tom Bertalan

2011 12 09
Simulation of Production of Dimethyl Ether from Methanol

Process Flow Diagram (PFD)

Page 7 of 7