Aspen Plus Methanol Synthesis Model

Aspen Plus
Aspen Plus Methanol Synthesis Model

Version Number: V12.1
May 2021
Copyright (c) 2018 by Aspen Technology, Inc. All rights reserved.
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Contents
1 Introduction .........................................................................................................5
2 Components .........................................................................................................7
3 Physical Properties ...............................................................................................9
4 Reaction Model ...................................................................................................15

Reaction Thermodynamics ............................................................................... 15
Reaction Kinetics ............................................................................................ 20
Reaction Model Validation ................................................................................ 22
5 ICI Synetix (Johnson Matthey) Methanol Process Model ....................................29

Methanol Synthesis Quench Reactor Model ........................................................ 32
Convergence – ICI Synetix Process Model ......................................................... 38
6 Lurgi Two-Stage Methanol Synthesis Process Model ..........................................39

Lurgi Two-Stage Methanol Synthesis Reactor Model ............................................ 42
Convergence – Lurgi Two-Stage Process Model .................................................. 46
7 Summary ............................................................................................................47
8 Primary Sources .................................................................................................49
Appendix 1: Implementation of the Reaction Model ..............................................51
Appendix 2: ICI/Synetix Methanol Process Model Results – Mass Balance ...........55
Appendix 3: Lurgi 2-Stage Process Model Results – Mass Balance ........................59
Appendix 4: Bill of Materials ..................................................................................63
Contents iii
iv Contents
1 Introduction
This document summarizes AspenTech’s Methanol Synthesis model. The

report describes the process, explains how the physical properties and
reaction kinetics have been validated, and describes some of the challenges
involves with simulating the process.
1 Introduction 5
6 1 Introduction
2 Components
The table below lists the key components in the process and the unique
identifiers used in the Aspen Plus files associated with this work.
Model ID Database ID Description Structure
H2 H2 Hydrogen H2
N2 N2 Nitrogen N2
CO CO Carbon monoxide CO
CO2 CO2 Carbon dioxide CO2
H2O H2O Water H2O
CH4 CH4 Methane CH4
MEOH CH4O Methanol CH3OH
ETOH C2H6O-2 Ethanol CH3CH2OH
DME C2H6O-1 Dimethyl ether CH3OCH3
AR AR Argon Ar
Each of the components listed above are available in the Aspen Plus pure
component databases.
2 Components 7
8 2 Components
3 Physical Properties
All the required pure component property parameters are drawn from the
Aspen Plus PURE36 database. The SRK (Soave-Redlich-Kwong) equation of
state is used throughout the model to calculate pure component and mixture
properties as well as phase equilibrium. The SRK method is selected because
it is appropriate for the high-pressure, high-temperature conditions in the
reactor.
The standard SRK method is not usually applied for polar compounds such as
methanol. A variation of this method, using the Mathias alpha function for
polar compounds, is available in Aspen Plus. This method was not selected,
however, because the default method for Aspen Plus includes a special alpha
function for systems containing hydrogen. Given the importance of hydrogen
in the methanol synthesis reactor, the default SRK method is the most
appropriate choice for this model.
Azeotrope data and several sets of TPXY data for water/methanol,
water/ethanol, and methanol/ethanol binary systems were extracted from the
NIST source database included with Aspen Plus. The Aspen Plus data
regression system was applied to regress the temperature-dependent SRK
binary parameters (Kij and Lij) binary parameters for these systems. The fitted
parameters and regression results are summarized in the tables and plots
below.
Regression Results: SRK Binary Parameters for

Methanol/Water System
Parameter Component Component Value (SI Standard
i j units) deviation
SRKKIJ/1 H2O MEOH -0.0505 0.0142

SRKKIJ/2 H2O MEOH -6.090E-05 3.779E-05
SRKLIJ/1 MEOH H2O -0.00503 0.05024
SRKLIJ/2 MEOH H2O 1.679E-04 1.324E-04
Regression Results: Measured and Predicted Azeotropes

for Methanol/Water System
Experimental Data Model Predictions
Temperature Pressure Mole Fraction Temperature Pressure MeOH Mole

Fraction
C bar MeOH C bar Liquid Vapor
250.02 84.05 0.773 250.02 84.05 0.773 0.804
3 Physical Properties 9
Regression Results: Measured and Predicted VLE for

The water/methanol phase equilibrium predictions using the fitted SRK binary
parameters are in good agreement with data at pressures below 30 bar. The
10 3 Physical Properties
results of this model were also found to be reasonably consistent with fitted
results based on the NRTL model. Since the methanol/water separation
columns operate near atmospheric conditions, the discrepancy at higher
pressures should not influence the model results significantly. However, these
parameters should not be used to simulate high-pressure separations since
the model does not reproduce the high-pressure azeotrope condition.

Ethanol/Water System
SRKKIJ/1 H2O ETOH -0.1090 0.0478

SRKKIJ/2 H2O ETOH 9.481E-05 1.424E-04
SRKLIJ/1 ETOH H2O 0.0980 0.1370
SRKLIJ/2 ETOH H2O 6.197E-06 4.038E-04
SRKLIJ/1 H2O ETOH 0.0390667 0.221008
SRKLIJ/2 H2O ETOH -1.651E-04 6.661E-04
It was not possible to closely approximate the known azeotropes of the

water/ethanol system without including both the Lij and Lji parameters in the
regression. Although the standard deviations of the fitted parameters are
somewhat high, the model predictions are quite reasonable as shown in the
tables and figures below. These parameters should be used with caution since
they don’t exactly reproduce the azeotropes. Since ethanol is a trace
component in the methanol synthesis process the parameters meet the needs
of this model.
Regression Results: Measured and Predicted Azeotropes

for Ethanol/Water System
Experimental Data Model Predictions
Temperature Pressure Mole Fraction Temperature Pressure ETOH Mole

Fraction
C bar ETOH C bar Liquid Vapor
78.27 1.014 0.894 78.28 1.012 0.894 0.898
112.58 3.446 0.882 112.72 3.439 0.882 0.886
136.68 6.902 0.874 136.39 6.883 0.874 0.877
164.19 13.809 0.862 163.86 13.754 0.862 0.865
182.60 20.732 0.852 182.11 20.630 0.852 0.855
Ethanol/Water System

Methanol/Ethanol System
SRKKIJ/1 MEOH ETOH 0.0645 0.0101

SRKKIJ/2 MEOH ETOH -1.90E-04 3.04E-05
SRKLIJ/1 ETOH MEOH 0.2443 0.0275
SRKLIJ/2 ETOH MEOH -6.69E-04 8.36E-05
The fitted binary parameters for the methanol/ethanol system yield

reasonable agreement with the data as shown below.
Methanol/Ethanol System
Additional binary interaction parameters were drawn from the Aspen Plus
databases as summarized below.
SRK Binary Parameters Used in This Model

Comp I Comp J Source Temp KAIJ KBIJ KCIJ
Units
H2 CH4 APV100 C -0.02449 0 0

SRK-ASPEN
CO CO2 APV100 C -0.01544 0 0
SRK-ASPEN
H2O ETOH Regressed C -0.10897 9.48E-05 0
MEOH ETOH Regressed C 0.064503 -0.00019 0
H2O MEOH Regressed C -0.05048 -6.09E-05 0
Comp Comp Source Temp LAIJ LAJI LBIJ LBJI

I J Units
ETOH H2O Regressed C 0.097977 0.039067 6.20E-06 -0.00017

ETOH MEOH Regressed C 0.244322 0 -0.00067 0
MEOH H2O Regressed C -0.00503 0 0.000168 0
During the development of this model, the predicted adiabatic temperature of

the reactor was found to be several degrees too high compared to
experimental reports. This was corrected by fitting the ideal gas heat capacity
(CPIGDP) parameters using published vapor enthalpy data from NIST
(Goodwin, 1987). The fitted parameters are summarized below.
Fitted Ideal Gas Heat Capacity Parameters for Methanol
C1 C2 C3 C4 C5 Tmin Tmax
-17969.3 611569 2766.44 190130 582.451 0 1226.85
4 Reaction Model
The primary steps responsible for methanol formation are the reverse water-
gas shift reaction and the methanol synthesis reaction (see reactions 1 and 2,
below). These highly reversible, gas-phase reactions are carried out on the
surface of a copper/zinc oxide catalyst supported on alumina at high pressure
(30-50 bar) and temperatures of 200-300 C. The model includes two
additional side reactions to represent the formation of higher alcohols
(lumped into ethanol) and dimethyl ether (DME). The side reactions are
assumed to be irreversible.
# Label Stoichiometry Description
1 MEOH-SYN CO2 + 3H2 = CH3OH + H2O Methanol Synthesis

2 RWGS CO2 + H2 = CO + H2O Reverse Water-Gas Shift
3 F-ETOH 2CO + 4H2  Ethanol + H2O Ethanol formation
4 DME-FORM 2 CH3OH  DME + H2O DME formation
Reaction Thermodynamics
The chemical equilibria of the water-gas shift and methanol synthesis
reactions have been reviewed in detail by Graff and Winkelman (2016) who
used their own experimental data together with published data from a wide
range of publications to establish the relationships between equilibrium
constants and temperatures over a wide range of conditions. The researchers
found that the equilibrium constants could be predicted accurately from
thermodynamics by making minor adjustments in the Gibbs Energy of
Formation for methanol and carbon monoxide, well within the range of
reported values. The value fit from equilibrium data may well be more
accurate than previously reported values based on calorimetry.
The table below summarizes the Gibbs energy values in the Aspen Plus pure
component database, the values reported by Graff and Winkelman (2016),
and the values used in this model. The value for methanol has been adjusted
slightly to match the methanol synthesis equilibrium constant data from Graff
and Winkelman.
Gibbs Free Energy of Formation (DGFORM), kJ/mole

Source PURE36 Database Graff & Winkelman This Model
Methanol -162.320 -161.751 -161.550

Carbon Monoxide -137.150 -137.218 -137.218
4 Reaction Model 15
The figure below shows the equilibrium constant predicted using parameters
from the Aspen Plus pure component database (solid orange line). The solid
blue line is the predicted equilibrium constant using the adjusted Gibbs Free
Energy of formation of methanol. The points are a sample of the data from
Graff and Winkelman (2016). The equilibrium constants from the Aspen Plus
model are calculated directly from predicted Gibbs energies:
− ∆ +∆ − 3∆ −∆
ln =
The second plot shows the predicted equilibrium constant as a function of

temperature at several pressures. As shown, the equilibrium constant for the
methanol synthesis is quite sensitive to both temperature and pressure, with
methanol production favored at high pressures and lower temperatures.
Equilibrium Constant for Methanol Synthesis at 1 Bar
16 4 Reaction Model
Equilibrium Constant for Methanol Synthesis at Pressures
of 1-50 Bar
0
CO2 + 3H2 --> CH3OH + H2O
-2
-4
-6
ln( Kp )
-8
-10
-12
-14
0.0017 0.0018 0.0019 0.002 0.0021 0.0022
Inverse Temperature, 1/K
1 bar 15 bar 30 bar 50 bar
The next chart compares the calculated equilibrium constant for the water-
gas shift reaction with the data from Graff and Winkelman (2016). The
equilibrium constant is calculated using the Gibbs energy of reaction, which is
derived from the Gibbs energy of the reactants and products.
− ∆ +∆ − 3∆ −∆
ln =
The predicted equilibrium constant agrees well with the measured values over
the full temperature range. The second chart below shows that the reverse
water-gas shift reaction is only weakly sensitive to pressure.
4 Reaction Model 17
Equilibrium Constant for Reverse Water Gas Shift Reaction
at 1 Bar
-3
CO2 + H2 --> CO + H2O
-3.5
-4
ln( Kp )
-4.5
-5
-5.5
-6
0.0017 0.0018 0.0019 0.002 0.0021 0.0022
Inverse Temperature, 1/K
Model Data
Equilibrium Constant for Reverse Water Gas Shift Reaction

at Pressures of 1-50 Bar
18 4 Reaction Model
The next two charts show the calculated heat of reaction for the methanol
synthesis and reverse water-gas shift reactions.
Heat of Reaction for Methanol Synthesis
Heat of Reaction for Reverse Water-Gas Shift
4 Reaction Model 19
Reaction Kinetics
The water-gas shift reaction and the methanol synthesis reaction have been
studied extensively over the past eighty years, and many dozens of proposed
rate expressions have been set forth. After testing several options, we settled
on a model published by Vanden Bussche and Froment (1996) which was
found to agree best with plant data and published experimental data.
Rate Expression for Primary Reactions
1−
,
= ( )
.
+ + +
1 1
= , − −
1−
,
= ( )
.
+ + +
1 1
= , − −
The adsorption terms are further defined as: ln = + /

Term Description
Rate of methanol formation, kmol/sec

Px Partial pressure, bar (x = H2, H2O, CH3OH, CO, CO2, etc)
Forward rate constant for reverse water-gas shift (kmol/kg-cat/sec)*
, Reference rate constant for reverse water-gas shift = 0.00165 kmol/kg-
cat/sec*
Activation energy for reverse water-gas shift reaction = 22.6342
kcal/mol-K
Forward rate constant for methanol synthesis (kmol/kg-cat/sec)*
, Reference rate constant for the methanol synthesis reaction = 7.07034
kmol/kg-cat/sec*
Activation energy for the methanol synthesis reaction = -8.76469
Reference temperature, 501.57 K (228.42 C)
, Equilibrium constant for reverse water-gas shift (partial pressure basis);
Calculated from Gibbs free energy.
, Equilibrium constant for methanol synthesis (partial pressure basis);
Calculated from Gibbs free energy.
Weight of the catalyst (specified in the reactor model)
Activity of the catalyst (specified in the reactor model; 1.0 = fresh
catalyst)
20 4 Reaction Model
Term Description
First adsorption term, AA = 0, BA = 0 (KA = 1.0)
Second adsorption term, AB = 8.14711, BB = 0
Third adsorption term, AC = -0.69125, BB = 2066.17
Fourth adsorption term, AD = -23.4383, BD = 14928.2
*Pressure units are implicitly in bar.

The side reactions are assumed to occur on the catalyst surface, however the
exact mechanisms of the side reactions are not well established. The
stoichiometry and rate expression for ethanol formation is loosely based on
that reported by Miranda et al (2015). However, the rate expression has been
modified to include a first order term for carbon monoxide (parameter “x” in
the rate expression shown below). The activation energy is drawn from the
original source. The reference rate constant has been adjusted to match
typical ethanol yields found in the methanol synthesis process.
Chiang and Lin (2017) studied DME synthesis on copper oxide catalysts. The
researchers reported the reaction second order with respect to methanol
partial pressure, with a low activation energy (5.14 kJ/mol) and an
equilibrium constant near 1.0. Since the copper oxide catalyst evaluated in
this study was optimized for DME production, we have adopted the rate
expression by refit the pre-factor to match typical DME to methanol ratios
reported for using standard methanol synthesis catalysts (approximately
0.002 to 1).
Rate Expression for Side Reactions

= ( )
1 1
= , − −
= ( )
1 1
= , − −
Term Description
Rate of ethanol formation, kmol/sec
Rate of DME formation, kmol/sec
Px Partial pressure, bar (x = H2, H2O, CH3OH, CO, CO2, etc)
Forward rate constant for reverse water-gas shift (kmol/kg-cat/sec)*
, Reference rate constant for alcohol formation = 1.0E-12 kmol/kg-cat/sec*
Activation energy for alcohol formation = 19.467 kcal/mol-K
Forward rate constant for DME formation (kmol/kg-cat/sec)*
, Reference rate constant for the DME formation reaction = 1.0E-11
kmol/kg-cat/sec*
Activation energy for the methanol synthesis reaction = 18.66 kcal/mol-K
Reference temperature, 501.57 K (228.42 C)
x Power-law exponent for CO = 1.0
4 Reaction Model 21
Term Description
y Power-law exponent for H2 = 1.5
z Power-law exponent for methanol = 2.0
Weight of the catalyst (specified in the reactor model)
Activity of the catalyst (specified in the reactor model; 1.0 = fresh catalyst)
*Pressure units are implicitly in bar.
The reaction kinetics are implemented using the “GENERAL” reaction model in
Aspen Plus. The primary reactions are defined using the LHHW (Langmuir-
Hinshelwood-Hougen-Watson) rate equation for heterogeneous catalysis. The
side reactions have been configured as simple power-law reactions. Since
very small amounts of ethanol and DME are produced, the side reactions have
been assumed to be irreversible (otherwise the models are difficult to
converge in equation-oriented mode). Screen shots of the reaction model are
included in Appendix A.
Reaction Model Validation

The kinetic model has been validated against the model results reported by
Vanden Bussche and Froment (1996), which in turn was validated against a
wide range of published experimental data. The results, summarized below,
demonstrate nearly perfect agreement between the Aspen Plus model and the
model of Vanden Bussche and Froment. This implies that the physical
properties, reaction thermodynamics, and reaction kinetics are all sufficient
for process design purposes.
The test model uses a plug-flow reactor (RPLUG) to simulate the experimental
packed bed using the conditions summarized below, assuming isobaric,
adiabatic operation.
Feed composition (mole %)

CO 4%
H2 82%
CO2 3%
Inert 11%
Reactor Conditions
Internal diameter 0.016 m
Length 0.15 m
Catalyst 34.8 grams (assumed 33% void fraction)
Base Case Feed Conditions

Temperature 220C
Pressure 50 bar
22 4 Reaction Model
Flow 2.8e-5 kg/s
Calculated Residence Time

3.43 s (based on void space only)
10.4 s (based on full reactor volume)
Model Results – Methanol Mole Fraction v Axial Profile (50

Bar, 220C Feed)
(Reference Figure 5A, Vanden Bussche & Froment, 1996)
4 Reaction Model 23
Model Results – Methanol Fraction v Pressure
Model Results – Carbon Dioxide Mole Fraction v Pressure

(Reference Figure 6C, Vanden Bussche & Froment, 1996)
24 4 Reaction Model
Model Results – Axial Temperature Profile v Pressure
(Reference Figure 6B, Vanden Bussche & Froment, 1996)
Model Results – Temperature Profile v Feed Temperature

4 Reaction Model 25
Model Results – Methanol Mole Percent v Axial Position at
Different Feed Temperatures
(Reference Figure 7B, Vanden Bussche & Froment, 1996)
The figure below compares methanol conversion data from Klier et al (1982)
with model results from Aspen Plus and the model results from Vanden
Busche and Froment (1996). The dotted line shows the equilibrium limit
(calculated from thermodynamics in Aspen Plus using the Gibbs reactor
model). The Aspen Plus model predicted somewhat lower conversions near
the peak point, although it found the peak at the same composition reported
by Klier et al. Further, the Aspen Plus model agrees somewhat better with the
Klier data compared to the Vanden Busche model. This reflects the better
accuracy of the Aspen Plus equilibrium predictions compared to the
correlation used by Vanden Bushe.
These results demonstrate that the Aspen Plus model accurately captures the
influence of feed composition, feed temperature, pressure, and residence
time.
26 4 Reaction Model
Model Results – Conversion v Feed Composition at 75 Bar
and 250C
(Reference Figure 8, Vanden Bussche & Froment, 1996)
4 Reaction Model 27
28 4 Reaction Model
5 ICI Synetix (Johnson
Matthey) Methanol Process
Model
The ICI Synetix low pressure methanol (LPM) process (currently licensed by
Johnson Matthey) is the most common industrial methanol process worldwide,
responsible for over 30 million metric tons of methanol per year. The Aspen
Plus sample model covers the methanol synthesis and purification sections of
the plant. The equipment sizes, operating conditions, and feed stream
conditions used in the sample model are drawn from the SRI Process
Economics Report 43D “Mega Methanol Plants” (Pavone, 2003) which claims
to be a representative amalgam of multiple industrial plants. The unit
operation tag numbers and stream numbers in the Aspen Plus model are
consistent with those in the SRI report to enable easy comparison between
the model predictions and the mass balance included in the SRI report. The
process flow diagram is shown in the figure below.
The methanol synthesis process is fed with clean, sulfur-free syngas with an
approximate molar composition of 68% hydrogen, 23% carbon monoxide, 7%
carbon dioxide, and small amounts of methane, water, and inert gases at a
pressure of 35.5 bar and a temperature of 38C. The syngas is typically
produced from a gas reformer with significant heat integration between the
reformer and methanol synthesis sections of the plant. Hypothetically, any
source of syngas could be used including that derived from coal, coke, or
biomass gasification plants.
The syngas feed is pressurized to 80 bar in compressor K201. A condensate
stream (S21) is taken off downstream of the compressor intercooler (K-
201HX). This gas is mixed with cooler recycle syngas (S22) from K202,
reaching a temperature of about 53C (stream S24). Approximately one third
of this stream is heated to 182C in the interchange heat exchanger E202.
This portion of the hot gas is fed to the top stage of the methanol converter.
The remaining cooler portion of the syngas stream is split in equal proportions
and fed to the next three stages of the converter to cool the intermediate
streams between catalyst beds, helping move the reaction forward.
5 ICI Synetix (Johnson Matthey) Methanol Process Model 29

ICI Synetix Methanol Synthesis Process Flow Diagram in
Aspen Plus
The ICI Synetix process uses a four-stage “quench” reactor (R201) to produce
methanol. Fresh, cool syngas is introduced between the four catalyst beds,
reducing the temperature generated by the exothermic reactions in the
upstream catalyst bed. The catalyst beds are each represented as packed,
plug-flow reactors using the RPLUG rate-based reactor model.
The product gas leaves the reactor at approximately 250C and 76 bar. This
gas is cooled to 191C in exchanger E210. In the licensed process, E210 is
used to preheat the water feed for the saturator in the upstream reformer
section of the plant. The cooled syngas flows through the hot side of the
interchange exchanger E202, shedding heat to the reactor feed gas. The
temperature of the product gas is further reduced to 74C in the air-cooled
exchanger E209, then partially condensed at 38C in condenser E207.
The condensed methanol is recovered from knockout drum V201. A portion of
the overhead light gases from V201 is recompressed by K202 and mixed with
the pressurized syngas feed to reduce the temperature of the gas feed to the
reactor. The remaining light gas stream is scrubbed with water in column
C201 to recover residual methanol. The overhead gas from C201 is heated in
exchanger E206 to prevent condensation in the let-down recovery turbine
K204. The light ends are mixed with light ends from column C301 and used
elsewhere in the process as fuel.
The condensed methanol from V201 (S18) flows through turbine K203 (which
powers the boiler feed water pump in the plant). The methanol stream (S29)
exits turbine K203 at approximately 2.5 bar and flows to vessel V202. The
bottoms product from C201 (S33) rejoins the methanol product stream in
V202. The methanol stream is let down to near-atmospheric pressure in
storage tank T351; a small vapor purge (S48) comes off the tank overhead.
30 5 ICI Synetix (Johnson Matthey) Methanol Process Model

The crude methanol contains residual methane and other light gases, as well
as heavy by-products such as dimethyl ether (DME), ethanol, and other
higher alcohols (lumped into ethanol in the model. Crude methanol from T351
is pumped by P301 to the cold side of the interchange exchanger E301 where
it is heated to 54C before flowing to the light ends column C301, where
residual light ends are stripped out and used for fuel elsewhere in the
process.
The methanol stream from the bottom of C301 (S37) flows to the methanol
product column, C302. Methanol is taken overhead (S40). The bottoms
product (S38) is nearly pure water, containing less than 1 weight PPM
methanol. A small side stream (S37) purges ethanol and other higher alcohols
from the column. The hot methanol product stream exchanges heat with the
crude methanol in interchange exchanger E301.
A detailed mass balance comparing the model results to the SRI report is
included in Appendix 2.
The table below summarizes the key unit operation in the process and the
method used to represent each unit operation.
Summary of Unit Operations

Tag Description Modeling Approach Operating Condition
K201 Syngas Simulate each stage as an Stage1 P=53.2 bar

compressor isentropic compressor with Stage2 P=80.0 bar
COMPR block
Efficiency = 72%
E203 Syngas HEATER block T=37.8C
compressor
intercooler
V208 Compressor FLASH2 block Adiabatic
knockout drum
E202 Main interchange Two HEATER blocks Reactor feed (cold out)
exchanger (E202C and E202H) linked temperature=182.2C
with HXFLUX block (E202- U=731 kcal/hr-sqm-K
HX) via heat streams
Assume P=0.34 bar on
each side of exchanger
R201 Methanol synthesis Four RPLUG blocks in Adiabatic
reactor series; see details below. Diameter = 9.15 m
Height = 32 m
Four-stage quench Quench gas fraction to (four beds 8 m deep)
reactor; each first stage specified in
Feed flow:
stage with fixed FSPLIT block B1.
bed of catalyst Bed 1: 33.00%
media Bed 2: 21.44%
FSPLIT block SPL-2 sets
inter-stage quench gas Bed 3: 22.78%
rates (fractions). B3d 4: 22.78%
Catalyst 6 mm diameter
Void fraction = 0.33
Density =1940 kg/m3
E210 Reactor product HEATER Outlet Temp=190.6C
cooler Assume P=0.34 bar

Tag Description Modeling Approach Operating Condition
E209 Air cooler (reactor HEATER Outlet Temp=73.9C
product) Assume P=0.34 bar
E207 Partial condenser HEATER Outlet Temp=37.8C
Assume P=0.34 bar
V201 Crude methanol FLASH2 Adiabatic
KO drum
K203 Liquid turbine PUMP as turbine with 70% P=2.4 bar
drive eff.
K202 Recycle gas Isentropic compressor P=80.0 bar;
compressor (COMPR) Efficiency=74%
C201 Purge gas scrubber RADFRAC, 10 stages Top stage P=76 bar
flash drum
T351 Crude methanol FLASH2 P = 1.01 bar
storage tank Adiabatic
P301 Crude methanol PUMP P = 1.84 bar
pump Efficiency = 70%
E301 Distillation Two heater blocks linked Column feed temperature
feed/product cross with an HX-FLUX block via T = 54.4C
exchanger heat streams
U = 730 kcal/hr-sqm-K
C301 Light ends column RADFRAC, 25 stages fed Reb. duty = 45.4 Gcal/hr
at stage 15. Condenser Condenser T = 45.5 C
and reboiler included.
P = 1.36 bar (top)
P = 0.34 bar
P302 Transfer pump PUMP P = 2.5 bar
Efficiency = 70%
C302 Methanol product RADFRAC, 50 stages fed Molar reflux ratio = 1.3
column at stage 30 with side Bottoms purity < 1PPM
stream off stage 45. methanol in water
Condenser and reboiler
Adjust reboiler duty to
included.
match purity specification
P = 1.36 bar (top)
P = 0.34 bar
Side stream rate = 4
MT/hr
P304 C302 bottoms PUMP P = 54 bar
Methanol Synthesis Quench

Reactor Model
The figure below shows the configuration and simulation results for the
methanol synthesis quench reactor model. The reactor diameter is drawn
from the SRI report; the bed depths and the flow ratios to the lower beds

have been adjusted to approach optimal conditions. The reactor is quite
sensitive to the quench injection rates between the stages. When the quench
feed rate is too high, the inlet temperature drops too low, leading to slow
reaction rates and low outlet temperature. If the quench rates are too the
temperature rises very quickly and reaches equilibrium near the top of the
bed, leading to low productivity in the lower sections of the bed.
The reactor model represents each bed as an ideal, adiabatic plug-flow
reactor. The model calculates the temperature profile based on the energy
balance (considering heat generated by the reactions). Pressure drop is
calculated on each stage using Ergun’s equations for packed beds. The
temperature profile in each bed follows an S shape because the exothermic
reactions raise the temperature, which in turn accelerates the reaction rates.
The temperature profile flattens out as the system approaches chemical
equilibrium. The auto-accelerating nature of the process makes the reactor
extremely sensitive to the feed temperature and the injection rates and
temperature of the quench gas fed between the beds.

Model Results – Methanol Synthesis Quench Reactor

The figure below shows the predicted temperature profile in each bed. As
shown above, R201-A is the top bed (feed side of reactor) and R201-D is the
bottom bed (effluent side of reactor).
Temperature Profiles in Each Stage of the Quench Reactor

Under normal operating conditions, each stage (bed) closely approaches the
chemical equilibrium limit, as shown in the figure below. The blue line shows
the trajectory through the bed. The feed comes in cold with very little
methanol. In the upper stage, the temperature rises to 278C and the
methanol concentration reaches close to the equilibrium limit. The effluent
from the first stage is mixed with cold quench gas, reducing the temperature
and the mole fraction of methanol. This process repeats across each stage of
the reactor. Although the reaction rates are faster at higher temperatures, the
chemical equilibrium favors higher methanol concentrations at lower
temperatures. The quench rates are adjusted to enable equilibrium at
successively lower temperatures in each stage, maximizing the overall
production rate and yield in the reactor.
Conversion/Temperature Profile in a Four-Stage Quench

Reactor
The two figures below demonstrate how sensitive the reactor performance is
to the feed ratios. Below a certain critical ratio, the reactor yield can drop off
very quickly. When too much gas is diverted to the quench streams, the
temperature of the lower beds drops too low; the reactions slow down
resulting in less heat generation, causing the temperature loss to travel
through the lower stages.

Reactor Yield (Methanol Generation Rate) versus Fraction
of Feed to the Top Stage
Methanol Production v Feed Fraction to First Stage
440
420
400 Operating Point
380
360
340
320
MEOH TONNE/HR
300
280
260
240
220
200
180
160
140
120
0.29 0.30 0.31 0.32 0.33 0.34 0.35 0.36 0.37 0.38 0.39 0.40 0.41 0.42 0.43 0.44 0.45 0.46 0.47 0.48 0.49 0.50
Fraction of Feed to Top Stage
Bed Temperatures versus Fraction of Feed to the Top

Stage

Convergence – ICI Synetix
Process Model
The model has been configured to work in the sequential modular (SM) or
equation-oriented (EO) mode. The sequential mode uses three convergence
blocks to solve the recycle and information loops. Block “INNER”
convergences stream S27, the hot feed to the reactor interchange exchanger.
The tolerance of this convergence block is tightened (to 5E-5) to ensure tight
closure of the mass balance. This loop is solved inside convergence block
“HX-202” which resolves the heat flow rate across the interchange exchanger.
This arrangement was found to be more robust than simultaneous
convergence schemes. Another convergence block, “HX-302”, is used to
resolve the heat flow rate across the distillation interchange exchanger.
The sample model is set to run near the maximum feasible capacity of the
plant. Increasing the feed stream beyond the feasible limit will cause the
convergence to fail. The model has been found to converge reliably when the
feed rate is reduced by as much as ten percent of the base case condition.
In equation-oriented mode, the DMO solver was found to be most reliable.
The homotopy option was found to be the most reliable way to ensure reliable
convergence when making any significant changes to the model.

6 Lurgi Two-Stage Methanol
Synthesis Process Model
Lurgi offers single-stage and two-state methanol synthesis process

configurations. The two-stage system is recommended for larger plants;
however, it should be noted that the design basis (from the SRI Report,
Pavone, 2003) may be beyond the typical scale of proven industrial
processes. The Aspen Plus sample model of this process closely follows the
SRI design basis, except as noted below. The process flow diagram is shown
below.
Process Flow Diagram: Lurgi Two-Stage Methanol

Synthesis Model
The Lurgi methanol synthesis process is fed with clean, sulfur-free syngas
with an approximate molar composition of 68% hydrogen, 23% carbon
monoxide, 7% carbon dioxide, and small amounts of methane, water, and
inert gases at a pressure of 35.5 bar and a temperature of 38C.
The syngas feed is pressurized to 90 bar in compressor K201. A condensate
stream (S21) is taken off downstream of the compressor intercooler (E203).
This gas is mixed with cooler recycle syngas (S22) from K202, reaching a
temperature of about 54C (stream S24). The syngas is heated by the reactor
6 Lurgi Two-Stage Methanol Synthesis Process Model 39

effluent in heat exchanger E202 before flowing to the tube side of the second
stage of the reactor (R201B), which heats the syngas to approximately 250C
before it passes to the first stage converter (R201A).
The first stage of the methanol converter (R201A) is a boiling water reactor,
raising high pressure steam at temperatures between 250-270C. Reactions
occur inside catalyst-packed tubes. The first stage operates at close to
isothermal conditions, enabling easier control and stability compared to
quench reactors as well as higher productivity per volume of catalyst.
The second stage of the converter (R201B) is a gas-cooled reactor. The
reactions occur in the shell side of the device, which is packed with catalyst.
R201B is cooled by incoming syngas used to feed the first stage of the
reactor. The streams flow in a counter-current arrangement, allowing the
temperature on the reaction side of the vessel to decrease along the direction
of flow, pushing the reaction towards higher equilibrium conversions.
The product gas leaves the reactor at approximately 232C and 88 bar. This
gas is cooled to 221C in exchanger E210, which heats the boiler feed water
to the shell side of R201A (the boiler feed water stream is not explicitly
included in the model). The temperature of the product gas is further reduced
to 74C in the air-cooled exchanger E209, then partially condensed at 38C in
condenser E207.
The downstream methanol recovery and purification sections are assumed to
be the same as that of the ICI Synetix process described in the previous
section. A detailed mass balance comparing the AspenTech Lurgi two-stage
methanol synthesis model results to the SRI report is included in Appendix 3.
The table below summarizes the key unit operation in the process and the
method used to represent each unit operation. Values shown in brackets are
model predictions.
Summary of Unit Operations – Lurgi Process

Tag Description Modeling Operating Condition
Approach
K201 Syngas compressor Simulate each Stage1 P = 55.0 bar
stage as an Stage2 P = 92.0 bar
isentropic Efficiency = 72%
compressor with [47.7 MW]
COMPR block
E203 Syngas compressor HEATER block T=37.8C [19 Gcal/hr]
intercooler
V208 Compressor FLASH2 block Adiabatic
knockout drum
E202 Main interchange Two HEATER Reactor feed (cold out)
exchanger blocks (E202C and temperature=190C
E202H) linked with U=731 kcal/hr-sqm-K
HXFLUX block Assume P=0.34 bar on each
(E202-HX) via heat side of exchanger
streams [Duty = 189 Gcal/hr]
40 6 Lurgi Two-Stage Methanol Synthesis Process Model

Approach
R201A Methanol RPLUG, with Coolant temp = 265C
converter stage 1 constant coolant 25,000 tubes
temperature Length = 5 m
Boiling water assumption Diameter = 4 cm
reactor with Catalyst 6 mm diameter
reaction on tube- Void fraction = 0.35
side. Gas flows Density =1940 kg/m3
downward through [Duty = -222 Gcal/hr]
catalyst-packed [Residence time 2.3 s]
tubes.
R201B Methanol RPLUG, with Length = 5 m
converter stage 2 counter-coolant Hydraulic Diameter = 5 m
temperature Catalyst 6 mm diameter
Gas-cooled reactor assumption Void fraction = 0.35
with reaction on Density =1940 kg/m3
Design spec B1 is
shell side; syngas [Duty = -94.8 Gcal/hr]
used to resolve
feed passes [Residence time 3.9 s]
coolant
through tube side.
temperature
Heat transfer
coefficient
adjusted to include
tube area
E210 Reactor product HEATER Outlet Temp=210C
cooler / boiler feed Assume P=0.34 bar
water heater [Duty -14.1 Gcal/hr]
E209 Air cooler (reactor HEATER Outlet Temp=73.9C
product) Assume P=0.34 bar
E207 Partial condenser HEATER Outlet Temp=37.8C
Assume P=0.34 bar
[Duty -76.4 Gcal/hr]
V201 Crude methanol KO FLASH2 Adiabatic
drum [Duty -122 Gcal/hr]
K203 Liquid turbine drive PUMP as turbine P=2.4 bar
with 70% eff. [Generates 687 kW]
K202 Recycle gas Isentropic P=80.0 bar;
compressor compressor Efficiency=74%
(COMPR) [Duty 8322 kW]
C201 Purge gas scrubber RADFRAC, 10 Top stage P=76 bar
stages
flash drum
T351 Crude methanol FLASH2 P = 1.01 bar
storage tank Adiabatic

Approach
P301 Crude methanol PUMP P = 1.84 bar
E301 Distillation Two heater blocks Column feed temperature
feed/product cross linked with an HX- T = 54.4C
exchanger FLUX block via U = 730 kcal/hr-sqm-K
heat streams [Duty = 8.6 Gcal/hr]
C301 Light ends column RADFRAC, 25 Reb. duty = 45.4 Gcal/hr
stages fed at stage Condenser T = 45.5 C
15. Condenser and P = 1.36 bar (top)
reboiler included. P = 0.34 bar
[Condenser -31.1 Gcal/hr]
P302 Transfer pump PUMP P = 2.5 bar
Efficiency = 70%
C302 Methanol product RADFRAC, 50 Molar reflux ratio = 1.5
column stages fed at stage Bottoms purity < 1PPM
30 with side methanol in water
stream off stage P = 1.36 bar (top)
45. Condenser and P = 0.34 bar
reboiler included. Side stream rate = 4 MT/hr
Adjust reboiler [Reboiler 287 Gcal/hr]
duty to match [Condenser -287 Gcal/hr]
purity specification
P304 C302 bottoms PUMP P = 54 bar
Lurgi Two-Stage Methanol

Synthesis Reactor Model
The figure below shows the configuration and simulation results for the Lurgi
methanol synthesis reactor model. The reactor sizes were not available from
the SRI report; each reactor has been sized based on reported residence
times and based on extrapolation from known designs of existing plants.
The fresh feed enters the second stage (R201B) on the tube side, where it is
heated to a temperature of 250-270C. The heated feed enters the first stage
(R201A) on the tube side. The first stage is often referred to as the
isothermal stage because it operates at nearly isothermal conditions due to
the presence of boiling water on the shell side. The temperature of the first
stage is controlled by the steam pressure on the shell side. The Lurgi reactor
has the advantages of generating high pressure stream which can be used
upstream in the syngas section of the process. The effluent from the first
stage flows back to the catalyst-packed shell side of the second stage, where
it flows counter-current to the syngas flowing through the tube sides. This
cools the product stream, allowing for higher conversions (see second and
third figures below).

Model Results – Lurgi Two-Stage Methanol Synthesis
Reactor
The first stage is modeled as an ideal, multi-tube plug-flow reactor with

constant heat transfer temperature. The heat transfer coefficient has been set
to a high value typical for rapidly boiling systems. The tube-side heat transfer
is also expected to be very high because of the turbulent flow across the
packing. The pressure drop across the tubes is calculated based on Ergun’s
equation for flow in packed beds. Although the model does not explicitly
include the shell-side steam generation, this could be easily added to the
model using a heater block and heat stream from the reactor.
The second stage converter is represented as a single-tube reactor with
counter-current cooling. When assuming counter-current coolant, the RPLUG
model calculates the coolant feed temperature based on a specified outlet
temperature. An external design specification is used to manipulate the
specified coolant outlet temperature to match the inlet temperature calculated
by the reactor model to actual inlet temperature of the coolant feed stream.
Since Aspen Plus does not consider shell-side reactions, the reactor is treated
as a single tube, with the specified diameter equal to the equivalent hydraulic
diameter of the packing-free shell side (the true shell diameter is not used
because the active reactor volume excludes the volume occupied by the
tubes). The heat transfer coefficient has been set to a very high value to
account for high surface area of the tubes (which are not explicitly treated in
the model).

The SRI report specifies a reactor feed temperature of 125C. Based on
simulation results, this appears to be infeasible (the energy balance does not
close). A feed temperature of 180-190C is indicated by the predicted outlet
temperatures of the second reactor; a value of 190C is assumed in the Aspen
Plus model. There are other discrepancies between the SRI flowsheet and the
simplified process flow diagrams shown in Air Liquide marketing materials.
The Air Liquide flowsheets do not show the intercooler E202 or cooler E207.
We have assumed the SRI flowsheet is correct and that these exchangers are
left out of the Air Liquide flowsheets for the sake of simplicity.
The figure below shows the predicted temperature profiles across the two
reactors. The syngas feed enters the bottom of the second stage (green line
on right side) and gets heated by the reactions on the shell side (blue line on
right side). The heated syngas enters the top of the first stage reactor where
the reaction exotherm quickly lifts the temperature (blue line on left side). As
the reactions near equilibrium the gas cools down to the steam temperature
(pink line). The reacting syngas flows back to the shell side of the second
stage reactor (blue line on right) and is cooled by the incoming syngas.
Axial Temperature Profile Across Each Stage of the Lurgi

Methanol Converter
The figure below shows the temperature and mole fraction trajectory within
the reactor. The dashed red line shows the equilibrium methanol mole
fraction, based on the feed composition and reactor outlet pressure.

Conversion/Temperature Profile – Lurgi Two-Stage
Methanol Synthesis Reactor
This figure illustrates a key aspect of the reactor design. As temperature

increases, the equilibrium methanol limit decreases. As the reacting syngas
cools down the reactions can shift towards higher conversion. However, lower
temperatures imply slower reaction rates. If the feed temperature is too low,
the reactor may exhibit lower yields. The sensitivity study shown below
demonstrate trade-offs between the syngas feed temperature, the isothermal
reactor operating (coolant) temperature, and the production rate of methanol.
The gain in productivity might be offset by the value of higher pressure steam
versus lower pressure steam produced ad lower operating temperatures.
Reactor Temperature Optimization

12685
12680
Production Rate kmol/hr
12675
12670
12665
12660
12655
12650
12645
12640
12635
235 240 245 250 255 260 265 270
Isothermal Reactor Operating Temperature

Feed Temp 190 C Feed Temp 200 C Feed Temp 210 C

Convergence – Lurgi Two-Stage
Process Model
The model has been configured to work in the sequential modular (SM) or
equation-oriented (EO) mode. The sequential mode uses five convergence
blocks to solve the recycle and information loops. Block INNER convergences
stream S27, the hot feed to the reactor interchange exchanger. The tolerance
of this convergence block is tightened (to 5E-5) to ensure tight closure of the
mass balance. This loop is solved inside convergence block HX-202 which
resolves the heat flow rate across the interchange exchanger. This
arrangement was found to be more robust than simultaneous convergence
schemes. Another convergence block, HX-302, is used to resolve the heat
flow rate across the distillation interchange exchanger.
Two system-generated convergence blocks address an information loop
related to the counter-current cooling in the second-stage reactor, R201-B.
The design spec B1 manipulates the specified reactor coolant outlet
temperature to match the calculated coolant inlet temperature to the
temperature of the coolant feed stream (calculated by the interchange
exchanger). This design specification is ignored in equation-oriented mode
which solves the coolant temperatures explicitly.
In equation-oriented mode, the DMO solver was found to be most reliable
choice of algorithms. The reactor model R-201B shows a synchronization
warning message when the model is switched from sequential to equation-
based (RPLUG does not fully support counter-current cooling). This message
is not correct; the system automatically and correctly handles the change in
specifications associated with the switch to EO mode.

7 Summary
These examples are intended to provide our customers with a strong starting
point to develop appropriate models of common industrial methanol synthesis
processes. The physical properties, thermodynamics, and reaction equilibrium
are believed to capture the real process behavior very accurately. The relative
reaction rates are reasonable, but the catalyst activity factors may need to be
tuned to match the specific catalyst activity of any given plant. Each catalyst
grade may have different initial activity as the level of ‘doping’ of active
ingredients vary. Catalyst activity may also degrade over time due to the
action of contaminants such as sulfur.
7 Summary 47
48 7 Summary
8 Primary Sources
Chiang C-L, Lin K-S, “Preparation and characterization of CuO-Al2O3 catalyst

for dimethyl ether
production via methanol dehydration”, International Journal of Hydrogen
Energy (2017).
Goodwin, Robert D., “Methanol Thermodynamic Properties from 176 to 673 K
at Pressures to 700 Bar”, J. Phys. Chem. Ref. Data, Vol 16 No 4, 799-892
(1987).
Graaf, Geert H. and Jozef G. M. Winkelman, “Chemical Equilibria in Methanol
Synthesis Including the Water-Gas Shift Reaction: A Critical Reassessment”,
Ind. Eng. Chem. Res. 55, 5854−5864 (2016).
Klier, K. M., V. Chatikavanij, R. G. Herman, and G. W. Simmons, “Catalytic
synthesis of methanol from CO and H2: IV. The effects of carbon dioxide”, J.
of Catalysis, Volume 74, Issue 2, 343-360. (1982).
Miranda, Julio C.C., Gustavo H. S. F. Ponce, Harvey Arcellano-Garcia, Rubens
Maciel Filho, and Maria R.M. Wolf, “Syngas to Higher Alcohols Using Cu-Based
Catalyst – A Simulation Approach”, Chemical Engineering Transactions, Vol.
43, 1519-1524 (2015).
Pavone, Anthony, “Mega Methanol Plants”, SRI Consulting Process Economics
Program Report 43D (2003).
Vanden Bussche, K. M. and G. F. Froment, “A Steady-State Kinetic Model for
Methanol Synthesis and the Water Gas Shift Reaction on a Commercial
Cu/ZnO/Al2O3 Catalyst”, Journal of Catalysis 161, 1-10 (1996).
Web Sources
Johnson Matthey on-line technical brochure:
http://www.jmprotech.com/images-
uploaded/files/JM%20Methanol%20Brochure.pdf
Air Liquide / Lurgi technical brochure:
http://www.zeogas.com/files/83939793.pdf
8 Primary Sources 49
50 8 Primary Sources
Appendix 1: Implementation
of the Reaction Model
Reaction model MEOH-SYN (General Kinetics Type), Configuration form.
Forward rate constants and reaction basis (Kinetics Summary form)
Driving force term for reverse water-gas shift
Appendix 1: Implementation of the Reaction Model 51

Adsorption Terms for Water Gas Shift
52 Appendix 1: Implementation of the Reaction Model

Power-Law terms for Methanol Synthesis reaction
Adsorption Terms for Methanol Synthesis (Absorption constants same as

above)
Kinetic Terms for Ethanol Formation
Appendix 1: Implementation of the Reaction Model 53

Kinetic Terms for DME Formation
54 Appendix 1: Implementation of the Reaction Model

Appendix 2: ICI/Synetix
Methanol Process Model
Results – Mass Balance
The mass balance below summarizes the results of the Aspen Plus model. Key
streams from the SRI report are shown in italics for comparison purposes.
Appendix 2: ICI/Synetix Methanol Process Model Results – Mass Balance 55

56 Appendix 2: ICI/Synetix Methanol Process Model Results – Mass Balance
Appendix 2: ICI/Synetix Methanol Process Model Results – Mass Balance 57
58 Appendix 2: ICI/Synetix Methanol Process Model Results – Mass Balance
Appendix 3: Lurgi 2-Stage
Process Model Results –
Mass Balance
The mass balance below summarizes the results of the Aspen Plus model. Key
streams from the SRI report are shown in italics for comparison purposes.
Appendix 3: Lurgi 2-Stage Process Model Results – Mass Balance 59

60
Stream ID FEED S20 S20A S21 S22 S23 S23A TO-R1 SRI Report TO-R201A TO-R201B X-R201B SRI Report
K201 Syngas to Syngas to Feed to Reactor 1 to Reactor Reactor
Description Syngas Feed Condensate Reactor reactor Reactor 1 Reactor 2 Outlet Outlet
From K201-S1 E203 V208 K201-S2 K202 B2 E202-C E202 R201-B R201-A R201-B R201
To K201-S1 E203 V208 B9 B5 B5 K202 R201-B R201 R201-A R201-B E210 E210
Temperature C 37.8 92.9 37.8 37.8 104.8 44.6 37.8 190.0 125.0 254.2 265.2 231.0 232.2
Pressure bar 35.5 55.0 55.0 55.0 92.0 92.0 86.6 91.7 92.3 91.7 89.0 88.0
Mass Vapor Fraction 1.00 1.00 1.00 0.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00
Mass Flows tonne/hr 513.0 513.0 513.0 1.1 511.9 1281.3 1281.3 1793.2 1502 1793.2 1793.2 1793.2 1503
H2 tonne/hr 62.0 62.0 62.0 0.0 62.0 181.7 181.7 243.7 181 243.7 194.7 187.2 123
N2 tonne/hr 4.0 4.0 4.0 0.0 4.0 130.5 130.5 134.5 126 134.5 134.5 134.5 126
CO tonne/hr 292.0 292.0 292.0 0.0 292.0 89.4 89.4 381.4 346 381.4 146.8 92.1 56
CO2 tonne/hr 137.0 137.0 137.0 0.0 137.0 382.3 382.3 519.3 374 519.3 408.4 411.2 256
H2O tonne/hr 2.0 2.0 2.0 1.1 0.9 0.6 0.6 1.5 2 1.5 47.0 45.9 51
CH4 tonne/hr 16.0 16.0 16.0 0.0 16.0 476.6 476.6 492.6 457 492.6 492.6 492.6 457
MEOH tonne/hr 0.0 0.0 0.0 0.0 0.0 20.1 20.1 20.1 16 20.1 368.9 429.1 432
ETOH tonne/hr 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0 0.0 0.2 0.4 1
DME tonne/hr 0.0 0.0 0.0 0.0 0.0 0.1 0.1 0.1 0 0.1 0.2 0.2 1
Stream ID S27 S27B S27C S27D S28 SRI Report S29 SRI Report S30 SRI Report S31 S32 SRI Report
Methanol Methanol Methanol Methanol Purge to Purge to Water to Scrubber Scrubber
Description KO Lights KO Lights KO Bottoms KO Bottoms Scrubber Scrubber Scrubber Overhead Overhead
From E210 E202-H E209 E207 V201 V201 K203 K203 B2 C201 C201
To E202-H E209 E207 V201 B2 V202 V202 C201 C201 C201 E206 E206
Temperature C 221.0 84.1 73.9 37.8 37.8 37.8 38.1 37.8 37.8 37.8 25.0 25.5
Pressure bar 87.6 87.3 87.0 86.6 86.6 88.4 2.4 88.4 86.6 88.4 90.0 86.5
Mass Vapor Fraction 1.00 1.00 0.78 0.74 1.00 1.00 0.00 0.00 1.00 1.00 0.00 1.00 1.00
Mass Flows tonne/hr 1793.2 1793.2 1793.2 1793.2 1319.5 1020 473.7 482 38.3 29 36.0 37.7 29
H2 tonne/hr 187.2 187.2 187.2 187.2 187.1 123 0.1 0 5.4 3 0.0 5.4 3
N2 tonne/hr 134.5 134.5 134.5 134.5 134.4 126 0.1 0 3.9 4 0.0 3.9 4
CO tonne/hr 92.1 92.1 92.1 92.1 92.1 56 0.1 0 2.7 2 0.0 2.7 2
CO2 tonne/hr 411.2 411.2 411.2 411.2 393.7 244 17.5 12 11.4 7 0.0 11.4 7
H2O tonne/hr 45.9 45.9 45.9 45.9 0.6 1 45.3 50 0.0 0 36.0 0.0 0
CH4 tonne/hr 492.6 492.6 492.6 492.6 490.8 454 1.8 3 14.2 13 0.0 14.2 13
MEOH tonne/hr 429.1 429.1 429.1 429.1 20.7 16 408.4 416 0.6 0 0.0 0.0 0
ETOH tonne/hr 0.4 0.4 0.4 0.4 0.0 0 0.4 1 0.0 0 0.0 0.0 0
DME tonne/hr 0.2 0.2 0.2 0.2 0.1 0 0.0 0 0.0 0 0.0 0.0 0
Appendix 3: Lurgi 2-Stage Process Model Results – Mass Balance

Stream ID S32B S32C S33 SRI Report S34 SRI Report S35 S35B SRI Report S48 SRI Report S35C S35D
Scrubber Scrubber V202 V202 Crude Crude MeOH to LE
Description Bottoms Bottoms Overheads Overheads Methanol Methanol Vent Vent Column
From E206 K204 C201 C201 V202 V202 V202 T-351 T351 T-351 T351 P301 E301-C
To K204 B7 V202 V202 B7 T-351 P301 P301 E301-C C-301
Temperature C 220.0 12.0 38.4 36.8 36.8 36.4 36.4 36.4 54.4
Pressure bar 86.5 2.4 86.5 2.4 2.4 1.0 1.0 1.8 1.6
Mass Vapor Fraction 1.00 1.00 0.00 0.00 1.00 1.00 0.00 0.00 1.00 0.00 0.00
Mass Flows tonne/hr 37.7 37.7 36.6 36 16.3 14 494.0 491.3 503 2.7 1 491.3 491.3
H2 tonne/hr 5.4 5.4 0.0 0 0.1 0 0.0 0.0 0 0.0 0 0.0 0.0
N2 tonne/hr 3.9 3.9 0.0 0 0.1 0 0.0 0.0 0 0.0 0 0.0 0.0
CO tonne/hr 2.7 2.7 0.0 0 0.1 0 0.0 0.0 0 0.0 0 0.0 0.0
CO2 tonne/hr 11.4 11.4 0.0 0 12.8 9 4.8 2.6 2 2.2 1 2.6 2.6
H2O tonne/hr 0.0 0.0 36.0 36 0.1 0 81.2 81.2 86 0.0 0 81.2 81.2
CH4 tonne/hr 14.2 14.2 0.0 0 1.7 3 0.0 0.0 0 0.0 0 0.0 0.0
MEOH tonne/hr 0.0 0.0 0.6 0 1.4 2 407.6 407.2 414 0.4 0 407.2 407.2
ETOH tonne/hr 0.0 0.0 0.0 0 0.0 0 0.4 0.4 1 0.0 0 0.4 0.4
DME tonne/hr 0.0 0.0 0.0 0 0.0 0 0.0 0.0 0 0.0 0 0.0 0.0
Stream ID S36 SRI Report S37 SRI Report S38 SRI Report S39 SRI Report S40 S44 SRI Report MEOH SRI Report
LE Column LE Column LE Columns LE Column C302 C302 Higher Higher C302 Waste Waste Methanol
Description Overhead Overhead Bottoms Bottoms Bottoms Bottoms Alcohols Alcohols Overhead Water Water Product
Appendix 3: Lurgi 2-Stage Process Model Results – Mass Balance

From C-301 C301 C-301 C301 C302 C302 C302 C302 C302 B9 E301-H C302
To B10 P302 P302 P304 P304 E301-H
Temperature C 45.5 40.6 83.2 83.3 117.2 114.4 106.4 72.7 116.8 49.8 48.9
Pressure bar 1.4 1.4 1.7 1.7 1.7 1.7 1.7 1.4 54.0 1.2
Mass Vapor Fraction 1.00 1.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Mass Flows tonne/hr 3.4 3 487.9 501 77.6 83 4.0 4 406.4 78.6 84 406.4 414
H2 tonne/hr 0.0 0 0.0 0 0.0 0 0.0 0 0.0 0.0 0 0.0 0
N2 tonne/hr 0.0 0 0.0 0 0.0 0 0.0 0 0.0 0.0 0 0.0 0
CO tonne/hr 0.0 0 0.0 0 0.0 0 0.0 0 0.0 0.0 0 0.0 0
CO2 tonne/hr 2.6 2 0.0 0 0.0 0 0.0 0 0.0 0.0 0 0.0 0
H2O tonne/hr 0.0 0 81.2 86 77.6 83 3.7 3 0.0 78.6 84 0.0 0
CH4 tonne/hr 0.0 0 0.0 0 0.0 0 0.0 0 0.0 0.0 0 0.0 0
MEOH tonne/hr 0.9 1 406.3 414 0.0 0 0.2 0 406.1 0.0 0 406.1 414
ETOH tonne/hr 0.0 0 0.4 1 0.0 0 0.1 1 0.2 0.0 0 0.2 0
DME tonne/hr 0.0 0 0.0 0 0.0 0 0.0 0 0.0 0.0 0 0.0 0
61
62 Appendix 3: Lurgi 2-Stage Process Model Results – Mass Balance
Appendix 4: Bill of Materials
File Name Description
Methanol synthesis v10 – data This file contains the physical property
regression.bkp data regression cases used to fit the SRK
binary parameters used in the methanol
synthesis examples.
Methanol synthesis v10 lab reactor.bkp This Aspen Plus case file is set up to
reproduce the experimental runs
reported in Klier et al. and in Vanden
Bussche & Froment.
methanol synthesis V10 - ICI Syntex Aspen Plus version 10 model of the ICI
Quench Reactor Process.bkp Syntex quench reactor process as
described in SRI report 43D “Mega
Methanol Plants”.
methanol synthesis V10 -Lurgi Two Aspen Plus version 10 model of the Air
Stage Process.bkp Liquide / Lurgi two stage methanol
synthesis process as described in SRI
report 43D “Mega Methanol Plants”.
Appendix 4: Bill of Materials 63

Aspen Plus Methanol Synthesis Model

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Aspen Plus

Aspen Plus Methanol Synthesis Model

Aspen Technology, Inc.

3 Physical Properties ...............................................................................................9

4 Reaction Model ...................................................................................................15

5 ICI Synetix (Johnson Matthey) Methanol Process Model ....................................29

6 Lurgi Two-Stage Methanol Synthesis Process Model ..........................................39

8 Primary Sources .................................................................................................49

Appendix 1: Implementation of the Reaction Model ..............................................51

Appendix 2: ICI/Synetix Methanol Process Model Results – Mass Balance ...........55

Appendix 3: Lurgi 2-Stage Process Model Results – Mass Balance ........................59

Appendix 4: Bill of Materials ..................................................................................63

This document summarizes AspenTech’s Methanol Synthesis model. The

Regression Results: SRK Binary Parameters for

SRKKIJ/1 H2O MEOH -0.0505 0.0142

Regression Results: Measured and Predicted Azeotropes

Temperature Pressure Mole Fraction Temperature Pressure MeOH Mole

Regression Results: Measured and Predicted VLE for

Regression Results: SRK Binary Parameters for

SRKKIJ/1 H2O ETOH -0.1090 0.0478

It was not possible to closely approximate the known azeotropes of the

Regression Results: Measured and Predicted Azeotropes

Temperature Pressure Mole Fraction Temperature Pressure ETOH Mole

Regression Results: SRK Binary Parameters for

SRKKIJ/1 MEOH ETOH 0.0645 0.0101

The fitted binary parameters for the methanol/ethanol system yield

SRK Binary Parameters Used in This Model

H2 CH4 APV100 C -0.02449 0 0

Comp Comp Source Temp LAIJ LAJI LBIJ LBJI

ETOH H2O Regressed C 0.097977 0.039067 6.20E-06 -0.00017

During the development of this model, the predicted adiabatic temperature of

-17969.3 611569 2766.44 190130 582.451 0 1226.85

1 MEOH-SYN CO2 + 3H2 = CH3OH + H2O Methanol Synthesis

Gibbs Free Energy of Formation (DGFORM), kJ/mole

Methanol -162.320 -161.751 -161.550

The second plot shows the predicted equilibrium constant as a function of

Equilibrium Constant for Methanol Synthesis at 1 Bar

1 bar 15 bar 30 bar 50 bar

Equilibrium Constant for Reverse Water Gas Shift Reaction

Heat of Reaction for Methanol Synthesis

Heat of Reaction for Reverse Water-Gas Shift

Rate Expression for Primary Reactions

The adsorption terms are further defined as: ln = + /

Rate of methanol formation, kmol/sec

*Pressure units are implicitly in bar.

Rate Expression for Side Reactions

Reaction Model Validation

Feed composition (mole %)

Base Case Feed Conditions

Calculated Residence Time

Model Results – Methanol Mole Fraction v Axial Profile (50

Model Results – Carbon Dioxide Mole Fraction v Pressure

Model Results – Temperature Profile v Feed Temperature

5 ICI Synetix (Johnson Matthey) Methanol Process Model 29

30 5 ICI Synetix (Johnson Matthey) Methanol Process Model

Summary of Unit Operations

K201 Syngas Simulate each stage as an Stage1 P=53.2 bar

5 ICI Synetix (Johnson Matthey) Methanol Process Model 31

Methanol Synthesis Quench

32 5 ICI Synetix (Johnson Matthey) Methanol Process Model

5 ICI Synetix (Johnson Matthey) Methanol Process Model 33

34 5 ICI Synetix (Johnson Matthey) Methanol Process Model

Temperature Profiles in Each Stage of the Quench Reactor

5 ICI Synetix (Johnson Matthey) Methanol Process Model 35