Andrzej Kraslawski and Ilkka Turunen (Editors) Proceedings of the 23

rd
European Symposium on
Computer Aided Process Engineering ESCAPE 23, J une 9-12, 2013, Lappeenranta, Finland
2013 Elsevier B.V. All rights reserved. 55
Pr oduction of Methanol and Dimethyl ether fr om
biomass der ived syngas a compar ison of the
differ ent synthesis pathways by means of flowsheet
simulation
M. Gdek
a
, R. Kubica
a
, E. Jdrysik
b
a
Silesian University of Technology, Department of Chemical and Process Apparatus
Construction, 7 Strzody St. 44-100 Gliwice, Poland
b
Central Mining Institute, Department of Energy Saving and Air Protection, 1
Gwarkw Sq., 40-166 Katowice, Poland
Abstr act
Increasing awareness of the environmental issues forces a strong drive towards the
development of new, sustainable processes for renewable energy production. Likewise,
the economic issues related to the increasing prices of crude oil, and its derivatives lead
to the recognition of advantages of alternative fuels, thus a significant interest in
biomass-derived, synthetic fuels is observed. Among various thermo-chemical
conversion processes, biomass gasification is one of the most effective, efficient and
sustainable solutions to the production of renewable energy. It provides a gaseous fuel,
composed mainly of carbon monoxide and hydrogen, suitable to produce chemicals,
heat, and energy. In particular, syngas can be used to obtain methanol (MeOH) and
dimethyl ether (DME), both energy carriers of great interest for many advanced energy
applications. The herein presented work provides the reader with a comparison of the
technicalities as well as economics of methanol and DME production from biomass-
derived syngas, by different pathways. For that purpose a process simulation by means
of the ChemCAD

commercial code was used. The developed simulation strategies

include both, optimization of the kinetic models and unique solution of fuel refinement.
Keywor ds: synthetic biofuels, syngas, methanol, dimethyl ether.
1. Intr oduction
Synthesis of MeOH from gaseous feed can be carried out by means of either 2-phase
reaction (gas-catalyst) and 3-phase reaction (liquid-gas-catalyst). Dimethyl ether
(CH
3
OCH
3
), in general, is produced by dehydration of methanol. Therefore it is
commonly found that its production is a two-step process; methanol synthesis and its
dehydration towards DME. On a large scale, the processes of methanol production and
dehydration are combined in one reactor so as to produce DME directly. The direct
synthesis of DME process requires a dual catalyst system. The following comparison of
different pathways to produce biomass derived, liquid fuels, was based on process
simulation done with the commercial code CHEMCAD

. It should taken into account

that gasification process and syngas upgrading are not a subject of herein presented
study.
2. Methanol and its synthesis
Methanol is a multipurpose based chemical - an alcohol, which is toxic, volatile,
composed of carbon, hydrogen, and oxygen. It is used as antifreeze, solvent, fuel,
56 M. Gdek

et al.
denaturant for ethyl alcohol, but also as a feedstock to produce formaldehyde, methyl
tertiary butyl ether (MTBE) and acetic acid. Methanol can be added to gasoline used to
power internal combustion engines, without necessity of their modification. It can be
also used directly by methanol fuel cells. It is produced by a catalytic process from
syngas or natural gas, as raw materials. The mixture of syngas species is converted into
the methanol, in the presence of a catalyst metal, at moderate temperatures and under
specific pressure conditions. The synthesis of MeOH from gaseous feed can be carried
out either by 2-phase reaction (gas phase-catalyst) or 3-phase reaction (liquid phase-gas
phase-catalyst) [G.H. Graaf, A.A.C.M. Beenackers, 1996]. The produced, crude
methanol is purified by distillation. In the topping column the low boiling point species
are removed, while the second, refining column is used for the separation of the heavier
products and water.
2.1. Two-phase methanol synthesis
Methanol is produced from syn-gas by three major commercial processes ICI,
Mitsubishi and Lurgi. ICI process was first applied in 1970, and currently accounts for
more than 70% of systems in operation. The ICI design consists of a number of
adiabatic catalytic beds, where cold gas is used to cool the reactant gases between the
beds. Although less common, the Lurgi process is of interest due to the application of
reactor designed as shell-and-tube heat exchanger. In such a design, the catalyst is
packed in the tubes while cooling steam is circulated on the shell side.
2.2. Three-phase Methanol synthesis (liquid phase MeOH LPMeOH)
The liquid-phase methanol synthesis process (LPMeOH) was first developed by Chem
Systems in the late 1970s. The novelty of this technology is that methanol is derived
from synthesis gas over a finely powdered Cu/Zn/Al
2
O
3
catalyst, dispersed in an inert
liquid. The slurry-phase operation facilitates heat removal, thus providing isothermal
conditions in the reactor system [A. Cybulski, 1994]. High agitation rates in the reactor
provide reaction conditions with limited temperature and concentration gradients. The
other advantages are a possible use of CO-rich syngas, and high once-through
conversion rates of syngas. Methanol synthesis is also carried out in a trickle bed
reactor, where the feed gas and the oil flow in a co-current regimen, over a bed of
catalyst, under a wide range of space velocities, and at a H
2
/(CO+CO
2
) ratio of 1.
Substantially high methanol yield and conversion are achieved when compared to a
slurry reactor, at similar space velocities. This is mainly due to a plug flow conditions,
provided by the trickle bed reactor, while in the slurry reactor a back mixing is
observed. [G.G. Pass et al., 1990].
3. Dimethyl ether (DME) and its synthesis
DME is a clean burning, synthetic fuel, completely soot-less. It is a substitute for diesel
fuel or liquefied petroleum gas (LPG). When used instead of diesel fuel, it reduces NOx
emissions by 90%, and offers a high cetane number. It can also be reformed into a
hydrogen fuel for fuel cells. It is produced from natural gas, but it can also be produced
from other sources like biomass and coal. DME is produced by an in-direct method as
well as in a one-step, direct process.
3.1. In-direct methanol synthesis
Dimethyl ether (CH
3
OCH
3
), in general, is produced by the dehydration of methanol.
Therefore, it is commonly found that its production is a two-step process in which
methanol synthesis is followed by the dehydration of alcohol towards DME.
Production of Methanol and Dimethyl ether from biomass derived synga 57
3.2. Direct DME synthesis
At large scale industrial plants, the processes of methanol production and dehydration
are combined in one reactor a single step method. In such a system DME is produced
directly from synthesis gas. The direct synthesis of DME process requires a dual
catalyst system that acts as a methanol synthesis catalyst and a methanol dehydration
catalyst, in a single unit. There are two major reactor types, namely CSTR (slurry, three
phase reactor) and PFR (two phase reactor) in a few commercial configurations by Air
Products, NKK etc. Micro-structured reactors, where chemical reactions take place in
the channels or slit-like arrangements of sub-millimetre range of dimensions, are an
alternative solution. A typical micro-reactor provides high surface-to-volume ratios and
a short distance to the wall, thus heat and mass transfer are greatly enhanced.
4. Pr ocess simulation
Within the herein presented work, the major effort was put to build reliable simulation
models, with the use of the commercial code ChemCAD(by Chemstations Inc.,
licence held by Central Mining Institute, Katowice, Poland). Steady state simulation
was used to compare the performance of the different kinetic reactors as well as for
apparatus sizing, and finally for the assessment of process economics.
4.1. Kinetics employed
At first, a kinetic reactor model was employed for sensitivity analysis and sizing. A
commonly used description of kinetics for both, methanol and DME synthesis, was
employed for simulation. For simulation of either, the 2-phase and 3-phase methanol
synthesis, the kinetic models by G.H. Graaf were adopted [G.H. Graaf, A.A.C.M.
Beenackers, 1996]. In the case of the 1-step DME synthesis, the kinetics description
was taken from the technical reports by [P. Xiang-Dong, 2002] and [B.L. Bhatt, 1993].
In the case of the 2-step DME synthesis, the description of methanol dehydration
kinetics [J . Bondiera, and C. Naccache, 1991] in combination with the methanol
synthesis description [G.H. Graaf, A.A.C.M. Beenackers, 1996], were used.
H2
CO
CO2
CO cont
H2 cont
CO2 cont
Methanol recycle
DME
CO cont
H2 cont
CO2 cont
H2
CO
CO2
N2
N2
Methanol
A
B

Fig.1. Process Flowsheet Diagrams of methanol (A) and DME (B) sythesis loop
58 M. Gdek

et al.
4.2. Modelling and simulation
Steady state simulation was carried out by the simple models, presented on figure 1 to
assess a possible performance of the considered synthesis pathways.
The models consisted of several major elements, namely: reactor, stream mixer (to
formulate the feed composition), different controllers handling the set point of H
2
/CO
ratio by H
2
molar flow rate, set point of CO
2
/CO ratio by CO
2
molar flow rate, set point
of H
2
/CO ratio by CO molar flow rate, set point of Reactor Recycle ratio (RR) by
divider flow ratio; heat exchanger - condenser of reaction products, multipurpose flash
for phase separation, and finally stream divider handling the recycle ratio.
The description of the kinetics, employed for simulation, was provided in a form
different than typical Arrhenius exponential equations and LangmuirHinshelwood
adsorption models, used for the specification of reactors operation in ChemCAD

.
Therefore relevant Visual Basic codes, describing kinetic rate expressions were
incorporated to flowsheet models. The created model was used to carry out a steady
state simulation of considered processes, as well as the successive sensitivity analysis.
The latest was meant for the analysis of the process and design parameters influence on
the quality and yield of the main product. The sensitivity analysis included the
following:
Productivity (MeOH and DME yield) the conversion vs. reactor volume,
MeOH and DME yield vs. reactor pressure (17 MPa),
MeOH and DME yield vs. reactor recycle rate (0.10.9),
MeOH and DME yield vs. the ration of H
2
and CO in the feed (0.23 w/w),
MeOH and DME yield vs. the ration of CO
2
and CO in the feed. (0.010.2 w/w).
5. The compar ison of DME and Methanol synthesis pathways
The developed models and obtained results enabled one to undertake a qualitative and a
quantitative assessment of the system performance, thus they constituted a basis for
selection and sizing procedures. The latest were used to built a steady state models,
representing commercial production plants, for MeOH and DME synthesis, having a
capacity of 50MW LHV. Based on the sensitivity study and technical analysis, the three
major pathways were considered; direct LPMeOH, direct LPDME and indirect DME -
methanol synthesis, followed by alcohol dehydration in PFR reactor.
The synthesis nodes, as presented on fig.1, were equipped with all the equipment,
including distillation columns, necessary to obtain the MeOH or DME, of commercial
grade. Such complete models (see fig.2. with exemplary PFD for methanol synthesis),
were used to compare process and economic performance of the different synthesis
pathways. ChemCAD package provided preliminary cost estimations for various types
of equipment. The cost estimates were based on the user-specified parameters and cost
indices. Total Plan Cost estimation was performed according to Chemical Engineering
Plant Cost Index (ChemCAD default). Finally, for assumed system yield, a comparison
of the total project costs, as well as utility consumption indices was produced.
The obtained results are given in table 1 and 2, respectively.
The results may indicate among others, that while the direct DME process incurs the
highest total project costs, it has the lowest requirement for the utilities. For a complete
cost-benefit analysis one should take into account the market prices of the products
obtained i.e. Methanol which is ~370 Euro/Mg when compared to ~680 for DME.

Production of Methanol and Dimethyl ether from biomass derived synga 59
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Fig.2. A flow-sheet of the plant for direct methanol production
60 M. Gdek

et al.
Table 1. Comparison of the Total Project Cost for different production plants, at 50MW LHV
capacity, expressed in thou. USD
Item MeOH Indirect DME Direct DME
Total major equipment costs 5 350 6 672 7 020
Installation 802 1 100 1 053
Piping 2 407 3 001 3 159
Instrumentation 535 667 702
Biulding & structure 535 667 702
Auxiliary equipment 1 337 1 547 1 755
Outside lines 802 1 100 1 053
Total direct costs 11 768 14 754 15 444
Engineering & construction 3 531 4 403 4 633
Contingencies 2 354 2 935 3 088
Total Plant Costs 17 653 22 092 23 165

Table 2. The indices of utilities consumption, for different production plants, at 50MW LHV,
expressed in kW/MW LHV
Item MeOH Indirect DME Direct DME
Power installed 92.0 89.3 66.6
Cooling water 705 738.5 329.5
Steam (HP and LP) 504 495.6 71.0
Refrigerants -50C - - 41.2
The proposed methodology, including the modelling of reaction systems by user
defined kinetics, allows one to assess the process performance of the different systems,
under consideration. It also gives cost estimates describing the economic performance
of different production plants.

Acknowledgements
The research was carried out within the frames of a SynCon project (Novel synthesis
process concepts for efficient chemicals / fuel production from biomass:
http://www.kic-innoenergy.com/innovation-projects/syncon.html) by Central Mining
Institute, a member of KIC InnoEnergy SE,.
Refer ences
B.L. Bhatt, 1993,Synthesis of dimethyl ether and alternative fuels in the liquis phase from coal-
derived synthesis gas, Technical Report, Air Products and Chemicals INC, Allentown, PA
18195-1501, http://www.osti.gov/bridge/purl.cover.jsp?purl=/6454471-PGQ0Ad/6454471.pdf
J . Bondiera, and C. Naccache, 1991, Kinetics of Methanol Dehydration in Dealuminated H-
Mordenite: Model with Acid and Base Active Centres, Applied Catalysis, 69, 139-148
A.Cybulski, 1994, Liquid-Phase Methanol Synthesis Catalysts, Mechanism, Kinetics, Chemical
Equilibria, Vapor-Liquid Eq, Cat. Rev. Sci. Eng. 36(4), 557-615
G.H. Graaf, A.A.C.M. Beenackers, 1996, Comparison of two-phase and three-phase methanol
synthesis processes, Chemical Engineering and Processing 35, 413-427
G.G. Pass, C. Holzhauser, A. Akgerman, and R.G. Anthony, 1990, Methanol Synthesis in a
Trickle Bed Reactor, AICHE J ., 36, 1054-1060
P. Xiang-Dong, 2002, Kinetic understanding of the syngas-to-dme reaction system and its
implications to process and economics, Technical Report, Air Products and Chemicals INC
2002, Allentown, PA 18195; http://www.osti.gov/bridge/purl.cover.jsp?purl=/816515/