CO Abatement Through A Methanol Production Process: C H E M I C A L E N G I N E E R I N G T R A N S A C T I O N S

A publication of
CHEMICAL ENGINEERING TRANSACTIONS

The Italian Association
VOL. 29, 2012 of Chemical Engineering
Online at: www.aidic.it/cet
Guest Editors: Petar Sabev Varbanov, Hon Loong Lam, Ji Jaromr Kleme
Copyright 2012, AIDIC Servizi S.r.l.,
ISBN 978-88-95608-20-4; ISSN 1974-9791 DOI: 10.3303/CET1229078
CO2 Abatement Through a Methanol Production Process

verton Simes Van-Dal, Chakib Bouallou
MINES ParisTech Centre nergtique et Procds (CEP)
60, boulevard Saint Michel, 75006 Paris, France
[email protected]
A CO2 to methanol process was simulated and optimized with Aspen Plus. The CO 2 comes from the
capture by chemical absorption from the flue gas of a coal thermoelectric plant. The thermoelectric
plant provides electrical energy for CO2 capture and the methanol plant. Hydrogen is produced from
the electrolysis of water using a carbon-free source of electricity. The methanol plant provides 46 % of
the steam necessary for CO2 capture, which remarkably reduces the impact of CO2 recovery on the
performance of the thermoelectric plant. The CO2 balance showed that it is possible to abate a large
amount of CO2 from the production of methanol if carbon-free hydrogen is available.
1. Introduction
Carbon dioxide is the main anthropogenic greenhouse gas, and its emissions increased significantly
during the last decades. At present, the carbon cycle, where CO2 is the major factor, does not work in a
9
balanced way. Anthropogenic emissions of CO2 were 2610 t in 2004, and keeping the current trends,
they are likely to double by 2050 (IFP, 2007). About 40 % of global anthropogenic CO2 comes from
thermoelectric plants fueled by natural gas and coal (Amann, 2007).
The use of CO2 as a raw material transforms what today is considered as a constraint on economic
opportunity. In this context, the recycling of CO2 as a feedstock for the production of hydrocarbon
substituents appears of great economical and environmental interest. Methanol can be produced from
the hydrogenation of CO2 and could replace gasoline, which therefore can potentially reduce the
consumption of fossil fuels and enhance CO2 recycling.
Methanol is a powerful candidate for replacing the gasoline due to its excellent combustion and lower
pollution. In addition, DME (dimethyl ether) is a possible substitute for conventional diesel and is
synthesized from the dehydration of methanol. Besides, methanol is a commodity of the chemical
industry where it appears as an intermediate in many reactions.
Nowadays, methanol is mostly produced from the catalytic conversion of synthesis gas which is a
mixture of CO, CO2 and H2. The synthesis gas can be produced from various carbon components;
however, today the majority of large-scale methanol is derived from natural gas.
Mignard et al. (2003) proposed a methanol synthesis process from CO 2 captured from flue gas and
electrolytic hydrogen. In order to have a significant abatement of CO 2, the process depends on
availability of waste heat in the power plant to provide thermal energy to the process. In the absence of
these thermal sources CO2 abatement is almost null. Mignard and Pritchard (2006) compared the
production of liquid fuels from the hydrogenation of CO2, including methanol.
Please cite this article as: Van-Dal E. S. and Bouallou C., (2012), CO2 abatement through a methanol production
process, Chemical Engineering Transactions, 29, 463-468
463
2. CO2 to methanol production process design
The process proposed in this paper uses CO2 captured from flue gas of a coal thermoelectric plant and
hydrogen produced from electrolysis of water. The electrical energy used in the recovery of CO 2 and
methanol synthesis comes from the coal plant, and that used in the electrolysis of water comes from a
renewable source or at least a carbon-free one (e.g. nuclear).
TM
The feed is stoichiometric with 88.0 t/h of CO2 and 12.1 t/h of hydrogen. Aspen Plus V7.2 software
was used for process simulation and design.
Figure 1: Bloc diagram of the process
The thermodynamic model used in equipments at more than 10 bar was the Redlich-Kwong-Soave
equation of state with modified Huron-Vidal mixing rules. In equipments of less than 10 bar, the model
used was NRTL-RK.
The commercial Cu/ZnO/Al2O3 catalyst was retained in this study. The kinetic model used is that of
Vanden Bussche and Froment (1996) with readjusted parameters of Mignard and Pritchard (2008).
The thermodynamic equilibrium constants are given by Graaf et al. (1986).
2.1 Water electrolysis

3
Hydrogen is produced from the electrolysis of water, with energy consummation of 4.8 kWhel/Nm .
Hydrogen is supplied to the process at 30 bar and 25 C, the conditions under which it leaves the
electrolyser. Oxygen is generated as a by-product of electrolysis.
2.2 Oxygen by-product

Carbon credits are generated by the sale of by-product oxygen via pipeline to a chemical plant which
uses it as feedstock. The ordinary production of oxygen by cryogenic air distillation consumes
0.42 kWh per tonne of O2 (Bolland et Sther, 1992). If a cryogenic process is used for the production
of oxygen, CO2 is emitted due to the consumption of electrical energy from fossil fuels. Thus, the
carbon credits generated are equivalent to the amount of CO2 that would be emitted if the oxygen is
produced by the cryogenic process.
2.3 CO2 capture

Amann (2007) studied the process of CO2 capture by chemical absorption of the flue gas of a
subcritical coal thermoelectric plant with desulfurization.
The net electrical power delivered by the plant is 556 MW el with a CO2 emission ratio of 857 g/kWhel.
For a capture rate of 85%, consumption is 44 kWhel per tonne of CO2 for the compression of feed and
464
3.2 GJth per tonne of CO2 for the regeneration of the solvent. This thermoelectric plant is considered for
this study.
In thermoelectric power plants where CO2 capture is present, LP steam used in the capture is bled
from the steam cycle of the plant. Given that there is an oversupply of steam in the methanol synthesis
unit, this steam is sent to the capture unit. Therefore, the amount of steam bled from the plant is lower
so is its impact on electricity production. The amount of steam sent corresponds to 46 % of the thermal
energy necessary to CO2 capture. Carbon dioxide is supplied to the process at 1 bar and 25 C,
conditions under which it leaves the capture unit.
2.4 Methanol synthesis and purification

Reactor
The reactor operates under adiabatic conditions, and is packed with 44500 kg of Cu/ZnO/Al 2O3
commercial catalyst. The conversion of CO2 is 33 % per pass in the reactor and the recycle ratio is 5.0.
The present models do not consider the generation of by-products in the reactor. However, 0.4 % of
by-product can be expected, most in form of methyl formate (NEDO and RITE, 1998; Mignard and
Pritchard, 2006).
Distillation
Methanol is purified in a distillation column. The column was simulated with the rigorous model
RadFrac Rate-Based of Aspen Plus. The BX structured packing was adopted, with 32.2 m of height
and 3.6 m of diameter. Aspen Plus calculates the pressure drop in the column by a vendor correlation.
Figure 2: Flowsheet of compression unit
Heat and electricity

Heat exchanger network design was based on Pinch analysis performed with Aspen Energy
TM TM
Analyzer V7.1. All heat exchangers were designed with Aspen Exchanger Design and Rating V7.1.
Steam is generated from the combustion with air of the purge and the gas stream leaving the top of the
second flash tank (stream 16).
The streams of hot water leaving the heat exchangers HX1, HX2, HX3, HX4, HX5, HX7, HX8, E103
and bottom of the distillation column are used to generate electricity through an organic Rankine cycle.
The work fluid is the R245fa.
465
Figure 3: Flowsheet of reaction and purification units
Flowsheet description
CO2 is fed at 1 bar and hydrogen at 30 bar, both at 25 C. They are compressed to 78 bar in a series of
compressors with intercooling. The two gases are mixed (MIX1) and then re-mixed with the recycle
stream (MIX2). The current is then heated (E101) to 210 C and injected into the adiabatic reactor. The
gases leaving the reactor are divided (DIV1) into two streams: the first (60 % of initial current) is used
to heat the fresh feed (E101), while the second is used in the reboiler (DT1REB) and also in the
heating the feed of the distillation column (E102). The two streams are re-mixed (MIX3) and cooled to
35 C by water (E103). Water and methanol, which were condensed in exchanger E103, are separated
from the non reacted gases in a flash tank (TKFLS1).
The liquid stream leaving the flash tank, called crude methanol is composed of methanol, water and
residual dissolved gases. Some of the non reacted gases (1 %) are purged to minimize the
accumulation of inerts and by-products.
The crude methanol is expanded to 1.3 bar in a valve (VLVDET1). Then, the residual gases are
removed in a second flash tank (TKFLS2). The remaining stream, which is composed of methanol and
water, is heated to 80 C in exchanger E102, and then sent to a distillation column (DT1). The water
comes out from the bottom of the column at 102 C, and contains 53 wt-ppm of methanol. Methanol
comes out from the top at 1 bar and 65 C, in liquid form, containing 10 ppm of water.
3. Results and discussion

The result of material, energy and CO2 balances are presented in Tables 1, 2 and 3, respectively. Not
including CO2 emissions caused by energy consumption, the yield is 0.67 tonnes of methanol per
tonne of CO2 supplied. As it is shown in Table 2, the energy used for electrolysis of water corresponds
466
to 97 % of the net electrical power consumed. The methanol synthesis unit does not need external heat
input, so 100 % of the thermal energy consumed is used in CO2 capture.
As shown in table 3, if the oxygen by-product is sold, the process developed in this study may abate
1.7 tonne of CO2 per tonne of methanol produced. If it is not sold, the figure is 1.2 t of CO2 per t of
methanol. However, if only 22 % of the power used in electrolysis comes from the coal plant, the CO2
balance becomes null.
Table 1: Global mass balance

Compound In (tonne/h) Out (tonne/h)
c
CO2 88.0aa 6.6 aa
H2O 108.1 aa 41.4 aa
Methanol 0 aa 59.3 aa
a b
O2 7.1 aa 96.0 aa
MEA 0.09 aa 0.09 aa
a
Oxygen from air used to burn the purge and the stream 16.
b
Oxygen generated by water electrolysis.
c
Sum of CO2 content in the purge and in the stream 16 with the CO2 produced by the combustion of
these streams.
Table 2: Energy balance

Unit Operation Amount
Water electrolysis Power to electrolysis 645.1 MW el
CO2 capture Compressing flue gas 3.9 MW el
Steam to regeneration column 77.7 MW th
Methanol synthesis Compressing fresh feed 15.9 MW el
Compressing gas recycle 2.9 MW el
Steam to methanol distillation 0 MW th
Steam generated 35.7 MW th
Electricity generated 1.9 MW el
Table 3: CO2 balance

In/Out With sale of O2 (tonne/h) Without sale of O2 (tonne/h)
CO2 fed to the process - 88.0 - 88.0
CO2 rejected by methanol synthesis + 6.6 + 6.6
Electricity consumption + 12.2 + 12.2
Carbon credits generated 0 - 34.6
CO2 balance - 69.2 - 103.7
4. Conclusions
A CO2 to methanol process was simulated and optimized with Aspen Plus. The methanol plant provides
46 % of the steam necessary to CO2 capture, which remarkably reduces the impact of CO2 recovery on
the performance of the thermoelectric plant. The CO2 balance showed that it is possible to abate a
large amount of CO2 from the production of methanol if carbon-free hydrogen is available. Thus,
methanol production is a viable way of CO2 abatement; the main challenge remains to produce large
flows of carbon-free hydrogen.
467
References
Amann J.M., 2007, Study of CO2 capture processes in power plants (In French), PhD Thesis from
MINES ParisTech.
Bolland O., Sther S., 1992, New concepts for natural gas fired power plants which simplify the
recovery of carbon dioxide, Energy Convers. Mgmt., 33, 467-475.
Graaf G.H., Sijtsema P.J., Stamhuist E.J. and Joostes G.E., 1986, Chemical equilibria in methanol
synthesis, Chemical Engineering Science, 41 (11), 2883-2890.
IFP, 2007, Capturing and storing CO2 to fight against global warming (In French),
<www.ifpenergiesnouvelles.fr>, Accessed 17/03.2012.
Vanden Bussche K.M. and Froment G.F., 1996, A Steady-State Kinetic Model for Methanol Synthesis
and the Water Gas Shift Reaction on a Commercial Cu/ZnO/Al 2O3 Catalyst, Journal of catalysis,
161, 1-10.
Mignard D., Sahibzada M., Duthie J.M. and Whittington H.W., 2003, Methanol synthesis from flue-gas
CO2 and renewable electricity: a feasibility study, International Journal of Hydrogen Energy, 28,
455-464.
Mignard D. and Pritchard C., 2006, Process for the synthesis of liquid fuels from CO2 and marine
energy, Chemical Engineering Research and Design, 84 (A9), 828-836.
Mignard D. and Pritchard C., 2008, On the use of electrolytic hydrogen from variable renewable
energies for the enhanced conversion of biomass to fuels, Chemical Engineering Research and
Design, (86), 473487.
NEDO and RITE, 1998, Project of CO2 Fixation and Utilisation Using Catalytic Hydrogenation Reaction
(Current State of Research and Development), Report issued by the New Energy and Industrial
Technology Development Organisation (NEDO) and the Research Institute of Innovative
Technology for the Earth (RITE), Japan.
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A publication of

CHEMICAL ENGINEERING TRANSACTIONS

CO2 Abatement Through a Methanol Production Process

Figure 1: Bloc diagram of the process

2.1 Water electrolysis

2.2 Oxygen by-product

2.3 CO2 capture

2.4 Methanol synthesis and purification

Figure 2: Flowsheet of compression unit

Heat and electricity

3. Results and discussion

Table 1: Global mass balance

Table 2: Energy balance

Table 3: CO2 balance

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