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Energy Procedia 63 (2014) 7968 – 7975

GHGT-12

CO2 Utilization Pathways: Techno-Economic Assessment and

Market Opportunities
Mar Pérez-Fortes*, Andrei Bocin-Dumitriu, Evangelos Tzimas
European Commission, Joint Research Centre, Institute for Energy and Transport,P.O. Box 2, 1755 ZG Petten, The Netherlands

Abstract

This paper assesses two different carbon capture and utilization (CCU) routes as disposal options for captured CO2 emissions.
The adopted methodology is presented and applied to the study of urea synthesis and methanol production. Process flow
modelling is used to analyze their technological performances. The adopted conceptual design strategy allows for the
contextualization of the modelled technologies and their comparison in terms of selected scales and process configurations. The
results highlight the potential benefit of CO2 utilization, by avoiding CO2 emissions. The proposed approach is amenable for the
screening of other prospective technologies: polymer synthesis, CO2 mineralization and formic acid production, which will be
addressed by the Joint Research Centre (JRC) in a follow-up study of CCU.
© 2013The
© 2014 TheAuthors.
Authors. Published
Published by by Elsevier
Elsevier Ltd. Ltd.
This is an open access article under the CC BY-NC-ND license
Selection and peer-review under responsibility of GHGT.
(http://creativecommons.org/licenses/by-nc-nd/3.0/).
Peer-review under responsibility of the Organizing Committee of GHGT-12
Keywords: Carbon capture and utilisation (CCU); CO2 utilisation; methanol synthesis; urea yield boosting; conceptual design, CO2 emissions.

1. Introduction

The European Union (EU) has set the objective to reduce greenhouse gas emissions (GHG) by 40% below the
1990 levels by 2030, and down to 80-95% by 2050. Key enabling technological actors in this context are carbon
capture and storage (CCS) and carbon capture and utilization (CCU), since predictions foresee that fossil fuels will
retain their central role in energy production worldwide. This implies that CCS and CCU (CCUS) will have to
acquire the recognition and confidence required to be a viable technology to contribute to any decarbonisation
scenario [1]. To promote CCUS, (i) capture technologies need to be demonstrated and improved until they become

* Corresponding author. Tel.: +31-224-565-309.

E-mail address: maria-del-mar.perez-fortes@ec.europa.eu

1876-6102 © 2014 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/3.0/).
Peer-review under responsibility of the Organizing Committee of GHGT-12
doi:10.1016/j.egypro.2014.11.834
 Mar Pérez-Fortes et al. / Energy Procedia 63 (2014) 7968 – 7975 7969

commercially competitive, (ii) best options for CO2 transportation networks need to be ascertained, (iii) storage sites
have to be identified and conditioned, (iv) industrial processes that use CO2 as feedstock need to be deployed and (v)
the general public needs to know and recognize the "CCUS chain" as an alternative to CO2 emissions mitigation.

Nomenclature

CCS carbon capture and storage

CCU carbon capture and utilization
CCUS carbon capture, storage and utilization
Conv conversion
CRI Carbon Recycling International
EU European Union
GHG greenhouse gases
JRC Joint Reseach Centre
KPI key performance indicator
P the whole system modelled (process)
R reactor
wt weight (on a mass basis)

CCU is a valuable complement to geological storage: its potential contribution to avoid CO2 emissions in the
short term has been evaluated at around 300 MtCO2/yr [2], used as feedstock in industrial processes and as a
working fluid. There are various carbon utilization technologies, which are at different levels of technological and
market readiness. Urea and methanol have mature markets and are currently produced via well-known conventional
processes (i.e. not using captured CO2 emissions from external sources).
The so-called urea (NH2CONH2) yield boosting aims at increasing the conversion of ammonia into urea by using
the surplus of ammonia from the upward process. In this case, the CO2 that is produced from the ammonia synthesis
process is the limiting reactant in the urea synthesis process if natural gas is used as feedstock. The increase of urea
conversion by recovering CO2 from the methane reformer used for the ammonia synthesis, has been already
achieved. Potentials for further urea yield boosting using captured CO2 from a coal power plant have been also
investigated [3]. Urea is mainly used as fertilizer and in polymer synthesis. This is one of the most common forms of
solid nitrogen fertilizer. The final product is usually a prilled or granulated solid, which once applied to agricultural
land reacts with water to release the CO2 and ammonia. The CO2 returns to the atmosphere and the NH3 decomposes
further to supply nitrogen at a controlled and appropriate rate to crops [4]. Its production worldwide was about 150
Mt in 2011, coming from 460 plants operating around the world, requiring 112-120 MtCO2/yr used as raw material.
The demand of urea is expected to grow up to 176 Mt by 2016. Melamine and urea-formaldehyde synthesis are
particularly promising options in terms of CO2 fixation. There are several commercialized processes to produce urea:
Stamicarbon, Snamprogetti, Chao, Uchino. Stamicarbon is recognized as one of the leading processes in urea
synthesis [5,6].
The use of captured CO2 in methanol (CH3OH) synthesis is almost implemented at commercial scale: Iceland,
Japan and Korea have large-scale pilot plants that use CO2 and renewable hydrogen [7]. Carbon Recycling
International (CRI) started the operation of its first commercial demonstration plant in 2011 in Iceland, using a
catalytic reaction to transform CO2 and H2 into CH3OH. Electrochemical CO2 reduction and H2 oxidation is another
methanol production route of interest for the storage of electricity produced by renewable sources. Methanol has a
large potential as an energy carrier for transportation application: it can be further transformed to replace gasoline
and to produce dimethyleter (DME) to replace diesel, or in a near future directly converted in fuel cells. An
important market of 40 Mt (in year 2007) nowadays already exists for methanol, mainly as feedstock for the
production of formaldehyde, methyl terbutyl ether (MTBE) and acetic acid [5,8].
In this paper, two carbon utilization options are modelled and evaluated: urea production and methanol synthesis.
They represent two well differentiated case studies: while urea already uses CO 2 as feedstock (i.e. the use of
captured CO2 is utilized to increase the yield in urea synthesis), methanol is traditionally produced by the Fischer-
7970 Mar Pérez-Fortes et al. / Energy Procedia 63 (2014) 7968 – 7975

Tropsch process (the catalytic conversion of syngas that comes from steam reforming of natural gas). The models
developed and used in this paper to assess these technological pathways, are first calibrated and validated against
bibliographic data. Urea production and methanol synthesis are then evaluated by key performance indicators
(KPIs): processes efficiency, utilities' requirements, amount of CO2 used and quantification of the investment cost.

2. Modelling approach

The conceptual models are implemented in ChemcadTM. Production during 7,884 hours per year (90% load factor)
is assumed. In both cases, the CO2 that enters the CO2 utilization plant, is 100% pure, and the electricity consumed
is provided from a pulverized coal power plant, generating emissions at 803 tCO2/GWh [9]. The ΔP considered in
all heat exchangers is 0.2-0.3 bar. Compressors have an efficiency of 0.75. The urea model uses UNIQUAC as
global K-value model, while in the absorption and stripping towers, the Non-Random Two Liquid (NRTL) as
thermodynamic model is used. The methanol model uses the Peng-Robinson (PR) state equation. Cooling water is at
15 °C and 1.01325 bar, and steam is at 170 °C and 4.8 bar. The total investment required per ton of used CO2, is
calculated following the Hand’s method. It includes the total cost of purchase, off-sites, design and engineering and
contingency items. This preliminary cost estimate has typically accuracy in the range of +/- 30 %. As starting point,
the estimated costs consider only carbon steel used as construction material [10].

2.1. Urea synthesis

The Stamicarbon process considered in our paper, is a "total recycle process" for reactants CO2 and NH3. To
further increase the conversion of the latter, the separation of the urea solution from the unreacted CO2 and NH3 in
liquid and gas phases in the Stamicarbon process, uses CO2 as stripping agent. This allows the conversion of
ammonium carbamate (NH2CO2NH4) into its original components. Urea is usually commercialized as a solid,
typically granules or prills. Their synthesis comprises four main steps. (A) Urea synthesis, where the urea solution is
produced. (B) Low pressure recirculation, where the urea solution stream is purified and CO2 and NH3 are recovered
and fed back into the urea synthesis section. In this section, the urea enters the urea solution tank. (C) Water
evaporation under vacuum conditions to obtain a urea solution with a concentration of 96-99.7wt%. (D) Granulation
or a final shaping step and water treatment1. The modelling effort in this work is focused on section A, the urea
synthesis loop.
NH3 is commonly produced by the Haber-Bosch process, from H2 and N2. H2 is usually obtained by steam
reforming of CH4 and N2 from air. Urea plants are connected to ammonia synthesizing plants, where relatively pure
CO2 is available from the ammonia process, explicitly from the H2 separation, as a part of the ammonia synthesis
process. The size of the urea plant is constrained by the upstream ammonia facility. If the price of urea is higher
relative to ammonia, there is an incentive to convert the surplus of ammonia into urea using recovered CO2. The
main emissions from the urea synthesis process are ammonia and particulate matter. Formaldehyde may be emitted
if it has been used as additive.
Reactions (1) and (2) take mainly place in the carbamate condenser and in the urea reactor. The first reaction is
exothermic, while the second one is endothermic, resulting in an overall exothermic process.
CO2 + 2NH3 ↔ NH2CO2NH4 (1)
NH2CO2NH4 ↔ NH2CONH2 + H2O (2)
Figure 1 depicts a simplified flow sheet of the urea synthesis looping. Compressed CO2 enters the CO2 stripper
acting as a stripping agent and decomposing unreacted carbamate into NH3 and CO2, which are therefore stripped
off from the liquid phase. The gas phase from the stripper enters the carbamate condenser, together with ammonia
and the liquid phase from the scrubber. The carbamate condenser is a heat exchanger where the heat generated in
reaction (1) in the tubes side, is used to produce low pressure steam at the shell side. Not all the reactants are

1
Stamicarbon brochure.
 Mar Pérez-Fortes et al. / Energy Procedia 63 (2014) 7968 – 7975 7971

converted here; reaction (1) is also takes place in the urea reactor, producing enough heat for reaction (2). In the urea
reactor, the use of trays increases the contact between liquid and gas phases. The liquid product from the reactor
overflows towards the stripper, while the gas phase, containing free NH3, CO2 and inert gases, are driven into the
scrubber. In the stripper, the steam on the shell side provides the needed heat to decompose the reminding carbamate
into urea in the tubes side [11,12].
Inert gases
Lean
carbamate
Scrubber

Unreacted
gases
CO2
stripper
Electricity Carbamate CO2
condenser Urea
Carbamate reactor
solution
WATER
HYDROLYSIS

Urea
H2 solution
NH3

AMMONIA
SYNTHESIS

N2

Fig. 1. Flow diagram of the synthesis section in a Stamicarbon process [4,11].

2.1.1. Model outline and validation

The modelled plant produces around 1600 t/day of a urea solution at 56 %wt. Generally, the reactions occur in
liquid phase. Exhaustive models of urea synthesis remain a challenge; specifically, in terms of adequate
thermodynamics model [6]. In the present case, the production of biuret is disregarded. The pressure and
temperature along the process are 141 bar and 180 °C. The CO2 entering the system is compressed in a 5-stage
compressor. Ammonia is pumped up to 160 bar. The carbamate condenser is modelled as a stoichiometric reactor
with a conversion fraction calculated with a controller that sets the urea reactor under approximate adiabatic
conditions. The urea reactor comprises two reactors and one separator: a Gibbs reactor for reaction (1), a
stoichiometric reactor for reaction (2), and a flash vessel, respectively. The conversion fraction in the second reactor
is adjusted to yield 33.9 wt% of urea in the outlet stream. The CO2 stripper is modelled by a stoichiometric reactor
for the decomposition of carbamate into NH3 and CO2 and a rigorous multi-stage vapor-liquid equilibrium (SCDS)
column, to separate the urea solution and recycle gases. The scrubber is also modelled with a Stoichiometric reactor,
in this case for reaction (1), and a SCDS column that represents the absorption step. The gases obtained from the
scrubber are sent to an absorption process before release into the atmosphere. The scrubber receives the carbamate
recycle stream from the low-pressure recirculation section, introduced in this model as an input stream [6,11,12]. A
set of controllers integrates the heat released/absorbed between the reactors and the subsequent water and steam
streams. The results of the model are contrasted with the data in [6, 11] and [12]. Overall, the range of error in the
model predictions is between +/- 15%, considering temperature estimations and flow rates, heat and electricity
streams.

2.2. Methanol production

Purified CO2 enters the system according to the amount of methanol to be synthesized. The H 2 inlet stream
corresponds to the stoichiometric amount of H2 required by reaction (3). Reaction (4) occurs in parallel and
decreases the conversion of CO2 into CH3OH. Therefore, the resulting water may be recycled to the CO 2 capture
7972 Mar Pérez-Fortes et al. / Energy Procedia 63 (2014) 7968 – 7975

plant to provide the needed water for the conversion of CO into CO 2, or may be used in electrolysis, to further
increase the efficiency of the plant.
CO2 + 3H2 ↔ CH3OH + H2O (3)
CO2 + H2 ↔ CO + H2O (4)
Doped metal oxides are usually used as catalysts for reaction (3). The kinetics described in reference [14] applies
to Cu/ZnO catalyst on Al2O3 substrate, and they follow the Langmuir-Hinshelwood-Hougen-Watson formalism.
Figure 2 depicts a simplified flow diagram of methanol plant.

COMP3

Electricity
HE1

WATER Purge
HYDROLYSIS

Flash1
COMP2
Conditioning
H2
system

HE1 Residual
CO2 Methanol gases
reactor
COMP1 COMP4

Flash2

Flash3

HE2

HE3
Distillation
column
Methanol
H2O

Fig. 2. Flow diagram of the methanol synthesis process [13,14].

CO2 is compressed up to 78 bar. H2 from the electrolysis enters the system at 30 bar. The mixture of both streams
is heated up to the temperature of the methanol reactor, which is a fixed bed reactor. HE1 is integrated with the
cooling down of a stream divided after the methanol reactor for this purpose. The conditioning system after the
reactor brings the mixture of CH3OH and water to 35 °C and 73.4 bar. The heat exchanger is integrated downstream
with HE2 and the reboiler. Flash1 separates the mixture, and the gas stream, mainly CO2, is recycled back to the
inlet mixture of CO2 and H2. COMP3 increases the pressure again until the inlet value. Then, the distillation column
that separates methanol and water works at almost atmospheric pressure. Flash2 separates any vapor fraction before
methanol purification. Further purification is achieved with the downstream COMP4 and HE3. The methanol end
product is at atmospheric pressure and 20 °C [13,14].

2.2.1. Model outline and validation

The modelled plant produces around 1300 t/day of methanol, at 98 %wt. The process is mainly composed by the
reactor and the distillation column, with the corresponding conditioning units. The pressure and temperature of the
system are 78 bar and 210 °C (temperature of reaction). CO2 is compressed in a 4-stage compressor up to the 78
bar, one stage is sufficient for H2. The methanol reactor is modelled by a Gibbs free energy reactor, at the reaction
temperature. A Controller sets up the split fraction of the stream that goes out of the unit, in order to integrate the
needed heat before the reactor with the cooling down before the distillation column. Two Controllers integrate the
conditioning system with two other heat exchangers, according to the heat requirements in the reboiler and before
the column. Before the recycling of CO2, there is a purge of 1% in mass basis. A second purge takes place after
main stream expansion to 1.2 bar, before entering the column at 80 °C. The system produces 0.56 tH2O/tCH3OH. The
results of the model are contrasted with the data from [13] and [14]. Overall, the maximum error obtained is 15%,
by checking flow rates and compositions.
 Mar Pérez-Fortes et al. / Energy Procedia 63 (2014) 7968 – 7975 7973

3. Preliminary results

Urea synthesis and methanol production plants are evaluated through the following, mainly technical KPIs:

‚ Product purity (wt%). This indicator refers to the wt% that urea and methanol represent in the product stream of
each plant modelled.
‚ CO2 converted in the reactor (%). This is a metric to evaluate the amount of CO2 that is converted in the
reactions (1) for urea, and (3,4) for methanol. The parameter is calculated as:

à CO FlowIn / CO2 FlowOut Ô

CO2ConvR ? ÄÄ 2 ÕÕ
(5)
Å CO2 FlowIn ÖRe actor

‚ CO2 converted in the complete process (%). This value evaluates the total conversion that takes place into each
process, i.e. taking into account recycle streams, and the outlet CO2 from purge and venting gas streams.

à CO2 FlowIn / CO2 FlowOut Ô

CO2 ConvP ? ÄÄ ÕÕ (6)
Å CO2 FlowIn Ö TheWholeSystem

‚ CO2 used (t/h). This metric is used in the next KPIs. This value is computed by subtracting the outlet flow of CO2
from the inlet flow of CO2, of the whole system (expressed as the numerator of Equation (6)). It does not take
into account the derived emissions from electricity consumption.
‚ Heat duty per CO2 used (MWh/tCO2used or tH2O/tCO2used). In the case of the urea synthesis loop, heat is
supplied/received by different water and steam streams. Heat duty in this case is expressed as the flow rates of
them. In the methanol synthesis, heat exchange occurs between streams of the process itself. Heat exchanges that
do not have a specific recipient/receiver, are reported here.
‚ Electricity duty per CO2 used (MWh/tCO2used). Electricity requirement for all the process; mainly coming from
streams compression. In the methanol case, the electricity consumed in the electrolysis process to produce the
needed amount of H2 is also taken into account (4.8 kWhel/Nm3 of H2 produced [14]).
‚ CO2 emissions (tCO2released/tCO2used). Directly accounted from the outlet streams of each system.
‚ Investment cost per CO2 used (MEUR2010/(tCO2used/h)). Only taken into account for the methanol production
plant, since the urea plant, theoretically and at the limits of the considered boundaries, does not need any extra
investment.

Tables 1 and 2 contain the obtained KPI values for each plant.

Table 1. KPIs evaluated for the urea synthesis loop.

KPIs
Product purity (wt%) 56%
CO2ConvR (%) 55%
CO2ConvP (%) 72%
CO2 used (t/h) 23.4
Heat duty (tH2O/tCO2used)
Cooling water 1.1
Steam generation 2.2
Steam condensation 1.9
Electricity requirement (MWh/tCO2used) 0.2
CO2 emissions (tCO2/tCO2used) 0.6
7974 Mar Pérez-Fortes et al. / Energy Procedia 63 (2014) 7968 – 7975

Table 2. KPIs evaluated for the methanol synthesis process.

KPIs
Product purity (wt%) 98%
CO2ConvR (%) 28%
CO2ConvP (%) 94%
CO2 used (t/h) 74.1
Heat duty (MWh/tCO2used) 1.2 (cooling needs)
Electricity requirement (MWh/tCO2used) 8.3
CO2 emissions (tCO2/tCO2used) 6.8 (0.5 w/t electrolysis)
Investment cost (MEUR2010/(tCO2used/h)) 1.6

It is important to remark that the KPIs in Table 1 refer to the whole urea synthesis loop. However, the urea yield
boosting contributes in a 10-15%, to CO2 used, heat duty, electricity requirement and CO2 released.
The CO2 emissions indicator (below the unit) highlights the beneficial CO2 balance for both processes, emitting
less than the total of CO2 used into each process, if electrolysis, using a conventional fossil fuel source as electricity
provider, is not included into the analysis. With the obtained models and the available data, it is possible to evaluate
the most adequate KPIs to consider the potential abatement of CO2 utilizing different CCU processes, as
demonstrated. The technical analysis will be complemented in the forthcoming months with (i) the comparison with
conventional processes to obtain urea and methanol and (ii) a market analysis to elucidate the competitiveness of
such investments, taking into account the prospective markets of each product.

4. Conclusions and perspectives

This work presents two validated conceptual models for a urea synthesis loop and a complete methanol synthesis
plant. The subsequent mass and energy balances are used to evaluate the selected KPIs. The preliminary results
show that the use of these two plants can potentially decrease the emissions of CO2. The paper also describes the
methodology that will be analogously used to analyze polymer synthesis, CO 2 mineralization and formic acid
production. The final purpose is to perform a realistic market study that evaluates current prices and demand for
prospective CO2 products and their foreseen market and price elasticity. The objective of the whole approach is to
develop a tool capable of evaluating economics and environmental parameters in the field of CCUS, based on a
unified framework. To our knowledge, this will be the first study that contemplates several CCU options together, to
set the basis for the objective comparison of their respective potential and advantages.

Acknowledgements

The authors are grateful to the fruitful discussions and provision of data from Ms. Elisa Puci and Mr. Joey
Dobree from Stamicarbon, and to ChemcadTM for their support in addressing modelling tasks issues. Responsibility
for the information and views set out in this work lies entirely with the authors and do not necessarily represent the
view of the European Commission.

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