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Evaluation of CO2 Purification Requirements and the Selection of Processes

for Impurities Deep Removal from the CO2 Product Stream

Article in Energy Procedia · December 2013

DOI: 10.1016/j.egypro.2013.06.120

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Energy Procedia 37 (2013) 2389 – 2396

GHGT-11

Evaluation of CO2 Purification Requirements and the

Selection of Processes for Impurities Deep Removal from the
CO2 Product Stream
Zeina Abbas, Toufic Mezher, Mohammad R.M. Abu-Zahra*
Masdar Institute of Science and Technology, PO Box 54224, Abu Dhabi, United Arab Emirates

Abstract

Depending on the reference power plant, the type of fuel and the capture method used, the CO 2 product stream
contains several impurities which may have a negative impact on pipeline transportation, geological storage and/or
Enhanced Oil Recovery (EOR) applications. All negative impacts require setting stringent quality standards for each
application and purifying the CO2 stream prior to exposing it to any of these applications.
In this paper, the CO2 stream specifications and impurities from the conventional post-combustion capture technology
are assessed. Furthermore, the CO2 restricted purification requirements for pipeline transportation, EOR and
geological storage are evaluated. Upon the comparison of the levels of impurities present in the CO2 stream and their
restricted targets, it was found that the two major impurities which entail deep removal, due to operational concerns,
are oxygen and water from 300 ppmv to 10 ppmv and 7.3% to 50 ppmv respectively. Moreover, a list of plausible
technologies for oxygen and water removal is explored after which the selection of the most promising technologies
is made. It was found that catalytic oxidation of hydrogen and refrigeration and condensation are the most promising
technologies for oxygen and water removal respectively.

© 2013 The
TheAuthors.
Authors.Published
PublishedbybyElsevier
Elsevier Ltd.
Ltd.
Selection and/or
and/orpeer-review
peer-reviewunder
underresponsibility of of
responsibility GHGT
GHGT

Keywords: CO2 capture; impurities; purification technologies

1. Introduction

CCS technology includes capturing CO2 from large point sources (i.e. power generation), compressing
it and transporting it to be stored in geological reservoirs, used for Enhanced Oil Recovery (EOR) or for
Enhanced Coal Bed Methane Recovery (ECBM) [1]. The focus of this paper is on a specific technical

*
Corresponding author. Tel.:+971-2-8109181; fax: +971-2-8109901.
E-mail address: [email protected]

1876-6102 © 2013 The Authors. Published by Elsevier Ltd.

Selection and/or peer-review under responsibility of GHGT
doi:10.1016/j.egypro.2013.06.120
2390 Zeina Abbas et al. / Energy Procedia 37 (2013) 2389 – 2396

challenge (which faces CCS), which is the need for CO2 processing, following the capture process, in
order to remove harmful impurities, such as sulfur oxides, nitrogen oxides, oxygen, carbon monoxide and
water [2]. If the CO2 stream was not purified to the right level, some possible threats faced include
corrosion of pipelines and unwanted side reactions with hydrocarbons. Therefore, it is important to know
what critical impurities are present in the CO 2 stream and what their purification requirements are prior to
their exposure to pipelines, EOR or geological storage. The extent of purification will vary depending on
the type and level of the impurities.
In this paper, the CO2 stream specifications and impurities from the conventional post-combustion
capture technology are assessed. Furthermore, the purification requirements for pipeline transportation,
EOR and geological storage are evaluated. Finally, a preliminary assessment of the different technologies
for the impurities deep removal is conducted.

2. Post-combustion CO2 Product Stream Specifications

The operating conditions and the range of possible compositions for the CO 2 product stream before
compression, as obtained from several sources, for post-combustion capture technology are presented in
Table 1. The compositions provided include those of Siemens coal-fired and NGCC PostCap technology
([3]&[4]) as well as other sources for the conventional MEA-based technology which have similar
operating temperature information ([5], [6] &[7]). It can be seen from Table 1 that water is the major
impurity in the CO2 stream, with 2.8% corresponding to the NGCC plant and 7.3% to the coal-fired plant.
Other impurities are present in smaller quantities (hundreds of ppmv levels and less). The operating
conditions of the CO2 stream are at atmospheric pressure and approximately 40°C.

Table 1. CO2 product stream specifications from Post-Combustion Capture

Component (mol% or ppmv) Post-Combustion Capture [5], [6], [7], [3] and [4]
Temperature (°C) 40-42
Pressure (bara) 1-2.85 [6]
CO2 92-97
H2O 2.8-7.3
Ar 10-25 ppmv
N2 0.02-0.13
O2 0.001-0.03
SO2 0.001

3. CO2 Purification Requirements

For the purpose of using the captured CO2 for storage or EOR applications, the capture technology
needs to provide the CO2 stream as purely as possible. The purification requirements vary depending on
the final use of the CO2 stream. For example, the CO2 pipeline transport system would mainly require the
removal of water and oxygen in order to prevent corrosion and other defects in the pipelines. As for EOR,
very low oxygen contents are permitted because oxygen could react with the hydrocarbons within the oil
field. In this work, the focus will be placed on the purification requirements for the three major
applications: pipeline transportation, EOR and geological storage.

3.1. Pipeline Transportation

The CO2 product is compressed to a pressure of more than 8 MPa at ambient temperature to reach
supercritical form ([8], [9] & [10]). The compressed CO2 is then transported via pipelines, ships, rail or
road at temperatures ranging between 286 K and 316 K and pressures between 8 MPa and 17 MPa ([11]&
 Zeina Abbas et al. / Energy Procedia 37 (2013) 2389 – 2396 2391

[8] & [10]). Pipelines are considered as the most attractive mode of transportation economically and
technically for CO2 emitted from large point sources [11]. Due to the presence of impurities in the CO2
stream, pipelines can face technical problems such as corrosion and two-phase flow, which lead to liquid
slugs in the pipeline and liquids in the injections compressor [12]. According to Anheden et al. [2], the
impurities present in the CO2 stream that are considered critical to pipelines are: H2O, H2S, Ar, O2, H2,
SOx, N2, CH4, and mercaptans.

3.2. Geological Storage

Three types of geological formations are eligible for storing CO2, namely: depleted oil and gas
reservoirs, deep saline formations and unminable coal beds. Injection of CO2 needs to occur at depths
more than 0.8 km below ground level to maintain super criticality [13]. According to Anheden et al. [2],
the two main concerns for geological storage are: possible leakage and geochemical reactions.
Geochemical reactions would further cause reduced permeability, increased pore pressures, corrosion and
hydrate formation. These concerns are mainly the result of the presence of numerous impurities in the
CO2 stream, namely: SOx, NOx, O2, N2, Ar, H2, CH4, CO, H2S and H2O.

3.3. Enhanced Oil Recovery (EOR)

The alternative to geological storage is to use the captured CO2 for EOR purpose. The CO2 stream will
replace water and natural gas, which are used generically for EOR, to pressurize the reservoir. For this
technology to be successful and safe, several issues should be addressed regarding the composition of the
CO2 stream being injected. The components considered to be hazardous for EOR applications and should
be limited are: H2O, H2S, SOx, COS, RSH, N2, Ar, H2, CH4, CO and O2 [5]. According to Anheden et al.
[2], the concerns that face EOR mainly are: overheating at the injection point due to a reaction between
oxygen and oil, and reproduction of toxic components at the pumping well when there is CO 2
breakthrough.

3.4. Collective Requirement of Applications

An overall minimum/maximum requirement level that covers the entire range of the three applications
is shown in Table 2 with the reasoning for each application (the minimum requirement is for the CO2
level and maximum
2392 Zeina Abbas et al. / Energy Procedia 37 (2013) 2389 – 2396

Table 2. Level of impurities for the overall range of applications

Overall Range for

Component requirements Level (vol% Reason
or ppmv)
Pipeline Transportation: To enable the mixture to dissolve with oil
CO2 >95% [5],[14],[15] and [11] [16]
EOR: Increase Minimum Miscibility Pressure (MMP) [15]
H2O <50 ppmv [11],[5] and [15] Pipeline Transportation: Corrosion and Hydrate Formation [2]
Pipeline Transportation: Hydrate Formation & toxicity [2]
H2S < (10-50) ppmv [15] and [5] Geological Storage: Potential deposition of sulphur if H2S is co-
injected with SOx [17]
Pipeline Transportation: Corrosion and Two-phase flow [2]
< 10 ppmv [15],[14], Geological Storage: Storage capacity reduction, decrease injectivity
O2
[11],[18],[5] and [19] and solubility trapping [20] and [17]
EOR: Reacts with oil [2]
< 4% (All non- Pipeline Transportation: Increases (MMP) [15] and [12]
N2 condensables) [16],[5] and Geological Storage: Same as O2
[15] EOR: Increase MMP [2] and [15]
Pipeline Transportation: Two-phase flow [2]
< 4% (All non-
H2 Geological Storage: Same as O2
condensables) [16] and [5]
EOR: Increase MMP [2]
Pipeline Transportation: Two-phase flow and volume efficiency [15]
< 4% (All non- and [2]
Ar
condensables) [16] and [5] Geological Storage: Same as O2
EOR: Increase MMP [2]
Pipeline Transportation: Health and Safety (H&S) consideration [15]
CO < 2000 ppmv [16] and [5]
Geological Storage: Same as O2
Pipeline Transportation: H&S [18]
Geological Storage: Corrosion [2]
NOx < 100 ppmv [18] and [17]
Can react with formation and cap rocks, affect injectivity and storage
integrity [20]
Pipeline Transportation: H&S [18]
Geological Storage: Formation of H2SO4 and corrosion[17] and [2]
SOx < 50 ppmv [18] and [17]
Can react with formation and cap rocks, affect injectivity and storage
integrity [20]
Pipeline Transportation: Hydrate formation and MMP [15]
Hydrocarbons (HCs) < 2% [15],[11],[18] and [5] Geological Storage: Same as O2
EOR: Increase MMP [2] and [15]

4. Required Deep Removal

The impurities in the CO2 stream which require deep removal and the levels to which they need to be
reduced, to meet the collective requirements of the three applications, are shown in Table 3. The lowest
CO2 purity is found to be 92% and needs to be increased to 95% [11, 14, 15]. The impurities which need
to be dealt with are: H2O and O2. Oxygen has a maximum share of approximately 300 ppmv and it needs
to be reduced to 10 ppmv, while H2O has a maximum share of around 7.3 mol% and it needs to be
purified down to 50 ppmv or 0.005 mol%.

Minimum Miscibility Pressure (MMP) is defined as the minimum pressure at which an injection gas (in this case CO2) can achieve
multiple-contact miscibility with the reservoir oil. Impurities, such as O2 , H2, Ar, CO and N2 increase the MMP because they are
immiscible in oil.
 Zeina Abbas et al. / Energy Procedia 37 (2013) 2389 – 2396 2393

Table 3. Required deep removal of impurities to match all the requirements of applications for post-combustion CO2 product

Level restriction of Post-combustion CO2 Level of treatment/control

Impurity
Applications product level From To
CO2 >95% 92.6-97% 92.6% 95%
H2O <50 ppmv 2.88-7.3% 7.3% 0.005%
<4% (All non-
Ar 11-23 ppmv -
condensables)
<4% (All non-
N2 0.02-0.13% -
condensables)
O2 <10 ppmv 0.001-0.03% 300 ppmv 10 ppmv
SO2 <50 ppmv 0.001% -

5. Preliminary Evaluation, Ranking and Selection of Purification Technologies

To separate oxygen and water impurities from the CO2 product stream, possible technologies that can
physically remove or convert these impurities need to be explored and evaluated. The results of this
evaluation will aid in ranking these technologies and selecting the most promising ones for further
detailed techno-economic evaluation.
The main criteria that determine the ranking position of the potential technologies include: process
impurity removal efficiency, operating conditions, energy requirement, estimated costs, safety
considerations, and whether there are similar applications in industry. Safety factor is considered to have
the most weight compared to the other criteria.

5.1. Oxygen Removal Technologies

The oxygen removal technologies evaluated in this work are: catalytic oxidation of carbon monoxide,
catalytic oxidation of propane, catalytic oxidation of methanol, cryogenic distillation, oxidation of coal,
catalytic oxidation of hydrogen and chemisorption of oxygen on copper. In order to compare some of
these technologies, a CO2 stream with flow rate of 242 tons/hr is used as a basis for the calculations. The
composition of the CO2 stream, its molecular weight and the molar flow used are shown in Table 4 [3-6].

Table 4. Data on the CO2 stream [3-6]

Component Composition (mol% or ppmv)

CO2 92.6
H2O 7.3
O2 300 ppmv
Ar 23 ppmv
N2 0.0677
Total mass flow (ton/h) 242
Total molar flow (mol/h) 5.75*106
Molecular Weight (g/mol) 42.1

Out of the preliminary evaluation of these seven different technologies for oxygen removal, the
technologies were ranked and their advantages, disadvantages and conclusions are shown in Table 5. It
should be noted that these technologies are placed from the most promising to the least promising (top
down order).
2394 Zeina Abbas et al. / Energy Procedia 37 (2013) 2389 – 2396

Table 5. Ranking of Oxygen Removal Technologies

Technology Advantages Disadvantages Conclusions

-Simple construction [27]
-Low investment costs [27]
Catalytic Oxidation -Continuous operation with one -Suitable operating
Increase of humidity [27]
of H2 reactor [27] conditions with low costs
-Low operating temperature
(OT) (80°C)
-High cost of equipment and
-High Energy Requirement
Cryogenic -Achieves 100% of impurities energy
-Costly equipment
Distillation removal in the CO2 stream -Compression needed (for phase
-Detailed evaluation required
change of CO2)
Catalytic Oxidation -Complete oxidation takes
-No side products -OT is relatively high (320°C)
of CH3OH place at high OT
-No additional humidity -For continuous operation, two
Chemisorption of O2 obtained [27] reactors necessary [27] -Quite energy-intensive
on Cu -Hydrogen content of less than -Higher investment and -Relatively high OT (200°C)
1 ppmv reachable [27] operational costs [27]
-Toxicity is associated with
Impurities will be formed such as
Oxidation of coal -Relatively low OT the formed CO from
CH4, CO and H2.
combustion
-C3H8 is converted into CO2,
-OT is relatively high (350°C)
which means more CO2 is -High costs
-High costs for propane
Catalytic Oxidation produced (higher purity). -High operating conditions
-High energy requirement
of C3H8 -The amount of C3H8 added -Purity of the CO2 stream is
-
does not affect the purity of the not affected
efficiencies
CO2 stream.
-Reasonable OT (200°C)
Catalytic Oxidation -No undesired side products -Highly toxic
- CO causes toxicity to CO2
of CO formed -Cooling is needed after oxidation
stream

As seen in Table 5, catalytic oxidation of hydrogen is the highest ranked technology. This is due to its
effective removal efficiency, lowest and most optimum operating conditions (80°C), low energy
requirement and considerable safety. The next two technologies- cryogenic distillation and catalytic
oxidation of methanol- have high energy requirements and unfavorable operating conditions (-56.6°C and
320°C, respectively) but have effective removal efficiencies and high safety, which make them the next
two potential technologies. Chemisorption of O2 on copper and catalytic oxidation of propane, on the
other hand, have high removal efficiencies and effective safety but have high operating conditions and
large costs are incurred with the operation of these technologies. This allocates them next in ranking.
The two lowest ranked technologies are catalytic oxidation of carbon monoxide and oxidation of coal due
to their unsafe conditions, which is related to the toxicity of CO (which is a reactant in the former
technology and an undesired by-product in the latter). To sum up, catalytic oxidation of hydrogen is
selected for further evaluation.

5.2. Water Removal Technologies

The three technologies for water removal which are considered in this work are: absorption using
ethylene glycol (EG)/triethylene glycol (TEG), adsorption using silica gel/molecular sieves/activated
alumina, and refrigeration and condensation.
A list of the advantages, disadvantages and conclusions are developed for the three water removal
technologies from most promising to least promising technology (see Table 6).
 Zeina Abbas et al. / Energy Procedia 37 (2013) 2389 – 2396 2395

Table 6. Ranking of Water Removal Technologies

Technology Advantages Disadvantages Conclusions

- low costs
- Heat integration
Refrigeration and -Low investment costs [29] -Modifications in compressor design are via Joule-
Condensation -No operational costs [28] necessary [28] Thomson effect
-No utilities
involved
-Smaller equipment size -High capital, maintenance and operating costs
-High costs
Adsorption using compared to glycol absorption [32]
-Regeneration
silica gel [28] -Sieve is exposed to deactivation and should be
easily achieved
-No solvent/CO2 loss [28] replaced every 3-5 years [32]
-Large equipment necessary[28]
-High investment, maintenance and operational
-Established process [28]
costs [28, 32]
-Flexible on circulation rate
Absorption using -Solvent and CO2 loss in each other [29] -High costs
[32]
EG -Operational problems due to solvent carryover -Solvent loss
-Water content of 21 ppmv is
to the CO2 compressor [29]
reachable [29]
-Environmental concern due to disposal of glycol
gas [28]

Due to its sufficient removal efficiency, high safety, low energy requirement and low costs,
refrigeration and condensation is viewed to be the most promising and highest ranked technology. When
comparing between adsorption using silica gel and absorption using ethylene glycol, both technologies
have similar energy requirements and costs. However, ethylene glycol disposal takes place following the
absorption process, which makes this process hazardous to the environment and unsafe. For this reason,
the absorption process is ranked as last and adsorption as second. Accordingly, the dehydration
technology which is selected for further evaluation is refrigeration and condensation.

6. Conclusions

Through comparison between the purification requirements of the three major applications and the
CO2 composition from post-combustion capture, it was concluded that the two impurities that require
deep removal are water (from 7.3% to 50 ppmv) and oxygen (rom 300 ppmv to 10 ppmv). Upon
evaluating several technologies for de-oxygenation and dehydration, the technologies that were viewed to
be the most promising and will further be evaluated economically in the second part of this work are:
catalytic oxidation of hydrogen and refrigeration and condensation, respectively.

Acknowledgements

The authors would like to thank Siemens for their financial and technical support throughout the
project.

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