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Impact of CCUS Impurities on Dense Phase CO2 Pipeline Surface
Engineering Design
Sawsan M. Ali, MEng, CEng, MIChemE, Santhanam Thyagarajan, Ashwani Kataria, Sami Al Ankar, and Amal Al
Marzooqi, ADNOC Onshore
Copyright 2021, Society of Petroleum Engineers
This paper was prepared for presentation at the Abu Dhabi International Petroleum Exhibition & Conference to be held in Abu Dhabi, UAE, 15 – 18 November 2021.
The official proceedings were published online on 9 December 2021.
This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents
of the paper have not been reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material does not necessarily reflect
any position of the Society of Petroleum Engineers, its officers, or members. Electronic reproduction, distribution, or storage of any part of this paper without the written
consent of the Society of Petroleum Engineers is prohibited. Permission to reproduce in print is restricted to an abstract of not more than 300 words; illustrations may
not be copied. The abstract must contain conspicuous acknowledgment of SPE copyright.
Abstract
Numerous CO2 injection pipeline applications have been developed and implemented in the past decades in
the UAE and all around the globe. Transporting the CO2 in dense phase, rather than in gas or liquid phases,
is well recognized of being techno-economically attractive with respect to its major CAPEX benefits of
optimized pipeline material of construction; which is driven by the high water solubility in dense phase CO2
as well as the optimized pipeline size which is greatly influenced by the density and viscosity characteristics
of supercritical/dense phase CO2.
In light of the active deployment of dense phase CO2 injection EOR pipeline transportation across the
various existing and future CO2 capture facilities across the UAE, ADNOC onshore technical expertise team
has been conducting intensive research analysis on the unique thermodynamic aspects of dense phase CO2
pipeline systems. The focus was directed towards understanding the transient characteristics, which directly
influence crucial design strategies including and not limited to CO2 purity specifications, CO2 pipeline
pressure and temperature operating envelopes as well as the developed operating philosophy which involves
start-up, shutdown and depressurization.
While optimizing the economics of the carbon capture units (CCUS) is a pivotal strategy mandating
rationalizing the dictated purity level of the captured CO2 and valorizing the projects. However, such thrifty
initiatives to moderate the costs of the selected CO2 removal technologies can lead to underlying cascading
effects of the lower purity recovered CO2 on systems design and its operation.
As part of the nation's strategic objective to reduce carbon footprint, CO2 has been recovered for EOR re-
injection applications. Relaxing the purity specification met by the CO2 capture units can positively improve
the cost of the recovery plant while may potentially have adverse impacts on CO2 pipeline integrity.
This paper provides a comprehensive analysis of the impact of the CO2 purity specification on the flow
assurance safety performance of dense phase CO2 pipeline. It is worth highlighting that the design of CO2
systems is challenged by the paucity of the available reference design guidelines since domain of CO2 itself
is still evolving under an active area of research.
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Although some previous publications have demonstrated the latent underlying effects of imputiries
such as (N2, H2, SO2, NO2, CH4, C2H6, and Argon) on the physical and thermodynamic behavior of CO2
systems, however, this was supported by literature experimental modelling without transient analysis. In
this paper, the behavior of varying CO2 purity levels on the design and operational aspects of CO2 pipeline
is substantiated and both steady state and transient flow assurance modelling are presented. Gauging the
system's design integrity cannot be solely assured from the perspective of steady state behavior and hence
this paper's findings provide additional information to that previously published with the detailed modelling
applied for varying purity scenarios of captured CO2 streams employed in EOR applications across the
UAE. The findings of the analysis are benchmarked against plausible worldwide CO2 compositions with a
wide range of impurity levels with further in depth demonstration of the transient effects which are usually
absent in the available literature.
Understanding CO2 Phase Behavior

The fundamental of an optimum CO2 pipeline design resides in the good understanding of the CO2 phase
behavior to accurately model both the steady state and transient transport phenomena aspects of CO2. Figure
1 represents 100% pure CO2 phase diagram. There are five distinct phases in which pure CO2 can exist
as shown in the P-T diagram. The critical point for pure CO2 is approximately 73.9 bara and 31 °C while
the triple point is approximately 5.2 bara and -56 °C. Above the critical point, CO2 can exist either in
supercritical or dense phase. It exists in supercritical phase when the operating temperature is greater than
critical temperature and in dense phase when operating temperature is less than the critical temperature. In
the supercritical phase, CO2 density is akin to gas phase density while in the dense phase CO2 density is
similar to liquid phase [1,8].
Figure 1—PURE CO2 PHASE DIAGRAM [8]
It may seem forthright to maintain the pressure and temperature of the system above the critical conditions
for an optimum CO2 pipeline steady state operation, however the control of the abrupt transient phase
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changes upon sudden deviations in pressure and temperature becomes complex due to the following unique
aspects of CO2:
a. The close proximity of the operating point especially near the critical conditions imposes abrupt
shifting between the gas and liquid phases upon the occurrence of slight deviations in pressure and
temperature.
b. As can be perceived from figure-2, which is generated by one the flow assurance modelling of a CO2
EOR pilot project using GERG 2008 equation, the narrow phase envelope of CO2 involves a single
saturation line demarcating the gas and liquid phases. A sudden drift in the pressure or temperature
will cause the operating trajectory to swerve between the phase boundaries segregated by this single
saturation line. In consideration of the narrow phase envelope of the pure CO2 fluid, various design
challenges emerge when attempting to accurately predict the transport properties of CO2. This also
cascades to modelling complexities and frequent non-convergence of flow assurance models due to
numerical instabilities as a result of the sudden shifts in phase equilibrium, which occur due to slight
changes in pressure or temperature [6].
Figure 2—COMPARISON BETWEEN 100% PURE CO2 AND 95.6% CO2
Even for the case of impure CO2, the phase envelope of a 95.6% CO2 portrayed in figure-2 below and
generated by OLGA software, in presence of small amount of impurities, the saturation line and phase
envelop opens up and diverge into a bubble and dew point lines forming a two phase region locked in
between the two equilibrium lines rather than merging into a single line as in the case of pure CO2. Despite
forming a bounded two phase region, the phase diagram still possess its narrowness feature and introduces
associated increase in vapor pressure, decrease in water solubility and changes in the fluid's thermophysical
properties as will be demonstrated in the upcoming sections.
Favorable Technoeconomic CO2 Pipeline Features

Although CO2 is an asphyxiant and a greenhouse gas, international business industries including ADNOC
and its group of companies have recognized this gas as a phenomenal fluid, which is crucially employed
in tertiary enhanced oil recovery mechanisms. The inherent ability of CO2 to perform efficient microscopic
sweeping in oil reservoirs makes it an attractive commodity for business development. It is of the norm to
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question the reason behind selecting CO2 transportation in dense or supercritical state rather than regular
liquid or gas phase. Figure 3 [8] which portrays the density of 100% pure CO2 as a function of pressure for
different isotherms, the density of CO2 steadily increases above its critical pressure ultimately reaching the
close proximity to that of liquid density over 800 Kg/m3.
Figure 3—DNV-GL-F104 CO2 DENSITY VERSUS PRESSURE [8]
For example, the density of CO2 at 200 barg and 13 °C approaches 800-900 Kg/m3 resembling the
incompressible liquid phase with a consistent trend as long as the pressure is above the critical pressure.
As this feature, from a pipeline hydraulics perspective, is quite discerned, the advantages of lower pressure
drop for the same pipeline capacity for CO2 in dense/supercritical phase over gas phase are significant.
This translates into CAPEX and OPEX benefits in constructing smaller pipeline sizes with relatively lower
lifecycle compression/pumping energy cost. This is mainly attributed to the lower pressure drop for the
same unit length of the pipeline in comparison with gas phase in addition to the significantly lower fluid
compressibility [1, 8]. In addition to the DNV representation of pure CO2 density increase beyond critical
pressure, flow assurance modelling of varying dense CO2 stream purity is generated in figure 4 where the
positive increase in density enhances the hydraulics of CO2 Pipeline systems.
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Figure 4—DNV-GL-F104 CO2 DENSITY VERSUS PRESSURE [8]
Further demonstrating of the cascading effects of density increase in dense phase (T<Tc) and supercritical
states (T>Tc), the following steady state modelling was performed considering a buried 8’’ 55 Km CO2
pipeline with the below two inlet conditions:
a. Supercritical condition with inlet temperature of 52 °C,
b. Dense phase condition with inlet temperature of 25 °C.
The minimum ambient winter temperature was specified at 13 °C. It can be demonstrated that greatest
extent of shrinkage is attributed to a greater temperature gradient between the inlet conditions and ambient
soil. This model result demonstrates that, the supercritical state experiences higher backpressure than dense
phase transportation. This is depicted by the differential at the pipeline boundaries and along the length of
the pipeline, the variation between dense and supercritical transportation states tend to diminish. Refer to
figure 5 below:
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Figure 5—STEADY STATE MODELLING OF SUPERCRITICAL VERSUS DENSE PHASE WINTER TRANSPORTATION (55 KM)
Above modeling closely matches with the modelling presented by Zhang et al. [7] for a steady state
pressure profile of a 350 Km CO2 pipeline transported under 15 °C ambient temperature with supercritical
and dense phase inlet conditions at 40 °C and 0 °C respectively.
CO2 & Pipeline Integrity

Natural gas exhibits a decline in water solubility as pressure increases, the same can be depicted from GPSA
gas water content plot shown in figure 6 below. This is why dehydration of hydrocarbon gas is favored at
higher operating pressure due to less water content in the gas entering the dehydration system leading to
an optimum design. However, the water content specification in sales gas shall cater for the worst case low
temperature, high pressure combination due to the greater risk of water drop out in free phase. The behavior
is unique and different for CO2. The water solubility of CO2 tends to augment above the critical pressure.
Figure 6 further elaborates the excellent moisture dissolving abilities exhibited in dense phase CO2. The
solubility of water exponentially increases as the pressure increases and further progressively increases at
higher temperatures. Accordingly, carbon steel pipeline represents a quintessential application for dense
phase CO2 transportation.
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Figure 6—WATER SOLUBILITY IN SWEET AND CO2 GASES [10]
Literature publications by Austegard et al. [1] utilized various equations of state for modelling water
solubility in CO2 where it can be deduced that at pressure above 80 barg; around 2.1 vol% of water can be
dissolved in pure CO2 at 30 °C. However, the same shall not be extended for impure CO2 streams as will
be explored in section 6.
Despite the fact that CO2 is an effective solvent of water, however, careful considerations shall focus on
the potential water drop out during pipeline prolonged shutdown, CO2 pipeline start-up and depressurization.
Accordingly, DNV-RP-F104 recommends safety factors of CO2 water specifications to cater for these
transient effects. Statoil Snovit offshore pipeline for example has the most stringent CO2 water specification
of 50 ppmv being an offshore pipeline with more probable exposure to low ambient seabed conditions and
in absence of the insulating properties of the soil unlike buried onshore pipeline. On the other hand, a study
by Dynamis recommends limiting the water content spec to 500 ppmv [9]. The same is supported by Ahmad
et al. where 500 ppmv of water in CO2 above 90 barg and at 5 °C temperature can be considered readily
dissolved [5].
Hydrate formation is strongly attributed to the fact that even for under-saturated CO2 fluid, there is a meta-
stable region where hydrate formation zone exists and CO2 molecules can become entrapped within a water
lattice [3,9]. However, there is potential for CO2 hydrate formation even in absence of free water since the
CO2 hydrate formation curve is on the right side of the water dew point line. Figure 7 below demonstrates
an OLGA modelling of 99% CO2 stream (anthropogenic steel plant captured CO2 from flue gas) where the
hydrate formation line is located to the right of the water dew point line and supporting the aforementioned
fact of hydrate formation in absence of free water. The shaded zone in figure 7 represents the water drop
out and hydrate formation zone, the bounded region shows that hydrates tend to form at pressure less than
40 barg and temperature less than 10 °C.
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Figure 7—WATER DROPOUT AND HYDRATE FORMATION FOR 99% CO2
Impurities in Captured CO2

The impurities emerging with the recovered CO2 streams from capturing plants strongly influence the quality
of the EOR injection fluid. The sources for CO2 capture can vary from associated hydrocarbon produced gas
to anthropogenic offgas stream discharging in various industrial processes, few such examples are below:
a. Post combustion units in steel industries, gas fired power plants, it is typical that, a 1000 MW gas
fired power plants can produce over 200 MMSCFD.
b. CO2 byproduct in coal gasification power plant processes and CO2 recovery from associated
hydrocarbon gas.
c. Engine Exhaust where 1 MMSCFD of exhaust gas is produced from 500 bhp engine [JMC].
d. Hydrogen and Ammonia production plants: wet saturated CO2 produced as a byproduct from ammonia
production plants [JMC].
From a reservoir performance perspective, the increase in light end impurities for instance methane
(CH4), tends to reduce the minimum miscibility pressure, which is required for an effective miscible CO2
EOR injection and recovery of the heavy crudes [9]. Impacts of impurities such as methane and heavy
hydrocarbons on the minimum miscibility pressure are demonstrated by John Campbell in [9].
The selection of the CO2 capturing technology is the key in determining the CO2 purity specification
and the degree of selectivity of CO2 over hydrocarbon and H2S components. CO2 removal mechanisms
vary among chemical absorption using amine solvents, physical absorption and membrane separation.
The residual impurities that remain in the recovered CO2 will not only determine the subsurface injection
parameters but also dictate the design and safety concerns when executing the surface facilities design of the
CO2 injection network. Table 1 below provides a typical recovered CO2 stream from a SRU tail gas treatment
absorber having predominantly CO2 and Nitrogen in the feed gas to the non-capturing CO2 compression
and dehydration plant.
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Table 1—TYPICAL OFFGAS COMPOSITION TO CCUS FROM SRU AMINE REGENERATOR
Parameter (Note) Unit Value
Temperature Deg C 49.8
Pressure Barg 0.06
Component
H2 mole % 2.8
CO mole % 0.07
CO2 mole % 27
CH4 mole % 0
N2 mole % 58.5
H2O mole % 10.8
H2S ppmv 50
COS mole % 0.126
Argon mole % 0.7
Table-2 on the other hand shows required composition of sour rich associated hydrocarbon gas produced,
which is to be processed in a CO2 capture facility. The feed stream predominantly contains hydrocarbon
alkane components along with high CO2 content of 50.8%.
Table 2—TYPICAL HC BREAKTHROUGH CO2 RICH COMPOSITION
CO2 Rich Breakthrough

associated gas
Parameter Unit Value
Temperature Deg C 73
Pressure Barg 15.36
Component
H2O mol% 2.4
H2S mol% 2.8
CO2 mol% 50.8
Nitrogen mol% 0.2
Methane mol% 28.6
Ethane mol% 5.7
Propane mol% 4.3
i-Butane mol% 0.9
n-Butane mol% 1.8
22-Mpropane mol% 0.0
i-Pentane mol% 0.6
n-Pentane mol% 0.6
Mcyclopentan mol% 0.1
psuedoC6* mol% 0.5
Cyclohexane mol% 0.1
psuedoC7* mol% 0.3

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CO2 Rich Breakthrough

associated gas
Parameter Unit Value
Mcyclohexane mol% 0.3
For such different feed streams, it is quite evident that the selection of the optimum CO2 removal
technology will be different and case dependent. The presence of higher hydrocarbon (Table-2) dictates a
more strict CO2 recovery mechanism to have a preferential selectivity over H2S and lighter Hydrocarbons
in order to meet the target H2S specification, as well as significantly minimum slippage of hydrocarbons
(C1, C2). On the other hand, table-1, which is showing predominant rich CO2-N2 mixture, may not require
such stringent requirements and bulk CO2 removal can be relatively more readily achieved.
Although there is no industry standard defining the threshold specifications for the various inert gases
and hydrocarbon in captured CO2 streams currently, the analysis of their impact on the CO2 transport
properties and material specification remains a crucial design responsibility. Imposing such stringent CO2
specifications on impurities, on the other hand, incurs higher CAPEX/OPEX. Therefore, such specifications
shall be optimum and be justified for the integrity and safety of the CO2 facilities, now the question in mind
is on what could be the extent of damage that impurities such as SOx, NOx, CH4 N2 and H2 will have on the
safety and integrity of the pipeline. The same is elaborated in upcoming sections.
Case Study & Effects on Phase Envelope

This section provides a quantitative flow assurance modelling performed by ADNOC Onshore's technical
team where the impact of increased impurities such as N2, H2 and CH4 in recovered CO2 from a CO2 rich
hydrocarbon gas similar to the table 2 in section 5. A case study is established for evaluating the effect
of impurities on various flow assurance aspects with further elaboration on the several implications in the
upcoming sections. The base case's original target purity of 95.6 % with less than 1 % impurity levels is
compared to two sensitivities cases of lower purities of 90.6% and 85% for sensitivity-1 and sensitivity-2
respectively. Sensitivity case-1 focuses on increase in methane content while sensitivity case-2 focuses on
a combined increase in nitrogen along with methane in the captured CO2:
Table 3—COMPOSITION ANALYSIS FOR EFFECT OF THE IMPURITIES
CO2 with 40lb/

Higher C1 Higher C1/N2
Component MMSCF H2O
Base case Sensitivity Case-1 Sensitivity Case-2
CO2 95.6 90.62 85.62
H2O 0.042 0.042 0.042
N2 1 1 4
Ar 1 1 1
Hydrocarbons 1 6 8
(C1, C2+)
H2 1 1 1
O2 0.00001 0.00001 0.00001
CO 0.2 0.2 0.2
H2S 0.04 0.04 0.04
SO2 0.01 0.01 0.01
NOx 0.01 0.01 0.01

SPE-207354-MS 11
CO2 with 40lb/

Higher C1 Higher C1/N2
Component MMSCF H2O
Base case Sensitivity Case-1 Sensitivity Case-2
NH3 0.005 0.005 0.005
COS 0.0005 0.0005 0.0005
Glycol 0.0000315 0.0000315 0.000315
Particulate 0.0001 0.0001 0.0001
Mercaptans / Sulfides 0.03 0.03 0.03
Total Sulfur 0.0035 0.0035 0.0035
It is important to understand the interesting impacts of impurities discussed in section 5 above on each
of the following:
a. Critical pressure and temperature
b. Saturation pressure and temperature
c. Forming an enclosed two-phase region bounded by the dew point and bubble point curves.
d. Effect on the physical transport properties of the CO2
e. Demonstrating the added risks of increasing the running ductile fracture induced by higher CO2
saturation pressures.
For all the above cases, a water specification of 20 lb/MMSCF was considered for a fair evaluation of
the impact of impurities on the thermodynamic CO2 aspects as well as the subsequent transient modelling.
Starting with the impact of the sensitivity cases on the phase envelope of the recovered CO2 streams, it
can be clearly depicted from figure 8 below that for sensitivity case-2 where a higher amount of methane
and nitrogen are present, the CO2 phase envelope involves a wider two phase zone in comparison with the
base higher purity case.
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Figure 8—CASE STUDY MODELLING FOR VARYING CO2 PURITY LEVELS
Comparing the three cases with respect to the wideness of the two phase envelop, following key
interpretations could be made:
▪ Increased critical pressure in sensitivity case-2 to as high as 85 bara in comparison with the pure CO2
critical pressure of 73 bara (figure-1).
▪ Reduced critical temperature to as low as 20 °C in comparison with pure CO2 which has a critical
temperature of 31 °C (figure-1).
Below table shows the comparison among the various cases with respect to critical pressure and
temperature:
Table 4—CRITICAL CONDITIONS FOR VARIOUS PURITY CASES
Case Critical Pressure (bara) Critical Temperature - °C
Base Case-95.6% 78 29
Sensitivity case-1- – 90% 81 24.97
Sensitivity case-2- – 85% 86 20
These key behavioral aspects determine the technical challenges encountered by the wider two phase
window in case of the increase in impurity levels of N2 and CH4 in CO2 EOR injection stream:
▪ Difficulties in maintaining the CO2 in dense/supercritical phase above the critical pressure. This has
a direct impact on the energy cost of compression and pumping.
▪ Imposing a strict operating philosophy concerning pipeline shutdown to avoid the formation of two
phase CO2.
▪ From a ductile fracture propagation perspective, the risk of CO2 decompression is higher than natural
gas due to the longer vaporization time mandated by travelling across the saturation line in case of
100% pure CO2. This is fundamentally driven by the increased critical saturation pressure due to the
SPE-207354-MS 13
inherent vaporization ability of CO2 when a transient effect occurs with concurrent depressurization,
Once the operating point crosses the saturation line, CO2 starts to exhibit higher decompression energy
with slower decompression speed in comparison with natural gas, refer to figure 9 below by DNV-
F104 [8].
This effect will be aggravated in case of a wider two-phase envelope as the decompression speed
of CO2 is expected to be on the left side of the pipe material's fracture propagating speed and hence
creates greater risk of inducing ductile fracture propagation. Further increase in critical pressure
imposes higher saturation pressure during CO2 decompression and greater risk of exceeding the
fracture pressure of the pipe material.
▪ Larger pipeline toughness is required for preventing the higher risk of ductile fracture propagation in
the event of higher saturation pressure (wider envelope and higher critical pressure) higher impurity
cases. This is in order to maintain the fracture propagation curve above the decompression speed
curve of CO2 and such that the pressure at the tip of the initiated fracture (when occurred) will always
be less than the fracture arrest pressure [8].
Figure 9—FRACTURE PROPAGATION OF CO2 VERSUS NATURAL GAS [8]
The case study was further extended to model the steady state pressure profile for a 14’’ 90 KM CO2
pipeline transporting 150 MMSCFD to the injection station which mandates a battery limit arrival pressure
of 245 barg. The demonstration of the impact of the impurities on the hydraulic pressure profile of this dense
phase CO2 pipelines presented in figure 10 below. The figure establishes that as the level of nitrogen and
methane increases for the 85% purity case (Sensitivity Case-2), the backpressure required downstream the
pumping station increases in comparison with the base case 95.6% purity.
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Figure 10—HYDRAULIC PRESSURE PROFILE OF 90 KM 14" PIPELINE WITH FIXED ARRIVAL PRESSURE OF 245 BARG
Table-5 below summarizes the required backpressure among the three cases:
Table 5—BACKPRESSURE REQUIREMENTS FOR VARIOUS PURITY LEVELS
Required backpressure
Case at the inlet of the
pumping station (barg)
Base Case-95.6% 275
Sensitivity case-1- – 90% 277
Sensitivity case-2- – 85% 280
The above is supported by the impact of the increase in impurities on the density of CO2, which is
portrayed in figure 11 below at a pressure of 275 barg for all curves. As the methane and nitrogen increase
in the CO2 stream, the density of the fluid decreases in comparison with the base high purity case. The
reduction in the density for the same transported CO2 quantity increases the velocity in the pipeline, which
consequently increases the encountered pressure drop.
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Figure 11—DENSITY OF VARIOUS CO2 PURITY CASES AGAINST TEMPERATURE
Demonstration shown in this section concerning the impact of impurities on CO2 phase envelope is in
good agreement with numerous literature publications that validate the impact of impurities such as N2, H2
and CH4. Energy Institute's standards depicted the widening effect of 5%-10% N2 on the CO2 resulting in an
elevated critical pressure of 80 barg (in comparison with pure CO2 critical pressure of 73 barg) and reduces
the critical temperature to 30 °C [1]. IPCC study (special report on carbon capture-UK-2005) revealed the
shifting in the CO2 widom saturation line towards 80 barg critical pressure even when CO2 purity was 96%
due to the combined presence of N2, CH4 and CO with H2 present at 2 mol% [1]. Hydrogen was found to be
the impurity with the most significant impact on CO2 Phase envelope [1]. Energy Institute also demonstrated
the impact of the impurities on CO2 density at a constant temperature of 4 °C and over a wide range of
pressure with 2% impurity level in each case, it also supports the fact that hydrogen and nitrogen have
significant impacts on density reduction [1].
Additionaly, the effect of pressure reduction on the density for sensitivity case-2 with 85% purity can
be clearly illustrated from figure 12 below where at 80 barg, the density reaches as low as 750 Kg/m3 in
comparison with figure 4 in section 3 where the base case 95.6% density reaches as high as 950 Kg/m3.
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Figure 12—DENSITY VARIATIONS FOR SENSITIVITY CASE-2
Effects on Water Solubility & Hydrate Formation

As explained in section 4, water specifications is the core parameter for ensuring safe transportation of CO2
in carbon steel pipeline. Any decline in water solubility with potential water condensation will induce risks
of corrosion attacks on the pipeline and subsequent failures. Unfortunately, there is a paucity of industrial
practiced on the investigation of water solubility in CO2 at various impurity levels. However, active R&D
has been empirically exploring the impact of multi-component CO2 mixtures on the water solubility [5].
Experimental testing was done by Ahmad et al. [5] for CO2 over a temperature and pressure range between
5-35 °C and 90-150 bar respectively. The presence of N2, O2 and CH4 along with CO2 contributed to
significant reduction in water solubility by 200 ppmv [5].
Therefore, in order to align the practical modelling established for this paper with literature analysis of
the impact of impurities on the water solubility in dense phase CO2, CPA-infochem was used to generate the
water drop out zone for each of the CO2 cases listed in table 3: base case 95.6%, sensitivity case-1 90% and
sensitivity case-2 85%. It must be noted that all cases considered the same water dehydration specification
of 20 lb/MMSCF. Refer to figure 13 below for the findings of the OLGA modelling:
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Figure 13—MODELLING OF VARYING PURITIES WATER DROP OUT CURVE
Comparing the base case of 95.6% CO2 purity to the other two lower purity cases, it can be clearly
apprehended that the risk of decline of water solubility is more prominent as the amount of C1 & N2 increases
in the recovered CO2. The blue curve representing the 85% CO2 purity (with a total of 12% of C1/N2)
imposes the limitation of forming free liquid water in the pipeline at a pressure of 48 barg in comparison
with a more comfortable range of operating pressure of 37 barg for the 95.6% purity CO2. Moreover, the
water drop out envelope shifts further to the right towards higher operating temperature (4 °C for the 85%
purity versus 1 °C for the 95.6% purity). Such model findings are congruent with the literature. Accordingly
the below precautions are to be considered:
▪ Increase in the N2 content as well as CH4 lighter hydrocarbons fraction in CO2 will impose more
conservative operating limits with regards to shutdown and pipeline depressurization.
▪ It is imperative for the design to perform CO2 flow assurance studies at early stages of project design
in order to establish the safe operating envelope of the CO2 system which can be jeopardized by not
only a wider two phase envelope but also higher water dew point temperature and pressure.
Sufficient degree of dehydration is a key strategy for prevention of hydrate formation and water drop
out during transportation. However due to the underlying meta-stable hydrate formation in absence of free
water and the paucity of the demonstrated impact of impurities on the stability of the L-V-S equilibrium of
CO2, operating procedure shall dictate frequent inspection of pipeline, instrumentation and valves to ensure
that any formed hydrates would not lead to dangerous blockages and damage to pipeline when dislodged
during operation. The concern mainly arises in offshore pipeline where the risk of hydrate formation drives
the specification of water content in transported CO2 [1, 3].
It is cautioned not to consider utilizing existing CO2 pipeline, which are designed for higher purities, to
transport CO2 at lower purities unless careful flow assurance analysis is conducted to eliminate all envisaged
risks as explained above.
18 SPE-207354-MS
Transient Modelling
Taking into consideration the absent current demonstration of the effects of impurities on the transient
operation of CO2 such as depressurization under maintenance and depressurization scenarios as well as
rupture leak incidents, this section establishes the performed OLGA modelling for depressurizing 14’’ –
95 Km pipeline from a maximum operating pressure of 255 barg. The vent is located at an intermediate
pipeline block valve station and the current modelling considers depressurization of the segment on the
upstream of the BVS.
For each of the CO2 purity cases presented in table 3, depressurization is performed until near atmospheric
pressure is reached in the pipeline. The outcomes of the modelling are compared with respect to the
following key significant parameters:
▪ Rate of depressurization
▪ Extent of isentropic expansion.
▪ Pressure profile during depressurization
▪ Degree of transgression into the two-phase envelope and the intersection of the water drop out zone.
The three depressurization trends are presented in figure 14 below. Leak-1 represents the base case
95.6%, leak-2 is sensitivity case-1 90% while leak-3 is sensitivity case-2-85% purity. The pressure profile
demonstrates that the rate of depressurization, after roughly 1 hour, becomes higher for sensitivity case-2 in
comparison with the high purity cases of 95.6%. This can be interpreted from the higher slope of pressure
profile of sensitivity case-2 (Leak-3 in figure 14). Such behavior is supported by the operating trajectory
of the subject case against the phase envelope in figure 15 where a sharp red line is abruptly crossing the
phase envelope with a prolonged dominance in the two phase envelope. The wider two phase envelope
(red curve in figure 15 for sensitivity case-2) makes depressurization faster after the operating point hits
the dew point line due to the presence of light impurities (N2 & CH4). Similarly, if we superimpose figure
13 which represents the water drop out and hydrate formation curves on figure 15, the risks of water drop
out and hydrate formation associated with sensitivity case-2 cannot be dismissed. Such superimposition is
portrayed by figure 15.
Figure 14—Pressure - time depressurization profile (leak-1 = 95.6% purity, leak-2= 90% purity, leak-3 = 85% purity)
SPE-207354-MS 19
Figure 15—Operating trajectory during depressurization for varying CO2 purity case (table-3)
Studying the thermal profile of the system under depressurization for each of the CO2 purity cases, it can
interpreted from figure 16 below that:
▪ The Joule Thompson expansion are more prominent in sensitivity case-2 pertaining to the presence
of light CH4 and N2 in comparison with the base case having predominantly the CO2 in liquid phase.
The initial temperature drop is sharper than the base case where the latter is maintaining warmer
temperature for the first 34 hours.
▪ The minimum locus of temperature profile for the lower purity cases occurs quite earlier than the
minimum locus for the higher purity case. This is driven by the lighter heat capacity of the fluid
stream and the higher joule Thompson coefficient as explained above. The same increase in Joule
Thompson coefficient is supported by Aghajani et al. [4].
▪ Isentropic expansion is almost absent in the case of sensitivity-1 & 2 in comparison with the
delayed depressurization for the base case (95.6% purity) which takes place after 23 hours from the
temperature dip of lower purity cases (leaks-2&3).
▪ The width of the temperature dip for each of the considered purity cases is longer for sensitivity cases
-1 & 2 (90% & 85%) in comparison with the high purity case (95.6%), this is mainly supporting the
isentropic expansion by higher liquid hold up in case of higher purity CO2.
▪ The pressure inside the pipeline throughout the depressurization process is higher for the sensitivity
cases-1 &2 in comparison with the base case. Pressure at the minimum temperature for 85% purity
case is 50 barg in comparison with 36 barg pressure experienced at the minimum temperature point
for the 95.6 % purity.
20 SPE-207354-MS
Figure 16—Temperature depressurization profile versus time (leak-1 = 95.6% purity, leak-2= 90% purity, leak-3 = 85% purity)
Based on the above results, it is established that the minimum temperature for all three cases is almost the
same. However, cautions are raised against sensitivity cases -1 & 2 where there is concern of having a higher
operating pressure inside the pipeline in conjunction with lower early temperature drop as well as longer
exposure time to that minimum temperature dip. Low purity cases induced greater potential exposure of the
pipeline material to higher stress induced by low temperature and higher pressure as well as less available
time for operator's intervention. On the other hand, higher purity base case exhibits delayed depressurization
cryogenic effects, this is due to the delayed liquid CO2 vaporization phenomena. Delayed depressurization
along with lower pressure inside the pipeline provides greater advantage to the integrity of the pipeline
during depressurization.
Furthermore, the higher pressure experienced during sensitivity-2 blowdown case supports the concern
raised in section 5 regarding the ductile fracture propagation phenomena and dictates increased pipeline
toughness in early design stages.
Conclusion & Recommendations

This paper highlights the significance of flow assurance modelling for CO2 pipeline systems especially when
proposals to reduce the purity levels of the injection CO2 streams are introduced. There are various downside
effects demonstrated by the conducted transient modelling for the increase in N2 and light hydrocarbons
(such as CH4) in recovered CO2 from capturing units. The performed transient OLGA modelling introduces
novel interpretations of the dynamic behavior of CO2 operating envelopes and is interpreted to be well
aligned with the limited available published literature on the effects of impurities on CO2 properties.
Although it may sound economically attractive to slip specific impurities with the captured CO2, however,
listed below are the non-dismissible crucial effects to be taken into consideration as part of CO2 pipeline
surface facilities design:
▪ Higher critical pressure associated with higher level of impurities mandates higher compression duty
for maintaining the CO2 in dense phase throughout the pipeline length.
▪ Increased compression/pumping requirements as a result of higher pressure drop for the higher
content of impurities with CO2 stream.
▪ Increased vapor pressure leading to greater susceptibility to running ductile fractures.
▪ Tendency for water dropout across the pipeline, which imposes more CAPEX/OPEX on the CO2
dehydration design loads to meet the water specification of the recovered CO2.
▪ Greater risk of CO2 hydrate formation impacting pipeline integrity especially under transient
conditions and prolonged shutdown scenarios.
SPE-207354-MS 21
▪ Increase in J-T coefficients leading to increased cryogenic effects of CO2 due to higher exposed
pressure during depressurization.
▪ Strict operating philosophy for maintaining the operating conditions (temperature, pressure) above
the two-phase envelope and water drop out zone, which tends to be wider under higher content of
impurities.
Nomenclature
CCUS Carbon Capture Units Systems
EOR Enhanced Oil Recovery
CO2 Carbon Dioxide
CAPEX Capital Cost
OPEX Operating Cost
MMSCFD Million Standard Cubic Feet per Day
J-T Joule Thompson
BVS Block Valve station
References
1. Good Plant Design and Operation for Onshore Carbon Capture Installations & Onshore pipeline,
Energy Institute, London, September 2010
2. K34: Flow Assurance Technical Transport, White Rose, November 2015
3. Ooosterkamp, A., Ramsen, J. (2008) State of the Art Overview of CO2 Pipeline Transport with
relevance to offshore pipeline".
4. Wetenhall, B., Aghajani, H., Chalmers, H., Benson, S.D., Ferrari, M-C., Li, J., Race, J.M.,
Singh, P. and Davison, J. (2014) "Impact of CO2 impurity on CO2 compression, liquefaction and
Transportation". Energy Procedia 63, 2764-2778.
5. Ahmad, M. and Gersen, S. (2014) " Water Solubility in CO2 Mixtures: Experimental and
Modelling Investigation". Energy Procedia 63, 2402-2411.
6. Ruden, T., Liu, L., Amundsen, J., Xu. Z., Selberg. M., Haugset. T, Langsholt. M., Liu. L. and
Amundsen. J. (2014) "Simulating Flow of CO2 with Impurities in OLGA, Dealing with Narrow
Phase Envelopes and the critical Point". Energy Procedia 63, 51, 344–352
7. Wang, D., Zhang, Y., Adu, E., Yang, J., Shen, Q., Tian, L. and Wu,L. (2016) "Influence of Dense
Phase CO2 Pipeline Transportation Parameters". International Journal of Heat and Technology,
Vol.34 No.3.
8. DNV-RP-F104, Design and Operation of CO2 Pipelines
9. CO2 Facilities, John Campbell, 1215 Crossroads Blvd, Norman, Oklahoma 73072

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Understanding CO2 Phase Behavior

Figure 1—PURE CO2 PHASE DIAGRAM [8]

Figure 2—COMPARISON BETWEEN 100% PURE CO2 AND 95.6% CO2

Favorable Technoeconomic CO2 Pipeline Features

CO2 & Pipeline Integrity

Impurities in Captured CO2

Table 1—TYPICAL OFFGAS COMPOSITION TO CCUS FROM SRU AMINE REGENERATOR

Parameter (Note) Unit Value

Temperature Deg C 49.8

Pressure Barg 0.06

H2O mole % 10.8

COS mole % 0.126

Argon mole % 0.7

Table 2—TYPICAL HC BREAKTHROUGH CO2 RICH COMPOSITION

CO2 Rich Breakthrough

Parameter Unit Value

Pressure Barg 15.36

H2O mol% 2.4

H2S mol% 2.8

CO2 mol% 50.8

Nitrogen mol% 0.2

Methane mol% 28.6

Ethane mol% 5.7

Propane mol% 4.3

i-Butane mol% 0.9

n-Butane mol% 1.8

22-Mpropane mol% 0.0

i-Pentane mol% 0.6

n-Pentane mol% 0.6

Mcyclopentan mol% 0.1

psuedoC6* mol% 0.5

Cyclohexane mol% 0.1

psuedoC7* mol% 0.3

CO2 Rich Breakthrough

Parameter Unit Value

Mcyclohexane mol% 0.3

Case Study & Effects on Phase Envelope

Table 3—COMPOSITION ANALYSIS FOR EFFECT OF THE IMPURITIES

CO2 with 40lb/

Base case Sensitivity Case-1 Sensitivity Case-2

CO2 95.6 90.62 85.62

H2O 0.042 0.042 0.042

O2 0.00001 0.00001 0.00001

CO 0.2 0.2 0.2

H2S 0.04 0.04 0.04

SO2 0.01 0.01 0.01

NOx 0.01 0.01 0.01

CO2 with 40lb/

Base case Sensitivity Case-1 Sensitivity Case-2

NH3 0.005 0.005 0.005

COS 0.0005 0.0005 0.0005

Particulate 0.0001 0.0001 0.0001

Mercaptans / Sulfides 0.03 0.03 0.03

Total Sulfur 0.0035 0.0035 0.0035

Table 4—CRITICAL CONDITIONS FOR VARIOUS PURITY CASES

Case Critical Pressure (bara) Critical Temperature - °C

Sensitivity case-1- – 90% 81 24.97

Sensitivity case-2- – 85% 86 20

Figure 9—FRACTURE PROPAGATION OF CO2 VERSUS NATURAL GAS [8]

Table 5—BACKPRESSURE REQUIREMENTS FOR VARIOUS PURITY LEVELS

Base Case-95.6% 275