Documente Academic
Documente Profesional
Documente Cultură
of
CO2 Pipeline Transport with relevance to offshore
pipelines
Antonie Oosterkamp
Joakim Ramsen
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Date
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Title:
Project number:
Report number:
E-0751
Number of pages:
POL-O-2007-138-A
Principal investigator:
Security level:
Antonie Oosterkamp
Date:
Open
Client:
87
Authors:
Antonie Oosterkamp
Joakim Ramsen
Client reference:
182603/I30
Summary:
This report provides the results of a study of the existing experience regarding the design
and operational aspects of CO2 transport by pipeline with relevance to future application
on the Norwegian Continental Shelf. The effect of expected new conditions like higher
pressures, offshore environment and impurities present in the CO2 mixture are taken into
account. The report concludes by summarizing the remaining uncertainties and R&D
needs that were identified in this study. In addition, an overview of competence holders is
given.
Principal Investigator
ANTONIE OOSTERKAMP
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Table of Contents
1
List of abbreviations ........................................................................................................... 5
Summary .................................................................................................................................... 6
2
Introduction ...................................................................................................................... 12
3
Existing CO2-pipelines ..................................................................................................... 13
4
Properties of Pure CO2 ..................................................................................................... 15
5
Expected Mixtures from Different Sources ..................................................................... 20
6
Effect of Impurities .......................................................................................................... 22
6.1 Density, Viscosity and Vapor Pressure ..................................................................... 22
7
8
9
10
11
12
13
14
15
16
6.2
6.3
9.3
9.4
9.5
Gaskets....................................................................................................................... 35
9.6
Metals ....................................................................................................................... 35
9.7
Hydrates ................................................................................................................ 40
10.4
16.3
Blowdown/depressurization .................................................................................. 60
16.4
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17
18
19
20
21
22
23
19.3
Weyburn Pipeline.................................................................................................. 68
19.4
20.3
20.4
20.5
Modeling ............................................................................................................... 75
20.6
20.7
References ........................................................................................................................ 78
Appendix 1 Details about existing CO2 pipelines ........................................................... 82
Appendix 2 Overview of Identified Competence Holders .............................................. 86
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1 List of abbreviations
BWRS
CCS
C-Mn Steel
DCG
DEG
EOR
EoS
ERW
HES
MAOP
MEG
MMP
LBC
LDS
LK
LNG
NIST
PA
PCTFE
PMS
PP
PPS
PR
PT
Benedict-Webb-Rubin-Starling
Carbon Capture and Storage
Carbon Manganese Steel
Dakota Gasification Company
Diethylene Glycol
Enhanced Oil Recovery
Equation of State
Electro Resistance Welding
Health, Environment and Safety
Mean Allowable Operating Pressure
Monoethylene Glycol
Minimum Miscibility Pressure
Lohrenz-Bray-Clark
Leak Detection System
Lee-Kessler
Liquified Natural Gas
National Institute of Standards
Polyamide
Polychlorotrifluoroethylene
Pipeline Modelling System
Polypropylene
Pressure Protection System
Peng-Robinson
Patel-Teja
PTFE
PTV
PVDF
PvT
Polytetrafluoroethylene
Patel-Teja-Valderama
Polyvinylidene fluoride
Pressure, volume , temperature
R&D
RK
RKS
SCADA
Redlich-Kwong- Soave
Supervision, Control and Data Acquisition
SSC
STEL
TEG
VLE
Triethylene Glycol
Vapour Liquid Equilibrium
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Summary
Transport of CO2 by pipeline will be necessary if large volumes of captured CO2 are to be
stored in geological formations at short to medium distance from the capture location. For a
number of countries, including Norway, the preferred storage locations will be offshore,
necessitating offshore pipelines between the capture and storage facilities. This report gives
an overview of the state-of-the-art of pipeline transport of CO2 of relevance for offshore
conditions. It provides an assessment what will be novel in an offshore context. The
implications of new capture sources on CO2 pipeline transmission systems are looked into.
The remaining uncertainties identified in this study concerning offshore transmission of CO2
with impurities present in the CO2 fluid stream are provided. The report concludes with
suggestions for the research and development needs to address these uncertainties.
CO2 transport by pipeline is routinely done in the USA for over 30 years. The existing
pipelines in the USA are land based and divided into relatively short sections; this reduces the
blow down and refilling times and limits the risk to the public in case of leaks. For offshore
pipelines this is expected to be different. The main block valves and metering will be located
at the inlet and outlet only; sectioning of offshore parts of the pipeline may not be a viable
option.
To transport CO2 efficiently by pipeline, the pressure is kept over the critical point and the
fluid is transported in dense phase.
Important properties of CO2 at typical operating conditions (dense phase) are:
Low viscosity.
Acts as a solvent.
The fluid composition of the CO2 to be transported depends on the source. Typically the CO2
originates from natural deposits and the fluid stream is relatively pure; few other components
are present. A pipeline will be designed for a long life time. Thus it can be expected that the
fluid composition in the pipeline will change when different capture sources are connected to
the pipeline infrastructure. The new capture methodologies can give lead to new compounds
in the captured stream for which there is little or no experience within CO2 transport.
Currently, no CO2 quality requirements have been decided upon that take into account these
new compounds.
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Toxicity: it can be impurity concentrations that determine the safe exposure limits for
the fluid instead of CO2 concentration.
Vapor pressure: raising of the vapor pressure means that higher minimum entrance
pressure or shorter recompression/booster station intervals are needed to keep the fluid
in dense phase.
Pipeline integrity: The vapor pressure sets the decompression pressure at a pipeline
break. Thus a high decompression pressure can facilitate further propagation of a
fracture. Presence of atomic hydrogen can lead to hydrogen embrittlement of the
pipeline steel or hydrogen induced cracking. Sulphide Stress Cracking (SSC) has to be
taken into account with presence of H2S (requirement for sour service).
Corrosion.
For pure CO2 there are developed reference equations of state (EoS) providing highly accurate
calculations. For the relevant CO2 mixtures, there is generally very limited data published
about the applicability of existing EoSs and the applicable mixing rules and parameters.
There is no real consensus which EoS should be used in flow modeling of CO2 pipeline
transport when the CO2 contains impurities. With respect to viscosity calculations, accurate
correlations have been developed for pure CO2. Within the course of this study not many
references were found to viscosity measurement data for the relevant CO2 mixtures. A search
and review of available thermodynamic data for the relevant CO2 mixtures concluded with
that measurements of PvT and VLE data at conditions relevant for CO2 pipeline transport are
few. This was found to be the case for binary mixture data for CO2 with components like H2,
SO2, NO, O2, CO, COS and Ar as well as multi component mixtures.
To transport CO2 in the dense phase has its effect upon the material selection process during
design. Care has to be taken when selecting materials and compounds for gaskets, valve seats,
sealants, coatings and lubricants. CO2 gives rise to higher susceptibility for explosive
decompression of elastomers in seals and gaskets.
When liquid water is present, CO2 will partially dissolve and form carbonic acid. This will
give rise to corrosion problems with the steel alloys commonly used in pipelines. Carbon steel
(C-Mn) can be used in the absence of free water. No corrosion problems have been reported
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where the CO2 is suitably dry or when stainless steel alloys are used. At high partial pressures
the existing models tend to overestimate the corrosion rates. In addition, the concentrations
and types of other impurities present in the CO2 mixture may influence the corrosion rates.
The mechanism of CO2 corrosion in the presence of impurities is not understood entirely.
There are different practices regarding the allowable water contents specifications used for the
existing CO2 pipeline systems. There are remaining uncertainties how to set the maximum
allowable water contents for a CO2 pipeline. The minimum water solubility limit at
operational conditions might be a non-conservative limit. The water contents in the CO2 may
also lead to the formation of hydrates. An offshore pipeline on the Norwegian Continental
Shelf will along most of its length transport CO2 within the hydrate stable region. Hydrates
will form when free water is present but might also form when the water contents is under the
saturation limit. What the effect is of impurities on both water solubility and hydrate
formation is another area of uncertainty.
CO2 pipelines are considered to be more susceptible to fast propagating ductile fractures than
gas pipelines. The first CO2 pipelines in the USA were designed with relatively short distance
between fracture arrestors. Alternatives to address the risk of running ductile fractures are to
increase the wall thickness or through use of material with higher fracture arrest properties.
The existing models for assessing fracture arrest are based upon tests with hydrocarbon
gasses. They are not necessarily directly applicable for use with CO2 pipelines without
additional experimental assessment.
Heat loss and elevation terms must be included in the energy balance calculations underlying
pressure drop estimation.
With respect to flow modeling, the sensitivity of density to temperature will make it more
difficult to predict flow for an offshore CO2 pipeline. Generally, offshore pipelines will have
less measurement points along the way to tune the thermal model used in simulating the flow
conditions. This means that accuracy of capacity calculations and leak detection for long
offshore pipelines will be more reduced compared to a sectored land based system.
Measurement and instrumentation is in principle similar to that used for natural gas pipelines.
For any instrumentation used on CO2 pipelines, the special requirements regarding material
choice of sealants and gaskets for dense phase CO2 have to be taken into account. For a CO2
pipeline made from carbon steel, measurement of actual water contents at the pipeline
entrance is a necessity.
Integrity monitoring of land based CO2 pipelines is typically done by visual inspection and
use of corrosion coupons. Integrity assessment of the pipeline with a smart pig is also viable,
but very few inspections runs with smart pigs are reported. Inspection pigging of CO2
pipelines is not routinely done and regarded as more difficult than natural gas pipeline
pigging. The big concern is the friction wear through the line. Two pipelines with
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computational leak detection systems have been identified within this study that use real time
transient modeling. CO2 is considered as a challenging fluid for computational leak detection.
Most important for leak detection of CO2 is the thermal modelling capability. Uncertainties
remain regarding the interaction of the escaping CO2 from a leak in a subsea pipeline with the
surrounding seawater.
A number of relevant issues regarding the operation of CO2 pipelines were identified:
RFO (Ready For Operation)
Dewatering and drying is even more critical than is the case with a natural gas
pipeline. It is advised to have a dewatering/drying strategy for all components of the
pipeline.
Care has to be taken during initial filling up of the pipeline to avoid rapid cooling
down of the expanding CO2 fluid behind the inlet valve.
Pressurizing with nitrogen after hydrostatic testing will allow for the detection of
remaining leaks that do not show up during hydrostatic testing with water.
Blow down/depressurization
The blow down facility must be specifically designed for CO2.
A blow down should be controlled through slow depressurization and sufficient heat
transfer from the ambience. For offshore pipelines we can expect that this is more
challenging as they are not likely to be sectored as land based pipelines.
The danger exists that low temperatures can cause instability of the pipeline due to the
freezing of the surrounding medium.
Stop and Start procedures
Dynamic effects should be considered.
Care must be taken to avoid large temperature drops over valves.
Health, environmental and safety risks are mostly associated to the release of CO2 to the
ambience. CO2 is an asphyxiant: it has an effect upon the respiratory system already at low
ambient concentrations. It is important to notice that CO2 is heavier than air so it will collect
in low laying terrain. Exposure to a stream of expanding CO2 can cause cold burn of the skin.
The expansion of the gas during the phase transition will also give a thrust, potentially
displacing a pipeline in case of a leak. When leaks occur, toxic impurities can be setting the
safe limits rather than the CO2 itself. This is specifically the case with H2S and SO2.
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Water content.
o Further investigation in to the effect of the impurities on water solubility, the
availability of experimental data and possibly further development of the
thermodynamic models to calculate the solubilities for actual CO2 mixtures.
This with the objective to be able to set safe water specifications.
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Blow down/Depressurization
o Modelling combined with experimental verification to set safe regimes for
depressurization of long offshore pipelines. If possible, link this to ongoing
work regarding this theme at StatoilHydro and SINTEF.
Fracture Propagation
o An assessment has to be made if fracture propagation is a real threat to CO2
pipelines and if the existing requirements from the design code are enough to
arrest a fracture. This assessment should include the applicability of existing
propagation models for CO2 pipelines and what work should be done to update
the models and the existing requirements.
Fluid Specification
o The potential chemical reactions between the impurities under relevant time,
pressures and temperatures and the potential negative effects of the products
need to be mapped. A specification should be made and agreed upon that
specifies for allowable levels of impurities in the CO2 for pipeline transport.
This is currently addressed in the EU Dynamis project. A link between this
project and the governmental projects for CCS from Krst and Mongstad
regarding setting of transport specifications in relation to the end use of the
CO2 would be advisable.
Correspondence to: A.Oosterkamp, Polytec R&D Foundation, Stoltenberggt.1, N-5527, Haugesund, Norway.
E-mail: oosterkamp@polytec.no
Reference to part of this report which may lead to misinterpretation is not permissible. The authors and Polytec
disclaim any liability to the client and to third parties in respect of the publication, reference, quoting, or
distribution of this report or any of its contents to and reliance thereon by any third party.
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2 Introduction
A better understanding of the relationship between CO2 emission and climate change has been
gained in the last decades. Therefore several projects around the world investigate the
possibility of capturing the CO2 resulting from burning fossil fuels and injecting it for storage
into geological formations. This can be one of the possible measures to avoid global warming.
The storage location will not necessary be located near the source. Thus an extensive transport
system must be applied. For large volume and short to medium distances, pipeline transport is
usually more cost effective than the other alternative, ship transport. For several countries the
actual storage locations will be located offshore e.g. Norway and the U.K.
Norway has a long experience with offshore pipeline transport of natural gas. In pipeline
transport, CO2 as a fluid shows behavior and properties that differ from natural gas. During
the last three decades, a lot of experience has been gained with land based transport in the
USA. Unfortunately, it is not easy to get a complete overview of design and operational
issues. The available literature describes either only some of the relevant aspects and/or is
relatively old. The only existing offshore pipeline for transporting CO2 is the Snhvit pipeline
which is due for operation. The relatively short timeline in capture projects at Krst and
Mongstad make it necessary to gain more knowledge about CO2 transport before operational
experience from Snhvit becomes available. In this report, the existing knowledge from land
based CO2 transport has therefore been included where relevant.
This report is the result of a 7 month study. The information gathering process comprised a
literature study, personal communication to experts and visits to CO2 pipeline operators in the
USA. The report gives an overview of the state-of-the-art, references to relevant literature,
overview of relevant competence holders and discussion of issues that need to be adressed.
The main focus has been to identify critical issues related to offshore pipeline transport, the
effect of expected impurities in the CO2 and the remaining R&D needs. References to
literature are given in the text. An overview of the relevant competence holders identified in
the course of this study is included in Appendix 1.
Acknowledgements are hereby given to the Norwegian Research Council, Gassco and Shell
Technology Norway for funding this study. We like to thank everybody who has contributed
to this study through interview, personal communication and sharing of their professional
opinion.
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3 Existing CO2-pipelines
An overview of the majority of the existing long CO2 pipelines is given in Table 3-1 below.
Table 3-1: Overview of some existing long CO2 pipelines
Name of pipeline
Operator
NEJD Pipeline*
Cortez Pipeline*
Bravo Pipeline
Transpetco Bravo Pipeline
Sheep Mountain part 1*
Sheep Mountain part 2 *
Central Basin Pipeline*
Este Pipeline
West Texas Pipeline
SACROC pipeline
Denbury Resources
Kinder Morgan
BP
Transpetco
BP
BP
Kinder Morgan
Exxon Mobil
Trinity
Weyburn Pipeline*
Canyon Reef Carriers
Bati Raman
Snhvit*
Dakota
Gasification
Company
Kinder Morgan
Turkish Petroleum
StatoilHydro
Length
(km)
295
808
350
193
296
360
191
204
354
Diameter
(in)
20
30
20
12
20
24
26 and 16
12 and 14
8 to 12
16
Capacity
(MT/year)
330
12 to 14
4.6
225
90
153
16
4.6
1.1
0.7
19.3
7.3
3.3
6.3
9.2
11.5
4.8
1.9
4.2
Country
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
USA
Turkey
Norway
All the pipelines shown in Table 3-1 are land based pipelines except Snhvit, which is the
first offshore CO2 pipeline. The Snhvit pipeline is planned to start-up in the fourth quarter of
2007.
The CO2 transported in the Snhvit pipeline is captured from natural gas from the Snhvit
field. The high CO2-contents from this gas is reduced before it is processed to Liquified
Natural Gas (LNG) at Melkya. One of the first pipelines designed and installed is the
Canyon Reef Carriers which started operation in 1972. The land based pipelines are typically
divided in sections by several valve or compressor stations where instruments are installed to
monitor, pressure and temperature. The CO2 typically originates from natural deposits and is
used for Enhanced Oil Recovery (EOR). The fluid consists of minimum 95% CO2, see
Chapter 8 for quality requirements. The pipelines are designed to operate above the critical
pressure so that two-phase flow is avoided. The pressure is typically below 200 bara. The
short distance (< 30 km) between main block valves, reduces the time for blow
down/depressurization and refilling operations. This also reduces the environmental
consequences of a pipeline rupture.
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Figure 3-2: Ground entry of a land based CO2 pipeline, Jackson Dome operated
by Denbury Onshore LLC.
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Critical point
Triple point
It is important to note that pure CO2 has a triple point at -56.6 C and 5.18 bara. It has its
critical point at 30.9782 C and 73.773 bara. This has its implications for both compression
and transport conditions. Note that above the critical point CO2 will not be able to separate in
two phases (except at very low temperature or high pressure where solid CO2 can form).
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Dense phase
Liquid
Gas
Two phase
This diagram can be used to estimate how the temperature changes during de-pressurization,
e.g. over a valve. Note the isotherms are almost vertical at low temperatures. This means that
a throttling in this region (liquid) will not alter the temperature significantly as long as the
CO2 is kept in one phase. The Pressure-Enthalpy diagram is also used to visualize the
thermodynamic path for compression and pumping. It can be seen from the diagram that in
the liquid region relatively low energy input is necessary to increase the pressure, compared to
compression of the gas (isentropic lines are steeper).
For all the relevant thermodynamic properties and its viscosity the reference is the NIST
chemistry webbook (3).
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Figure 4-3 below shows the density as function of temperature and pressure.
Density
1100
1000
900
Density [kg/m3]
800
700
600
200 bara
500
150 bara
400
100 bara
300
80 bara
200
100
0
0
10
20
30
40
50
60
Temperature [C]
As can be seen from Figure 4-3 above, the density of CO2 has a stronger dependency on
temperature than pressure at lower temperatures.
It can also be seen that the density is very sensitive to small temperature changes near the
critical point. Density is an important factor in flow calculations. This means that accurate
knowledge of inlet temperature, ambient temperature and heat transfer is necessary to model
the flow correct, especially if conditions are close to the critical point.
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It is the combination of high molecular weight and low compressibility factor (Z-factor) that
makes CO2 density so temperature dependent. The compressibility factor at different
temperatures and pressures is shown in Figure 4-4 below. Figure 4-4 shows that ideal gas
assumption for CO2 is not applicable. The compressibility factor is used to alter the ideal gas
equation to account for the real gas behaviour. For an ideal gas, the Z-factor will be one,
independent of pressure and temperature. The compressibility factor needs to be taken into
account to give correct density in flow calculations.
Z-factor
0.7
0.6
Z-factor [-]
0.5
0.4
80 bara
0.3
100 bara
0.2
150 bara
200 bara
0.1
0
0
10
20
30
40
50
60
Temperature [C]
Figure 4-4: Compressibility factor (z-factor) at different pressures and temperatures (3)
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Viscosity
0.14
0.12
Viscosity [cP]
0.1
0.08
200 bara
150 bara
0.06
100 bara
0.04
80 bara
0.02
0
0
10
20
30
40
50
60
Temperature [C]
CO2 has a low viscosity compared to some other high density fluids; e.g. olive oil (80 cP),
water (0.89 cP). Viscosity of CO2 versus temperature at different pressures is shown in Figure
4-5. As can be seen from the figure above, also the viscosity of CO2 shows a strong
temperature dependency, especially near the critical point.
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Canyon
Reef
Carriers (4)
Central
Basin
Pipeline (5)
Sheep
Mountain
(6) (7; 8)
Bravo
Dome
Source (9)
Cortez
Pipeline
(10)
Weyburn
(11)
Jackson
Dome,
NEJD
CO2
85-98
98.5
96.8-97.4
99.7
95
96
CH4
0.2
1.7
1-5
0.7
N2
2-15
C6H14
<0.5
98.799.4
Trace
1.3
0.6-0.9
0.3
H2S
<200 ppm
< 20 ppm
(spec)
<10 ppm wt
(spec)
257 ppm wt
--
0.002
<300
ppm
0.9
0.3-0.6
-
Trace
-
129 ppm wt
257 ppm wt
C2+
CO
O2
NOx
SOx
H2
Ar
H2O
50 ppm wt
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Trace
2.3
0.1
<50 ppm wt
Trace?
20 ppm vol
Different methods are under development to mitigate anthropogenic emissions of CO2. The
R&D focus is mainly on power production with CO2 capture since this industry is a large
emitter. The three main methods for power production with CO2 capture are:
Trace
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Within these methods different capture technologies can be used which will produce CO2 with
different levels of impurities. For Post-Combustion, the absorption technology using amines
is considered to be a technology that will be used in near future, which provide very pure
CO2. The impurity levels present in the CO2 mixture resulting from Pre-combustion or
Oxyfuel will vary with the capture technologies employed.
Table 5-2 below shows typically compounds that can be present from different technologies.
Their exact concentration will depend on several factors, but without purification and cocapture of other compounds, the maximum level indicated here can be reached. Especially
SO2 and H2S will normally be present in the final CO2 mixture in much lower concentration
than the maximum levels indicated in this table.
Table 5-2: Compounds from different power production methods with CO2 capture. :ote these are
indicative maximum values and not most likely values.
Post-Combustion1 (12)
CO2
CH4
N2
H2S
C2+
CO
O2
NOx
SOx
H2
Ar
COS
>99 vol%
<100 ppmv
<0.17 vol%
Trace
<100 ppmv
<10 ppmv
< 0.01 vol%
< 50 ppmv
<10 ppmv
Trace
Trace
Pre-Combustion
(13) (12)
>95.6 vol%
<350 ppmv
<0.6 vol%
<3.4 vol%
<0.01 vol%
<0.4 vol%
Trace
--<3 vol%
<0.05 vol%
?
[ Oxyfuel
(12), (13) (14)
>90 vol%
-<7 vol%
trace
-Trace
<3 vol%
<0.25 vol%
<2.5 vol%
Trace
<5 vol%
A pipeline will be designed for a long life time (~50 years). Thus it can be expected that the
fluid composition in the pipeline will change when different capture sources are connected to
the pipeline infrastructure. By comparing Table 5-1 and Table 5-2 it is clear that Ar, H2, SOx
and NOx will be new compounds in the CO2 mixture for which there is little or no experience
within CO2 transport. O2 and H2S are to some extent transported today but at much lower
concentrations. Currently, no CO2 quality requirements have been decided upon that take into
account these new compounds and their effect upon the pipeline transport system. This will be
further discussed in Chapter 8.
Amine absorption
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6 Effect of Impurities
mpurities
Impurities in the CO2 affect the design of the pipeline and the compression facilities.
Impurities affect the phase behavior,
behavior, the thermodynamic properties and the viscosity. For
example small amounts of hydrogen
ydrogen in the CO2 will increase the vapor pressure significantly.
The relationships between the source,
source, the requirements, the pretreatment and their effect upon
pipeline design and operation are shown schematically in Figure 6-1.
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Density [kg/m]
800
CO2-CH4
700
CO2-H2
CO2-N2
600
CO2-Ar
500
CO2-SO2
400
CO2-H2S
300
CO2-O2
0
10
20
30
40
50
60
Temperature [C]
Figure 6-2: Density at 100 bara with different temperatures for CO2 with 2 mole% of another component.
SO2 is the only component that increases the density compared to pure CO2. The estimated
density for this mixture is very uncertain since no mixture parameters were available. From
this figure it can be seen that H2S has minimal impact on the fluid density while H2 has a
significant impact.
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In Figure 6-3 below the viscosity are shown for different mixtures of CO2 at 100 bara.
Viscosity [cP]
0.1
0.09
CO2 (100%)
0.08
CO2-CH4
0.07
CO2-H2
0.06
CO2-N2
0.05
CO2-Ar
0.04
CO2-H2S
0.03
CO2-O2
0.02
0
10
20
30
40
50
60
Temperature [C]
Figure 6-3: Viscosity at 100 bara with different temperatures for CO2 with 2 mole % of another
component.
Note that the SO2 is not included in the diagram since REFPROP did not calculate viscosity
for this mixture.
The figure indicates that impurities typically will reduce the viscosity.
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Figure 6-4 below shows the vapor pressure for the different mixtures. Again, CO2 is mixed
with 2 mole% of another component.
Vapour Pressure
90
80
Pressure [bara]
CO2 (100%)
70
CO2-CH4
CO2-H2
60
CO2-N2
50
CO2-Ar
CO2-SO2
40
CO2-H2S
CO2-O2
30
0
10
15
20
25
30
35
Temperature [C]
Figure 6-4: Vapor pressure for different mixtures (98 mole% CO2)
It can be seen that the presence of impurities have a significant effect on the vapour pressure.
Exceptions are H2S and SO2. As with the other properties, the values for CO2-SO2 mixture are
very uncertain since the mixing parameters were estimated and not based on any actual
measurement data (16). The presence of impurities implies that a two phase region will be
present.
.
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Y+X
Data
CH4
CO2
+ PvT
PvT
VLE
VLE
Number of
data points
7
91
6
21
Temperature
(C)
15
-48 - 127
28
15-20
Pressure
(Bar)
55-145
21-358
70-77
56-82
Mole
Fractiona
0.96
0.98
0.97-0.99
0.83-0.99
N2 + CO2
PvT
PvT
VLE
VLE
VLE
VLE
VLE
64
39
13
22
22
18
15
27-57
0-200
28-30
-40 - 25
15-30
15-20
0
23-331
4-88
72-81
37-127
61-103
60-97
41-118
0.98
0.98
0.96-1.00
0.63-0.97
0.81-0.99
0.85-1.00
0.70-0.99
CO2 + H2
PvT
VLE
VLE
42
58
42
5-20
-53 - 17
5-20
48-193
11-203
48-193
0.01-0.16
0.00-0.14
0.01-0.16
CO2 + O2
VLE
VLE
72
72
-50 - 10
-50 - 10
10-132
10-132
0.01-0.78
0.00-0.39
CO2 + Ar
PvT
PvT
VLE
5
12
12
15
15
15
83-145
57-98
57-98
0.06
0.06-0.021
0.06-0.17
Mole fractions of component X in the saturated liquid phase for VLE data.
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Below are described data sets for other mixtures obtained and/or found reference to in the
course of the investigation:
CO2-O2
In information received from NIST (16), 33 PvT data points from Muirbrook (18) were found,
but only one data point was below 5 mole% O2; at 0 C and 52 bar.
CO2-H2S
In information received from NIST 169 PvT data points from Stouffer (19) were found for the
lowest concentration of H2S ( 6.07%). The data includes pressure from 1 to 236 bar and
temperatures from 16 to 177 C.
CO2-CO
Kunz et al (17) reports 75 data points but only for 43 mole% CO and low pressure from 1 to
65 bara.
No reference to measurement data for CO2 mixed with SO2, NO or COS were identified.
Some multi-component data for CH4-N2-CO2 and N2-CO2-H2 exist but only at low CO2
content (<80%) and low pressure (<83 bar) (17).
It seems that experimental PvT and VLE data at conditions relevant for CO2 transport are few.
This is the case for binary mixture data for CO2 with components like H2, SO2, NO, O2, CO,
COS and Ar as well as for multi-component mixtures.
Technische Universitt Hamburg-Harburg, TUHH, conducts a research project looking into
the thermodynamics of CO2 mixtures that are typical for the oxyfuel process. Unfortunately,
more detailed information was not received about this project within the course of our
investigations.
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Some of the impurities, like NOX, CO and especially H2S and SOx are highly toxic. When a
leak occurs, a cloud of CO2 will disperse. The safe concentration of the dispersed CO2
mixture can be driven by the allowable concentration of these impurities from occupational
and environmental values (12). An example of this is in case of H2S. An assumed STEL
(Short Term Exposure Levels) of 30,000 ppm. for CO2 (20) and 15 ppm. for H2S, means that
for H2S concentrations over 2000 ppm. in the CO2 compositional mixture, H2S will be the
limiting factor.
Impurities have also an effect upon the design and operation of blow down facilities. If a
combustible compound is present which is not allowed to be vented to atmosphere (e.g. H2S)
a possible solution is to connect the blow down facility to a flare (It should also be noted here
that combusting H2S produces SO2 which is also highly toxic). This again implies that a fuel
gas system needs to be incorporated in the design. In such a case, the CO2 needs to be
mingled with enough fuel so combustion can take place.
Impurities have a high impact on the transport capacity. Studies on the qualitative and
quantitative effect of the impurities on the pressure drop and transport capacity are reported in
(8) (21). For example, CO2 plus 5 % methane decreases the flow by 16 % (flow adjusted to
have an 82.7 Pa/m pressure drop at 10 341 kPa and 16 C in 406 mm pipeline) (8). In
addition, impurities take up space in the pipeline that otherwise is utilzed for transporting
CO2. Compared to transporting pure CO2, 5 vol% impurities will reduce the volume of CO2
transported by 5%.
Since CO2 is transported as a dense fluid it will be relatively easy to compensate for losses of
capacity by boosting the pressure using a pump, as long as the pipeline is not already
operating close to Mean Allowable Operating Pressure (MAOP). An investigation into the
effect of impurities on the minimum distance between recompression/boosting stations is
presented in (21).
Especially hydrogen is shown here to have a large effect. A CO2 mixture containing 3 mole%
of hydrogen halves the minimum distance between recompression stations compared to pure
CO2. When recompression is not an option, with a given pressure loss along the pipeline
route, the minimum entrance pressure will have to be raised when the vapor pressure of the
fluid is higher due to the presence of impurities. This in turn can necessitate to design the
pipeline for higher operating pressures leading to for example large pipe wall thickness or
stronger materials.
The impurities can also have an effect upon the pipeline integrity. The vapor pressure sets the
decompression pressure at a pipeline break. Thus a high decompression pressure can facilitate
further propagation of a fracture: This is further described in detail in Chapter 11.
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Presence of atomic hydrogen can lead to hydrogen embrittlement of the pipeline steel or
hydrogen induced cracking. For atomic hydrogen to occur, free water needs to be present. The
underlying mechanism is that atomic hydrogen diffuses into the metal matrix and combines
again to hydrogen molecules. This creates local internal pressure which reduces the ductility
and tensile strength of the steel. The atomic hydrogen may also embrittle the steel through its
interference with the plastic flow during deformation.
Carbon steels used for pipelines can be specified with additional requirements to remediate
this potential problem. Measures can include lower sulphur contents of the steel, limiting the
hardness and alloying of the steel.
Presence of H2S is another issue of concern. Even without the presence of free water H2S
poses a potential problem (with free water also atomic hydrogen is produced). A reaction
between iron and H2S will occur at the pipe inner surface, creating a thin surface of iron
sulphide and atomic hydrogen. This is called Sulphide Stress Cracking (SSC). The sensitivity
for this can be reduced by for example adding nickel to the steel alloy composition. For
pipeline operations, the presence of H2S implicates that the steel has to be specified for socalled sour service
The presence of Oxygen is considered problematic from a corrosion point of view, especially
when free water is present.
Finally, impurities can affect the water solubility and hydrate formation conditions. This will
be further discussed in Chapter 10.
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7 Standards/Pipeline Code
In the USA, CO2 pipelines fall under the Department of Transport 49-CFR 195 as they are
considered hazardous liquid pipelines and the ANSI/ASME B31.4 pipeline code. For Canada
the Canadian Standard Association Z662 applies. Department of Transport 49-CFR 195 puts
requirements on issues like material compatibility, pipeline integrity, monitoring, reporting of
accidents, etc.
For offshore pipelines the most widely used code is DNV-OS-F101. This code does not
provide special considerations for the transport of CO2. It is described in this code as a nonflammable, non-toxic gas at ambient temperature and atmospheric conditions. This means it
falls under the codes fluid classification C. With this classification, CO2 pipelines fall under
design criteria for safety class Low or Normal (when in areas with human activity). However
it is questionable if large releases of CO2 (due to pipeline rupture) are as harmless as this
classification would indicate. In addition, there are differences between natural gas pipeline
transport and transport of CO2. On top of this, future parts of the existing hydrocarbon pipeline
infrastructure might be considered to be used for CO2 transport. In order to address this, DNV
is currently conducting a gap analysis and is assessing how to update the DNV-OS-F101 code
for offshore transport of CO2 (22).
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Compound
CO2
Nitrogen
Hydrocarbons
Water
Oxygen
Glycol
Specification
95%
4%
5%
257 ppm wt.
10 ppm wt
4*10-5 l/m3
Min.
Max.
Max.
Max
Max
Max
Issue/Remark
MMP concern
MMP concern
MMP concern
Corrosion (Specified as 30lbs/MMscf)
Corrosion
Operations (Specified as 0.3 gal/MMscf)
Temperature
50 C
Max
For some of the other pipelines, details about the CO2 mixture are given in Appendix 2.
No internationally accepted standard for the specification of CO2 mixtures exists for pipeline
transmission systems. The fluid specification will largely depend upon an assessment
performed during the design phase including flow assurance, pipeline integrity and safety, and
the requirements put upon the CO2 purity by the end user/destination.In (24), a very recent
Dutch study of possible barriers of the CCS chain components with respect to coal fired
power plants the impact of impurities upon the transport system was assessed. The study
proposes the following transport conditions (see Table 8-2):
Table 8-2: Proposed transport conditions from Ecofys study (24)
Compound
CO2
Nitrogen
CH4
Water
Specification
95%
<4%
< 4% (vol)
<500 ppm
Issue/Remark
Min.
Max.
Max.
Max
Oxygen
SO2
NO
H2S
Hydrogen
Ar
Temperature
<4 % (vol)
< 4% (vol)
< 4% (vol)
30 C
Max
Max
Max
Max
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The requirements to be put upon the CO2 purity are further addressed in the EU Dynamis
project (25) and the ENCAP project (26). In (12), an initial investigation of the effect of
impurities in the CO2 stream on the transport systems is presented. This work concludes that
strict requirements on CO2 quality should be avoided to reduce the cost of the capture process
Knowledge gaps are identified regarding the effect of the impurities upon the pipeline
transmission system. The initially proposed quality recommendation of the Dynamis project is
shown in Table 8-3.
Table 8-3 Dynamis proposed specifications (25)
Compound
H2S
CO
SOx
NOx
H2O
O2
CH4
N2 , Ar, H2
CO2
Concentration limit
200 ppm
Remarks
Health
and
safety
considerations
2000 ppm
Health
and
safety
considerations
100 ppm
Health
and
safety
considerations
100 ppm
Health
and
safety
considerations
500 ppm
Technical limit
Aquifer <4 vol% (all non Technical limit; storage issue
cond. gases), EOR >100 ppm
Aquifer < 4 vol%, EOR <2 Like ENCAP
vol% (all non cond. gases)
<4 vol% (all non cond. Like ENCAP
gases)
> 95%
Result of other compounds in
CO2
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9 Material Aspects
Transporting CO2 by pipeline has an effect upon the material choice of the pipeline and
pipeline components during the design process.
Firstly, supercritical CO2 is used as an industrial solvent; for example in the production of
medication and decaffeinated coffee. This solving ability must be taken into account in the
materials selection process.
Secondly, when liquid water is present, CO2 will partially dissolve and form carbonic acid.
This will give rise to corrosion problems with the steel alloys commonly used for long
pipelines. This will be discussed in detail in Chapter 10.
Thirdly, in transient situations involving rapid depressurization of parts of the pipeline the
material can be exposed to temperature drops below the triple point (-56.6 C).
Fourthly, CO2 pipelines are considered to be more susceptible to fast propagating ductile
fractures compared to gas pipelines. This can put additional requirements on the fracture
properties of the material. This will be discussed in more detail in Chapter 11.
When transporting dense CO2, care has to be taken when selecting materials and compounds
for gaskets, valve seats, sealants, coatings and lubricants. In (27) an overview of tests
regarding the effect of supercritical CO2 on materials is provided. Another overview based
upon several sources is provided in (28). Information regarding compatibility of materials
with supercritical CO2 can also be found in (29). In (30) a best practice for injection well
technology for CO2 as used in EOR is given. This includes the material selection process. In
general the following can be said regarding the material selection for use with dense phase
CO2.
9.1
Elastomers
Generally, elastomers do not respond well to exposure to supercritical CO2. Problems have
been reported with the use of standard Nitrile, Polyethylene, some fluorelastomers,
chloroprene and to some extent ethylene-propylene compounds. Swelling of the elastomer is
attributed to the solubility/diffusion of the pressurized CO2 into the bulk material. With dense
phase CO2 explosive decompression of the elastomer can occur. This phenomenon occurs
when system pressure is rapidly decreased and the gases that have permeated or dissolved into
the elastomer expand. In a mild case, the elastomer will only show blistering (due to the
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expansion of the diffused CO2), but potentially rupture may occur. These issues may be more
severe with higher operating pressures and larger pressure differentials.
Ethylene-propylene co-polymers are reported to be a better option. For high pressure gas
filling connectors as used in CO2 tanks and cylinders, EPDM seals are used. These are
reported to show significant swelling during use. Problems can be alleviated by choosing the
right shore hardness for a specific application. Silicon is reported to be suitable but shows a
high rate of permeability for dense phase CO2.
9.2
Petroleum based products will dissolve when in contact with supercritical CO2. Some grease
will decompose and create gum like deposits or harden when in contact with CO2; the main
constituents will dissolve leaving behind the hard gum and wax additives of the grease. This
can seize valves and compressor shafts. Special lubricants and greases for use with dense
phase CO2 are available from a number of suppliers.
9.3
Coatings (internal)
Experimental work reported in (27) on epoxy (both force cured and fused), phenolic (both
baked and fused), nylon-epoxy-amide (force cured), glass (fused) and vinyl (cemented)
coatings/linings showed that only force cured epoxy gave rise to de-bonding after long term
exposure testing to supercritical CO2. Fused epoxy was reported to show no adverse affect.
We did not come across sources referring to the use of pipeline coatings in existing CO2
pipeline. At the SACROC unit, powder applied phenolic epoxy and glass fiber reinforced
epoxy has successfully be used to coat carbon steel pipe (30).
9.4
Valve Seats
There is some uncertainty in the literature about the use of nitrile and teflon in valve seats.
Recommended is EPDM, but only in the absence of hydrocarbons. For hard valve seats
chrome plating is recommended. When the valve seats are in contact with CO2 one can use
anodized aluminum. There exist considerable experience regarding the use of valves with
dense phase/supercritical CO2; it is a matter of specifying the use with dense phase CO2 to the
valve supplier. For example Cooper Cameron supplies a whole range of ball valves for use
with CO2 to the pipeline industry. In (31) the observation is made that ball valve seats should
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be made to seal by injecting sealant into the seating area. This is related to the problems
observed with leaking of mechanical connections with gaskets or seals.
9.5 Gaskets
In (31) the use of stainless/asbestos spiral wound gaskets in combination with standard raised
face flanges is advocated.
9.6
Metals
Carbon steel (C-Mn steel) can be used under the provision that there will be no free water
inside the pipeline. When free water is present, stainless steel has to be used. Experience
shows that S316L functions well. There is mixed experience with S304L. In (30) the use of
S410L is reported to have given pitting corrosion problems at the SACROC unit. Regarding
other metals; dry CO2 functions well with aluminum, brass and copper.
9.7
Engineering Plastics
The following engineering plastics are reported to perform satisfactory with CO2 in dense
phase:
PTFE, PCTFE, PVDF, KYNAR , PA, NYLON, PP
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10.1 Corrosion
Occurrence of free water will lead to dissolution of CO2. This will form carbonic acid, H2CO3.
The free water will thus in effect be present as a weak acid. This gives rise to corrosion
problems for the carbon steels of choice for pipelines. CO2 corrosion has been studied
extensively and forms a serious problem for pipeline operations where the chosen material is
carbon steel. For longer pipelines, carbon steel is about the only economically feasible
material choice for dense phase transport of CO2, balancing material cost with the mechanical
strength needed to withstand the internal high pressures and the external loads. Dry CO2 (all
water is dissolved in the CO2) has both in laboratory experiments and from pipeline operating
experience shown to give very low corrosion rates for C-Mn steel. For example, in a study
conducted in connection with the design and engineering of the SACROC pipeline, the
experimental corrosion testing program reported corrosion rates of less than 0.0005 mm/yr on
X-60 ERW steel when there is no liquid water present (27). When liquid free water is
present, corrosion of carbon steel will definitely occur. Corrosion reactions are
electrochemical in nature. For the CO2 - Fe corrosion system there are several anodic and
cathodic reactions, because in presence of liquid water as electrolyte, CO2 will partially
dissolve and forms carbonic acid. These components participate in the reaction chemistry as
well. The basics of this are well described in (32). The possible electrochemical reactions
occurring with CO2 corrosion of carbon steel are shown in Figure 10-1 and the resulting
corrosion in Figure 10-2.
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10-1: Corrosion reactions of water saturated CO2 with carbon steel (32)
10-2: Example of CO2 corrosion attack on a carbon steel pipeline segment (32)
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When free, liquid, water is present, corrosion will occur and at very high rates. Rates up to
and beyond 10 mm/year are reported (33). Furthermore, the corrosion mechanism is an on/off
process somewhat complicating prediction of corrosion rates. Corrosion attacks will be
typically localized at initial initiation sites, this is attributed to the galvanic effect, leading to
high local corrosion rates that may lead to weaknesses or leaks in the pipe wall within short
periods of time.
CO2 corrosion has been researched extensively and is relatively well understood. Major
studies have been conducted regarding CO2 corrosion in oil and gas pipelines for
hydrocarbons containing several mole% CO2. However, very little experimental work has
been carried out regarding CO2 corrosion in pipelines at the high partial pressures encountered
when transporting high purity CO2. A multitude of corrosion models have been developed for
hydrocarbons containing CO2, but it has been registered by (32) (34) that the results can vary
by a factor 100. This is attributed to corrosion, and the corrosion effect of CO2, to be linked to
a multiple of mechanisms. Several CO2 dependent chemical, electrochemical and mass
transport processes occur simultaneously. These are depending on a variety of parameters,
including CO2 partial pressure and temperature. All this will have to be accounted for in the
models. At high partial pressures the existing models tend to overestimate the corrosion rates.
All this makes it a challenging task to specify a corrosion allowance based upon incidental
occurrence of free water in a CO2 pipeline. In addition, the concentrations and types of other
impurities present in the CO2 mixture will influence the corrosion rates. The presence of O2,
H2S, SO2 and NOx all have an influence towards higher corrosion rates. In (34) it is
underlined that the mechanism of CO2 corrosion in the presence of impurities is not entirely
understood. Setting a corrosion allowance is therefore probably not a suitable way to deal
with the danger of CO2 corrosion in a carbon steel CO2 pipeline.
There are however several other ways to mitigate this for natural gas transmission pipelines:
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The reported experiences with CO2 corrosion with likely pipeline alloy candidates are shown
inFigure 10-3.
10-3: overview of corrosion rates and experiences reported in the literature for candidate steels for CO2
pipelines (34)
The state of the art approach to this problem is to set and maintain a specification on
maximum water contents of the CO2 in the pipeline. The objective is to avoid forming of free
water within the operational window (pressure and temperature) of the pipeline.
This will still leave open the question what measures should be taken in case there is
incidental free water ingress into the pipeline. This can for example happen when the capture
plant delivers moisture saturated CO2 to the pipeline (for example due to dehydration
equipment failure). In (35) MEG or use of a commercial corrosion inhibitor is suggested. In
(34) the recommendation is given that for transportation of CO2 in C-Mn pipelines the risks of
corrosion at actual flow conditions should be investigated. The consequence of impurities and
an evaluation of inhibitors should be included. Impurities in the CO2 will both affect the water
solubility and the corrosion mechanisms.
Another source of free water can be the reactions between impurities; during this study we did
not encounter any work that describes potential chemical reactions between impurities at
pipeline operating conditions. For example; impurities containing molecular hydrogen (like
for example H2S) might under certain conditions react with O2 creating additional water.
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10.2 Hydrates
Forming of hydrates (clathrate hydrates) during CO2 transport is similar to that occurring in
natural gas transport. Clathrate hydrates are solids in which gas molecules occupy a vacancy
in a cage made up of hydrogen bonded water molecules. CO2 is just one of the light molecular
gas weight molecules that can form hydrates together with water. Some of the impurities that
can be present in the CO2 can also form hydrates, like CH4, H2S, N2, Ar as well as some
higher hydrocarbons (like C2H6 and C3H8). These hydrates are actually not chemical
compounds; their formation and decomposition are actual phase transitions. In appearance
hydrates remind of ice. Contrary to ice, it should be noted that hydrates can form at
temperatures above 0 C. This phase transition point is also highly pressure dependent.
Hydrates become more stable with increasing pressure. Hydrates can form plugs in pipelines,
either blocking valves, fouling up instrumentation or in the extreme case block the entire bore
of the pipeline at a certain location. During depressurization the acceleration of a hydrate plug
can cause structural damage to the pipeline wall in small radius bends. Hydrates have been
observed to have an affinity for building up at the pipeline walls. When they occur they can
be decomposed by either lowering the pressure, increasing the temperature or reduce the
water content.
Measures that can be taken to avoid hydrates:
Use of thermodynamic inhibitors; MEG and DEG to lower the hydrate forming
temperature (effectively an antifreeze). This works for natural gas hydrates, but no
references were found how well this will function with CO2.
Use of kinetic inhibitors; they slow down the kinetics of formation.
Use of anti-conglomerants; they allow hydrates to form but not to stick together
Raising the operational temperature window of the pipeline (maintaining the pressures and
temperatures outside the hydrate formation conditions)
Lowering the water dew-point in the hydrate forming regime (dehydration)
Research addresses the development of so-called low dosage gas hydrate inhibitors that
either act to delay nucleation or prevent growth while being present at low concentrations
(typically less than 1% of the water contents) (36).
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The Phase equilibrium diagram for the system CO2/H2O is shown in Figure 10-4.
The CO2-H2O hydrate system has been studied by for example (37), (38).
As Figure 10-4 illustrates, within the operating window for offshore CO2 pipelines, hydrates
will be stable when the temperature is below 283 K (9.85C). It should be noted that the
experimental work behind this figure is based upon water saturated mixtures of CO2. The
presence of free water will definitely enhance hydrate formation. There are indications that
hydrates also can form under conditions above the water dew point of the actual CO2-H2O
system. These are reported to be difficult to create under laboratory conditions. The following
conditions are necessary to get hydrates (39).
The right combination of temperature and pressure (low temperature, high pressure)
Presence of hydrate forming molecules
A suitable amount of water.
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The equilibrium in the hydrate region depends on the amount of water present:
For a large amount of water, the equilibrium is between water and the hydrate
For a small amount of water, the equilibrium is between a gas and the hydrate
If the mixture is very lean on water, no hydrate will form.
As the figure shows, water saturated CO2 will form hydrates below 283 K (9.85 C).
The water saturation condition can occur when there is a temperature drop of the CO2 in
relation to pressure reduction. This is encountered for example during the blow down of a
pipeline or downstream a valve during part filling of the pipeline. Dehydrating the mixture is
likely to reduce the hydrate forming temperature. We did not find reports of occurrence of
hydrates for the existing land based CO2 pipelines in the USA. This can be due to the fact
some of them operate most of the time above the hydrate temperature (although winter
temperatures in the USA can be low enough to get into the hydrate stable region) or due to the
low water contents (much lower than theoretically needed to avoid free water.
The Weyburn pipeline is expected to encounter low enough temperatures during winter, but
due to the separation process, the CO2 here has a very low water contents. When sufficient
water is present as is the case in injection of CO2 for EOR in oil wells, hydrate formation is
taken into account and dealt with. An offshore pipeline on the Norwegian Continental Shelf
will along most of its length transport CO2 within the hydrate stable region.
Within the scope of this study we found very little information about hydrate forming
conditions in both pure CO2 and CO2 with impurities when there is an absence of free water.
The question remains if the water solubility limit is a non-conservative limit for the allowable
water contents of the CO2. When taking into account that CO2 hydrates are likely to form
below 283 K rather than free water (although we can expect equilibrium between these two as
well), the question remains what the maximum allowable water content is to avoid formation
of stable hydrates.
We can at this stage not rule out that these water levels are below the limit needed to avoid
liquid water drop out. As the fluid is exposed to turbulent flow, possibly more factors are
governing hydrate formation than the thermodynamic equilibrium alone. This is an area that
should be further investigated, including how the impurities affect the formation of hydrates
in unsaturated (dry) CO2.
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Mole % water
0,35
82.8 bar
0,3
103.4 bar
0,25
137.9bar
0,2
0,15
0,1
0,05
0
-20
-15
-10
-5
10
15
20
Degrees Celcius
10-5: maximum water solubility in CO2 (38).
It must also be noted that the water solubility of CO2 shows a minimum value within the gas
phase at pressures directly under the vapor pressure (35). The solubility of water in gaseous
CO2 at a given temperature will decrease to a minimum with increasing pressure. Further
increasing the pressure will lead to the phase transition to dense phase/liquid CO2 and the
water solubility increases again. This can be used to remove water during compression, but
can also lead to free water when pressure releasing CO2 in the dense liquid phase. The
presence of impurities in the CO2 will also influence the water solubility. Some of the
impurities will lower the water solubility. This is for example the case with H2S and CH4. In
(35) experiments and calculations for the solubility of water in pure CO2 are compared with
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that of a mixture containing methane. The water solubility in the dense phase is shown to be
significantly lower. Measurements presented in (42) show that in the dense phase the
solubility can be as much as 30% lower for a mixture containing 5.3% CH4 compared to pure
CO2. In (43) the results of a literature investigation indicate that for low concentrations (up to
200 ppm) the effect of H2S on water solubility is not significant, while CH4 decreases water
solubility significantly. The same publication also reports that it did not find evidence of
cross-effects of O2 and N2 on water solubility. In (44) a water saturation prediction model is
described for CO2 mixtures with up to 5 mole% in total of CH4 and N2 in the pressure range
0.1-27.7 MPa. The model predicts water saturation values in the non-hydrate region only.
This work concludes with that at constant temperature and pressure, dilution of the CO2 by
CH4 and/or N2 will reduce the water saturation value.
To predict the solubility of H2O in CO2 it is important to note that the original form of the
Redlich-Kwong-Soave (RKS) nor the Peng-Robinson (PR) equation of state accurately
reproduces the vapor pressure of water (45). Therefore modifications of these equations must
be used, which are available (45) (35).
In (45), the results from a commercial tool using a two fluid approach are compared to
existing measurement data for pure CO2 and show reasonable agreement. A recent study (40)
from Sintef and StatoilHydro compared the calculated results for water solubility using RKS
EoS with both the Van der Waals and Huron Vidal mixing rules and the CPA (Cubic Plus
Association) with literature collected experimental data for CO2 mixtures containing CH4.
The conclusions from this study were that SRK model with Huron Vidal mixing rule is able to
calculate the solubility of H2O in these mixtures most accurate (from 3 to 9.3% average
deviation). The RKS model with Van der Waals mixing rule was found not to be able to
calculate the mutual solubilities correctly. The CPA model was found to be able to calculate
the solubilities but with less accuracy (from 9 to 35% deviation).
For the different carbon dioxide pipelines in operation, different practices for maximum
allowable water contents are used (Table 5-1). It is therefore not clear what the optimum
water contents specification is, especially with the presence of impurities. Further
investigation in to the effect of the impurities on water solubility, the availability of
experimental data and possibly further development of the thermodynamic models to
calculate the solubilities for actual CO2 mixtures will be needed to set safe water
specifications.
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It starts with the initiation of a fracture (for example through external force)
When the driving force (internal pipeline pressure) is above a certain level, the crack
will propagate in one or both directions along the pipeline.
As long as the driving force in the region of the crack tip is above this threshold level,
the crack tip will continue to propagate. The propagation velocity is close to the speed
of sound in the pipeline steel.
As soon as the crack opens, and the fluid medium starts to leak, a pressure relief front
starts propagating in both directions.
If the pressure relief front moves faster than the crack propagates, at some point in
time the driving force at the crack tip disappears and the crack arrests
It is thus a race between these two velocities; the speed of crack propagation versus
the speed of the pressure relief front. When the pressure relief front catches up with
the crack tip, the fracture might arrest. Otherwise the fracture will keep on running
until some other barrier arrest it.
The fracture arrest properties at a given temperature and pressure depend on the wall
thickness and the material properties, particularly fracture arrest toughness. In some of the
existing CO2 pipelines the risk of fast running ductile fractures is addressed through the use of
fracture arresters. These are normally rings of metal, tightly bonded to the outer surface of the
pipeline. They function as a local increase of the wall thickness. In addition, on segmented
lines the housings of the inline block valves can double as fracture arrestors.
As mentioned above, a ductile fracture will not propagate if there is insufficient driving force
in the system to overcome the resistance to propagation of the fracture. The Batelle Two
Curve Methodology is a model of the fracture process, expressing this balance in terms of the
fracture velocity and decompression velocity curve. Supercritical CO2 decompresses as an
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elastic liquid first and then as a two phase fluid (this differs from natural gas dense phase
which will decompress as a gas only, while rich gas will decompress as a gas first and then as
a two phase fluid). The implication of this is that CO2 decompresses first rapidly down to the
saturation pressure (as a liquid) and then maintains the saturation pressure during
decompression as a two phase fluid (for quite some time; there is no rapid depressurization as
with a natural gas pipeline). The risk is that the high, sustained, vapor pressure maintains the
driving force for fracture propagation. The implication of this decompression characteristic is
that the necessary toughness to arrest a fracture can be estimated by using saturation and
arrest pressure (the arrest pressure is the pressure in the pipe below which a running ductile
fracture cannot occur: it is a function of the strength and toughness of the pipeline steel, and
the diameter and wall thickness of the pipe). This approach is in reality a simplification,
ignoring the decompression of the two-phase fluid and leads to a conservative estimate. This
is further described in (46) (47).
In order to stop a fast running ductile fracture, the saturation pressure must be less than the
arrest pressure. The initial temperature and pressure at fracture initiation as well as the
presence of impurities will all have an influence on the pressure at which the decompression
path crosses the vapor liquid equilibrium in the phase diagram. This sets the saturation
pressure. The worst case here is a situation where the initial pressure is low and temperature
high. It is therefore not the design pressure that defines the worst case.
Cosham (46) reports the existence of gas decompression models with the capability to model
the decompression of mixtures that contain CO2. These are not optimized for high proportions
or pure CO2, especially with the expected impurities present in captured CO2. In (22) the
recommendation is given to full scale test the applicability of the existing models for CO2
pipelines. The motivation is that fast fracture propagation and arrest mechanisms are not
completely understood and that the existing models for assessing fracture arrest are based
upon tests with hydrocarbon gasses. For offshore pipelines the prediction is more complicated
because of the interaction of the escaping fluid with the water. In (48) it is mentioned that the
methods for calculating fracture arrest conditions are conservative when applied for offshore
pipelines, however this is not confirmed for CO2 pipelines.
Another potential dangerous effect is that the leakage of CO2 through the fracture may cool
down the pipeline steel locally due to the phase transition and consecutive expansion of the
gas. Local thermal stresses might occur that can add to the driving force at the crack tip. In
addition, carbon steels can be considered to be more brittle at low temperatures. To which
extent this is a risk for offshore pipelines, with heat transfer to the surrounding seawater is
questionable and could be further evaluated.
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12 Flow Assurance
Flow assurance in the wider sense of the word means the measures that have to be taken to
guarantee the flow of a fluid from the source to the delivery location. The following needs to
be calculated/modeled along the pipeline route:
mixture composition
fluid temperature
fluid pressure
flow
This is required to ensure that conditions for corrosion, hydrate formation and/or phase
changes do not occur anywhere along the pipeline.
Important for flow calculations in CO2 pipelines operating in the dense phase region are:
Principally these requirements can be addressed with several of the available flow pipeline
modeling software available today to model steady state flow. Care however should be taken
that the way the algorithms are implemented in the software will allow for these requirements.
As with any other fluid flowing through a pipeline, its pressure and temperature are subject to
continuous change. The pressure of the fluid in the supercritical state is mainly depending on
three factors:
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The effective pressure gain in its most simple way can be calculated by the accumulated effect
of the elevation differences between the start and end points multiplied with averaged
densities. This can be refined by applying several discretized pipe lengths thus minimizing the
introduced error.
As with other fluids, the calculation of the frictional pressure loss can be accomplished by
using the Darcy-Weisbach relationship, but only when dense (single) phase conditions are met
along the entire pipeline.
For calculation of the Darcy friction factor, the Colebrook White relationship (or one of the
approximations) can be used. Within the friction factor calculation, usually a pipe roughness
is defined. For design of pipelines, values around 50 microns are often used (21). This friction
factor is used to tune the pipeline model to the actual measured flow conditions, and often
established during a capacity test. Alternatively, a pipeline efficiency factor can be tuned.
Since the density is an important factor in both the calculation of friction loss and static head
it is recommended to have frequent calculations along the pipeline (detailed model
configuration).
The temperature of the fluid in the pipeline is depending on:
Choosing the correct values for ambient temperatures and the heat exchange to the ambient
through the pipe wall is of significance as pressure and temperatures are affected by it. As
mentioned, this is especially important for modeling flow in CO2 pipelines as the density is
highly sensitive to the fluid temperature. Heat transfer is thus important for both steady state
and transient conditions. Estimating the heat transfer can be challenging for offshore pipeline
where direct readings of ambient temperature are not available and the total heat transfer
coefficient is dependent on several uncontrolled transient factors like sea water current, burial
depth, thermal conductivity in soil etc. StatoilHydro is currently studying the exterior heat
transfer coefficient for their Snhvit pipeline (49) (50)
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There are limited reports regarding the suitability of the different flow equations when used
for one dimensional fluid flow for single phase transport of CO2. In (8), the AGA equation is
reported to give good results on CO2 as it also includes the compressibility of the fluid. As a
minimum the key properties of the fluid have to be considered (compressibility factor,
density, temperature, elevation and friction factor).
In the design phase one should try to avoid occurrence of two phase flow whenever possible.
This is due to the reduced transmission efficiency and related problems like slugging.
When two phase flow is expected/needed to be accounted for, the Beggs and Brill equation
with Moody friction factor has been recommended (51) (52). This is a hybrid method with a
number of advantages:
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connection to this study indicate that variation in viscosity may not affect the pressure drop as
much as an equivalent variation in density.
Regarding the use of equations of state to predict the properties of both pure CO2 and its
mixtures: early literature refers to the use of the Benedict-Webb-Rubin-Starling (BWRS)
equation of state (8) (47) for both purposes. It is noted here that the compressibility factor Z,
which is an output value from an EoS, varies a lot more as function of temperature and
pressure within the pipeline transport regime than is the case with natural gas. In addition it
changes non-linearly with pressure for both pure CO2 and high purity CO2 mixtures. To use a
linear approximation would most likely give rise to too high velocity and pressure drop
predictions (8). For this reason it is recommended to use an EoS for accurate point-to point
calculations of the relevant properties. This is further compounded with the presence of
impurities in the CO2.
A reference equation of state for pure CO2 has been proposed by Span and Wagner (57)
showing differences between predicted and measured values for density in the range of
0.05%. This EoS is a fundamental equation of state expressed as function of the Helmholtz
energy. Data generated with this EoS is available at the NIST webbook (15).
One can find in the literature other equations of state reported as suitable for CO2 as a pure
fluid. One of these is the Patel-Teja-Valderama (58). This adaption from the Patel-Teja (PT)
EoS reduces the mathematical complexity through eliminating the need to solve the third
cubic equation (additional compared to the basic cubic equations of state) of the P-T EoS.
This is accomplished through using the critical compressibility factor as generalizing
parameter. Another option is the generalized cubic EOS for pure fluids from Kiselev and Fly
(59). This is an EoS with 10 adjustable parameters. According to (59) this EOS is able of
reproducing the thermodynamic and transport properties of CO2 within 0.5-2% accuracy.
Some reviews of the applicability of EoS for determining the thermodynamical properties of
CO2 have been published in recent years. In (60) the ability of common cubic equations of
state; Redlich-Kwong-Soave (RKS), Peng-Robinson (PR) and PT to predict density of pure
CO2 and binary mixtures were reviewed. In addition the effect of volume shifting of PR and
RKS was examined. The results for pure CO2 were that RKS showed absolute average errors
from 6.31% in the supercritical region upto 13.38% in the liquid region. With Peneloux
volume correction these errors became respectively 2.49% and 2.83%. Using the PR EoS
showed absolute average errors from 2.11% in the supercritical region up to 2.20 % in the
liquid region. With Peneloux volume correction these errors became respectively 2.32% and
1.81%. The PT-Mathias EoS gave the following results: absolute average errors from 2.12%
in the supercritical region upto 3.06% in the liquid region. With the original PT EoS these
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errors became respectively 7.14% and 2.83%. For the mixtures, a comparison was made with
existing data on CO2-H2S mixtures. The general observations here were similar to that of the
pure component results.
Another recent review of the suitability of different EoSs (35) compared density data from
NIST for pure CO2 with predictions from Lee-Kesler (LK), BWRS and RKS equations of
state. The LK EoS was found to be the most accurate, falling within 4.7% within the
considered temperature range from 0 to 37 C and pressure range from 20 to 100 bar.
The RKS model showed the largest deviation of 26% while the BWRS model shows 12%.
The deviations are largest in the dense fluid phase, especially at temperatures close to the
critical point. However, RKS under predicted density consistently in the fluid phase over the
entire pressure and temperature range. In (61) a comparative study of EoS for pipeline
transport of CO2 is presented. In this study BWRS, RK, PR, PRBM (PR with Boston-Mathias
alpha function) and RKS simulations were compared quantitatively for CO2 and mixtures.
The simulations were performed with the Aspen simulation tool and were not verified against
experimental data. Mixtures that were considered were binary CO2 with respectively N2, Ar,
H2S and SO2. Critical temperature, bubble point pressure and density were considered. The
conclusions from this work are that RK is least suitable to predict critical temperature and
density while RKS is not suitable for predicting density. The work also shows simulation
results of a 320 km 32 pipeline transporting two different CO2 compositions. The predicted
outlet temperature and pressure were compared for the five EoSes. The results showed that
the BWRS results were inconsistent with the others.
For the relevant CO2 mixtures as presented in Chapter 5, there is generally very limited data
published about the applicability of existing EoS and the applicable mixing rules and
parameters. Most of the EoS mentioned here are developed for hydrocarbons with a low
partial pressure of CO2. In (17), the GERG2004 EoS is described. This wide-range EoS, for
natural gases and other mixtures, is based upon largest experimental set of data for relevant
CO2 mixtures that we could find within the scope of this study. There is at least a partial
overlap with the expected compositions presented in Chapter 11. This EoS has a calculated
error of 0.1% in density and 0.5-1% in speed of sound for pure CO2. In addition it is based
upon measurement data on a number of binary mixtures of high purity CO2.
There is no real consensus which EoS should be used in flow modeling of CO2 pipeline
transport, especially when impurities are present. RKS is reported from several sources to
give large errors while PR is deemed more applicable due to its higher accuracy for near pure
CO2. The GERG2004 is probably today the most suitable within the range of the actual high
purity CO2 mixtures it is based upon. For different CO2 mixtures different EoSes might be
the preferred choice; not one EoS may cover all possible mixtures to the same degree of
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accuracy. In addition, the complexity of the EoSes varies a lot, which will have an effect
upon the choice for use in flow simulation.
It is therefore still advisable to check the accuracy and consecutively tune the EoS of choice
against experimental data for the actual CO2 mixture to be transported.
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collects on blades and accumulates in bearings. This gives extra drag, affecting thus the
accuracy. Problems were reported regarding seals on measuring equipment. Best experience
was with EPDM seals that have 85 durometer hardness. This can handle explosive
decompression during a blow down. Problems with seals become more severe with wider
variations in operating conditions. For provers (sample taking) seals were a real challenge
as they must be both wear resistant and be able to deal with CO2. The worst combination
reported was teflon on a chrome plated surface. Contamination of meter tubes and meters by
lubricants that gets into the CO2 stream from compressors was observed as a problem for
measurement accuracy.
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a wear perspective. Long offshore pipelines will give larger distances over which the pig
needs to travel from launcher to receiver. The distance travelled can be a lot longer than is the
case for land based pipelines, where additional pig receivers and launchers are easily included
along the route.
SCADA (Supervision, Control and Data Acquisition) systems for CO2 pipelines are in
principal similar to that used to control other gas and liquid pipelines. A SCADA system
monitors, processes, transmits and displays pipeline data for the controller/operator. At its
basic level the SCADA system collects real time data from the field instruments, settings of
valves etc. Advanced SCADA systems can include predictive modelling to deal with what
if-scenarios and handle automatic start-up and shutdown. SCADA systems can be used
directly for leak detection, they might provide support for the Leak Detection System (LDS)
or the LDS operates independent from it. The LDS relies on data from the field instruments.
Both the Snhvit and Weyburn pipeline have advanced computational leak detection systems.
These systems use real time transient modeling. Real time transient modelling involves real
time modelling/computer simulation of the pipeline. It predicts the size and location of the
leak through comparing the measured data for a segment of the pipeline with the predicted
model conditions.
A 3 step process is followed in order to detect the presence of a leak:
1. The pressure flow profile is calculated based upon the measurements at the
pipeline segment entrance.
2. The pressure flow profile is calculated based upon the measurements at the
pipeline segment exit.
3. The two profiles are overlapped and a leak is located there where the two profiles
intersect (and exceeding a set tolerance).
The model can be tuned to distinguish between instrument errors, normal transients and leaks
The system used on the Weyburn pipeline uses input from two Coriolis mass flow meters at
each end of the pipeline. The pressure and temperature measurements at the 12 intermediate
valve stations are used within the model for adaptive tuning of the thermal conditions along
the pipeline route. A potential leak location can be detected within three kilometres and the
total volume lost is reported by the system. The system is based upon the use of proprietary
flow modeling software and the system was developed and installed by Advantica in Houston.
It uses real time transient modelling to detect leaks. The Snhvit pipeline uses a system
supplied by Kongsberg.
CO2 is considered as a challenging liquid, partially due to its compressibility, and is therefore
challenging for computational leak detection. Most important for leak detection of CO2 is the
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thermal modelling capability and the choice of heat transfer coefficients and ambient
temperatures (due to temperature dependency of density). This is much more important than
the accuracy of pressure prediction. This poses particularly a challenge for long offshore
pipelines, where pressure and fluid temperature measurement will be limited to inlet and
outlet.
In connection to this there is uncertainty about the interaction of the escaping CO2 from a leak
in a subsea pipeline with the surrounding seawater. There is a potential that hydrates and dry
ice are formed around the leak. This can potentially interfere with leak detection.
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16 Operational issues
The issues related to the operation of CO2 pipelines are discussed in this Chapter.
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to erosive wear of the valve seats. The reason for this is that the phase transition leads to a
high volumetric expansion causing very high gas velocities.
16.3 Blowdown/depressurization
Land based pipelines in the USA are often segmented by block valves. The pipeline can then
be isolated in shorter sections. This gives the possibility to depressurize one segment at a
time. Blow down facilities must be specifically designed for CO2 and account for the phase
transition from dense phase liquid to gas when emitting to the atmosphere. A typical blow
down arrangement for a sectored land based pipeline is described in (65). A blow down test
with such equipment is also described in this publication. A blow down of a 12 km long, 16
pipeline section from 138 bara to atmospheric pressure was conducted within 5 hrs. During
this test the ground CO2 concentrations and the temperature of the exiting carbon dioxide
were measured. The maximum concentration of CO2 measured was 0.2 % occurring after 40
minutes, downwind of the pipeline in a depression in the terrain. The pressure/temperature
profile of the test showed that the temperature does not drop significantly until the saturation
pressure is reached. From saturation pressure down to 20 bara, the temperature did drop
significantly, reaching -2 C. From 20 bara down to atmospheric pressure the temperature
went up again. Theoretical calculations in the same publication of blow down of a 16 km
long 16 pipeline indicated a minimum temperature reached of -47 C. A typical blow down
configuration for a land based CO2 pipeline is shown in Figure 16-1.
Figure 16-1: Blow down facility at the Jackson Dome, operated by Denbury Onshore LLC.
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Figure 16-1 shows the blow down equipment at the Jackson Dome, operated by Denbury
Onshore LLC. The blow down equipment consists of two 8 stack pipes at either side of the
20 ball valve separating the pipeline from the processing equipment. Between the two 8
stacks there is a 3 bypass. This is used to equalize pressure during opening and closing of the
main ball valve. The blow down stack itself is isolated from the pipeline by an 8 ball valve.
At the end of the 8 stack pipe there is a 4 stack pipe ending in a cheaper globe valve. The
pressure is equalized during closure of the 20 ball valve. After the main valve is closed, the
bypass valve is also closed and the 8 ball valve opened. Subsequently the 4 globe valve at
the end of the blow down stack is opened and blow down commences. The system is
regulated manually and phase transition from liquid to gas occurs in the 4 globe valve. The
4 valve is sacrificial as expansion of CO2 in the valve body causes high gas velocities. This
can cut the valve seats. Reported blow down times for a 20 km long section of the 20
pipeline is 8 hours.
Dry ice can be seen during blow down, but blockage of the passages does normally not occur.
For blow down the atmospheric conditions are considered important. On overcast, rainy days
without wind, experience tells that the CO2 will collect at ground level without dispersing. At
sunny, windy conditions no problems are reported. The experience thus says that for short
pipeline sections the temperature during blow down can be controlled by slow
depressurization and sufficient heat transfer from the ambience.
For offshore pipelines it will be impossible to blow down in segments as the blow down stack
will be located onshore. Experience with blow down of CO2 pipelines on land might therefore
not be directly transferrable. For very long offshore pipelines, especially with large elevation
differences, problems might arise. Dry ice and hydrate formation might be an issue due to the
cooling down of the expanding medium, if the blow down has to be performed within a
reasonably short time interval. For subsea pipelines cooling of the pipe wall below the
freezing point of the ambient seawater might lead to build up of ice on the outside of the
pipeline. This can cause instability of the pipeline due to positive buoyancy of the external
ice layer. For a trenched pipeline, freezing of liquefied masses surrounding the pipeline can
cause instability in a similar manner.
StatoilHydro has constructed a test rig that can be used to study the blow down of a long,
offshore pipeline amongst other transient operational phenomena. The test rig was constructed
to establish the operation window and specifications of subsea CO2 pipelines and to train the
operators of the Snhvit pipeline. The rig and some of the work conducted are described in
(49), (50). Test results from this rig are used to verify a depressurization model. Initial test
and modeling results show that during depressurization the flow regime changes from single
phase to two phase flow. A transition front moves through the pipeline starting at the blow
down location and propagating further along the pipelines as the pressure at each location
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drops below the boiling point. With dropping pressure, the temperature also drops. When the
liquid is completely vaporized, the flow becomes single phase. During depressurization tests
conducted with this test rig, temperatures as low as -30 C were encountered.
During a controlled blow down of a long offshore pipeline, one possible solution is to first
replace the fluid CO2 by nitrogen gas and then depressurizing the nitrogen filled pipeline. This
would be a costly option and might not be feasible in case of an emergency blow down (when
there is for example a leak).
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17 Maintenance Aspects
Some special considerations have to be taken with regard to the maintenance of CO2
pipelines. The following special requirements apply (28) (63) (66) :
Maintenance of valves
Ball valves that use grease for sealing need to be repacked periodically. At Dakota
Gasification Company the interval is every three months. The reason for this is that even
when dedicated lubricants are used, CO2 will slowly dissolve it over time.
Inspection pigging
Inspection pigging is performed to check for external corrosion and external damage to buried
CO2 pipelines. Internal corrosion checks, dimensional checks and structural integrity checks
can also be performed during pigging. Intelligent pigging is further described in Chapter 16.
Scraper pigging
After commissioning very little moisture drop-out (free water) is witnessed. A number of
sources from the USA report that the need for scraper pigging is more or less redundant (28).
Internal Corrosion Monitoring
The established method is the use of corrosion coupons. Intervals differ from site to site.
Hop tap welding
Hottap procedures for CO2 pipelines have been developed and been successfully carried out
for land based pipelines (66).
Pipeline Intervention
Within this study it did not become clear if there are differences for pipeline intervention of
an offshore CO2 pipeline compared to other offshore pipelines.
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Figure 18-1: Footage of a CO2 pipeline leak caused by nearby digging operations.
Figure 18-1 shows a leak in an 8 CO2 pipeline after nearby digging activities accidentally
damaged the pipeline. The digger operator suffered non-life threatening injuries. The
resulting leak was sealed off shortly after the accident and later a new piece was welded into
the pipeline.
In (68) (67) risk reviews of CO2 transport are presented. Statistics of pipeline incidents from
the Office of Pipeline Safety from the US Department of Transportation show that during the
period from 1990 to 2001 10 incidents were reported in the USA for CO2 pipelines. There will
thus be incidents with CO2 pipelines and these therefore must be designed, constructed,
operated and maintained to mitigate the adverse effects of incidents.
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Incidents can results from outside force, corrosion, pipe material or weld failure, operational
mistakes etc. The density of CO2 is higher than that of air and will collect in lower areas,
displacing air and thus potentially acting as an asphyxiant.
The USA EPA reported that during the period from 1948-1999, there were 62 incidents with
CO2 leading to 119 deaths and 152 injuries, most related to accidents with fire extinguishing
systems. In 1986, a cloud of natural CO2 erupted from Lake Nyos in Cameron, sweeping
down surrounding valleys leading to the death of more than 1700 people.
An overview of the acute toxicity of CO2 is given in (67). In itself CO2 has a low toxicity, but
when levels rise above 2% it has a physiological effect, raising breathing rate and causing
dizziness, headache, higher blood pressure and heart beat rates. Above concentrations of 4%,
CO2 exposure may give rise to health problems. Above 7% unconsciousness occurs and
subsequent death may occur when levels exceed 10%. The actual effect of CO2 exposure on
individuals however differs from person to person.
It is important to notice that CO2 is heavier than air so it will collect in low laying terrain.
Liquid CO2 has a very high expansion factor as it changes phase when decompressing. It is
recommended to depressurize a CO2 pipeline prior to any repair (28).
When leaks occur, toxic impurities can be setting the safe limits rather than the CO2 itself.
This is specifically the case with H2S and SO2. The original level of the impurities might
actually set the necessary dilution factor of the CO2 with the ambience to fall within safe
limits for human exposure. This has been further discussed in (13), (24), (43) and in Chapter
6. Some of the impurities are highly flammable, like hydrogen and methane. The venting
system of CO2 stream containing components that are poisonous should be considered to be
flared (63). With a release of CO2 from a leak, vent or depressurization stack, low
temperatures might be reached for both the CO2 stream and the local pipeline material.
Exposure to a stream of expanding CO2 can cause cold burn of the skin. The expansion of the
gas during the phase transition will also give a thrust, potentially displacing a pipeline in case
of a leak.
Dispersion of a CO2 pipeline rupture has been modeled (69). This work concludes that the
risk associated with an accidental release from a CO2 pipeline cannot be dismissed. They will
likely endanger workers and surrounding population. At Gexcon, work is ongoing to develop
CFD based dispersion models that also account for underwater dispersion of CO2 in case of a
leak. There is currently no reference available about the effect of a subsea accidental release
of CO2 through a pipeline rupture upon marine life. In such a case there can also be an
associated risk for nearby vessels through the loss of buoyancy when a CO2 gas cloud
surfaces.
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Questionable if all the pig launchers and receivers are necessary. The motivation was
to be able to pig for sweeping out free water. In the first two years of operation there
were no incidents of free water.
The sizing of relief and blow down systems must account for the amount of thrust
generated with the expansion of the gas to the atmosphere.
Include sacrificial valves in the blow down system due to the erosion of the valve seats
and valve body due to the high velocity of the expanding fluid.
Internal corrosion has not occurred during the first two years of operations. Therefore
the necessity of corrosion resistant valve trim should be reevaluated.
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Problems with elastomeric sealing materials do occur; best results were achieved with
high purity EPDM. The biggest problems occur with seals in dynamic situations (large
pressure differentials within short time periods).
Mechanical connections should be restricted to locations that can be isolated from the
mainline pressure in order for repairs to be made without depressurizing the main line.
Flanged end valves should be restricted to stations and isolated from the main line by a
welded end type valve.
The sizing of the blow down system must take into account the thrust associated with the
expansion of the CO2 from liquid to gas.
Moisture monitoring equipment experienced fouling of the probes with glycol (from
the dehydration unit).
Densitometers were not accurate enough, changing to a different supplier solved this
problem.
Actual pipeline temperatures turned out to be higher than produced by the pipeline
model.
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Operational Philosophy
Typically, the pipeline is run in steady state operation. If a stop occurs at DCG the pipeline is
packed down to a minimum pressure. If a stop occurs at Weyburn the pipeline is packed up to
MAOP. After that, the valves are shut or the compressors are run in cycling.
Because of the toxicity of H2S, blow down of the pipeline is done through the flare at the
Gasification Plant, in order to combust the H2S. The CO2 flow is mixed with combustible
gasses from the plant and the mixture is ensured to have at least 17 MJ/Sm3.
Blow down is a manual operation, controlled by pressure, using constant enthalpy lines in the
enthalpy diagram as a guide to avoid that pipeline steel and fluid temperatures are not getting
too low.
Experience during 7 years of operation
Water hammer effects have not been witnessed: This might be attributed to the care that is
taken during initial filling. This is done slowly to avoid acceleration of a liquid slug of CO2.
No significant Joule Thomson effects are witnessed, even though the pipeline is lying in hilly
terrain. This is attributed to the pipeline being buried and the soil being a large heat sink.
During operation there were not witnessed any hydrates. Corrosion checking with both
pigging and coupons show that there has not been any measurable corrosion. DCG has not
vented a section of the line entirely down to atmospheric pressure without filling it first with
pressurized nitrogen. Thus the issues related to vaporising liquid CO2 inside the pipeline were
not relevant.
Few operational problems occurred. There is no evidence that free water has ever occurred
during operation. If it would occur it is not perceived as a problem as it will dissolve in the
dense phase of subsequent batches of dry CO2. Some minor problems were encountered with
seal design and o-ring compatibility for the compressors, but none are reported regarding
seals and gaskets in valves, flanges etc.
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were installed during 2007. A short, 8 natural gas pipeline was recently converted to be
used for CO2 transport. Another natural gas pipeline will be converted for CO2 service in the
course of 2007. A new, nearly 500 km long pipeline is currently under study with a goal of
having it installed and operational in 2009. The experience of Denbury Onshore with CO2 pipelines is thus extensive.
Pipeline design considerations
Pipeline material used for the main lines is ERW API85-5XPL60, specified for sweet service.
The pipeline does not have an internal coating or a corrosion allowance. The outside coating
is fusion bonded epoxy. Cathodic protection is applied. The pipeline is buried to 36 top of
pipe depth. Although the existing pipeline was installed with crack arrestors the new pipelines
will not need them. For valves valve trims special materials are used; trims and seats have to
be specified to be CO2 compatible. Normal gas valves will give problems as the CO2 will
permeate through the seals. Normally, no dimensional/tolerance changes from natural gas
valves are needed. Pipe, flanges and fittings are standard except seats and seals in valves.
Both gate valves and ball valves are used. The pipelines are segmented in shorter sections.
The main reason for having short sections is to be able to refill quickly after depressurization
due to a maintenance activity.
Pipeline Measurement and Control
Supervision of the pipelines is from the control centre which receives and collects SCADA
data into a database. Moisture, Composition, Pressures, Temperatures and flow are
monitored. The LDS is based on a volume balance check, including a once a month interval to
detect small leaks. Automatic leak detection is considered difficult because of the medium
densities dependence on the temperature; the density prediction can be 5% wrong and then
affect the volume balance and pressure predictions. Leak detection is also warranted through
aerial inspection; flying once a week over the pipelines. This is a visual detection, looking for
patches and dry ice.
Pigging
Pigging facilities are included but the main pipeline has never been pigged. The smaller CO2
pipelines are pigged when contaminated with water. The procedure for this is as follows: first
displace the CO2 with nitrogen (totally) and then run pigs; once 15 gallons of water were thus
removed by pigging from a 15 miles long 8 pipeline caused by heater failure in a dewatering
unit. Inspection (smart) pigging has not been conducted yet.
Operational Philosophy
The operational philosophy is to run in steady state but the experience shows that the
pipelines are highly transient systems. When there are shutdowns at the delivery site the
pipeline will be packed up to the maximum pressure available from the dehydration units.
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If there is a shutdown at the supply site, the other end also shuts down. The lowest level to
which the pipeline ever was de-packed is 55 barg.
Blow-down is a manual operation; the operator therefore has to carry a CO2 monitor to
warrant his safety. At the plant the only CO2 monitoring equipment is included at areas where
CO2 can accumulate
Experience during 22 years of operation
No significant problems occurred during operation. There has been no indication of low
temperatures due to Joule Thomson effect. No hydrates have been witnessed. There once was
a leak in a transverse weld due to improper post weld treatment, but otherwise no failures
except for external intervention. No plugging of blow down valves experienced. Orifice plates
can wear out/bend which will give incorrect flow. Experience is that one can get steel
temperatures as low as -73 C during depressurization/filling without this leading to
noticeable problems with the steel. During 22 years of operation, no significant internal
corrosion of the pipeline material was witnessed (analyzing corrosion coupons and line pipe
taken out from tie-ins in 22 years of operation). The entire pipeline has never been
depressurized, but some sections have. The reasons can be a leak (seldom) or to install tie inns
for branch lines to new wells or customers for the CO2. The pipeline is sectioned in up to 24
km long lengths (branch/trunk lines to customers and EOR fields). A typical blow down time
of a 20 pipeline, 24 km long section from 97 barg to ambient pressure takes 8 hours.
During blow down, the plugging of valves is not considered a problem, but the high
expansion rate of dense phase CO2 to gas gives high thrust and velocity through the throttled
valve. This can erode the valve seats. Experience with blow down is that temperature is
locally decreased in the blow down stack. Dry ice formation is witnessed during blow down
but is not leading to blockage of the passage.
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R&D needs:
For applications of C-Mn steel where there is a risk of free water, further studies on
corrosion with high partial pressure CO2 with impurities, and development of suitable
corrosion models are needed.
Evaluate the need for additional material compatibility testing in cases where CO2
transport incorporates higher pressures and/or in the presence of new impurities.
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R&D Needs:
The testing and possibly further development of smart CO2 pipeline pigging at
higher operational pressures and for longer travel distances. Initial testing on land
based pipelines would be desirable (easier to retrieve the pig).
20.5 Modeling
Depressurization
When the pipeline termination is subsea, as will be the case with storage in subsea aquifers,
the only blow down location is at landfall of the pipeline or at the capture plant. With the
need to control the temperature of pipeline components during a blow down, the
depressurization times can become rather large. Development of accurate modeling methods
are needed in order to understand temperature development of fluid and pipeline components.
The developed methods are then used to set safe regimes for depressurization of long offshore
pipelines.
Uncertainties remain regarding:
1. Temperature development of pipeline components during blow down of a long
offshore pipeline.
2. To establish safe depressurization procedures for long offshore CO2 pipelines, accurate
modeling is required. This necessitates accurate descriptions of the heat transfer
processes and the thermodynamic and transport properties of the actual CO2 mixture.
R&D Needs:
SINTEF and StatoilHydro are currently developing a model for depressurization of the
Snhvit CO2 pipeline. It is uncertain if commercial software for two-phase flow is
available for this purpose. It is currently not clear to what extent the results of this
work will be available for other interests. Assess the need for an additional or parallel
activity based on applicability of available modeling tools. This work should result in
the setting of safe regimes for depressurization of long offshore pipelines through
modeling combined with verificiation through experimental work.
Fracture Propagation
Dense phase CO2 has different decompression characteristics than natural gas, showing a
holding pressure during a pipeline rupture that potentially drives a running fracture. The
possibility of long running fractures has to be addressed in the design stage.
Uncertainties that are remaining:
1. Current gas decompression models are not optimized for high proportions or pure
CO2, especially with the impurities present in the captured CO2.
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2. The hydrostatic pressure from the sea water acting on the pipe wall might contribute to
lowering the risk of a running fracture.
3. The contribution from the interaction of the escaping CO2 with the ambient seawater
during a pipeline rupture.
4. Actual experience with CO2 pipeline fracture is reported to be scarce: no report of an
actual occurrence of a running fracture, nor test data were identified within this
investigation.
R&D Needs:
Equation of State
Equations of State are used to calculate fluid properties that are used in flow modeling: for
pure CO2 accurate EoS are available. Uncertainties remain regarding:
1. which EoS should be used for CO2 with impurities; no single recommendation has
been found which EoS to use with which composition.
2. Large variations in critical fluid properties like density when applying different
commonly used EoSes are reported.
R&D Needs:
A further assessment should be made on which EoS is valid under what conditions for
the relevant mixtures within the applicable temperature and pressure range for
offshore pipelines. When more experimental data becomes available, the accuracy of
the EoS of choice should be checked and were necessary EoS and mixing rules be
modified to match the data.
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2. For natural gas pipelines the maximum allowable O2 level is set very low. It is not
clear what the safe O2 levels can be in a CO2 pipeline (Oxyfuel capturing may give
higher Oxygen levels).
3. The specification due to HES can be different for an offshore pipeline since the
toxic components may dissolve into the water.
4. The most important component that needs to be limited is the water. See above
about Water Content.
R&D Needs:
The potential chemical reactions between the impurities under relevant time, pressures
and temperatures and the potential negative effects of the reactions products need to be
mapped.
A specification should be made and agreed upon that specifies for allowable levels of
impurities in the CO2 for pipeline transport. This is currently addressed in the EU
Dynamis project. It is advisable that a link between this project and the governmental
projects for CCS from Krst and Mongstad regarding setting of transport
specifications is made.
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43. DYAMIS CO2 quality recommendations. de Visser, E. Trondheim : Ecofys, 2007. 4thh
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47. Design Considerations for carbon dioxide pipeline. King, G.G. : Pipeline Industry, 1981.
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P : and Downie, J D. San Diego : OMAE, 2007. Proceedings of OMAE2007.
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exploring new uses for natural gas pipelines.
50. Experiments and modelling of CO2 pipeline de-pressurisation Multi-phase transient flow.
de Koeijer, G., et al. Trondheim, 2007. The 4th Trondheim Conference on CO2 Capture,
Transport and Storage.
51. Hein, M. Rigourous and approximate methods for CO2 pipeline analysis. [book auth.]
G.F. Brooks and J. Martinez. Facilities, Pipelines and Measurement A workbook for
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56. Investigation of physical properties for CO2/H2O mxitures for use in semi-closed
O2/CO2 gas turbine cycle with co capture. Ulfsness, R.E., et al.
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62. Summary of Measuring and Metering CO2 for Enhanced Oil recovery methods and
Problems. DeBusk, F. New Mexico, 1984. Measuring and Metering CO2 for Enhanced Oil
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analyzing equipment is installed at the receipt and delivery stations of the pipeline. All signals
are sent by remote transmission to the SCADA system.
Cortez Pipeline (70)
The Cortez pipeline transports CO2 from the McElmo Dome natural source to the Wasson oil
field. The 808 km, 30 pipeline originates at the Cortez station and runs via two metering
stations, three pressure reducing stations, a pump station to end at the Denver City meter
station. Capacity is 28 MSm3/d (19.3 MT/yr). The pipeline is designed to operate from 96 to
186 bara at a maximum temperature of 43 C. The pipeline material is API-5LX-65. The
pipeline could not be designed with sufficient fracture toughness to arrest a propagating
ductile fracture, so crack arrestor rings are installed. These are made from 17.5 mm thick 32
line pipe in the same material, bonded with epoxy to the pipeline at 300 meter intervals. The
wall thickness of the pipeline has five spec. breaks varying from 17.5 to 25.4 mm to handle
the pressure changes due to the elevation differences.
The fluid composition is 95% minimum purity CO2 with a 4 mole % limit on N2 and a 5
mole% limit on hydrocarbons. The limit on H2S is 0.002 mole%. The maximum allowable
water contents is 257 ppm wt.
The entrance of the pipeline is separated from the gathering lines by block valves. In
connection with each block valve are moisture analyzers. Moisture concentration in the line is
monitored with an alarm value set at 171 ppm wt. These are not linked to automatic closure of
the block valves. Pressure and temperature measurement are also included at the block valves.
At the end of each gathering line there is a metering station. The metering stations have 10
orifice runs. The fluid quality at the pipeline entrance is checked with three analyzers: a water
content analyzer, a H2S contents analyzer and a gas chromatograph for measuring nitrogen,
carbon dioxide and other hydro carbons.
There is over 900 meter height difference between the originating and delivery point. This
represents a static pressure gain of about 83 bara. To keep the pressure down, pressure
reduction stations are incorporated to keep the pipeline pressure below 148 bara downstream
the Sandia Mountains. The pressure reducing stations are designed to keep the pipeline above
the critical pressure for CO2. Their basic design contains two sets of three parallel 3 meter
long runs of small diameter pipe. The runs include a 3.5 diameter run, a 4.5 diameter run
and a 6,5 diameter run with control valves. Only one of the runs is active at any one time.
At the pumping station, a 3000 hp centrifugal pump is installed. The adaption of the pump for
pumping CO2 includes a high pressure seal oil lubricating system. This is necessary as CO2 is
essentially a non-lubricating fluid. .
Central Basin Pipeline (5)
The Central Basin pipeline receives carbon dioxide from the Bravo, Cortez and Sheep
Mountain pipelines. The 278 km long pipeline runs from Denver City to McCamey in Texas.
Capacity of the pipeline is 11.5 MT/yr. The pipeline has a number of spec breaks along the
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route on both diameter and wall thickness as CO2 is delivered to oilfields along the route. The
first 7 kilometers are 20 with a pressure rating of 151 bara. The next 120 km is 26 and also
pressure rated to 151 bara. The next 31 km is 24 and pressure rated to 158 bara. The next 25
km is 20 and pressure rated to 165 bara. The final 41 km is 16 and pressure rated to 172
bara. The pipeline has crack arrestors every 400 meters. Cathodic protection is employed.
The fluid composition is 95% minimum purity CO2 with a 4 mole % limit on H2 and a 5
mole% limit on hydrocarbons. The limits on H2S is 20 ppm, 10 ppm on O2 and 10 ppm on
sulphur. The maximum allowable water contents is 257 ppm wt. The pipeline has pigging
facilities located at each diameter change. Meter stations contain flow, pressure and
temperature measurement and are collected in a SCADA system. Mass flow is measured by a
single run orifice meter in combination with a densitometer
Report number
POL-O-2007-138-A
Date
8 January 2008
Security level
Open
Page 85 of 87
model of the pipeline. This system was made by Advantica in Houston for the Dakota
Gasification Company who operates the pipeline. This system is claimed to the first of its
kind for a CO2 pipeline. In connection with this pipeline also a smart pig was developed,
capable of functioning with CO2 at 186 barg. BJ Pipeline Inspection Services has developed
this together with DCG and in 2004 the 14 part of the pipeline was successfully pigged using
this technology, monitoring the pipeline for internal and external corrosion as well as external
damage.
:EJD Pipeline (earlier called Choctaw Pipeline)
The NEJD pipeline, operated by Denbury Onshore LLC, runs from the Jackson Dome to the
oil fields in Louisiana. The pipeline is 20 and 295 km long. The pipeline has been operating
for the last 22 years. The Jackson Dome provides CO2 with a purity of 99.3% CO2, 0.3% CH4
, 0.3% N2 and the remainder hydrocarbons. H2S is present at ppm levels. The CO2 is
dehydrated to 171 ppm wt by using both a glycol and glycerol based drying process. The
pipeline is made from carbon steel, ERW API85-5XPL60, specified for sweet service. The
pipeline is buried most of the way (0.9 meters from top of pipe). All buried pipe is coated
with bonded epoxy. The pipeline has crack arrestors. To protect the pipeline cathodic current
protection is used. Test posts are included at 1.6 km intervals. The pipeline is divided in at
least 24 km long sections or at locations of trunk lines. Each section incorporates a valve
station with blow down facilities as well as temperature and pressure measurement. The
pipeline has metering facilities at the entrance of the pipeline. These included temperature and
pressure measurements, flow measurement through an orifice tube, gas composition sampling
(especially for H2S) and measurement of water contents.
Snhvit CO2 Pipeline (49) (72) (73)
The Snhvit CO2 pipeline transports CO2 from the Snhvit Liquified Natural Gas plant at
Melkya to an offshore storage site, the Tuben formation . This pipeline is the first offshore
CO2 pipeline. The transported CO2 originates from the natural gas from the Snhvit field that
contains 4-9 mole% CO2. The 8 pipeline has a length of 153 km from the onshore
compressor facilities to the 300 meter subsea injection template. The high purity CO2 enters
the pipeline at 150 bara and 25 C. At the end of the pipeline the temperature and pressure are
around 5 C and 150 bara. The pipeline is not sectored. There is an onshore blow down
facility. The pipeline is intended to transport around 0.7 MT/year. The CO2 is dried with
molecular sieves to 50 ppm water contents. The pipeline is supervised by a so-called dynamic
production model, which gives the possibility to incorporate a real time mode and look ahead
simulation of the pipeline, leak detection, pig tracking and automatic model tuning. The
system is based upon D-Spice simulation software and delivered by Kongsberg.
The pipeline is expected to commence operating during the fourth quarter of 2007.
Report number
POL-O-2007-138-A
Date
8 January 2008
Security level
Open
Page 86 of 87
Houston TX
Plano TX
Beulah ND
Midland TX
Stavanger
Ankara
London
Los Angeles
Midland TX
USA
USA
USA
USA
Norway
Turkey
Great Britain
USA
USA
Houston TX
Trondheim
Stavanger
Houston
USA
Norway
Norway
USA
Houston TX USA
Kongsberg
Norway
R&D Organisations
National Institute of Standards
Sintef Energy Processes
Centre for Pipeline Engineering
StatoilHydro R&D
IFE
Gexcon
Los Alamos National Lab
GERG
ENSR
Boulder
Trondheim
Newcastle
Trondheim
Kjeller
Bergen
Los Alamos
Brussels
Worldwide
Report number
POL-O-2007-138-A
USA
Norway
Great Britain
USA
Norway
Norway
USA
Belgium
Date
8 January 2008
Security level
Open
Page 87 of 87
Universities
Bergen University
University Ruhr/Bochum
University of Newcastle
Technische Universitt Hamburg-Harburg
Bergen
Bochum
Newcastle
Hamburg
Norway
Germany
Great Britain
Germany
Oslo
Washington
Norway
USA
Calgary
Houston
Canada
Texas
Pipeline services
BJ Services
Inline Services Inc
Report number
POL-O-2007-138-A
Date
8 January 2008
Security level
Open