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A publication of

CHEMICAL ENGINEERING TRANSACTIONS

The Italian Association
VOL. 36, 2014 of Chemical Engineering
www.aidic.it/cet
Guest Editors: Valerio Cozzani, Eddy de Rademaeker
Copyright © 2014, AIDIC Servizi S.r.l.,
DOI: 10.3303/CET1436104
ISBN 978-88-95608-27-3; ISSN 2283-9216

CO 2 Transportation with Pipelines - Model Analysis for

Steady, Dynamic and Relief Simulation
Luigi Raimondi
Process Simulation Services, Via Piave 17, 20027 Rescaldina, Italy
luigi.raimondi@xpsimworld.com

“Carbon dioxide or CO 2 capture and storage” (often defined by its acronym CCS) is the term used to
describe a set of technologies aimed at capturing carbon dioxide emitted from industrial and energy-
related sources before it enters the atmosphere, by compressing and injecting it underground in secure
geological formations. The scope would be the mitigation of greenhouse effects and the reduction of
related global warming and climate changes. A large number of papers have been devoted to this topic,
Some recent publications, also in this series, has been devoted to the risk assessment of CO 2 relief
(Vianello et al. 2012) and overall risk analysis of CO 2 transportation (Samadi et al. 2012). It is not the aim
of this paper to discuss the effectiveness of the technology but to only focus on the transportation of CO 2
from production points to the storage location. The only feasible way of performing this task is the use of
pipelines of high-capacity. Though carbon dioxide is not very poisonous, however its relief in large
quantities combined with its density higher than air could fill populated regions with large dangerous
effects. This paper analyses the thermodynamic methods required for a reliable simulation of steady state
as the initial requirement for the subsequent calculation of relief conditions (flow rate, pressure and
temperature) as a preliminary critical step to the calculation the dispersion effects. The availability of
reliable calculation methods of the most relevant CO 2 properties (enthalpy, entropy, density and viscosity)
which play a key role in the fluid-dynamic calculations required by for safe and cost-effective pipeline
design. These projects are usually carried out by means of commercially available process simulators
(HYSYS, AspenPlus, ChemCad, etc.) and fluid-dynamics simulators (OLGA, LedaFlow, etc.). The
selection of convenient equations of state and numerical methods is a key factor in engineering design as
well as in the identification of possible hazards scenarios and the calculation of consequences. In
summary the requirements of a reliable and high-precision simulation tool for overall engineering design
are presented.

1. Thermodynamic
In the simulation of carbon-dioxide and CO 2 -rich mixtures the selection of models represent a very
important aspect. From a numerical solution point of view, the simulation of pure components using
temperature and pressure as independent variables (TP plane) presents a discontinuous phase change
from vapour to liquid. At constant pressure below the critical point and across the vapour pressure line a
change of temperature as small at will can produce a complete shift from to vapour to the liquid phase or
vice-versa.

Table 1: Pure carbon-dioxide thermodynamic parameters

Property Value
Critical temperature 30.97 °C
Critical pressure 73.773 bar
Triple point temperature -56.6 °C
Triple point pressure 5.18 bar
Acentric factor 0.22394

Please cite this article as: Raimondi L., 2014, Co2 transportation with pipelines – model analysis for steady, dynamic and relief
simulation, Chemical Engineering Transactions, 36, 619-624 DOI: 10.3303/CET1436104
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Some key chemical-physical parameters important for the next discussion are collected in Table 1. One of
the most notable characteristic of carbon dioxide is that a normal-boiling point does not exist since no
liquid phase can exist at 1 atmosphere and a solid phase is obtained when the vapour is cooled down
below approximately –78.5 °C. It means that below triple point pressure, a reduction of temperature of the
vapour phase (as often happens during depressurization) produces the direct formation of solid without the
transient formation of an intermediate liquid phase. Practically pure carbon-dioxide is not obtained by gas
purification in the CCS capture step; CO 2 is usually accompanied by small quantities of other gases. Their
effect on the phase equilibrium behaviour is to lower the temperature of both the bubble point and dew
point lines. For example, Figure 1 shows the phase envelope of a rich CO 2 mixture with small amounts of
methane (molar composition: CO 2 94%, CH 4 4%, N 2 2%) and the pure CO 2 vapour pressure curve.

Figure 1: Pure Carbon Dioxide vapour pressure line and CO 2 -CH 4 mixture

The leakage of a CO 2 pipeline represents the major risk of CO 2 transportation in pipelines. In case of a
leak, the CO 2 is released at a very low temperature as a mixture of cold gas and solid particles into the
environment. While in case of smaller leaks, CO 2 clouds disperse after short time, in case of larger leaks,
the cold gas/solid mixture forms dense-gas clouds which rest over the terrain and can gather at low points
(depressions, low-situated rooms in buildings), displacing hereby the ambient air (danger of asphyxiation,
toxic effects at higher concentration). The cooling effect in the CO 2 rich plume can cause localized
condensation of atmospheric water into fine aerosol droplets which create regions of very low visibility that
can drift with the prevailing wind. Cooling down of the pipeline material due to the leakage could result in
local fragility of the pipe steel potentially forming the starting point of long running ruptures.

2. Equations of State and Thermodynamic Models

The selection of suitable equations of state is very important step in the design of a CCS project due to the
impact in many areas from steady state and dynamic simulation, HSE risk evaluation including pipeline
depressurization either during planned operations or in case of unforeseen events.
In these fields the use of commercial simulators such as HYSYS (Aspen Technology or Honeywell
versions) and AspenPlus is a common practice. Standard cubic equations of state as the Soave-Redlich-
Kwong SRK (Soave, 1974) and Peng-Robinson PR (Peng and Robinson, 1978) are proposed as default
choices and are usually assumed to be the most reliable tools. For the simulation of pure CO 2 transport,
one of the leading fluid-dynamics simulation software (OLGA) has recently introduced the use of the
Wagner equation (Span and Wagner, 1996).
The assessment of simulation results in the frame of feasibility studies or more detailed engineering
projects represent a problem due to the lack of experimental data in this field. As a substitution of
experimental data, the use of the Span-Wagner or GERG equations of state is a possible solution. With
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respect to the Span-Wagner equation which applies only to pure CO 2 , the GERG model can be applied
also to CO 2 mixtures containing light hydrocarbons (C1, C2, C3 etc.) and inert gases (N 2 and O 2 ), etc.
The GERG-2004 equation of state has been developed and published (Kunz et al., 2007) as a research
project supported by the “Groupe Européen de Recherches Gazières”. The natural gas industry requires
the accurate knowledge of the thermodynamic properties of natural gases and other mixtures of natural
gas components for the basic engineering, performance assessment of existing plants, gas metering,
transmission, and storage. Processing, transportation, and storage of natural gas requires property
calculations for a wide range of mixture compositions and operating conditions in the homogeneous gas,
liquid, and supercritical regions, and also for vapor-liquid equilibrium states. Most of the standard natural
gas applications, such as gas transmission and storage, are located in the “classical” natural gas region,
i.e. the gas phase at temperatures from 250 K to 350 K and pressures up to 30 MPa, this range is of main
interest for the calculation of thermodynamic properties and is addressed by this new equation. To
reproduce experimental values, for both pure components and mixtures, within experimental errors, the
GERG-2004 equation uses a larger number of regressed parameter with respect to cubic equations of
state
The GERG-2004 equation of state is explicit in the Helmholtz free energy with density and temperature as
independent variables:

a( ρ , T ) = a 0 ( ρ , T ) + a r ( ρ , T ) (1)
0 r
where a represent the ideal part and a the residual part. Usually, the Helmholtz free energy is used in
dimensionless form and by introducing the adimensional variables τ=T c /T and δ=ρ/ρ c is finally written
as:

α (δ ,τ ) = a 0 (δ ,τ ) + a r (δ ,τ ) (2)

There is no sufficient space here to detail how the GERG-2004 equation expands the ideal and residual
Helmoltz energy parts by means of a large number of complex polynomial and exponential terms. The
level of complexity of the equation can be guessed by noting that it uses up to 110 parameters to define
the pure fluid behavior and 89 binary coefficients for each component-component interaction.
These figures are astonishingly high when compared to 3 pure component parameters and one interaction
coefficient used by cubic equations of state.

3. Carbon-dioxide transportation
To compare the selected equations of state and models, we have chosen a complex case of a long
distance pipeline, about 525 km long, designed to transport pure carbon dioxide generated by some
electric-power-plant located on a sea coast to an oil field at higher elevation. At the delivery point CO 2 will
be either stored or used for enhanced oil recovery. The profile of the transfer line is shown on the next
Figure 2. Transported fluid is assumed to be pure CO 2 and the very small impurities are excluded from the
simulation. At the pipeline inlet the fluid is received at 55°C and at 250 bar. The initial flow-rate considered
is 600,000 kg/h and number of calculations with different internal diameters are performed to select a
viable combination. The target final pressure should be nearer but not over 120 bar. As a usual practice in
flow-assurance analysis, two different scenarios (summer and winter) characterized by different ambient
temperature are simulated. An internal diameter equal 0.463 m represents a possible solution for the
specified flowrate and is used to perform sensitivity calculation with the selected thermodynamic models.
Calculation are performed using the XPSIM (eXtended Process SIMulator, 2013) simulation software
which allows the selection of other complex equations of state in addition to the standard cubic equations
such as SRK and PR. The results are shown on Table 2 and the values calculated using the GERG
equation would be considered as the reference experimental data.

Table 2: Carbon-dioxide transport results (winter case)

Equation Final Pressure Final Temp °C
bar
GERG 116.08 0.32
LK 115.92 -0.30
SRK 115.47 -0.07
PR 116.31 -0.26
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The fluid is transported in the dense gas phase region; the pressure is always above the critical pressure
and the crossing of the critical temperature at 31 °C does not show any discontinuities in the calculated
fluid properties. Formally the fluid is vapour at the pipeline inlet and liquid at the pipeline outlet. In this
case, calculated final pressure and temperature are quite similar and the cubic equations of state perform
well.

Figure 2: Pipeline elevation profile

The profile of pressure and temperature along the pipeline is shown on the next Figure 3.
From the model testing point of view, the above simulation is not much interesting. A more interesting
simulation is when the pure CO 2 enters the two-phase region and some segments of the pipeline will
operate in two phase flow exhibiting liquid hold-up and thermal effects associated to condensation and
evaporation.

Figure 3: Pressure and temperature profile – Single phase transport case

For the thermodynamic simulation of CO 2 transport some simulators use the Span-Wagner equation of
state (Span, 1996). This equation has some drawbacks since it can strictly applied only to pure CO 2 .
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Using XPSIM the GERG-2004 model can be used; it provides thermodynamic values for pure CO 2 with
the same precision of the Span-Wagner model, in addition it can be used to simulate fluids not composed
of pure CO 2 : light hydrocarbons, water, nitrogen and other gases are treated by the GERG-2004 equation
of state.
The simulation of pure fluid transport in dense phase is not a difficult task. More interesting and difficult
simulations are encountered when the formation of coexisting vapour and liquid phases appear along the
pipeline. In this case the formation of an equilibrium phase entrains the evaluation of the liquid holdup and
isenthalpic flash calculation are required to evaluate the pressure-temperature profile.
This case can be obtained by decreasing the inlet pipeline pressure from 250 bar to 210 bar and keeping
the initial temperature at 55 °C. This produces an higher pressure drop with corresponding lower final
pressure. So at about 473 km the fluid crosses the critical temperature and soon after enters in the two-
phase coexistence region. As shown in the next Figure 4, at this point the liquid hold-up sharply increases
to 1.0 and then diminishes with the pressure lowering reaching a value of 0.25 at pipeline exit.
In this case the simulation shows important differences when the equations of state are changed. Results
are shown on the next Table 3. The difference in the values obtained for the final pressure become critical
from the engineering design point of view. While the two non-cubic models (GERG and LK) show coherent
results the two cubic equations (PR and SRK) sharply diverge in the final calculated pressure, temperature
and hold-up values.

Table 3: CO 2 transport – Summer case with 2-phase flow

Case Equation Final Pressure, Final Temperature, Vapour Fraction
bar °C
1 GERG, k=SRK 62.61 23.84 0.4545
2 LK, k=SRK 63.40 24.39 0.4697
3 SRK 53.81 17.36 0.4881
5 PR, k=PR 59.50 21.64 0.4397

Figure 4: Pressure and temperature change – Two phases transport case

4. Pipeline Depressurization
Another point where the selection of equation and models represent a critical point is the simulation of
pipeline depressurization. Since the depressurization of a long distance pipeline can last many days, the
analysis of the effect of the various models in this field has been performed by considering a pipeline
section 4 km long, with nominal diameter of 24”, and the leak or pressure-safety-valve size is assumed to
have a diameter equal to 50 mm. The initial conditions are assumed to be 150 bar and 30 °C. Two sets of
the simulation results performed using the GERG and Peng-Robinson models are summarized by the
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curves presented in Figure 5. Pressure differences can be considered relatively small while a significant
temperature difference is found at the end of the simulation.

Figure 5: Pipeline depressurization – Pressure and temperature profiles for PR and GERG models

5. Conclusions
Though the use of widely popular cubic equations of state, as implemented in commercial simulators,
supplies in general reliable simulation results, in the case of CCS projects, they can produce large
differences when applied in regions where vapour and liquid phases coexist. The use of more complex
models such as the GERG equation of state becomes an almost mandatory step for the general
verification of thermodynamic simulation in the CCS application field and research.

References
Span R., Wagner W., 1996, A New Equation of State for Carbon Dioxide Covering the Fluid Region from
the Triple Point Temperature to 1100 K at Pressures up to 800 MPa, J. Phys. Chem. Ref. Data, Vol 25,
no 6,1509-1596.
Kunz O., Klimeck R., Wagner W., Jaeschke, M., The GERG-2004 Wide-Range Equation of State for
Natural Gases and Other Mixtures, Groupe Européen de Recherches Gazières, 2007
Lee B.I., Kesler M.G., 1975, A generalized thermodynamic correlation based on three-parameter
corresponding states, AIChE J., 21, 510-527.
Peng D.Y., Robinson D.B., 1976, A new two-constant equation of state, Ind. Eng. Chem. Fund. 15, 59–64.
Samadi J., Garbolino E., 2012, Dynamic Analysis of Safety Performance Indicators for CO2 Capture,
Transport and Storage Activities, Chemical Engineering Transactions, vol. 26, CISAP 5 (Milan).
Soave G., 1972, Equilibrium constants from a modified Redlich-Kwong equation of state, Chem.Eng.Sci.
27, 1197-1203.
Vianello C., Macchietto S., Maschio, G., 2012, Conceptual Models for CO2 Release and Risk Assessment:
a Review, Chemical Engineering Transactions, vol. 26, CISAP 5 (Milan).
XPSIM (eXtended Process SIMulator), 2013, Reference Manual, Version 2.01., Process Simulation
Services, www.xpsimworld.com.