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Proceedings of the 2012 9th International Pipeline Conference IPC2012 September 24-28, 2012, Calgary, Alberta, Canada

IPC2012-90461

THE DECOMPRESSION BEHAVIOUR OF CARBON DIOXIDE IN THE DENSE PHASE


Andrew Cosham Atkins Newcastle upon Tyne, UK David G Jones Pipeline Integrity Engineers Newcastle upon Tyne, UK Keith Armstrong GL Noble Denton Spadeadam Test Site, UK

Daniel Allason GL Noble Denton Spadeadam Test Site, UK ABSTRACT Pipelines can be expected to play a significant role in the transportation infrastructure required for the successful implementation of carbon capture and storage (CCS). National Grid is undertaking a research and development programme to support the development of a safety justification for the transportation of carbon dioxide (CO2) by pipeline in the United Kingdom. The typical CO2 pipeline is designed to operate at high pressure in the dense phase. Shock tube tests were conducted in the early 1980s to investigate the decompression behaviour of pure CO2, but, until recently, there have been no tests with CO2-rich mixtures. National Grid have undertaken a programme of shock tube tests on CO2 and CO2-rich mixtures in order to understand the decompression behaviour in the gaseous phase and the liquid (or dense) phase. An understanding of the decompression behaviour is required in order to predict the toughness required to arrest a running ductile fracture. The test programme consisted of three (3) commissioning tests, three (3) test with natural gas, fourteen (14) tests with CO2 and CO2-rich mixtures in the gaseous phase, and fourteen (14) tests with CO2 and CO2-rich mixtures in the liquid (or dense) phase. The shock tube tests in the liquid (dense) phase are the subject under consideration here. Firstly, the design of the shock tube test rig is summarised. Then the test programme is described. Finally, the results of the dense phase tests are presented, and the observed decompression behaviour is compared with that predicted using a simple (isentropic) decompression model. Reference is also made to the more complicated (non-isentropic) decompression models. The differences between decompression through the gaseous and liquid phases are highlighted.

Julian Barnett National Grid Warwick, UK

It is shown that there is reasonable agreement between the observed and predicted decompression curves. The decompression behaviour of CO2 and CO2-rich mixtures in the liquid (dense) phase is very different to that of lean or rich natural gas, or CO2 in the gaseous phase. The plateau in the decompression curve is long. The following trends (which are the opposite of those observed in the gaseous phase) can be identified in experiment and theory: Increasing the initial temperature will increase the arrest toughness. Decreasing the initial pressure will increase the arrest toughness. The addition of other components such as hydrogen, oxygen, nitrogen or methane will increase the arrest toughness. INTRODUCTION Carbon Capture and Storage (CCS) is one of the technologies proposed for the mitigation of climate change. It is an example of a bridging technology in the transition to a sustainable, low-carbon economy. CCS involves capturing carbon dioxide (CO2) from large industrial emitters, such as coal and gas fired power stations, and transporting it to permanent storage sites, such as a depleted oil or gas reservoirs, or saline aquifers. Pipelines can be expected to play a significant role in the transportation infrastructure required for the successful implementation of CCS. National Grid is undertaking a research and development programme to support the development of a safety justification for the design, construction and operation of pipelines to transport CO2 in the United Kingdom [1]. The pipeline industry in the United States of America (USA) has over 40 years experience of the design, construction

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and operation of CO2 pipelines [2-4]. The Canyon Reef Carriers pipeline system in West Texas, the first onshore CO2 pipeline, was commissioned in 1972 [5]. There are over 6,611 km (4,111 miles) of high-pressure CO2 pipelines in North America, with almost all being in the USA [4]. Outside of North America, there are (currently) perhaps less than about 500 km (about 300 miles) of CO2 pipelines [2]. Most of the experience relates to enhanced oil recovery. CCS introduces a number of differences, most notable the routeing of pipelines through more densely populated areas (as in the UK), and different components (impurities) in the anthropogenic CO2-rich stream to be transported through the pipelines. The composition of the CO2-rich stream captured at the emitter will depend on the technology used to capture the CO2, but only indicative ranges of compositions have been defined [6]. The actual composition will vary from project to project. Components that may be presented in the CO2-rich stream that are not present in the natural or anthropogenic CO 2 that is currently transported in pipelines include hydrogen and argon, and in low concentrations carbon monoxide, NOx and SOx (i.e. combustion products)1,2. Nitrogen and methane are transported in the existing pipelines in North America 3. Hydrogen in particular has significant effect on the toughness required to arrest a running ductile fracture (as will be shown). There are similarities and differences between the transportation of CO2 in a pipeline and the transportation of natural gas or hydrocarbon liquids. One of the differences is the decompression behaviour of CO2. The decompression behaviour of CO2 can be similar or very different to that of natural gas, depending on whether the CO2 is in the liquid phase or the gaseous phase [7]. Pipelines transporting gaseous fluids, two phase fluids, dense phase fluids, or liquids with a high vapour pressure are susceptible to long running fractures. Long running fractures are prevented by specifying an adequate pipe body toughness to arrest the fracture or by using mechanical crack arrestors. In order to predict the toughness required to arrest a running ductile fracture in a pipeline it is necessary to be able to predict the decompression behaviour of the fluid in the pipeline. The decompression behaviour depends upon (in simple terms) the initial pressure and temperature of the fluid (i.e. prior to the rupture), and the composition of the fluid. There is little by the way of experimental data on the decompression behaviour of CO2. The Battelle Memorial Institute conducted seven tests on pure CO2 in the early 1980s;
Low here is (arbitrarily) considered to be less than 0.25 mol.%. At this level, impurities will not significantly affect the decompression behaviour, but may still have implications for safety or integrity. 2 The Souris Valley Pipeline (the Weyburn Pipeline) transports anthropogenic CO2 from the Great Plains Synfuels Plant that contains 0.1 mol.% CO [6]. 3 The CO2-rich stream quality specifications for the pipelines in North America permit up to 4 mol.% N2 and 5 mol.% CH4 or higher hydrocarbons (but at least 95 mol.% CO2) [6]. The composition of the CO2 that is transported is, however, generally purer than that permitted in the quality specification [6]. The Canyon Reef Carriers pipeline transports 5 mol.% CH4. The Souris Valley Pipeline transports 3 mol.% CH4 and higher hydrocarbons. The Cortez Pipeline transports 1.3 mol.% N2.
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one in the gaseous phase, one in the liquid phase, three in the dense phase, and two in the two-phase region [8,9]. No tests had been conducted on CO2-rich mixtures, i.e. CO2 plus other components, at least until very recently. The typical CO2 pipeline is designed to transport CO2 at high pressures, well above the critical pressure, i.e. in the liquid or dense phase. National Grid is interested in the transportation of CO2 in the liquid or dense phase, and in the gaseous phase. Transportation in the gaseous phase is of practical interest when the volumes of CO2 to be transported are relatively low, or when re-using existing pipelines. The decompression behaviour of a fluid is measured using a shock tube (also referred to as an expansion tube). A shock tube is a length of constant cross-section, straight pipe that is closed at one end by an end cap and at the other end by a rupture or bursting disc. The disc is designed to fail nearinstantaneously to give a full-bore opening of a diameter greater than or equal to the bore of the shock tube. The shock tube is instrumented with fast-response pressure transducers to measure the propagation of the expansion wave along the shock tube. The results of a shock tube test are typically presented in the form of a decompression wave velocity curve, i.e. a plot of pressure versus the velocity of the decompression wave. A decompression curve is used in a model, such as the Two Curve Model, to predict the toughness required to arrest a running ductile fracture (the arrest toughness). National Grid has commissioned and successfully completed a programme of shock tube tests to investigate the decompression behaviour of CO2-rich mixtures4. The test programme includes tests on CO2 in the gaseous phase and in the liquid (or dense) phase. It is the dense phase tests that are the subject of this paper, though reference is also made to the gaseous phase tests. The gaseous phase tests are reported in Barnett & Jones (2011) [10] and Cosham et al. (2011) [11]. The tests were conducted on behalf of National Grid at GL Noble Dentons Spadeadam Test Site in Cumbria, UK. National Grid intends to conduct a full-scale fracture propagation test using a dense phase CO2-rich mixture at the Spadeadam Test Site. The results of the shock tube tests have been used in the design of the full-scale test. Firstly, the development of a simple (isentropic) decompression model is described. The model is referred to as DECOM (after GASDECOM). It adopts identical assumptions to the models developed for natural gas, such as GASDECOM and DECAY, but uses reference (i.e. the most accurate) equations of state for CO2 and CO2-rich mixtures. DECOM is used to predict the results of the tests. Secondly, the shock tube test programme is described. The results of the tests are then presented and compared with predictions made using DECOM. Finally, the implications of the results are discussed.
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National Grid is also supporting a PRCI, APIA and EPRG project to conduct shock tube tests on CO2 and CO2-rich mixtures at the TransCanada/NTRC Shock Tube Test Facility in Didsbury, Alberta, Canada.

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pi, Ti (v, si, c, u, etc.)

si, p (T, v, c, u, etc.)

si

si
ps

si

liquid-vapour phase boundary

Fig. 1 Isentropic decompression

PREDICTING DECOMPRESSION BEHAVIOUR A rupture in a pipeline initiates a decompression (expansion) wave in the fluid that propagates through the fluid in both directions away from the rupture. The flow out of the opening is choked. The leading edge of the decompression wave travels at the acoustic velocity (the speed of sound) of the fluid at the initial pressure and initial temperature, less the initial velocity of the fluid (prior to the rupture). The fluid decompresses behind the leading edge of the expansion wave. The velocity at any point in the decompression wave is equal to the local acoustic velocity less the local outflow velocity toward the rupture. The decompression is rapid and it is therefore generally considered to be an isentropic (constant entropy) expansion process. This is a simplifying assumption. A number of simple decompression models have been developed for predicting the decompression behaviour of a fluid (such as a rich gas) in a pipeline following a rupture, as discussed in Cosham et al. (2010) [13]. Probably the most widely used for applications involving lean and rich gas is GASDECOM, developed by Kenneth E. Starling on behalf of the Battelle Memorial Institute in the late 1970s [12,14,15]. GASDECOM has been validated against a large number of fullscale fracture propagation tests and shock tube tests involving natural gas, and several shock tube tests involving CO2 [8,9,12,14-16]. The simple decompression models all assume onedimensional flow, isentropic decompression and homogeneousequilibrium, and, as a boundary condition, that the velocity of the fluid prior to the rupture is very small (compared to the acoustic velocity and the outflow velocity). This reduces the problem of modelling the decompression of a fluid following a rupture to that of the centred expansion wave problem

described in standard texts on thermodynamics. The effects of friction and heat transfer are not considered in the simple decompression models5. An equation of state is required to calculate the thermodynamic properties along the isentropic decompression path. An equation of state defines the thermodynamic state of a fluid; it is a mathematical representation of the phase diagram. The isentropic decompression path is defined by the composition, and the initial pressure, pi, and initial temperature, Ti, of the fluid, as illustrated in Fig. 1. pi and Ti define the entropy, si, and also the density and the acoustic velocity, at the initial conditions. The isentropic decompression path is then fully defined in terms of si and p. The local decompression wave velocity at any point along the decompression path follows from the fully defined isentropic decompression path. The only difference between the various decompression models is in the particular equation of state that is used (and, to a lesser extent, the accuracy and stability of the numerical algorithms). GASDECOM uses Benedict-Webb-RubinStarling (BWRS) [14]. DECAY uses Peng-Robinson [16]. Therefore, it follows that it is preferable, where practical, to use the most accurate equation of state that is available for any given fluid. Then, any differences between the predicted and observed decompression curve are more likely to be due to the assumptions in the model, rather than the equation of state. The most accurate equations of state are the so-called reference equations of state. The reference equations are designed to represent the experimental data to within their experimental uncertainty and to behave reasonably in regions characterised by poor data. Currently, there is no reference equation of state for CO2-rich mixtures, but there is one for natural gas mixtures. Computational fluid dynamics methods have been used to develop decompression models that do not assume that the expansion process is isentropic, e.g. Picard & Bishnoi (1988) [17], Mahgerefteh et al. (2006, 2012) [18,19], Wen et al. (2011) [20] and Xu et al. (2012) [21]. All of these non-isentropic models assume one-dimensional flow and homogeneousequilibrium. The advantage of these more complicated models over the simpler decompression models is that the effects of friction and heat transfer can be investigated. In particular, the effect of diameter can be investigated. However, in most practical applications, the difference between these simple and complex models is small. DECOM A one-dimensional, isentropic and homogeneousequilibrium model has been developed to predict the results of the shock tube tests commissioned by National Grid. The assumptions in the decompression model, hereafter referred to as DECOM, are identical to those in GASDECOM, except that the BWRS equation of state has (in effect) been replaced with the appropriate reference (i.e. most accurate) equation of state for the fluid in question.
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This is implicit in the assumption that the expansion process is isentropic.

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component CO2 CO2-rich mixtures natural gas nitrogen

equation of state Span and Wagner (1996) [22] GERG-2008 [23] GERG-2008 [23] Span, Lemmon, Jacobsen, Wagner and Yokozeki (2000) [24]

Table 1 The reference equations of state used in DECOM

The equations of state that are used in DECOM are given in Table 16. Span & Wagner is the reference equation of state for CO 2 [22]. GERG-2008 is the reference equation of state for natural gas mixtures7 [23,25]. GERG-2008 was developed for standard and advanced natural gas applications, such as pipeline transportation, natural gas storage and processes involving liquefied natural gas (LNG). It was not specifically developed for CCS applications, i.e. for mixtures with a very high proportion of CO2. The equation is designed to behave reasonably in regions characterised by poor data, and so it is considered to be the most accurate equation of state that is currently available. The numerical algorithms used in DECOM to calculate the thermodynamic properties along the isentropic decompression path are identical to those in the National Institute of Standards and Technology (NIST) Reference Fluid Thermodynamic and Transport Properties Database (REFPROP): Version 9.0 [26]. THE SHOCK TUBE TEST RIG The shock tube test rig consists of a 144 m long, 168.3 mm (6.625 in.) outside diameter test reservoir and a smaller diameter circulating loop attached to either end of the shock tube, see Fig. 2. The shock tube test rig was designed and constructed by GL Noble Dentons Spadeadam Test Site in Cumbria, UK. The test reservoir is constructed from ASTM A333 Grade 6 low carbon steel seamless pipe with a nominal wall thickness of 10.97 mm (i.e. Schedule 80). The internal diameter of the test reservoir is approximately 146.36 mm. The wall thickness, internal diameter, straightness and surface roughness of each length of pipe in the test reservoir were measured during construction. The smoothest lengths of pipe were placed towards the open end, with some re-ordering to minimise the internal hi-lo at the girth welds. The average surface roughness (mean of absolute values, Ra) is 0.005 mm (and the maximum is 0.0063 mm). A gauging plug with a diameter of 144.0 mm
It is worth noting that other simple (isentropic) decompression models that are based on the Span & Wagner and GERG-2008 equations of state, such as that described in Cosham et al. (2010) [13], are, in effect, identical to DECOM in all but name. 7 The GERG-2008 equation of state was completed in 2004 (as GERG-2004) and was subsequently extended in 2008 [23,25]. The only difference between GERG-2008 and GERG-2004 is that the extended equation is applicable to mixtures that contain three additional components: n-nonane, n-decane and hydrogen sulphide. Except for mixtures that contain the three additional components, GERG-2004 and GERG-2008 are identical.
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was pulled through the test reservoir after fabrication to prove the bore of the test reservoir. An outlet flange with a bore of approximately 146.36 mm (i.e. the same as the pipe) is welded to the end of the test reservoir. A rupture disc (see below) is held in place between the outlet flange and the retaining flange. The nominal bore immediately downstream of the rupture disc is approximately 210 mm, i.e. significantly larger than the bore of the test reservoir. The shock tube tests are initiated by explosively cutting the rupture disc. This ensures a near-instantaneous, full-bore release. The diameter of the cut is larger than the bore of the test reservoir (to ensure an unrestricted release). A smaller diameter circulating loop runs parallel to the test reservoir, see Fig. 2. The circulating loop is used for mixing the CO2-rich mixtures and for controlling the temperature of the fluid (i.e. heating or cooling). It contains a pump and heat exchangers. The circulating loop is connected to each end of the test reservoir through an isolation valve and a weldolet. The test rig is insulated with a 25 mm thick layer of closedcell rubber foam insulation. The test reservoir is firmly anchored to a heavy concrete support at the open end and at regular intervals along its length. A concrete anchor block is installed behind the closed end of the test reservoir to react against the force of the expanding fluid when the test is initiated. The design of the shock tube test rig is similar to that of other test rigs (see Jones & Gough (1981) [16] and Botros et al (2004, 2007, 2010) [27-29]). The one significant difference between this shock tube test rig and others is that here the tests are initiated by explosively cutting a rupture disc. The other method of initiating a shock tube test is to use a bursting disc 8. Initiating the test by explosively cutting a rupture disc provides for a greater degree of control over the initial conditions (pressure, temperature and composition). In a test with a rupture disc, it is not necessary to increase the pressure in the shock tube (i.e. add fluid to the shock tube) in order to initiate the test. Tests were also conducted using a bursting disc, in order to investigate whether the different initiation techniques had any effect on the decompression behaviour of the fluid (although, the dense phase test with a bursting disc, Test 18, was unsuccessful, see below). The shock tube test rig was designed for both gaseous and dense phase tests. It is a long shock tube. The length over which data can be recorded before the arrival of the reflected wave from the closed end of the shock tube increases as the length of the shock tube increases. This is of particular importance for testing dense phase CO2 because the initial speed of sound is very high. A long shock tube can also be instrumented with more pressure transducers towards the open end of the shock tube (there is more physical space).

In the technical literature, the terms bursting disc and rupture disc are used synonymously. Here, bursting disc is used to describe a disc fired by pressure (the disc is designed to fail at a specified pressure), and rupture disc is used to describe a disc fired by explosively cutting the disc.

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test reservoir (146.36 mm nominal internal diameter, 144 m long)

circulating loop

heat exchanger

pump
Fig. 2 The shock tube test rig

distance from the open end, m 0.0864 0.34 0.54 0.74 0.94 1.24 1.84 2.44 3.64 4.84 6.04 9.04 13.54 18.04 22.54 30.04 42.04 54.04 66.04 77.94 89.94 101.94 113.94 125.94 137.94 143.775

pressure transducers P01,P02 P03,P04 P05,P06 P07,P08 P09,P10 P11,P12 P13,P14 P15,P16 P17,P18 P19 P20 P21 P22 P23 P24 P25 P26 P27 P28 P29 P30 P31 P32 P33 P34 P35

temperature transducers T01

T02

T03

T04 T05 T06 T07 T08 T09 T10 T11 T12 T13,FT07 T14,FT01

Notes: 1. The distance is measured to the release point (i.e. the end of the constant cross-section). In Tests 23 to 31, the effective distance is 0.039 m less than indicated above because of a modification that was made to the retaining flange in order to reduce the magnitude of the pressure transient associated with the detonation of the explosive charge. 2. P denotes a fast-response pressure transducer. 3. T denotes a temperature transducer mounted on the external surface of the test reservoir. These transducers measure the pipe wall temperature. 4. FT denotes a temperature transducer mounted on a probe in the centre of the shock tube. These transducers measure the fluid temperature. Table 2 Location of the pressure and temperature transducers

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Test No. 1 #1 #2 18 19 20 21 22 23 24 25 26 27 28 29 30 31

10

11

12

13

14

15

16

17

18

19 20-25 26

27

28

29

30

31 32-35

Note: 1. A shaded cell indicates a location where a pressure transducer was either not installed or did not record usable data. Table 3 A list of the pressure transducers in each shock tube test

Computational fluid dynamics was used to investigate the effect of length, diameter, surface roughness and heat transfer. The results of these provided independent confirmation of the design of the test rig. The analyses were conducted for National Grid by University College London and Kingston University London. INSTRUMENTATION Two Druck PTX-610 static pressure transducers record the pressure in the test reservoir and the circulating loop, respectively. Thirty five (35) Kulite CT-375M fast-response pressure transducers are set out along the length of the test reservoir, see Table 2, to measure the expansion wave. The pressure transducers are temperature compensated. The transducers are mounted in bosses and are flush with the internal bore of the shock tube. The spacing between the transducers increases with increasing distance from the open end of the shock tube. At the first nine locations from the open end (to approximately 3.6 m), there are transducers installed at both the 12 oclock and 3 oclock positions. The remainder of the transducers are installed at 12 oclock. In the later tests, pressure transducers were not installed at all locations, and some pressure transducers did not record usable data in some tests. Table 3 summarises which pressure transducers recorded useable data in each test; at the other locations a pressure transducer was either not installed or did not record usable data. Fourteen (14) welded tip, PTFE insulated Type T thermocouples are set out along the length of the test reservoir, see Table 2, to measure the pipe wall temperature. The

temperature transducers are spot welded on to the external surface of the pipe (i.e. beneath the insulation). The temperature transducers are installed at the same distance from the open end as some of the pressure transducers (as listed in Table 2), but at 45 to the pressure transducers at the 12 oclock position. Two (2) thermocouples were mounted on probes in the centre of the shock tube to measure the fluid temperature. The internal thermocouples were located near to the closed end of the shock tube, at the same distance from the open end as two of the external thermocouples (see Table 2)9. The composition of the fluid in the shock tube is measured off-line using gas chromatography. An array of oxygen sensors and thermocouples is positioned in several arcs in front of the open end of the shock tube to measure the dispersion of the release. All of the instrumentation is calibrated. THE TEST PROCEDURE The test rig is purged with CO2 and then filled with the fluid required for the test. In tests of CO2-rich mixtures, the rig is partially pressurised with CO2, and then the other components are weighed and added. Then, additional CO2 is added to achieve the required test pressure. The fluid is circulated through the circulating loop whilst the rig is being filled in order to obtain a homogeneous mixture. During the final stages of filling, the temperature is adjusted to the test temperature by heating or cooling using the
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In the gaseous phase tests, internal thermocouples were only used in Tests 16 and 17, see Cosham et al. (2011) [11].

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critical pressure, bara

heat exchanger. A sample is taken from the test reservoir and the composition is measured using gas chromatography. The mixture is considered to be uniform if the results of two consecutive samples taken at intervals of at least an hour are essentially similar. Once the required test conditions are attained, i.e. pressure and temperature, and for CO2-rich mixtures, composition, the isolation valves are closed to isolate the test reservoir. The pressure and temperature in the test reservoir are then allowed to stabilise. The shock tube test is then initiated. The time elapsed between the closing of the valves and initiating the test is typically 10 to 15 minutes. THE SHOCK TUBE TEST PROGRAMME The shock tube test programme consisted of three (3) commissioning tests, three (3) tests with natural gas, fourteen (14) tests with CO2 or CO2-rich mixtures in the gaseous phase, and fourteen (14) tests with CO2 or CO2-rich mixtures in the liquid (dense) phase. The dense phase tests are the main subject of this paper, namely Tests 18 to 31. Table 4 presents the test conditions for the three commissioning tests. Test #0 was to confirm the effectiveness of the cutting of the rupture disc with an explosive charge. Tests #1 and #2 were conducting with 100 mol.% N2, the first without the weldolets for the circulating loop attached (see Fig. 2) and the second with them attached. Table 5 presents the initial pressure and initial temperature, and composition of all of the shock tube tests with CO2 or CO2rich mixtures. The initial pressure (pi) is the pressure measured by the static pressure transducer in the test reservoir. The initial temperature (Ti) is the average of the temperatures measured by all of the external thermocouples (i.e. average pipe wall temperature) in the 30 s prior to the test. Rationale for Tests 19 to 31 The thirteen (13) tests with CO2 or CO2-rich mixtures were designed to confirm the predicted trends in behaviour (see Cosham et al. (2008, 2010) [13,30] and Cosham (2009) [7]) and to validate the decompression model (DECOM) for pure CO2, binary and tertiary mixtures, and then for higher order mixtures. The tests were conducted at pressures from 38 to 150 barg, and at temperatures from +5 to +35C. The minimum operating temperature of a buried onshore pipeline (in the UK) is typically +4 to +5C. At 4C, CO2 is a liquid at pressures greater than 37.7 barg. At 5C, it is a gas at pressures greater than 38.7 barg. 150 barg represents an upper bound to the maximum operating pressure (for an onshore pipeline in the UK), and 100 to 150 barg represents a typical range of operating pressures. +5 to +35C represents a typical range of operating temperatures. The lower pressures (down to 38 barg) and the higher temperatures (up to 35C) provide additional information on the effect of the initial pressure and the initial temperature on the decompression behaviour.

100 90 80 70 60 CO2 N2O NO Ar O2 N2 CO


C2H6

NO2
H2S SO2

50 40 30 20 10 0 -300
H2

CH4

C3H8 nC4H10 nC5H12 iC4H10 iC5H12 C6+

-200

-100 0 100 200 critical temperature, C

300

Fig. 3 The critical temperature and critical pressure of CO2, hydrocarbons and components that may be found in anthropogenic CO2-rich mixtures

Other components that may be present in an anthropogenic CO2 mixture include hydrogen (H2), nitrogen (N2), carbon monoxide (CO), argon (Ar), oxygen (O2), methane (CH4), hydrogen sulphide (H2S), and NOx and SOx. These other components will all affect the decompression behaviour. For transportation in the liquid or dense phase, increasing the concentration of the non-condensables (H2, N2, CO, Ar, O2 and CH4) is expected to increase the toughness required to arrest a running fracture because the critical temperature is lower than that of CO2, see Fig. 3. The non-condensables increase the bubble point pressure for a given temperature (see Fig. 11). Conversely, increasing the concentration of H2S, NOx or SOx is expected to decrease the toughness, see Fig. 3. National Grid is developing an entry-specification for the composition of CO2 to be transported in pipelines, see Table 6. The limits in this specification are based on a number of considerations, including the effect of the other components on the thermodynamic properties of the CO2 mixture. For transportation in the dense phase, the specification limits H2 to 3 mol.%, N2 to 4 mol.%, and H2S, NOx and SOx, combined, to less than 0.05 mol.%. The minimum concentration of CO2 is 96 mol.%. The composition of the CO2-rich mixtures considered in the test programme is based on the limits in the specification, but also on practical constraints. CO, H2S and NOx or SOx (or an analogue such as sulphur dioxide) were not tested because of the practical difficulties in handling these substances in large quantities (and the entryspecification limits their concentration to a low level). The gas chromatographs were not able to separately measure O2 and Ar, so Ar was not tested.

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Table 4 The commissioning tests

Test No. #0 #1 #2

composition, mol. % test of explosively cutting the rupture disc 100 mol.% N2 without the weldolets for the circulating loop 100 mol.% N2 with the weldolets for the circulating loop

pressure, barg 148.9 151.0

temperature, C 17.2 15.2

Table 5 The shock tube tests of CO2 and CO2-rich mixtures

Test No. 02 03 04 05 06 07 08 09 10 11 12 13 14 16 18 19 20 21 22 23 24 25 26 27 28 29 30 31

composition, mol.% CO2 H2 100 100 100 96.99 3.01 95.97 99.14 95.70 3.30 94.81 88.89 89.23 3.24 100 100 100 100 100 100 100 100 100 100 100 100 95.96 97.38 2.62 91.71 4.00 96.19 0.90 93.03 0.95 91.03 1.15

N2

SO2

O2

CH4

4.03 0.86 1.00 1.04 1.07 1.24

4.15 7.92 3.84

1.11 1.32

1.01 1.13

4.04 4.29 1.03 2.02 4.00

0.97 1.87 1.87

0.91 2.13 1.95

pressure, barg 38.0 38.1 38.0 38.0 37.9 38.0 38.0 38.0 38.0 38.0 35.8 35.8 35.8 37.8 152.9 152.4 37.9 45.3 100.5 149.4 60.4 100.9 140.4 141.0 140.6 140.2 140.2 149.5

temperature, C 4.9 5.1 20.2 5.1 5.3 9.9 10.0 10.0 5.1 5.0 16.3 10.9 10.9 5.0 14.0 5.0 0.1 5.0 20.0 35.6 20.0 20.0 19.7 19.9 19.8 20.0 19.9 10.0

Notes: 1. Tests 02 to 14 and 16 are gaseous phase tests. Tests 18 to 31 are liquid or dense phase tests. 2. Tests 01, 15 and 17 were conducted with natural gas. 3. A rupture disc was used in Tests 01 to 11, 14, 16, and 19 to 31. A bursting disc was used in Tests 12, 13, 15 and 18.

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Table 6 The National Grid entry-specification for the transportation of CO2 in the dense phase

component carbon dioxide (CO2) component nitrogen (N2) argon (Ar) oxygen (O2) hydrogen (H2) methane (CH4) carbon monoxide (CO) NOx SOx hydrogen sulphide (H2S)

minimum concentration, mole percent 96.0 maximum concentration, mole percent 4.0 4.0 3.0 3.0 2.0 0.2 0.01 0.01 0.002 (20 ppmv)

Note: 1. The limits on the maximum concentration of each of the non-condensables (H2, O2, N2, Ar and CH4) are indicative. The limit on the total concentration of the non-condensables, and the relative proportion of each of the non-condensables, will depend upon the geometry, grade and toughness of the line pipe steel, and the saturation pressure of the mixture. 2. The concentration of O2 will likely, in practice, be restricted to less than 10 ppmv (0.001 mol.%) in order to prevent aerobic conditions from developing in the storage site [6]. 3. The limits on CO, NOx, SOx and H2S may change as additional information becomes available, but will be at least an order of magnitude less than the non-condensables. The limit on the water content to ensure dry conditions in the pipeline is to be defined.

Tests 19 to 25 were 100 mol.% CO2. Test 19 was conducted at 150 barg, 5C10. Test 21 was conducted at 45 barg, 5C. This is near to the phase boundary. Tests 19 and 21 were conducted to confirm the (expected) trend that decreasing the initial pressure would result in an increase in the plateau level and hence an increase in the arrest toughness. Tests 22 and 25 were conducted at 100 barg, 20C. Test 25 is a repeat of Test 22. Test 24 was conducted at 60 barg, 20C. This is near to the phase boundary. Tests 22 and 24 were conducted to confirm the (expected) trend that decreasing the initial pressure would result in an increase in the plateau level and hence an increase in the arrest toughness. Test 23 was at conducted at 150 barg, 35C. Tests 19 and 23 were conducted to confirm the (expected) trend that increasing the initial temperature would result in an increase in the plateau level and hence an increase in the arrest toughness. Test 23 is also a repeat of an unpublished test conducted using a bursting disc. Test 20 was conducted at 38 barg, 0C. The test was conducted to illustrate the different behaviour of CO2 in the gaseous and liquid phases (i.e. a short and long plateau, respectively), through comparison with Test 03 (a gaseous phase test). Tests 19, 22 and 23 bound the typical operating conditions of a dense phase pipeline (in the United Kingdom).

Tests 19 to 25 illustrate the effect of the initial pressure and the initial temperature on the decompression behaviour for a range of different initial conditions. A modification was made to the retaining flange between Tests 22 and 23 in order to reduce the magnitude of the pressure transient associated with the detonation of the explosive charge. Tests 22 and 25 are before and after tests. Tests 26 and 27 were binary mixtures, i.e. CO2 plus one additional component. Test 27 was with 3 mol.% H2 and Test 26 was with 4 mol.% N2, based on the limits in the entry-specification. Tests 26 and 27 were conducted at 140 barg, 20C (a higher temperature is more severe than a lower temperature)11. Test 28 was a ternary mixture, i.e. CO2 plus two additional components. Similar components and concentrations to Tests 26 to 27 were tested, to build on the results from the previous tests. The test was conducted at 140 barg, 20C. Tests 29 to 30 were higher order mixtures, with similar components and concentrations as Tests 26 to 28, but with the addition of O2 and CH4. The compositions were based on the worst case that would be acceptable to the specification. Test 31 was another higher order mixture. The test was conducted at 150 barg, 10C. The test conditions were intended to be similar to the conditions that would be specified in the full-scale fracture propagation test. In Tests 28, 30 and 31 the concentration of CO2 is less than the minimum of 96 mol.% CO2 quoted in the entry11

10

The conditions quoted in the text are the nominal test conditions. The actual test conditions are quoted in Table 5.

Tests 26 to 30 were to be conducted at 100 barg, 20C. The pressure was increased to 140 barg because of difficulties that were encountered in mixing during the filling of the shock tube.

Copyright 2012 by ASME

160 140 120

160 140 120

pressure, barg

100
80 60

pressure, barg
Test 19, CO2

100
80 60

40
20 0 0 5 10 15 20 25 30 35 40 45 50 time, ms

40
20 0 0 5 10 15 20 25 30 35 40 45 50 time, ms
Test 31, CO2+H2+N2+O2+CH4

Fig. 4 Pressure-time traces for Test 19 (partially smoothed)

Fig. 5 Pressure-time traces for Test 31 (partially smoothed)

specification. This was to investigate the effect of adding higher levels of the other components. Rationale for Test 18 Test 18 was conducted to investigate if the initiation technique had any effect on the observed decompression behaviour. The more commonly used method of initiating a shock tube test is to use a bursting disc (e.g. Jones & Gough (1981) [16], Botros et al. (2004, 2007, 2010) [27-29]). Test 18 was 100 mol.% CO2 and was conducted at nominally 150 barg and ambient temperature. The test was initiated using a bursting disc12. Test 19 was to be a repeat of Test 18, but with a rupture disc. However, Test 18 was not successful because the bursting disc only partially failed. The opening was not full-bore. Bursting discs had previously been successfully used in Tests 12 and 13 (100 mol.% CO2 in the gaseous phase) and Test 15 (natural gas). These bursting discs were rated to 38 barg and 85 barg, respectively. CO2 in the liquid or dense phase is less compressible than in the gaseous phase, and decompresses more rapidly. The force to break the bursting disc dissipates more rapidly. A larger diameter bursting disc rated to 150 barg is thicker and stiffer than one rated to a lower pressure or a smaller diameter. Additional work would be required in order to determine whether or not a bursting disc can be used in a 168.3 mm (6.625 inch) shock tube when testing with liquid or dense phase CO2. In lieu of Test 18, Test 23 is a repeat of an unpublished test conducted using a bursting disc. Test 23 is used to investigate the effect of the initiation technique (see below).
12

THE RESULTS A shock tube test is used to measure the decompression behaviour of a fluid. The fast-response pressure transducers set out along the length of the shock tube record the change in pressure versus time as the expansion wave propagates along the shock tube. The data recorded in the first 50 ms of Tests 19 and 31 is presented in Fig. 4 and Fig. 5, respectively. A sampling frequency of 100 kHz was used. The data in Fig. 4 and Fig. 5 is partially smoothed using the loess method of locally weighted polynomial regression13 [31]. A time interval of 0.5 ms was used. The smoothed data is used to construct a fan diagram (a plot of time versus distance) and then the decompression wave velocity curve, i.e. a plot of pressure versus velocity. In constructing the fan diagram, the data is further smoothed in some places, using an interval of up to 2 ms. The times at which a given pressure wave arrives at each pressure transducer lie on a straight line, for the transducers located close to the open end of the tube (before the effects of friction become significant). The reciprocal of the gradient of this line is the velocity of the pressure wave. The gradient of each set of data points is determined using the least trimmed squares method to identify outliers in the data14 [32]. In simple terms, this is equivalent to identifying the relevant data points and fitting a straight line by eye, but it is statistically robust (and independent of the owner of the eye). The number of transducers used in the linear regression varies over the
The loess method locally fits a cubic polynomial to the data using the method of weighted least squares. It tends to preserve more of the features of the data than a simple moving average. 14 The least trimmed squares method is based on the method of least squares, but it is a more robust method of linear regression, i.e. it is less sensitive to the presence of outliers in the data.
13

The bursting disc in Test 18 was a Fike SCRD Disc. This is a cross-scored disc.

10

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decompression curve. Friction has an increasing effect on the expansion wave as the outflow velocity increases and as the distance from the open end of the shock tube increases. In the decompression curve for Test 19 (see Fig. 6), the number of transducers used is 18-20 at high pressures, but 10-12 at low pressures. The results of Tests 19 to 31 are presented in the form of a comparison of the observed (measured) decompression curve with the predicted decompression curve. Fig. 6 and Fig. 7 Test No. 02 03 04 05 06 07 08 09 10 11 12 13 14 16 predicted plateau pressure, barg 37.3 37.3 23.1 35.0 33.9 34.1 32.8 32.5 34.2 35.0 22.9 27.0 27.0 36.7 measured plateau pressure, barg 31.0-32.0 30.0-31.0 17.5-18.5 26.5-27.5 26.0-27.0 26.5-27.5 25.0-26.0 25.0-26.0 26.5-27.5 27.0-28.0 14.5-15.5 17.5-18.5 19.5-20.5 30.0-30.5

Table 7 A comparison of the predicted and measured plateau pressures for the gaseous phase tests

Test No. 19 20 21 22 23 24 25 26 27 28 29 30 31

predicted plateau pressure, barg 30.8 33.6 38.0 48.3 58.8 55.1 48.3 64.0 68.4 95.7 65.1 76.3 79.9

measured plateau pressure, barg 27.0-28.5 (31.0-31.5) 29.5-30.5 (30.5-31.0) 28.0-30.0 (34.0-34.5) 43.0-45.0 (45.0-47.0) 55.0-60.0 (61.0-62.0) 45.5-50.0 (47.5-48.5) 33.0-38.0 (42.5-43.0) 52.0-58.0 (60.0-62.5) 58.5-64.0 (66.5-68.5) 96.5-98.5 (97.0-99.5) 53.0-59.0 (58.5-59.5) 65.5-70.5 (69.5-70.5) 65.5-71.0 (78.5-79.5)

present the results for Tests 19 to 25, 100 mol.% CO2, and also for two of the gaseous phase tests, Test 03 and 04. The predicted isentropic decompression paths for all of these tests are given in Fig. 8. Fig. 9 and Fig. 10 present the results for Tests 26 to 31, the CO2-rich mixtures. The phase boundary and the predicted isentropic decompression path for Tests 19 and 31 are given in Fig. 11. The plateau in the decompression curves (see Fig. 7 to Fig. 10) corresponds to the transition from the liquid phase to the two-phase region. The pressure at which the plateau is observed in each gaseous phase test is tabulated in Table 7 and for each dense phase tests in Table 8, and also compared with the predicted pressure. The observed plateau is consistently lower than the predicted plateau, with the exception of Test 23 (a high initial temperature) and Test 28 (a high concentration of H2). The most likely explanation for the trend is considered to be delayed nucleation, as discussed further below. The plateaux in the data recorded by the pressure transducers increases as the distance from the open end of the shock tube increases. This results in a rising plateau in the decompression curves. The rising plateau is consistent with less delayed nucleation as the distance from the open end increases, and an increased effect of friction at greater distances. The results of analyses conducted by University College London and Kingston University London indicate that the effects of friction are not significant within the first 3.6 m of the open of the shock tube. In Tests 19 to 22, pressure transducer numbers P03 and P04 did not record useable data, see Table 3. The observed plateaux in Table 7 may, therefore, slightly overestimate the minimum value of the plateau in these tests. The differences between Tests 22 and 25 (repeat tests), which otherwise show reasonable agreement (see Table 8 and Fig. 6), can also partly be attributed to the different pressure transducers that recorded usable data, see Table 3. Tests 19 and 31 Firstly, in order to illustrate and explain some general features of the tests, the results of Tests 19 and 31 are described. Then, the trends in the results of all of the tests are summarised. Fig. 4 and Fig. 5 present the data recorded by the pressure transducers in the first 50 ms of Tests 19 and 31, respectively. Test 19 was 100 mol.% CO2. Test 31 was a higher order mixture. The shape of the pressure versus time traces are similar, but they become more elongated as the distance of the transducer from the open end of the shock tube increases. The near instantaneous full-bore rupture is created by explosively cutting the rupture disc. The pressure at each pressure transducer remains constant until the arrival of the leading edge of the expansion (decompression) wave. The leading edge of the expansion wave moves at the speed of sound in the fluid at the initial pressure and initial temperature. The leading edge of the expansion wave is preceded by a pressure transient associated with the detonation of the explosive charge. The transient also moves at the initial speed

Note: 1. The measured pressure at the plateau is shown for the pressure transducers close to the open end of the shock tube, typically between 0.3 and 2.4 m (approximately) from the open end, and, in parentheses, for the pressure transducers approximately 3.6 m from the open end. The increase in the level of the plateau as the distance from the open end increases, and the scatter in the data, is represented by the range of values. Table 8 A comparison of the predicted and measured plateau pressures for the dense phase tests

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160
pi, barg Ti, C

160
Test 19 152.4 Test 21 45.3
Test 22 100.5

CO2

140 120

5.0 5.0
20.0

140 120

pressure, barg

100 80 60 40 20 0 0

Test 24 60.4
Test 25 100.9

pressure, barg

Test 23 149.4

35.6 20.0
20.0

100 80 60 40 20
liquid

CO2
100 200 300 400 500 velocity, m.s-1 600 700

gas

0 -20 -10 0 10 20 temperature, C 30 40

Fig. 6 Observed and predicted decompression curves for Tests 19 and 21 to 25 (dense phase), all 100 mol.% CO2

Fig. 8 Isentropic decompression paths for Tests 03 and 04 (gaseous phase) and Tests 19, 20, 21, 22, 23, 24 and 25 (dense phase), all 100 mol.% CO2

70
60 50

CO2

40 30
pi, barg Ti, C Test 03 38.1 Test 04 38.0 Test 20 37.9 Test 21 45.3 Test 24 60.4 5.1 20.2 0.1 5.0 20.0

20
10 0 0 100

200 300 400 velocity, m.s-1

500

600

Fig. 7 Observed and predicted decompression curves for Tests 03 and 04 (gaseous phase) and Tests 20, 21 and 24 (dense phase), all 100 mol.% CO2

of sound. The transient is not observed in tests initiated with a bursting disc (Tests 12, 13, 15 and 18). The transient observed in the dense phase tests is larger than that observed in the gaseous phase tests (see Cosham et al (2011) [11]) because the fluid has a higher density. The transient in Test 31 is smaller than in Test 19 because of the modifications that were made to the retaining flange after Test 24. The arrival of the leading

edge of the expansion wave is defined by the time, after the transient, at which the pressure equals the initial pressure. The pressure transient does not have a significant effect on the results. A number of tests demonstrate that this is the case. The observed decompression curves for Tests #1 and #2 (100 mol.% N2) are in good agreement with the predicted curves, see Fig. 12 (and similarly with the results of Tests 01, 15 and 17 with natural gas). The observed decompression curves for Tests 13 (with a bursting disc) and 14 (with a rupture disc) are similar, and in good agreement with the predicted curves, see Fig. 1315. The observed decompression curve for Test 23 (with a rupture disc) is in good agreement with that of a similar, unpublished, test conducted with a bursting disc. The decreasing pressure describes the propagation of the expansion wave along the shock tube. The rate at which the pressure decreases after the arrival of the leading edge of the expansion wave is a function of the local state of the fluid (i.e. pressure, temperature, density, etc.). It is different for different fluids, or for the same fluid at different initial conditions. CO 2 in the liquid or dense phase is very different to CO2 in the gaseous phase. The pressure at the origin drops to a constant value as choked flow is established. The pressure drops more slowly with increasing distance from the open end of the shock tube. In Test 19, 100 mol% CO2, the initial pressure is 152.4 barg and the initial temperature is 5.0C. The fluid initially decompresses through the liquid (dense) phase. The pressure drops rapidly. Then a change of phase occurs; bubbles
15

pressure, barg

The slightly lower plateau in Test 13 is attributed to a difference between the average pipe wall and fluid temperatures, as discussed in Cosham et al. (2011).

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160
140 120

160
pi, barg Ti, C

140 120

Test 29 140.2 Test 30 140.2 Test 31 149.5

20.0 19.9 10.0

pressure, barg

100 80 60
100% CO2 (140 barg 20C)

pressure, barg

100 80 60
100% CO2 (140 barg 20C)

40 20 0 0

Test 26 96.0%CO2+4.0%N2 Test 27 97.4%CO2+2.6%H2 Test 28 91.7%CO2+4.0%H2+4.3%N2

40 20 0
100% CO2 (150 barg 10C)

100

200 300 400 velocity, m.s-1

500

600

100

200 300 400 velocity, m.s-1

500

600

Fig. 9 Observed and predicted decompression curves for Tests 26 and 27, binary mixtures, and Test 28 a ternary mixture

Fig. 10 Observed and predicted decompression curves for Tests 29 to 31, higher order mixtures

of gas form in the liquid. The onset of vaporisation is marked by the plateau (see Fig. 4). The local speed of sound in the two phase fluid (liquid and vapour) is lower than in the single phase fluid (liquid). The end of the plateau is not clear in the data (which was recorded for 2.5 s). The level of the plateau is similar to the level at which chocked flow is established. The level of the plateau increases significantly as the distance from the open end of the shock tube increases. There is a perturbation in the data for Test 19 at approximately 60 barg (and increasingly slightly as the distance from the open end increases). This is associated with a reflection from the weldolet near to the start of the shock tube (see below). In Test 31, a higher order mixture, the initial pressure is 149.5 barg and the initial temperature is 10.0C. The results for Test 31 show the same features as Test 19, except that the plateau occurs at a higher pressure, and the end of the plateau is clear in the data. The rate of depressurisation decreases before the plateau, increases immediately after the plateau, and then decreases, but at a slower rate than before (see Fig. 5). The level of the plateau increases as the distance from the open end of the shock tube increases. The length of the plateau also increases. The plateau is higher and shorter because the bubble point curve of the higher order mixture is higher than that of CO2, and the change in density across the bubble point curve is smaller. There is perturbation in the data for Test 31 at approximately 120 barg, associated with a reflection from the weldolet near to the start of the shock tube, but it is smaller than that in Test 19 (because the pressure transient is smaller as a result of the modifications to the retaining flange). The results of the two commissioning tests, Tests #1 and #2 demonstrate that the perturbation is caused by a reflection from

160
140 120

pressure, barg

100 80 60 40 20 0 -20 -10 0 10 20 temperature, C 30 40


pi, barg Ti, C Test 19 152.4 Test 31 149.5 5.0 10.0

Fig. 11 Isentropic decompression paths and phase boundaries for Tests 19, 100 mol.% CO2, and 31, a higher order mixture

the weldolet near to the start of the shock tube (see Fig. 2). The perturbation is visible in the data for Test #2, but not that for Test #1. It manifests in the decompression curve for Test #2 as a kink in the curve, see Fig. 12. There is an interaction between the pressure transient associated with the detonation of the explosive charge and the perturbation (and hence the kink in the decompression curve), because the kink in the decompression

13

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curves is smaller in the tests initiated using a bursting disc. This is illustrated in the results for Tests 13 and 14, see Fig. 13. The kink in the decompression curves for Tests 19 to 31 is associated with the reflection. The leading edge of the expansion wave hits the back of the shock tube and is reflected back towards the front end. The arrival of the reflected wave is clearly visible in the data, though not shown in Fig. 4 or Fig. 5. The measured pressure is only representative of an expansion wave propagating through a long pipeline prior to the arrival of the reflected wave. Friction increasingly affects the decompression behaviour as the distance from the open end of the shock tube increases. The plateau in Test 31, a higher order mixture, is higher than that in Test 19, 100 mol.% CO2. The shape and size of the respective phase boundaries are different, as illustrated in Fig. 11. The bubble point curve of the higher order mixture is higher than that of CO2. The isentropic decompression path of the higher order mixture crosses the bubble point curve at a higher pressure, see Fig. 11; the predicted and observed saturation pressure in Test 31 is higher than that in Test 19. The differences between Tests 19 and 31 are consistent with the change in the shape and size of the respective phase boundaries. Having described the observed behaviour with reference to Tests 19 and 31, the trends observed in the results of the shock tube tests are now summarised. THE TRENDS IN THE RESULTS 1. The results of the two commissioning tests with N2, Tests #1 and #2, show no significant differences, see Fig. 12. This demonstrates that the weldolets for the circulating loop do not have a significant effect on the measured decompression behaviour. 2. The predicted decompression curves and the experimental curves for the two N2 tests, Tests #1 and #2, show good agreement, see Fig. 12. 3. The predicted decompression curves and the experimental curves for the three tests with natural gas and the fourteen gaseous phase tests show good agreement, see Cosham et al (2011). 4. The plateau observed in the gaseous phase tests is consistently lower than the predicted plateau, see Table 7. 5. The predicted decompression curves and the experimental curves for the thirteen dense phase CO2 tests show reasonable agreement. The observed speed is typically slightly lower than the predicted speed. 6. The decompression behaviour of CO2 in the gaseous phase, e.g. Tests 03 and 04, is very different to that of CO 2 in the dense phase, e.g. Test 20, see Fig. 7. 7. The observed plateaux are lower than the predicted plateaux in all of the tests but Test 23 (CO2) and Test 28 (CO2+H2+N2), where it is similar or slightly higher. The initial temperature in Test 23 was 35.6C, the highest initial temperature in all of the tests. The concentration of H 2 in Test 28 was the highest in all of the tests. 8. The observed plateau in the decompression curves is a rising plateau in most of the tests. The plateau observed

9.

10.

11.

12.

13.

14.

15.

16.

17.

18.

in the pressure-time data is lower than the predicted plateau at transducers close to the open end of the shock tube. The plateau increases as the distance of the transducer from the open end of the shock tube increases. In some, but not all of the tests, it increases to the predicted plateau or higher. The rising plateau is consistent with less delayed nucleation as the distance from the open end increases, and an increased effect of friction at greater distances. The experimental decompression curve for Test 23, initiated using a rupture disc is in good agreement with that of a similar, unpublished, test conducted using a bursting disc. This confirms that the initiation mechanism has no significant effect on the measured decompression behaviour of CO2. The experimental decompression curves for Test 22 and Test 25 (repeat tests) show reasonable agreement16, see Fig. 6. The plateau observed in Test 21 is higher than that in Test 19, see Fig. 6; the initial pressure in Test 21 was lower than that in Test 19. Similarly for Tests 24 and 22. This is consistent with the predictions. The plateau observed in Test 23 is higher than that in Test 19 see Fig. 6; the initial temperature in Test 23 was higher than that in Test 19. Similarly for Tests 21 and 24. This is consistent with the predictions. The plateaux observed in Tests 26 (CO2+N2) and 27 (CO2+H2) are higher than those in Tests 19 to 25, see Fig. 9 and Table 8. This is consistent with the predictions (the plateau in Test 23 is higher than in Test 26 because of delayed nucleation). The plateaux observed in Tests 26 and 27 are lower than the predicted plateaux. The plateau observed in Test 27 (CO2+H2) is higher than that in Test 26 (CO2+N2), see Fig. 9. This is consistent with the predictions. The plateau observed in Test 28 (CO2+H2+N2) is higher than those in Tests 26 and 27, see Fig. 9. This is consistent with the predictions. The plateau observed in Test 28 is slightly higher than the predicted plateau. The plateau observed in Test 29 (a higher order mixture) is slightly higher than that in Test 26 and lower than that in Test 27, see Table 8. This is consistent with the predictions. The plateau observed in Test 29 is lower than the predicted plateau. The plateau observed in Test 30 (a higher order mixture) is lower than that in Test 28 and higher than that in Test 27 and 29, see Fig. 10 and Table 8. This is consistent with the predictions. The plateau observed in Test 30 is lower than the predicted plateau. The plateau observed in Test 31 is similar to that in Test 30, which, in turn, is higher than that in Test 29, see Fig. 10. This is consistent with the predictions. The plateau observed in Test 31 is lower than the predicted plateau

16

Tests 22 and 25 are nominally identical tests. However, in Test 22 there were no pressure transducers close to the open end of the shock tube.

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160
140 120

N2

100 80 60 40 20 0 0 100 200 300 velocity, m.s-1 400


Test #2 pi, barg Ti, C Test #1, N2 148.9 151.0 17.2 15.2

The decompression in the shock tube is rapid. The fluid may temporarily become supersaturated, i.e. a gas under conditions where it should be two-phase (gas and liquid) or a liquid under conditions where it should be two-phase (liquid and gas). The phase change will then occur at a lower pressure than predicted assuming equilibrium conditions, i.e. the plateau is lower than predicted. The conditions under which a phase change must occur can be predicted. The difference between the observed and predicted plateau is less than the difference between the theoretical limit and the predicted plateau, i.e. consistent with some degree of supersaturation, but it is less than the theoretical limit. In the dense phase tests, the observed plateau would be lower than the predicted plateau if the initial pressure was higher than measured or if the initial temperature was lower than measured. However, neither of these is considered to be likely, for the following reasons: 1. The initial pressure is measured using a static pressure transducer in the test reservoir. There is also a second static pressure transducer in the circulating loop. The measurements of the two static pressure transducers are consistent. The pressure would need to be 50-100 bar higher in Test 19, 30-50 bar higher in Test 22 and over 100 bar higher in Test 25, in order to explain the differences between the observed and predicted plateaux. An increase in pressure of this magnitude would also cause a significant increase in the initial speed of sound. This is not consistent with the results. The initial temperature is the average pipe wall temperature. The fluid temperature would need to be 35C lower than the average measured temperature in Tests 19 and 22, and more than 10C lower in Test 25, in order to explain the differences between the observed and predicted plateaux. Measurements made in Tests 19 to 31 indicate that the average fluid temperature is slightly higher than the average wall temperature, and that the different is typically less than 1C.

Fig. 12 Observed and predicted decompression curves for Tests #1 and #2, 100 mol.% N2

pressure, barg

40

CO2

30

2.

pressure, barg

20

14
13

10
Test 14

pi, barg Ti, C Test 13, CO2 35.8 35.8 10.9 10.9

0 0 50 100 150 velocity, m.s-1 200 250

Fig. 13 Observed and predicted decompression curves for Tests 13 (with a bursting disc) and 14 (with a rupture disc)

DELAYED NUCLEATION? The observed plateaux are consistently lower than the predicted plateaux. In all of the gaseous phase tests, the observed plateau is lower. In all but two of the dense phase tests (Tests 23 and 28), the observed plateau is lower. The most likely explanation for the trend is considered to be delayed nucleation.

Therefore, the trend in the results is not attributable to experimental error. Similarly, the over-prediction of the plateau is not attributable to errors in the equation of state. Span & Wagner accurately describes the experimental data for CO2 [22,23]. GERG-2008 was developed for application to natural gas mixtures, not CO2-rich mixtures. Li et al. (2011) have reported that GERG-2008 is not as accurate for CO2-rich mixtures as it is for natural gas mixtures [33]. However, the over-prediction is observed in tests of 100 mol.% CO2 and tests of CO2-rich mixtures. There is some evidence in the results of the shock tube tests commissioned by National Grid to suggest that the effect of delayed nucleation is less for a higher initial test temperature

15

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(e.g. Test 23) and, possibly, that the errors are greater for higher concentrations of H2 (e.g. Test 28)17. The only other published shock tube tests of 100 mol.% CO2 are those conducted by the Battelle Memorial Institute in the early 1980s [8,9]. The Battelle Memorial Institute conducted seven shock tube tests with CO2, one (1) in the gaseous phase, one (1) in the liquid phase, three (3) in the dense phase, and two (2) in the two-phase region18. The shock tube tests were initiated using a bursting disc. Maxey (1986) [9] presents the decompression curves for the three tests that were conducted in the dense phase and the one test in the liquid phase. There is no consistent trend in the data. The difference between the observed and predicted initial speed of sound in these four tests is higher than that in Tests 19 to 31. The observed plateau was lower than the predicted plateau in the test at 80F (26.7C), but higher in the test at 108F (42.2C), see Cosham et al. (2010) [13]. In the other two tests the observed and predicted plateaux are similar19. It is an open question as to whether the delayed nucleation that is observed in a shock tube test will also be observed in a pipeline. A rupture creates a slit in the pipeline. As the fracture travels from the origin, the fractured area behind the crack tip becomes wedge shaped and then the full crosssectional effective opening area develops close to, but slightly behind, the crack tip. Therefore, the pressure decays more slowly than it would if there were an instantaneous full-bore release. This is the opening effect [14]. In a shock tube test there is a near-instantaneous full-bore release and no opening effect. Three West Jefferson Tests, conducted on behalf of National Grid, suggest (but do not confirm) that less delayed nucleation occurs in a rupture in a pipeline [34]. The issue of delayed nucleation requires further investigation in order to understand it in more detail. THE VALIDATION OF DECOM AND OTHER DECOMPRESSION MODELS The trends in the plateaux observed in the shock tube tests are consistent with the trends predicted using the reference equations of state, Span & Wagner and GERG-2008. The trends in the experimental data are consistent with the phase boundary (compare Fig. 8 with Fig. 7 or Fig. 6), and the effect of non-condensables on the bubble and dew point curves. Increasing the initial temperature increases the saturation pressure. Decreasing the initial pressure increases the saturation pressure. The addition of non-condensables, i.e. H2, O2, N2, Ar or CH4, increases the saturation pressure. H2
The assumption is then that the good agreement between the observed and predicted plateau in Test 28 is, in fact, because the prediction is too low. Liquid-vapour equilibrium experiments would be required to confirm, or otherwise, this supposition. 18 Four tests are described in Maxey (1983), one in the gaseous phase, one in the liquid phase and two in the two-phase region; and four in Maxey (1986), three in the dense phase and one in the liquid phase. Experiment 80-14 in Maxey (1983), in the liquid phase, is considered to be the same as the test at 70F in Maxey (1986). 19 It is interesting to note that in the one gaseous phase test reported in Maxey (1983) [8], the observed plateau is lower than the predicted plateau.
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has a more severe effect than the others. The plateau in the decompression curve for CO2 in the dense phase is very long (relative to that for rich gas). The length of the plateau decreases as the temperature increases or as the concentration of non-condensables increases, but it is still a long plateau. The long plateau indicates that the toughness required to arrest a running ductile fracture in a pipeline transporting CO2 in the liquid (dense) phase can be conservatively estimated using the saturation pressure (the plateau pressure). The saturation pressure can be determined without calculating the whole of the decompression curve. The agreement between the observed and predicted decompression curves is reasonable. The predicted plateaux are consistently higher than the observed plateaux. This is a conservative trend. In Tests 23 and 28, the observed plateaux are similar to the predicted plateaux, as discussed above. The results of the shock tube tests validate a simple decompression model such as DECOM. The assumptions in the simple decompression models, i.e. isentropic decompression, one-dimensional flow and homogeneousequilibrium, are reasonable (if conservative). Simple decompression models, such as DECOM, can be used to conservatively predict the decompression behaviour of CO 2 and CO2-rich mixtures in the gaseous, liquid or dense phases. DECOM uses the reference equations of state. Other equations of state (e.g. Peng-Robinson or some modification thereof) give slightly different results. A new reference equation of state may be developed for CO2-rich mixtures as more experimental data becomes available. There is currently no clear answer to the question: Which is the best equation of state to use for CO2-rich mixtures? It is a relatively trivial exercise to change the equation of state in a simple decompression model. The use of a more accurate reference equation of state would not be expected to affect the applicability of the simple decompression models. The results of the shock tube tests also validate the complex models that do not assume isentropic decompression. Mahgerefteh et al. (2012) [19] and Xu et al. (2012) [21] report comparisons of their models against the gaseous and dense phase shock tube tests commissioned by National Grid, and show a similar level of agreement to that reported here. The observed plateaux are lower than the predicted plateaux (because the complex models also assume equilibrium behaviour). A decompression curve calculated without assuming isentropic decompression is identical to one calculated assuming isentropic decompression, except at lower pressures (and lower decompression wave velocities) where the effects of friction become significant. The issue of delayed nucleation requires further investigation. The assumption of homogeneous-equilibrium is conservative, but it is necessary to discard it if the plateau is to be more accurately predicted. Delayed nucleation implies non-equilibrium behaviour. In practical terms, at this time, this additional accuracy is not necessary because the current predictions are conservative.

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National Grid is planning to conduct a full-scale fracture propagation test to validate the predictions of the semiempirical methods for estimating the toughness required to arrest a running ductile fracture. CONCLUSIONS Thirteen (13) shock tube tests with CO2 or CO2-rich mixtures in the liquid (dense) phase have been successfully completed. The following conclusions can be drawn: The decompression behaviour of CO2 and CO2-rich mixtures in the liquid or dense phase is very different to that of lean or rich gases, or of CO2 in the gaseous phase. The plateau in the decompression curve is long. A simple (isentropic) decompression model based on reference equations of state, such as DECOM, can be used to predict the decompression behaviour, as can more complex (non-isentropic) models. There is reasonable agreement between the observed and predicted decompression curves. The observed plateaux are consistently lower than the predicted plateaux. This is a conservative trend. The most likely explanation for this trend is considered to be delayed nucleation. There is some evidence that less delayed nucleation occurs as the initial temperature increases. The trends in the saturation pressure observed in the shock tube tests are consistent with the trends predicted using the decompression model, and are consistent with the shape of the phase boundary. The trends for decompression through the liquid phase are the opposite of those for decompression through the gaseous phase. In the liquid (dense) phase, the following trends (which are the opposite of those observed in the gaseous phase) can be identified in experiment and theory: Increasing the initial temperature will increase the arrest toughness. Decreasing the initial pressure will increase the arrest toughness. The addition of other components such as hydrogen, oxygen, nitrogen or methane will increase the arrest toughness. ACKNOWLEDGEMENTS The authors acknowledge National Grid for permission to publish the paper. The authors also acknowledge technical discussions with Phil Cleaver and Andrew Laughton (GL Noble Denton) and Julia Race (Newcastle University). REFERENCES
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