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Supercritical CO2-Brine Relative Permeability Experiments in Reservoir RocksLiterature Review and Recommendations

Transport in Porous Media ISSN 0169-3913 Volume 87 Number 2 Transp Porous Med (2011) 87:367-383 DOI 10.1007/ s11242-010-9689-2

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Transp Porous Med (2011) 87:367383 DOI 10.1007/s11242-010-9689-2

Supercritical CO2 -Brine Relative Permeability Experiments in Reservoir RocksLiterature Review and Recommendations
Nadja Mller

Received: 7 July 2010 / Accepted: 18 November 2010 / Published online: 17 December 2010 Springer Science+Business Media B.V. 2010

Abstract The relative permeability of carbon dioxide (CO2 ) to brine inuences the injectivity and plume migration when CO2 is injected in a reservoir for CO2 storage or enhanced oil recovery (EOR) purposes. It is common practice to determine the relative permeability of a uid by means of laboratory measurements. Two principal approaches are used to obtain a relative permeability data: steady state and unsteady state. Although CO2 has been employed in enhanced oil recovery, not much data can be found in the open literature. The few studies available report wide ranges for CO2 relative permeability in typical sedimentary rocks such as Berea sandstone, dolomite, and others. The experimental setups vary for each study, employing steady and unsteady state approaches, different experimental parameters such as temperature, pressure, rock type, etc. and various interpretation methods. Hence, it is inherently difcult to compare the data and determine the origin of differences. It is evident that more experiments are needed to close this knowledge gap on relative permeability. This article concludes that standards for lab measurements need to be dened a. to establish a reliable CO2 -brine relative permeability measurement method that can be repeated under the same conditions in any lab and b. to enable comparison of the data to accurately predict the well injection and uid migration behavior in the reservoir. Keywords CCS Carbon sequestration Relative permeability CO2 -brine Experiments 1 Introduction Carbon dioxide (CO2 ) release to the atmosphere is considered the major drive behind climate change. Geologic storage of CO2 in deep saline aquifers is proposed as a climate mitigation solution (IPCC 2005). In deep saline aquifers CO2 can be trapped structurally, by dissolution in formation waters, through capillary forces (residual trapping), or by mineralization

N. Mller (B ) CO2CRC Ltd., School of Earth Sciences, The University of Melbourne, Room 449/Level 4, Melbourne, VIC 3010, Australia e-mail: muller.nadja@gmail.com

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reactions. These trapping parameters are directly inuenced by the interaction of the reservoir rock or caprock formations with CO2 and brine in terms of CO2 /water/rock interactions and uid transport characteristics. The injectivity of CO2 is inuenced by properties of the rock, the uids in the host formation, pressure and temperature. The formation uids and CO2 ow together in porous media. Multiphase ow systems behave differently from single-phase ow systems. The phases are less mobile than in single-phase ow (Dullien 1992). The mobility determines the injection rate and pressure increase during CO2 injection and the distance that the injected (CO2 ) and replaced (brine) uid travels from the injection point through the formation (plume migration). Usually reservoir simulations are used to predict the injection capacity and plume migration in a reservoir. The key parameters used to determine the mobility are relative permeability and capillary pressure, in addition to porosity and permeability. The uncertainty of a simulation result is greatly inuenced by these parameters. Whereas porosity and permeability can be obtained from logs or routine core lab measurements, relative permeability, and capillary pressure are inherently more difcult to derive and require special experimental protocols and equipment. This study focuses on the review of experimental methods for gasliquid relative permeability and the supercritical CO2 and brine relative permeability laboratory experiments available in the open literature. In addition, future laboratory protocols are proposed. 2 CO2 Properties and Factors Inuencing Relative Permeability Currently not much data are available on CO2 -brine relative permeability. CO2 storage is a relatively new eld. Enhanced oil recovery by CO2 injection has now a large global application and was rst utilized in the 1970s during the high oil price period. The largest ongoing CO2 EOR operation is located in the carbonates of the Permian Basin, Texas (Manrique et al. 2007). However, the knowledge in this eld is limited. Questions arise in regard to dense phase behavior of supercritical CO2 and the reactivity of carbonic acid, once CO2 dissolves in brine. Does supercritical CO2 have different wetting behavior on a reservoir rock than other uids known in hydrocarbon production? Does the carbonic acid interaction with the various minerals of the host rock result in porosity and permeability changes? How do these factors affect relative permeability? Mineralogical changes can be observed in nature and in laboratory experiments. Usually, quartz- and feldspar-rich clastic sediments show very limited alteration in aqueous CO2 systems. Clay minerals and carbonates on the other hand react with carbonic acid quite rapidly, which can lead to pore space geometry changes in a relatively short time (Grigg and Svec 2003; Marini 2007). Clay minerals in particular are very susceptible to changes in the surface layer chemistry, which affects the wettability and consequently the relative permeability (Busch et al. 2008). CO2 is a supercritical uid under reservoir conditions (critical pressure and temperature: 7.38 MPa, 31 C). Above and below the critical point its density and solubility in water changes significantly. In its supercritical state, CO2 becomes denser with increasing pressure to a point where its density can exceed water at standard pressure and temperature conditions. More water dissolves into supercritical CO2 than gaseous CO2 . The solubility of water into CO2 is an order of a magnitude less than the solubility of CO2 into water (Spycher et al. 2003). The solubility of water into CO2 can lead to formation dry-out close to the injection point (Muller et al. 2008; Pruess and Muller 2009).

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In most cases when gas and water are present in a porous medium, the water will be the wetting phase. The few laboratory measurements conrm the same behavior for CO2 -brine systems, although CO2 can exhibit weakly wetting behavior under certain conditions (Chalbaud et al. 2007; Chiquet et al. 2007b). Weakly wetting means that the contact angle is between 170 to 130 . Contact angle laboratory measurements by Chiquet et al. (2007b) showed a substrate and phase dependency. In their experiment, supercritical CO2 wetted the surface of muscovite more than quartz. At low pressure and CO2 in gas phase, was for both substrates between 170 and 150 . A more CO2 wetting behavior was observed under supercritical conditions: quartz was 140 and mica 120 . Chalbaud et al. (2007) modeled a decreased contact angle of 125 , when the substrate (carbonate core and glass micromodel) was pre-treated with asphaltenes. The wettability also depends on the interfacial tensions (IFT) of the CO2 /water. Various laboratory experiments demonstrated that IFT values decrease with increasing pressure (Chiquet et al. 2007b; Chun and Wilkinson 1995; Hebach et al. 2002). The pressure range between 7 and 10 MPa correlates to 70 to 25 mN m1 . The IFT changes rapidly around the critical point of CO2 . At pressures above 10 MPa, IFT is rather constant, ranging between 25 and 35 mN m1 . The range above 10 MPa is comparable to most gasoil systems (Dake 1978). Small changes in pressure and temperature, especially around the critical point, can lead to significant variations in capillary pressure, because the capillary pressure changes with the cosine of the wetting angle. 3 Experimental Methods Overview The measurement of relative permeability in the laboratory can usually be obtained by two principal approaches: steady state and unsteady state. Most experimental set ups consist of a Hassler-type core holder with a pressurized sleeve to exert conning pressure. The cylindrical cores are capped with porous disks at both ends to provide a mixed and evenly distributed ow. Fluid ows axially through the core, entering at the inlet and exiting at the outlet. Most tests start with the core sample at 100% saturation of the wetting phase (drainage experiment, Fig. 1). The outlet is usually maintained at a constant pressure, using a backpressure regulator. The uid ow and pressure are controlled by pumps, and the temperature has to be maintained constant. The uid saturations are measured during the displacement. The traditional methods average the saturation on the core face and provide a saturation of each uid. Examples for traditional methods: Volumetrically, where the volume of uids in vs. uids out are compared. Weighing the core, knowing the uid densities of both uid phases. The advanced methods utilize continuous techniques, where the uid saturation prole is recorded along the core axis during the displacement. Examples for advanced techniques: 1. Electric resistance method, where electrodes are inserted in the test section, and the resistivities of the different uids have to be known. 2. X-ray CT scans, where the accuracy depends on the contrast in absorption by the two uids, e.g., the non-wetting uid CO2 is less absorbing than the wetting uid (brine). Depending on the set up and type of CT-scan, the images can be resolved in 3D high resolution microtomography.

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Fig. 1 Schematic drawing of a steady state set up (graph on the left) and an unsteady sate experiment (graph on the right)

3.1 Steady State Technique The steady-state method can be described as driving a xed ratio of two phases at constant rate through a porous medium until the saturation and the differential pressure along the sample become constant and the produced ratio equals the injected ratio (Abaci et al. 1992; Dullien 1992; Bear 1988). To obtain relative permeability curves, the injection ratio of CO2 to brine is repeatedly changed. At each injection ratio the uids are owing until the system is in a steady state mode. The saturation at each injection ratio is measured. The injection ratio is varied until a complete relative permeability curve is obtained (Dullien 1992). The differential pressure and uid production data are used to derive relative permeability curves by numerical modeling. The saturation proles have to be known for numerical modeling, which can only be established by method 1 and 2 listed above. As mentioned, all steady state methods need to be corrected for the capillary end effects, when capillary forces at the outlet retain an articially high saturation of the expelled phase. The capillary end effect can be strong in gaswater drainage experiments and reduces the saturation range due to apparent high residual water saturations. Usually steady state experiments require a long time for ow stabilization, depending on the sample rock properties. 3.2 Unsteady State Technique In the unsteady state method only one uid phase is displaced from the core by injecting another uid (Fig. 1). Both, the wetting and non-wetting uid will exit the core (Fig. 1). Contrary to the steady-state techniques, ow and pressure stabilization are not required, thus unsteady state experiments have a shorter duration (Abaci et al. 1992; Dullien 1992; Bear 1988). The ratio of gas versus water is derived from the cumulative gas injected over time and cumulative water produced over time. The pressure and saturation transients are usually analyzed by numerical modeling to determine the relative permeability. If capillary pressure Pc can be neglected, one can assume BuckleyLeverett displacement and the interpretation can be done by an analytical solution. In reality, Pc cannot be neglected, and is imperative for a correct interpretation from simulations. Unsteady-state techniques are particularly sensitive to heterogeneity; hence the necessity to monitor the uid saturation with, e.g., CT scans.

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Solutions have been proposed to overcome this issue (Maas et al. 1999). Similarly, unsteady state methods need to be corrected for capillary end effects. 3.3 Challenges Several factors impact uid displacement experiments and have to be considered for data interpretation. Core homogeneity/ heterogeneity Core material mechanical competence Fluid saturation (uids should ow through the entire core, not only parts) Capillary end effect (the holdup of the preferentially wetting phase at the outlet of a porous medium during the simultaneous ow of two or more uids) (Hadley and Handy 1956) Gravitational forces (gravity can cause segregation of two uids, depending on density difference) Fluid solubility, compressibility, and diffusion Most interpretation tools can correct the effects listed above, with the exception of rock homogeneity and the mechanical competence. Homogeneity is often an issue because all natural samples, irrespective of origin, have a varying degree of heterogeneity. The mechanical competence of the core can be compromised by its origin, e.g., unconsolidated and friable rock material or by the sampling/retrieve technique, e.g., sidewall cores. Both may lead to incomplete uid saturation of the core and cause problems in interpreting data. Capillary end effects occur at both the ends of the core plug, where the capillary pressure abruptly changes between rock and the inlet/outlet interface. The design of the uid inlet and outlet can help to mitigate the end effects. However, capillary end effects can never be entirely prevented and have to be corrected for. Gravitational forces can interfere with the measurement, if the ow is not vertical. In general, relative permeability and capillary pressure interfere with each other during the experiments. Hence, corrections have to be made. Numerical simulation tools can evaluate both factors in parallel. Several simulation runs and data sets are required, since one simulation cannot produce a unique solution from a single data set. Upscaling laboratory results to reservoir conditions imposes great uncertainty on reservoir simulations, regardless if one experiments with oilwater, gaswater, or supercritical CO2 -brine systems. How representative are the properties of the few pieces of rock for the entire reservoir? Associated with the upscaling issue is the size of grid blocks that dene the geometry of a simulated reservoir. In general, the lab experiments are conducted on small core plugs, size ranging from 0.05 to 0.15 m, but the grid blocks of reservoir model can range from 0.1 to 1,000 m (Christie 2001). Solutions were proposed using generalized mathematical relative permeability functions by (Brooks and Corey 1964; Burdine 1952; Corey 1954; Mualem 1976; van Genuchten 1980) and many others, but these are usually either restricted to a specic reservoir or cannot predict multi-phase ow in unconsolidated, heterogeneous, carbonate or shaly rocks within a permitted uncertainty range. Another phenomenon appears when the core is alternatingly ooded with gas and water, the so called hysteresis. Drainage (when the non-wetting gas invades the pores) never leads to 100% non-wetting ( = gas) saturation because of non-continuous ow behavior. At residual water saturation water will occupy the small pores and cover the large pores with a lm, but is rendered immobile. During imbition (water is pushed through the pores) the residual saturation of the non-wetting gas limits the maximum wetting saturation. The de-saturation

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is irreversible. The gas phase becomes discontinuous and snaps-off, leading to hysteresis. The hysteretic effect increases with repeated cycles of imbibition and drainage, decreasing the relative permeability of CO2 (Juanes et al. 2006). Particular challenges arise when experimenting with supercritical CO2 -brine systems, as follows: High pressure and temperature, at least above the critical conditions of 7.38 MPa and 31 C, which inict high strain on selected material of the experimental setup, the various connections pieces, and a more elaborate setup with ovens, uid baths, etc. for temperature control. Corrosive nature of dissociated CO2 , carbonic acid attacking experimental equipment and the rock material itself. Still unknown magnitude of rock wettability changes due to the presence of supercritical CO2 . Through the following review of the open literature it becomes evident that the assorted authors have attempted to solve the manifold challenges by various means. Some proposed to use analogue uids such as inert gas (N2 ) or oil (n-decane) to overcome the problem of material corrosion, rock alteration, high pressure, and temperature. The results of those experiments remain inconclusive whether the measured relative permeabilities and residual saturation endpoints are representative for in-situ CO2 -brine oods. Others successfully setup high pressure and temperature equipment and used supercritical CO2 , but did not achieve complete uid displacement due to core heterogeneity, uid gravity segregation and rock internal capillary effects. 4 Steady-State Experiment of Brine-CO2 Relative Permeability by Perrin et al. (2009) In this experiment, the core was mounted in a sleeve and an aluminum coreholder. Water was injected around the sleeve to create conning overburden pressure. An electric heater inside the coreholder warmed the water to reservoir temperature. CO2 and brine were co-injected simultaneously by a synchronized dual pump system. The pumps were cooled to 5 C to ensure constant CO2 volume. The liquids were heated to reservoir temperature in a water bath and mixed before entering the core face at the inlet. At the outlet of the core, brine, and CO2 were separated by gravity in a separator. Both uids were recycled and constantly in contact with each other to achieve thermodynamic equilibrium. A backpressure pump kept the pore pressure at least 1.3 MPa above reservoir pressure to avoid leakage in the core sleeve. The pressure drop across the core was measured with pressure transducers at the inlet and outlet of the core. The temperature in the coreholder was monitored, as well as the injection rate and pressure and the volume of each pump. X-ray CT was used to continuously scan the saturation along the core. First the brine permeability was measured at several ow rates while the pressure drop was recorded. Applying Darcys law, using uid viscosity and densities at reservoir temperature and pressure, the permeability was calculated. The drainage permeability was evaluated by injecting CO2 and brine in different proportions of fractional ows. For each fractional ow the pressure drop and gas saturation were measured. Once they were stabilized, steady state was assumed. The process was continued with different fractional ows until 100% CO2 was injected. Two different rocks were subjected to CO2 -brine core ooding, sandstone from the Otway Basin/Australia and red Berea sandstone. The cores were 5.08 cm in diameter and 15.24 cm long. Both exhibited heterogeneity, more pronounced in the case of the Otway

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Fig. 2 Saturation maps of CO2 -brine core ooding of Otway Basin sandstone (Perrin et al. 2009)

sandstone, which had porosity variation of 6 % along the axes. The saturation map of the Otway sandstone exhibits very strong heterogeneity perpendicular to the horizontal ow direction (Fig. 2). Reservoir temperature was 63 C and pressure 12.4 MPa. The average porosity was 18.2% and the permeability 50 mD. 6,000 ppm NaCl and 500 ppm CaCl2 brines were employed. The core was drained at 2 ml/ min. At 100% CO2 fractional ow the residual water saturation was high, Sw = 44% and krg = 0.6. At 100% brine fractional ow, Sw = 90% and krw = 0.5. The high saturation end points indicate that the displacement of the brine was not complete. The porosity of the Berea sandstone appeared at rst glance quite homogenous along the core axes at 20.3% on average, with a variability of 1%. The permeability was 430 mD. Reservoir temperature was 50 C and pressure 12.4 MPa. The NaCl rich brine had 10,000 ppm. Relative permeability was measured at three different ow rates: 2.6, 1.2, and 0.5 ml/ min. Incomplete gas saturation is visible at all ow rates (Fig. 3a). Apparently capillary barriers prevented ow of CO2 to the bottom part of the core, enhanced by the buoyant nature of CO2 . The effect though could not be modelled with TOUGH2 MP ECO2N (Pruess 2004) (Fig. 3b). Another experiment was conducted with the core turned 180 along the horizontal axis. The orientation of the residual water saturation did not change despite the different position, which indicates incomplete uid replacement. In addition, a ow-rate dependency was observed. At the highest injection rate (2.6 ml/l) CO2 was most mobile (Swr = 57% and krg = 0.1), where as at 0.05 ml/l Swr equalled 73%. At 100% fractional ow of brine and 2.6 ml/l injection rate Sw = 95% and krw = 0.5. The ow-rate dependent results, the high saturation end points, and saturation prole seem to indicate heterogeneity. It was not reported if the Otway sandstone was ooded at different ow rates. No model results have been presented for the Otway sandstone. Both experimental data appear to be heavily inuenced by sample heterogeneity and the horizontal setup with long cores, which lead to incomplete uid displacement. 5 Unsteady-State Experiment of Brine-CO2 Relative Permeability by Bennion and Bachu (2006) The core ood experiments were conducted in Hastelloy C or titanium equipment. The 3.81 cm diameter core was mounted in the coreholder with a pressurized sleeve. Two ports

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Fig. 3 a Saturation map of Berea core at 100% fractional CO2 ow. b Comparison simulation result with saturation map (Perrin et al. 2009)

were tapped to the inlet and outlet of the core to allow uid displacement and pressure measurement. Radial distribution plates capped both ends of the core to promote uniform uid ow. Pulsation-free pumps facilitated continuous uid displacement. The uids were pumped through a lter before entering the core face to prevent particles from clogging the core. A valve regulated the backpressure and the pressure between inlet and outlet was measured with quartz strain gauges. The coreholder and injection uids were contained in an oven to maintain the temperature at reservoir conditions. Routine air permeability and porosity tests were conducted on the cores. Capillary pressures were measured by high-pressure (400 MPa) mercury injection. The core was saturated with gas-free brine. The brine was displaced by CO2 -equilibrated brine until a constant gas water ratio (GWR) was achieved. At this point, the brine permeability was obtained. Then water-equilibrated CO2 was injected until at the outlet a stabilized pressure drop and a GWR >15,000m3 /m3 were observed. The total gas and water rates as well as the pressure drop were recorded. These data were used to generate drainage kr curves using a numerical regression model. Apparently multiple ow-rate experiments were performed to verify the kr endpoints and to evaluate capillary end effects, but the ow rate numbers were not reported. The saturation prole in the core was not veried; no X-ray CT scan or other method was reported.

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To evaluate imbibition, CO2 -saturated brine was injected until the GWR of the efuent equalled the GWR of the injected uid and the pressure drop stabilized. This was apparently done with multiple displacement rates, but once more, no ow rates were reported. After the ood, the core was depressurized and the remaining uid extracted by the DeanStark method (Dandekar 2006) to measure the residual uid saturation and verify the Sw and Sg endpoints. In summary, three data sets were generated. First the brine permeability was determined. In primary drainage the core was ooded with CO2 and the gas kr endpoints determined. In imbibition the core was ooded with brine, where CO2 was partly displaced, partly trapped. A strong hysteretic behavior was observed. The kr curves were generated by computer history matched models and the Corey coefcients determined. 14 drainage and 10 imbibition CO2 -brine oods were measured on different rock samples. The rock samples comprised reservoir rocks like sandstone and carbonate, as well as two shale and one anhydrite caprock. The temperatures ranged from 35 to 75 C, the pressure between 8.6 to 27 MPa, and salinity varied from 27,000 to 250,000 ppm. In the 11 experiments, the relative permeability of CO2 observed is rather low. In the drainage cycle, the average krg is 0.27 at maximum Sg , excluding the three caprock samples. The average maximum Sg is 50%. Two samples showed higher relative permeability and lower residual water saturation, the Cardium#1 and Basal Cambrian sandstone (Fig. 4). Both had a CO2 kr of 53% and an irreducible water saturation of 20 and 30%. In the 10 imbibition experiments, half of the CO2 is left behind. Starting with 50% Sg , residual gas saturation at the end of the brine ood is 25%. The average relative brine permeability is 0.22. Only the Cardium#1 sandstone had a brine krw of 90% at 10% Sgr (Fig. 4). Cores from the same lithological unit and higher median pore size had generally higher porosity and brine permeability. All data start at 100% brine permeability. The measurements commenced by ooding the water-saturated core rst by gas-saturated water. The relative permeability of brine will always be 100% under those conditions. The low CO2 kr end points indicate incomplete displacement of the brine either due to end effects or rock heterogeneity. Since no saturation proles were measured during the experiment, it is impossible to say which effect impaired the relative permeability of CO2 .

Fig. 4 Relative permeability versus CO2 saturation. Left gure: Cardium# 1 sandstone drainage and imbibition. Right gure: Basal Cambrian sandstone drainage (Bennion and Bachu 2008)

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6 Unsteady-State N2 -Brine and CO2 -Brine Relative Permeability Experiments by Chalbaud et al. (2007) and Egermann et al. (2006) Both studies followed the similar procedures and were conducted by the same authors. In both studies carbonate samples were used with the core plug dimension of 20 cm in length and 5 cm in diameter. The porosity of the samples was determined by a weighting technique and by the nuclear magnetic resonance (NMR). The permeability was 4 mD and porosity 23.6%. Mercury porosimetry gave a threshold capillary pressure of 0.3 MPa for a mercury-air system. The BuckleyLeverett function was used to correlate this data to CO2 -brine system. The carbonate relative permeability properties were rst evaluated by N2 -water ood. An unsteady-state technique was applied, by which the core was rst water saturated and then nitrogen injected at ambient conditions. A constant pressure differential pressure was maintained between the outlet at atmospheric conditions and the inlet. The core was placed in vertical position and the gas injected at the top. History matching the experimental data with numerical modeling derived the relative permeabilities of gas/water. The gas/water capillary pressure was calculated scaling the mercury-porosimetry data with the Leverett function. Both data sets were able to match the experimental data. Gas relative permeability was extrapolated numerically until 100% Sg , although the experimental data reached only 80% Sg (Fig. 5). To test the inuence of wettability on the mobility of CO2 , the core was rst measured under water-wetting (WW) conditions. The same core was prepared for intermediate-wetting (IW) conditions by aging the material with an asphaltic crude oil at zero water saturation for 3 weeks. During the treatment the absolute permeability was reduced by a factor of 4. Porosity remained the same. Wettability indexes were estimated from Pc curves obtained in a centrifuge. The indexes were calculated using the USBM method (Anderson 1986; Donaldson et al. 1980). For the CO2 -brine experiment under reservoir conditions, a Hastelloy core holder and pumping system were used to inject gas into the brine saturated (5 g/l) core. CO2 was pushed by water injection though a buffer cell. The core holder and the buffer were located in an

Fig. 5 N2 - water relative permeability, experimental and model data (Chalbaud et al. 2007)

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oven to work in a controlled temperature environment. The inow line from the pumps to the buffer cell and core holder was heated. The entire system was put under pressure using backpressure equipment. The plugs were coated with a non-permeable, temperature resistant lateral material to avoid CO2 uptake, a process commonto elastomer and rubber materials. The same sample used in the ambient N2 injection experiment was set in the horizontally positioned core holder transparent to X-rays. The local saturation proles were measured during the experiment to follow the transient evolution and to conrm the stabilization at the end of each step. The stabilized saturation proles exhibited uctuations though, which is either due to sample heterogeneity or incomplete uid displacement due to the horizontal setup. Four injection rates were investigated for each multi-rate unsteady-state experiment: 5, 20, 25, and 100 cm3 /h. The pressures ranged from 8, 10, 14, and 18 MPa at 60 and 80 C. The differential pressure and brine production were recorded. When gas injection commenced in the water-wet rock, a distinctive pressure increase of 200 mbar was recorded when CO2 reached the inlet face of the core. This is due to the threshold pressure that has to be overcome to push the gas into the pores. This was seen as an indication that CO2 is non-wetting. In the case of intermediate wetting, the pressure evolution was smoother (Fig. 6). The brine production increased more or less linearly until CO2 broke through at the outlet. Brine production was slightly less than gas injection because CO2 dissolved in the water in the core. After gas breakthrough the differential pressure dropped and stabilized after a while together with the brine production. Different gas saturations were observed for different ow rates. At high ow rate (100 cm3 /h), however, the scatter in the data was high. Probably the pressure had not stabilized at highest ow rate, which was due to the pump limitation to 2 l. The uid ow stopped before uid pressure stabilized. The comparison of IW and WW CO2 and N2 injection tests show different replacement mechanisms (Fig. 6), which can be attributed to higher solubility of CO2 into water. Also the IFTs are different; IFT of N2 is 2.5 times higher than CO2 . The relative permeabilities were numerically derived. The modelled water relative permeability is 20% higher in the IW CO2 injection test than under water-wet conditions. No difference of water relative permeability was observed between WW and IW conditions in the N2 injection tests. Similar observations in micro glass models conrmed this behavior (Chalbaud et al. 2007). The relative permeability of CO2 under IW and WW were the same, although a different pressure prole was observed. CO2 relative permeability was 100% at Sw = 20%. The other end point was at krg = 0.001 and Sw 95% (Fig. 6).

Fig. 6 Left gure: N2 and CO2 production data under wetting and intermediate wetting conditions. Right gure: relative permeability of CO2 and water. Water has higher kr at intermediate wetting conditions (Chalbaud et al. 2007)

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The comparison of the experiments at different temperature and pressure was difcult, if not impossible. These difculties were attributed to CO2 density and solubility variability. The experimental data look reasonable, although the modelled results are not conclusive. The different production behaviors were not included in the modeling effort. Hence, the relative permeabilites and saturation endpoints are questionable. 7 Steady-State Experiment of Brine-Oil-CO2 Relative Permeability by Dria et al. (1993) Although the three-phase relative permeability of oil, brine, and CO2 were evaluated in this experiment (steady-state), the study was included to reect earlier attempts to measure CO2 relative permeability. In this steady-state experiment, the saturations were determined by tracer co-injection. The sample was a 5 by 45 cm dolomite core with a granular matrix. The X-ray CT scan conrmed a heterogeneous permeability. The absolute permeability was measured on a small core with 2.54 cm length. The brine permeability was 24 mD at 100% Sw , and the average porosity equalled 20.2%. Three uids were pumped through the long core: 20,000 ppm CaCl2 brine, n-decane, and CO2 . The phase properties were estimated and the viscosities, ow rates, and fractional ows calculated. The water/oil/gas were constantly replenished at 71 C and average core pressure of 9.65 MPa. The ow-through set-up was required to collect the efuents and analyze tracer concentration. The ow was controlled with constant injection rate coupled with downstream pressure control. The saturations were monitored until a constant pressure drop was achieved at the four internal pressure ports and the inlet and outlet of core faces, and constant efuent ow rate. The three-phase ow velocity was regulated to 0.12 m/day. The experiment was set up to emulate an EOR eld situation. The gas-free core was saturated in oil, with residual water remaining. Under these conditions, the initial water saturation had to equal the residual water saturation, and Sg had to be zero. The core was rst ooded with water and then with CO2 . The brine injection would commence an oil/brine two-phase ow and intermediate two-phase steady-state saturation. The gas injection would decrease the oil fractional ow. The brine fractional ow would remain at the two-phase ow value with following saturation prole: 1. Decreasing brine saturation 2. Decreasing oil saturation 3. Increasing gas saturation Apparently the experiment started with a low injection rate (the ow rates were not specied). The permeability was measured and the two and three-phase saturations attained as by step 2 and 3 above. Then the core was ooded with n-decane and ready for next three-phase experiment. The saturation values were evaluated by tracer detection. Large uctuations at the intermediate pressure ports were observed at the endpoint gas experiments, when the fractional ow of gas was 100%. High ow rates were necessary to obtain measurable pressure drop from inlet to outlet. The differential pressure measurements from the 2nd and 3rd port were taken to calculate kr to minimize capillary end effects that would be recorded at inlet and outlet of core. The relative permeability reference was kr brine. The total mobility of three-phase ow was low. The gas and oil permeability were similar, probably due to the miscibility of CO2 in oil. CO2 concentration in oil was

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Supercritical CO2 -Brine Relative Permeability Experiments in Reservoir Rocks Table 1 Fitted relative permeability end points of three-phase ow oil/brine/CO2 (Dria et al. 1993) Phase Brine Oil Gas K rj 0.36 0.57 0.28 Srj 0.36 0.16 0.16 j (Corey exponent) 3.1 1.1 1.1 j (Corey exponent) 379

0.6 to 0.7 mole fraction. Also, oil and CO2 wetted the dolomite similarly. CO2 approached values of oil wettability. The Corey exponents for oil and brine were between 2 and 4. The relative permeability end point of brine at secondary imbibition was kr = 0.365 at Sw = 84%. The experimental parameters were tted to a simple Corey model, deriving following permeabilities for three-phase ow (Table 1). Oil and CO2 were observed as non-wetting and water as the strong wetting phase. The kr of each phase seemed to depend on the saturation of the same phase, not on others. The twophase and three-phase experiments coincide on this observation. The data points of the two and three-phase experiments are quite scattered, which could be for many reasons, e.g., capillary end effects, rock heterogeneity, gas not in contact with tracer, steady-state not reached, etc. The results were compared with other three-phase experiments by Oak et al. (1990) and Schneider and Owens (1970). The comparison was based on that all experiments used parafn oils, the samples were water wet and well sorted clastic rocks, and that the brine/oil/ N2 behaved similar as brine/oil/CO2 . Oak et al. experiments showed that the N2 relative gas permeability was higher than for CO2 . Relative brine permeability behaved similarly though. The kr of oil differed from kr of N2 , whereas the Dria et al. experiments produced similar kr for CO2 and oil. The wetting behavior was comparable: N2 strong non-wetting, oil intermediate wetting, and brine wetting. The experiments of Schneider and Owens presented similar brine data. The N2 relative gas permeability was higher than kr CO2 , but not as high as in the experiments from Oak et al. The conclusion from these comparisons was that CO2 is less mobile than N2 and will probably lead to lower well injectivity. The low kr CO2 end point indicates that the displacement of the brine was not complete. It is difcult to judge if capillary end effects, rock heterogeneity, or the horizontal setup with the long core sample leading to incomplete uid displacement impaired the relative permeability of CO2 , since no saturation proles are available. 8 Conclusions and recommendations Two steady-state and two unsteady-state studies have been reviewed, at temperatures from 50 to 75 C, pressures from 9.6 to 27 MPa and mostly low salinities. Typical reservoir rocks were tested, namely sandstones and carbonates. The summary of the experiments is given in Table 2. In general, low relative permeabilities are observed for CO2 ow in the experiments, except in the study of Chalbaud et al. and Egerman et al. The relative permeability of brine is higher in general. Especially during the second imbibition brine seems to effectively trap CO2 and limits its ow. The low kr endpoints indicate rock heterogeneity. The saturation

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380 Table 2 Comparison of various relative permeability experiments (Perrin et al. 2008) (Bennion and Bachu 2008) Unsteady-state Sandstones and carbonates (11) 3575 8.627 27.1248 0.367 (brine) 0.07@0.48 Sw 0.54@0.29 Sw 0.27@0.75 Sw 0.9@0.9 Sw Only 4 imbibition tests for brine (Chalbaud et al. 2007; Egermann et al. 2006) Unsteady-state Dolomite (Dria et al. 1993) Steady-state Dolomite N. Mller

Method Rock type

Steady-state Sandst.: Berea/Warre C

T ( C) P ( MPa) S (mg/g) k (mD) K r CO2 (fraction) K r brine (fraction) Remarks

63/50 12.4 10/6 NaCl 430/50 0.6@0.44 Sw /0.1@0.57 Sw 0.5@0.9 Sw /0.5@0.95 Sw Berea K r ow-rate dependent

60 10 5 NaCl 4 1@0.2 Sw

71 9.65 20 CaCl2 24 (brine) 0.28@0.16 Sg

0@0.25 Sw Measurements started at 100% brine saturation

0.36@0.36 Sw Three-phase ow experiment: CO2 /brine/oil

prole of Perrin et al. shows heterogeneity during CO2 ooding. The study of Bennion and Bachu and Dria et al. did not present saturation measurements, so it is impossible to say whether rock heterogeneity or experimental issues, e.g., capillary end effects caused low kr . In horizontal experimental set ups difculties occur when the brine volume has to be displaced by the gas phase throughout the entire core plug. The less viscous gas phase does not replace the more viscous brine phase in a piston like motion. Viscous ngering can occur, which leads to quick gas breakthrough at the core outlet, without the gas ever reaching all parts of the core plug. In addition, gravity affects the experiments in segregating the gas and brine phase. CO2 is more buoyant that brine and tends to ow to the top of the coreplug, resulting in incomplete brine displacement. Having a vertical setup instead of a horizontal can mitigate this issue. In most of the experiments the CO2 was equilibrated with water to avoid measurements artifacts due to the solubility into water. Chalbaud et al. and Egermann et al. used unsaturated brine and compensated for the solubility effect by modeling their results. A comparison of N2 /brine and CO2 /brine relative permeabilities is difcult; it appears that the different properties of the gases, e.g., IFT result in different relative permeabilities. CO2 has a lower interfacial tension with the same substrate than N2 , about 2.5 times lower (Chiquet et al. 2007b; Chun and Wilkinson 1995; Hebach et al. 2002). The capillary pressure is similar related, the CO2 /brine capillary threshold pressures are about 2.5 times lower. In general CO2 behaves as the non-wetting phase in most of the experiments. Exceptions were the experiments of Chiquet et al. and Chaldbaud et al. observed weak intermediate wetting behavior at supercritical conditions on muscovite substrate. Chaldbaud et al. observed intermediate wetting behavior when the substrate was treated with asphaltic crude oil.

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Supercritical CO2 -Brine Relative Permeability Experiments in Reservoir Rocks 381

Due to the difculties to compare the acquired data by provided documentation, the data remains inconclusive in terms of the preferences towards steady state or unsteady state set up. Both set ups seem to suffer experimental drawbacks or inconclusive interpretation. There is a need for accurate, repeatable, and reliable measurements. Laboratory measurements have to be ascertained that are standardized and comparable. The recommendations are as follows: Establish rst the appropriate measurement protocol with a core material that (a) will not alter during the core ood due to the corrosive nature of carbonic acid and (b) is homogenous, before measuring real core material of a potential storage formation. The usage of a clean and homogenous quartz sandstone or articial core plug like sintered ceramics or glass would be optimal. These materials allow X-ray penetration during the core ood. Conrm homogeneity of core material with X-ray CT scan and/or NMR methods. Set up experimental equipment in a fashion that allows continuous X-ray CT scan to monitor the saturation prole while ooding. Set up the equipment in such a way that gravitational forces are eliminated (e.g vertical and/or short measurement time). Maintain the same parameter space. For example, use the same temperature, pressure, brine consistency, CO2 saturation, uid velocity, uid fractions, etc. to compare different core materials with each other. Monitor and if possible quantify the changes in porosity and permeability distribution throughout the core due to reactive ow by repetitive measurements on the very same sample. When interpreting the measurement results, observe if the uids where saturated in respect with each other, if the thermodynamic uid behavior has to be accounted for (mutual solubility, diffusion, etc). Once the experimental protocol has been successfully established, it can be applied with reasonable condence on heterogeneous and real rocks. In principal, these recommendations do not differ drastically from any oil and gas relative permeability measurement. The novel aspect is the reactivity of the core material with the core ood uid and the resulting permeability, porosity, and wettability alteration. This has to be factored in the experimental procedure and interpretation.
Acknowledgments Shell International Exploration and Production (SIEP) and Carbon Capture Project (CCP) SMV team supported the literature review. I would like to thank to the colleagues at SIEP and CO2CRC, who provided valuable input, and the anonymous reviewers of the manuscript.

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