Ricardo D. G. de Freitas Filho1, Ronaldo G. dos Santos2, Osvair V. Trevisan3

Copyright 2012, Brazilian Petroleum, Gas and Biofuels Institute - IBP
This Technical Paper was prepared for presentation at the Rio Oi & Gas Expo and Conference 2012, held between September, 1720, 2012, in Rio de Janeiro. This Technical Paper was selected for presentation by the Technical Committee of the event according to the information contained in the final paper submitted by the author(s). The organizers are not supposed to translate or correct the submitted papers. The material as it is presented, does not necessarily represent Brazilian Petroleum, Gas and Biofuels Institute’ opinion, or that of its Members or Representatives. Authors consent to the publication of this Technical Paper in the Rio Oil & Gas Expo and Conference 2012 Proceedings.

Interactions between acid brines and reservoir rocks are especially important in CO 2 injection processes due to feasible alterations in the reservoir characteristics caused by the rock dissolution. This study reports the results from an experimental investigation on the dissolution of porous carbonate rocks by CO2 aqueous solutions under reservoir conditions. Pressure was up to 9,000psi and temperature was kept constant at 65o.C. Changes on the rock porosity and permeability were particularly investigated for limestone and dolomite samples whose properties were found to be similar to Brazilian pre-salt reservoir rock. Experiments were carried out in a high-pressure vessel during 240h at 48h partial steps, in which porosity, permeability and mass from samples were determined and X-ray tomography was taken. Dissolution was confirmed by mass alteration and increasing of calcium and magnesium concentration in the aqueous phase. Porosity and permeability changes were related to the fine grains produced during the dissolution process leading to the partial blockage of porous. The results show that dissolution should be considered in the projects and operations of CO2 injection processes, mainly WAG and CO2 sequestration, which produces acid aqueous solutions able to react to the carbonate rock and produce continuous changes on the rock properties and consequently the oil production system.

1. Introduction
Water-rock relative interactions is great concern to flow properties in porous media, since they promote changes on the solid surface and consequently on the flowability. They are particularly important in oil recovery and sequestration processes which are based in the carbon dioxide injection into aquifers and oil reservoirs. In these processes, the CO2 is able to react with the water, yielding an acid aqueous phase that chemically interacts with reservoir rocks. This is especially important in carbonate reservoir rocks. It is well known that when CO 2 dissolves in the water present in the reservoir forming carbonic acid (H2CO3), which will react with the carbonate (CaCO3) present in the carbonate rock causing the dissolution of this compound, changing the reservoir permeability and porosity. This is also an important matter in projects of CO2 sequestration in deep saline aquifers. Fred and Floger (1998) studied the dissolution rate of calcite in various pH using HCl. Authors found that this property is influenced by the rate of transport of reactants to the surface, the kinetics of the surface reaction, and the rate of transport of products away from the surface. Liu et al. (2005) investigated the dissolution rate of dolomite and limestone samples, using water continuously bubbled with CO2 gas. The dissolution rate of dolomite was far lower than that of limestone, and the dolomite dissolution was mainly homogeneous and determined by surface reaction. Eight different rock types that varied in composition from 0 to 100% dolomite was used by Taylor et al. (2006) in a rotating disk together with HCl solutions. They found that the dissolution rate of carbonate reservoir rocks in HCl acid will generally increase as the concentration of calcite increases. This trend is changed if significant amounts of clay are present in the rock. It was also observed that the anhydrite contained in the carbonate disks seems to have formed fine needles after the experiments that might cause formation damage in tight carbonate reservoirs.

______________________________ 1 Student, Mechanical Engineer - UNICAMP 2 Researcher, Ph.D., Chemical Engineer - UNICAMP 3 Professor, Ph.D., Mechanical Engineer - UNICAMP

Rio Oil & Gas Expo and Conference 2012 A laboratory flooding system was used by Bacci et al. (2010) to study the changes in injectivity due to dissolution near wellbore and far field by acid injection on carbonate rocks. Results indicated that pressure changes has no substantial effect on the rock injectivity. On the other hand, the temperature variation were found to be able to promote precipitation and permeability reduction. Grigg et al. (2005) reported findings on five large core flooding experiments performed on limestone and dolomite samples with co-injection or alternating injection of CO2 and brine in reservoir condition. They report dissolution occurring causing porosity and permeability increases and deposition occurring causing the reduction of these properties. In addition, their results showed a higher concentration of Ca +2 than that of Mg2+ for limestone sample, while dolomite showed a inverse behavior. Core flooding experiments with CO 2 injection in carbonate core have shown that dissolution and precipitation can both occur in the core during a given experiment with increases and decreases of permeability (Izgec et al., 2005; Zecri et al., 2009). Luquot and Gouze (2009) studied a set of four flow-through experiments in limestone samples using decreasing CO2 partial pressures to mimic the increase in distance from the injection well. Also the brine composition was changed as the distance from the injection well changed to mimic the ions transportation as the injection wave propagates. The three experiments that simulate the distances nearer to the injection indicated an increase in permeability, whereas the one experiment that simulated a point in the far field presented a decrease in the permeability. Studies using X-ray microtomography applied to evaluate reactive surface area has indicated that dissolution occurs in areas where the pore connectivity is the highest and that the porosity changes were not evenly distributed (Noiriel et al., 2009). Yadav et al. (2008) conducted static experiments using buffer solutions with various pH to study the dissolution kinetics of calcite, dolomite, leucogranite and gneiss. Using SEM microtomography it was found that although the samples were ultrasonically cleaned prior to experiment, the calcite grains seem to be attached with very few ultrafine particles, while the dolomite grains presented many ultrafine particles adhering to them. The authors suggested that decrease in the specific surface areas of dolomite is most likely due to rapid preferential dissolution of fine particles and other highly soluble phases during the short experimentation period. The present study was designed to evaluate changes in porosity and permeability during dissolution of carbonate rocks in carbonated water under pressures up to 9,000 psi. For that, ten static experiments took place with limestone and dolomite. Measurements of mass, permeability and porosity were made together with X-ray tomography to determine how the dissolution affected the rock.

2. Experimental Section
2.1. Materials In this study, carbonate rocks were dolomite (from Silurian Formation, USA) and limestone (from Morro do Chaves Outcrop, Brazil). Samples were plugged as 1in diameter by 1in height cylinders. Carbon dioxide was obtained from Air Liquide (99.999%) and fresh water was used. 2.2. Methods Carbonate dissolution was evaluated through measurements of sample property changes promoted by rock reaction with carbonate water (CO2 in water solution). Dissolution was carried out in a closed high-pressure vessel by 5 successive reaction cycles of 48 hours until a total period of 240 hours. After each reaction cycle, mass, porosity and permeability of the sample were measured, in addition to the determination of calcium and magnesium ion concentration in the aqueous phase and the scanning of X-ray computed tomography (CT) of the dried samples. Sample was inserted in the closed high-pressure vessel along with 20 ml of fresh water left in an air heater bath to keep constant the temperature at 64oC, which has been assumed as a typical temperature for Brazilian Pre-salt reservoirs. Then, pure CO2 was injected into the vessel by means of a high pressure displacement pump (DBR, USA) up to the assigned pressure. Tests were carried out under total pressure of 500, 2000, 4500, 6500 and 9000 psi. The vessel containing the CO2/water/rock system was kept at rest by 48 hours, completing a cycle. Figure 1 illustrates the experimental apparatus.


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Figure 1. Experimental apparatus. The gas permeability was obtained using Ultra-pore 300 (CoreLab Instruments, USA) with N2 and porosity was measured with Ultra-perm 500 (CoreLab Instruments, USA) with pure air. X-ray tomographies were obtained using Somaton X-ray CT (Siemens, German) at 130 kV. The samples were dried at 80 oC for 16 hours before the measurements and tomography examination. Analysis of Ca2+ and Mg2+ aqueous concentration was performed by Inductively Coupled Plasma Atomic Absorption Spectroscopy (ICP-AAS) using ICAP 6300 instrument (Thermo Scientific, USA). Five dolomite samples and five limestone samples were used in the experiments to perform the 5 pressure levels investigated. The permeability and porosity measurements were taken at 5 different pressure levels, so that a standard deviation can be calculated. The measurements of permeability were made always before the measurements of porosity.

3. Results and Discussions
Carbonate rock investigation with regard to CO2 effects on sample properties was carried out on consecutive reaction cycles. Between every two successive cycles, reaction was stopped and analysis was performed. Sample mass loss through the reaction cycle was the main parameter to evaluate the rock dissolution. Figure 2 and Figure 3 present the dimensionless variations of mass for limestone and dolomite samples, respectively. Limestone showed higher changes in mass than dolomite. Dolomite reached a zero variation of mass in the end of the experiments showing that the dissolution reaction was stopping after 240h, while this reaction time was not enough to conclude the process for limestone dissolution. Aqueous phase analysis after the experiment show concentrations of Ca 2+ varying from 4.21 mg/L to 12.7 and of Mg2+ from 66.3 mg/L to 147 mg/L for the dolomite samples, and concentrations of Ca 2+ varying from 29.6 mg/L to 276 mg/L and of Mg2+ from 5.02 mg/L to 14.7 mg/L for the limestone sample, such as it is shown in Table 1 and Table 2. These data indicated the dissolution extension and it is in agreement with the data of mass loss in Figure 2 and Figure 3. Also, analysis support the previous works where remaining water indicated that the dissolution of Mg + predominated over Ca2+ for dolomite and the dissolution of Ca2+ predominated over Mg+ for limestone. Porosity and permeability of all limestone samples are shown in Figure 4 and Figure 5, respectively. For the dolomite samples, porosity and permeability are shown in Figure 6 and Figure 7, respectively. Before proceeding, it is important to point that the dissolution test for the limestone sample at 9000 psi, failed at t = 196 h. That is why another run had to be made and there was a little variation on the permeability and porosity in the failed test that had to be computed. Also the dolomite sample used in the dissolution test at 4500 psi, fractured after the test at t = 96 h. To continue the test the sample was reconstituted and the changes in porosity and permeability were computed. These minor occurrences did not affect the general behavior of these properties for the samples. It is noticeable that although the mass variation curves (figures 2 and 3) for every sample and also the dissolution water analysis indicated that only dissolution happened, the visual inspection of the system indicated that precipitation also took place. The porosity and permeability changes of the samples are sensitive to the reaction occurrence and it tends to be more affected when a higher amount of CO2 is present in the aqueous phase. The tomography images taken of each sample before and after every test did not have the necessary resolution to display the changes, so they are not shown in the present work.


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Figure 2. Limestone relative mass variation (mi is the initial mass).

Figure 3. Dolomite relative mass variation (mi is the initial mass). Table 1. Aqueous phase analysis for dolomite Dolomite P (Psi) [Ca2+] (mg/L) 500 4.87 500 4.4 500 12.7 4,500 4.21 4,500 6.3 4,500 5.24 9,000 4.21 9,000 9.66 9,000 3.2

Sample D1 D1 D1 D4 D4 D4 D6 D6 D6

t (hrs) 48 144 240 48 144 240 48 96 144

[Mg2+] (mg/L) 74.9 73.9 66.3 88.7 96.3 103 88.7 104 147 4

Rio Oil & Gas Expo and Conference 2012 D6 D6 192 240 9,000 9,000 6.21 5.94 98.2 103

Table 2. Aqueous phase analysis for limestone Limestone P (Psi) [Ca2+] (mg/L) 500 156 500 43.1 500 31.3 4,500 70.1 4,500 35 4,500 29.9 9,000 276 9,000 37.5 9,000 42.2 9,000 38.7 9,000 28.6

Sample C2 C2 C2 C4 C4 C4 C8 C8 C8 C8 C8

t (hrs) 48 144 240 48 144 240 48 96 144 192 240

[Mg2+] (mg/L) 11.5 6.48 5.02 14.1 7.64 5.14 14.7 9.57 8.67 7.25 5.94

Figure 4. Porosity changes of limestone (Pori is the initial porosity).


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Figure 5. Permeability changes of limestone (Permi is the initial permeability).

Figure 6. Porosity changes of dolomite (Pori is the initial porosity).


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Figure 7. Permeability changes of dolomite (Permi is the initial permeability).

4. Conclusion
Carbonate rock samples from outcrops showed measurable mass loss if they are put in contact with water containing CO2 dissolved. This mass change shows that dissolution reactions between carbonate rock and acid water are susceptible to occur. Carbonate sample properties, porosity and permeability, were found to be significantly altered by the dissolution. Limestone was more reactive than dolomite and its reaction takes a longer time to be concluded. Very fine grains were present in the end of the reaction, indicating that precipitation must be occurred. Precipitation followed by fine grain formation inside the porous media must be a major account to cause the mass changes over time to not be a representative model for dissolution reaction kinetic of these samples.

5. Acknowledgements
The authors acknowledge Repsol Sinopec Brasil for funding of this work.

6. References
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Rio Oil & Gas Expo and Conference 2012 YADAV, S. K., CHAKRAPANI, G. J., GUPTA, M. K., 2008. An experimental study of dissolution kinetics of Calcite, Dolomite, Leucogranite and Gneiss in buffered solutions at temperature 25 and 5 oC. Environmental Geology 53, 1683-1694. ZEKRI, A. Y., SHEDID, S. A., ALMEHAIDEB, 2009. Investigation of supercritical carbon dioxide, aspheltenic crude oil, and formation brine interactions in carbonate formations. Journal of Petroleum Science and Engineering 69, 6370.