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An Experiemntal Investigation of Reaction-Transport Phenomena During CO2 Injection
An Experiemntal Investigation of Reaction-Transport Phenomena During CO2 Injection
The experiments were conducted with limestone. Limestone is highly flowrate dependent. This coupling of transport and
very reactive with acids. Dissolution figures obtained from reaction is a characteristic of carbonate dissolution. It is an
CO2 injection are presenting strong analogies with dissolution unstable dissolution process leading to different dissolution
patterns named wormholes occurring when acid is injected in regimes, with the so-called wormhole pattern being the most
the wells as a stimulation treatment. Acid injection in characteristic. Dissolution figures are controlled by the acid
carbonates was investigated in IFP in various conditions and injection flow rate. Three dissolution regimes have been
dissolution patterns were classified according to the identified. At very low flowrate, the acid is spent locally and
experimental conditions 13,14. We used these results as a the dissolution pattern is compact. When the flow rate
guideline for the definition of the experiments presented here. increases, acid is not completely spent locally and remaining
acidity is transported farther. The dissolution regime is called
The paper is organized as follows. The first section is a short the wormholing regime. At very high flowrate, the high acid
literature background on dissolution/precipitation mechanisms filtration from the wormhole walls makes the dissolution
in carbonates. We reported experimental results obtained by pattern very ramified. The dissolution pattern is named
previous investigators in relation with CO2 injection in various "ramified wormhole" or uniform dissolution.
conditions of temperature and pressure. We reviewed
dissolution mechanisms occurring in carbonates with HCl. Reactive transport phenomena during CO2 injection have been
Although the acidity of the solution is very high in the later studied both on sandstones 15 and carbonates 16,17. The
case, some analogies could be raised. The second part experimental results showed that either a permeability
described our experimental device and the conditions of the improvement or a permeability impairment can be obtained 3.
experiments. The study is turned to the application, and These results demonstrate that the injectivity issue during CO2
conditions are representative of what can be found in the field. injection is very case dependent because it is related to the
We investigated various brine compositions to evaluate the rock fabric, the brine composition and also the thermodynamic
onset of the re-precipitation mechanisms and their effect on conditions. Therefore, it is of primary importance to work
the permeability. The third part is devoted to the presentation under representative conditions (fluids, rock and
of results and to a discussion in light of the preceding analysis pressure/temperature) in order to derive relevant
of dissolution/precipitation mechanisms. It gives indications recommendations for field applications. Available
for future work. experimental data sets have been obtained either through
carbonated brine injection or co-injection of CO2 and brine.
Background on dissolution/precipitation Dissolution patterns have been observed in most of these
mechanisms in carbonates. experiments and also in the field18. Surprisingly, little attention
CO2 dissolves in water forming H2CO3, which then dissociates has being paid to date on the influence of the hydrodynamic
to give an acid that reacts with the calcite present as carbonate. regime on these mechanisms in spite this is a key parameter in
The chemical reactions are the following: the near wellbore region where the fluid velocity varies a lot
CO 2 + H 2 O ⇔ H 2 CO 3 ⇔ H + + HCO 3− over a short distance 11. This coupling between transport and
reaction is prone to generate specific porosity/permeability
H + + HCO 3− + CaCO 3 ⇔ Ca 2+ + 2HCO3 − relationships according to the flow regime. These relations are
This set of reactions indicates clearly that acid is formed by very important to introduce in numerical model in order to
contact of CO2 with water. As long as the CO2 gas is injected properly reproduce the pressure field around the well and the
and is contacting the water phase, acid will form. In this stress variations that can be detrimental for the wellbore
situation, acid concentration is "unlimited": even though acid integrity. This work is an experimental contribution to better
is spent by reaction, complete spending will never occur and understand these mechanisms in the context of the CO2
there is in the system an almost unlimited source of acidity. geological storage.
At this step, it is important to note that the dissolution Reservoir condition experiments
potential of the system with two phases, i.e. a water phase and Core selection and preparation
a CO2 phase flowing simultaneously, is very different from the All the experiments were conducted on limestone samples
situation where a water phase, saturated in CO2, is the only plugged in the same quarry rock and in neighbor locations.
mobile phase. In the first case, as seen before, the dissolution The typical size of the plugs was 5 cm in diameter and 7 cm in
potential is unlimited whereas in the second case, the acidity is length. The limestone was selected due to its good level of
removed progressively as the dissolution proceeds. Studies homogeneity at the core scale, which is highly desirable when
dealing with the injection of water saturated with CO2 are permeability evolutions have to be compared from one test to
investigating only one face of the problem. another. The corresponding mercury porosimetry curve and
the NMR T2 response are provided in Figure 1 and Figure 2.
Bazin and co-workers13,14 have conducted acidizing The shape of the mercury porosimetry curve indicates that the
experiments using both limestone and dolomite and acid fluids pore throat distribution can be considered as monomodal. The
with a wide concentration range. Acid dissolution of NMR T2 response also indicates only one main peak located
carbonates is controlled by acid mass transfer kinetics and is at 62 ms suggesting that the pore size distribution exhibit also
SPE 93674 3
the brine meaning that a precipitation of insoluble salts measurements demonstrate the importance of the coupling
probably occurred with the SO42- containing seawater brine. effect between the geochemical reaction and the flow regime.
The porosity profile evolutions are plotted in Figure 6 for
several injection rates. The CT-scanner measurements enable Petrophysical characterization
to evaluate the lateral extension of the dissolution within the The evolution of the normalized pressure drop as a
sample but also the amplitude of the porosity variation as a function of time showed also a specific trend depending on the
function of the distance. From the measured data, it is clear presence of SO42- in the injected brine (Figure 10 and Figure
that both of these parameters are strongly related to the 11). All the pressure drop curves have been normalized by the
injection rate. The higher the rate, the deeper the dissolution pressure drop generated by the fully brine saturated sample for
patterns. The lower the rate, the higher the amplitude of the the same total injection rate in order to plot comparable curves
porosity variation at the inlet face. These results are in line from one test to another.
with previous works on acidizing. When the injection rate is When seawater brine has been used, the pressure drop
high, the wormhole regime is favored, which leads to systematically increased suggesting a continuous plugging of
numerous, deep dissolution figures. When the injection rate is the porous medium (Figure 11). These observations are in line
low, the compact dissolution process is favored, which with the chemical analysis, which proved the precipitation of
conducts to massive and large dissolution at the inlet face. anhydrite. When SO42- was removed, the normalized pressure
The spatial distribution of the dissolution pattern can also drop continuously decreased over a time period corresponding
be obtained within the sample through a 3D reconstruction of approximately to 15 PV injected suggesting permeability
the CT-scanner data. An example is provided in Figure 7 for improvement (Figure 10). On the same figure we can also
the case of high injection rate. distinguish a sudden, limited in time, increase of the pressure
drop (around 20 PV). It is suspected that this effect results
Chemical analysis of the produced fluids from solid particle displacement mobilized by the fluids,
The analysis of the produced water is very usefull to which plugged temporarily the porous medium. At the end of
understand the chemical reactions that are taking place during the experiment (30 PV), the pressure drop decreased again and
the experiment. Both the Ca2+ and the SO42- concentrations stabilized at a level consistent with the previous decreasing
were recorded as well as the pH evolution as a function of trend.
time. At low flowrate (Figure 8), the Ca2+ concentration
continuously increases during the experiment from its initial These observations are consistent with the brine
value around 400 ppm up to 1100 ppm at the end of the permeability measurements that have been conducted at the
injection. This variation is directly related to the dissolution end of the experiment when all the CO2 (gas phase and from
patterns of calcite that are observed at the injection face of the solution) has been removed miscibly through fresh brine
core. The trend is completely different for the SO42- injection. When SO42- was present in the brine, the lower the
concentration, which decreases continuously from its initial rate the higher the permeability impairment. This is also
value around 2850 ppm down to 2300 ppm. This variation consistent with the chemical analysis results (Figure 12). The
suggests that some precipitation of anhydrite occurred during experiment conducted at high rate with no SO42- in the brine is
the experiment due to the solubilization of the Ca2+ in presence the only one that exhibits a permeability improvement
of SO42-. The pH follows a decreasing trend, starting from 8.4 meaning that only dissolution occurred in this case.
down to 7.6. At high flowrate (Figure 9), the general trends
are exactly the same but it is worth mentioning that the curves The NMR T2 measurements that have been performed
do not stabilize at the same level. The Ca2+ concentration after the pore structure has been modified by the CO2-brine
increases up to 1500 ppm (comparing to 1100 ppm) and the injection showed a systematic trend when compared with the
SO42- concentration down to 2700 ppm only (comparing to initial T2 distribution. All the T2 responses were shifted to
2300 ppm). The pH also decreases down to 7.3 comparing to lower values meaning that the ratio V/S decreased
7.6. (Volume/Surface). Because the macroscopic porosity
variations were found to be very small, these measurements
This analysis enables to identify two main phenomena that result from a surface increase of the pore structure due to the
have a strong influence on the petrophysical parameters to coinjection experiment. This effect was found to be more
measure. First of all, it is confirmed that anhydrite precipitated pronounced at low injection rate (T2 divided by a factor two:
during the experiments, when SO42- was present in the brine. Figure 13). It is certainly associated with an increase of the
This precipitation process can impact the permeability specific surface due to the dissolution mode or/and the
drastically by clogging the pore throats. Secondly, the amount precipitation process, which is favored at low flowrate.
of the precipitated anhydrite strongly depends on the
hydrodynamic regime. When the flowrate is small, the Discussion
residence time of the fluids into the porous medium is higher, Geochemical calculations
which favors the completion of the chemical reactions leading Calculations were run with the geochemical simulator
to more anhydrite precipitation. Therefore, these PHREEQ. They aimed at evaluating the
precipitation/dissolution mechanisms occurring during the
SPE 93674 5
CO2 flow. Two equilibrium situations in a closed system were regime). The analysis of the experimental data has confirmed
investigated: (1) an equilibrium of CO2 with seawater that both precipitation and dissolution can take place in the
corresponding to the injected solution; (2) an equilibrium with core during a given experiment leading to opposite effects on
CO2, seawater and calcite representing the ultimate situation, the permeability evolution. It is interesting to mention that
i.e. at equilibrium. The composition of the solution and the high rates tend to limit the permeability reduction due to
saturation indices are reported in Table 2. Calculations were precipitation, because the residence of the fluids within the
run at 100 bars and 90°C. pore space is shorter in this case. It makes the system be far
from the geochemical equilibrium leading to lower amount of
The equilibrium of CO2 and seawater resulted in a solution precipitated calcium sulfate. From a practical point of view, it
pH of 3.2 (Table 2 - Step 1). Saturation indices are negative, suggests that severe permeability impairment in the near
indicating a dissolution potential for calcite. The equilibrium wellbore can be avoided in spite of unfavorable geochemical
with CO2, seawater and calcite shows a sur-saturation with conditions if the injection rate is high enough to displace the
respect to calcium sulfate (Table 2 - Step 2). The calcium equilibrium area of precipitation far from the well.
concentration increased to 1,610 mg/l due to the dissolution of
calcite. The brine becomes oversaturated with respect to These results also demonstrate that the pore structure
calcium sulfate with a saturation ratio of 0.20 (in log units). evolution is very dependent on the flow regime. Therefore, a
Precipitation of calcium sulfate is expected. The remaining specific porosity/permeability relationship has to be
calcium and sulfate concentrations are of 1,428 and 2,371 mg/l introduced in the numerical model as a function of the flow
respectively. These results are very comparable to the results regime to get relevant results. This is particularly important to
obtained at low flow rate where calcium and sulfate properly reproduce the pressure field around the well, where
concentrations were of 1,200 and 2,300 mg/l respectively. It is the flow rate varies significantly and can induce severe stress
concluded that calcite dissolution resulted in an increase of the variations that can be detrimental to the wellbore integrity.
calcium concentration in seawater and is followed by calcium
sulfate precipitation.
Conclusions
This analysis is also very consistent with the measured An experimental study of CO2 injection in carbonate cores
values of pH performed under high and low injection rates. (limestone) under reservoir conditions has been presented. The
The pH value was found to be lower (7.3) under high injection objective was to investigate experimentally the various
rate meaning that the producing fluids have a higher potential situations that may occur during CO2 injection in underground
of interaction with the rock comparing to the low injection rate formations for geological storage purposes. CO2 was in
case (pH equal to 7.6). It confirms that high injection rate supercritical state under the applied pressure and temperature
favors out of equilibrium mechanisms of interaction between conditions. Various brine compositions have been investigated
the fluids injected and the rock. to evaluate the onset of dissolution/re-precipitation
mechanisms and their effect on the permeability evolution.
Importance of the multiphase flow
Some experimental observations like the abnormal These phenomena have been quantified using various non-
pressure drop response, obtained under high injection rate, destructive observation techniques for the cores (NMR, CT-
strongly suggest that solid particles displacement can occur. scanner) and chemical analyses of the effluents.
These phenomena can lead to severe permeability impairment
and is certainly activated both by the fragility of the pore It has been demonstrated that both the flow rate and the
structure consecutively to the dissolution process and by the composition of the fluids initially present in the core play a
simultaneous flow of CO2 and brine, which contributes to major role in the rock-fluid interactions.
generate higher pressure gradient for a given flowrate.
Dissolution patterns, comparable to the wormholes during
The simultaneous flow of CO2 and brine is also important acidizing processes, have been observed. Their density and
to consider because it limits the access of the reactive brine to extent depend on the flow rate and the brine composition.
a fraction of the most accessible pore space. Gas CO2 phase, • High flow rates give longer dissolution forms, while low
being non-wetting, cannot access small pores with high flow rates lead to more compact dissolution.
capillary pressure threshold. Therefore, pore structure • Presence of SO42- in the brine favors re-precipitation of
modifications by dissolution or precipitation, and the insoluble salts leading to shorter wormholes and to
associated permeability evolutions, occur in a selective way. permeability decrease.
Implications for the well injectivity These results have implications in the well injectivity
The results of this experimental study demonstrate that the studies and in the far field modeling. The coupling between
injectivity issue is very complex because it results from a geochemical reactions and flow regime has to be properly
combination between many parameters (the rock fabric, the taken into account in the field to optimize the injection
fluid compositions, the thermodynamic conditions, the flow
6 SPE 93674
conditions and in the large-scale numerical models to get 6 Pittaway, K.R. and Runyan, E.E.: "The Ford Geraldine Unit
relevant results. CO2 Flood: Operating History", SPE 17278 presented at the
• Permeability impairment in the near well bore could be Permian Basin Oil and Gas Recovery Conference, Midland,
limited in spite of unfavorable geochemical conditions if 10-11 March 1988.
the flow rate is high enough to keep the equilibrium area
for precipitation far from the well. 7 Kamath, J ., Nakagawa, F.M., Boyer, R.E. and Edwards,
• Specific porosity/permeability relationships as a function K.A..: "Laboratory Investigation of Injectivity Losses during
of the flow regime have to be elaborated and introduced in WAG in West Texas Dolomites", SPE 39791, Permian Basin
the numerical models. Oil and Gas Conference, 23 - 26 March, 1998.
In future work the impact of rock composition and of the 8 Christman, P.G. , Gorell, S.B.: " Comparison of laboratory
initial pore structure needs also to be investigated. and field observed CO2 tertiary injectivity", SPE 17335, JPT,
February 1990, p.226.
Acknowledgements
The authors gratefully thank IFP (Institut Français du Pétrole) 9 Roper, M.K. , Pope, G.A. and Sepehrnoori, K.: " Analysis of
for permission to publish these results. The authors also Tertiary Injectivity of Carbon Dioxide", SPE 23974 presented
acknowledge E. Brosse, C. Magnier for the fruitful discussions at the Permian Basin Oil and Gas Recovery Conference held
and J. Behot, F. Deflandre, C. Fichen, E. Rosenberg and B. in Midland, Texas, March 18-20, 1992.
Prempain for their key contributions in the experimental work.
10 Thibeau, S., Barker, J.W. and Morel, D.: Simulation of
Nomenclature Sour gas Injection into Low Permeability Oil reservoirs", SPE
84362 presented at the Annual Technical Conference, Denver,
DP: Differential Pressure 5-8 October 2003.
PV: Pore Volume
SI: Saturation Indice 11 Dibble, W.E. and Potter J.M.:”Effect of fluid flow rates on
T2: NMR transverse relaxation time geochemical processes”, SPE 10994, Annual Technical
V/S: Volume/Surface ratio Conference and Exhibition, September 26-29 1982, New
Orleans, LA.
3 Rogers, J.D. and Grigg, R.B.: "A literature Analysis of the 14 Bazin, B.: "From Matrix Acidizing to Acid Fracturing: a
WAG Abnormalities in the CO2 Process", SPE 59329 Laboratory Evaluation of Acid /Rock Interactions", SPE
presented at the SPE/DOE Improved Oil Recovery 49491 presented at the 8th Abu Dhabi International Petroleum
Conference, Tulsa, Oklahoma, 3-5 April 2000. Exhibition and Conference held in Abu Dhabi, U.A.E., 11-14
October 1998.
4 Goodrich, J.H.: " Review and Analysis of Past and Ongoing
Carbon Dioxide Injection Field Tests", SPE 8832 presented at 15 Ross, G.D., Todd, A.C., Tweedie, J.A. and Will A.G.:” The
the Symposium on Improved Oil Recovery at Tulsa, April 20- dissolution effects of CO2-brine systems on the permeability of
23, 1980. U.K. and North Sea calcareous sandstones”, SPE/DOE 10685,
Symposium on Enhanced Oil Recovery, April 4-7 1982, Tulsa,
5 Flemming E.A, Brown L.M, Cook R.L: " Overview of TX.
Production Engineering Aspects of Operating the Denver Unit
CO2 Flood", SPE/DOE 24157 presented at the 8TH SPE/DOE 16 Grigg, R.B. and Svec, R.K.:”Co-injeted CO2-brine
Enhanced oil recovery Conference, Tulsa, 22-24 April 1992. interactions with Indiana Limestone”, SCA 2003-19, Int.
Symposium of the Society of Core Analysts, September 21-24
2003, Pau, France.
SPE 93674 7
17 Svec, R.K. and Grigg, R.B.:”Physical effects of WAG 18 Mathis, R.L., Sears, S.O.:”Effect of CO2 flooding on
fluids on carbonate core plugs”, SPE 71496, Annual Technical dolomite reservoir rock, Denver Unit, Wasson (San Andres)
Conference and Exhibition, 30 September- 3 October 2001, field, TX”, SPE 13132, Annual Technical Conference and
New Orleans, LA. Exhibition, September 16-19 1984, Houston, TX.
8 SPE 93674
Step 2
Step 1Before After
precipitation precipitation
pH 3.2 4.8 4.8
Ca2+ (mg/l) 415 1,610 1,428
SO42- (mg/l) 2,850 2,850 2,371
SI (CaCO3) -3.50 0.00 0.00
SI (CaSO4) -0.30 0.20 0.00
Saturation Indices (SI) in log units.
Figure 2 : NMR T2 response
1 .E + 0 4
Back pressure
1 .E + 0 3 Bleed off line of valve
the inlet
Brine
pump
1 .E + 0 2
Pc Hg (bar)
Differential pressure
1 .E + 0 1
Sampling device
By-pass
CO2 Oil DP
1 .E + 0 0
1 0 .8 0 .6 0 .4 0 .2 0
1 .E -0 1 water water
1 .E -0 2 CO2
pump
S H g ( f r a c t io n )
Confining
cell
0.01 0.1 1 10
Throat size (microns)
Figure 4 : dissolution patterns (inlet face)
3000 8.6
without SO4-- with SO4--
8.4
2500 SO4 --
8.2
2000
pH
1500 7.8
7.6
Figure 5 : wormhole longitudinal extension at high 1000
injection flowrate (250/250 cm3/hr)
Ca ++ 7.4
500
7.2
0.06
0 7
0 5 10 15 20 25 30
0.05 PV injected
3000 8.6
0.02
SO4 --
8.4
2500
0.01
8.2
2000 pH
[SO4-- ] and [Ca++]
0 8
0 5 10 15 20 25 30
pH
Length into the core (cm) 1500 7.8
Ca ++
Figure 6 : variation of porosity profiles at 3 7.6
injection rates with the seawater 1000
7.4
500
7.2
1 cm 0 7
0 5 10 15 20 25 30 35
PV injected
2
1.8 Solid particles
1.6 displacement
1.4
Normalized DP
1.2
1
0.8
0.6
0.4
0.2
0
0 10 20 30 40
Total pore volume injected
1.2
1
0.8
0.6
0.4
0.2
0
0 10 20 30 40
Total pore volume injected
1.3
1.2
1.1 Brine with SO4 2-
1 Brine without SO4 2-
K final / K initial
0.9
0.8
0.7
0.6
0.5
0.4
0.3
1 10 100 1000
Total flowrate (cm3/hr)