School of Mining and Geosciences

Petroleum Engineering Department

REPORT
Title: CO2 trapping by fines migration

Performed by Marzhan Zhandildina,

2nd year PhD student, Petroleum Engineering

Checked by Dr. Peyman Pourafshary,

Associate Professor, Petroleum Engineering

Nur-Sultan, 2022
 1. Introduction

Nowadays it is generally recognized that human activity adversely affects the carbon
cycle of our planet. In recent decades, our excessive burning of fossil fuels (coal, oil, gas) for
energy production, heating, meeting the needs of industry and transport has been
continuously increasing, which causes an increase in the amount of carbon dioxide emitted
into the atmosphere.
Carbon capture, utilization, and storage (CCUS) will play a critical role in future
decarbonization efforts to meet the Paris Agreement targets and mitigate the negative effects
of climate change. Whilst there are many well developed CCUS technologies there is the
potential for improvement that can encourage CCUS deployment.
Overall, 196 countries signed the Paris Agreement— an international treaty on climate
change in 2015. Its main goal was to prevent a global increase in temperature and reduce the
amount of carbon dioxide emissions into the atmosphere. Today, carbon neutrality is an
indicator that companies around the world are striving to achieve [2].
Kazakhstan plans to achieve carbon neutrality by 2060. At the same time, industrial
production in the country is currently characterized by a high level of carbon intensity. The
country has created a legislative and institutional framework for Kazakhstan’s transit to the
“green” economy. In particular, the new Environmental Code of the Republic of Kazakhstan
came into force in 2021. One of its principles was the implementation of the clause “the
polluter pays and corrects”.
To evaluate significance of fines migration as an injectivity issue and forecast its long-
term fate in aquifers involves laboratory experiments in different scales and requires the use
of different methodologies described in the next part.

2. Materials and methods

This part of the report describes the methods of each article.

Core-flooding is a common experimental technique for determining CO2 injectivity.
During this process, data on fluid flow is obtained, which is then followed by a series of core
analyses.

1) The underlying system of governing equations' analytical and numerical solutions are
found to be very similar. They conduct injection tests on four Berea sandstone cores to verify
their hypothesis. A certain amount of CO2-saturated water with a specified salinity—0, 0.17,
0.51, or 1.03 M NaCl—is injected into each core. They included both analytical and
numerical solutions in this study.
The steps taken for each core are listed below: a. Fill the core with water that has a
certain amount of sodium chloride. b. To prevent CO2 from diffusing through the rubber
sleeve within the core holder, cover the core with a lead sleeve. c. Attach a Hassler core
holder to the lead sleeve. d. To test initial permeability, inject additional water with the same
salinity as step a. e. Using a continuous flow rate of 2.5 ml/min, inject 60 pore volumes (PV)
of CO2-saturated water into the core.
They constructed a basic system of governing equations for CO2 injection. Section 3.1
gives the basic equations for mass balance, dissolution, and fines-retention kinetics.
Fig. 3 presents the four zones (0, I, II, and III) that are defined in this model.
They described each zone in this part of the paper and did solutions on them.
Table 3 summarizes the analytical solution. Equations in the first row define the
boundary of each zone. Equations listed in the second and third rows of the table provide the
equations that can be used to obtain normalized porosity (Ф) and dissolved carbonate mineral
concentration.
The analytical solution is derived for four zones and the values of parameters used in
the modelling can be obtained from the experimental data. The analytical solution was found
to be in close agreement with the numerical solution of the basic system of governing
equations.

2) We use the captive bubble method to measure contact angle of CO2-brine on Berea
and Obernkirchener sandstones, and their mineral components.
X-ray powder diffraction (XRD) and x-ray fluorescence (XRF) analysis show that these
sandstones consist primarily of five minerals: quartz, kaolinite, chlorite, microcline, and
muscovite (every of them were described in the paper). All contact angles were measured
under a pressure of 5.5 MPa–13.8 MPa at temperatures of 38 C and 55 C. Scanning electron
microscopy (SEM) and Energy Dispersive X-ray Spectroscopy (EDS) analyses are performed
on mineral surfaces before and after measurements to examine surface changes after contact
with CO2 and brine.
The contact angle of the two types of sandstone indicates that their wettability was not
clearly related to pressure and temperature. Quartz is found to be strong water-wet. Kaolinite,
chlorite, and muscovite are found to be weak water-wet at 38 C, whereas Microcline and
muscovite show neutral-wettability at 55 C. For chlorite, the contact angle is found to
increase for the first 30 min, which is not observed for other minerals.
Capillary forces or wettability can also affect injectivity due to fines migration. Pore
blockage due to fines migration reduces CO2 injectivity. This low-pH water can dissolve
intergranular cement, which generates fines. We used contact angle measurements on thin
slices to characterize wettability of Berea and Obernkirchener sandstones and the minerals
they contain.
A synthetic 0.171 molarity (M) NaCl brine was made from deionized (DI) water and
pure sodium chloride. Samples having length ¼ 25 � 2.0 mm, width ¼ 15 � 2.0 mm, and
thickness ¼ 3 � 1.0 mm were prepared from (1) Berea and Obernkirchener sandstone, and
(2) each of the following pure minerals: quartz, kaolinite, chlorite, muscovite, and microcline,
comprising a total of seven samples.
Two HIP manual pressure generator pumps were used to inject brine and CO2 into the
cell.
Dry nitrogen was run through the gas flow line, and the brine flow line was flushed
with distilled water and then 0.171 M brine. The visual cell was cleaned with ethanol to
remove any contamination, and then flushed and dried using nitrogen.
CO2-brine wettability of Berea and Obernkirchener sandstone and of their component
minerals quartz, kaolinite, chlorite, muscovite, and microcline was experimentally
characterized. The captive bubble method was used to measure CO2/brine/rock and
CO2/brine/mineral contact angles. Scanning Electron Microscopy (SEM) and Energy
Dispersive X-ray Spectroscopy (EDS) analyses were performed to detect any surface changes
during the contact between minerals and CO2-brine. Results were analysed to draw
implications for fines migration and injectivity reduction during CO2 injection in aquifers.
The following conclusions can be drawn. � Contact angle measurements showed distinct
difference between Berea and Obernkirchener sandstones. This can be attributed to their
different mineral compositions. � Minerals exhibited different degrees of wetting. Quartz
showed strong water-wet, and its contact angle did not change with temperature or pressure.
Kaolinite was weak water-wet, and raising the temperature caused the mineral’s contact angle
to somewhat increase. Chlorite was strong water-wet at low pressure and weak water-wet at
high pressure. Muscovite’s contact angle was strongly influenced by pressure and
temperature. Muscovite was weak waterwet at 38 �C and neutral-wet at 55 �C. Microcline
was neutral-wet, and its contact angle depends on pressure. � SEM and EDS analyses were
performed on each mineral’s surface both before and after experiments. Kaolinite, chlorite,
and muscovite showed surface changes. Surface changes such as surface roughness are
known to affect wettability. No changes in the surface of quartz or microcline were observed.
� Except chlorite, none of the minerals and sandstones show significant change in
wettability with time. Chlorite began as strong water-wet but became weak water-wet with
exposure to CO2-saturated brine. � The inconsistency among studies in reporting contact
angle for the above minerals could be attributable to heterogeneity and impurities, as were
found in the mineral samples we analysed. � The effect of mineral wettability change was
analysed. We conclude that the increase in contact angle can increase the maximum
detachment force. Fines will then be more easily dislodged from the rock surface during CO2
injection in aquifers. � In addition to wettability, creation of surface asperities due to the
exposure of mineral surface to CO2 and CO2-saturated brine, can stimulate dislodgement of
fines due to increased drag force. The dislodged fine

3) This study investigates fines migration and mineral reactions as a mechanism for CO2
residual trapping. We perform imbibition experiments using a sintered glass core and seven
Berea sandstone cores. The cores receive four injection stages: water, CO2-saturated water,
watersaturated CO2, and finally water or CO2-saturated water.
Fines migration and mineral reactions can lead to higher residual CO2 saturation. For
Berea cores, residual CO2 saturation was dependent on the quantity of CO2- saturated water
injection, which is known to cause fines migration and mineral reactions. Following 25 and
50 pore volumes of CO2-saturated water injection, residual CO2 saturation was 22% and
23%, respectively, compared to 16% for where no CO2- saturated water was injected. For the
glass core, CO2-saturated water injection had negligible effect on CO2 residual trapping.
This is attributed to the absence of fines migration and mineral reactions in the glass core. In
addition, fines migration and mineral reactions did not affect pressure difference or endpoint
water relative permeability during water imbibition. • For both the glass core and Berea
cores, CO2 residual trapping presented distinctive differences between water and CO2-
saturated water imbibition, due to dissolution during water imbibition. Both water imbibition
and CO2-saturated water imbibition can occur near the edges of CO2 plume during a real
CO2 sequestration project. Water imbibition led to a later breakthrough by 0.27 PVI for the
glass core and 0.18 PVI for Berea cores, respectively, compared to that during CO2-saturated
water imbibition.
Post-breakthrough pressure difference reduced during water imbibition but remained
fairly constant during CO2-saturated water imbibition. Due to the dissolution effect, residual
CO2 saturation for the glass core was 4% after water imbibition versus 34% after CO2-
saturated water imbibition, and for Berea cores was 16% after water imbibition versus 42%
after CO2-saturated water imbibition. Due to the limited capacity of our equipment, CO2-
saturated water imbibition was not performed for experimental runs with CO2-saturated
water injection before drainage. Such experiments should be performed to further assess the
effect of fines migration and mineral reactions on CO2 residual trapping. In conclusion, fines
migration and mineral reactions were found to be a CO2 residual trapping mechanism. The
induced residual trapping contributes to safer storage because it reduces the amount of free-
phase CO2 that may be in contact with the caprock. Additionally, we observed a dissolution
effect during water imbibition but not during CO2-saturated water imbibition.

4) CO2-water drainage relative permeability is usually measured in laboratory using a

three stage unsteady-state flooding on cores. This three-stage flooding involves injecting
water, then CO2-saturated water, and finally water-saturated supercritical CO2.

The injection of CO2-saturated water has been previously found to generate fines due
to mineral dissolution. The generated fines can flow with injected fluids and cause pore
blockage. This paper examines the effect of fines migration and mineral reactions on CO2-
water drainage relative permeability measurements, using a sintered glass core and eight
Berea sandstone cores. Three-stage and two-stage flooding are performed on the cores.
Three-stage flooding sequence is same as literature. Two-stage flooding involves injection
only of water and then water-saturated CO2, to avoid the chemical reactions brought about by
CO2- saturated water injection and thereby reduce mineral reactions. Pressure difference
across the cores and volumes of water produced are recorded. These data are used to generate
CO2- water drainage relative permeability functions.

Coreflooding experiments on glass and Berea sandstone were performed to examine the
effect of fines migration and mineral reactions on CO₂-water drainage relative permeability
estimation. Our observations lead to the following conclusions: • The injection of CO2-
saturated water in Berea cores results in cation production during water-saturated CO2
injection. The produced cations were mainly Ca2+ , Fe3+ , and Mg2+ , with small amounts
of K + , Mn2+, and Si4+ . Cation production was not observed in experiments performed on
a glass core. • Injectivity for experiments performed on a glass core had negligible effect of
CO2- saturated water injection. However, injectivity in Berea cores significantly reduced
when CO2-saturated water had been injected, and this was more pronounced when more
CO2-saturated water was injected. • For the glass core, because fines migration and mineral
reactions are absent, CO2- water drainage relative permeability was not affected by the
injection of CO2- saturated water. Hence, the effect of CO2 dissolution in water during two-
stage flooding was negligible. • For Berea cores, CO2 drainage relative permeability was
reduced due to the injection of CO2-saturated water, and this was more pronounced when
more CO2-saturated water was injected. Water relative permeability was not affected by the
injection of CO2-saturated water. • When CO2-saturated water was not injected, CO2-water
drainage relative permeability of Berea cores was the same whether 0 g/L or 60 g/L water
were used. In conclusion, the injection of CO2-saturated water leads to reduction in the
estimated CO2 drainage relative permeability. This is due to fines migration and mineral
reactions. Therefore, we propose that CO2-saturated water injection be avoided to minimize
this effect and thereby generate a more accurate CO2-water relative permeability.

5) The core-flooding experiments were carried out on quartz-rich sister sandstone cores
under a two-step sequence. In order to simulate the actual sequestration process while also
controlling the amount and sizes of fines, mono-dispersed silicon dioxide in CO2-saturated
brine was first injected prior to supercritical CO2 (scCO2) injection. The CO2 injectivity
alteration was calculated using the ratio between the permeability change and the initial
permeability. Results showed that there is a direct correlation between salinity and severity of
injectivity alteration due to salt precipitation. CO2 injectivity impairment increased from 6 to
26.7% when the salinity of brine was raised from 6000 to 100,000 ppm.
Pore size distribution of Berea sandstone used in this research work showing average,
median and mode pore diameter of 1.4, 33.8 and 36.6 μm, respectively.
Experimental method for evaluating injectivity of CO2 mainly include core-flooding,
using a variety of fluids during which fluid flow data are collected followed by a series of
core analysis.
This work presents the results of scCO2 core-flooding experiments conducted to assess
the combined effect of salt precipitation and fines migration on CO2 injectivity changes. It
was found that brine salinity had a significant influence on injectivity change of sandstone
rock after scCO2 injection. Injectivity impairment up to about 13.6% could be induced by salt
precipitation alone. The injectivity decreased with increase in brine salinity. The precipitated
solid salt saturation in the core increases with increasing brine salinity as was supported by
images of the injected face of the core samples after CO2 injection. Moreover, the results
showed that fines migration further increased the injectivity impairment as compared to salt
precipitation alone as the brine salinity increases. Injectivity impairment up to about 29% was
recorded for the combined effect of salt precipitation and fine mobilisation induced by as low
as about 0.3%wt of particles in the injection fluid. Larger particle sizes can induce up to
three-fold injectivity alteration, possibly due to particle piping/plugging at a different
jamming ratio. The present work serve as a preliminary evaluation to quantify the effect of
fines migration on injectivity change as compared to salt precipitation. Although further work
is needed to investigate and establish the effect of various range of injection flow rates,
temperature, rock permeability to describe the combined impact of salt precipitation and fines
migration on CO2 injectivity changes, the present work gives adequate insight and confirms
the reported findings in the literature from analytical studies. This validatory studies are
important for improving large-scale modelling and properly planning CO2 injection
operations to incorporate the effect of both salt precipitation and fines mobilisation.

6) To evaluate the injectivity potential during the forthcoming full-scale CO2 injection,
we conducted three core-flooding experiments using reservoir core plugs from the well
Harvey-1. We aimed to investigate whether the injection of CO2 leads to fines migration and
permeability reduction due to the relatively high kaolinite content (up to 13%) in the injection
interval of the target formation (i.e. the Wonnerup Member of the Lesueur Formation). We
imaged the core samples before flooding to verify the presence of kaolinite at the pore-scale
using scanning electron microscopy (SEM). We also examined the pore network of the core
plugs before and after the core-flooding experiments using Nuclear Magnetic Resonance
(NMR). Moreover, to gain a better understanding of any kaolinite fines migration, we
delineated surface force using two models based on Derjaguin−Landau−Verwey−Overbeek
(denoted by DLVO) theory coupled hydrodynamic force: (1) sphere/flat model representing
interaction between kaolinite/quartz, and (2) flat/flat model representing interaction between
kaolinite/kaolinite
Our core-flooding experimental results showed that CO2/brine injection triggered
moderate to significant reduction in the permeability of the core samples with a negligible
porosity change. NMR measurements supported the core-flooding results, suggesting that the
relatively large pores disappeared in favour of a higher proportion of the medium to small
pores after flooding. The DLVO calculations showed that some kaolinite particles probably
lifted off and detached from neighbouring kaolinite particles rather than quartz grains.
Moreover, the modelling results showed that the kaolinite fines migration would not occur
under normal reservoir multiphase flow conditions. This is not because of the low
hydrodynamic force. It is rather because the geometries of the particles dominate their
interplay. Overall, both of the experimental and analytical modelling results point to the fines
migration to be the most likely cause of the permeability impairment observed during core-
flooding experiments.
To simulate CO2 injection in the field, we used three different fluids to conduct the
core-flooding experiments: (1) dead synthetic formation brine (brine with no dissolved gas),
(2) CO2-saturated brine (brine saturated with CO2 at in-situ reservoir conditions), and (3)
vapour-saturated scCO2 (scCO2 saturated with water vapour at in-situ reservoir conditions).
7)
 References

1 Analytical model for fines migration due to mineral dissolution during CO2 injection
2 Wettability of sandstone rocks and their mineral components during CO2 injection in
aquifers: Implications for fines migration
3 Fines Migration and Mineral Reactions as a Mechanism for CO2 Residual Trapping
during CO2 Sequestration
4 Effect of Fines Migration and Mineral Reactions on CO2-Water Drainage Relative
Permeability
5 Experimental study of CO2 injectivity impairment in sandstone due to salt
precipitation and fines migration
6 Fines migration during CO2 injection: Experimental results interpreted using surface
forces
7 The effect of fines migration during CO2 injection using pore scale characterization