Materials Science for Energy Technologies 2 (2019) 647–656

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Materials Science for Energy Technologies

CHINESE ROOTS
GLOBAL IMPACT
journal homepage: www.keaipublishing.com/en/journals/materials-science-for-energy-technologies

Separation and sequestration of CO2 in geological formations

Vijeta Arora a, Rishabh Kumar Saran b, Raj Kumar c, Shashikant Yadav d,⇑
a
Department of Chemical Engineering, Deenbandhu Chhotu Ram University of Science and Technology, Murthal, Sonipat, Haryana 131 039, India
b
Department of Civil Engineering, Indian Institute of Technology Bombay, Powai, Mumbai 400 076, India
c
National Institute for Interdisciplinary Science and Technology, Thiruvananthapuram, Kerala 695 019, India
d
Department of Chemical Engineering, Dr. B. R. Ambedkar National Institute of Technology Jalandhar, Jalandhar, Punjab 144 011, India

a r t i c l e i n f o a b s t r a c t

Article history: One of the biggest environmental concerns today is that of global warming. The formation of a variety of
Received 21 June 2019 international organizations has been formed in an attempt to deal with these issues. Currently, three
Revised 22 August 2019 main areas are being explored which when operated together are known to stabilize fluctuating levels
Accepted 23 August 2019
of greenhouse gases (GHG). These include increasing the efficiency of energy sources and utilising less
Available online 4 September 2019
carbon-intensive sources of energy as well as finding different and effective ways to sequester carbon.
The trapping and storage of CO2 in geological formations form one of the best strategies to stabilize
Keywords:
atmospheric concentrations of CO2. This review aims at covering the separation an capture of CO2 from
CO2 capture
CO2 sequestration
a range of sources as well as providing insight into possible problems that may be encountered when
CO2 separation deep injection of CO2 into geological formations occur.
Geological sequestration Ó 2019 The Authors. Production and hosting by Elsevier B.V. on behalf of KeAi Communications Co., Ltd.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-
nd/4.0/).

1. Introduction in geological foundations such as saline aquifers or coal seams

which are inaccessible due to its depth and poor quality. It also
As time passes, more and more people are trying to find sustain- includes a discussion on the possible problem that may be
able and quick solutions that will be able to exert positive effects encountered during and after the deep injection of CO2 as well as
while reversing the current issues associated with rising carbon comments on the environmental, safety and health issues that
levels, global warming and climate change [1]. Carbon sequestra- may result due to the leaking of GHG’s to the surface.
tion is defined as a method by which carbon and related forms
are removed from the Earth’s atmosphere and put away into
1.1. The greenhouse effect and greenhouse gases
long-term storage either in a liquid or solid form [2–4]. Storage
usually occurs in sinks such as oceans, soil and forests [5]. This
The greenhouse effect is one of the most well-known theories
can occur via natural or artificial processes with the main aim of
discussed in atmospheric science today. The Sun fuels the Earth’s
slowing down global warming and avoiding the extreme effects
environment by giving off energy in the visible or near visible part
of climate change [6,7]. Carbon sequestration, also known as geo-
of the spectrum. The Earth’s atmosphere then takes in and reflects
logical sequestration forms a technologically feasible and safer
this radiation from the Sun, acting as a kind of cover that traps this
option that aids in stabilising atmospheric CO2 concentrations
incoming heat. A significant amount of the solar energy reaching
which in turn assists in the fight against climate change [8,9]. This
the Earth’s atmosphere is directed back to space directly [10]. In
study focuses on the separation, capture and storage of CO2 from a
addition, about two-thirds are absorbed by the Earth’s surface
range of stationary sources as well as the sequestration of this GHG
and the atmosphere itself.
A greenhouse is defined as a small house made of glass that is
used to grow a range of plant varieties and which traps the Sun’s
⇑ Corresponding author.
energy within and prevents the heat from escaping to the sur-
E-mail address: [email protected] (S. Yadav).
rounding environment outside. Similarly to the glass of the green-
Peer review under responsibility of KeAi Communications Co., Ltd.
house which traps heat inside, so does the atmosphere lock heat
near the Earth’s surface. This is defined as the greenhouse effect
[11]. This effect is thus responsible for heating the surface of the
earth and generating life as we know it. However, human-
Production and hosting by Elsevier
induced sources of CO2 have severely enhanced the greenhouse

https://doi.org/10.1016/j.mset.2019.08.006
2589-2991/Ó 2019 The Authors. Production and hosting by Elsevier B.V. on behalf of KeAi Communications Co., Ltd.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
648 V. Arora et al. / Materials Science for Energy Technologies 2 (2019) 647–656

effect [12]. These anthropogenic sources include the use of fossil 1.3. Impacts of climate change
fuels such as coal to produce electricity and oil to power vehicles
and deforestation for additional increases in agricultural activities. The impacts of global warming are vast with the increase of
All of these factors in combination are known to contribute to oceanic temperatures resulting in the thermal expansion of oceans.
global warming [6,13]. This together with meltwater from glaciers results in the continu-
Nitrogen and oxygen form two of the most abundant gases in ous rise of sea levels which may in turn influence global patterns of
the atmosphere. While these two gases wield a minimal oceanic circulation [14]. The rate and vigour of natural disasters
greenhouse effect, more complex gases like carbon dioxide, nitrous like heat waves, cyclones, floods and droughts have increased over
oxide, methane and ozone contribute significantly [14]. Gases can the last few years and are expected to continue increasing [12].
absorb infrared radiation and trap heat and are known as green- Changes in rainfall and related precipitation levels may lead to
house gases. Fluctuations in the atmospheric concentration of extremes such as water shortages or intense flooding which can,
greenhouse gases can cause a change in the equilibrium of heat in turn, affect agricultural activities such as shifts in growing crops
transfer resulting in an intensification of the greenhouse effect. and soil erosion [11,12]. Flooding may also increase the mobility of
Several components of the climate cycle such as plants, clouds, waterborne disease vectors thereby putting affected communities
oceans and living organisms are known to disturb the levels of at risk of related diseases like malaria [19,25,26]. In addition, this
these atmospheric greenhouse gases [12]. For example, plants may also lead to extreme wave damage to coastlines and subse-
which absorb CO2 and water from the atmosphere and transform quent downstream effects on many low lying islands. The effects
these into carbohydrates via photosynthesis, as well as anthro- on the environment will also be vast with related changes in sur-
pogenic happenings such as deforestation or burning of fossil fuels, rounding communities and resultant socioeconomic status. These
lead to the addition of more greenhouse gases into the atmosphere include changes in the availability of water resources, food secu-
which in turn intensifies the greenhouse gas effect and subsequent rity, human health, ecosystem functioning and biodiversity [27–
warming of the Earth. The ability of respective GHG’s to take up 29]. In addition, increases in temperature may subsequently affect
heat is known to vary, with methane (CH4) trapping a great deal ecosystem habitats and lead to accelerated rates of extinction with
more energy per molecule than CO2 [15]. certain species [1,11].

1.4. The carbon cycle

1.2. Climate change
Carbon forms the fourth most plentiful element in the earth and
The word climate refers to a description of statistics surround- is imperative for life on our planet. Most of the Earth’s carbon is
ing weather and related conditions of temperature, precipitation, hidden in rocks, oceans, plants, soil, fossil fuels and the atmo-
wind, humidity, soil moisture and so on. The United Nations sphere. These are known as sinks or reservoirs [15]. Carbon move-
Framework Convention on Climate Change (UNFCCC) defines cli- ment between each reservoir through an exchange is known as the
mate change as ‘a change of climate which is attributed directly or carbon cycle and deviations to this cycle will affect each reservoir
indirectly to human activity that alters the composition of the global and result in the shifting of carbon out of one reservoir and into
atmosphere and which is in addition to natural climate variability another with subsequent downstream effects. The increased burn-
observed over comparable time periods.’ [16]. ing of fossil fuels and related climate change causing activities have
Numerous studies have shown that the climate has been and resulted in the increased mobilisation of fossilised carbon into the
continues to change with time [9,14]. These changes occur as a atmosphere which has, in turn, pushed the Earths carbon cycle out
result of changes in the climatic system which is often influenced of balance [5,30,31]. Excess carbon in the atmosphere will result in
by both natural and anthropogenic sources. Over the last warmer temperatures and increased plant growth while excess
10,000 years, temperatures have increased resulting in subsequent carbon in oceans will raise the acidity of water which may, in turn,
warming of the earth’s surface [15]. Recording of temperature, pre- affect the health of marine life [6,32].
cipitation and a range of other weather elements began around Previous studies have shown that seasonal changes in atmo-
1861, but over the twentieth century, it was estimated that the spheric CO2 concentrations are a result of either extraction and/
universal mean surface temperature raised by about 0.6 °C with or additions to the atmosphere from the terrestrial biosphere in
the 1990s being recorded as one of the hottest periods [15,17]. This which CO2 is extracted from the atmosphere via photosynthesis
data together with changes in GHG concentrations and natural and added via respiration and decay of decomposing matter [33].
processes such as deviations in the earth’s orbit, solar radiation In addition changes in land usage has resulted in enormous
and the El Nino effect has led to long-term shifts in temperature amounts of CO2 being released into the atmosphere globally.
and precipitation which inevitably contributes to climate change The carbon cycle can be broken up into two parts, namely the
[18–20]. geological and biological component. The geological component
Developed climate models allow scientists to decipher and of the carbon cycle runs over millions of years and includes the
understand the causes of climate changes while still being able movement of carbon through various levels of the Earth while
to make projections of changes that may occur in the future [6]. the biological carbon cycle operates over a smaller time frame
Data obtained from these models indicate that recent changes and involves the absorption and transformation of carbon by living
are primarily due to increasing greenhouse gas concentrations organisms. The geological component of the carbon cycle takes
and that unless these changes are stabilised, this warming effect place during natural processes such as weathering and precipita-
will continue to occur [15,21,22]. Previous studies measuring the tion [34,35]. Carbonic acid forms as a result of reactions with atmo-
ambient CO2 concentration on Mauna Loa, Hawaii show a correla- spheric carbon dioxide and water which eventually reach the
tion between CO2 and overall changes in average surface tempera- surface as precipitation. Here it interacts with minerals at the
ture. Information obtained on CO2 concentrations from ice cores Earth’s surface which eventually dissolves them into their respec-
show a constant CO2 concentration of 280 ppmv until about tive ions through chemical weathering. These ions are transported
1800 when a rise was observed with levels reaching approximately in water sources towards the ocean where they precipitate out as
380 ppmv in 2010 [23,24]. Much of this rise is believed to coincide minerals like calcite (CaCO3) [9]. Over time the calcite sediment
with the increased reliance on fossil fuels during the same period will form rocks of limestone with sedimentary layers forming on
[15]. the ocean floor. Over time carbon on the oceanic floor is pushed
 V. Arora et al. / Materials Science for Energy Technologies 2 (2019) 647–656 649

deeper into the Earth by tectonic forces. Here they are often subject storage is one of the most feasible short to medium term
to high temperatures and pressures where it eventually dissolves approaches for reducing the amount of CO2 present in the atmo-
and can re-join the surface where it is released as CO2 either vio- sphere [53–55]. These sources can be mobile or stationary with
lently through volcanic eruptions or steadily through vents and examples of common fixed sources such as fossil fuel based power
CO2-rich hot springs [36]. The biological component of the carbon generators, oil refineries and iron or steel plants. After capture, CO2
cycle is the cycling of carbon between land, ocean and the atmo- is then compressed and conveyed to a site for permanent storage.
sphere and involves the rapid exchange of carbon among living This is known as sequestration. Transportation generally occurs via
things via photosynthesis and respiration. This usually occurs on a pipeline, but it can also be transported by a range of vehicles like
a much shorter timeline as when compared to the geological car- trucks, trains or ships. Storage generally occurs in geological sites
bon cycle. such as oils and gas fields [56–60]. One of the most well-known
examples of CO2 sequestration is the Sleipner project in Norway
1.5. GHG emissions and major sinks for CO2 where removed CO2 is stored in a geologic aquifer [61,62]. Electric
power generation plants that are fired by fossil fuels contribute to a
In recent years many countries have developed a means of mon- large portion of the global CO2 in the atmosphere with power
itoring individual pollutants. This is usually done through a type of plants having some of the highest densities of CO2 emissions
emission inventory which is used as a tool for developing atmo- [6,63].
spheric models as well as for developing strategies and policies to
aid and track reductions in GHG emissions. CO2 emissions occur 2.2. Common issues with capturing CO2
as a result of various industrial, agricultural and transportation
events with studies showing that fossil fuel combustion currently CO2 can be captured either before (pre-combustion) or after
serves as the biggest source of CO2 emission in the United States combustion (post-combustion). However, capturing will depend
of America [17]. GHG sinks serve as a repository for gases that have on the best area of the technology being used as well as ideal oper-
been removed from the atmosphere with the biosphere and geo- ating conditions. During post-combustion gas collection, CO2 forms
sphere reportedly serving as the major sinks for CO2. The terrestrial a product of combustion in the flue gas, and if not controlled, this
biosphere itself serves as a major site for CO2 sequestration due to CO2 will leave the power station and move into the atmosphere
recent changes in agricultural activities making it one of the most uncontrollably. In pre-combustion, CO2 is generally captured in
suitable options due to relatively low cost [37,38]. Tress and forests, the gasification process where the transformation of the carbon
however, serve as a temporary form of CO2 sequestration as over in the coal occurs into CO2 or CO [64–66]. The location of the cap-
time, trees will die and decompose back to CO2 meaning that these turing technology being used is important as well as the presence
trees that serve as CO2 sinks today may actually become sources of of pollutants. Pollutants such as SO2, NOx, Hg, H2S and NH3 will
CO2 in the future [21]. The development of international policies for have a substantial impact on the CO2 capturing technology being
reductions in GHG emission requires an estimation of both current used as these pollutants are corrosive. This means their presence
and future emissions [27,30,39]. Kaya et al. developed a method may complicate separation processes. Some may even result in
known as the Kaya Identity which relates the GHG emissions to irreversible chemical reactions [67,68]. In addition, current air
energy usage, economic growth and population growth. These fac- quality standards and haze regulations may impose additional
tors will, in turn, determine the level of human impact on emissions restrictions on SO2 and NOx emissions which may need to be con-
of carbon dioxide thereby allowing for predictions on the impact of trolled subsequently. Furthermore, the quantity of CO2 being
climate change [27,40]. removed from the point source of generation will also affect cap-
turing methods. The purity level required prior to emission in the
atmosphere as well, as the quantity of sequestration required, will
2. Curbing high CO2 emissions have a direct impact on the quantity of energy and cost necessary
for capture.
There is a range of methods that can be used to decrease overall Common carbon capture techniques include the wet scrubbing
carbon concentration in the atmosphere [41–44]. One method is of solvents with physical or chemical adsorbents, solid dry scrub-
the decrease in energy consumption via conservation and improved bing with chemical or physical adsorbents, cryogenic methods
utilization of resources [6,35,39]. A second method aimed at stabil- and separation via gas membranes. These capture technologies
ising the atmospheric levels of CO2 involves changing to fuels that are fitted onto existing power plants or incorporated into new
are not as carbon intensive and which produces more energy when power producing facilities. Capture selection technologies usually
combusted [45,46]. Carbon sequestration forms a third and more rely on a range of factors such as partial pressure of CO2 in the
popular storage approach and involves the trapping of CO2 directly gas stream, amount of required CO2 for recovery; purity of the
from human-generated origins followed by the disposal of this CO2 anticipated CO2 product, sensitivity to impurities as well as initial
underground for extended time periods [9,14,47–50]. In order for and overall operating costs of the capture procedure together with
this technique to be successful, economical and reliable technology subsequent environmental impacts [67].
should be used which allows for efficient CO2 sequestration. In
addition, the cost should be significantly low and the technology 2.3. Methods for capturing CO2
used should be reliable and well developed so as to maintain public
health and safety. If these methods are used individually, there will
not be a significant reduction or stabilization in the atmospheric 2.3.1. Wet scrubbing
levels of CO2 as each serves a different part in the overall carbon Wet scrubbing is used to describe the process carried out by a
management process and a combination of the above methods range of devices that can eliminate pollutants from flue gas or
are required to yield more significant results [51,52]. other gas streams. These processes are divided into two main
types, namely methods where a chemical reaction between the
2.1. CO2 capture and sequestration CO2 and solvent is carried out or where the CO2 is physically dis-
solved in the solvent. Chemical and physical solvents can be used,
One of the first steps in sequestration is the collection and sep- but their use depends on various factors. Chemical solvents are
aration of CO2 from human-generated sources. Carbon capture and chosen when lower concentrations of CO2 are present in com-
650 V. Arora et al. / Materials Science for Energy Technologies 2 (2019) 647–656

busted gases while physical solvents are generally used when high absorption and the desorption temperature. In addition, it is
pressures and lower concentrations of inert gases are present advantageous since only 1 mol of the sterically hindered amine is
[6,69]. Chemical processes consist of a reaction between a chemical needed to react with 1 mol of CO2. Previous studies have also
adsorbent and treated gas. These processes usually consist of one shown sterically hindered amine systems to have lesser heats of
or more reversible chemical reactions between CO2 and an aque- absorption and regeneration when likened with other amines like
ous solution of an absorbent such as an alkanolamine. When the MEA thereby making these amines suitable sources for CO2 elimi-
product is heated, the bond between the absorbent and CO2 will nation in power-generation systems [82–84].
be destroyed, and a stream containing CO2 is produced. A fre-
quently used solvent in this process is monoethanolamine (MEA). 2.5. New adsorption techniques
Physical processes, on the other hand, involve inorganic or organic
liquids which take in gaseous phases from the mixture. Absorption Research into a range of new adsorption techniques is currently
liquids are then regenerated due to temperature increases or pres- being done with studies investigating the use of aqueous NH3 as a
sure reductions. This method is generally used to process high- solvent for elimination of CO2 from flue gas [85]. On the other
pressure CO2 rich streams [6,69]. During physical processes, the hand, Kohl and Nielsen (1997) conducted a study in which NH3
gas solubility in the absorbent solutions is proportional to the par- was collected from coke oven gas and used to scrub H2S [86]. Other
tial pressures of the solubilized gases in the feed. In addition, the studies have looked into pursuing the NH3 scrubbing method to
extent of heat absorption is lesser than that in chemical absorption. remove CO2 from flue gas while Huang et al. (2002) have reported
The selection of suitable processes for the removal of acid gases is on the development of an ion-exchange resin method to rejuvenate
affected by a range of parameters such as partial pressure of the spent NH3 solutions. Additional studies are also looking at the pos-
acid gas impurities, feed gas total pressure, feed gas inlet temper- sible use of fertilizers [87]. Zheng et al. (2002) showed the use of
ature, amount of removal, available utilities, energy and initial CO2, NH3 to produce NH4HCO3 using simulated flue gas [88].
costs, surrounding flora, size, weight, location, and environmental
restrictions [70,71]. Previous studies conducted by Meisen and 2.5.1. Physical adsorption
Shuai (1997) showed that drawbacks of chemical absorption pro- Physical adsorption depends mainly on the attraction of CO2 to
cesses are based on their restricted CO2 loadings and significant the surface of a substance without the formation of a chemical
energy requirements. In addition, extensive equipment is also bond and is used in a range of industries for gas purification. Absor-
required [72]. bents can either be a physical solvent or a mixed solvent consisting
of both a physical and chemical solvent such as an amine [89,90].
2.3.2. Chemical adsorption In a mixed solvent, the removal properties of the physical solvent
A commonly used solvent for chemical processes is MEA how- are joined with the amines capacity to obtain a low residual acid
ever diethanolamine (DEA), and methyldiethanolamine (MDEA) gas levels with all this usually being done in a single step. Required
as well as other mixtures of amines with additives can also be used properties of physical solvents are such that they should have low
[15]. One of the major requirements for adsorptive solvents used in viscosity and low or moderate hygroscopic affinities. They should
CO2 regeneration and H2S removal is the dissociation of any com- also have little vapour pressure at ambient temperatures and
pounds made between the acid gas and solution itself. In addition should be noncorrosive to common metals. They should also be
strong alkali salts with weak acids offer a range of advantages such nonreactive with the other components in the gas stream. They
as the adsorption of H2S and CO2. Many common processes have should be cost effective and readily available. Major advantages
been designed for H2S and CO2 adsorption and these processes associated with this method include lower heat requirements
use aqueous solutions of Sodium or Potassium compounds. Exam- and lower circulation rates [15].
ples of these processes include the use of hot K2CO3 solutions and There are three popular physical solvent commercial technolo-
processes using ambient temperature Na2CO3 or K2CO3 solutions. gies that are used for CO2 sequestration. These are Selexol, Rectisol,
Amines are usually added to improve the transfer and adsorption and Morphysorb. The Selexol method has been used to eliminate
of large amounts of CO2 as well as to restrict corrosion, inhibitors CO2 from NH3 synthesis gas and has a range of advantages. These
and activators [73,74]. include the selective absorption of H2S and CO2 to ppm levels,
and reduced and no heat requirements for H2S and CO2 removal
2.3.3. Amine scrubbing respectively. It is noncorrosive and requires low vapour pressure
Amine chemical absorption technique is usually used in the and it is nonreactive with other gas components. In this process
clean-up of CO2 from low-pressure flue gases. Much research has the Selexol solvent dissolves and absorbs the acid gases at high
been conducted on the use of amines to improve the energy pressure followed by steam stripping to release and recover acid
requirements and costs associated with processes for CO2 storage gases such as H2S and CO2. The Rectisol method depends on
[75,76]. These areas of research include the use of new solvents methanol as a physical organic solvent and functions at much
with superior absorption capacity, amine degradation and concen- lower temperatures than most of the other physical processes. This
tration of the amine in the aqueous solutions. Despite this, there is process allows of the separation of impurities produced during coal
still a great deal of disadvantages associated with the use of amines gasification as well as facilitating the dehydration and inhibition of
such as the increased heat of absorption with CO2 requiring more ice and water formation at the lower temperatures used during
energy in subsequent regeneration steps as well as the poor adsorp- method runs. The Morphysorb process uses a mixture of N-
tion of MEA with CO2. In addition, the concentration of MEA in the formyl morpholine and N-acetyl morpholine for the elimination
presence of O2 is limited due to enhanced corrosion [77–79]. of acid gases such as H2S, CO2, CS2 and mercaptans. The biggest
benefits of this process include the high solvent loading and low
2.4. Properties of solvents circulation rates, low adsorption of hydrocarbons and low oxidiza-
tion and environmental hazards [15].
Common wet scrubbing solvents include formulated or mixed
solvents and sterically hindered amines which contain an amino 2.5.2. Dry scrubbing
group combined to a heavy alkyl group such as 2-amino-2- Dry scrubbing, unlike wet scrubbing, does not saturate the gas
methyl-1-propanol (AMP) [80,81]. This alkyl group is a major stream. These systems are used to remove acid gases from com-
player in the efficiency of the process by influencing the level of bustible sources or for the removal of corrosive gases from
 V. Arora et al. / Materials Science for Energy Technologies 2 (2019) 647–656 651

wastewater treatment plants. This process utilises a solid rather is defined as a relatively non-reactive gas under ambient
than a liquid scrubbing medium and involves gas-solid interactions conditions. It is easily compressed into a liquid below the critical
which may be able to regenerate. The CO2 may be physically or point which is the most common way to store and transport it for
chemically absorbed pending interaction parameters. Chemical industrial applications. Within the geosphere, however, the critical
adsorption usually involves heterogeneous gas-solid chemical temperature will be exceeded which means that during geological
reactions whereby CO2 is subjected to a chemical reaction with sequestration, CO2 will be gaseous or supercritical. CO2 in liquid
an active compound that is existing on the solid. This aids forma- form or denser gaseous CO2 form ideal solvents for small hydrocar-
tion of a new product such as a carbonate or bicarbonate. Physical bons and aromatic compounds making supercritical CO2 ideal for
adsorption, on the other hand, involves the adsorption of CO2 onto extraction of small molecules from coal or other geological media
the surface of the solid with no chemical reactions occurring to when injected.
form a new species. Many factors are known to affect the adsorp- Natural brine is known to have high salinity which can subse-
tion abilities of dry scrubbing process. These include the size and quently affect the solubility of CO2 [98]. Previous studies have
volume of pores, surface area and the affinity of the solid for bond- shown that when the concentration of CaCl2 increases by approx-
ing the CO2 [76,91,92]. imately 30%, the solubility of CO2 decreases by a factor of 3 or 4
[99]. This, in turn, means that aquifers with higher salinity will
2.5.3. Solid chemical adsorption have a much smaller capacity for trapping gases than those with
These reactions are usually heterogeneous and occur in the out- low to moderate salinity. Wiebe and Gaddy (1940) also investi-
ward area of the solid to generate a new chemical species. These gated the effect of temperature and pressure ranges on brine
reactions also involve the neutralization of CO2 with a base com- sequestration and revealed that solubility increases with increas-
pound either on or within the solid. These acid/base neutralization ing pressure [100]. Another factor of CO2 that will significantly dis-
reactions are most often used in wet scrubbing processes however turb its fate when stored geologically is its acidity. When CO2 is
they can be similarly applied to gas/solid systems [28]. Much dissolved in water, it forms carbonic acid (H2CO3), which subse-
thought must be paid to the physical form of the solid in these reac- quently reduces the overall solution pH. Increased acidity increases
tions as if the solid requirements are such that it should be regen- the solubility of minerals, which in turn may lead to increased
erable and going to be used over multiple cycles then maintaining porosity and permeability as well as secondary precipitation of car-
the structural integrity is quite important. In addition, minimisa- bonate minerals [98,101,102]. Thus as the pressure rises, the pH
tion of attrition is also important, and this is usually done by depo- drops, and as the temperature rises, the pH drops.
sition of the metal compound into a solid substrate with a higher
strength that serves as a form of support. This wearing down pro- 2.9. Sequestration of CO2 in lower coal seams with concurrent
cess into finer materials can be either physical via frictional move- production of CH4
ment or chemical via changes in volume. Desirable solid CO2
chemical adsorbents should have the following properties, namely Coal seam sequestration is the packing of CO2 from human-
to have a high equilibrium capacity, be able to obtain separation generated sources in coal seams that are far below ground and
under gas conditions of low pressure and high temperatures, low which cannot be reached. This is done for extended periods of time
equilibrium concentrations and production of a pure CO2 stream. regardless of the recovery of natural gas [5,6]. Previous studies
conducted showed that CH4 is quickly replaced from coal when
2.6. Separation of CO2 using membranes CO2 or other gases such as pure N2 and flue gas are injected
[103–105]. This process is known as enhanced coal bed methane
Membranes can be used for CO2 separation and removal when recovery (ECBM) and when performed using CO2 it becomes
CO, H2, H2O, H2S, N2, O2, H2O, SO2, and HCl (flue gas) are present. known as CO2 - ECBM. When the main purpose is to sequester
These processes require less upkeep and energy than other similar CO2 while still producing CH4 it becomes known as CO2 – ECBM/
absorption systems involving alkanolamine or alkaline salt solu- sequestration. This approach has proven to be a more viable option
tions [86]. For these processes, a membrane material allowing to stabilising atmospheric concentrations of CO2 as it reduces the
the selective diffusion of exclusion of CO2 is required. Chemical costs linked with the capture of CO2 from large point sources while
affinity membranes may also be used. These contain a scrubbing moving it to a suitable underground storage site. The technology
solution or chemical functional group such as an amine which is needed to pump CO2 into geological sites is suitably designed
selective for CO2. Numerous studies have been carried out using and have been used during enhanced gas recovery (EGR) and
CO2 - selective membranes based on inorganic materials such as enhanced oil recovery (EOR) processes for tens of years.
zeolites, carbon, alumina, and silica. In addition, polymer mem-
branes have been used for the isolation of CO2 from natural gas 2.10. Chemical, physical and thermodynamic hypotheses for CO2
streams [93–95]. injection into a coalbed

2.7. Geological sequestration of CO2 Despite numerous experimental studies, the fate of CO2 when
injected into a coal seam remains uncertain. To aid understanding
The injection of CO2 into live oil fields for improving the rate of and development of CO2-ECBM/sequestration as well as to further
production has an added benefit in that CO2 is captured below understand what causes the operational problems and to develop
ground in the process making this one of the earliest methods of solutions to these, numerous hypotheses pertaining to the chemi-
CO2 sequestration [37]. The location and large size of these deep cal, physical, and thermodynamic properties that occur have been
saline aquifers make them a suitable storage site as over time there proposed. While these are thoroughly explained in other studies,
is likely to be an increase in the amount of CO2 being produced they are still yet to be tested and confirmed [5,106,107].
[39,96,97].
2.11. Recovery of CH4 from coalbeds
2.8. Chemical and physical properties of CO2
CO2 – ECBM/sequestration is carried out by first identifying a
Understanding the properties of CO2 is imperative in being able coal seam deep below ground that has the correct properties. These
to redirect the behaviour of when stored in underground sites. CO2 include depth, thickness, permeability and gas content [108]. CH4
652 V. Arora et al. / Materials Science for Energy Technologies 2 (2019) 647–656

can then be recovered from coal via drilling into the coalbed either underground carbon sequestration. It arises when dissolved CO2
vertically or horizontally. Often at least two wells are drilled but up interacts with aqueous species to precipitate as a solid such as cal-
to seven can be drilled, one of which is used for CO2 injection. cium, magnesium or iron carbonate [49,118]. One of the major
These drilled holes act as the CH4 transport and recovery system benefits associated with this method is that it results in permanent
allowing diffusion of the gas from a section of high pressure within CO2 trapping that is not subjected to any leaking. However, there
the coalbed to a section of low pressure which is usually up the may be some form of premature pore clogging as a result of min-
borehole. CO2 is injected into the coal seam while CH4 and water erals which result in a decrease in the permeability and overall
are formed at the recovery wells. In addition, the rate of gas diffu- storage capacity.
sion is governed by the amount of water present with increased
CH4 diffusion occurring after water is pumped out of the coal. This 2.14. Effects of CO2 injection on deep saline aquifers
causes the pressure in the seam to decrease and results in about
50% of the CH4 in the coalbed [109]. In addition, the injected gas The variation in permeability of saline aquifers caused by CO2
does not need to be pure CO2 and mixes of CO2 and inert gases like injection forms one of the major issues today as it may greatly
N2 can also be used. influence the feasibility of the rate of injection. This change in per-
meability is often difficult to produce due to the complexity of the
2.12. Storage of CO2 in deep saline aquifers chemical equilibriums in addition to the variability among aquifer
formations. Previous studies have shown variance in permeability
Presently there is a range of large-scale studies being carried with an increase, decrease and no change at all [119]. These studies
out all over the world whose main aim is to demonstrate and study showed that CO2 dissolution which leads to decreased pH and sub-
the effects and feasibility of CO2 injection into deep saline aquifers sequent release of fine particles may lead to a decrease in the per-
on an industrial scale. One example of this is the Sleipner natural meability while secondary precipitation of carbonates may also
gas field in the North Sea off the coast of Norway [62,110,111]. contribute to decreased permeability as well. In addition, if
Studies have shown that the natural gas gathered from this field increased pressure at the bottom of a formation rises too much,
contains up to 9% CO2 using an amine system. CO2 is injected into the reservoir rock and cap rock could become fractured which
a saline aquifer that lies 1000 m below the seabed and is one of the could, in turn, result in failure of the reservoir and leaking of CO2
first projects where CO2 has been captured underground for the upwards to the surface.
mitigation of GHG’s. A second example is a pilot scale CO2 injection In order to predetermine the behaviour of injected CO2 as well as
study that is being run by the Texas Bureau of Economic Geology to determine ideal conditions for injection and storage, two kinds of
on the Gulf coast of Texas in which CO2 is injected into the Frio for- computer simulated models have been run, namely reservoir and
mation. This site has ideal characteristics of geological formations geochemical models. The primary focus of reservoir models is on
that aid CO2 sequestration and is located ideally near to numerous the physical characteristics of the aquifer and that of injected CO2
power plants which emit CO2 [112]. Through all these projects, in order to establish the rate of injection and overall universal
much research is being carried out to study the long-term beha- capacity while geochemical models emphasize the chemical reac-
viour and formation of the gas as CO2 is injected in order to develop tions induced by injection of CO2. These models use thermody-
a base of knowledge that can be called upon as similar practices namic and kinetic data to establish how the chemical properties
begin to be adopted worldwide. of the brine and mineral matrix will change the overall mineral
trapping, hydrodynamic properties and solubility in the long term.
2.13. Fate of CO2 in deep saline aquifers
2.15. Natural analogs
One of the biggest concerns for CO2 sequestration in saline aqui-
fers is subsequent effects after CO2 is injected and stored over time.
Despite field and laboratory experiments as well as computer
Much research has been done to determine the safety and integrity
models, it remains fairly complex to predict long-term behaviour
of certain storage sites as well as what parameters will affect the
of injected CO2 in saline aquifers. To aid with this problem,
duration for which the CO2 will remain below ground. In addition,
research is currently being done on natural events of deep under-
these studies aim to determine methods to circumvent any sharp
ground storage sites such as the Bravo Dome in northeastern New
and hasty releases of the gas to the surface or any slow releases
Mexico and the McElmo Dome in southwestern Colorado. These
which might contribute to groundwater contamination or filter
sites are commonly referred to as natural analogs since there are
into surrounding homes. Three main processes effectively illus-
so many occurring around the world which are thought to have
trate the fate of sequestered CO2 in a deep saline aquifer. These
held trapped CO2 for millions of years. These analogs can serve
are hydrodynamic trapping, solubility trapping and mineral trap-
as exceptional research sites, providing vision into the effects of
ping [113–115].
extended periods of below ground CO2 storage. In addition, these
Hydrodynamic trapping results in the CO2 remaining in a sepa-
sites will also aid in gaining public acceptance if research can prove
rate and undissolved gaseous phase which is separate from the
that they have already been storing CO2 for extremely long periods
brine. It is prohibited from moving vertically to the surface by an
of time and remain stable with no harmful secondary effects [41].
overlying and almost impermeable layer. This layer is known as
a cap rock. Studies have shown that as long as the cap rock itself
is not compromised and is able to prevent the vertical flow of 3. Environment, health and safety concerns linked to CO2
buoyant CO2 in the area of the injection point, the CO2 will not sequestration
escape for millions of years [111,116,117]. In solubility trapping,
the CO2 is dissolved in the formation water and is not subjected 3.1. Induced seismic activity due to injection of fluids underground
to buoyancy. Therefore it is less reliant on the integrity of the
cap rock. The overall storage capacity is increased as a result of The injection of CO2 into geological formations could possibly
the reduction in pressure per a given amount of injected CO2. In lead to earthquakes. There have been many recordings of anthro-
addition, the lower pH may result in a series of subsequently initi- pogenically induced seismic activity with popularly known ones
ated chemical reactions. The third mechanism is known as mineral occurring in South Africa, Germany and Denver. The major causes
trapping which is one of the most stable and long-term forms of of these induced activities happen when an external factor is
 V. Arora et al. / Materials Science for Energy Technologies 2 (2019) 647–656 653

acquainted with a local tectonic system. This, in turn, may lead to are formed during ECBM production. This water is a brine solution
mechanical failure of the rock due to increased stress that may comprising Na+, Cl and HCO3 as well as other dissolved solids
reactivate the fault. Previous studies have shown a correlation which in turn form a source of contaminants [126–129].
between the frequencies of earthquakes with the volume of con-
taminated wastewater being injected into an area with epicentres
being recorded nearby to the site of injection [120]. Initially, seis-
3.3. Monitoring of geologically sequestered CO2
mic activity occurs near to the point of injection. Variations in
injection pressure and rate are known to affect seismic activity
The monitoring of sequestered CO2 is imperative as it can pre-
with the rate of injection affecting the scale of seismic events.
vent environmental catastrophes, aid in protecting public health
The greater the amount of injection, the higher the magnitude of
and safety while considerably decrease the dangers associated
seismic activity [121–123]. There is a range of factors that can trig-
with geological sequestration of CO2. Monitoring should be done
ger seismic events. These include the transfer of stress, hydraulic
on extremely long time scales that run for over 1000 s of years
fractures, contraction of rocks as a result of extracted fluids, min-
after CO2 injection takes place [5,130]. A range of techniques are
eral precipitation and increases in density [124]. The confining
required for the monitoring and quantification of geologically
pressure of a geological formation can be measured or predicted
sequestered CO2 such as geophysical methods and the use of
which allows scientists to determine if a seismic event will be trig-
chemical tracers. The knowledge gained from extensive monitor-
gered based on the injection pressure. In addition, the injection
ing can serve as a model for monitoring the integrity of the seques-
pressure to be applied is affected by rock permeability and poros-
tered CO2 and in determining when and how much CO2 will
ity. These two factors can be measured which in turn means that
migrate from place to place. Techniques should be designed to dis-
estimating the seismic potential of a given saline aquifer injection
tinguish the source of CO2 and CH4 reaching the surface. This is
is possible.
usually done using 13 °C isotope ratio mass spectrometry. The
development of monitoring programs can produce significantly
3.2. Environmental aspects
valuable information such as leak rate of gases to the surface as
well as recognise areas at the surface where the flux of CO2 is most
3.2.1. Geological sequestration
significant. It can also generate information on the storage capac-
One of the concerns related with geological sequestration is the
ity, CO2 residence time as well as potential leakage pathways and
probability of CO2 discharge to the surface either through a fast or
monitor CO2 movements.
slow leak [8,9]. While CO2 forms an asphyxiant in high concentra-
A suitable monitoring program should include the concurrent
tions, atmospheres containing 10% or higher may lead to uncon-
application and integration of results from a range of methods
sciousness and death [15]. CO2 is non-flammable, not explosive,
and technologies. These include geochemical methods involving
non-carcinogenic, and relatively not toxic in low concentrations.
tracers, measurements of CO2 flux in gases from soils, seismic data
Breathing high concentrations can cause problems associated with
and flow simulators. While each technique yields different infor-
respiratory rates, headaches, sleepiness, and dizziness; however,
mation, this data when combined with the other generated data
these are reversible. Previous studies have also shown that contin-
will provide a complete picture that will aid efficient monitoring.
uous exposure to atmospheres containing at least 1.5% CO2 can
result in physiological changes [125].
Environmental impacts and contamination constitute a signifi-
cant source of concern as it is possible that during sequestration, 3.4. Various monitoring methods
brine is moved into the overlying freshwater aquifers which may,
in turn, result in contamination of water sources. In addition, water Pressure monitoring is one of the simplest monitoring tech-
flow through a coal seam can result in subsequent reactions that niques available as it should remain fairly constant when no extra
lead to the dissolution of CO2 into the water. This dissolved CO2 CO2 is injected. Pressure measurements are usually made at the
and related reaction products can be mobilized from the coal seam surface. Other methods include the use of isotopic ratios of CO2,
in the flowing water to areas of low pressure and eventually chemical tracers, and visual inspections for dead vegetation on
migrate to the surface. The movement of trace metals, metalloids the surface. Another successful method is through monitoring leak
and radionuclides forms another source of concern as previous detections of CO2 and CH4. By determining the flux of CO2 and CH4
studies have shown the dissolution of trace metals when leaking from a sequestration site, it is possible to monitor the rate of leak-
CO2 reaches shallow drinking water aquifers. age [131]. By measuring the isotopic compositions of the CO2 and
CH4 emanating from the soil before and after sequestration is
3.2.2. ECBM started, one will also be able to distinguish between natural CO2
A significant source of atmospheric CH4 is obtained from natu- and CH4 emissions. Measurements of the concentration of chemi-
rally leaking faults and fractures. As a result of this, a major con- cal tracers added to the CO2 are imperative since they quantify
cern arises if CH4 can find a way to reach the surface because the rate of leakage to the surface. In addition, the use of geophys-
this means that there is a possibility that CO2 can too. Thus when ical tools is vital as they show where the CO2 front within the geo-
injecting CO2 during CO2 – ECBM/sequestration, it is imperative logical area is thereby marking the boundaries for upward gas
that the fracture pressure of the cap rock is not be exceeded as this migration.
could lead to fracturing and provision of a CO2 escape route. In Chemical tracers are defined as extraneous substances that are
addition, the environmental, health and safety issues could be added to CO2 and can either be radioactive or chemical in nature.
heightened as recovery of CH4 from coalbeds often necessitates They serve as a means to monitor the detection of a slow CO2 leak
dewatering which lowers the water pressure in the seam, thereby to the surface. Identifying the rate of migration of tracers is impor-
allowing CH4 to transfer into the cleat system and subsequently tant as if it is strongly adsorbed by surrounding geological media or
flow from areas of high to low pressure. This dewatering process dissolved in produced water, it will not be able to migrate with the
requires millions of litres of water which could, in turn, result in CO2 thereby rendering it useless. Geophysical monitoring is
variations in underground water pressure which in turn allow pre- another method commonly used that allows for sequestered CO2
viously adsorbed gases to migrate through any faults and fissures to be monitored by following the movement of reservoir fluids at
and ultimately to the surface. In addition, large volumes of water localities that are further from the point of injection.
654 V. Arora et al. / Materials Science for Energy Technologies 2 (2019) 647–656

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