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Mehdi Ansarizadeh

Calgary, Alberta, Canada Carbon DioxideChallenges and Opportunities


Kevin Dodds
Australian National Low Emissions Coal
Research and Development
Canberra, Australian Capital Territory, Australia
In the early days of the oil and gas industry, companies noted that carbon dioxide had
Omer Gurpinar
Lawrence J. Pekot corrosive effects on well internals; operators later found opportunities to use the
Denver, Colorado, USA
compound to their advantage. Projects now underway in the oil field reflect several
lker Kalfa prioritiesmanaging carbon dioxides corrosive effects, using it to recover more oil
Secaeddin Sahin
Serkan Uysal after waterflood and storing it in underground formations. Because of its role in
Turkish Petroleum Corporation
climate change, carbon dioxide has emerged as a topic of significant public interest
Ankara, Turkey
and scientific investigation as well as the focus of hydrocarbon producers.
T.S. Ramakrishnan
Cambridge, Massachusetts, USA

Norm Sacuta
Carbon dioxide is in the news. Whether because of this compound, ranging from studies of carbon
Petroleum Technical Research Centre
Regina, Saskatchewan, Canada the link to climate change and its consequences or dioxidemethane hydrates in the 1940s to current
for the concept of long-term storage, carbon diox- studies on corrosion.2 Although anthropogenic
Steve Whittaker ide has captured the interest of the public and the human-generatedcarbon dioxide plays a nega-
Commonwealth Scientific and Industrial global scientific community.1 The oil and gas indus- tive role in climate change, its role is positive in
Research Organisation try has a long history of addressing the effects of enhanced oil recovery (EOR).
Perth, Western Australia, Australia

Oilfield Review 27, no. 2 (September 2015).


Copyright 2015 Schlumberger. 100
id
1. Zimmer C: Ocean Life Faces Mass Extinction, Broad qu CO2 supercritical
i

CO2 solid CO2 liquid


dl

Study Says, The New York Times (January 15, 2015), 10 fluid
Solid an

http://www.nytimes.com/2015/01/16/science/earth/
study-raises-alarm-for-health-of-ocean-life.html Sublimation d gas
1.0 id an
(accessed January 15, 2015). point Liqu Critical point,
Pressure, MPa

Fountain H: Turning Carbon Dioxide Into Rock, and 31.1C, 7.37 MPa
Burying It, The New York Times (February 9, 2015), 0.1
http://www.nytimes.com/2015/02/10/science/burying-a- Triple point,
mountain-of-co2.html (accessed June 1, 2015). 56.6C, 0.519 MPa
Cannell M, Filas J, Harries J, Jenkins G, Parry M, Rutter P, 0.01
as

Sonneland L and Walker J: Global Warming and the E&P


dg
an

Industry, Oileld Review 13, no. 3 (Autumn 2001): 4459. 0.001


lid

CO2 gas
2. Unruh CH and Katz DL: Gas Hydrates of Carbon
So

DioxideMethane Mixtures, Journal of Petroleum


0.0001
Technology 1, no. 4 (April 1949): 8386. 140 120 100 80 60 40 20 0 20 40 60 80 100
Choi Y-S, Young D, Neic S and Gray LGS: Wellbore
Integrity and Corrosion of Carbon Steel in CO2 Geologic
Temperature, C
Storage Environments: A Literature Review,
International Journal of Greenhouse Gas Control, 16S Figure 1. Carbon dioxide phases. Phase boundary lines (blue) define the
(January 2013): S70S77. areas in which each CO2 phase exists. At the triple point, all three phases
3. Global EcologyUnderstanding the Global Carbon solid, liquid and gaseous CO2coexist in thermodynamic equilibrium. Along
Cycle, Woods Hole Research Center, http://whrc.org/ the solid-gas line below the triple point, CO2 sublimesconverts directly
global/carbon/ (accessed January 15, 2015). from a solid to a gas without going through a liquid phase. The marked
Falkowski P, Scholes RJ, Boyle E, Canadell J, Canfield D, sublimation point corresponds to 0.101MPa [14.7 psi] of CO2 vapor. Along
Elser J, Gruber N, Hibbard K, Hgberg P, Linder S, the solid-liquid line above the triple point, solid CO2 melts to a liquid. Along
Mackenzie FT, Moore B III, Pedersen T, Rosenthal Y, the liquid-gas line above the triple point, liquid CO2 evaporates to a gas. At
Seitzinger S, Smetacek V and Steffen W: The Global
Carbon Cycle: A Test of Our Knowledge of Earth as a the critical point, the liquid and gaseous states of CO2 are indistinguishable,
System, Science 290, no. 5490 (October 13, 2000): and phase boundaries no longer exist. These attributes at the critical point
291296. and at higher temperature and pressure characterize the area in which CO2
4. Riebeck H: The Carbon Cycle, NASA Earth Observatory, is a supercritical fluid (green). (Adapted with permission from Bassam Z.
http://earthobservatory.nasa.gov/Features/CarbonCycle/ Shakhashiri, University of WisconsinMadison, USA.)
(accessed January 15, 2015).
5. Riebeck, reference 4.

36 Oilfield Review
2

Temperature change, F
1
CO
CO22

CO22
Photosynthesis 0

1890 1920 1950 1980 2010

Plant Anthropogenic Year


Plant Anthropogenic
respiration
respiration carbon
carbon
CO
C
COO22 CO
CO22
CO22

Decomposition Photosynthesis Decomposition


Soil carbon

Ocean sediment carbon

Carbon, one of the two constituents of carbon prime causes for changes in the fast carbon which helps arrest atmospheric accumulation.
dioxide [CO2], is an essential element on Earth. cycle.5 Plants, trees and microscopic marine For EOR, CO2 enables increased yield from oil
The mass of carbon on Earth is 5.37 1016 kg plants are important components of the fast car- fields after primary recovery and waterflood. This
[11.83 1016 lbm], which is distributed among bon cycle. During decay, burning and consump- article discusses and illustrates these aspects of
several reservoirs: the Earths atmosphere; tion of these life forms, carbon, present as CO2, is CO2, its effect on climate change and its role in
plants; animals; soil; minerals; the shallow and released and accrues in the atmosphere. the oil and gas industry. Examples from oil and
deep ocean; and coal, oil and gas.3 The movement Similarly, much of the CO2 from anthropogenic gas fields in Canada, Algeria and Turkey demon-
of carbon between these reservoirsthe carbon activities also accumulates in the atmosphere. strate the use and storage of carbon dioxide.
cyclemaintains a balance between carbon in Plants and the oceans absorb about 55% of this
the atmosphere and in the ocean and rocks.4 This anthropogenic CO2, but the rest stays airborne. Carbon Dioxide Characteristics
cycle has two components: a slow cycle that takes Scientists attribute persistent changes in the Carbon dioxide, a molecule that consists of two
100 to 200 million years to move carbon between composition of the atmosphere, such as the oxygen atoms covalently bonded to a single carbon
Oilfield Review
the oceans, soil, rock and the atmosphere and a increasing COSPRING
2 content,15
to be an important driver atom, has a molecular weight of about 44g/mol.
fast cycle that takes 50 to 100 years to move car- of climate change.
CO2 Fig Opener Depending on temperature and pressure, CO2 can
bon through the biosphere. The role ofORSPRNG 15 CO2change
CO2 in climate Openeris signifi- exist as a solid, liquid or gas (Figure 1). At tem-
Historically, the carbon cycles have resulted cant, but the compound has a different function peratures and pressures at or above the critical
in a nearly constant level of carbon in the atmo- in the oil and gas industry. Carbon dioxide can be point, CO2 is a supercritical fluid, which has some
sphere, but that is changing. Current data point captured and stored in depleted reservoirs, properties of a gas and some of a liquid. As a super-
to deforestation and combustion of fossil fuels as critical fluid, CO2 develops miscibilitythe ability

September 2015 37
to mix homogeneouslywith crude oil and Carbon dioxide may be produced in several while in silicate reservoirs, the reactions are gen-
improves oil recovery. ways. Natural sources of CO2 production include erally much slower. These reactions may result in
Carbon dioxide is stable in the atmosphere. plant and animal respiration and decay, fires and some of the CO2 being mineralized and perma-
Its concentration in the atmosphere depends on volcanic release. Anthropogenic sources include nently trapped.9
competing processes within the carbon cycles fossil fuel combustion and certain manufacturing Another important set of reactions involving
that consume or release CO2. Photosynthesis is activities, including cement and ammonia produc- CO2 is associated with corrosion. Carbon dioxide
one chemical reaction that involves CO2. During tion, natural gas processing and petrochemical may be corrosive or noncorrosive depending on
photosynthesis, plants, algae, ocean plankton manufacturing. Humans release CO2 indirectly the materials employed, temperature at the con-
and certain types of bacteria use light energy to through deforestation.7 tact surface, water vapor concentration and CO2
convert CO2 and water to oxygen, carbohydrates Carbon dioxide may undergo several reac- partial pressure. The most likely metal to corrode
and water.6 Each year, more than 10% of the atmo- tions of interest in the oil field. For example, dis- is carbon steel in storage environments and cas-
spheric CO2 is reduced to carbohydrates by pho- solved in water, CO2 forms carbonic acid [H2CO3] ing and tubular steel in wells. At a moderate pres-
tosynthesis. Plants, algae and plankton use and other H2CO3 analogs.8 The CO2 may also react sure of 1.0 MPa [145 psi], the corrosion rate of
carbohydrates for growth whereas animals, with the minerals of the reservoir; in carbonate X65 pipeline steel is independent of temperature
including humans, use it as an energy source. reservoirs, the reaction can be relatively rapid from 50C to 130C [120F to 270F].10 Increasing
water concentration, on the other hand, causes a
significant increase in corrosion for steel. For
example, at a pressure of 8 MPa [1,160 psi] and a
temperature of 40C [104F], increasing the
A
water concentration in supercritical CO2 from
1,000 to 10,000 parts per million (ppm) causes
Rock formation the corrosion rate of steel to increase by 87%.11
Annular cement
Well casing Similarly, for carbon steel in aqueous CO2 solu-
B tions at 25C [77F], increasing the CO2 partial
pressure from 0.1 MPa [14.5 psi] to 1 MPa pro-
duces a corrosion rate increase of about 450%.12
Another potential area of concern for oilfield
Cement well plug
operators is the effect of CO2 on cement in
C wells.13 Carbon dioxide saturated with water
deteriorates the cement used in wells. This dete-
rioration can occur in cement that is adjacent to
the well casing either in the annulus between
the casing and rock or at the interface between
D
the casing and a cement well plug (Figure 2).14
Therefore, the cement used in CO2 injection wells
must be able to resist the damaging effects of
CO2 because operational periods can last from 25
E
to 100 years and mandated safety periods that
last much longer. For wells to reach these time
objectives intact, using additives that make the
cement more resistant to harm from CO2 may be
advantageous. Reaction of CO2 with wellbore
F cement is slow in a well in which good construc-
tion practices and appropriate materials were
used; in these cases, CO2 should not pose a prob-
lem. Many old, abandoned wellscompleted
and shut in using practices and cement accept-
Figure 2. CO2 migration. Wells offer several potential pathways for gas able at the timeare not suitable to use in long-
migration. The pathways consist of the following: between the casing and term CO2 storage systems. Leakage from
the annular cement (A), between the cement plug and casing (B), through
the cement plug and annular cement pore space as a result of deterioration abandoned wells has been identified as a signifi-
(C), through the casing as a result of corrosion (D), through fractures in the cant risk in geologic storage of CO2.
annular cement (E) and between the annular cement and rock (F). (Adapted
with permission from Michael Celia, Princeton University, New Jersey, USA.) Greenhouse Gas Effect and Climate Change
The greenhouse gas (GHG) effect is the process
by which atmospheric insulation, imparted by
certain gases, keeps the Earth warmer than it

38 Oilfield Review
would be without them (Figure 3).15 Although the
concept of climate change associated with green-
house gases may seem recent, the idea of the
GHG effect dates back to the 19th century.16
Scientists then were intrigued by the possibility
Solar
that lower levels of CO2 might explain the ice radiation
ages. In 1896, Swedish scientist Svante Arrhenius
calculated that industrial emissions from coal
combustion might someday cause an increase in
the Earths surface temperature.17 More recently,
in the 1960s and 1970s, Russia considered ways to
Atmosphere Infrared
warm its large areas of icy tundra and convert radiation
Earths surface
them to fertile farmland through human-engi-
neered climate change. These and subsequent
attempts to alter the climate are encapsulated by
the term climate engineering, also known as geo-
engineering.18 Geoengineering is the intentional
manipulation of planetary-scale processes to Figure 3. Greenhouse gas effect. Most solar radiation (left) is absorbed by
affect Earths climate systemfor example, to and warms the Earths surface while some radiation is reflected by the Earth
cool down the Earths atmosphere or remove CO2 and the atmosphere back into space. Some solar radiation that reaches
Earths surface is emitted as infrared radiation (right), some of which passes
from the Earths atmosphere. directly back through the Earths atmosphere into space. Greenhouse gas
The GHG effect comprises a natural and an molecules absorb and reemit infrared radiation in all directions, including
enhanced component. Warming of the Earths sur- back toward the Earths surface. The net effect is a warming of the Earths
face associated with indigenous gases is the natu- surface and lower atmosphere. (Adapted from the USEPA, reference 15.)
ral GHG effect. The main GHGs are, in order of
abundance, water vapor [H2O], CO2, methane
[CH4], nitrous oxide [N2O], ozone [O3] and other
minor components. These gases in the atmosphere and other fluorinated hydrocarbons.19 Increased and transportation contributed 28%. Industry
heat the Earths surface by absorbing and reradiat- concentrations of these gases add to the atmo- accounted for 20% and the remaining 20% was
ing some of the infrared radiation coming from the spheres insulating qualities, thereby increasing attributable to emissions from residences, com-
surface. In addition to the natural GHG effect, an Earths surface temperatures. mercial buildings and agricultural activity. The
enhanced effect occurs when human activities In 2012, CO2 accounted for 82% of all GHG end result of the enhanced GHG effect and
increase the level of greenhouse gasesprimarily emissions in the US.20 Electrical power genera- increased concentrations of CO2 is that the
CO2 but also CH4, N2O, sulfur hexafluoride [SF6] tion was responsible for 32% of the CO2 emitted, Earths surface is getting warmer.
6. Whitmarsh J and Govindjee: The Photosynthetic 12. DeBerry DW and Clark WS: Corrosion Due to Use of 16. Weart SR: The Discovery of Global Warming. Cambridge,
Process, in Singhal GS, Renger G, Sopory SK, CO2 for Enhanced Oil Recovery, US Department of Massachusetts, USA: Harvard University Press, 2008.
IrrgangK-D and Govindjee (eds): Concepts in Energy, Report DOE/MC/08442-1, September 1979. 17. Svante Arrhenius was a recipient of the 1903 Nobel Prize
Photobiology: Photosynthesis and Photomorphogenesis. 13. Rutqvist J: The Geomechanics of CO2 Storage in Deep in chemistry for his electrolytic theory of dissociation.
Dordrecht, The Netherlands: Springer Science+Business Sedimentary Formations, Geotechnical and Geological He also proposed what came to be known as the
(1999): 1151. Engineering 30, no. 3 (June 2012): 525551. Arrhenius equation, which shows the temperature
7. Overview of Greenhouse Gases: Carbon Dioxide 14. Ramakrishnan TS: Climate Initiative and CO2 Oilfield Review dependence of reaction rate constants.
Emissions, US Environmental Protection Agency, http:// Sequestration, presented at the Fourth AnnualSPRING 15 18. Keith DW: Geoengineering the Climate: History
www.epa.gov/climatechange/ghgemissions/gases/co2.
html (accessed January 10, 2015).
Conference on Carbon Capture and Sequestration, CO2 Fig 3 and Prospect, Annual Review of Energy and the
Alexandria, Virginia, USA, May 25, 2005. Environment 25 (November 2000): 245284.
8. When CO2 dissolves in water, it forms H2CO3* and
ORSPRNG 15 CO2 3
Gasda SE, Bachu S and Celia MA: Spatial Caldeira K, Bala G and Cao L: The Science of
H2CO3. The former is the concentration of H2CO3 Characterization of the Location of Potentially Leaky Geoengineering, Annual Review of Earth and
present and is typically about 0.3% of the CO2. The latter Wells Penetrating a Deep Saline Aquifer in a Mature Planetary Sciences 41 (May 2013): 231256.
is another state entirely and could be called liquid CO2. Sedimentary Basin, Environmental Geology 46, no. 67 19. Sulfur hexafluoride [SF6] is used for high-density
For more on H2CO3 states: Langmuir D: Aqueous (October 2004): 707720. plasma etching and as a dielectric. According to the
Environmental Geochemistry. Upper Saddle River, New
Celia MA, Bachu S, Nordbotten J, Gasda S and Intergovernmental Panel on Climate Change, SF6 is the
Jersey, USA: Prentice Hall, 1997.
Kavetski D: Implications of Abandoned Wells for Site most potent greenhouse gas and has a global warming
9. Cardoso SSS and Andres JTH: Geochemistry of Selection, presented at the International Symposium potential of 23,900 times that of CO2 based on a 100-year
Silicate-Rich Rocks Can Curtail Spreading of on Site Characterization for CO2 Geological Storage, timeframe. For more on the warming potential of SF6 in
Carbon Dioxide in Subsurface Aquifers, Nature Berkeley, California, USA, March 2022, 2006. relation to the other greenhouse gases: Direct Global
Communications 5, article 5743 (December 11, 2014). Warming Potentials, Intergovernmental Panel on
Ide ST, Friedmann SJ and Herzog HJ: CO2 Leakage
10. Sim S, Cole IS, Choi Y-S and Birbilis N: A Review of the Through Existing Wells: Current Technology and Climate Change, http://www.ipcc.ch/publications_
Protection Strategies Against Internal Corrosion for the Regulations, in Proceedings of the 8th International and_data/ar4/wg1/en/ch2s2-10-2.html (accessed
Safe Transport of Supercritical CO2 via Steel Pipelines Conference on Greenhouse Gas Technologies. May 10, 2015).
for CCS Purposes, International Journal of Greenhouse Kidlington, Oxford, England: Elsevier Ltd. (2006): 20. Overview of Greenhouse Gases: Carbon Dioxide
Gas Control 29 (October 2014): 185199. 25312536. Emissions, reference 7.
11. Sim S, Bocher F, Cole IS, Chen X-B and Birbilis N: 15. Cannell et al, reference 1.
Investigating the Effect of Water Content in
US Environmental Protection Agency (USEPA): Climate
Supercritical CO2 as Relevant to the Corrosion of Carbon
Change Indicators in the United States, 2nd ed.,
Capture and Storage Pipelines, Corrosion 70, no. 2
Washington, DC: USEPA, Report 430-R-12-004,
(February 2014): 185195.
December 2012.

September 2015 39
peratures is well documented.24 Less well docu-
400 mented is the effect of increased atmospheric
CO2 on global oceans.
380 Researchers believe that the effects of
increased CO2 can be observed in global oceans.25

CO2, ppm
360 Oceans absorb about one-third of the CO2 added
to the atmosphere. Ocean absorption of CO2 is
450 340
not benignCO2 has caused a significant
increase in ocean acidification. The weather sta-
400 320
tion at Mauna Loa, Hawaii, USA, measured atmo-
1960 1970 1980 1990 2000 2010 2015 spheric CO2 and ocean pH from 1990 to 2010.
350 Year
During that 20-year period, atmospheric CO2 rose
CO2, ppm

300
from 352 ppm in 1990 to 387 ppm in 2010.
Concomitant with this rise in CO2, the ocean pH
250
decreased from 8.12 to 8.08, indicating an
increase in ocean acidification.26
200 Acidification of oceans and the warming
effects from climate change are leading to the
400,000 350,000 300,000 250,000 200,000 150,000 100,000 50,000 0 extinction of some types of ocean animal life.27
Years before 1950 Coral reefs are sensitive to both acidification and
Figure 4. Increase in CO2 in the atmosphere. The levels of atmospheric CO2 can be measured from the warming. The net effect of acidification is an
distant past by analyzing ancient air bubbles trapped in polar ice. Data from 400,000years before 1950 increase in the hydronium ion [H3O+] concentra-
and to the present show a cyclic pattern dipping lower than 200ppm during cold cycles and rising to tion and a corresponding decrease in the carbon-
nearly 300ppm during warmer periods. Starting in the mid-1950s (inset), atmospheric CO2 level rose
ate ion [CO32], which results in less coral being
above 300ppm and continues to rise to the current levelslightly more than 400ppm. (Adapted from
Global Temperature and Trends in Atmospheric Carbon Dioxide: Recent Monthly Average Mauna formed than in healthy ocean waters.28 Coral reefs
Loa CO2, reference 23.) are also sensitive to increases in temperature as
small as 1C to 2C [1.8F to 3.6F] over times that
Global surface temperatures measured since The CO2 level in 1900 was typical of levels for are too short for the corals to adapt. These changes
1900 have risen 0.79C [1.4F].21 During the the 400,000years before 1950, in which the CO2 in temperature affect many of the microscopic and
same period, the CO2 level in the atmosphere level was never above 300ppm (Figure 4).23 The higher marine life forms that live in a symbiotic
rose from 296ppm in 1900 to 392ppm in 2010.22 effect of rising CO2 on the Earths surface tem- relationship with coral.
21. Five independent government agencies or their Ocean Acidification: The Other CO2 Problem, Annual West Siberian and Volga Ural basins; in South America
predecessors have measured surface temperatures Review of Marine Science 1 (January 2009): 169192. and Mexico, the Maracaibo and Villahermosa Uplift
annually since 1900. These agencies are the US National 26. Since pH is on a logarithmic scale, this 0.5% decrease in basins; in the US, the Permian basin; and in Europe,
Aeronautics and Space Administration Goddard Institute pH represents a 9.6% increase in the acidity as the North Sea Graben basin.
for Space Studies, the US National Oceanic and measured by the hydronium [H3O+] ion concentration. 32. In miscible conditions, two or more fluids mix in all
Atmospheric Administration National Centers for proportions and form a single homogeneous phase. In
27. Zimmer, reference 1.
Environmental Information, the Met Office Hadley Centre immiscible conditions, two fluids are incapable of
and the University of East Anglia Climatic Research Unit McCauley DJ, Pinsky ML, Palumbi SR, Estes JA,
forming molecularly distributed mixtures or attaining
in England and the Japan Meteorological Agency in JoyceFH and Warner RR: Marine Defaunation: Animal
homogeneity.
Japan. Data from all these agencies show nearly Oilfield ReviewLoss in the Global Ocean, Science 347, no. 6219
For more on the evolution of CO2 flooding: Holm LW:
SPRING 15 (January 16, 2015): 1255641-11255641-7.
identical long-term trends and variations. Despite
Evolution of the Carbon Dioxide Flooding Processes,
Subtle Differences, Global Temperature Records CO2in Fig 4 Urban MC: Accelerating Extinction Risk from Climate
Journal of Petroleum Technology 39, no. 11
Close Agreement, NASA Goddard Institute for Space Change, Science 348, no. 6234 (May 1, 2015): 571573.
ORSPRNG
Studies (January 13, 2011), http://www.giss.nasa.gov/ 15 CO2 4 (November 1987): 13371342.
28. Coral reefs are composed of calcium carbonate [CaCO3]
research/news/20110113/ (accessed May 17, 2015). 33. Holm LW and OBrien LJ: Carbon Dioxide Test at the
and small amounts of other minerals. Coral formation is
Mead-Strawn Field, Journal of Petroleum Technology
22. USEPA Office of Air and Radiation: Climate Change dependent on the concentrations of the calcium ion and
23, no. 4 (April 1971): 431442.
Science Facts, Washington, DC: USEPA, Report the carbonate iona decrease in the carbonate ion
430-F-10-002, April 2010. means less coral is formed. Hill B, Hovorka S and Melzer S: Geologic Carbon
Storage Through Enhanced Oil Recovery,
23. Global Temperature, NASA Global Climate Change: 29. Lake LW, Schmidt RL and Venuto PB: A Niche for
Energy Procedia 37 (2013): 68086830.
Vital Signs of the Planet, http://climate.nasa.gov/ Enhanced Oil Recovery in the 1990s, Oilfield Review 4,
vital-signs/global-temperature/ (accessed May 29, 2015). no. 1 (January 1992): 5561. 34. Martin FD and Taber JJ: Carbon Dioxide Flooding,
Journal of Petroleum Technology 44, no. 4
Trends in Atmospheric Carbon Dioxide: Recent Monthly Al-Mjeni R, Arora S, Cherukupalli P, van Wunnik J,
(April 1992): 396400.
Average Mauna Loa CO2, NOAA Earth System Edwards J, Felber BJ, Gurpinar O, Hirasaki G, Miller CA,
Research Laboratory Global Monitoring Division, Jackson C, Kristensen MR, Lim F and Ramamoorthy R: 35. Mohan H, Carolus M and Biglarbigi K: The Potential for
http://www.esrl.noaa.gov/gmd/ccgg/trends/ Has the Time Come for EOR?, Oilfield Review 22, no. 4 Additional Carbon Dioxide Flooding Projects in the
(accessed May 17, 2015). (Winter 2010/2011): 1635. United States, paper SPE 113975, presented at the
SPE/DOE Improved Oil Recovery Symposium, Tulsa,
24. Although surface temperatures appear to be directly 30. International Energy Agency Greenhouse Gas R&D
April 1923, 2008.
correlated with CO2 levels, this has not been proven Programme (IEAGHG): CO2 Storage in Depleted
from first principles. This correlation is based on Oilfields: Global Application Criteria for Carbon Dioxide 36. IEAGHG, reference 30.
evidence-based fact. Enhanced Oil Recovery, Stoke Orchard, Cheltenham, 37. Mohan et al, reference 35.
25. Archer D, Eby M, Brovkin V, Ridgwell A, Cao L, England: IEAGHG, Technical Report 2009-12, 38. Benson S: Status and Opportunities in CO2 Capture,
Mikolajewicz U, Caldeira K, Matsumoto K, Munhoven G, December2009. Storage and Utilization, presented at the American
Montenegro A and Tokos K: Atmospheric Lifetime of 31. The 10 basins in the world that have oil recoverable Physical Society Workshop on Energy Research and
Fossil Fuel Carbon Dioxide, Annual Review of Earth and using CO2 are the following: In the Middle East, the Applications for Physics Students and Postdocs,
Planetary Sciences 37 (2009): 117134. Mesopotamian Foredeep, Greater Ghawar Uplift, Zagros San Antonio, Texas, USA, March 1, 2015.
Doney SC, Fabry VJ, Feely RA and Kleypas JA: Fold Belt and the Rub Al Khali basins; in Russia, the

40 Oilfield Review
Carbon Dioxide Flooding
The oil and gas industry injects CO2 into oil and Purchased CO2 Injected CO2 Recycled CO2
gas fields for two primary purposesrejuvenating
producing fields and storing in depleted or unused
reservoirs; these processes contribute to the
global effort to minimize climate change. Carbon
Industrial plant Producer
dioxide can be used in EOR to recover additional Zone of efficient sweep well
oil following primary production and waterflood.29
In addition, CO2 can be captured from a variety of
sources and stored underground.
Immobile oil
The amount of technically recoverable oil
worldwide has been estimated at 450 billion bbl
[72 billion m3].30 Oil that could theoretically be Dissolved Stored Drive CO2 Water CO2 Miscible Oil Oil
recovered using CO2 is concentrated in ten large CO2 CO2 water zone bank recovery
basins worldwidein the Middle East, Russia,
South America, Mexico, the US and Europe.31 Oil
recovery on this scale using CO2 EOR would Immobile oil
require large sources of CO2 close to the reser-
voir; proximity to a CO2 source is a challenge for Figure 5. Miscible CO2 flooding. Purchased and recycled CO2 are injected into a formation (top left);
water is also injected and acts as a driver. Some of the CO2 dissolves in the oil and is stored in the
most basins. Because the volume of potential formation (bottom left). The remainder of the CO2 causes vaporization of the lighter oil fractions into
recoverable oil worldwide is large, operators have the CO2 phase (bottom center) while the CO2 condenses into the oil phase. Driven by the water flood,
been able to use a variety of EOR techniques to the oil, and any residual CO2, reaches the production well (bottom right) and both are pumped to the
surface. At the surface (top right), the oil and CO2 are separated, and the CO2 is recycled back to the
recover additional oil from reservoirs for decades,
injection point. (Adapted with permission from the IEAGHG, reference 30.)
despite the difficulty of matching CO2 sources
with sinks.
In the 1950s, researchers looking at CO2
flooding found that the compound was miscible At constant temperature, the lowest pressure Permian Basin, Texas, from the McElmo Dome,
in oil at pressures above 700psi [5MPa].32 at which liquids achieve miscibility is defined as which is located near the border between Utah
Building on this and subsequent findings about the minimum miscibility pressure (MMP). and Colorado and has one of the worlds largest
CO2 behavior in oil, operators conducted the Miscible CO2 flooding is applicable in many reser- accumulations of naturally occurring CO2.
early successful field test of miscible CO2 flooding voirs and is most effective when the reservoir has Industrial sources of CO2 within the US
at the Mead-Strawn field near Abilene, Texas, a pressure greater than the MMP. Typically this include natural gas processing plants in Texas,
USA, in 1964.33 Test results showed a 35% increase occurs at a depth greater than 760 m [2,500ft].35 Oklahoma, Wyoming and Michigan, an ammonia
in incremental oil recovery using CO2 over the Additionally, the oil should have greater than plant in Oklahoma, a coal gasification plant in
Oilfield Review
results of conventional waterflooding. Since that 22 degree API gravity [less than 0.92SPRINGspecific15 North Dakota and power plants that have carbon
field test, many successful operations using mis- CO2 Fig 5 capture capability. In Europe, significant indus-
gravity] and less than 10cP [10mPa.s] viscosity.
cible CO2 flooding have been conducted. For best results, the reservoir needs toORSPRNG
have oil 15 CO2CO52 sources are located in the UK, the
trial
Carbon dioxide flooding for EOR can be saturation greater than 20% of the pore volume. Netherlands, Belgium, France and Germany.
grouped into two broad categoriesmiscible and Ideally, a typical miscible flood injects CO2 However, none of these sources have yet been
immiscible. The process that is ultimately at one end of the desired zone and recovers oil used for CO2 EOR operations.
employed by the oilfield operator will depend on driven to producer wells (Figure 5).36 Although
reservoir conditions and characteristics of the miscible floods account for the majority of CO2 Carbon Dioxide Storage
oil. Miscible CO2 flooding is the most common EOR projects, some systems may benefit from More than 80% of the worlds energy comes from
application although immiscible flooding may be immiscible flooding. Immiscible CO2 EOR proj- the combustion of fossil fuels, and a rapid transi-
applied in some situations because of oil density ects depend on a reduction in oil viscosity tion to low-carbon energy sources will likely be
or reservoir pressure.34 accompanied by oil swelling to achieve addi- difficult and expensive.38 One method of mitigat-
Several factors make miscible CO2 flooding an tional oil recovery. Projects that would benefit ing the effects of CO2 on climate change is carbon
effective method for additional oil recovery. from immiscible CO2 EOR have low-gravity crude capture and storage (CCS). Because about 7,400
Carbon dioxide is soluble in crude oils, swells net oil and reservoir pressures less than the MMP. industrial sources worldwide have CO2 emissions
oil volume and reduces oil viscosity even before it A dependable source for CO2 is a prerequisite greater than 100thousand metric tons/yr
achieves miscibility. As the point of complete mis- for both miscible and immiscible CO2 flooding. [110thousand tonUS/yr], CCS and other strate-
cibility is approached, the CO2 phase and the oil Natural and industrial sources of CO2 are avail- gies will be necessary over a 50-year period just to
phase start to flow together homogeneously as a able.37 In 2008, the US produced about 3 bil- arrest the increase of CO2 in the atmosphere. To
result of reduced interfacial tension and the lionft3/d [80million m3/d] of CO2, primarily from actually reduce CO2 will require an even greater
increase in volume of the combined oil-solvent natural sources in New Mexico, Colorado and effort (See Taming Carbon Dioxide Emissions,
phase relative to the water phase. Mississippi. Approximately 75% of the naturally page 42).
produced CO2 in the US is sent by pipeline to the (continued on page 44)

September 2015 41
Taming Carbon Dioxide Emissions

Data about the state of the Earth suggest that growth and reducing the absolute level of plot of carbon emission rate versus time helps
CO2 must be brought under control to arrest those emissions over the next 15 to 35 years. explain the concept and its application to con-
the deleterious effects of climate change. Climate change caused by CO2 and other fac- trolling CO2 levels in the atmosphere (Figure S1).
Although not the only culprit, of all potential tors can be arrested and reduced, but con- To frame CO2 emissions stabilization and
factors, CO2 carries the most weight in influ- crete action must be taken now to accomplish how it might be achieved, the stabilization tri-
encing undesired changes in the atmosphere, the task. angle is divided into eight wedges. Each
surface temperatures and oceans. A variety of wedge represents the amount required from
proposals have been suggested to bring CO2 Stabilization Wedges an area of focus, or major effort, to accomplish
under control. Two such proposals illustrate The stabilization wedge concept, introduced this objective. Carbon dioxide capture and
the magnitude of the CO2 emissions challenge in 2004 and refined in 2007, shows how CO2 storage is recognized as one area of focus
and show workable paths for halting emissions emissions could be brought under control.1 A (Figure S2). The strategies in each area can

Carbon Wedge Strategy


Efficiency Double the fuel efficiency of 2 billion cars from 13 to 25 km/l
[30 to 60 mi/galUS].
Carbon emission rate, billion metric tons/yr

16
Extrapolated Decrease the distance traveled by hydrocarbon-fueled cars by half.
emissions path Use best energy efficiency practices in all residential and
Eight carbon commercial buildings.
wedges Produce coal-based electricity that has twice that of todays
efficiency.
Reduced Fuel switching Replace 1,400 coal-fired electric plants with natural
8 Historical emissions path gasfired plants.
emissions
Constant Carbon capture Capture and store emissions for 800 coal-based electric plants.
emissions path and storage
Produce hydrogen from coal at six times that of todays rate
and store captured CO2.
50 years Capture the carbon from 180 coal-to-synfuel plants and store
the captured CO2.
0 Nuclear power Double the current global nuclear capacity to replace
1950 2000 2050 2100
coal-based electricity.
Year
Wind power Increase electricity generated by wind by 10 times the current
Figure S1. Stabilization triangle and wedges. Historical carbon emission rate to be achieved by a total of 2 million windmills.
rates (red line) are shown up to 2007, at which time the emission rate
Solar power Increase electricity generated from solar radiation to 100 times
was about 8billion metric tons/yr [9billion tonUS/yr]. If extrapolated the present capacity.
along the current path (black dashed line) for 50years, the emission rate
Use 40,000 km2 [15,000 mi2] of solar panels to produce
could reach about 16billion metric tons/yr [18billion tonUS/yr], and the hydrogen for fuel cell cars.
atmospheric CO2 level could be nearly 850ppm in 2057. The triangle
(green) formed by the constant emissions path (orange line)defined Biomass Increase ethanol production from biomass by a factor of 12
using farms that have an area equal to one-sixth of the
here as a 50-year spanand the extrapolated emissions is called the worlds croplands.
stabilization triangle. The area of this triangle quantifies the amount of
carbon that must be removed to stabilize atmospheric CO2 at close to Natural sinks Eliminate tropical deforestation.
current levels. The stabilization triangle can be divided into eight carbon Adopt the practice of conservation tillage in all agricultural
wedges. Within each wedge, the carbon emission rate grows from zero soils worldwide.
to 1billion metric tons/yr [1.1billion tonUS/yr] of carbon after 50 years
and, consequently, its area represents 25 billion metric tons [28 billion Figure S2. Carbon stabilization wedges and strategies for lowering CO2
tonUS] of carbon emissions. Therefore, the area of the stabilization emissions to Earths atmosphere.
triangle represents 200billion metric tons [220billion tonUS] of carbon
that will not be released to the atmosphere over the 50-year span. Once
emissions have stabilized, industry and the public must begin to employ
technologies that reduce emissions (right, blue line). (Adapted with
permission from the Carbon Mitigation Initiative, Princeton University,
New Jersey.)

42 Oilfield Review
10.5
An alternative path to taming and eventu-
INDC scenario
ally reducing CO2 emissions has been devel-
oped by the International Energy Agency
Carbon emission rate, billion metric tons/yr

(IEA).3 This concept, called the bridge sce-


10.0
nario, seeks a more aggressive approach to
battling carbon emissions than does the INDC
scenario. Implicit in the bridge scenario is the
recognition that global economic output and
9.5 energy-related GHG emissions are indepen-
dent phenomena. The bridge scenario calls for
Bridge scenario implementing five policy measures:
Increase energy efficiency.4
9.0 Reduce the use of inefficient coal-fired
power plants.
Increase investment in renewable energy.5
2015 2020 2025 2030
Year Phase out subsidies for fossil-fuel
consumption.
Energy efficiency increase Inefficient coal use reduction
Subsidy reform Upstream methane reduction Reduce upstream methane emissions.
Renewables investment Adoption of these measures is a start
toward achieving a maximum surface temper-
Figure S3. Bridge scenario. Two bounding curves define the emissions
reduction envelope of the bridge scenario. The upper curve (black) is the ature rise of 2C [3.6F] from current levels.
trend line for the carbon emission rate if the global community honors However, other measures will be required to
its INDC pledges. The bottom curve (red) represents the emission rate achieve the goal.
reduction possible under the bridge scenario. The largest contributor to
If these five strategies are fully employed
reduced carbon emissions in 2030 is energy efficiency (light orange), which
contributes a 49% reduction. Increased investments in renewable energy immediately worldwide, under the bridge sce-
sources (green) provide a 17% reduction. Upstream methane reduction nario, the carbon emission rate will peak in
(light blue), fossil fuel subsidy reform (purple) and reducing inefficient coal 2018 followed by a steady reduction. When
use (brown) make up the remaining 34% reduction. (Adapted from the IEA,
compared with the INDC scenario, the bridge
reference 2.)
scenario promotes a reduction of 1.3billion
metric tons/yr [1.4billion tonUS] from the
calculated 2030 carbon emission rate to the
eventually reduce global carbon emissions by Bridge Scenario 2010 emission rate of 8.9 billion metric tons/yr
1billion metric tons/yr [1.1billion tonUS/yr] A major climate meeting, the 21st Conference [9.8billion tonUS/yr].
by 2057. of the Parties (COP21) to the United Nations
Framework Convention on Climate Change,
1. Pacala S and Socolow R: Stabilization Wedges:
Solving the Climate Problem for the Next 50 Years will take place in Paris in December 2015. In
with Current Technologies, Science 305, no. 5686 advance of the COP21 conference, countries
(August 13, 2004): 968972.
Stabilization Wedges Introduction, Princeton
have pledged to make intended nationally
University Carbon Mitigation Initiative, http://cmi. determined contributions (INDCs) for reduc-
princeton.edu/wedges/intro.php (accessed
March 24, 2015).
ing energy-related greenhouse gas (GHG)
2. International Energy Agency (IEA): Energy and emissions toward the objective of slowing the
Climate Change: World Energy Outlook Special pace of climate change.2 Under this INDC sce-
Report, Paris: IEA, 2015.
3. IEA, reference 2.
nario, if countries adhere to their pledges, the
4. Energy efficiency is using less energy to provide the growth of the carbon emission rate is pro-
same service. jected to slow down but not stop (Figure S3).
5. Renewable energy sources include solar, wind,
hydropower and biomass.

September 2015 43
Carbon capture and storage technologies can
be applied to much of the 60% of the CO2 emis-
Electrode Case sions that come from stationary sources such as
power plants, cement plants and refineries. The
remaining 40% is released to the atmosphere and
Gas bubble comes from other stationary sources that emit
CO2 such as residences, commercial buildings,
Liquid conductor
small cement kilns, small steel plants and com-
bustion of biomass.
Implementing CCS requires four sequential
steps: CO2 capture, compression, transport via
pipeline or marine transport and storage or reuse.39
For power plants, options for CO2 capture include
precombustion, such as coal gasification, postcom-
bustion and oxygen combustion. Each option has
its advantages and disadvantages, and no single
option fits every situation.40 The next stepcon-
version of CO2 to a liquid stateis a mature tech-
nology and requires CO2 compression to 7.6MPa
[1,100psi] or higher. Pipeline transport is also a
mature technology; 3,000mi [4,800km] of pipe-
lines are in place in the US alone. This pipeline
network continues to slowly increase. Storage, the
last step in CCS, is more complex.
Figure 6. Tiltmeter. A tiltmeter, which measures surface deformation, is similar to a sensitive Depleted oil and gas reservoirs and deep
carpenters level. The tiltmeter can measure a tilt of about 1 109radians [57 109degrees], which is
saline formations either onshore or offshore are
equivalent to lifting one end of a 4,000km [2,500mi] long beam just 0.64cm [0.25in.] from level. To
measure deformation of this size, the tiltmeter uses a sensor that has a glass case that contains a gas options for geologic storage of CO2. To store CO2,
bubble, conductive liquid and several electrodes (inset). When the tiltmeter case tilts to one side, the the gas is injected into reservoirs that are at
gas bubble changes position, and the resistance between the electrodes changes. This resistance depths of 1km [0.6mi] or greater to ensure the
change is calibrated to give the degree of deformation. (Photograph courtesy of Steven Hunter,
CO2 remains in a dense liquid or supercritical
Lawrence Livermore National Laboratories, California, USA.)
fluid state. Several mechanisms trap and keep
CO2 immobile.41 The primary trapping mecha-
39. The potential for reuse in the oil and gas industry is Conference on CO2 Capture, Storage and Utilization, nism is usually a seal of low-permeability rock
limited. Most of the CO2 in the reuse category will go to San Diego, California, November 24, 2009.
CO2 flooding. For more on the Sleipner project: Bennaceur K, GuptaN,
above the storage area, similar to that for natural
40. Benson SM: Carbon Capture and Sequestration (CCS) Monea M, Ramakrishman TS, Randen T, Sakurai S and oil and gas accumulations. Secondary mecha-
101, presented at the Stanford University Global Climate Whittaker S: CO2 Capture and StorageA Solution
and Energy Project Symposium, Stanford, California, Within, Oilfield Review 16, no. 3 (Autumn 2004): 4461.
nisms include solubility trapping, a mechanism
September 2829, 2010. 47. Fairley P: A Coal Plant That Buries Its Greenhouse by which a portion of the CO2 dissolves in water,
Alvi A, Berlin EH, Kirksey J, Black B, Larssen D, Gases, MIT Technology Review 118, no. 1 (January/ and residual gas trapping, a mechanism by which
CarneyM, Chabora E, Finley RJ, Leetaru HE, February 2015): 8487.
MarstellerS, McDonald S, Senel O and Smith V: 48. IEAGHG, reference 30.
the CO2 is trapped by capillarity.42 In some forma-
CO2 SequestrationOne Response to Emissions, tions, CO2 can be eventually trapped by its reac-
49. Barnhart WD and Coulthard C: Weyburn CO2 Miscible
Oilfield Review 24, no. 4 (Winter 2012/2013): 3648.
Flood Conceptual Design and Risk Assessment, tion with the rock and conversion to solid
41. Benson, reference 38. paper 95-120, presented at the Sixth Petroleum
42. Capillary action, or capillarity, is the phenomenon in Conference of the South Saskatchewan Section of the minerals. These secondary trapping mechanisms
Oilfieldof ReviewSociety of Canadian Institute of Mining, Metallurgy
which surface tension draws fluid into the interstices tend to become more effective over time, yield-
a material. SPRING 15 and Petroleum, Regina, Saskatchewan, Canada, ing, in most cases, a more secure storage site.
October 1618, 1995.
CO2 Fig 6
43. Zoback MD and Gorelick SM: Earthquake Triggering
and Large-Scale Geologic Storage of Carbon Dioxide,
ORSPRNG Brown K, Jazrawi W, Moberg R and Wilson M: Role of
15 CO2 6 An ideal storage site is close to stationary
Proceedings of the National Academy of Sciences 109, Enhanced Oil Recovery in Carbon SequestrationThe
no. 26 (June 26, 2012): 1016410168. Weyburn Monitoring Project, a Case Study, presented
sources of CO2, has the capacity to contain the
44. Hunter S: The Tiltmeter: Tilting at Great Depths to Find at the First National Conference on Carbon projected volume of material over a long period
Oil, Lawrence Livermore National Laboratory Science Sequestration, Washington, DC, May 1417, 2001.
of time, is able to sustain a high injection rate
and Technology Review (October 1997): 1415. 50. Protti G: Win-Win: Enhanced Oil Recovery and CO2
Granda J, Arnaud A, Pays B and Lecampion B: Case Storage at EnCanas Weyburn Oilfield, paper and has a low-permeability barrier to act as a
Studies for Monitoring of CO2 Storage Sites, Based on WPC-18-0986, presented at the 18th World caprock or seal. In addition, the storage site
Ground Deformation Monitoring with Radar Satellites, Petroleum Congress, Johannesburg, South Africa,
paper C01, presented at the Third EAGE CO2 Geological September 2529, 2005. must be at an appropriate depth for CO2 to be
Storage Workshop: Understanding the Behaviour of CO2 Bennaceur et al, reference 46. liquid and have good mechanical strength to
in Geologic Storage Reservoirs, Edinburgh, Scotland, 51. For more on the Great Plains Synfuels Plant: Dakota
March 2627, 2012.
withstand injection pressures.
Gasification Company, http://www.dakotagas.com/index.
45. Benson, reference 38. html (accessed May 12, 2015). The injection of high volumes of fluid under
46. Wright I, Ringrose P, Mathieson A and Eiken O: An 52. Fairley, reference 47. high pressure into fault zones near a CCS site may
Overview of Active Large-Scale CO2 Storage Projects,
paper SPE 127096, presented at the SPE International
create problems; doing so may cause faults to slip
and generate microseismic activity.43 Passive seis-

44 Oilfield Review
mic methods may be used to monitor and record
S a s k a t c h e w a n M a n i t o b a
any injection-induced seismicity. Increased forma-
Weyburn
tion pressure may cause some degree of uplift, 0 km 100
which can be monitored using interferometric syn- 0 mi 100
Estevan
thetic aperture radar (InSAR) satellite imagery or
tiltmeters (Figure 6).44
The practice of carbon capture and storage
continues to expand worldwide. Eight operating
N o r t h D a k o t a C A N A D A
industrial-scale projects have come on stream in
the past 40 years. These projects represent storage
U N I T E D
of about 14million metric tons [15million tonUS] Beulah S T A T E S
Bismarck
of CO2 annually.45 Eight additional projects are CO2 pipeline tap
under construction, representing 13 million CO2 pipeline
metric tons [14 million tonUS] of CO2 annual Oil field
storage capacity.
At the Sleipner project in the North Sea, CO2
is produced with natural gas, separated offshore Figure 7. Weyburn-Midale project. Located near Weyburn, Saskatchewan, Canada, this project uses
CO2 for enhanced oil recovery and stores it in underground formations. The Weyburn-Midale reservoir
and then injected into a disposal interval. About is located principally in North Dakota, USA, and Saskatchewan; the fields extend west into Montana,
1 million metric tons [1.1 million tonUS] of the USA, and east into Manitoba, Canada. Most of the CO2 used at the Weyburn-Midale project is piped
produced CO2 has been injected annually into the (red) from a coal gasification plant near Beulah, North Dakota; the remainder comes from the nearby
Boundary Dam Project at Estevan, Saskatchewan.
Utsira formation over a 15-year period.46 The
Boundary Dam Power Plant CCS project is
located at Estevan, Saskatchewan, Canada. produced at the Beulah plant is compressed to [2,500tonUS/d] to the Weyburn-Midale field.52
SaskPower, the owner and operator of the proj- 2,200psi [15MPa] and transported 210mi Storage of CO2 was initiated in September 2000 in
ect, invested more than US$ 1 billion to equip one [340km] via pipeline to the Weyburn-Midale field. a limited area of the field. This early phase of the
of its generators for carbon capture. SaskPower Deliveries of CO2 from the Beulah plant vary, rang- operation had 16 vertical and 13 horizontal injec-
sells the captured CO2 to Cenovus Energy Inc. ing from 6,000 to 8,500 metric tons/d [6,600 to tion wells. A study of this injection area is ongoing
who uses it for EOR to boost output from matur- 9,400tonUS/d]. The nearby Boundary Dam CCS and will address all of the technical aspects of
ing wells nearby.47 SaskPower also operates its project supplies an additional 2,300metrictons/d long-term geologic storage (Figure 8).
own injection well at the power plant site.
Although CCS is a major initiative in several
oil fields, CO2 is also being used for EOR in many
production environments. A project in Canada is
a good example of combined EOR and CCS.
S a s k a t c h e w a n
Miscible CO2 Flooding and Storage
Williston basin
Cenovus Energy Inc. has embraced a long-term
commitment to use CO2 for miscible flooding and
Regina
to store excess amounts underground at the
Weyburn-Midale field in Canada. This project is Weyburn
at the forefront of combined CO2-EOR and geo-
logic CO2 storage.48
The Weyburn-Midale field, discovered in 1954, is Pro
jec
located in southeast Saskatchewan (Figure 7).49 The t ar
ea
operation covers 180 km2 [70mi2] and is one of the
largest medium-sour oil reservoirs in Canada.
N
Original oil in place (OOIP) was estimated at 1.4bil-
lion bbl [220million m3]. Following initial produc-
tion over a 9- to 10-year period, the operator started
waterflooding in 1964 followed by horizontal drilling Oilfield Review
in the 1990s. Although these measures helped pro- SPRING 15
Figure 8. Weyburn-Midale research project.CO2
The Petroleum
Fig 7 Technology Research Centre (PTRC) conducted
duction, the operator opted to use CO2 EOR to research at the Weyburn-Midale project. The project 15
area encompasses a 100,000km3 [24,000mi3]
ORSPRNG CO2 7
reverse the long-term production decline and to volume (dashed lines) and is part of the Williston basin (red line). The oil reservoirs and the levels above
demonstrate large-scale geologic storage of CO2.50 and below them in the area earmarked for CO2 storage were characterized before the initial injection.
During the injection of CO2, measurements were made in a smaller area (gray rectangle) of the Weyburn-
The Dakota Gasification Company operates a
Midale field. In this field, PTRC scientists carried out an array of monitoring and verification research that
synfuel plant in Beulah, North Dakota, that gener- included soil, gas and water sampling, subsurface monitoring, seismic monitoring, sampling from wells
ates natural gas from coal.51 The byproduct CO2 and risk assessment; these studies are ongoing. (Adapted with permission from PTRC.)

September 2015 45
Miscible CO2 EOR and geologic storage have
been successful at the Weyburn-Midale field, giv-
ing the field new life and potentially extending its
operational period by more than 25 years.
Currently, the field produces about 26,000bbl/d
[4,100m3/d] of light crude oil (Figure 9). Carbon
dioxide injection has tripled oil production from
50,000 the estimated lowest production rate for the
field, about 8,000 bbl/d [1,200m3/d] in 1988.
40,000 To date, about 24 million metric tons [26mil-
lion tonUS] of CO2 have been stored, and about
Production, bbl/d

30,000 55million metric tons [61 million tonUS] will be


stored underground over the life of the project.
20,000
Carbon Dioxide Storage at In Salah
The In Salah Gas (ISG) project, a joint venture
10,000
between Sonatrach, BP and Statoil, is currently
executing a phased development of eight gas fields
0
1955 1970 1985 2000 2015 in the Ahnet-Timimoun basin in the Algerian cen-
Year tral Sahara desert (Figure 10). These fields com-
Primary and waterflood Horizontal infill wells
prise an area of 25,000 km2 [9,600mi2] and have
estimated recoverable gas reserves of 0.23trillionm3
Vertical infill wells CO2 EOR
[8.1trillion ft3].53 The gas from these fields contains
1% to 10% CO2, which is removed at the Krechba
Figure 9. Weyburn-Midale production. This facility (inset) has produced oil since 1955. It and others at
the Weyburn-Midale field have been used for production during four distinct phases (bottom). In the first central processing facility (CPF). Carbon dioxide
phase, primary production and waterflood produced a total of 3.3 million bbl [0.52 million m3] of oil. The and any residual hydrogen sulfide [H2S] in the pro-
second and third phases, which used vertical and horizontal infill wells, produced a total of 5.9 duced gas are removed by monoethanol amine
millionbbl [0.94 million m3] of oil. The last phase, CO2 EOR, has produced 9.4 million bbl [1.5million m3] to (MEA) absorption. The cleaned up gas from the
date. (Adapted with permission from Cenovus Energy Inc.)
Krechba CPF contains 0.3% or less CO2 and is trans-
ported by pipeline to export terminals. The ISG proj-
ect started production in 2004 and is currently
producing 9 billion m3/yr [320billion ft3/yr] of gas
for export.
Carbon dioxide recovered from the produced
PORTUGAL

S P A I N
gas was injected about 1,900 m [6,200 ft] into the
water-filled downdip flank of the Krechba gas field.
The three CO2 injection wells have horizontal sec-
tions measuring up to 1.8 km [1.1 mi] in length
TUNISIA (Figure 11). The joint venture conducted extensive
MOROCCO monitoring of CO2 storage using a variety of tech-
Hassi RMel
niques such as surface and soil gas monitoring,
downhole gas measurements and tracer chemical
LIBYA tagging. Geophysical and InSAR satellite monitor-
Krechba CPF ing were also conducted to check for ground
deformation and microseismicity (Figure 12).54
ISG pipeline 53. In Salah Southern Fields Development Project, Algeria,
Hydrocarbons Technology, http://www.hydrocarbons-
Gas export pipeline
Oilfield Review technology.com/projects/in-salah-southern-fields-
Gas field development-project/ (accessed December 12, 2014).
SPRING 15 A L G E R I A
Export terminal 54. Mathieson A, Midgley J, Dodds K, Wright I, Ringrose P
CO2 Fig 9
MAURITANIA

and Saoul N: CO2 Sequestration Monitoring and


ORSPRNG 15 CO2 9 Verification Technologies Applied at Krechba, Algeria,
The Leading Edge 29, no. 2 (February 2010): 216222.
M A L I 0 km 300
Shi J-Q, Sinayuc C, Durucan S and Korre A: Assessment
0 mi 300 of Carbon Dioxide Plume Behaviour Within the Storage
Reservoir and the Lower Caprock Around the KB-502
Injection Well at In Salah, International Journal of
Figure 10. In Salah Gas (ISG) project. The In Salah CO2 storage project in central Algeria consists of Greenhouse Gas Control 7 (March 2012): 115126.
several gas fields and a central processing facility (CPF, inset) at Krechba, where CO2 and other impurities Stork AL, Verdon JP and Kendall J-M: The
are removed from the produced natural gas. The cleaned up gas is sent by pipeline to a distribution Microseismic Response at the In Salah Carbon Capture
station at Hassi RMel, Algeria, for further shipment to export terminals and markets in Europe. and Storage (CCS) Site, International Journal of
Greenhouse Gas Control 32 (January 2015): 159171.

46 Oilfield Review
20
Cretaceous sandstones 2005
and mudstones
Carboniferous mudstones 20

Gas 15 15
Water
10

Vertical deformation, mm
Pipeline
+ KB-503
Well casing + KB-502 5
10

North, km
0
Gas CO
C 2
production
d i injection + KB-14
5
KB-11
+ 10
5
+ KB-501
15

20
+
KB-12
Gas 0

ath
Flight p Water

20
Second pass
Figure First
11. Carbon 2007
pass dioxide injection at Krechba. At the In Salah project, the
Krechba central processing facility (CPF, inset) consists of several 20
sectionspower generation (right), CO2 removal and dehydration (center)
15
and CO2 injection. Recovery and injection of the CO2 removed from the 15
natural gas are straightforward. The producing gas reservoir is about 20m 10

Vertical deformation, mm
[66ft] thick and lies about 1,900m [6,200ft] deep below a 950m [3,100ft]
+ KB-503
thick caprock formation of Carboniferous mudstones. A 900m [3,000ft] thick + KB-502 5
layer of Cretaceous sandstone and mudstone lies above the mudstone
10
North, km

section. Produced gas from the reservoir is treated at the CPF to remove 0
CO2, H2S and other impurities. The treated CO2 is then reinjected into + KB-14
5
water-saturated rock of the same reservoir from which the gas is produced.
KB-11
+ 10
5
+ KB-501
15

20
+
KB-12
t path 0
Fligh

Second pass
First pass Displacement toward satellite 20
2.83 cm 0 2009
20

15 15

10

Vertical deformation, mm
+ KB-503
+ KB-502 5
10
North, km

0
+ KB-14
5
Oilfield Review KB-11
SPRING 15 + 10
CO2 Fig 11 5
+ KB-501
ORSPRNG 15 CO2 11 15

20
Displacement toward satellite
+
KB-12
0
2.83 cm 0
0 5 10 15 20
East, km

Figure 12. Monitoring ground deformation. Ground deformation is monitored at the In Salah project using interferometric synthetic aperture radar (InSAR).
This technique uses a dedicated satellite (left) to collect infrared radar images of the ground elevation using side-beam radar. Measurement of the vertical
and horizontal displacements requires two passes of the satellite. Displacements are determined by comparing the wave phase changes of the radar signal
between the two passes. The deformation and CO2 plume spreads at Oilfield Review
each well (marked by a cross) were estimated from the InSAR data for 2005, 2007 and
SPRING (scale,
2009 (right). The color intensity indicates the degree of vertical deformation 15 far right) while the size of the colored area around each well infers the
horizontal spread of the CO2 plume. CO2 Fig 12
ORSPRNG 15 CO2 12

September 2015 47
RUSSIA
B U LG A RI A B l a c k
S e a
GEORGIA
Istanbul

Ankara ARMENIA

T U R K E Y

IRAN
Bati Raman

IRAQ
M e SYRIA
CYPRUS
d i t
e r r a LEBANON
n e a n S e a

Figure 13. Bati Raman project. The Bati Raman field and associated CO2 EOR project in Turkey are located about 720km
[450mi] southeast of Ankara. The Bati Raman project has two CO2 injection stationsAP2 (inset) and 3TP2 (not shown).
(Photograph used with permission from the Turkish Petroleum Corporation.)

Since 2004, approximately 3.5million metric tons and produces from a Garzan limestonea het- The Dodan field is 55mi [89km] from the Bati
[3.9million tonUS] of CO2 have been separated erogeneous carbonate from the Cretaceous Raman field and produces gas that is mostly CO2
from the produced gas and reinjected into the period.56 The heavy crude produced at the Bati and has 3,000 to 4,000ppm H2S. The wellhead
Krechba reservoir. Raman field has 11 degree API gravity [0.99 spe- pressure at the Dodan field is about 1,050psi
Important lessons were learned about CO2 cific gravity], high viscosity and low solutiongas [7.2MPa]. After it is cleaned up, the CO2 from
storage during the design, startup and operation content. The OOIP was estimated to be 1.85bil- the Dodan field is sent to the Bati Raman field
of the ISG project, including the need for lion bbl [300million m3]. From 1965 to 1970, the via pipeline (Figure 14).
detailed geologic and geomechanical character- number of producing wells increased from almost Before implementing full-scale CO2 flooding
ization of the reservoir and the overburden.55 20 to more than 130. at the Bati Raman field, TP performed a pilot test
Oilfield Review
These data helped the operator develop the During
SPRINGthe 15
primary production period from using 17 CO2 injection wells in the western part
injection strategy and ensured the long-term 1961 toCO21986, reservoir
Fig 13 pressure decreased from of the field. The original plan was cyclic injection
integrity of the storage facility. The operator about ORSPRNG 15 CO2 13to as low as 400psi
1,800psi [12MPa] of CO2 followed by water. After studying the pilot
also realized the importance of flexibility in the [2.8MPa] in some parts of the field. Similarly, test results, TP engineers converted the initial
design and control of the capture, compression crude production declined from a peak rate of 55. Ringrose PS, Mathieson AS, Wright IW, Selama F,
and injection well systems. 9,000bbl/d [1,400m3/d] in 1969 to 1,600bbl/d Hansen O, Bissell R, Saoula N and Midgley J: The
InSalah CO2 Storage Project: Lessons Learned and
[250m3/d] in 1986. During the primary produc- Knowledge Transfer, Energy Procedia 37 (2013):
Immiscible CO2 Flooding tion period, recovery was estimated to be less 62266236.
The Bati Raman field, in southeast Turkey, is one than 2% of OOIP. 56. Sahin S, Kalfa U and Celebioglu D: Bati Raman Field
Immiscible CO2 ApplicationStatus Quo and Future
of the largest oil fields in that country (Figure 13). Following the primary recovery period, the Plans, SPE Reservoir Evaluation & Engineering 11, no.4
Owned and operated by the Turkish Petroleum operator studied several processes for EOR and (August 2008): 778791.

Company (TP), the field was discovered in 1961 chose immiscible CO2 flooding primarily
because of the proximity of the Dodan gas field.

48 Oilfield Review
Dodan Gas Plant Bati Raman Recycle Station

CO2 Pipeline To refinery

Compressor
Tank
H2O Vent
Separator
CO2

H2O absorber
Reboiler Tank

Separator Oil and CO2 production

Regeneration
H2S absorber

Flare

H2O absorber
CO2

Flash tank Reboiler

Flash tank
Reboiler
Recycle compressors

Production well Injection wells

Figure 14. Dodan and Bati Raman process flow. At the Dodan gas plant (left), goes to refining and the gas to cleanup. The cleaned up CO2 is compressed
produced gas is stripped of H2S and water, compressed and sent by pipeline and sent to the injection wells. (Adapted with permission from the Turkish
to the Bati Raman process facility, where it is injected (right). At the Bati Petroleum Corporation.)
Raman facility, oil and CO2 in the produced stream are separatedthe oil

injection plan to CO2 flooding. The operator made


15,000
several observations based on the pilot test: CO2
injection helped produce a considerable amount
12,500
of oil, and diffusion of CO2 into the oil was effec-
tive for displacing oil in the fractured carbonate
10,000
Production, bbl/d

reservoir. After evaluating the results from the


pilot test, TP engineers gradually extended the
7,500
CO2 flooding to the rest of the field. Currently,
95% of the production wells in the Bati Raman
field are influenced by CO2 flooding. 5,000

In 2012, the CO2 injection project was 25years


old, far beyond what was envisioned during the 2,500
Primary Production Immiscible CO2 Injection
initial field design. More than 6% of the OOIP has
now been recovered, a significant increase over 0 Oilfield Review
SPRING 1970
1961 1965 15 1975 1980 1985 1990 1995 2000 2005 2010 2014
the less than 2% recovered during primary field CO2 Fig 14 Year
Figure 15. BatiORSPRNG 15 CO2 14
production. Primary recovery was 32million bbl
Raman production history. The Bati Raman field started producing in 1961, and as
[5.1millionm3] while total field production, additional wells were brought on stream, production ramped up and peaked in 1970 at almost
including that from primary, secondary and EOR 10,000bbl/d [1,600m3/d]. Following this peak, production declined because of decreasing reservoir
recovery, was 114million bbl [18millionm3] as of pressure. Water flooding started in 1975 and slowed the rate of production decline but did not reverse
it. In 1986, primary production reached a low of about 2,000bbl/d [300m3/d], and CO2 injection for EOR
the end of 2014 (Figure 15). was initiated. After CO2 EOR was introduced, production peaked around 1992 at about 15,000bbl/d
[2,400m3/d]. Production decreased until 2004 when the practice of integrated reservoir management
was implemented and arrested the decline. Production has held steady at about 7,500bbl/d [1,200 m3/d]
since that time. (Adapted with permission from the Turkish Petroleum Corporation.)

September 2015 49
CO2

KOH
Asphalt
700C

50 nm Treated
asphalt

Figure 16. Carbon dioxide capture. Asphalt (left) is carbonized by treating it with potassium hydroxide
[KOH] at 700C [1,300F]. This process yields treated asphalt (center) that has a surface area of nearly
2,800 m2/g. At a pressure of 30 bar [440psi] and at room temperature, the treated asphalt (right) can
absorb 93% of its weight in CO2. The CO2 can be desorbed using a simple pressure swing absorption
process. (Adapted with permission from Jalilov et al, reference 58.)

Carbon Dioxide and the Future The unfavorable characteristics of current away from storage sites. Although extra costs
Scientists have had an interest in CO2 for more sorbents such as MEA have led researchers to associated with large-scale geologic storage of
than a century. The business sector, government develop new onesboth solid and liquid. One of CO2 will be incurred, these costs are fundamen-
regulators and the public have joined scientists these new sorbents is solid, microporous carbon tally no different than additional costs already
in the quest to slow the atmospheric accumula- that is synthesized from asphalt (Figure 16).58 borne by the public for cleaner water and air.
tion of CO2. The oil industry is tackling this chal- This sorbent is inexpensive, has high surface area The consequences of climate change are
lenge in part by injecting CO2 underground, both CO2 uptake and excellent properties for revers- potentially enormous. In the last decade, as evi-
for EOR and for long-term storage purposes. ibly capturing CO2. Another new sorbent is a liq- dence for the effects of climate change mounts,
In addition to EOR and storage, the industry uid carbonate enclosed within polymer moving beyond maintaining the status quo and
can also take advantage of new, less-expensive microcapsules with shells of highly permeable doing business as usual has become important.
sorbents for CO2 capture, which will also help silicone.59 These microcapsules are reported to Although it can help to reduce the problem, the
reduce CO2 emissions into the atmosphere. have rapid CO2 uptake and release. oil and gas industry can offer only some solutions.
Current technology depends on absorbents, Although new sorbent technology can help, it Worldwide, industries, governments and the pub-
including aqueous MEA, to remove CO2 from is only part of the solution for emissions. The lic must be educated and ready to support a vigor-
streams such as power plant flue gas.57 The MEA reduction and mitigation of GHG emissions will ous effort to arrest climate change. DA
solution is corrosive, degrades into toxic byprod- require simultaneous implementation of several
ucts and requires a large amount of energy to technologies and significant governmental action
clean it up for reuse. on a worldwideOilfield
basis.Review
These technologies range
from efficiencySPRING 15
improvements to alternate energy
57. Vericella JJ, Baker SE, Stolaroff JK, Duoss EB,
HardinJO IV, Lewicki J, Glogowski E, Floyd WC,
CO2 Fig 16soil tillage. Likewise, gov-
sources to conservation
ValdezCA, Smith WL, Satcher JH Jr, Bourcier WL, ORSPRNG 15 CO2 16
ernments can help, for example, by reducing sub-
Spadaccini CM, Lewis JA and Aines RD: Encapsulated
Liquid Sorbents for Carbon Dioxide Capture, Nature sidies for inefficient hydrocarbon use and
Communications 6, article 6124 (February 5, 2015). intelligent mandates on fuel efficiency.
58. Jalilov AS, Ruan G, Hwang C-C, Schipper DE, Tour JJ,
Li Y, Fei H, Samuel ELG and Tour JM: Asphalt-Derived One area in which the oil and gas industry can
High Surface Area Activated Porous Carbons for play an important role is geologic storage in CCS.60
Carbon Dioxide Capture, ACS Applied Materials and
Interfaces 7, no. 2 (January 21, 2015): 13761382. A technical challenge related to geologic storage
59. Vericella et al, reference 57. is risk associated with faulty CO2 confinement.
60. Bryant S: Geologic CO2 StorageCan the Oil and Gas The oil and gas industry has the technical tools to
Industry Help Save the Planet?, Journal of Petroleum
Technology 59, no. 9 (September 2007): 98105. assess the potential and risk for CO2 migration

50 Oilfield Review