Issues for Carbon dioxide Storage in India Dr. B. Kumar Project Adviser/Consultant Carbon Sequestration National Geophysical Research Institute, India Hyderabad-500 007, India Ph. 91 -40 -23434680 (Off. ), 91 -9849934935 (Mob. ) Fax: 91 -40 -23434651 E-mail: baleshk@yahoo. com
What is CO 2 storage ? CO 2 storage/Carbon Sequestration is the placement of CO 2 into a depository in such a way that it remains safely stored and not released to the atmosphere. The viable options are storage of CO 2 into underground geological formations, oceans, terrestrial ecosystems and bio - sequestration.
Issues for CO 2 Storage in India • R&D Technologies • Geology & Tectonics • Protocols, Mechanisms & Forums - Kyoto Protocol; Clean development Mechanism (CDM); Carbon sequestration Leadership Forum (CSLF); UN Framework Convention Treaty on Climate Changes (UNFCC), Asia Pacific Partnership on Clean Development and Climate (AP 6) etc. - India has signed the Kyoto Protocol in 2003 but is not obliged to reduce the emission by 2012 as the per capita emission is very low (~1 metric ton /year). India is a member of CSLF, CDM, AP 6 and also stands by UNFCC. • Safety & Environment • Economics - The current cost estimates range from 20 to 80 US$/t. CO 2 for capturing the CO 2 and 5 to 20 US$/t. CO 2 for transportation and storage
Ice cores indicate that in the past 420, 000 years, the concentration of CO 2 in the atmosphere has ranged from 180 to 280 parts per million by volume (ppmv). The current CO 2 atmospheric concentration is ~375 ppmv; this dramatic increase is primarily the result of human combustion of fossil fuels (Modified after Falkowski and others, 2000).
Projected Temperatures for the 21 st Century Are Significantly Higher Than at Any Time During the Last 1000 Years www. clivar. org
Carbon dioxide emissions – 2002 Description : Carbon dioxide emissions: Anthropogenic carbon dioxide emissions s stemming out from the burning of fossil fuels, gas flaring and the production of cement Source : UN Common Database (CDIAC) Category : Environment Year : 2002 Units : Giga Metric Tons 5. 8 1. 2
Carbon dioxide emissions per capita Description : Source : Category : Ranking : Carbon dioxide emissions per capita Anthropogenic carbon dioxide emissions stemming from the burning of fossil fuels, gas flaring and the production of cement. UN Common Database (CDIAC) Environment 54 (2002) Unit of measurement: Metric tons per capita India has signed and ratified the Kyoto Protocol in 2003 but is not obliged to cut emissions up to 2012. India is also a member of CSLF, CDM, AP 6 & stands by UNFCC. (Tons CO 2 person) INDIA
Geological Storage Deep underground formations • Depleted oil and gas reservoirs • Coal beds • Deep Saline formations • Industrially generated CO 2 is pumped into deep under ground formations and dissolves in the native formation fluids. Some of the dissolved CO 2 would chemically react and become part of solid mineral/ coal matrix. Once dissolved or reacted to form minerals, CO 2 is no longer buoyant and would not rise to the ground surface. Physical and geochemical processes that enhance storage security
CO 2 Trapping Mechanisms I Hydrodynamic Trapping • Closed Stratigraphic Trapping II Geochemical • Solubility Traps • Ionic Traps • Mineral Traps Solubility Trapping CO 2 (gaseous) + H 2 O Ionic Trapping H 2 CO 3 (aqueous) + OH HCO 3 (aqueous) + OH Mineral Trapping CO 3 (aqueous) + Ca++ H 2 CO 3 (aqueous) Ca. CO 3 (solid)
Storage Security Mechanisms and Changes Over Time Ø When the CO 2 is injected, it forms a bubble around the injection well, displacing the mobile water laterally and vertically within the injection horizon. Ø The interactions between the water and CO 2 phase allow geochemical trapping mechanisms to take effect. Ø Over time, CO 2 that is not immobilized by residual CO 2 trapping can react with in situ fluid to form carbonic acid i. e. , H 2 CO 3 called solubility trapping that dominates from tens to hundreds of years. Ø Dissolved CO 2 can eventually react with reservoir minerals if an appropriate mineralogy is encountered to form carbon-bearing ionic species i. e. , HCO 3– and CO 32– called ionic trapping which dominates from hundreds to thousands of years. Ø Further breakdown of these minerals could precipitate new carbonate minerals that would fix injected CO 2 in its most secure state i. e. , mineral trapping which dominates over thousands to millions of years. Storage expressed as a combination of physical and geochemical trapping. The level of security is proportional to distance from the origin. Dashed lines are examples of million-year pathways Source: IPCC Report
T CO 2 PLAN POWER CO S 2 tore d in Geolo gical F ormati ons Potential CO 2 storage reservoirs
CO 2 sequestration in depleted oil/gas reservoirs can enhance production of oil/gas. Enhanced Oil Recovery (EOR) can be either miscible or immiscible depending primarily on the pressure of the injection gas into the reservoir. Miscible phase: CO 2 -EOR, the CO 2 mixes with the crude oil causing it to swell and reduce its viscosity, whilst also increasing or maintaining reservoir pressure. The combination of these processes enables more of the crude oil in the reservoir to flow freely to the production wells from which it can be recovered. Immiscible phase: CO 2 -EOR, the CO 2 is used to re-pressure the reservoir and as a sweep gas, to move the oil towards the production well. CO 2 enhanced oil recovery
• In India, the Oil & Natural Gas Corp. (ONGC) has proposed CO 2 -EOR for Ankleshwar Oil Field in Western India. • The CO 2 is planned to be injected @ 600, 000 m 3/d and is sourced from ONGC gas processing complex at Hazira. • The experimental and modeling studies have indicated an incremental oil recovery of ~ 4 % over the project life of 35 years besides the potential to sequester 5 to 10 million tons of CO 2 Pipeline from Hazira Plant First row of oil Producer. To be closed after reaching GOR of 500 v/v Second row of oil Producer. To be continued on production till GOR reaches 500 v/v CO 2 Injector CO 2 moves through formation mobilizing residual oil by swelling, vaporization and reduction in residual oil saturation Ankleshwar Sands S 3+4 : 69. 33 MMt Waterflood Recovery : 54% Envisaged Tertiary Recovery : 5 -7% After, Suresh Kumar, Abstract, IWCCS-07
Weyburn–Midale CO 2 Monitoring and Storage Project, Canada • It is one amongst the largest ongoing projects for CCS in the world. • The Encana Cooperation has been injecting 5, 000 tonnes of CO 2 per day into in the Weyburn oil field for the dual purpose of enhancing oil recovery and the CO 2 storage while increasing the field’s production by an additional 10, 000 barrels per day. Injection of CO 2 in the Oil Producing Formations of the Weyburn Field • About 30 million tones of CO 2 will be injected and permanently stored over the life of project producing at least 130 million barrels of incremental recovered oil. After, EERC, North Dakota.
Enhanced Coalbed Methane Recovery (ECBM) Coal beds typically contain large amounts of methane rich gas that is adsorbed onto the surface of the coal. The injected CO 2 efficiently displaces methane as it has greater affinity to the coal than methane. CO 2 enhanced coal bed methane production
Density of CO 2 and CH 4 as a function of pressure for various Temperatures based on data from Vargaftik et al. (1996).
The Coal Bed Methane Potential of India : ~ 1000 bcm DGH, Annual Report, 2005 -06
CO 2 Storage in Deep Saline Aquifers • Saline aquifers at depths of ≥ 800 m provide a suitable alternative for the storage of CO 2. • The high porosity and permeability of the aquifer sands along with low porosity cap rocks such as shales provide favorable conditions for CO 2 storage. • The CO 2 can be stored in the miscible and/or mineral phase. • With time, CO 2 gets dissolved in the brines and reacts with the pore fluids/minerals to form geologically stable carbonates. Studies in India • The Department of Science & Technology , India has initiated studies aiming at identification of deep underground saline aquifers and their suitability for CO 2 sequestration in Sedimentary basins of India namely Ganga, Rajasthan and Vindhyan basins. • The Central Ground Water Board and Geological Survey of India have established the presence of saline aquifers up to depths of ≥ 300 m below ground level in the Ganga basin. • Deep Resistivity studies carried out at 9 sites around New Delhi have shown the presence of saline aquifers at depths of 800 m and beyond, around Palwal and Tumsara. ICOSAR Bulletin, Vol. 2
Storage of CO 2 in Saline Aquifer (Sleipner Project) • Utsira Aquifer is located 800 m below the bed in the North Sea. • ~I million tonnes of CO 2 injected per year since 1996 • CO 2 separated from Natural Gas produced from Sleipner West is injected in the Utsira aquifer Characteristics of the Utsira Sand • Mio-Pliocene age. • High porosity sand (21 -37%) capped with low porosity shale. • Estimated to be capable of storing 600, 000 MT of CO 2. Seismic reflection data prior to sequestration After 2 million tonnes of CO 2 injection, showing amplitudes of high reflection corresponding to CO 2 saturated rocks.
CO 2 sequestration in Onshore Hunton Aquifer • Devonian-Silurian carbonates of the “Hunton Aquifer” contain a number of highly porous intervals. • Favorable sequestration attributes of the Hunton aquifer include; relatively high porosity (up to 15%), permeability, lateral continuity over a multistate area, thickness (up to 2000+feet) and confinement of the aquifer intervals between two aquitard intervals. • Estimated CO 2 sequestration volumes range up to 42 billion tons (726 trillion cubic feet). Stratigraphy of Hunton Aquifer After MIDCARB Project
‘Geological CO 2 Sequestration in Basalt Formations of India: A Pilot Study’ Objective Evaluation of Basalt Formations of India for environmentally safe and irreversible long time storage of CO 2.
Why Basalts are attractive proposition for CO 2 sequestration ? Ø Deccan Basalts cover an area of 500 x 103 sq. km. and form one of the largest flood eruptions in the world. Ø Composed of typically 48 flows. Ø The thickness of basalts varies from few hundreds of meters to > 1. 5 km. Ø Basalts provide solid cap rocks and thus high level of integrity for CO 2 storage. Ø Basalts react with CO 2 and convert the CO 2 into the mineral carbonates that means high level of security. Ø Intertrappeans between basalt flows provide major porosity and permeability along with vescicular, brecciated zones with in the flows. Ø Tectonically the traps are considered to be stable. Ø Geophysical studies have revealed presence of thick Mesozoic and Gondwana sediments below the Deccan Traps.
Deccan basalts vs Columbia River basalts Ø The most common flow type of the Deccan Trap and Columbia River Basalt is the Pahoeho sheet flows. Due to the lesser viscosity and less strain it forms large horizontal sheets. Ø Both Deccan Flood Basalts and Columbia River Basalts are tholeiitic (cinopyroxene and plagioclase) in nature and the eruptions are of fissure type. Ø Both are continental basalts. Columbia River Basalt is fully continental and Deccan Traps are partly continental. Ø Both the basaltic flows have traveled as much as 300 to 500 km from their sources. Ø Chemical composition of both the basalts are similar.
Major Flood Basalt Provinces Name Volume 5 Age 3 CRB Keeweenawan (1. 7 x 10 km ) (4 x 105 km 3) Deccan (106 km 3) Parana Karroo Miocene Precambrian 2 NW US Superior area Cret. -Eocene 6 India (area > 10 km ) early Cret. 6 Locality 3 (2 x 10 km ? ) Brazil early Jurassic S. Africa
CO 2 Storage in Basalt Formations CO 2 is injected in basalt formations above its critical temperature and pressure Minimum depth 800 m Supercritical CO 2 Hydrodynamic Trapping Solubility Trapping Mineralisation • Physico – chemical properties between those of liquid and gas. • Dense gas • Solubility approaching liquid phase • Diffusivity approaching gas phase
Variation of CO 2 density with depth, (based on the density data of Angus et al. , 1973). Carbon dioxide density increases rapidly at approximately 800 m depth, when the CO 2 reaches a supercritical state. Cubes represent the relative volume occupied by the CO 2, and down to 800 m, this volume can be seen to dramatically decrease with depth. At depths below 1. 5 km, the density and specific volume become nearly constant.
Mineralization reactions in basalt formations CO 2(g) CO 2(aq) + H 2 O CO 2(aq) HCO 3 - + H+ (Ca, Mg, Fe)x Siy. Ox+2 y +2 x. H+ +(2 y-x)H 2 O (Ca, Mg, Fe)2+ + HCO 3 - x(Ca, Mg, Fe)2+ + y. H 4 Si. O 4(aq) (Ca, Mg, Fe)CO 3 + H+ Induction Time for Calcite Precipitation Depth, (m) Lab. scale & geo-chemical modeling studies by PNNL, USA T, °C t p, d 800 35 964 900 38 822 1000 42 678 1100 48 534 1200 56 397 1300 67 275 Calcite deposition on basalt • Basalt is rich in Ca, Mg & Fe Silicates • Mineralisation reaction rate is fast on geological time scale • Mineralisation is appeared to be controlled by mixing behaviour of CO 2 and not by kinetics of the reactions
Methodology Site identification § Evaluation of available geological, geophysical and tectonic data to identify one or two areas in basalt formations of Western India with basalt thickness of 800 m. • Adsorbed soil gas surveys • Magnetotelluric studies • Drill location analysis • Identification of most suitable site, land acquisition and permission Planning of Schedule For borehole drilling and CO 2 injection • Detailed engineering planning for borehole drilling, piping and cementing • Identification of vendors for drilling, casing, cementing of borehole, supply and injection of CO 2 • Theoretical simulation and modeling • Pre-characterization of shallow surface soils and ground waters by geochemical & isotopic studies. • High-resolution seismic studies
Borehole drilling and injection of CO 2 Post injection characterization, monitoring & modeling • Drilling of 8 -10’’ dia. borehole up to depth of 800 50 m • Borehole logging • Core sampling • Lining and cementing of borehole • Pre-injection modeling • Injection of ~ 100 tons of CO 2 per day at a pressure of 2000 psi for 10 days along with tracers • Drilling of 2’’ dia observation boreholes • Post injection characterization of soil and ground water • Monitoring, modeling and verification of mineralization • Document basalt formations of India as a geological sequestration option.
Significance The Indian study will globally establish basalt formation as potential storage for CO 2 by leveraging study carried out in Columbia River basalt group under US-Dept. of Environment.
CO 2 Sequestration in Methane Hydrates Ø Methane Hydrates are class of solids in which methane molecules occupy cages made up of hydrogen- bonded water molecules. Ø CO 2 can also be stored as hydrates with simultaneous conversion of in situ methane hydrates into natural gas. Ø At temperatures below 10°C, there is a pressure range in which methane hydrate is unstable while CO 2 hydrate is stable. Ø The heat released from the formation of CO 2 gas hydrate is greater than that needed for CH 4 hydrate dissociation: CH 4(H 2 O)n CH 4 + n. H 2 O; Hf = 54. 49 KJ/mole CO 2(H 2 O)n CO 2 + n. H 2 O ; Hf = 57. 98 KJ/mole where n is the hydration number for CH 4 hydrate and CO 2 hydrate Ø n is dependent on pressure, temperature and the composition of the gas in the gas phase which implies that under certain pressure and temperature conditions, the replacement of CH 4 in the hydrate with CO 2 is thermodynamically possible. After Gas Technology Institute, USA
Ocean Sequestration CO 2 is soluble in ocean water, and oceans absorb and emit huge amounts of CO 2 into the atmosphere through natural processes. Ocean Sequestration has huge potential as a carbon storage sink, however, enough R&D have to be carried out to understand about the physio-chemical processes which occur between seawater and pumped CO 2. Storage of CO 2 in deep oceans has been suggested as a means of reducing inputs of greenhouse gases to the atmosphere.
Terrestrial Sequestration Terrestrial carbon sequestration is defined as either the net removal of CO 2 from the atmosphere or the prevention of CO 2 net emissions from the terrestrial ecosystems into the atmosphere. The following ecosystems offer significant opportunity for carbon sequestration: • Forest lands • Agricultural lands • Biomass croplands • Deserts and degraded lands • Wetlands and peat lands -- Storage of C in soils and plants has the potential to offset CO 2 emissions to the atmosphere in the coming decades while new ‘clean’ energy production and CO 2 sequestration technologies are developed and deployed. What is needed is basic research to improve our fundamental understanding of natural phenomena controlling soil C sequestration and basic and applied R&D to bring new management and technology to the challenge.
• The solar energy is collected using Fresnel lens devices/parabolic concentrator and a fibre optic light delivery system is The concept of photosynthetic conversion used to stimulate biological organisms like to fix carbon dioxide using bacteria or cyanobacteria or micro-algae in a micro-algae under a controlled environment. bio-generator to produce useful by-products from carbon dioxide. Bio-sequestration : • For uniform growth of the organisms, the distribution of photosynthetic photon flux light in the wavelength range of 400– 700 nm needs to be delivered to the bioreactor. • The photo-bioreactor system makes use of the natural process ‘photosynthesis’ to convert light, heat and carbon dioxide to useful products, such as carbohydrates, hydrogen and oxygen. 6 CO 2 (aq) + 6 H 2 O(l)+ light + heat C 6 H 12 O 6(aq) +6 O 2(g) Conceptual diagram of Photosynthetic conversion of carbon dioxide to biomass. • Assuming that the carbon uptake rate of 1. 5 g/day for the particular micro-organism, Synechocystis aquatilis, up to 2. 2 ktonne C/year could be sequestered from the environment. (After Energy Conv. and Manag. 46 (2005) 403– 420)
Breakthrough Technologies Biomimetic Sequestration - It implies the use of a particular aspect of biological process for resolving a specific non biological problem. The Carbonic Anhydrase (CA) is used as a catalyst for the conversion of CO 2 into bicarbonates and later to carbonates or amino acids. Iron Fertilization - Iron Fertilization implies the introduction of iron to the upper ocean to increase productivity of marine food chain which in turn increases CO 2 sequestration from the atmosphere into the oceans. Marine plankton growth is enhanced by physically distributing the iron particles in other wise nutrient rich but iron deficient ocean water using suitable delivering systems based on biomaterials. Soil Productivity ?
Conclusions - CO 2 storage R&D is still in early stage in India and developing cost effective technologies for CCS are the major challenges to the scientist and researchers. -The environmental risks involved in the storage of CO 2 particularly in geological formations and oceans have to be evaluated in detail by monitoring and modeling in terms of long term stability. - Funding mechanisms to support R&D projects for CCS have to be evaluated. 0. 5% cess on power generation in the line of oil cess may be good enough to sustain the same. The cess can be operated by Energy Security Development Board, under the aegis of Ministry of Power. ‘If every country was to spend just 2 -3% of their GDP, the impact of possible global climate change could be mitigated’ - R. K. Pachauri, Economic Times Corp. Excellence Award for 2006 -07, New Delhi (29 th Oct. , 2007)
International Partners FRANCE: Institut de Physique du Globe de Paris INDIA: National Geophysical Research Institute RUSSIA: Vernadsky Institute of Geochemistry and Analytical Chemistry of the Russian Academy of Sciences CANADA: Bio. Cap Canada Semiarid Prairie Agricultural Research Centre NETHERLANDS: Wageningen Universiteit, Lab of Soil Science and Geology NORWAY: Det Kongelige Olge - Og Energidepartement Institute for Energy Technology Norwegian University of Science & Technology Research Council of Norway, Hanshaugen SINTEF Petroleum Research
Recommendations • Develop collaborative project on geological sequestration of CO 2 with US laboratories. • Set up centers of excellence on geological sequestration of CO 2 and carbon capture. • Organize IInd Workshop on Carbon Sequestration during January 2007.
Recommendations • Carbon capture and storage research offers an opportunity to mitigate global concerns about climate change and sustainable future • Suggested expansion of support to research and CO 2 infrastructure from DST and other concerned sectors of economy, under the National Programme on CO 2 Sequestration Research • Establish Centre for Advanced Studies in India for CCS technology to lead R&D projects on Carbon Capture, Geological Sequestration of CO 2, Monitoring, Modeling & Simulation studies and Clean Energy Development • Organize a special session on India’s initiatives on Carbon Capture and Storage R & D during 2008 at an international event. • Give more thrust to basalt pilot study using sub-basalt imaging techniques and establish baseline for concentration of CO 2 in atmosphere and soil and dissolved inorganic carbon (DIC) in shallow aquifer. • Facilitate inter and intra-networking between national and international projects on CCS technology. • Indian CO 2 Sequestration Applied Research Network to have institutional members and hold periodic meetings to develop an activity profile and framework for support. • Develop new knowledge partners with multi-disciplinary and multi-stage collaborations for sustainable energy future.
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