METHANE HYDRATES FOR SUSTAINABLE ENERGY APPLICATIONS Dr. Alevtina Smirnova Alevtina.Smirnova @sdsmt.edu SDSMT 2011 New Horizons in Oil and Gas Conference October 5-8 2011
AGENDA 1. MH resources around the world 2. GHs discovery and physical properties 3. MH detection 4. MH extraction 5. Electricity production from MH using SOFCs 80% efficiency? YES SOLID OXIDE FUEL CELL
Sustainable Energy Energy Resources Alternative Fossil fuels Nuclear energy Methane hydrates Energy Generating and Storage Devices Renewable Solar Wind Geothermal Tides/Waves Biomass Methane hydrates Solid Oxide Fuel Cells+CO 2 sequestration
Abundance: Methane hydrate sites around the world T&P Gas in MH: 10 16-10 19 SCF M. Walsh, D. Sloan, et al., Energy Economics 31 (2009) 815 823
CLATHRATES: HISTORY OF DICOVERY Clathrates = inclusion (host-guest) compounds Priestley (1790) SO 2 and SO 3 *nh 2 O Faraday (1823) Cl 2 *nh 2 O Wroblewsky (1892) CO 2 *8H 2 O Powell (1948) Pipeline blockage Pipeline blockage https://www.llnl.gov/str/durham.html 1929 - Kazakhstan 1934 - Hammerschmidt GH rather than ice 1998 - Telluride, Colorado G + nh 2 O G nh 2 O
METHANE HYDRATE FORMATION Type I 46 H 2 O Cubic a 12.1 Type II 136 H 2 O Cubic a 17.2 Hydrogen bonds Van der Waals weak forces Type H n H 2 O Hexagonal a 12.2; c 10.1
Sources of methane: TG and BG gases Oceans of methane on Titan (moon of Saturn) early analog of Earth CH 4 trapped inside the mantle
Physical properties of methane hydrates Thermal conductivity(wm -1 K -1 ) MH Water Ice MH bearing sediments 0.45 0.56 2.0 2.35-2.77 J. Henninges and E. Huenges, In-situ thermal conductivity of gas B11206 http://woodshole.er.usgs.gov/operations/hi_fi/methane.html Specific Heat Capacity (KJ/kg K) MH Water Ice 2.09 4.187 2.108 1. Crystal structure 2. Stability at P,T 3. Water salinity 4. Density 5. Hardness/strength 6. Morphology 7. Expansion 8. Energy density Waite, W.F., Stern, L.A., Kirby, S.H., Winters, W.J. and Mason, D.H., 2007, Simultaneous determination of thermal conductivity, thermal diffusivity and specific heat in S-I methane hydrate, Geophysical Journal International, 169 (2007) 767-774
Methane Hydrate Stability Zone Depth in meters Temperature o C http://esd.lbl.gov/research/projects/tough/software/tough+.html http://woodshole.er.usgs.gov/operations/hi_fi/methane.html http://www.killerinourmidst.com/methane%20and%20mhs2.html Water-sediment boundary Base of methane gas
Sampling Locations in the Gulf of Mexico Klapp, Marine and Petroleum geology 27 (2010) 116-125
Morphology Samples associated to oil-stained sediments TVG-10 Bush Hill, Gulf of Mexico Klapp, Marine and Petroleum geology, 27 (2010) 116-125
Morphology and Microstructure (SEM) TVG-10 sii Dense and solid Tirelike microstructure Wt. % of MH in the sediment Drilling capability Extraction capability CG-6 si Chapopote asphalt volcano Mesoporous structure C p(h20) =4.187 kj/kg K C p(ice) =2.108 kj/kg K C p(mh) 1/2C p(h20) =2.09kJ/kg K TVG-10 sii Dense and solid; Tire-like microstructure Klapp, Marine and Petroleum geology 27 (2010) 116-125
Physical Properties and Energy Density Conventional fossil fuel vs. MH C:H:O Energy density (MJ/kg) Dry biomass (or peat) 1:2:1 10-30 Coal 1:0.8:0.1 20-35 Crude oil 1:1:0.015 42-43 Refined petroleum 1:2:0 44-47 Natural gas 1:4:0 50 Gas from Methane hydrate 1:4:0 The same as that of a compressed gas Physical Properties MW(g) 957.04 T mp ( o C) 4-5 P atm 50 D (g/cm 3 ) 0.95 Hardness 2.5 (finger nail)
MH Locations: OCEAN Identified MH locations (green) Subduction zones (red lines)
Nankai Trough (Nagoya) Sea of Japan 1999-3 wells in Tokyo Bay Distance: 50km off the coast of Japan Depth: 950m BSR depth: 290m below the sea floor (1240m meters below sea level). GH volume: 20vol.% Pore space : 80% Total GH volume: 525 million m 3 /km 2 Pacific Ocean MH deposits: 16 to 27 trillion m 3 Lithology (rock formation and properties ) controls GH deposits The Drill Ship M.G. Hulme 2001-16yrs MH exploration program $65-100mil 250 people from 30 organizations
PERMAFROST Permafrost depth : >600 meters GHSZ > 600m GH within the permafrost and below it 130-200m <GHSZ< 600-2000m 1998 Mallik program Japan-US-Canada Recognition for commercial possibilities: 230bil m 3
MH Exploration: Detecting and quantifying methane hydrate deposits Seismic methods Geophysical methods Electric conductivity Chemical methods
MH Exploration Sonar image (Seismic data) of the seafloor sediments "sub-floor" 5km Sonar reflection: gas vs. MH -simulating reflector," or BSR
Inland deepwater seas and lakes Black Sea 600m<GHSZ<700m Total GH area: 68.5% of the Black sea area Thickness: 303m GHs=4.8x10 13 km 3
Lake Baikal (2006 & 2009) Russian Academy of Sciences Kitami Institute of Technology Hokkaido University 1,637m deep 25milyrs old Holds 20%of all fresh water 400m Dissociation chamber Lake bed Methane hydrate Depths: approximately 400 meters http://www.nature.com/news/2008/080728/full/news.2008.986.html
Challenges behind the deep-water and permafrost drilling Gas production is technically feasible: 1. Depressurization 2. Thermal heating 3. Models: 1+2 is the best choice 4. SOFC? Drill rig Mallik gas-hydrate program (2002) Offshore platform in the Gulf of Mexico (2009)
SOFC vs. other Power Generating Devices
ANODE SUPPORT ANODE CATHODE ELECTROLYTE H 2 O CO CO 2 CO+H 2 O CO 2 +H 2 (1) CH 4 +H 2 O CO+3H 2 (2) DIFFUSION ION TRANSPORT DIFFUSION CH 4 H 2 O H 2 O O 2 2- H 2 O 2 O 2 (Air) H 2 +O 2- H 2 O+2e - (3) H 2 +O 2- H 2 O+2e - (4)
Zero Emission SOFC operating on methane derived from methane hydrate SOFC CH 4 CO 2 HEAT MH CO 2 gas hydrate CH 4 gas tank THANK YOU FOR YOUR ATTENTION!