The Methanol Economy G. K. Surya Prakash Loker Hydrocarbon Research Institute and Department of Chemistry University of Southern California Los Angeles, CA 90089-1661 USA Sustainable Methanol: An Alternative Green Fuel for the Future Workshop IASS Potsdam, Germany November 22-23, 2011 World population (in millions) Projection 1650 1750 1800 1850 1900 1920 1952 2000 2050 * 545 728 906 1171 1608 1813 2409 6200 8000 to 11000 * Medium estimate. Source: United Nations, Population Division Petawatt-hours (10 15 watt-hours) 200 History Projections 189 180 175 162 v150 petawatt-hours ~ 15 terawatts 160 148 (15,000 power plants of 1 gigawatt) 140 121 120 107 102 v21 TW by 2025 100 91 84 80 71 61 v30 TW by 2050 60 40 20 0 1970 1975 1980 1985 1990 1995 2002 2010 2015 2020 2025 World Primary Energy Consumption, 1970 to 2025 Based on data from Energy information Administration (EIA) Coal More than 80% of our 26.0% energy comes from Other fossil fuels 0.6% Combustible Renewables & Waste Oil 10.1% 34.4% Hydro 2.2% Nuclear 6.2% Natural gas 20.5% Total 11 741 Mtoe Distribution of the World Total Primary Energy Supply in 2006. Based on data from the International Energy Agency (IEA) Key World Energy Statistics 2008 Increasing world population Increase in standard of living Increase in fossil fuel use Increase in carbon dioxide -Oil, gas, coal (hydrocarbons) content of the atmosphere Finite sources – non-renewable Greenhouse effect On the human timescale (Global warming). 390 ppm Hydrocarbon Sources 17th-19th Century - industrial revolution coal 19th Century coal, oil 20th Century coal, oil, natural gas (fossil fuels) 21st Century fossil fuels carbon dioxide Petroleum products In United States, 67% of the petroleum is currently used in transportation as gasoline, diesel, jet fuel, etc.! Transportation sector is utterly dependant on petroleum oil Proven Oil and Natural Gas Reserves (in billion tonnes of oil equivalent) from 1960 to 2003 Year Oil Natural Gas 1960 43 15.3 1965 50 22.4 1970 77.7 33.3 1975 87.4 55 1980 90.6 69.8 1986 95.2 86.9 1987 121.2 91.4 1988 123.8 95.2 1989 136.8 96.2 1990 136.5 107.5 1993 139.6 127 2002 156.4 157.6 2003 156.7 158.2 Oil and Natural Gas Reserve to Production (R/P) Ratio 70 Oil Natural gas 60 50 40 (years) Ratio 30 R/P 20 10 0 1980 1982 1984 1986 1988 1990 1992 1994 1996 1998 2000 2002 2004 Regional Distribution of World Oil Reserves in 2004 Asia, 3.5% Middle East, 61.7% North America, 5.1% Saudi Arabia, 22.1% South and Central America, 8.5% Iran, 11.1% Africa, 9.4% Iraq, 9.7% Kuwait, 8.3% Europe and Eurasia, 11.7% United Arab Emirate, 8.2% Others, 2.3% Total: 1189 billion barrels Distribution of World Natural Gas Proven Reserves in 2004 Eurasia Europe 5.1% 3.8% Asia 7.9% Russia 26.7% Africa 7.8% North America 4.1% South and Central America 4.0% Qatar Rest of Middle East 14.4% 10.9% Iran 15.3% Total: 180 trillion m 3 About 67% of the natural gas reserves are in Middle East and Russia Coal World Proven Coal Reserves Distribution India, 10% China, 12% Australia, 9% South Africa , 5% Ukraine, 4% Kazakhstan, 3% Russia, 17% Rest of the World, 12% United States , 27% Total Proven Reserves: 909,000 Mt Enough for more than 160 years at current rate of consumption! Coal is a dirty fuel. It also emits much more CO2 per unit of energy produced than petroleum and natural gas Non-conventional fossil fuels •Tar sands Exploited on a large scale in Canada (2 million barrels /day) •Tight gas sands and shale Already accounts for 15% of the natural gas production in US Already exploited Already •Coalbed methane Currently represents about 10% of the natural gas production in US •Oil shale •Methane hydrates Both have large potential but ways to exploit them economically To be developed To have to be found Annual Global CO2 Emissions- 1750-2005 35,000 Total Coal 30,000 Petroleum Natural gas 25,000 Cement production Gas flaring 20,000 15,000 10,000 Million tonnes carbon dioxide / year carbon dioxide tonnes Million 5,000 - 1750 1800 1850 1900 1950 2000 Source: Carbon Dioxide Information Analysis Center, Oak Ridge national Laboratory Worldwide contribution of greenhouse gases to the increased greenhouse effect induced by human activity Halogenated compounds 10% Nitrous oxide 6% Methane Carbon dioxide 19% 65% Global Warming Potentials (GWPs) of greenhouse gases Global warming potential a Atmospheric lifetime (years) Carbon dioxide CO2 1 Methane CH4 23 12 Nitrous oxide N2O 296 114 Hydrofluorocarbons (HFC) 12-12,000 0.3-260 Examples: HFC-23 CHF3 12,000 260 HFC-32 CH2F2 550 5 HFC-134a CH2FCF3 1,300 14 Fully fluorinated species 5,700-22,200 2,600-50,000 Examples: Perfluoromethane CF4 5,700 50,000 Perfluoroethane C2F6 11,900 10,000 Sulfur hexafluoride SF6 22,200 3,200 a Over a 100 year time horizon Based on data from IPCC, Third Assessment Report, 2001 Daily usage of fossil fuels v85 Million Barrels of Oil is consumed! v8 Billion m3 of Natural Gas v16 Million Tonnes of Coal 30 billion tonnes of CO2 released into the atmosphere per year Contributing to greenhouse effect – Global Warming Ethanol economy: in the US, 7 billion gallons of ethanol is produced per year (~175 million barrels) from corn. Equivalent to 115 million barrels of oil: 1.3 days supply! In Brazil, 7 billion gallons of ethanol from sugar cane is Produced Biodiesel a lot smaller: requires more land Biomass CO2 fixation by photosynthesis (carbon neutral) CO2 Fixation by Photosynthesis (carbon neutral) Chlorophyll nCO2 + nH2O n(CH2O) + nO2 Sunlight Biofuels- Ethanol, butanol, vegetable oils (biodiesel)- a small % of the energy mix. * Land availability and use * Water resources- Irrigation * Food security vs Energy security * Fertilzer use (nitrogen fertilizers from NH3 (N2 and H2 (syngas)) * Processing technologies, energy use * Overall energy balance Sun is the source of most energy on Earth- past, present and future 130,000 TW continuous- A reliable nuclear fusion reactor! Alternative Energies Hydropower Geothermal energy Wind energy Solar energy Biomass Ocean energy (waves, tides, thermal) Nuclear energy Electric Energy Generated in Industrial Countries by Non-Fossil Fuels (%, 2004) Country Fossil Fuels Hydroelectric Nuclear Geothermal, Solar, Wind, Total Wood and Waste Non-Fossil France 9.4 10.9 78.6 1.1 90.6 Canada 25.7 58.0 14.7 1.6 74.3 Germany 61.9 3.6 27.5 6.9 38.1 Japan 62.2 9.2 26.4 2.2 37.8 South Korea 62.8 1.2 35.9 0.1 37.2 United States 71.0 6.7 19.8 2.4 29.0 United Kingdom 75.5 1.3 20.0 3.2 24.5 Italy 81.1 14.1 0.0 4.8 18.9 Source: Energy Information Administration, International Energy Annual 2007, World Net Electricity Generation by Type, 2004 Energy Storage Most of the alternative energies (solar, wind, geothermal, nuclear) produce electricity ; solar and wind are intermittant Problem: How to store electricity in a convenient form and on a large scale? •Batteries: Low capacity •Fly wheel •Water Limited capacity •Compressed air •In a liquid or gas: Hydrogen, Methanol, etc. If it was easy to store electricity, we would all be driving electric cars! Hydrogen Economy Hydrogen economy (clean fuels, fuel cells) • Hydrogen is not a primary energy carrier, b.p. = -253 °C • Tied up in water and fossil fuels • Incompatible with 20% oxygen in the air • Liquid hydrogen has 1/3 Volumetric energy density of gasoline • 2 grams occupy 22.4 liters of volume at NTP (high pressurization is required) • Infrastructure is very expensive (hydrogen diffuses easily) • Highly flammable (colorless flame) Carbon Conundrum Environmental effect Essential element for terrestrial life Excessive CO2 production Nature's carbon cycle contributes to global warming Burning of fossil fuels, living Limited fossil fuel resources are organisms increasingly depleted Natural and industrial sources (natural Nature's carbon cycle takes a long gas production, geothermal wells, time. Technological CO2 recycling via varied industries) Methanol Economy is a possibility The Methanol Economy Methanol, fuel and feed-stock: The Methanol Economy In Internal Combustion High octane (ON= 100) Engines clean burning fuel, 15.8 MJ/liter. M-85 Fuel CH3OCH3, high cetane clean burning diesel fuel, LNG and LPG substitute. As Dimethyl In Direct Ether (Diesel Methanol Fuel, Fuel Cells� Household CH3OH� Fuel)� Conversion to olefins- gasoline, diesel, etc.� Methanol properties vMethanol (methyl alcohol, wood alcohol) is an excellent internal combustion engine/turbine fuel- It is a liquid (b.p 64.7 oC). vMethanol has a high octane number (~ 100)- used in Race cars. vM85- used in Flex-Fuel vehicles (similar to E-85). vHalf the volumetric energy content of gasoline (15.8 MJ/liter), but more efficient and cleaner burning. vMethanol can be blended into Biodiesel (Esterification). Converted to dimethyl ether and dimethyl carbonate. vMethanol is an excellent hydrogen carrier -easily reformed to H2 (syngas) at modest temperatures. Methanol in ICE v Octane number 100- fuel/air mixture can be compressed to smaller volume-results in higher compression ratio v Methanol has also has higher “flame speed”- higher efficiency v Higher latent heat of vaporization (3.7 times higher than gasoline)- can absorb heat better- removes heat from engine- air cooled engines v Methanol burns better- cleaner emissions v Safer fuel in fires than gasoline vMethanol can be dispensed in regular gas station requiring only limited modifications vCompatible with hybrid (fuel/electric) systems " " Drawbacks v Methanol is miscible in water - corrosive for Al, Zn, Mg Solution: use compatible materials - Flexfuel vehicles vMethanol has low vapor pressure at low temperatures Solution: spike it with gasoline- M85 vIngestion > 20 mL can be lethal - Dispensing should not be a problem vSpillage - very safe to the environment methanol used in water treatment plants for denitrification" Dimethyl ether (DME) - H2O 2CH3OH CH3OCH3 b.p.