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

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

40 (years)

Ratio 30 R/P

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

developed be 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 / dioxide carbon 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. -24.8 °C; m.p. -141 °C vExcellent diesel fuel substitute with a cetane number of 55-60 (45-55 for regular diesel) and very clean burning vAlready used in spray dispenser DME truck in Japan vNon-toxic, Safe and does not form peroxides vSubstitute for LNG and LPG vEasy to produce, ship and dispense v Sootless ﬂame for glass blowing DME bus in Denmark

Advanced methanol-powered fuel cell vehicles

On-board generation of hydrogen through methanol reforming

Reforming Proton Exchange membrane (PEM) CH3OH H2 + CO2 H2O Catalyst Fuel cell + H2O

Methanol has no C-C bonds: reforming at low temperatures (250-300 °C)

Avoids the problem of on-board hydrogen storage under high pressure or in cryogenic liquid form (-253 °C) Direct oxidation methanol fuel cell (DMFC)Direct Oxidation USC, Methanol JPL - FuelCaltech Cell

e- Anodic Reaction: e- - + Pt-Ru (50:50) + - CO2 + 6 H + 6 e H+ CH3 OH + H2 O CH OH o 3 O2 / Air E = 0.006 V + H O 2 H+ Cathodic Reaction: + - Pt 3/2 O2 + 6 H + 6 e 3H 2 O H+ Eo = 1.22 V CO H+ H O 2 2 Overall Reaction: + H 2O - + CH3 OH + 3/2 O2 CO2 + H2 O Anode Cathode + electricity Pt -Ru Pt catalyst layer catalyst layer Ecell = 1.214 V

Proton Exchange membrane (Nafion-H)

US Patent, 5,599,638, February 4, 1997; Eur. Patent 0755 576 B1, March 5, 2008. Direct Methanol Fuel Cell Advantages v Methanol, 5 kWh/Liter – Theoretical (2 X Hydrogen) vAbsence of Pollutants H O and CO are the only byproducts 2 2 vDirect reaction of methanol eliminates reforming Reduces stack and system complexity Silent, no moving parts vCapable of start-up and operation at 20 °C and below Thermally silent, good for military applications vLiquid feed of reactants Effective heat removal and thermal management Liquid ﬂow avoids polymer dryout Convenient fuel storage and logistic fuel

Methanol as a fuel and feedstock

* Electricity production by combustion in existing gas turbines

* Electricity generation through fuel cells Fuel cells not limited by weight and space: other types of fuel cells can be used; PAFC, MCFC and SOFC

* Use of methanol as cooking fuel in developing countries Much cleaner burning and efﬁcient than wood

* Methanol is a feed for single cell proteins- as a feed for animals

METHANOL AS HYDROCARBON SOURCE

-2H2O 2CH3OH CH2 CH2 CH3 CH CH2 Zeolites or bifunctional catalysts

HYDROCARBON FUELS AND PRODUCTS (Gasoline, Diesel, etc.) CH3OH Sources

Industrial production Natural occurance

Syn-gas (from coal or natural gas) Wood, Biological processes (microbial or enzymatic Direct methane conversion transformations )

Carbon dioxide reduction Recently discovered enormous galactical methanol clouds CH3OH from syn-gas

Syn-gas is a mixture of H2, CO and CO2

CO + 2H2 CH3OH H298K = - 21.7 kcal / mol

CO2 + 3H2 CH3OH + H2O H298K = - 11.9 kcal / mol

CO + H2O CO2 + H2 H298K = - 9.8 kcal / mol

moles H S = 2 S=2 ideal for methanol moles CO

Syn-gas can be produced from any source of carbon: natural gas, petroleum, coal, biomass, etc.

However, not all give an ideal S ratio for methanol synthesis CH3OH from methane v Syn-gas from natural gas – steam reforming

Ni Cat. CH4 + H2O CO + 3H2 H298K = 49.1 kcal / mol S=3

Excess H2 generally used for ammonia (NH3) production v Partial oxidation of methane

CH4 + 1/2 O2 CO + 2H2 H298K = - 8.6 kcal / mol S=2

CO + 1/2 O2 CO2 H298K = - 67.6 kcal / mol

H2 +1/2 O2 H2O H298K = - 57.7 kcal / mol v Dry reforming with CO2 Ni Cat. CO2 + CH4 2CO + 2H2 H298K = 59.1 kcal / mol S=1

Reactions occur at high temperatures (at least 800-1000 °C) CH3OH through bi-reforming

Combination of steam and dry reforming: bi-reforming

2CH4 + 2H2O 2CO + 6H2

CO2 + CH4 2CO + 2H2

Overall: 3CH4 + 2H2O + CO2 4CO + 8H2 4CH3OH CH3OH from coal A proven technology

Catalysts 3C + 3/2 O2 3CO

2CO + 2H2O 2CO2 + 2H2

CO +2H2 CH3OH

3C + 2H2O + 3/2 O2 2CO2 + CH3OH

China is currently adopting this approach on a massive scale based on its large coal reserves

100 plants in construction or planned!

Due to the low H/C ratio of coal: a lot of CO2 is produced! CH3OH through methane halogenation

Br2 + H2O

Br2 CH4 CH3Br + HBr Solid or liquid acids

H2O

CH3OH (or CH3OCH3) + HBr

Overall reaction: CH4 + 1/2 O2 CH3OH CH3OH through intermediates other than syn-gas

Homogeneous catalyst Pt, Hg, Au based CH4 + 2H2SO4 CH3OSO3H + 2H2O + SO2

CH3OSO3H + H2O CH3OH + H2SO4

SO2 + 1/2 O2 + H2O H2SO4

CH4 + 1/2 O2 CH3OH (Overall reaction)

Advantage: low temperature reaction (180-250 °C), much lower than syn-gas generation (800-1000 ° C)

Inconvenient: need to recycle concentrated and corrosive H2SO4 CH3OH from methane without CO2 production

~ 900 oC Methane decomposition: CH4 C + 2H2

Methanol synthesis: CO2 + 3H2 CH3OH + H2O

Overall reaction: 3CH4 + 2CO2 2CH3OH + 2H2O + 3C

Advantage: all the carbon in methane ends up in carbon, a solid which is easy to handle and store

We could make extensive use of our natural gas reserves without

CO2 emissions Methanol from biomass

• Biomass includes any type of plant or animal material: Wood, wood wastes, agricultural crops and by-products, municipal waste, animal waste, aquatic plants and algae, etc.

• Transformed to methanol by gasification through syngas- very efficient Biomass Syn-gas Methanol CO + H2 • Any biomass is fine to make methanol

• Large amount of biomass needed- can convert biomass to biocrude and it can be shipped.

• Methanol from Biogas (mixture of CH4, CO2) Biocrude • Methanol through aquatic biomass- micro-algae

Biomass alone can not fulﬁll all our increasing energy needs

Biomass to Liquids (Methanol)

Lignocellulose

Fast Pyrolysis, 550 oC

Condensate + Char + Slurry, 90%

Gasification with Oxygen, 1200 oC

CO + H2 Syngas, 78%

Methanol or other liquids Efficient Ways to Capture CO2 and Its Electrochemical Conversion

Why Focus on Carbon Dioxide? • Linear molecule

• Very stable – Hard to efficiently reduce

• Trace gas – 0.039% of the atmosphere

– Amount of CO2 in the atmosphere is increasing

• With declining fossil fuel reserves, CO2 may become the best source of carbon US Patent, 7,605, 293, October, 20, 2009 US Patent, 7,608, 743, October, 27, 2009 Sour ces of CO2 Geothermal Vents Fossil Fuel Burning Power Plants Fermentation Processes Aluminum Plants Natural Gas Wells Air Itself Cement Plants Electrochemical Reduction of CO2 to Syngas and Formic Acid

Standard Electrochemical Reduction Potentials of CO2 at pH=7, NHE, NTP Conditions

- o CO2 + e CO2 E = -1.96 V (1) + - o CO2 + 2H + 2e CO + H2O E = -0.53 V (2) + - CO2 + 2H + 2e HCOOH Eo = -0.61 V (3) + - o CO2 + 4H + 4e HCHO + H2O E = -0.48 V (4) + - o CO2 + 6H + 6e CH3OH + H2O E = -0.38 V (5) + - o CO2 + 8H + 8e CH4 + 2H2O E = -0.24 V (6)

H OCH3

MeOH O H2O + CO H2 + CO2 H OH A Fuel & Feed-stock

Direct Formic Acid Fuel Cell Solar Thermal Conversions

CO2 + 3 FeO CO + Fe3O4

Fe3O4 3 FeO + 1/2 O2

Overall

CO + 1/2 O2 CO2

Sunshine to Petrol: Sandia National Laboratory Project Methanol from CO2 imitating nature Sources of carbon dioxide: •Industrial ﬂue gases: Fossil fuel burning power plants, steel and cement factories, etc. •The atmosphere itself (390 ppm)

Hydrogenation of CO2

CO2 + 3H2 CH3OH + H2O

Electrochemical reduction of CO2 Electrons CO2 + 2H2O CO + 2H2 + 3/2 O2 Electrode catalyst

CH3OH Electricity needed to produce hydrogen or for the reduction can come from any renewable (wind, solar, etc.) or nuclear energy source US Patent, 7,704,369, April 27, 2010 � �

� Chemical Recyclin g� of CO2 CO2 Capture: Solution absorption and membrane technologies, nanostructured supported amino po� lymer absorbent system- convenient revesible absorption and desorption- USC Technology Hydrogen Generation: Photoche mical, thermal or electrochemical means Water Electrolysis CRI in Iceland, H2O H2 + 1/2 O2 using their cheap Overall Cu/Zn catalysts geothermal energy! CO2 + 3H2 CH3OH + H2O Methane Bireforming: Catalyst 3CH4 + 2H2O + CO2 4 CH OH 2 CH OCH + endothermic 3 3 3 Overall 2 H2O

3CH4 + CO2 2 CH3OCH3 US Patent, 5,928,806, July 27, 1999 Carbon Capture and Recycling (CCR) Basis of the Methanol Economy

Renders carbon containing fuels and products environmetally neutral

Provides sustainable, universally available regenerative carbon source via carbon dioxide recycling using any energy source (alternates with emphasis on solar and atomic) and hydrogen of water

Replaces diminishing fossil fuels freeing humanity from dependence on coal, oil and natural gas

Offering solution to the costly and potentially dangerous carbon capture and storage (CCS) The Methanol Economy Worldwide Development of the Methanol Economy

USC - Honeywell - UOP: Concepts, new enabling chemistry and technology, IP and licencing

Iceland: First geothermal CO2 conversion plant to methanol (George Olah Renewable Methanol Plant, Carbon Recycling Int.)

Japan: Industrial CO2 to methanol demonstration plant (Mitsui)

China: Major low carbon technology energy initiative includes carbon capture, storage or recycling of CO2 from coal burning power plants (Government, CAS, Industry)

China, Japan, South Korea: Operating and building 50-100 multi- million t/yr coal or natural gas based methanol and DME plants with CO2 capture, storage or recycling to be added CRI Carbon Recycling International

“George Olah CO2 to Renewable Methanol Plant” Groundbreaking HS Orka Svartsengi Geothermal Power Plant, Iceland, October 17th 2009 Production capacity: 10 t/day, planned expansion to 100 t/day

geothermal CO2 + 3H2 CH3OH + H2O

electrolysis using geothermal electricity

H2O US Patents 7,605,293 and 7,608,743 Int. Pat. Appl., WO2010011504 A2 January 28, 2010

Acknowledgments Professor G. A. Olah Robert Aniszfeld Patrice Batamack Carlos Colmenares Alain Goeppert Thomas Mathew Sergio Meth Suresh Palale Federico Viva $$$$ USC-Loker Institute US Dept. of Energy Universal Oil Products (UOP)