The Methanol Economy G. K. Surya Prakash - IASS Potsdam
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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
15
Petawatt-hours (10 watt-hours)
200
History Projections 189
175
180
162 v150 petawatt-hours ~ 15 terawatts
160
148 (15,000 power plants of 1 gigawatt)
140
121
120
102
107 v21 TW by 2025
100 91
84
80
61
71
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
R/P Ratio (years)
40
30
20
10
0
1980
1982
1984
1986
1988
1990
1992
1994
1996
1998
2000
2002
2004
Regional Distribution of W orld 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%
3
Total: 180 trillion m
About 67% of the natural gas reserves
are in Middle East and RussiaCoal
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 gasNon-conventional fossil fuels
•Tar sands
Already exploited
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
•Coalbed methane
Currently represents about 10% of the natural gas production in US
To be developed
•Oil shale
•Methane hydrates
Both have large potential but ways to exploit them economically
have to be foundAnnual Global CO2 Emissions- 1750-2005
35,000
Total
Coal 30,000
Petroleum
Million tonnes carbon dioxide / year
Natural gas
25,000
Cement production
Gas flaring
20,000
15,000
10,000
5,000
-
1750 1800 1850 1900 1950 2000
Source: Carbon Dioxide Information Analysis Center, Oak Ridge national LaboratoryWorldwide 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 C 2 F6 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, 2001Daily 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, 2004Energy 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 possibilityThe Methanol Economy
Methanol, fuel and feed-stock: The Methanol Economy
In Internal
Combustion High octane (ON= 100)
clean burning fuel,
Engines 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 DenmarkAdvanced methanol-powered
fuel cell vehicles
On-board generation of hydrogen through methanol reforming
Proton Exchange
Reforming
CH3OH
H2 + CO2
membrane (PEM)
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
Direct Oxidation Methanol Fuel Cell
(DMFC) USC, JPL - Caltech
e-
e-
Anodic Reaction:
e- - +
H+
CH3OH + H2O
Pt-Ru (50:50)
CO2
+ 6 H+
+
6 e-
CH3OH O 2 / Air Eo = 0.006 V
+ H 2O
H+ Cathodic Reaction:
H+
3/2 O2 + 6 H+ + 6 e-
Pt
3H2O
Eo = 1.22 V
CO 2 H+ H2 O Overall Reaction:
+ H 2O
- +
CH3OH + 3/2 O2
CO2 + H2O
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
H2O and CO2 are the only byproducts
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 fuelMethanol 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 animalsMETHANOL 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 cloudsCH3OH 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 H2
S =
moles CO
S=2 ideal for methanol
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 synthesisCH3OH 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 4CH3OHCH3OH 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
O2
Br2
CH4 CH3Br + HBr
Solid or liquid acids
H2O
CH3OH (or CH3OCH3) + HBr
Overall reaction: CH4 + 1/2 O2 CH3OHCH3OH 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 H2SO4CH3OH 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 emissionsMethanol 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 needsBiomass to Liquids (Methanol)
Lignocellulose
Fast Pyrolysis, 550 oC
Condensate + Char + Slurry, 90%
Gasification with Oxygen, 1200 oC
CO + H2 Syngas, 78%
Methanol or other liquidsEfficient 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, 2009Sour 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
CO2 + e- CO2 Eo = -1.96 V (1)
CO2 + 2H + + 2e - CO + H 2O Eo = -0.53 V (2)
CO2 + 2H + + 2e- HCOOH Eo = -0.61 V (3)
CO2 + 4H + + 4e- HCHO + H2 O Eo = -0.48 V (4)
CO2 + 6H + + 6e- CH 3OH + H2 O Eo = -0.38 V (5)
CO2 + 8H + + 8e- CH 4 + 2H 2O Eo = -0.24 V (6)
O
H OCH 3
MeOH
O
H2 O + CO H2 + CO 2
H OH
A Fuel &
Feed-stock
Direct Formic Acid Fuel CellSolar Thermal Conversions
CO2 + 3 FeO CO + Fe3O4
Fe 3O 4 3 FeO + 1/2 O 2
Overall
CO + 1/2 O2
CO2
Sunshine to Petrol: Sandia National Laboratory ProjectMethanol 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 Recycling of CO2
CO2 Capture:
�
�
Solution absorption and membrane technologies,
nanostructured supported amino polymer absorbent system-
convenient revesible absorption and desorption- USC Technology
Hydrogen Generation: Photochemical, thermal or electrochemical means
Water Electrolysis
CRI in Iceland,
H 2O H2 + 1/2 O2 using their cheap
Overall Cu/Zn catalysts geothermal energy!
CO2 + 3H2 CH3OH + H2O
Methane Bireforming:
Catalyst
3CH4 + 2H2O + CO2 4 CH3OH 2 CH3OCH3 +
endothermic
Overall 2 H2O
3CH4 + CO2 2 CH3OCH3US 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, 2010Acknowledgments
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
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