G.K. Surya Prakash - IASS Potsdam

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)
1650 1750 1800 1850 1900 1920 1952 2000
Projection
2050 *
545 728 906 1171 1608 1813 2409 6200 8000 to 11000
* Medium estimate. Source: United Nations, Population Division
200
180
160
140
120
100
80
60
Petawatt-hours (10 15 watt-hours)
History
91
84
71
61
102
107
121
Projections
148
162
175
189
v 150 petawatt-hours ~ 15 terawatts
(15,000 power plants of 1 gigawatt)
v 21 TW by 2025
v 30 TW by 2050
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)

More than 80% of our
energy comes from
fossil fuels
Oil
34.4%
Coal
26.0%
Other
0.6%
Combustible
Renewables &
Waste
10.1%
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
- Oil, gas, coal (hydrocarbons)
Finite sources – non-renewable
On the human timescale
Increase in carbon dioxide
content of the atmosphere
Greenhouse effect
(Global warming). 390 ppm

Hydrocarbon Sources
17 th -19th Century - industrial revolution coal
19 th Century coal, oil
20 th Century coal, oil, natural gas
(fossil fuels)
21 st 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 World Oil Reserves in 2004
Asia, 3.5% Middle East, 61.7%
North America, 5.1%
South and Central America,
8.5%
Africa, 9.4%
Europe and Eurasia, 11.7%
Saudi Arabia, 22.1%
Iran, 11.1%
Iraq, 9.7%
Kuwait, 8.3%
United Arab Emirate, 8.2%
Others, 2.3%
Total: 1189 billion barrels

Distribution of World Natural Gas Proven
Reserves in 2004
Russia
26.7%
Eurasia
5.1%
Europe
3.8%
Asia
7.9%
Africa
7.8%
North America
4.1%
South and Central
America
4.0%
Qatar
14.4%
Rest of Middle East
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%
Russia, 17%
Kazakhstan, 3%
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 CO 2 per unit of energy
produced than petroleum and natural gas

Non-conventional fossil fuels
Already exploited
To be developed
• 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
• 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
have to be found

Annual Global CO 2 Emissions- 1750-2005
Total
Coal
Petroleum
Natural gas
Cement production
Gas flaring
35,000
30,000
25,000
20,000
15,000
10,000
5,000
Million tonnes carbon dioxide / year
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
Nitrous oxide
6%
Halogenated
compounds
10%
Methane
19%
Carbon dioxide
65%
Global Warming Potentials (GWPs) of greenhouse gases
Global warming potential
Carbon dioxide CO 2
1
a
Atmospheric lifetime
(years)
Methane CH 4 23 12
Nitrous oxide N 2 O 296 114
Hydrofluorocarbons (HFC) 12-12,000 0.3-260
Examples:
HFC-23 CHF 3
12,000 260
HFC-32 CH 2F 2
550 5
HFC-134a CH 2
FCF 3
1,300 14
Fully fluorinated species 5,700-22,200 2,600-50,000
Examples:
Perfluoromethane CF 4
5,700 50,000
Perfluoroethane C 2
F 6
11,900 10,000
Sulfur hexafluoride SF 6
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
v 85 Million Barrels of Oil is consumed!
v 8 Billion m 3 of Natural Gas
v 16 Million Tonnes of Coal
30 billion tonnes of CO 2 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
CO 2 fixation by photosynthesis (carbon neutral)
CO 2 Fixation by Photosynthesis (carbon neutral)
nCO 2
+ nH 2 O
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 NH 3 (N 2 and H 2 (syngas))
* Processing technologies, energy use
* Overall energy balance
Chlorophyll
Sunlight
n(CH 2 O) + nO 2
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,
Wood and Waste
Total
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 CO 2 production
contributes to global warming
Burning of fossil fuels, living
organisms
Natural and industrial sources (natural
gas production, geothermal wells,
varied industries)
Nature's carbon cycle
Limited fossil fuel resources are
increasingly depleted
Nature's carbon cycle takes a long
time. Technological CO 2 recycling via
Methanol Economy is a possibility

The Methanol Economy

Methanol, fuel and feed-stock: The Methanol Economy
CH 3 OCH 3 , high cetane
clean burning diesel fuel, LNG
and LPG substitute.
In Internal
Combustion
Engines
High octane (ON= 100)
clean burning fuel,
15.8 MJ/liter.
M-85 Fuel
As Dimethyl
Ether (Diesel
Fuel,
Household
Fuel)
CH 3 OH
In Direct
Methanol
Fuel Cells
Conversion
to olefinsgasoline,
diesel, etc.

Methanol properties
v Methanol (methyl alcohol, wood alcohol) is an excellent internal
combustion engine/turbine fuel- It is a liquid (b.p 64.7 o C).
v Methanol has a high octane number (~ 100)- used in Race cars.
v M85- used in Flex-Fuel vehicles (similar to E-85).
v Half the volumetric energy content of gasoline (15.8 MJ/liter),
but more efficient and cleaner burning.
v Methanol can be blended into Biodiesel (Esterification).
Converted to dimethyl ether and dimethyl carbonate.
v Methanol is an excellent hydrogen carrier -easily reformed to H 2
(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 speedhigher
efficiency
v Higher latent heat of vaporization (3.7 times
higher than gasoline)- can absorb heat betterremoves
heat from engine- air cooled engines
v Methanol burns better- cleaner emissions
v Safer fuel in fires than gasoline
v Methanol can be dispensed in regular gas
station requiring only limited modifications
v Compatible with hybrid (fuel/electric) systems

Drawbacks
v Methanol is miscible in water - corrosive for Al, Zn, Mg
Solution: use compatible materials - Flexfuel vehicles
v Methanol has low vapor pressure at low temperatures
Solution: spike it with gasoline- M85
v Ingestion > 20 mL can be lethal - Dispensing should not be
a problem
v Spillage - very safe to the environment
methanol used in water treatment plants for denitrification

Dimethyl ether (DME)
2CH 3 OH
- H 2 O
CH 3 OCH 3
b.p. -24.8 °C; m.p. -141 °C
v Excellent diesel fuel substitute with
a cetane number of 55-60 (45-55 for
regular diesel) and very clean burning
v Already used in spray dispenser
v Non-toxic, Safe and does not form
peroxides
v Substitute for LNG and LPG
v Easy to produce, ship and dispense
v Sootless flame for glass blowing
DME truck in Japan
DME bus in Denmark

Advanced methanol-powered
fuel cell vehicles
On-board generation of hydrogen through methanol reforming
CH 3 OH
+ H 2 O
Reforming
Catalyst
H 2 + CO 2
Proton Exchange
membrane (PEM)
Fuel cell
H 2 O
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 -
e - - +
Anodic Reaction:
CH 3 OH + H 2 O Pt-Ru (50:50) CO 2 + 6 H + + 6 e -
CH 3
OH
+ H 2
O
H +
H +
H +
O 2
/ Air
Cathodic Reaction:
E o = 0.006 V
3/2 O 2 + 6 H + + 6 e - Pt
3 H 2 O
CO 2
+ H 2
O
Anode
Pt -Ru
catalyst layer
-
H +
+
Cathode
Pt
catalyst layer
H 2
O
Overall Reaction:
CH 3 OH + 3/2 O 2
E o = 1.22 V
CO 2 + H 2 O
+ electricity
E cell = 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)
v Absence of Pollutants
H 2 O and CO 2 are the only byproducts
v Direct reaction of methanol eliminates reforming
Reduces stack and system complexity
Silent, no moving parts
v Capable of start-up and operation at 20 °C and below
Thermally silent, good for military applications
v Liquid 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
-2H 2 O
2CH 3 OH CH 2 CH 2 CH 3 CH CH 2
Zeolites
or bifunctional
catalysts
HYDROCARBON FUELS AND PRODUCTS
(Gasoline, Diesel, etc.)

CH 3 OH Sources
Industrial production
Natural occurance
Syn-gas (from coal or natural gas)
Direct methane conversion
Carbon dioxide reduction
Wood, Biological processes
(microbial or enzymatic
transformations )
Recently discovered enormous
galactical methanol clouds

CH 3 OH from syn-gas
Syn-gas is a mixture of H 2 , CO and CO 2
CO + 2H 2 CH 3 OH
CO 2
+ 3H 2 CH 3 OH + H 2 O
H 298K = - 21.7 kcal / mol
H 298K = - 11.9 kcal / mol
CO + H 2 O CO 2
+ H 2
H 298K = - 9.8 kcal / mol
S
=
moles H 2
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 synthesis

CH 3 OH from methane
v Syn-gas from natural gas – steam reforming
Ni Cat.
CH 4 + H 2 O CO + 3H 2
H 298K = 49.1 kcal / mol
Excess H 2 generally used for ammonia (NH 3 ) production
S=3
v Partial oxidation of methane
CH 4 + 1/2 O 2 CO + 2H 2
1/2 O 2
H 298K = - 8.6 kcal / mol
S=2
CO
+
CO 2
H 298K = - 67.6 kcal / mol
H 2
+ 1/2 O 2
H 2 O
H 298K = - 57.7 kcal / mol
v Dry reforming with CO 2
CO 2
Ni Cat.
+ CH 4 2CO + 2H 2
H 298K = 59.1 kcal / mol
S=1
Reactions occur at high temperatures (at least 800-1000 °C)

CH 3 OH through bi-reforming
Combination of steam and dry reforming: bi-reforming
+ 2CO
2CH 4 2H 2 O + 6H 2
CO 2
+ CH 4 2CO + 2H 2
Overall:
3CH 4 + 2H 2 O + CO 2 4CO + 8H 2
4CH 3 OH

CH 3 OH from coal
A proven technology
3C + 3/2 O 2
Catalysts
3CO
2CO + 2H 2 O
2CO 2 + 2H 2
CO +2H 2
CH 3 OH
3C + 2H 2 O + 3/2 O 2
2CO 2 + CH 3 OH
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 CO 2 is produced!

CH 3 OH through methane
halogenation
Br 2 + H 2 O
CH 4
Br 2
O 2
Solid or liquid acids
CH 3 Br + HBr
H 2 O
CH 3 OH (or CH 3 OCH 3 ) + HBr
Overall reaction:
CH 4 + 1/2 O 2 CH 3 OH

CH 3 OH through intermediates other
than syn-gas
Homogeneous catalyst
Pt, Hg, Au based
CH 4 + 2H 2 SO 4 CH 3 OSO 3 H + 2H 2 O + SO 2
CH 3 OSO 3 H + H 2 O CH 3 OH + H 2 SO 4
SO 2 + 1/2 O 2 + H 2 O H 2 SO 4
CH 4 + 1/2 O 2 CH 3 OH (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 H 2 SO 4

CH 3 OH from methane without CO 2
production
Methane decomposition:
Methanol synthesis:
~ 900 o C
CH 4 C + 2H 2
CO 2 + 3H 2
CH 3 OH + H 2 O
Overall reaction:
3CH 4 + 2CO 2
2CH 3 OH + 2H 2 O + 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
CO 2 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
CO + H 2
• Any biomass is fine to make methanol
• Large amount of biomass needed- can convert biomass to
biocrude and it can be shipped.
Methanol
• Methanol from Biogas (mixture of CH 4 , CO 2 )
• Methanol through aquatic biomass- micro-algae
Biocrude
Biomass alone can not fulfill all our increasing energy needs

Biomass to Liquids (Methanol)
Lignocellulose
Fast Pyrolysis, 550 o C
Condensate + Char + Slurry, 90%
Gasification with Oxygen, 1200 o C
CO + H 2 Syngas, 78%
Methanol or other liquids

Efficient Ways to Capture CO 2 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 CO 2 in the atmosphere is increasing
• With declining fossil fuel reserves, CO 2 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 CO 2
Geothermal Vents
Fermentation Processes
Natural Gas Wells
Cement Plants
Fossil Fuel Burning Power Plants
Aluminum Plants
Air Itself

Electrochemical Reduction of CO 2 to Syngas and Formic Acid
Standard Electrochemical Reduction Potentials of CO 2 at pH=7, NHE, NTP Conditions
CO 2 e - + CO 2 E o = -1.96 V (1)
CO 2 + 2H + + 2e - CO + H 2 O E o = -0.53 V (2)
CO 2 + 2H + + 2e - HCOOH E o = -0.61 V (3)
CO 2 + 4H + + 4e - HCHO + H 2 O E o = -0.48 V (4)
CO 2 + 6H + + 6e - CH 3 OH + H E o 2 O = -0.38 V (5)
CO 2 + 8H + + 8e - CH E o 4 + 2H 2 O = -0.24 V (6)
O
H
OCH 3
H 2 O + CO
O
H OH
A Fuel &
Feed-stock
MeOH
H 2 + CO 2
Direct Formic Acid Fuel Cell

Solar Thermal Conversions
CO 2 + 3 FeO CO + Fe 3 O 4
Fe 3 O 4 3 FeO + 1/2 O 2
Overall
CO 2
CO + 1/2 O 2
Sunshine to Petrol: Sandia National Laboratory Project

Methanol from CO 2
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 CO 2
CO 2
+ 3H 2
CH 3 OH + H 2 O
Electrochemical reduction of CO 2
Electrons
CO 2
+ 2H 2 O
Electrode catalyst
CO + 2H 2 +
3/2 O 2
CH 3 OH
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 CO 2
CO 2 Capture:
Solution absorption and membrane technologies,
nanostructured supported amino polymer absorbent systemconvenient
revesible absorption and desorption- USC Technology
Water Electrolysis
H 2 O H 2 + 1/2 O 2
Overall Cu/Zn catalysts
CO 2 + 3H 2
CH 3 OH + H 2 O
Methane Bireforming:
3CH 4 + 2H 2 O + CO 2
3CH 4 + CO 2 2 CH 3 OCH 3
Hydrogen Generation: Photochemical, thermal or electrochemical means
Overall
Catalyst
endothermic
4 CH 3 OH
CRI in Iceland,
using their cheap
geothermal energy!
2 CH 3 OCH 3 +
2 H 2 O

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 CO 2 conversion plant to methanol
(George Olah Renewable Methanol Plant, Carbon Recycling Int.)
Japan: Industrial CO 2 to methanol demonstration plant (Mitsui)
China: Major low carbon technology energy initiative includes
carbon capture, storage or recycling of CO 2 from coal burning
power plants (Government, CAS, Industry)
China, Japan, South Korea: Operating and building 50-100 multimillion
t/yr coal or natural gas based methanol and DME plants
with CO 2 capture, storage or recycling to be added

CRI Carbon Recycling International
George Olah CO 2 to Renewable Methanol Plant Groundbreaking
HS Orka Svartsengi Geothermal Power Plant, Iceland, October 17 th 2009
Production capacity: 10 t/day, planned expansion to 100 t/day
geothermal CO 2
+ 3H 2
H 2 O
US Patents 7,605,293 and 7,608,743
Int. Pat. Appl., WO2010011504 A2 January 28, 2010
CH 3 OH + H 2 O
electrolysis using
geothermal electricity

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)