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Home , Methanol economy

Beyond Oil and Gas: The EconomyR

G. K. Surya Prakash Loker Hydrocarbon Research Institute and Department of Chemistry University of Southern California Los Angeles, CA 90089-1661

PROMSUS Gotenburg Sweden May 6-7, 2014

Increasing world population Increase in standard of living

Increase in use Increase in -Oil, gas, (hydrocarbons) content of the atmosphere Finite sources – non-renewable Greenhouse effect On the human timescale (Global warming). 400 ppm 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 Hydrocarbon Sources

17th-19th Century - industrial revolution coal

19th Century coal, oil

20th Century coal, oil, (fossil fuels)

21st Century fossil fuels carbon dioxide

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

5 000 year / dioxidecarbon tonnesMillion

- 1750 1800 1850 1900 1950 2000

Source: Carbon Dioxide Information Analysis Center, Oak Ridge national Laboratory More than 30 billion tonnes of CO2 per year released into the atmosphere!

About half the CO2 emissions accumulate in the atmosphere Presently around 15 billion tonnes per year 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 Ocean Acidification is a Bigger Problem!

Daily usage of fossil fuels

85 Million Barrels of Oil is consumed!

8 Billion m3 of Natural Gas

16 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, 13. 9 billion gallons of ethanol is produced per year (~330 million barrels) from corn. Equivalent to 225 million barrels of oil: 2.5 days supply! In Brazil, 5.57 billion gallons of ethanol from cane is Produced a lot smaller: requires more land World's Top Ten Countries with Large Natural Gas Reserves (2012 data)

Coventional Tight Shale Coal-bed Methane

Russsia 105 tcm 112 tcm 114 tcm 141 tcm

USA 36 tcm 45 tcm 71 tcm 73 tcm

China 3 tcm 5 tcm 42 tcm 51 tcm

Iran 37 tcm 41 tcm NA NA

Saudi Arabia 36 tcm 38 tcm 39 tcm NA

Australia 5 tcm 13 tcm 26 tcm 28 tcm

Qatar 26 tcm 27 tcm NA NA

Argentina 2 tcm 3 tcm 25 tcm NA

Mexico 3 tcm 4 tcm 22 tcm NA

Canada 4 tcm 6 tcm 18 tcm 22 tcm

tcm: trillion cubic meters Israel (Tamar: 0.25 TCM; Leviathan: 0.5 TCM; Levant: 3.4 TCM) European Shale Gas

639 TCU

Hydrogen Economy economy (clean fuels, fuel cells) • Hydrogen is not a primary , b.p. = -253 °C • Tied up in water and fossil fuels • Incompatible with 20% oxygen in the air • Liquid hydrogen has 1/3 Volumetric of • 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) The Methanol Economy: Methanol as a fuel and feed-stock

In Internal Combustion High octane (ON= 100) Engines clean burning fuel, 15.8 MJ/liter. M-85 Fuel CH3OCH3, high cetane clean burning , LNG and LPG substitute.

Dimethyl Ether In Direct (Diesel and Household Fuel) Cells CH3OH

Conversion to olefins- gasoline, diesel, etc. Methanol properties

Methanol (methyl alcohol, alcohol) is an excellent internal combustion engine/turbine fuel- It is a liquid (b.p 64.7 oC). Methanol has a high octane number (~ 100)- used in Race cars. M85- used in Flex-Fuel vehicles (similar to E-85). Half the volumetric energy content of gasoline (15.8 MJ/liter), but more efficient and cleaner burning. Methanol can be blended into Biodiesel (Esterification). Converted to and dimethyl carbonate.

Methanol is an excellent hydrogen carrier -easily reformed to H2 () at modest temperatures.  Methanol as a direct Diesel substitute. Methanol as marine fuel

Availability, distribution and storage

Engine technology and adjustment to the ship

Environment and cost benefit

Safety and regulations Flex-Fuel Conversion Kit

Methanol (M70) Based Gardening Tools Methanol (M70) Based Portable Generators Fully-Automated Methanol/Gasoline Fueling Station

Future of Natural Gas

An Interdisciplinary MIT Study

2012 FINDING The potential for natural gas to reduce oil dependence could be increased by conversion into room temperature liquid fuels that can be stored at atmospheric pressure. Of these fuels, methanol is the only one that has been produced for a long period at large industrial scale. Methanol has the lowest cost and lowest GHG emissions, but requires some infrastructure modification and faces substantial acceptance challenges. Natural gas derived gasoline and diesel have the advantage of being drop-in fuels, but carry a higher conversion cost. Dimethyl ether (DME)

- H2O 2CH3OH CH3OCH3 b.p. -24.8 °C; m.p. -141 °C

Excellent diesel fuel substitute with a of 55-60 (45-55 for regular diesel) and very clean burning

Already used in spray dispenser DME truck in Japan Non-toxic, Safe and does not form peroxides

Substitute for LNG and LPG

Easy to produce, ship and dispense

 Sootless flame for glass blowing DME bus in Denmark

Advanced methanol-powered 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) M. Beller et al, Nature, 2013, 495, 85-89 Direct oxidation methanol fuel cell (DMFC)Direct Oxidation USC, Methanol JPL - FuelCaltech Cell

e- e- Anodic Reaction: e- - + Pt-Ru (50:50) + - CH OH + H O CO2 + 6 H + 6 e H+ 3 2 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 + CO2 H H2O 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

Methanol, 5 kWh/Liter – Theoretical (2 X Hydrogen)

Absence of Pollutants H O and CO are the only byproducts 2 2 Direct reaction of methanol eliminates reforming Reduces stack and system complexity Silent, no moving parts

Capable of start-up and operation at 20 °C and below Thermally silent, good for military applications

Liquid feed of reactants Effective heat removal and thermal management Liquid flow avoids polymer dryout Convenient fuel storage and logistic fuel Smart Fuel Cells (SFC), Germany 70 Wh to 3 kWh Portable Devices 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

CH3OH Sources

Industrial Production Natural Sources From Wood (wood alcohol) Syn-gas (from coal or natural gas)

Direct Methane Conversion Recently discovered enormous galactical methanol clouds Gasification (460 billion km in diameter near nascent stars) Carbon Dioxide Reduction 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

 Syn-gas from natural gas –

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

Excess H2 generally used for ammonia (NH3) production

 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

 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) Bireforming of methane

-1 Steam reforming2C4+2H2O 2+C6H2OH28 9K=c .5omal9l .1 k

-1 Dry reforming C4+CH2O2+C2H2OH28 9K=c .4omal9l .1 k

Bi-reforming3C4+2H2O+C2O4+C8H2O43OCHH

The production of methanol is generally conducted at pressures of 30 to 50 bars.

Conducting the steam and dry reforming or the bi-reforming at higher pressure would therefore be advantageous to avoid the need for compression of the syn-gas.

US Patent, 7,846,978, December 10, 2010 US Patent, 7,909,559, March 15, 2011 G. A. Olah, A. Goeppert, M. Czaun, G. K. S. Prakash, JACS, 135, 648-650 (2013) G. A. Olah, G. K. S. Prakash, A. Goeppert, M. Czaun, T. Mathew, JACS, 135, 10030-10031 (2013). Dry reforming side reactions

Carbon forming side reactions: Dry reforming of methane at 100 psi Bi-reforming of methane at 100 psi

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

O2

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

R. Periana, H. Taube and others 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 (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 Bio-DME from Black Liquor

CHEMREC pilot Bio-DME filling Volvo DME plant in Sweden station powered truck (4 t/day Bio-DME) Bio-Methanol from

Further expansions in steps of 200 000 kT capacity planned

BioMCN commercial methanol plant with a 200 000 kT/year capacity The Netherlands Efficient Ways to Capture CO2 and Its Electrochemical Conversion

Why Focus on Carbon Dioxide? • Linear molecule

• Very stable – Hard to efficiently reduce

• Trace gas – 0.040% of the atmosphere

– Amount of CO2 in the atmosphere is increasing

• With declining fossil fuel reserves, CO2 will become the best source of carbon US Patent, 7,605, 293, October, 20, 2009 US Patent, 7,608, 743, October, 27, 2009 CO2 separation and Capture technologies

Absorption Adsorption Cryogenics Membranes Algal and microbial systems Alumina Dry ice formation at low temperature Chemical Activated carbon Polymer based MEA, DEA Poly(phenylene oxide) KOH, NaOH, MgO Poly( oxide) Etc. Poly(ionic liquid)

Inorganic Physical membranes Ceramic based Solexol Zeolite based Rectisol Etc.

Regeneration method

Pressure swing Temperature swing Moisture swing And combination thereof Efficient capture from air remains challenging Structure of branched polyethylenimine (PEI)

Reaction of polyethylenimine (PEI) with CO2 Support characteristics Fumed silica synthesis

Fumed silica: primary particle size ~ 7 nm, fluffy powder, very low density

Volume Pore Bulk tapped between volume density particles Absorbent support (cm3/g) (cm3/g) (cm3/g) Presence of large volume

Fumed SiO2 (Aldrich) 0.961 ~ 20 ~ 19 mesopores and Fumed SiO2 (Aerosil 300) 0.714 ~ 20 ~ 19

Fumed SiO2 (Aerosil 150) 0.426 ~ 20 ~ 19 macropores to which PEI

Precipitated SiO2 (Hi-Sil T-600) 0.704 ~ 20 ~ 19 Silica gel 1.094 2.55 ~ 1 can easily access and

still allow facile CO2 diffusion

Adsorption of CO2 from the air at 25 °C on PEI/Fumed Silica Inset: Desorption at 85 °C

Goeppert, A.; Czaun, M.; May, R. B.; Prakash, G. K. S.; Olah, G. A.; Narayanan, S. R. J. Am. Chem. Soc. 2011, 133, 20164 Adsorption of CO2 from the air at 25 °C on FS-PEI-50 (PEI/fumed silica 1/1)

Total CO2 adsorption: 75 mg/g

1.71 mmol/g

CO2 free air 39 mg CO2/g

0.88 mmol/g Breakthrough

CO2 / air

Amount of catalyst : 2.72 g Flow rate: 335 mL/min air

Goeppert, A.; Czaun, M.; May, R. B.; Prakash, G. K. S.; Olah, G. A.; Narayanan, S. R. J. Am. Chem. Soc. 2011, 133, 20164 Adsorption of CO2 from the air at 25 °C on FS-PEI-33. Effect of humidity

Conditions mg/g adsorbent mmol/g adsorbent mg/g PEI mmol/g PEI Dry 52 1.18 156 3.55 Humid 78 1.77 234 5.32

Positive effect Consistent with the of humidity formation of bicarbonates

Humid conditions: 67% relative humidity at 25 °C

In the case of , humidity stops the adsorption of CO2 almost entirely Adsorption of CO2 from the air at 25 °C on PEI/Fumed Silica under dry and humid conditions

FS-PEI-50: 50% PEI in adsorbent FS-PEI-33: 33% PEI in adsorbent

Goeppert, A.; Czaun, M.; May, R. B.; Prakash, G. K. S.; Olah, G. A.; Narayanan, S. R. J. Am. Chem. Soc. 2011, 133, 20164 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)

O

H OCH3

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

Direct Formic Acid Fuel Cell 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 (400 ppm)

Hydrogenation of CO2 Cu/ZnO 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 Water Electrolysis

39.4 kWh/kg H2 needed at 100 % theoretical efficiency In practice closer to 50 kWh/kg H2

At 4 ¢/kWh the cost to produce H2 is about $2.6 /kg Main driver is cost of electricity Capital and operating costs are a minor part of the cost

At 4 ¢/kWh the cost of producing methanol is estimated to be about $0.5 /kg or $1.8 per gallon New Photochemical Processes are also being developed to split water Methanol from Geothermal Sources

CRI Carbon Recycling International

“George Olah CO2 to Renewable Methanol Plant” HS Orka Svartsengi Geothermal Power Plant, Iceland Production capacity: 10 t/day

About 40 kWh needed to produce one gallon of methanol 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 Ubiquitous Methanol as a Fuel and Feedstock

Natural (Shale) Gas (higher hydrocarbons)

Coal CH3OH Biomass, waste or any carbon source

CO2 Low Hanging Fruit The Methanol Economy

Anthropogenic Carbon Cycle

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