2010.12.15. (Wed.)
Takuya Matsumoto (B4)

Literature Seminar

Beyond Oil and Gas: The Methanol Economy

Authoers : George A. Olah, Alain Goeppert, G. K. Surya Prakash
Beyond Oil and Gas: The Methanol Economy. Angew. Chem. Int. Ed. 2005, 44, 2636~2639.
Chemical Recycling of Carbon Dioxide to Methanol and Dimethyl Ether: From Greenhouse Gas to Renewable,
Environmentally Carbon Neutral Fuels and Synthetic Hydrocarbons. J. Org. Chem. 2009, 74, 487~498.

George Andrew Olah was born in Budapest,
Hungary in 1927.
His research involves the generation andreactivity of carbocations via superacids. For
this research, Olah was awarded a Nobel Prizein Chemistry in 1994. He has also been awarded
the Priestley Medal, the highest honor grantedby the American Chemical Society.
George Andrew OlahDistinguished Professor of Chemistry and Chemical Engineering and Materials
Science and Donald P. and Katherine B. Loker Chair in Organic Chemistry

Contents
1. What is the Methanol Economy?
1.1 What is the Methanol Economy? (Overview)
1.2 Why We Must Think the Methanol Economy? (1-7)
1.2.1 Diminishing Fossil Fuels
1.2.1.1 Oil
1.2.1.2 Natural Gas
1.2.1.3 Coal
1.2.1.4 Methane Hydrate

1.2.2 Fossil Fuels and Climate Change

1.3 Why Methanol? (8-10)
1.3.1 Renewable Energy Resources and Atomic Energy
1.3.1.1 Renewable Energy
1.3.1.2 Atomic Energy

1.3.2 Why Not Hydrogen? (the Hydrogen Economy)

1.4 the Methanol Economy (11,13,14)
1.4.1 Methanol and DME
1.4.2 Methanol as a Fuel1.4.3 Direct Methanol Fuel Cell (DMFC)
1.4.4 Methanol-Based Chemicals

2.How to make methanol (12)2.1 Methanol via Syn-Gas
2.1.1 Syn-Gas to Methanol
2.1.2 Fossil Fuels (Methane) to Syn-Gas

2.2 Methanol without Syn-Gas
2.2.1 Direct Oxidation of Methane
2.2.2 Catalytic Gas-Phase Oxidation of Methane
2.1.3 Catalytic Liquid-Phase Oxidation of Methane
2.2.4 Methane into Methanol Conversion throughMonohalogenated Mathanes
2.1.5 Methanol from Methane by Enzyme

2.3 Chemical Recycling of Carbon Dioxide toMethamol
2.3.1 Methanol Production using Cabon Dioxide
as a Carbon Source
2.3.2 Cabon Dioxide Caputuring Methods
11. What is the Methanol Economy?
1.1 What is the Methanol Economy? (Overview)H2 is from electrolysis
of H2O by using
renewable resources
or atomic energy.

High density CO2 fromplans,etc. may be thefirst source but,
ultimately quite low
density CO2 in the air.

Problems must be solved- the efficient way to capture CO2 (Chemistry)- the efficient way to make methanol (Chemistry)- Adapting the society to the Metanol Economy from the conventional fossil fuel economy(Technology, Politics, Economy, etc...)

1.2 Why We Must Think the Methanol Economy?
1.2.1 Diminishing Fossil Fuels
Of the largest 21 fields, at least 9 are in decline. In April,
2006, a Saudi Aramco spokesman admitted that its
mature fields are now declining at a rate of 8% per year(with a national composite decline of about 2%). This
information has been used to argue that Ghawar, whichis the largest oil field in the world and responsible forapproximately half of Saudi Arabia's oil production overthe last 50 years, has peaked.
The world's second largest oil field, the Burgan field in
Kuwait, entered decline in November 2005.
According to a study of the largest 811 oilfields
conducted in early 2008 by Cambridge Energy Research
Associates, the average rate of field decline is 4.5% per
year. The IEA stated in November 2008 that an analysis of
800 oilfields showed the decline in oil production to be
6.7% a year, and that this would grow to 8.6% in 2030.

[wikipedia : Peak Oil]
Hubbert peak theory- The Proved Oil Reserves in 2009 was 1333.1 Thousand Million barrels.
The Oil Consumption in 2009 was 84076.8 Thousand barrels daily.
So, we are left 43.44 years!!!
[From : BP Statistical Review of World Energy June 2010]- In the case of gas, 187.49 Trillion m3 was proved reserves in 2009, the consumption was 2940.4 Billion m3.
So, we left 63.76 years!
2

- Some researchers insist that the oil production in the world experience its peak
between 2005 - 2015, supposing that the 90% of easily recoverable oil has been almost found (thissuppose is based on the assumption that 3/4 of oil reserves in the world exists in about 370 oil fields,
which were completely investigated and that the peak of mining new fields have already passed
in 1960's).
* Oil reserves are the quantities of crude oil estimated to be commercially and technically feasible to mine .
* There are other fosil fuels except oil such as gas, coal, etc...
* So, these data don't simply indicate the end of fosil fules.

It is not without saying that Oil is the most important resources.
(and, gas is next)
Why are fossil fuels so important?

World primary energy consumption[From : BP Statistical Review of World Energy June 2010]

Regional primary energy consumption patterns

Fosil fuels have accounted for more than 90% of primary energy since long before!
Primary energy is energy found in nature that has not been subjected to any conversion or transformation process.
i.e. Solar energy, Wind power, Fossil fuels, Hydro power, Nuclear fuels (Some nuclear fuels, such as plutonium are notfound in nature in any quantity, thus are secondary energy sources), Geothermal power, Tidal power, Wave power,
Biomass etc...

1.2.1.1 Oil
World Oil Consumption in 2008
Industry10%Non-energy
use
16%
Transport
61%
Other
13%

*Other : Includes agriculture, commercial and public
services, residential, and non-specified other.

- Oil is mainly composed of various kinds ofhydrocarbones, including alkanes, alkenes, cycloalkanes,
Aromatic hydrocarbons.
- Oil is used for various kinds of petrochemical products,
but this accounts for only apporoximately 6% of the oil
consumption.
- Main usages of oil are heating, electoronic power,
industry, and overwhelmingly transportation(60%).
- In fact, 95% of fuel used in the transportation sections allover the world is from oil.

[From : Key World Energy Statistics 2010]

Although alternative resources (gas, renewable sources,etc) are started to be used among power plants orindustries, there aren't any prospect of replacement in thecase of transportation.

3

[from : BP Statistical Review of World Energy June 2010]

Oil : Proved reserves (1980-2009)
1400.01200.01000.0
800.0
600.0
400.0
200.0
0.0

Total

Total
North
America
5% Total Africa

Oil : Proved reserves(region)
Asia
Pacific
3%

10%
Total Europe &Eurasia10%- The oil reserve has doubled in the last 30 years,
and R/P ratio hasn't changed much for 25 years.

Saudi Arabia
20%- However, the future demand and prices is (nomatter how modestly I say) uncertain.
(Surely the demand will swell, and preces won't
see its ceiling.)

Iran
10%
Kuwait8%

Total S. & Cent.
AmericaOther
15%
Middle East3%

- What's more, the oil distribution lacks balance.
Iraq
9%

UnitedArab
Emirates
7%

Unconventional Oil Resources- Tar Sand : "dead" oil field- Oil Shale : "pre-born" oil field

It is said that the these resources are the same order or somemore than conventional oil respectively.

1.2.1.2 Natural Gas
World Gas consumotion in 2008
Industry
35%

Other
48%

Transport
6%

Non-energy use
11%- More than 95% of Natural gas is composed of methaneand ethane (in many case methane composes more than90%.).
- Natural gas burns very cleanly, and is easy to use.
suitable fuel for domestic use- Natural gas emmits the least amount of CO2 among all
fossil fuels, and the number of plants using natural gas tomake electricity is getting bigger.

*Other : Includes agriculture, commercial and public
services, residential, and non-specified other.
[From : Key World Energy Statistics 2010]4

Natural Gas : Proved reserves (19802009)
200.00Algeria2%

Other
United Arab
Middle East
Emirates
4%
3%
Saudi
Arabia4%

150.00100.00

Other Africa
3%
Nigeria3%

Total Asia
Pacific9%

Other North Venezuela
3%
America
Other S. &1%
Cent. America
US
4%

1%
RussianFederation
24%

Qatar
14%
Iran
16%

50.00
0.00

Turkmenistan
4%[From : BP Statistical Review of World Energy June 2010]

Other Europe &Eurasia
6%

Natural Gas : Proved reserves in 2009 (region) (> 2%)- Although natural gas emitts only the little amount of CO2 per energy (this is because thehydrogen/carbon ratio of methane is 4, which is the largest among all hydrocarbons.), methane itself has
much stronger (about 23 times) warming effect than CO2.
- Things seem better than oil (R/P ratio is 20 years more), but, the distribution completely loses balance.

The top has 24% of the world reserves and 54% of world's Natural Gas is in top 3!!!
- The biggest problem is methane is GAS under standard condition.
Gas is transported to consuming place from producing place.
In the case that pipeline is out of choice (due to the distance, etc.), gas must be converted into liquid.
There are two choice; 1) one is liquid methane (LNG)
2) the other is synthetic hydrocarbon
1) Liquefaction of mehtane (bp : -162oC) is quite complicated, expencive and enrgy-consuming process,and gigantic LNG tanker can cause disasters.
It is said that the explosion of one LNG tanker gives devastating damage within 500m radiusand second degree burn within 2km radius.
Japan, Korea and Chinese Taipei import more than 60% of LNG!!!
2) Methane is first converted into Syn-Gas (synthesis gas), the mixture of H2 and CO, and thenthis syngas is converted into various hydrocarbons including methanol (vide infa).
But, this Gas to Liquid process also have many problems, especially during this process, 45% of
crude gas is consumed.

Unconventinal Natural Gas Resources- Coalbed Methane : methane adsorbed into the solid matrix of the coal under high pressure- Tight Sands and Shales : methane adsorbed into the solid matrix of tight sands
It is said that the same order or some more than conventional natural gas is exist in coalbed methane.
However, the real reserves are still unclear.

51.2.1.3 Coal
- R/P ratio of coal is more than 150 years,
and at least it is said that coal can be used at least
for two centuries.
(the reason why R/P ratio is less than expected is that
there are not any incentive for developing new mines.
For example, Chinese, 45.6% of all coal was
comsumed in China in 2009 , ratio was only 38 in 2009.)- The reason why we can't rely on coal much is that coal is"dirty" compared with oil and gas.
Burning coal emits quite large quantity of polluting
substances without any care such as NOx, SOx, dust
paricles and heavy metals like Hg, Pb, As, U, etc.
But, the most important pollution is CO2.
- Now, things are being improved.

1.2.1.4 Methane Hydrate- Methane hydrate is a solid clathrate compound in which a large
amount of methane is trapped within a crystal structure of water,
forming a solid similar to ice.
- It is difficult to develop this resource with the present technology,
and how much gas hydrate exists all over the wold is quite
controversial.
- But, one of the achieved consensus is that is huge. (see below)- Anyway, gas hydrate is still unrealistic resource.

[From : National Institute of Advanced Industrial Science and Technology][From : U.S. Geological Survey ]Summary of Fossil Fuels- It is indispensable for useful oil and gas to dry up near future.
- If so, there will be some substitutes such as coal, methane hydrate, etc.
However, these resorce must take more economical and ecological cost.
- So, we must seek other useful and environmental-friendly fuels.
suggestive paper about "the future of coal"
The end of ceap coal. R. Heinberg; D. Fridley, Nature 2010, vol.468, 367~340.

6

1.2.2 Fossil Fuels and Climate Change(a)[From : Marland, G., T.A. Boden, and R. J. Andres. 2005. Global, Regional,
and National CO2 Emissions. In Trends: A Compendium of Data on Global
Change. Carbon Dioxide Information Analysis Center, Oak Ridge National
Laboratory, U.S. Department of Energy, Oak Ridge, Tenn., U.S.A.](b)[From : (a) IPCC, Fourth Assessment Report, Climate Change 2007 :The Physical Scientific Basis (b) IPCC, Third Assessment Report,
Climate Change 2001 : The Scientific Basis ][From : C.D. Keeling, T.P. Whorf, and the Carbon Dioxide
Research Group at the Scripps Institution of Oceanography(SIO), University of California, La Jolla, California USA 92093]- I t is definitely certain that Atmospheric CO2 concentrations has incresed by human activity.
And, it is strongly suggested that the cause of these 140 years' increasing temparature is due tohuman activity.
- As long as we live in present fossil fuel economy, we must continue to upset the balance of global
carbon cycle.
- The storage of CO2 is only the temporary and risky solution.
- However, the prohibitation of carbon is unrealistic.

1.3 Why Methanol?
1.3.1 Renewable Energy Resources and Atomic Energy
1.3.1.1 Renewable Energy Resources- There are many renewable energy resources such as Hydropower, Geothemal energy, Wind enegy,
Solar energy (Photovoltaic or Thermal), Bioenergy, Ocean energy (Tidal, Wave and Thermal power).
- There sources are superior to fossil fuels in terms of CO2 emission, but this fact does not necessarilymean that these are environmentaly-friendly energy sources.
- Each source is obtained from only limited areas all over the world, so able to meet omly the partial ofpresent electronic demands.
In other word, individual resources will never substitute fossil fuels.
(However, we must seek the way to use these resources collaborately.)- The biggest problems of renewable energies are(1) Energy except from bioenergy cannot be reserved, so some carriers are needed to transport.
(2) These energies cannot meet demands for hydrocarbon products directly.

Methanol will be able to solve these problems!!! (vide infa)
7

1.3.1.2 Atomic Energy
Nuclear fission

Uranium : Proved reserves (region)

Nuclear energy : world consumption
3000.02%(1965-2009)

2500.04%

2000.0

5%

2% 2%

3%

2% 1% 3%Australia
Kazakhstan

31%

Canada5%
5%1500.01000.0Russia
5%
9%

500.0

South Africa

12%9%Namibia

0.0

Brazil5 7 9 1 3 5 7 9 1 3 5 7 9 1 3 5 7 9 1 3 5 7 9
6 6 6 7 7 7 7 7 8 8 8 8 8 9 9 9 9 9 0 0 0 0 0
9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 0 0 0 0 0
1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 2 2 2 2 2[From : BP Statistical Review of World Energy June 2010]

Niger[From : Uranium 2009: Resources, Production and Demand]

the number of nuclear power plants
Reactors in operation(1995-2010)

Reactors under construction

104

1

59

54

1

3

61
27 20 19
18 17 17 15 1126
10
10 6
6
2
0
0
0
0

11

* Indonesia and Vietnam are now constructing 4 reactors
respectively (included in 11 other under constructiong).
[From : the Power Reactor Infomation System]- The grouth rate of nuclear energy consumption has rapidly slowed down due to the fear for the safty of
nuclear power among developed countries in recent years, but being rethought in terms of CO2 emission
these days.
And, new reactors are energetically being constructed among developing countries.
- Uranium price, which is stable before, is rising rapidly.
However, the price of uranium is tiny cost of all.
- According to IAEA's 2009 data, R/P ratio of uranium wasabout 85, and it is probable that the reserve swells 6 times!
Moreover, by adopting fast reactor technology,
this period would be lengthen to over 2500 years!! (vide infa)

the energy contained in resources (kcal/g)
150,000

3.5

7

10

11

Wood

Coal

Oil

Natural gas

Uranium(light-water- The safty of nuclear power plants has been reinforced toreactor)incredible level thanks to the anti-nuclear movement.
In the case of radiation, people living in the stone, bick or concrete house are exposed to moreradiation than pelple living in the nuclear power plants' sites.
In fact, nuclear power plant emmits less radiation than coal thermal power plant (the cinder of coalincluds uranium and thorium).

- What's important is that consumer nuclear reactors are never able to explode like nuclear bomb.
(vide infa)- By retreating nuclear fuel and adopting Fast Breeder Reactor, the problem of nuclear wastes will partialy
solved.

The problems with nuclear energy are highly ethical, social and political ones!

8

(Nuclear reprocessing and Fast Breeder Reactor)- The actual fuel of conventional (light-water, one through) reactor is fissile 235U.
One through means the fuel is used only once.
In other words, 238U, composing the most part of fuel, is discarded without any use.
(The reason why consumer nuclear reactors are never able to explode like nuclear bomb is that in thecase of bomb, 235U must be concentrated to at least 90%, and this fuel is used in device speciallydesigned for bomb.)- However, 238U is converted into 239Pu, the more fissile isotope, with fast neutron.
- Nuclear reprocessing is the process to separate useful isotope, especially the remaining uranium andthe newly-created plutonium, from the fission products and other radioactive waste.
- The Fast Breeder Reactor is a fast neutron reactor designed to produce more 239Pu than consumed(therefore, called bredeer).
- It is said that if we adopted this thechnology, we could extend the uranium reserve to double figures.
But, one of the biggest problems of the Fast Breeder Reactor is the treatment of 239Pu.
The half-life of 239Pu is 2.411*104 y (in this connection, 235U is 7.038*108 y, and 238U is 4.468*109 y.)This means 239Pu is much much more radioactive and toxic (the threat of terrorism).
- We must disscuss the risk and benefit of nuclear energy, and make decision based on accuratescientific knowledge.

"No oil, No gas, No coal, No choice."by Claude Mandil, the French General Director for Energy and Raw Materials at the Ministry of Industry
Nuclear fusion (the technology of a few decades later forever)2

D + 3T- There are two ways for achiving nuclear fusion.
(1) Magnetic confinement fusion(2) Inertial confinement fusion

Magnetic confinement fusion (Tokamak type)

6

Li + 1n7
Li + 1n4

He + 1n + 17.6MeV
4

He + 3T
4
He + 3T + 1n'

Inertial confinement fusion (Laser)- The main stream of nuclear fusion today is Tokamak type.
9

- Thinking of many aspects (environmentally effects, the distribution of resources, the safty, etc...),
it is not without saying that nuclear fusion is the best.
- And, the dream of making "artificial sun" is certainly coming.
- However, ITER - a multi-billion-euro international(EU, Japan, South Korea, Russia, India, China,
United States) experiment boldly aiming to prove atomic fusion as a power source - is being faced
ballooning costs and growing delays.
about the difficulties ITER has faced, see:
Fusion reactor faces cost hike. G. Brumfiel, Nature 2008, 453, 829.
Fusion dreams delayed. G. Brumfiel, Nature 2009, 459, 488~489.
Fusion delays sow concern. G. Brumfiel, Nature 2009, 461, 855.
Delays prompt reshuffle at ITER fusion project. G. Brumfiel, Nature 2010, 463, 721.
- We cannot rely on nuclear fusion yet.

Summary of Renewable Resources and Atomic Energy- In the future, we cannot help relying on the nuclear energy with renewable
resources complimenting.
- If so, however, the problems of energy carriers and the alternative source ofhydrocarbon products will be still unsolved.
- So, we must seek other useful and environmental-friendly energy carriers.

1.3.2 Why Not Hydrogen? (the Hydrogen Economy)

Are the hydrogen fuel cells the genome ofpharmaceutical industry?

about the H2 economy, especially the problems of Storage and Delivery of H2, see Mr. Saga's lit. seminar (07/07/10)- Hydrogen doesn't exist as H2 gas in the Earth. H2 is merely a energy carrier.

Energy contained per volume
9000
8000
7000
6000
5000
4000
3000
2000
1000
0

- The energies contained in hydrogen (liquid or highpressure) per volume are less than conventional fuels
or some liquid organic solvents.
- In fact, 10-15% of hydrogen energy is lost during theprocess of compression, and 30-40% duringliquefaction (b.p. of H2 is -252.9oC).
- Small hydrogen gas easilly diffuses through almost
all materials, therefore deteriorates materials,
especially under high pressure and high temperature.

Coal Sources of Hydrogen Electrol
ysis of18%
water
Natural4%
gas
48%
Liquid- H2 is produced almost all from fossile fuels (96%).
(actual procedure of making H2, vide infa)- Electrolysis of H2O costs 3-4 times more than fromfossil fuels.
- H2 gas is important for the Methanol Economy,
and ultimately H2 must be produced from electrolysis
of H2O with electricity from renewable or nuclear
energy in terms of carbon neutral cycle.
- Innovation of this field is strongly desired.

hydroca
rbons
30%

10

(Interesting examples of making H2 from H2O)
(1) Iodine-Sulfur Themochemical Cycle- The pyrolysis of H2O occurs at around 2000oC.
But, by utlizing thermochemical cycle effectively, thisreaction occurs efficientry at around 1000oC.
- This cycle is composed of three steps.
: Bunsen Reaction and decomposition of HI and H2SO4
Bunsen reaction : I2 + SO2 + 2H2O

2HI + H2SO4- This cycle is expected to be achieved with solar thermalenergy or high-temperature future generation nuclear
fission reactor.
(2) Photocatalyst using TiO2 (details see, Mr. Itano's lit. seminar (09/10/05))- The Hydrogen Economy must solve many social, economical or political problems as well as technicalones.
Conventional infrastracturs for oil, natural gas, etc. can't be used for hydrogen.
In other words, for the realization of the hydrogen economy, we must construct infrastructures from the
beginning.
At that time, the hydrogen economy will suffer from a chicken-and-egg headache.
Without enough infrastructure, there will be no demand for hydrogen.
Without enough demands, there will be no incentive for investing.
(Without enough hydrogen stations, who bought hydrogen cars?
And, without enough demands for hydrogen, who built hydrogen station?)As the similar proplem, how do we change over the fossil fuel economy to the hydrogen economy?
Present Japanese or American fire defense law prohibits putting hydrogen refuelinng equipment in gas
stations (transition period problem).
In other words, stations must be run as either gas station or hydrogen station.
(The "merest TV" requires the most careful preparation.)
How about the problems of hydrogen usage by the public without any special scientific knowledge,
usually even the specialist with large knowledge deal with the gas with great care?
- The Hydrogen economy promoting parties may emphasis on the superiority of fuel cell to Internalcombustion engine.
Authors basically agree to that idea, and say that in terms of thermodynamic-energy efficiency,
engine will be taken place by fuel cell (But, authors also emphasis on the engine development during
last 100 years, which fuel cell didn't experience).
But, is it necessary for hydrogen to be transported from hydrogen plants to consumer?
(Is it better to produce hydrogen in the lower stage, for example at hydrogen station
or ultimatelly on vehicles?)Moreover, is it inevitable for fuel cell to use hydrogen other than another energy carrier?

In the view of the quite difficult situation of hydroen usage as fuel,
Energy Secretary Steven Chu announced that the Department of Energy was putting the
breaks on research into automotive hydrogen fuel cells, and cut budgets in May 2009.
Hydrogen Cars : Fad or the Future? science 2009, 324, 1257~1259.

From 1.2 and 1.3, we must think about(1) The energy cariier easily and safly usable by the public, which must be applycable toconventional infrastructures(2) The way to meet demands for hydrocarbon products after the age of fossil fuels(3) Increasing the concentration of CO2 in the atmosphere, which will harm our human beings.

Liquid hydrocarbon, easily obtained from CO2 and converted to other hydrocarbons!!!
11

1.4 The Methanol Economy- Authors advocate that we should use methanol as substitution of oil and dimethyl ether (DME)as that of natural gas.

1.4.1 Methanol and DME- Methanol can be produced by the oxidation of CH4 and the reduction of CO2.
And, DME can be produced easily from the dehydration of methanol.
- Although ultimately methanol should be produced from CO2 in the air, at the biginning it can beproduced from natural gas or other CH4 sources lile methane hydrate and the high comcentrated CO2
from factories or plants, which will be able to slow down the consumptoin of fossil fuels .
- Existing inflastructures for oil (vessels, railroads, trucks, pipelines, etc.) can be used for methanol(although materials must be changed to ones compatible with methanol.).
- A gas station can be converted into a methanol station within million dollars in a weak(A hydrgen station costs more than 10 million!).
- Without taken too much (25~90 ml), methanol is at least as safe as gasoline.
- DME has broad Flammability limit (3.4~17 vol%), which means DME must be handled under strict
safty measure.
However, the direct effects of DME to human body is less than CO2.
Different from some ethers such as diethyl ether, THF, etc., DME doesn't produce peroxide.
(In order to make detectable quantity of peroxide, DME needs to be expose to UV, air and added
some additives.)- As methanol can blend with water infinitry, in the case of outflow into the environment,
methanol rapidly diffuses to get under harmless level density and be decompose by bacteria(In fact, methanol can be "nutrition". vide infa).
- In the case of DME, it vapors and is decomposed in the troposhere, the lowest portion of Earth's
atmosphere (half-life is five days).

Methonol can be produced from CO2 (carbon neutral), adapted to existing inflastructuresand is friendly to both humans and environment !!!

1.4.2 Methanol as a Fuel
MethanolIt seems Methanol and DME will work well!!!

- The histry of attempts to use alchols (methanol and ethanol) as the fuel of Internal-combustion
engine is the histry of Internal-combustion engine itself.
- During World War II, the development of alternative resource had been strongly promoted in termsof the independence of energy.
However, after the war, cheap oil had got easily accessible and the spotlight to alchol has
drastically disappered (since this time, the developmments of these resources has closely relatedwith the oil price).
In 1973, when the oil shock has happened, T.B. Reed and R.M. Lerner advocated the use of methanol(not as the broader part of alchol) as the fuel of Internal-combustion engine for the first time in the US.
(Methanol : A Versatile Fuel foe Immediate Use, Science 1973, 182, 1299~1304.)
This was also the first time the word "the Methanol Economy" was appeared.
In this paper, they reported that 15% methanol blended gasoline had dramatically improved
perfomances, mileage and exhaust gas of vehicles.
In the middle 1980's, the oil price had been drastically fallen and the development of alternative
sources was done only in terms of exhaust gas, vehicles using M85, a blend of 85% methanol and 15%
unleaded gasoline with minimam tuned equipments, proved to work well without any special troubles
by the experiment over 4 years.
(Methanol-Powred Cars Get Ready to Hit the Road, A.S. Moffat, Science 1991, 251, 514~515.)
However, in the beginning of 1990's, some technologies which lesson the exhaust gas dramatically has
been developed one after another, and the interest in methanol, which loses cost to oil, has almost
disappeared again.
- Today, any vehicles can use maximam 10% methanol blended gasoline without any conversion.
And, the conversion to the flexible-fuel vehicle (FFV), an alternative fuel vehicle with an internal
combustion engine designed to run on more than one fuel (usually gasoline blended with either
ethanol or methanol fuel), only costs a few hundred dollars.
This means the transition from oil to methanol is smothlly realized during transition period.
12

- Conventional Internal-combustion engines has been best adapted to gasoline for a century,
so there is no use comparing gasoline with methanol based on present engine.
But, it is said that if the engine adapted to methanol is developed, the milage of that engine will
surpass the gasoline engine.
- As purified methanol and DME don't contained sulfure (no wander!) and C-C bond, which is hardto cut completly, and burn at lower temperature than gasoline, these fuels don't emitt SOx, NOxand particulate matter (Particulate matter is constantly produced in deasel engine, which one of thebiggest problems of this engine.).
In fact, the exhaust gas is expected to clear easily the world's strictest regulation.
- The Problems of methanol are(1) Political or Economical problems (for example, the opposition from oil industry or related groups,
the oil price and the policies of energy security or environmental affairs)(2) Methanol has large dipole moment and permittivity, which make methanol the powerful solvent foreasily ionizing materials such as water, acid, base and some resins.
These harm engines.

Dimethylether- DME can be the substitution for diesel fuel.
The development of DME as a diesel fuel is proceeded more than methanol as alternative to gasoline
because of the exhaust gas problems.
Authors say it is certain DME takes place conventional diesel fuel.
- DME can be also the substitution for LPG (Liquefied Petroleum Gas) as town gas.
- Methanol or DME can be used at Fossil fuel power station without any troubles.
Comparison of phisical properties between DME, Diesel fuel and LPG
main constituents of LPG

Physical property

DME

Diesel fuelb.p. (oC)
Vapor pressure (20oC, bar)
Concentration of liquid(20oC, kg/m3)
Heat of combustion (kcal/kg)
Cetane number
Spontaneous combustion
temparature (oC)
Flammability limit (air, vol%)-24.9

180~360

Propane-42.1

Butane
-0.5

5.1

-

8.4

2.1

668

840~890

501

610

6,880
55~60

10,15040~55

11,090-10,920-350

200~300--

3.4~17

0.6~6.5

2.1~9.4

1.9~8.4

1.4.3 Direct Methanol Fuel Cell (DMFC)- In order to overcome the difficulties of hydrogen storage and transportation, the ways to makehydrogen gas from hydrocarbon on vehicles or at stations on demand are enegetically developed.
- Steam reforming of methanol needs only much lower temparature than other hydrocarbons such as
gasoline, which make reforming equipments able to put on vehicles (vide infa).
Methanol doesn't have C-C bond, in other words, among all hydrocarbons methanol has the mosthydrogen per carbon.
In fact, 1L methanol at r.t. has more hydrogen than 1L liquid hydrogen at -253oC. (The former has 98.9g,
and the latter has 70.8g. Methanol is the more efficient hydrogen carrer than hydrogen itself!)
The fact should be noted that during the liquefaction of hydrogen the 40% of potential hydrogenenergy is lost.
Among the wide varieties of hydrocarbons, methanol is the only liquid one experienced as the fuel ofvehicular fuel cell in practical scale.
- However, the disadvantages of this system are heavy, complicated and expensive(you must carry both fuel cell and steam reforming equipment if you want to get hydrogen on vehicle
on demand.).
- In order to solve some of these problems (heavy and complicated), the way reforming methanol tohydrogen at hydrogen stations is examined.
In this case, reforming equipments need not be carried on each vehicle, but the problem of how tocarry hydrogen efficientry rises again.
13

(Pt/Ru)(Pt)

Electrocatalysis of Direct
Methanol Fuel Cells
From Fundamentals to
Applications. Edited by
Hansan Liu and Jiujun
Zhang. Wiley-VCH,
Weinheim 2009. 606 pp.

- To reform the current situation of hydrogen fuel cells drastically, Direct Methanol Fuel Cells (DMFCs) arebeing developed energetically in the last two decades.
- DMFC is a fuel cell using methanol as a fuel without producing hydrogen gas during the processes.
Anode : CH3OH + H2O
CO2 + 6 H+ + 6 e3 H2OCathode : 1.5 O2 + 6 H+ + 6 eTotal : CH3OH + 1.5 O2

CO2 + 2 H2OGeneral accepted passways
Anode

CathodeCH3OH + Pt
Pt-CH2OH + Pt
Pt-CHOH + Pt
Pt-CHO
Ru + H2O
RuOH + Pt-CO

Pt-CH2OH + H+ + ePt-CHOH + H+ + ePt-CHO + H+ + ePt-CO + H+ + eRuOH + H+ + ePt + Ru + CO2 + H+ + e-

CH3OH + H2O+

CO2 + 6 H + 6 e

O2 + Pt
Pt-O2 + H+ + ePt-HO2 + Pt
Pt-HO + Pt-O + 3 H+ + 3 e-

Pt-O2
Pt-HO2
Pt-OH + Pt-O
2 Pt + 2 H2O

O2 + 4 H+ + 4 e-

2 H2O

-

- The Problems of DMFC are(1) The diffusion of methanol from anode to cathode makes this system quite inefficient although theideal efficiency is around 97% (new membranens best adjusted to methanol is strongly eagered).
(2) Noble metals, in fact Platinium Metal Groups, the most expensive ones during noble
metals, must be used as electrodes to proof against highly acidic conditions.
This is a common problem with fuel cells run under acidic conditions.

Toshiba Dynario : the first commercially mass produced DMFC charger
Yamaha FC-Dii : DMFC-drive motorcycle
about DMEC see:
DMFCs : From Fundamental Aspects to Technology Development.
A.S. Arico; S. Srinivasan; V.Antonucci, Fuel Cells 2001, 1, 133~161.
International activities in DMFC R&D : status of technologies and potential applications.
R. Dillon; S. Srinivasan; A.S. Arico; V. Antonucci, Journal of Power Sources, 2004, 127, 112~126.

14

Direct Hydrazine Fuel Cell (another interesting Direct Fuel Cell)
A Platinum-Free Zero-Carbon-Emission Easy Fuelling Direct Hydrazine Fuel Cell for Vehicles.
H. Tanaka, et al. Angew. Chem. Int. Ed. 2007, 46, 8024~8027.
(reported by scientists of Daihatsu Motor Co., Ltd., National Institute of Advanced Industrial Science and Technology,
Otsuka Chemical Co., Ltd. and Kobe University)

CNG = compressed natural gas.

Sample
a
b
c
d
e
f
g

Fuel
Anode
CathodeHydrazine
Ag/C
Ni
Hydrazine
Ag/C
Ni
Co-PPY-C Hydrazine
Ni
Hydrazine
Ag/C
Co
Hydrazine
Ag.C
Co
Methanol
Pt/C
Pt-Ru/C
Hydrogen
Pt/C
Pt/C

Polymer
Anion A
Anion B
Anion A
Anion A
Anion B
Naflon
Naflon

PPY: polypyrrol.
cell temperature: 80oC. Hydrazine was dissolved (0.67m) in 1m KOH
aqueous solution. a~e) Hydrazine (+20 kPa); f) methanol (+100 kPa); g)hydrogen (+20 kPa).
Two types of anion-exchange polymer electrolytes both containtetraalkylammonium cation groups as pendant groups with a polyolefin
main chain.
The chemical constitution of electrolyte A is homogeneousand that of electrolyte B is heterogeneous.

Durability test of direct hydrazine anion-exchange PEFCs.
Current density: a1, d1; internal resistance: a2, d2(a corresponds to the Ni anode catalyst; d corresponds to
the Co anodecatalyst).

Influence test on
carbon dioxide
poisoning of anionexchange PEFC
sample d(Co,Ag/C,
hydrazine,Anion A).
The test was
conducted withincreasing CO2
concentration.

- Run under alkali condition, platinium groups metal-free-erectrode fuel cell exhibiting equivalent
power generation characteristics to the conveninal hydrogen fuel cell using Pt/C erectrode.
- Hydrazine can be made from N2 in the air, salt (NaCl) and H2O efficientry (the total energy
efficiency is 79%!).
- Although ideal erectronode is noble metals free (sample c), the performance with the Co anodecatalyst decreases drastically after 40 h.
However, it is good enough if the Ni anode catalyst and Ag/C cathode catalyst work properly for apractical period (sample a and b).
- In the case of DMFC, it is predicted that the high concentration CO2 at anode catalyst decreas theperfomance.
But, these result can be useful knowledge to DMFC to some extent.
15

1.4.4 Methanol-Based Chemicals
key word : C1 chemistry
Dimethyl ether(DME)

OlefineGasoline

Ethylene, Propylene

Polyethylene, Polypropylene

Aromatic hydrocarbons
Formaldehyde
Methyl t-butylether(TMBE)
Acetic acidAcetaldehyde
Acetic anhydride
Chloromethane
Methanol

Urea Resin
Bakelite
Melamine resin
Xylene resin
Polyacetal
Methane-diisocyanate (MDI)
Butane diol
PolyolIsoprene
Hexamine (1,3,5,7,-tetraazaadamantane)other

Ethyl methacrylate(MMA)

Poly(methyl methacrylate) (PMMA)
Methacrylate ester
Paint resin

Methyl formate

Formamide
HCN
Formic acidN,N-dimethylformamide (DMF)

Methyl amine

Methyl ethanol amine
Dimethyl acetic amide (DMAC)
Tetramethyl ammonium hydroxide(TMAH)
Carbamic acid ester
Fatty amine

Dimethyl terephthalate(DMT)

Polyethylene terphtalate (PET)

HydrogenSingle Cell Protein
Biochemical products
otherSingle Cell Protein ("Food from Oil")- Single cell protein (SCP) typically refers to sources of mixed protein extracted from pure ormixed cultures of algae, yeasts, fungi or bacteria used as a substitute for protein-rich foods, inhuman and animal feeds.
Large-scale production of microbial biomass has many advantages over the traditional methods for producing
proteins for food or feed.
1. Microorganisms have a high rate of multiplication to hence rapid succession of generation(algae: 2~6 hours, yeast: 1~3 hours, bacteria: 0.5~2 hours).
2. They can be easily genetically modified for varying the amino acid composition.
3. A very high protein content 43~85 % in the dry mass.
4. Strains with high yield and good composition can be selected or produce relatively easily.
5. Microbial biomass production occurs in continuous cultures and the quality is consistent since the growth isindependent of seasonal and climatic variations.
6. Land requirements is low and is ecologically beneficial.
7. A high solar energy conversion efficiency per unit area.
8. Solar energy conversion efficiency can be maximized and yield can be enhanced by easy regulation of physicaland nutritional factors.
9. Algal culture can be done in space which is normally unused and so there is no need to compete for land.
[From : Wikipedia, Single Cell Protein]16

Summary and Future Outlook of "the Methanol Economy"- Methanol is easy to store and transport and environmentaly and phisically harmless.
Moreover, methanol has most hydrogen among all organic compounds.
These mean methanol is one of the best energy career.
- Methanol will be produced at first from high-concentration CO2 emmited by industies in the near
future, and this multi-times utilization of unrecorverable resources will slow down (or at least steady)the spead of fossil fuels consumption.
And, ultimately CO2 in the air will be the source of methanol, completing a carbon neutral cycle.
- Currently, sutudies on materials are now on enthusiatically going in order to adjust conventional
equipments and infrastructures to methanol and DMF for the realization of the metahnol economy.
- Petrochemical products can be produced also from methanol, and Internal-combustion engine andfuel cell can work with methanol and DME.
These fuels can be used as town gas and at fossil fuel power stations.
- In the case of transportation, at first Flexible-Fuel Vehicle will be introduced, next M100 (Methanol100%) Vehicle, and then Direct Methanol Fuel Cells wil take place Internal-combustion engines.

As far as I read the book, even with current thechnology, methanol alreadyhas the ability to replace present fossil fuels completely.
However, the biggest problem of the methanol economy,
I think, is...

How to make this fundamental liquid efficiently(The price of methanol decides all following!!!)This is where we chemists can give the greatest contributions!

17

2.How to Make Methanol- Today, almost all methanol is produced from Syn-Gas (synthetic gas).
Syn-Gas is the mixture of CO and H2 including little amount of CO2.
Syn-Gas is obtained from any carbon allotropes or hydrocarbons used with O2 and/or H2O together.
Among all carbon sources, natural gas (methane) is used the most because of the least impuryties.

2.1 Methanol via syn-Gas
2.1.1 Syn-Gas to Methanol
CO + 2 H2

CH3OH∆H298K = - 21.7 kcal/mol

CO2 + 3 H2

CH3OH + H2O ∆H298K = - 11.9 kcal/mol

CO2 + H2

CO + H2OS=∆H298K = 9.8 kcal/mol(moles H2 - moles CO2)
(moles CO + moles CO2)

- Methanol is produced from Syn-Gas on heterogenious catalyst along the three epuations above.
These reactions are all reversible, so the yield is strongly dependent on conditions.
- The composition of Syn-Gas is usually indicated by stoichiometory value S.
The ideal S value for synthesizing methanol is 2 or a little more.
- As I mentioned, natural gas includes least ammount ofotherMitsubishi Kellogg
3%
1%
Gas
impurities of all fossil fuels, especially sulfur.
ChemicalThe quite little amount of sulfur destroies catalyst systems.
CompanyLurgi
8%
By using clean Syn-Gas from natural gas, more efficient and27%
Johnsonmilder catalyst systems had been realized.
Matthey61%- Today, the methanol producing processes converge on only
a few ones : Johnson Matthey, Lurgi, MGC, Kellogg and other.
- These processes all use catalyst, mainly composed of
CuO/ZnO, under 50~100 atm at 200~300oC.
Share of total installed capacity- The latest plants produce methanol 99% selective andmore than 70% energy efficiency.
[From : Johnson Matthey]

2.1.2 Fossil Fuels (Methane) to Syn-Gas- Steam methane reforming, carbon dioxide methane reforming and oxy methane reforming are
the three basic processes for the production of Syn-Gas.
And, in actual plants, two or three pocesses are combined for the adjustment of S value orthermochemical viewpoint.
Process

Reaction

Steam reforming CH4 + H2O
Oxy reforming(Partial oxidation) CH4 + 1/2O2
CO2 reforming
CH4 + CO2
(Dry reforming)

H2/CO ratio∆H298K (kcal/mol)

CO + 3H2

3:1

49.1

CO + 2H2

2:1

- 8.6

2CO + 2H2

1:1

59.1

Steam Reforming and Water Gas Shift
CH4 + H2O

CO + 3H2∆H298K = 49.1kcal/mol(Steam reforming)

CO + H2O

CO2 + H2

∆H298K = - 9.8kcal/mol (Water gas shift)- During steam refoming, methane reacts endothermic with H2O to give CO and H2 on the surface ofNi catalyst at high temperature (800~1000oC).
Obtained CO reacts with another H2O to give CO2 and H2 (Water Gas Shift).
These processes givinig four H2 from one methanol is a quite efficient process for obtainig H2.
In fast, 50% of H2 produced all over the world and 90% in the US are obtained from these processes.
By adjusting temperature or pressure, the second step can be decleased.
- The S value is three, so H2 is excess.

18

- Carbon from reactions below destroies the catalyst and reactor, so excess amount of H2O or
short remaining time are needed.
CH4

C + 2H2∆H298K = 18.1kcal/mol

2CO

C + CO2∆H298K = - 40.8kcal/mol (Boudouard reaction)

Oxy reforming (Partial oxidation)
CH4 + 1/2O2

CO + 2H2∆H298K = - 8.6kcal/mol- During oxy refoming, methane reacts exothermic with insufficient O2 to give CO and H2 on thesurface of Ni catalyst or non-catalyst at high temperature (800~1500oC).
- The biggest advantage of this process is the ideal ratio Syn-Gas (S = 2) is obtained.
- However, the biggest problem is undesirable oxidations of H2 and CO.
Emitted heat of which are so high that these reactions are problems not only for the uselessconsumption of resources but also for fear of safty.
more details about Syn-Gas production through catalytic oxy reforming see:
Energy-Efficient Syngas Production through Catalytic Oxy-Methane Reforming Reactions.
T. V. Choudhary; V. R.Choudhary, Angew. Chem. Int. Ed. 2008, 47, 1828~1847.

CO2 reforming (Dry reforming)
CH4 + CO2

2CO + 2H2

∆H298K = 59.1 kcal/mol- Since this reaction doesn't include H2O, this reaction is called "Dry".
During the dry refoming, methane reacts exothermic with CO2 to give CO and H2 on thesurface of Ni catalyst at high temperature (800~1000oC).
- The S value is one, so H2 is defficient.
- This prosess gives the efficient way for synthesizing metahnol from CO2.

Syn-Gas from other Fossil Fuels
from Petroleum Oil and Higher Hydrocarbons
CnHm + n H2O
CnHm + n/2 O2n CO + (n + m/2) H2
n CO + m/2 H2(Steam reforming)(Oxy reforming)from CoalC + 1/2 O2CO

C + H2O

CO + H2

CO + H2O

CO2 + H2 ∆H298K = - 9.8 kcal/mol

C + CO2

2CO∆H298K = - 29.4 kcal/mol (Oxy reforming)(Steam reforming)∆H298K = 31.3kcal/mol∆H298K = 40.8kcal/mol(Boudouard reaction)

Combinations of three basic processes(1) Autothermal reforming- Autothermal reforming is the combination of endothermeric Steam reforming andexothermeric Oxy reforming.
In this process, the addition or elimination of large amount of heat aren't needed, in other words,"Autothermaly".
- This prosess is used in the latest methanol plants.
Although each step is conducted in one pot, since the optium reaction temperature and pressure aredifferent from each other, each step is conducted step by step.

19

(2) Bireforming
3CH4 + 2H2O + CO2

4CO + 8H2

4CH3OH- Bireforming is the combination of Steam reforming and Dry reforming.
Fundamentally, Steam reforming produces exess amount of H2, and Dry reforming does insufficient.
So, both complement each other.
- Since the optium reaction temperature of both is close, these reaction can be conductedin one step.
Both reactions are endothermic, so the energy must be added from external sources, for example
atomic energy, renewable resources, etc.
- There are no byproducts in this process, and according to the author, this is present one of the mostefficient ways to synthesize methanol from CO2! (utilizing hydrogens of methane to the maximum)(3) Trireforming- Trireforming is the combination of all three basic processes.
more details about Tri-reforming see:
Tri-reforming of methane : a novel concept for catalytic production of industrially useful synthesis gas with desired H2/CO rations.
Chunshan Song; Wei Pan, Catalysis Today 2004, 98, 463~484.

(Methanol from Methyl Formate)
CH3OH + CO
HCOOCH3 + 2H2
CO + 2H2

HCOOCH3
2CH3OH
CH3OH

In order to reduce the high temperature and pressure
required present methanol productions and to improve
the thermodynamic efficiency, alternative milder
methanol production process utilizing H2/CO has beenstudied for a long time.
Among them, the most remarkable one, authors say, isthe route from methyl formate first proposed in 1919.

- This process is composed of two phases; 1) Carbonylation of methanol giving methyl formate,2) Hydrocracking of methyl formate giving two methanol.
Reactions can be conducted under 10~50 atm and at 80~120 oC (conventional way is under 50~100 atm
and at 200~300 oC).
- First step is catalized by CH3OK or CH3ONa in liquid phase, and second catalized by Cu systems in gas
or liquid phase.
Althogh these reactions are usually conducted in different reactors, studies to conduct these reactions
in one pot are now undergoing (In fact, in the case of second step, Ni systems give high reactivity andselectivity, but Ni has the possibility of producing highly toxic Ni(CO)4).
Since carbonic acid destroies methoxide in the first step, H2O and CO2 in Syn-Gas must be removed
thoroughly.
- Methyl formate can be obtained from folmaldehyde (esterification with methanol) or formic acid
(Cannizzaro-type reaction), the peroxidated products during direct oxidation of methane to methanol.
This suggsts the possibility of mild and efficient way for synthesizing methanol without Syn-Gas.

2.2 Methanol without syn-Gas- As mentioned, 50% of organic compounds in nature is methane, and the reserve is fuge.
Conventional Syn-Gas method is fundamentally inefficient because methane is first oxidized to CO/H2,
and then various organic compounds including methanol are produced through reduction.
Ideally methane should be oxidized directrly to methanol by oxygen used as a terminal oxidant.

2.2.1 Direct Oxidation of Methane- It's idal to use only oxygen, but it's quite difficult to realize both high conversion and selectivity.
In fact, oxidized products (CH3OH, HCHO, HCOOH) are oxidized easier than methane itself.

CH4∆H298K

CH3OH- 30.4 kcal/mol- 35.6 kcal/mol

HCHO

CO
- 58.1 kcal/mol

CO2- 67.8 kcal/mol- Remarkable results are reported by groups in Tokyo Institute of Technology in 2010.
They obtained oxidized products (methanol and formaldehyde) from the methane and oxygen mixed gas
in around 30% yield under atmospheric pressure at r.t. for the first time by utilizing Atmosphericpressure plasma conducted in capillary (1.5mm diameter, 5cm long).
about this work see: Associate Professor Tomohiro Nozaki's homepage and publications therein (http://www.plasma.nu/index.html)
20

2.2.2 Catalytic Gas-Phase Oxidation of Methane- In homogeneous catalytic gas-phase oxidative reaction, methane is reacted with oxygen under highpressure (30~200 atm) at high temperatue (200~500 oC).
- To controll the unexpected production of CO2, oxygenates (CH3OH, HCHO, CO, HCOOH) are collectedwith non-react methane cyculated.
- As mentioned, folmaldehyde and folmic acid can be converted into methanol.
- Many catalysts have been reported for now, but most of them lack reproducivility.
And, the methane conversion rates don't exceed 10%.
- A notable result was obtained from FePO4 utilized with H2-O2 gas or H2-N2O gas.
In this system, binuclear Fe unit, the same as natural MMO (Methane Monooxygenase)(vide infa),
bridged multiply by phosphoric acid catalyzes reactions.
What's interesting is both Fe and P play important roles.
(V, Cr, Mn, Co, Ni, Cu, Zn, Al and Zr didn't gave any oxygenates, and the conversion rate of FeAsO4
was about one-fourth of FePO4's and FeSbO4 was one-eighth.
- By using N2O insted of O2 as a oxidant, almost 100% selectivity was realized at 500 oC in 3% yield.
However, N2O has the strongest potential of destroying ozone layer and global warmin effect.
In fact, the emmition of N2O is strictly regulated, and thinking of production cost it won't be a attractive
choice.
- In the case of O2, it's difficult realizing both high conversion rate and selectivity.

Effect of H2 on the rate of CH4 conversion(A) and the product selectivity (B).
(A) (a) in the presence of 50 kPa H2; (b) in
the absence of H2.
(B) circle CH3OH; square HCHO; up top
triangle CO; down top triangle CO2.
Black symbols, in the presence of 50 kPa
H2; white symbols, in the absence of H2.
Reaction conditions: P(CH4)=33.8 kPa,
P(O2)=8.4 kPa and W/F=0.208 g h/dm3.

about FePO4 see: Direct conversion of methane into oxygenates.
Kiyoshi Otsuka; Ye Wang, Applied Catalyst A: General 2001, 222, 145~161.

2.2.3 Catalytic Liquid-Phase Oxidation of Methane- In order to decrease the generation of byproducts and increase the selectivity of methanol and in termsof industrial process, it's ideal to do reaction at lower temperature (< 250oC).
This drove to the reserches on catalytic liquid-phase methane oxidation.
- In 1970's, G. A. Olah and coworkers reported that they obtained methanol from methane in high yieldand selectivity at r.t. by utilizing superacid media (SbF5/HF) and H2O2.
However, these reaction are stoichiometric or use expensive reagents and thus are not practical
for the large-scale.
- Highly efficient and selective homogenious metal catalyzed conversion was first reported in 1993.
In this reaction, the oxidation of methane is catalyzed by Hg(II) in 100% sulfic acid to produce methyl
bisulfate, water and sulfur dioxide under mild condition (180oC).
50% methane conversion and 85% selectivity to methylbisulfate (the major byproduct is CO2) was
achieved.
The Hg(II) ion reacts with methane to produce CH3HgOSO3H.
Under the reaction conditions, this compound readily decomposes to CH3OSO3H and the reduced
species Hg2(II).
The catalytic cycle is completed by the reoxidation of Hg22+ with H2SO4 to regenerate Hg(II).
21

CH4 + 2H2SO4Metal

CH3OSO3H + 2H2O + SO2- Since Hg is higily toxic, other metals, especially platinium group metals such as Pt, Ir, Rh, Ru and Pd,
have been investigated.
Among them, Pt complex in sulfonic acid gave the best result (> 70% yield, 90% selectivity).
(The AuI/AuIII redox cycle using H2SeO4 in 96% H2SO4 was also reported .)C-H Activation :Hg(OSO3H)2 + CH4

CH3HgOSO3H + H2SO4

Functionalizaion :CH3HgOSO3H + 1.5 H2SO4
Reoxidaion :0.5 Hg2(OSO3H)2 + 1.5 H2SO4

CH3OSO3H + 0.5 Hg2(OSO3H)2 + H2O + 0.5 SO2Hg(OSO3H)2 + H2O + 0.5 SO2- The problems of these systems are1) The separation of CH3OSO3H from H2SO4 and following the deompotision to CH3OH are quite energy
consuming process.
2) The harsh conditions (> 85% H2SO4, ~ 200oC (although lower temperature than other processes)) areneeded because produced H2O or CH3OH bind much more tightly to the catalyst than CH4, the poorest
ligand. This destroies catalitic systems.
- Other types of catalyst systems (using cheaper metals or less acidic media) are strongly eagered.
the review of methal catalyzed methane oxidation, including the concepts and designs of catalysts and reaction systems see:
Perspective on some challenges and approaches for developing the next generation of selective, low temperature, oxidation
catalysts for alkane hydroxylation based on CH activation reaction.
R.A. Periana, et al., J. Mol. Catal. A: Chem. 2004, 220, 7~25.
about each metal catalyst see:Hg : A mercury-catalyzed, high-yield system for the oxidation of methane to methanol.
R.A.Periana, et al., Science 1993, 259, 340~343.
Pt : Platinum Catalysts for the High-Yield Oxidation of Methane to a Methanol Derivative.
R.A.Periana, et al., Science 1998, 280, 560~564.
Au : Selective oxidation of methane to methanol catalyzed, with C-H activation, by homogeneous, cationic gold.
R.A.Periana, et al., Angew. Chem. Int. Ed. 2004, 43, 4626~4629.

2.2.4 Methane into Methanol Conversion through Monohalogenated Mathanes- Another type of conversion is through catalytic monohalogenation of methane followed by hydrolysis
giving methanol and hydrogen halide.
The catalytic cycle is completed by the oxidation of hydro halogens to halogen by uisng oxygen.
- The classical hlogen displacement reaction of methane is free radical reaction.
However, there are no selectivity to mono substituted.
- In 1970's, Olah and coworkers reported that methane reacted with SbF5-Cl2 or Br2 in SO2ClF solution
at -78oC to give CH3Cl and CH3Br high selectively although the yield was quite low.
- Olah and coworkers also reported in 1985 that the catalytic monohalogenation (chlorination andbromination) of methane was achieved over either supported solid acid (such as FeOxCly/Al2O3,
TaOF3,/Al2O3, NbOF3/AI2O3, ZrOF2/Al2O3, SbOF3/Al2O3, SbF5/C, and Nafion-H/TaF5) or platinum metal(Pt/Al2O3 and Pd/BaSO4) catalysts. The reactions were carried out at temperatures between 180 and 250o
C giving 8~58% conversions with selectivity in methyl chloride (bromide) generally exceeding 90%.
Limited methylene halide formation accompanies the reactions, but no formation of haloforms or carbon
tetrahalides was observed.
In order to avoid byproducts such as methylene halide or ethane formation, excess amoun of methane is
used.

22

- Thinking of the catalytic cycle of halogenes, Br is better than Cl in that Br- is easily oxidized to Br2 byoxygen even though the conversion of HCl to Cl2 by oxygen as a terminal oxidant is practicabele inindustrial scale.
- In the case of iodine, Periana and coworkers reported that elemental iodine dissolved in 96 % H2SO4
containing 2.5% SO3 generates a stable, active species that catalyzes the functionalization of methane tomethyl bisulfate at 195 oC in 45% yields (based on methane) at 95% selectivity (the rest is CO2).
The reaction mechanism is thought to be the same as the case of Hg, Pt and Au.
- Another problem of this monohalogenated species seems to be the difficulty of hydrolisis to obtainmethanol.
Of course, the excess amount of water shifs the equillibrium to the methanol formation, but the
separation of a littele amount of methanol from excess amount of water may be the quite energy
comsuming process.
Idealy, methanol should be obtained from CH3X with as littele amount of water as possible.
Olah and coworkers also reported catalytic hydrolysis of methyl halides over γ-Al2O3-supported metaloxide/hydroxide catalysts such as ZnO/AI(OH)3/γγ-Al2O3.
However, the conversion rates never exceed 10%.
And, it was also found that the little the ratio of water is, the more DME is produced.
In fact, when H2O/CH3Cl = 5, more than 50% is DME.
- There are many difficulties with this monohalogenated methane method, BUT in terms of Japanese
middle term National Element or Security Polycy, this method may be one of the solutions to Japanesefuel affairs.
Japan is said to be one of the richest countries with methane hydrate.
For now, large quantity were found on Pacific side.
Bromine is obtained from sea water, and what's quite important is Japan has the most reserve of iodine
in Chiba Prefecture all over the world (In fact, Chiba Prefecture has more than 60% of world's reserve!).

Distribution of methan
hydrate around Japan[From : ResearchConsortium for
Methane Hydrate
Resources in Japan]

about the chlorination
by super acid see:Electrophilic Reactions at Single Bonds. XVII. SbF5, AICl3, and AgSbF6, Catalyzed Chlorination and Chlorolysis of Alkanes andCycloalkanes. G.A. Olah, et al., J. Am. Chem. Soc. 1973, 95, 7686~7692.
by supported solid acid and subsequent hydrolysis see:
Selective monohalogenation of methane over supported acid or platinum metal catalysts and hydrolysis of methyl halides overγ-alumina-supported metal oxide/hydroxide catalysts. A feasible path for the oxidative conversion of methane into methyl
alcohol/dimethyl ether. G.A. Olah, et al., J. Am. Chem. Soc. 1985, 107, 7097~7105.
about process for converting hydrogen chloride to chlorine see:
Process for Converting Hydrogen Chloride to Chlorine. T.T. Tsotsis, et al., Ind. Eng. Chem. Res. 1994, 33, 2996~3003.
about methyl bisulfate conversion via iodo mehtane see:High yield conversion of methane to methyl bisulfate catalyzed by iodine cations. R.A. Periana, et al., Chem. Commun. 2002,
2376~2377.

232.2.5 Methanol from Methane by Enzyme- In nature, enzyme called MonoMethane Oxygenase (MMO) performs the conversion of methane tomethanol.
MMO is the first enzyme in the metabolic pathway of methanotrophs, bacteria that use methane as theirsole source of carbon and energy. There are two kinds of MMO systems.
One is a solble form (sMMO), and the other is membrane-bound or particulate form (pMMO).
Although pMMO is universal among all methanotrophs, and sMMO is expressed by limited number ofmethanotrophs only under copper-deficient conditions, sMMO has far attracted most of the attentions
because it is much easier to be purified than pMMO.
On one hand sMMO contains carboxilate-bridged non-heme dinuclear ion center at its active site, on theother hand pMMO does mono or dinuclear copper center.

- As another type of enzyme oxidizing hydrocarbon, P450, which has ion-porphyrin complex at its active
cite, has also drown attantions.
Although the yield is low, genom engineered P450 enzyme which has the ability to oxidize ethane toethanol has reported.
- Utilizing or mimicing these enzymes are interesting in terms of using base metals as catalyst.
However, the fact natural catalytic cycles aren't completed until coenzymes activated by solar energy
complement them should be noted.
This fact means additional energy are needed to oxidize methanol, and at application stage theseenergy may not be from solar power, but hydrogen or something.
Ideally, methane should be oxidized without any external energy carrier.
the reviews of sMMO see:
Mechanistic studies on the hydroxylation of methane by methane monooxygenase.
M.-H. Baik; M. Newcomb; R.A. Friesner; S.J. Lippard, Chem. Rev. 2003, 103, 2385~2419.
Dioxygen activation by enzymes containing binuclear non-heme iron clusters.
B.J. Wallar; J.D. Lipscomb, Chem. Rev. 1996, 96, 2625~2657.
Enzymatic activation of alkanes: constraints and prospective.
M. Ayala; E.Torres, Appl. Catal. A: General 2004, 272, 1~13.
about pMMO see:
Crystal structure of a membrane-bound metalloenzyme that catalyses the biological oxidation of methane.
R.L. Lieberman; A.C. Rosenzweig, Nature 2005, 434, 177~182.
Conversion of Methane to Methanol at the Mononuclear and Dinuclear Copper Sites of Particulate Methane Monooxygenase(pMMO): A DFT and QM/MM Study.
K. Yoshizawa; Y. Shiota, J. Am. Chem. Soc. 2006, 128, 9873~9881.
about engineer enzyme oxidizing ethane to ethanol see:
The heme monooxygenase cytochrome P450cam can be engineered to oxidize ethane to ethanol.
F. Xu; S.G. Bell; J. Lednik; A. Insley; Z. Rao; L.-L. Wong, Angew. Chem. Int. Ed. 2005, 44, 4029~4032.

Summary of 2.1 and 2.2

These methods above all depend on methane as carbon source.
However, for the realization of carbon neutral economical cycle,
we should use carbon dioxide as carbon source!
24

2.3 Chemical Recycling of Cabon Dioxide to Methanol
2.3.1 Methanol Production using Cabon Dioxide as a Carbon Source- It is not difficult to synthesize methanol from H2 and CO2, and chemists had already recognized
how to do this conversion in the early 20th century.
In fact, in the methanol plants working in the US during 1920's to 1930's, CO2 from byproduct offermentation was widely used.

CO2 + 3H2

CH3OH + H2O- Pilot plants and commercial plants start working in these five years.
The catalysts for these plants are Cu/Zn systems quite similar to those for metanol production
from Syn-Gas (H2 + CO), and reaction temperature is also close.
A pilot plant of Mitsui Chemicals (started working on May 2009) (Japan) realized 95% H2 and CO2
conversion and 99.8% methanol selectivity by single path.
- However, what I want you to note is the one-third of H2 is in principle consumed merely for thegeneration of H2O only by reactiong CO2 with H2 (the compression of H2 consumes 10~20%, and theliquefaction does 30~40%.).
Since H2 is obtained from methane at present (or even if the efficient electrolysis is developed in the
future), I can't help but saying this method is far from perfect.
This problem arises from the simple fact that the numbers of oxygen of CO2 and CH3OH are different fromeach other.
- The conversion CO2
CO + 0.5 O2. is ideal, but the ways for doing this efficiently don't exist still.
- Here, I want to forcus on how to incorporate CO2 with conventional CH3OH production methods.

In the book, authors introduce three methods:
1) The Combination of Methane Pyrolysis and Methanol Synthesis
2) The Combination of Methane Pyrolysis and Dry Reforming3) Bireforming (the Combination of Steam Reforming and Dry Reforming)

1) The Combination of Methane Pyrolysis and Methanol Synthesis> 800oC

CH4
CO2 + 3H2

C + 2H2 ∆H298K = 17.9 kcal/mol
CH3OH + H2O

3CH4 + 2CO2

(Methane Pyrolysis)(Methanol Synthesis)

2CH3OH + 2H2O + 3C

2) The Combination of Methane Pyrolysis and Dry Reforming
CH4 + CO2

2CO + 2H2

CH4

C + 2H2

2CH4 + CO2(Dry Reforming)(Methane Pyrolysis)

2CO + 4H2 + C

2CH3OH + C

3) Bireforming (the Combination of Steam Reforming and Dry Reforming)

CH4 + CO2

2CO + 2H2

(Dry Reforming)

CH4 + H2O

CO + 3H2(Sterm Reforming)

3CH4 + 2H2O + CO2

4CO + 8H2

4CH3OH1)

2)

3)- CO2/CH4 value indicates how effective the process recycles CO2.

CO2/CH4

2/3

1/2

1/3

CH3OH/CH4

2/3

1

4/3

- CH4/CH3OH value indicates how effective the process produces
CH3OH.

CO2/CH3OH

1

1/2

1/4

The lager each value is, the better- CO2/CH3OH value indicates how effective the process decreases
total CO2 emission (because CH3OH becomes CO2 after utilized).
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- Evaluations of these three processes should be based on all three values.
Based on this, the process 1) is virtually zero CO2 emission because carbon of utilized CH4 is fixd to C
(Solid carbon is much easier to store than gas CO2, and can be sold as material).
The process 3) is the best way producing CH3OH by using CO2.
And, the process 2) is the middle of them.
You can see that there is no way to realize efficiently both reduction of CO2 emission andincrease of CH3OH production.
- By the way, Carbon can be used as carbon source of another CH3OH via Boudouard reaction if external
H2 is added.
However, in terms of carbon neutral cycle, these steps are nonsense because all efforts to fix CO2
will be in vain.
This is an effective way for producing CH3OH from coal and CO2 (Coal Gasfication).

(Boudouard Reaction)

C + CO2

2CO

CO + 2H2CH3OH (Methanol Synthesis)

C + CO2 + 4H2

2CH3OH- As mentioned, ideally CH3OH is produced from CO and H2 via CO2
CO + 0.5 O2.
- For realizing this decomposition efficiently, electrolysis of CO2 in solvent such as water or organic one
and metal oxide-catalyze pyrolisis are studied (both are the same methodology as water decomposition).
Especially, electrolysis of carbonated water gives H2 and CO simultaneously.
Metal oxide-catalyze pyrolisis is first the deoxygenetion of high valent metal oxide under O2 depleted
condition at extremely high temperature.
Next, low valent metal oxide deprives oxygen of CO2 to give CO at low temperature.
Both technologies are greatly expected to realize, however, far from feasible on the industrial scale atpresent.
(example of metal oxide-catalyze CO2 pyrolisis)

Fe2O3
2FeO + CO2
CO2

2FeO + 0.5O2
Fe2O3 + CO
CO + 0.5O2

2.3.2 Cabon Dioxide Caputuring methods- For the realization of the carbon newtral economy, the CO2 caputure technology plays a critical role
because CO2 is the only source of following all carbon products.
- Although large scale have never been done yet, collecting CO2 have already been developed enough.
The system utilizing amine solution such as monomethanol amine or monoethanol amine for CO2
absorption and emission have been widly used for sepalation from mixed gas of many plants.
The problems of this system are the need for large energy in emitting CO2, the corrosion by amine anddecomposition of amine.
- Recently, Metal-Organic Frameworks with exceptional high capacity for storage of CO2 under 30 bar
at r.t. has been reported, and following researchs are actively ongoing.
- Ultimately, CO2 must be collected from low concentrated air because more than half of CO2 emission isfrom domestic.
In other word, each emitts only so littele amount that it's out of problems from economical viewto collect individually.
- This seems extremelly difficult, but the collection from air is alredy practiced by utilizing somebasic-absorbents such as Ca(OH)2 , NaOH and KOH although vast amounts of cost and energy areneeded.

Schimatic overview of air capture including Air
Separation Unit
26

- Additional developments and improvements are expected for meeting economical need.
the reviews of CO2 capture see:Cabon Dioxide Capture: Prospects for New Materials.
D.M. D'Alessandro; B. Smit; J.R. Long, Angew. Chem. Int. Ed. 2010, 49, 6058~6082.
the reviews of Metal-Organic Frameworks for storage of CO2 see:
Synthesis, Structure, and Carbon Dioxide Capture Properties of Zeolitic Imidazolate Frameworks.
A. Phan; O.M.Yaghi, et al., Accounts of Chemical Research 2010, 43, 58~67.
the pioneering work of Metal-Organic Frameworks for storage of CO2 see:
Metal-organic frameworks with exceptionally high capacity for storage of carbon dioxide at room temperature.
A.R. Millward; O.M. Yaghi, J. Am. Chem. Soc. 2005, 127, 17998~17999.
about the CO2 capture process from air see:
Energy and material balance of CO2 capture from ambient air.
F. Zeman, Environ. Sci. Technol. 2007, 41, 7558~7563.

Summary and Future Outlook of "the Methanol Synthesis"- Today's methanol (and hydrogen) productions are almost all depending on fossil
fuels (mainly methane) via Syn-Gas.
This method is fundementally inefficient in that methane is first oxidized to Syn-Gas
and then reduced to methanol.
It can be said that the difference between methanol and hydrogen as a fuel is that theformer needs more energy in synthesis on the one hand while the latter needs instorage and transportation.
Methane should be oxidized directly to methanol.
Furthermore, the effective way to recycling carbon dioxide (even if not perfectrecycling) to methanol by utilizing methane and external hydrogen from electrolysis ofwater in order to exploit diminishing fossil fuels to the full should be also developed.
Ultimatelly, methanol should be obtained from CO2 and H2O, however, one-third ofhydrogen will be spent to produce water simply by reducing CO2 with H2.
This problem should be solved by the way not depending on unrenewable resources.
- Followings are the list of problems must be solved by "CHEMISTS"!
(0. Efficient way for oxidizing CH4 directly to CH3OH)
1. Efficient way for capturing and collectiong CO2
2. Efficient way for H2O decomposition to H2 and O2
3. Efficient way for CO2 decomposition to CO and O2
4. Efficient way for synthesizing CH3OH from CO and H2

Closing
Before encountering this book, I thought vaguely that after the Fossil Fuel era the next
comes the Hydrogen Economy and what chemists contribute are Hydrogen Fuel Cells
and Metal Hydrides.
Of course, the next will be no doubt Hydrogen in that Hydrogen can be the medium ofenergy, but this is the first time for me to have a detailed discussion on how to use
Hydrogen among whole societies.
As authors mention in the book, I don't also think that Methanol is the only acceptable
solution.
Finally, it is my great pleasure if this seminor helps, as the original book did to me, eachof you to get the coming situation in perspective and think what to do to contribute futuresocieties.

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