Methanol Economy

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DanishMethanolAssociation

Methanol Economy

BIO-METHANOL TM01-2e


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Copyright 2011 Danish Methanol Association, Denmark.

George Andrew Olah

Distinguished Professor of Chemistry and

Chemical Engineering and Materials Science andDonald P. and Katherine B. Loker Chair in OrganicChemistry.

One of the world's preeminent scholars ofhydrocarbon chemistry, Professor George Olahreceived the 1994 Nobel Prize in Chemistry forgroundbreaking work on superacids and hisobservations of carbocations.

His most recent research centers on theconversion of greenhouse gases into useful fuelsand products. Olah is working to develop new,cleaner and renewable fuels, based on methanoland he launched the Methanol Economy Concept.

Nobel Laureate Prof. Olah is an honorary memberof Danish Methanol Association.

Danish Methanol Association

Danish Methanol Association share Professor Olah's vision of a methanol economy as presentedin his book "Beyond Oil and Gas: The Methanol Economy" and we have the overall objective toimplement a methanol economy in Denmark.

More specifically a concrete goal is to pave the way for industrial production of methanol inDenmark (1) partly based on agricultural waste and (2) partly by recycling carbon dioxide in

power plant smoke.

1. Agricultural waste is gasified and the generated syngas is converted into methanol. Theapproach builds on proven technology and our model is VrmlandsMetanol AB inSweden who right now (2011) has begun plant construction.

2. The elegant and ultimate method is, however, to reduce carbon dioxide in power plantsmoke using hydrogen made from water with wind power. As an example serves the

plant Carbon Recycling International these days (2011) is putting into operation inIceland.

Although the specific projects mentioned can be realized on proven technology, there is need forresearch and development to promote Danish interests. We therefore encourage Danish researchefforts for the production and use of methanol.


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INTRODUCTION

METHANOLAN IDEAL ENERGY CARRIER

Any energy source can be converted intomethanol - be it coal, natural gas,biomass, etc. Methanol, however, is not abasic energy source in itself - it acts justas an energy carrier and can be madefrom many sources and by many processroutes. Since it is easy and safe to storeand handle it is an ideal replacement forgasoline. It is true that it has only half thecalorific value, but because of a highoctane number the mileage per litre ismore or less the same as for gasoline(The Research Octane Number (RON) is109). Synonyms for Methanol: Methylalcohol, wood alcohol, wood naphtha orwood spirits.

FuelHHVMJ/kg

LHVMJ/kg

Densityg/cm3

Methanol 22,9 20,1 0,794Dimethyl ether (DME) 31,7 28,9 0,665Ethanol 29,8 27,0 0,789Gasoline, conventional 44,9 44,9 0,745Diesel, conventional 46,5 43,4 0,837Diesel, Fisher-Tropsch 45,5 43,2 0,797

Source: GREET Transportation Fuel Cycle Analysis Model.HHV = Higher Heating Value. LHV = Lower Heating Value

The world still has significant amounts offossils fuels, but the dwindling amounts ofoil makes it essential to find areplacement. Because 60% of all oilproduced is used for transportation wehave an energy carrier problem - not an

energy problem - and here methanol is awelcome replacement.

It is far easier and safer than any otheralternative hydrogen, electric batteriesetc.

and it is clean!

CHEMISTRY

Methanol is the simplest of alcohols. It isa light, volatile, colorless, flammable

liquid with a density of 0.794 gcm-3

and aboiling point of 65 C. Methanol burns inair forming carbon dioxide and water:

2 CH3OH + 3 O2 2 CO2+ 4 H2O

The higher heating value (HHV)assuming all the water is in liquid state atthe end of combustion is 22,9 MJ/kg. Thelower heating value (LHV) assuming thatthe latent heat of vaporization of water is

not recovered is 20,1 MJ/kg.

Methanol is toxic to humans. Theingestion of 25-100 ml may be fatal if nottreated in time. Several treatments lead tocomplete recovery if timely administered.

METHANOL MANUFACTURE.

Steam-methane reforming or SMR is oneof several methods. At 40 bar andtemperatures around 850 C the methanecomponent in natural gas reacts withsteam on a nickel catalyst to producesyngas in an endothermic reaction:

CH4+ H2O CO + 3 H2

Methane can also undergo partialoxidation with oxygen to produce syngasin an exothermic reaction:

2 CH4+ O2 2 CO + 4 H2

When the two processes are combined, itis referred to as autothermal reforming.

The ratio of CO and H2can be adjustedby the water-gas shift reaction in order toprovide the appropriate stoichiometry formethanol synthesis:

CO + H2O CO2+ H2

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The syngas (carbon monoxide andhydrogen) then react on a secondcatalyst to produce methanol. A widelyused catalyst is a mixture of copper, zinc

oxide, and alumina. At 50100 bar and250 C it can catalyse the production ofmethanol from carbon monoxide andhydrogen:

CO + 2 H2 CH3OH

The excess hydrogen in the syngas isutilized by injecting carbon dioxide intothe methanol synthesis reactor, where itreacts to form methanol:

CO2+ 3 H2 CH3OH + H2O

Natural gas is the most economical andwidely used feedstock for methanolproduction, but other feedstocks can beused as well to produce syngas via steamreforming. In China, coal is the dominantfeedstock. Also, existing technology forbiomass gasification to syngas isindustrially matured.

Most elegantly methanol can be producedfrom carbon dioxide by catalytichydrogenation with hydrogen obtainedfrom water electrolysis with electricalpower from renewable energy sourcessuch as wind, hydroelectricity and solar.

In effect, all of them allow free energy tobe stored in easily transportable

methanol:CO2+ 3H2 CH3OH + H2O

The necessary carbon dioxide rawmaterial would be captured from industrialflue gases from electrical power plants,cement factories and district heatingplants. Eventually the CO2content in theair could be captured. This process isactually copying natures photosynthesis.

DIMETHYL ETHER (DME)

By methanol dehydration in the presenceof catalyst dimethyl ether (DME) is

produced.

2 CH3OH CH3OCH3+ H2O

Alternatively, DME can be produced by aone-step synthesis, using a dual catalystsystem that permits both methanolsynthesis and dehydration in the sameprocess unit. Both processes arecommercially available.

The Volvo Group has unveiled its first truck equippedwith a DME (dimethyl ether) engine and regards DMEas one of the most efficient renewable fuels withextremely low exhaust emissions.

DME is the simplest of ethers, acolourless gas with boiling point 23.6 C;ideal as a substitute for propane in LPG(Liquefied Petroleum Gas). DME is alsoan excellent fuel in diesel engines owingto its high cetane number (55). Only

moderate modification is needed to run adiesel engine on DME.

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RAW MATERIALS

Worldwide, over 90 methanol plants havethe capacity to produce over 50 million

tons of methanol annually. The traditionalfeedstock is natural gas, but this is beingreplaced by coal due to the explosivegrowth in the coal based Chineesemethanol production.

Both coal and natural gas is releasing thegreenhouse gas carbon dioxide, so thisroute is not acceptable. More carbondioxide neutral raw materials like biomassmust be used.

BIOMASS AS RAW MATERIAL.

Biomass, a renewable energy source, isbiological material such as agriculturalresidues, forest residues, householdwaste etc.

Fluidized bed gasifier for the High-TemperatureWinkler (HTW) process particular suited for bio-masses, such as straw, wood, peat and even householdwaste.

DANISH RAWMATERIALS

Available biomassin Denmark

EnergyPJ

as isapprox. t

Methanolequivalentapprox. t

Straw, 85% DM 55 3.500.000 1.500.000

Wood, 55% DM 40 3.500.000 1.000.000

Other, 80% DM 70 5.000.000 1.500.000

Total 165 12.000.000 4.000.000

Source: Danish Energy Agency.1 PJ (petajoule) = 277.777.778 kWh

Theoretically a fluidized bed gasifier mayturn 60% biomass energy into methanoland 40% into heat available for district

heating.In comparison the annual Danish motorfuel consumption is roughly 5 million m3(~200 PJ) half gasoline and half diesel.

A blend of all gasoline with 10% methanol(M10) requires 200.000 t (5 PJ) methanol.Less than a quarter of available straw issufficient to cover present targetreplacement of gasoline with methanol. A

similar quantity of DME will cover 10% ofdiesel as well.

CARBON DIOXIDE AS RAW MATERIAL.

Carbon dioxide is easily captured fromflue gas. Oxygen combustion improvesthe capture.

The limiting resource is electricity forsplitting water in oxygen and hydrogen.

Only the use of electricity fromrenewables makes sense.

In Denmark it is obvious to take windpower from our growing number of windmills often with power in excess ofactual needs.

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VRMLANDSMETANOLAB

VrmlandsMetanol AB, Hagfors, Swedenhas begun construction of a factory that

will convert forest waste into methanol.The plant can handle 45 tonnes of woodchips per hour and annual production is100,000 tonnes of methanol. Moreover,15 MW of waste heat is generated, whichlargely covers Hagfors' needs for districtheating.

The investment is in the range of SEK 3billion and the plant will break even at amethanol price around SEK 3.40 per lmethanol (~ EUR 0,48/kg).

The syngas (Product Gas) is synthesized to methanoland the crude methanol is refined to fuel standard.

ADANISH COPY

Although the Swedish factory ispioneering conversion of forest waste into

methanol it is, however, built on proventechnology.

Photomontage of VrmlandsMetanol AB with Hagforsin the background.

A similar plant in Denmark is of coursebased on agricultural waste such as strawsupplemented with available waste ofother origin. 250-300.000 t straw per yearis all it takes to supply a factory that size.

Theoretically, our current consumption ofpetrol and diesel may be replaced bymethanol and DME respectively,produced from existing quantities ofbiomass, if everything could be collected.

According to proposal amending Directive98/70/EC, ANNEX V, ENVIRONMENTALSPECIFICATIONS FOR MARKET FUELS TOBE USED FOR VEHICLES EQUIPPED WITHPOSITIVE-IGNITION ENGINES is maximumlimits for methanol unchanged 3% and ethanolincreased from 5% to10 %v/v.

The European Committee for Standardization(CEN) is a major provider of European Standardsand technical specifications inclusive standards for

blends of petrol and alcohols. A Nordic initiativetowards a M10 standard has been taken.


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Hagfors, Sweden.

The VrmlandsMetanol AB factory isbeing built in a forest area near Hagforscity - see photo montage on opposite

page.

It will have a capacity of 400.000 litres ofmethanol per day based on 1100 t of woodchips.

The factory is owned by a thousandshareholders, primarily the founder BjrnGillberg, Miljcentrum, LRF, Hagforsmunicipality and many other privateinvestors.


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CARBON RECYCLING INTERNATIONAL

Carbon Recycling International (CRI) hasbuilt a plant for recycling carbon dioxidein Iceland. Reduction of carbon dioxideoccurs with hydrogen produced by thehydrolysis of water with electricity fromgeothermal energy.

The plant is being commissioned andexpected to be operational summer 2011.

Carbon Recycling International wasfounded in 2006 as a joint Icelandic-

American enterprise, supported byacademic institutions and energycompanies, among others.

It is no coincidence that the business wasfounded in 2006: the company makes aprofit when its fuel can be sold for overUSD 50 per barrel and oil prices passedUSD 50 in early 2005. The current priceof oil is more than double that amount.

Mitsui Chemical Inc. of Japan has since 2009 operated a test

plant (100 t methanol/year) capturing carbon dioxide fromtheir own flue gas and reduced it to methanol. The hydrogenis made with electricity from solar panels.

CARBON RECYCLING IN DENMARK

In Denmark we will use excess windpower to generate the hydrogen andcapture the carbon dioxide from powerplant exhaust.

Our potential annual national renewableenergy resources are in excess of 1.500PJ, which can be compared to presentenergy consumption of 830 PJ. The majorresource is wind, which alone representsmore than 1.200 PJ.(Source: Energy 2050, Energinet.dk).

Most of the potential renewable energyresources are fluctuating and methanolcan help to smooth out.


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Iceland is known for its geothermalenergy.

The Industrial Scale Plant, named

The George Olah RenewableMethanol Plant at 5 million liters ofRenewable Methanol to beoperational in 2011 is located onSvartsengi close to HS Orka powerstation.

A Commercial Scale Plant at 100million litres is planned for end of2013 under cooperation with theMunicipality of Grindavik and HS

Orka.


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MARKET &ECONOMY

World's largest methanol producerMethanex publishes daily price of

methanol.

This methanol, however, is producedfrom natural gas and does therefore notcompete with biomethanol made frombiomass or by recycling carbon dioxide.

Practically any petrol based product can be made from

methanol instead.

BIO-ETHANOL IS THE ONLY COMPETITOR.

Sources: CEPEA [Brazilian sugarcane ethanol prices];USDA-AMS [Corn ethanol prices]; UNICA [Transportationcosts= $0.15/gal for Brazilian ethanol, $0.10/gal for U.S.ethanol]. Prices are US$ per gallon. $2.81/gal ~ EUR 0,65/kg.

Currently, bio-methanol is not on themarket. Only significant competitor is bio-ethanol. (Price fuel grade ethanol T1 as per January 2011according to Platts: EUR 480/t FOB Rotterdam).

Yield of methanol by gasification ofbiomass calculated on dry matter varylittle from type to type. 1 t biomass drymatter yields around 520 kg of methanolwhether the starting point is straw orwood.

It is different with ethanol produced byfermentation. Highest yield obtained withpine is 240 kg of ethanol per tonne dry

wood against 160 kg of ethanol per tonne


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of dry straw. This gives ethanolproduction cost of SEK 3.17/kg (EUR0,35/kg) from pine and SEK 5.45/kg(EUR 0,61/kg) from straw.

(Source: Flexibility in wheat bioethanol plants - Conditionsfor conversion to lignocellulosic feedstock by Hanna Nilsson,Department of Chemical Engineering, Lund University,March 2008).

VrmlandsMetanol AB breaks even atSEK 4.30/kg (EUR 0,48/kg) methanol.

Bioethanol is fermented starch / sugarfood crops. New enzymes make itpossible to produce "second generation"bio-ethanol based on the cellulosic parts

of the plants and moving so thecompetition for raw materials from food tobio-methanol. There may be morecompetition for raw materials in thefuture. Also power stations are interestedin straw direct combustion.

Flue gas is, however, deadly. Centre forEnergy, Environment and Health reportsthat 3400 Danes die annually because ofair pollution. In Denmark, air pollution

costs society DKK 28 billion per year.(Source: J. Brandt et al., 2011: Assessment of Health-CostExternalities of Air Pollution at the National Level using theEVA Model System, CEEH Scientific Report No 3, Centrefor Energy, Environment and Health Report series, March2011, pp. 98.)

Burning biomass is carbon dioxideneutral, but the pollution is extreme.

The methanol route is far more flexibleand

it is clean!

Portable fuel cells runningdirectly on methanol is onthe market and such DirectMethanol Fuel Cells(DMFC) are beingdeveloped for use in electricvehicles. DMFC makes thecar independent of anelectrical outlet and requiresonly small batteries.

The world is currently consuming about 85million barrels of oil a day, and about two-thirdsas much natural gas equivalent, both derivedfrom non-renewable natural sources. In theforeseeable future, our energy needs will come

from any available alternate source. Methanol isone such viable alternative, and also offers aconvenient solution for efficient energy storageon a large scale.

In this updated and enlarged edition, renownedchemists discuss in a clear and readilyaccessible manner the pros and cons ofhumankind's current main energy sources, while

providing new ways to overcome obstacles.

Following an introduction, the authors look atthe interrelationship of fuels and energy, and at

the extent of our non-renewable fossil fuels.They also discuss the hydrogen economy and itssignificant shortcomings. The main focus is onthe conversion of CO2 from industrial as wellas natural sources into liquid methanol andrelated DME, a diesel fuel substitute that canreplace LNG and LPG.

Wiley

Read the full story.


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Danish Methanol AssociationAgro Food Park, DK-8200 Aarhus N, Denmark

Phone: +45 8793 0000 www.starch.dk/methanol [email protected]
mailto:[email protected]://www.starch.dk/methanol

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