About Methanol

I recently read two related articles regarding methanol which were somewhat conflicting and perked my interest in methanol.  The first was the announcement of a new plant for producing methanol.

Methanol Holdings (Trinidad) Limited (MHTL) announced that its M5000 methanol plant achieved first methanol production on September 23, 2005 and expected to achieve full production of 5400 tons per day, making it the largest methanol plant in the world, during the first week of October.  The total production capacity of MHTL's four plants is now about 4 million metric tons per annum (11,000 tons per day).

My immediate naive reaction was that converting stranded natural gas to methanol was an inexpensive way, less expensive than FT synthesis, to convert the gas to a liquid which would make the transportation much less complex (stranded gas refers to gas that is not in sufficient supply to justify converting it to LNG).  Methanol could be used as a vehicular fuel, so there should be a market for it.  Shortly after I saw the above announcement I saw an article in the Oil & Gas Journal about an overcapacity situation in methanol.  According to the article:

During its 5-year study period, beginning in 2006, CMAI in its 2006 World Methanol Analysis, forecasts world demand for methanol to be about 38 million tonnes/year. Meanwhile, nearly 27 million tpy of new capacity is planned for the same period and most expansions are not demand-driven, it said.

The largest absolute growth for methanol will be fueled by the Middle East and Northeast Asia, most notably China, as this country continues to build infrastructure to support its economic development.

Methanol demand in North America will decline as the methyl tertiary butyl ether phase-out programs sweep the US by 2007. This will eliminate the use of 9 million tonnes of MT BE by 2008, the equivalent of more than 3 million tonnes of methanol. Also, Europe is rapidly replacing MT BE with biofuels. It is expected to reduce MT BE production by 1.8 million tonnes (about 600,000 tonnes of methanol) from the 2000 peak consumption time frame to the end of the study period.

CMAI said the probability is high for the planned methanol-to-olefins complex in Nigeria in 2009. This addition, which will interact independent of the methanol industry and derivatives, will create almost 2.2 million tonnes of new demand.

Methanol is the simplest alcohol and has a chemical formula of CH3OH. It is clear and colorless but has a characteristic pungent odor. It is a volatile and flammable liquid and may be fatal or cause blindness if swallowed. Hence, it is certainly not a drinking alcohol but rather an extremely versatile industrial chemical used in the manufacture of a wide range of raw materials including Formaldehyde, MTBE, Acetic acid Dimethyl Terephtalate (DMT), Methyl Methacrylate (MMA) Methyl amines, fuel, and antifreeze.  These are used to make a wide variety of products such as plastics, solvents, dyes, glues, wood products, polyester fibers and fabrics for clothing.

Developing markets for methanol are in fuel cells as the source of hydrogen and as a precursor for olefins; benzine, butadine, ethylene, propylene, styrene and toluene; which are some of the most important building blocks of the petrochemical industries and used to make such consumer products as plastics, packaging, automobile parts, small appliances, carpet backing, synthetic rubber and nylon fibers.

The use of methanol as a vehicular fuel intrigued me and I found these arguments for its use as proposed by Vanderzee:

• The world-wide energy crisis is driven by the cost and availability of gasoline.
• The U.S. has a 200+ year supply of usable fuel in the form of coal.
• We can convert coal to methanol using proven technology in “zero discharge” plants.
• Methanol is a high performance motor fuel – just ask the Indy car drivers.
• Methanol can be stored in tanks, transported by pipeline or tanker and pumped into our cars just like gasoline, which minimizes conversion costs for our fuel infrastructure.
• Auto manufacturers can produce methanol engines at the same cost as gasoline engines.
• Methanol is not a threat to groundwater, per the EPA.
• We can build coal to methanol plants in Illinois, Ohio, Kentucky, and West Virginia – creating jobs in regions that need investment.

The department of energy has this to say about flexible fueled vehicles:

A flexible fueled vehicle (FFV) has a single fuel tank, fuel system, and engine. The vehicle is designed to run on unleaded gasoline and an alcohol fuel (usually ethanol) in any mixture. The engine and fuel system in a flex-fuel vehicle must be adapted slightly to run on alcohol fuels because they are corrosive. There must also be a special sensor in the fuel line to analyze the fuel mixture and control the fuel injection and timing to adjust for different fuel compositions.

This tells me that a vehicle that is classed as flexible fuel rated for ethanol probably cannot use methanol.  To explore this further I wanted to know what had to be done to modify a vehicle to run on methanol - it couldn't be that hard because I have known of relatively low cost dragsters that run on it. Zumerchik has this to say about this subject:

Automobiles that are designed to run on methanol need a few modifications to become flexible fuel vehicles (vehicles that run on either gasoline or methanol). First, for the fuel tank, fuel lines and fuel-injection equipment, the vehicle needs noncorrosive materials such as stainless steel and high-fluorine elastomers. Second, since methanol is a lower energy density fuel, fuel injectors must be larger to provide greater volumes of fuel, and vehicles must be equipped with larger fuel tanks to achieve a range comparable to a gasoline vehicle. Third, a fuel sensor that detects fuel composition is needed to relay information to the on-board computer. And finally, the lower volatility and higher heat vaporization of methanol requires a special starting system for convenient cold weather start-ups.

I found other sources that said that special starting systems were not needed unless the methanol concentration was greater than 85%.  It sounds to me that, except for the fuel sensor that detects fuel composition, which is not necessary to run ethanol, a car that can run methanol can run ethanol.  There are thousands of cars running on M85 methanol in California to meet stringent emissions standards and I found a large fleet running on methanol in Arizona. 

There are a couple of safety concerns with methanol because it is very poisonous and the fact that when it burns the flames from pure methanol are colorless, but fires are easier to put out than gasoline fires.  There have been several reports of the corrosiveness of alcohols when used in standard diesel engines.

EPA has found that the efficiency of methanol fueled engines was 33% higher using 100% methanol rather than gasoline, while ethanol had 25% higher efficiency than gasoline in advanced high efficiency engines. 

The chart to the left from Kreith offers quite a bit of insight as to the efficiencies of various fuel combinations that could be used in cars.  Gasoline in an ICE is off the bottom of the chart.  H2 is produced by steam reforming unless noted as being by electrolysis.  The fuel cell with methanol does not look very well in this analysis, I have to assume that is methanol made from natural gas.

With our large coal reserves making methanol from coal would be less expensive than making diesel or gasoline from coal.  A 2004 DOE report (p 6) indicated that methanol could be made from coal for $0.50 per gallon.  The tests for this study were made at a Tennessee Eastman chemical plant that was already gasifying coal to produce chemicals.  The $0.50 per gallon figure was obtained assuming methanol was coproduced from an IGCC plant.  Making methanol from biomass is also possible, competitive with gasoline according to a ALTENER report, but more expensive than making it from coal.  ALTENER studied the gasification of black liquor to make methanol, a process also being studied by the U.S. DOE.

Production of methanol from natural gas as practiced by MHTL is broken down into four steps:

1. FEED PURIFICATION - The two main feedstocks, natural gas and water, both require purification before use. Natural Gas contains low levels of sulfur compounds and undergo a desulfurization process to reduce, the sulfur to levels of less than one part per million. Impurities in the water are reduced to undetectable or parts per billion levels before being converted to steam and added to the process. If not removed, these impurities can result in reduced heat efficiency and significant damage to major pieces of equipment.
2. REFORMING - Reforming is the process which transforms the methane (CH4) and the steam (H2O) to intermediate reactants of hydrogen (H2), carbon dioxide (CO2), carbon monoxide (CO). Carbon dioxide is also added to the feed gas stream at this stage to produce a mixture of components in the ideal ratio to efficiently produce methanol. This process is carried out in a Reformer furnace which is heated by burning natural gas as fuel.
3. METHANOL SYNTHESIS - After removing excess heat from the “reformed gas” it is compressed before being sent to the methanol production stage in the synthesis reactor. Here the reactants are converted to methanol and separated out as as crude product with a composition of methanol (68%) and water (31%). The crude methanol formed is condensed and sent to the methanol purification step which is the final step in the process.
4. METHANOL PURIFICATION - The 68% methanol solution is purified in two distinct steps in distillation columns to yield a refined product with a purity of 99% methanol.

My conclusion after all of this is that ethanol is probably a better fuel than methanol if used directly in an ICE, although if it ever looks like we cannot produce enough ethanol from biomass, producing methanol from coal is very attractive.  Methanol offers some potential to be used direct methanol fuel cells, if the time ever arrives that that is an option.  It eliminates all of the infrastructure for making and distributing hydrogen, although according to the chart this is not an efficient option.

Resources:

Methanol Holdings (Trinidad) Limited, Trinidad, West Indies 
CMAI forecasts flooded methanol market, Oil&Gas Journal e-newsletter, November, 2005
Yogi and Gasoline, Peter J. Vanderzee, Energy Security, March 28, 2005
Methanol, John Zumerchik, Macmillan Encyclopedia of Energy, 2001
Research in alcohol Fueled-Engines at EPA NVFEL , Matthew Brusstar, U.S. EPA National Vehicle and Fuel Emissions Laboratory February 25, 2003
Commercial-Scale Demonstration of the Liquid Phase Methanol (LPMEOH tm) Process, Air Product Liquid Phase Conversion Company, June 2004
"Technical and Commercial Feasibility Study of Black Liquor Gasification with Methanol/DME Production as Motor Fuel for Automotive Uses - BLGMF" , ALTENER, European Union, December 2003
"Gauging Efficiency from Well to Wheel", Frank Kreith and R.E. West, Mechanical Engineering 2003

More blogs about methanol, coal, fuel cells, natural gas, alternative energy, renewable, renewable energy, energy

Comments

[J. R. McCormick]

Interesting commentary on methanol. I would be interested in discussing this further. Please glance at my url
http://dr_methanol.home.att.net for much personal opinion on various alternative motor fuels especially methanol.
J. R. McCormick

[barry hanson]

A recent book by George Olah at USC, The Methanol Economy, sheds alot of light on the prospects for methanol. Olah is a Nobel prize winner in chemistry.

[James R. Crocco]

I started the global methanol consulting business back in early 1983. At that time I also organized the First World Methanol Conference in Brussels in early December of that year. One of the speakers was a VP of Ford for Europe and he gave a talk on
M-100, or Ford's experience in developing its Escorts to burn 100% methanol in California. Another speaker was from the Dutch TNO, or Road Institute, who gave a paper on "The Alcohol/Petrol Ratio Sensor", a device that could be installed in cars to allow vehicles to burn methanol or gasoline, or any percentage of the two, quite easily. That evening I saw the two, from Ford and the TNO, having dinner together.

A few years later Ford came out with its version of the Flexible Fueled Vehicle, or FFV. It soon became apparent that simply allowing the customer to pump methanol or gasoline into his fuel tank was going to be problematical. At high concentrations of alcohol there were cold starting problems, as mentioned in the above article,and, should a fire occur, the flame would hardly be luminous in daylight, as also mentioned. Therefore, shortly after the introduction of the FFV in the USA M-85 was developed. This was a pre-blend of 85% methanol and 15% premium unleaded gasoline pumped through a special system at some gasoline stations.

After a perhaps almost a decade the FFV and M-85 fell out of interest. This was partly because Big Oil only gave lip service to the program since only less than 100 service stations in the country, with most of them in California, had M-85 available. Also, in the mid 1990's methanol prices went through the roof, reaching $1.80 per gallon wholesale and in large quantities, that made it economically unfeasible.

The FFV is now coming back in favor but with E-85 (ethanol). But ethanol is also now getting quite high in pricing as it recently reached over $5.00 per gallon in the spot market in the New York Harbor. Similar to M-85, E-85 is also quite limited in consumer outlets that are focused mostly close to where ethanol is being produced - in the Midwest. There are said to be over 5 million E-85 FFV's in this country and that figure will grow mostly in the rent-a-car industry. But the actual use of ethanol will not grow accordingly in the near term at least since ethanol is so expensive. The drivers will fill up on gasoline for the most part. However, the auto makers get a credit against their CAFE efficiencies wherein, because they build and sell FFV's regardless of whether or not they use E-85, they will get MPG credits that they can use to build and sell bigger and more gasoline guzzling cars that will require additional imported oil or gasoline.

In a nutsahell the FFV does not cost much more to produce - around $200 per unit, and they can use E-85 or M-85 with no changes in systems.

[Gray Kinnie]

J R McCormick didn't expound much on Prof Dr Olas' book, so I would like to note: the beauty of Methanol is that since it can burn either in an internal combustion engine or in fuel cells, under development and refinement, and it is so much easier to transport and store than hydrogen, it provides a smooth path to the post oil and gas era. If you have energy, co2 and water, you can always make methanol and from it, almost any other petroleum product.

[J. R. McCormick]

Sorry, my url was incorrectly quoted above as http://dr_methanol.home.att.net.
My correct URL is:
dr-methanol.home.att.net.
As to Professor Olah's book: "Beyond Oil and Gas, the Methanol Economy", I would say that the main thrust of this work is comparisons of statistics of the oil,gas and coal industries and rather incidently deals with the Methanol Econamy. And even there mainly emphasizes the possibilitry, even probability that methanol may eventually be made by direct oxidation of methane. This is a highly desirable goal, and one that has been investigated for many years, so far to no practical avail.
That being said, The U. S. does not have an abundance of methane and even now we are importing methane as cryogenic liquid and essentially all our methanol is manufactured abroad from stranded methane. The oil industry has a major hand in this and the recent history of methanol pricing shows that it too is linked to the price of crude oil.

[J. R. McCormick]

I consider that remarks about the toxicity of methanol are a red herring. Ethanol and gasoline are toxic too. Before Prestone, huge quantities of methanol were used safely as auto antifreeze, and even now, methanol is readily available as fuel line antifreeze. Evidently, post prohibition, people learned not to drink methanol. It can be abused, of course, but then, what cant.
The other red herringis the corrosiveness of methanol. It seems weell known that the presence of a few percernt of water in methanol prevents it reactivity with aluminum and magnesium. I have examined this point in a rudimentary way and observe no reactvity with ordinary anodized aluminum. Incidently, the few percent of water has no effect on combustability. The corrosion problem also arose in early work from the film of water left om cylinder surfaces when methanol evaporated. Gasoline will do the same thing--evaporative cooling condensing water from the air--gasoline however contains higher boiling oils which act to protect the iron surfaces. A trace of oil dissolved in the methanol wud presumably have the same effect.

[J. R. McCormick]

I have recently learned that a Ford Taurus of unknown vintage has a notation in its Computer that it is METHANOL capable. Interesting! Can anyone confirm this for their Taurus?
J. McCormick

[ycsts]

Initially it would be of great advantage to stop the insane transport of LNG, and instead transport methanol which can be made from Natural Gas at less than $1 per gallon.

For example large reserves in the Mackenzie Delta, a lot cheaper to convert it to methanol and ship the methanol in tankers, then to build an environmentally controversial $20 billion pipeline to transport some of it to southern markets. And it is both safe from disastrous explosion (i.e. LNG) and environmental damage if spilled (i.e. Petroleum), to transport by tanker.

The toxicity of methanol (actually not from methanol but the formic acid that is produced from it in the body after 10-24 hours post ingestion) is an issue, but it is routinely used in Northern countries as a gasline antifreeze, and sold in grocery stores in flimsy plastic bottles (they wouldn't let you buy gasoline like that). The addition of a few parts per billion of Bitrex and a simple colorant would make accidental ingestion a non-event, and there isn't a chance in hell that methanol poisoning deaths would even minutely approach deaths due to gasoline fires & carcinogenic fumes, never mind toxic automobile exhaust or prescription drug overdose deaths.

I put some aluminum, black iron, copper, brass, & galvanized steel in a jar of methanol and the same in a jar of pure water over a month ago. I see zero sign of corrosion in the methanol jar, but definite rust scunge in the water jar. Conclusion, I reckon the handling of water in our cooling systems and house plumbing systems, must have taken some extraordinary breakthroughs in materials science!

As for cold weather starting of methanol fueled engines, the trend and the ideal would be to burn methanol in hybrids in which cylinder preheat is a trivial (& desirable) matter, just as the Prius preheats their Atkinson engine. And a methanol fueled high compression, turbo-charged, port fuel injected, spark ignition engine/generator would be ideal, for a series hybrid EV. At 43% efficiency, unlike the useable ICE TDI diesel vehicle maximum engine efficiency of about 32%.

And I don’t get this pungent odor thing, I don’t smell but the faintest odor, very pleasant to work with, unlike gasoline which burns the skin and has a strong carcinogenic odor. Also I stick a torch in an open jar of methanol and nothing happens, no flame, with gasoline I would burn my face doing the same thing. You have to place the flame almost right on the methanol to get it to burn, very safe, a nice gentle clean flame when ignited. That’s why it is required for use in racing cars or a mix with ethanol.

And, methanol is present in fruit juice already, and entirely nontoxic to the environment. If you spill fuel oil or gasoline, call in the environment people to dig up all the soil and transport it to a toxic waste disposal site (or you could be arrested), methanol wash it down with water, it dissipates harmlessly in the environment.

[husky air compressor]

I'm working on a green house project. I'm really interested by this Methanol and I really would like to know if it's reliable for single housing application.
thanks a lot!
Husky air compressor
Husky air compressor parts