Methanol and Ethanol
- Main articles: Methanol fuel, Ethanol fuel
Methanol and ethanol can both be derived from fossil fuels, biomass, or perhaps most simply, from carbon dioxide and water. Ethanol has most commonly been produced through fermentation of sugars, and methanol has most commonly been produced from synthesis gas, but there are more modern ways to obtain these fuels. Enzymes can be used instead of fermentation. Methanol is the simpler molecule, and ethanol can be made from methanol. Methanol can be produced industrially from nearly any biomass, including animal waste, or from carbon dioxide and water or steam by first converting the biomass to synthesis gas in a gasifier. It can also be produced in a laboratory using electrolysis or enzymes.
As a fuel, methanol and ethanol both have advantages and disadvantages over fuels such as petrol (gasoline) and diesel fuel. In spark ignition engines, both alcohols can run at a much higher exhaust gas recirculation rates and with higher compression ratios. Both alcohols have a high octane rating, with ethanol at 109 RON (Research Octane Number), 90 MON (Motor Octane Number), (which equates to 99.5 AKI) and methanol at 109 RON, 89 MON (which equates to 99 AKI). Note that AKI refers to 'Anti-Knock Index' which averages the RON and MON ratings (RON+MON)/2, and is used on U.S. gas station pumps. Ordinary European petrol is typically 95 RON, 85 MON, equal to 90 AKI. As a compression ignition engine fuel, both alcohols create very little particulates, but their low cetane number means that an ignition improver like glycol must be mixed into the fuel with approx. 5%.
When used in spark ignition engines alcohols have the potential to reduce NOx, CO, HC and particulates. A test with E85 fueled Chevrolet Luminas showed that NMHC went down by 20-22%, NOx by 25-32% and CO by 12-24% compared to reformulated gasoline. Toxic emissions of benzene and 1,3 Butadiene also decreased while aldehyde emissions increased (acetaldehyde in particular).
Tailpipe emissions of CO2 also decrease due to the lower carbon-to-hydrogen ratio of these alcohols, and the improved engine efficiency.
Methanol and ethanol fuels contain soluble and insoluble contaminants. Halide ions, which are soluble contaminants, such as chloride ions, have a large effect on the corrosivity of alcohol fuels. Halide ions increase corrosion in two ways: they chemically attack passivating oxide films on several metals causing pitting corrosion, and they increase the conductivity of the fuel. Increased electrical conductivity promotes electrical, galvanic and ordinary corrosion in the fuel system. Soluble contaminants such as aluminum hydroxide, itself a product of corrosion by halide ions, clogs the fuel system over time. To prevent corrosion the fuel system must be made of suitable materials, electrical wires must be properly insulated and the fuel level sensor must be of pulse and hold type, magneto resistive or other similar non-contact type. In addition, high quality alcohol should have a low concentration of contaminants and have a suitable corrosion inhibitor added. Japanese scientific evidence reveals that also water is an inhibitor for corrosion by ethanol. The experiments are done with E50, which is more aggressive & speeds up the corrosion effect. It is very clear that by increasing the amount of water in fuel ethanol one can reduce the corrosion. At 2% or 20,000 ppm water in the fuel ethanol the corrosion stopped. The observations in Japan are in line with the fact that hydrous ethanol is known for being less corrosive than anhydrous ethanol. The reaction mechanism is 3EtOH + Al -> Al(OEt)3 +3/2H2 will be the same at lower-mid blends. When enough water is present in the fuel, the aluminum will react preferably with water to produce Al2O2, repairing the protective aluminum oxide layer which is why the corrosion stops. The aluminum alkoxide does not make a tight oxide layer, which is why the corrosion continues. In other words water is essential to repair the holes in the oxide layer.
Methanol and ethanol are also incompatible with some polymers. The alcohol reacts with the polymers causing swelling, and over time the oxygen breaks down the carbon-carbon bonds in the polymer causing a reduction in tensile strength. For the past few decades though, most cars have been designed to tolerate up to 10% ethanol (E10) without problem. This include both fuel system compatibility and lambda compensation of fuel delivery with fuel injection engines featuring closed loop lambda control. In some engines ethanol may degrade some compositions of plastic or rubber fuel delivery components designed for conventional petrol, and also be unable to lambda compensate the fuel properly.
"FlexFuel" vehicles have upgraded fuel system and engine components which are designed for long life using E85 or M85, and the ECU can adapt to any fuel blend between gasoline and E85 or M85. Typical upgrades include modifications to: fuel tanks, fuel tank electrical wiring, fuel pumps, fuel filters, fuel lines, filler tubes, fuel level sensors, fuel injectors, seals, fuel rails, fuel pressure regulators, valve seats and inlet valves. "Total Flex" Autos destined for the Brazilian market can use E100 (100% Ethanol).
One liter of ethanol contain 21.1 MJ, a liter of methanol 15.8 MJ and a liter of gasoline approximately 32.6 MJ. In other words, for the same energy content as one liter or one gallon of gasoline, one needs 1.6 liters/gallons of ethanol and 2.1 liters/gallons of methanol. The raw energy-per-volume numbers produce misleading fuel consumption numbers however, because alcohol-fueled engines can be made substantially more energy-efficient. A larger percentage of the energy available in a liter of alcohol fuel can be converted to useful work. This difference in efficiency can partially or totally balance out the energy density difference, depending on the particular engines being compared.
Methanol fuel has been proposed as a future biofuel, often as an alternative to the hydrogen economy. Methanol has a long history as a racing fuel. Early Grand Prix Racing used blended mixtures as well as pure methanol. The use of the fuel was primarily used in North America after the war. However, methanol for racing purposes has largely been based on methanol produced from syngas derived from natural gas and therefore this methanol would not be considered a biofuel. Methanol is a possible biofuel, however when the syngas is derived from biomass. In theory, methanol can also be produced from carbon dioxide and hydrogen using nuclear power or any renewable energy source, although this is not likely to be economically viable on an industrial scale (see methanol economy). Compared to bioethanol, the primary advantage of methanol biofuel is its much greater well-to-wheel efficiency. This is particularly relevant in temperate climates where fertilizers are needed to grow sugar or starch crops to make ethanol, whereas methanol can be produced from lignocellulose (woody) biomass.
Ethanol is already being used extensively as a fuel additive, and the use of ethanol fuel alone or as part of a mix with gasoline is increasing. Compared to methanol its primary advantage is that it is less corrosive and additionally the fuel is non-toxic, although the fuel will produce some toxic exhaust emissions. From 2007, the Indy Racing League will use ethanol as its exclusive fuel, after 40 years of using methanol. Since September 2007 petrol stations in NSW, Australia are mandated to supply all their petrol with 2% Ethanol content
Methanol combustion is: 2CH3OH + 3O2 → 2CO2 + 4H2O + heat
Ethanol combustion is: C2H5OH + 3O2 → 2CO2 + 3H2O + heat
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