Alcohols used as fuel for internal combustion engines
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Various alcohols are used as fuel for internal combustion engines. The first four aliphatic alcohols (methanol, ethanol, propanol, and butanol) are of interest as fuels because they can be synthesized chemically or biologically, and they have characteristics which allow them to be used in internal combustion engines. The general chemical formula for alcohol fuel is CnH2n+1OH.
Most methanol is produced from natural gas, although it can be produced from biomass using very similar chemical processes. Ethanol is commonly produced from biological material through fermentation processes. Biobutanol has the advantage in combustion engines in that its energy density is closer to gasoline than the simpler alcohols (while still retaining over 25% higher octane rating); however, biobutanol is currently more difficult to produce than ethanol or methanol. When obtained from biological materials and/or biological processes, they are known as bioalcohols (e.g. "bioethanol"). There is no chemical difference between biologically produced and chemically produced alcohols.
One advantage shared by the four major alcohol fuels is their high octane rating. This tends to increase their fuel efficiency and largely offsets the lower energy density of vehicular alcohol fuels (as compared to petrol/gasoline and diesel fuels), thus resulting in comparable "fuel economy" in terms of distance per volume metrics, such as kilometers per liter, or miles per gallon.
Methanol and ethanol can both be derived from fossil fuels, biomass, or 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.[1]
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 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).[2] 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 few particulates, but their low cetane number means that an ignition improver like glycol must be mixed into the fuel at 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[3] went down by 20-22%, NOx by 25-32% and CO by 12-24% compared to reformulated gasoline.[4] 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 improved engine efficiency.
Methanol and ethanol fuels contain soluble and insoluble contaminants.[5]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, clog 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. Scientific evidence reveals that water is an inhibitor for corrosion by ethanol.[6]
The experiments are done with E50, which is more aggressive and speeds up the corrosion effect. It is very clear that by increasing the amount of water in fuel ethanol one can reduce corrosion. At 2% or 20,000 ppm water in the ethanol fuel the corrosion stopped. In line with the observations in Japan, hydrous ethanol is known to be less corrosive than anhydrous ethanol. The reaction mechanism is 3 EtOH + Al -> Al(OEt)3 + 3⁄2 H2 at lower-mid blends. When enough water is present in the fuel, aluminum will react preferably with water to produce Al2O3, repairing the protective aluminum oxide layer. The aluminum alkoxide does not make a tight oxide layer; water is essential to repair the holes in the oxide layer.
Methanol and ethanol are incompatible with some polymers. The alcohol reacts with the polymers causing swelling, and over time 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 includes both fuel system compatibility and lambda compensation[clarification needed] 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. [citation needed]
"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).[citation needed]
One liter of ethanol releases 21.1 MJ in combustion, 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 released by combustion of 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,[citation needed] 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 fuel was primarily used in North America after the war. [clarification needed] 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 sustainably sourced biomass and ultimately carbon dioxide, and by hydrogen electrolysis using nuclear power, geothermal power or some other renewable energy source (see Carbon Recycling International). 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 unfertilized 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 non-toxic, although the fuel will produce some toxic exhaust emissions. Since 2007, the Indy Racing League has used ethanol as its exclusive fuel, after 40 years of using methanol.[7] Since September 2007 petrol stations in NSW, Australia have been mandated to supply all their petrol with 2% ethanol content[8]
Propanol and butanol are considerably less toxic and less volatile than methanol. In particular, butanol has a high flash point of 35°C, which is a benefit for fire safety, but may be a difficulty for starting engines in cold weather. The concept of flash point is, however, not directly applicable to engines as the compression of the air in the cylinder means that the temperature is several hundred degrees Celsius before ignition takes place.
The fermentation processes to produce propanol and butanol from cellulose are fairly tricky to execute, and the Weizmann organism (Clostridium acetobutylicum) currently used to perform these conversions produces an extremely unpleasant smell, and this must be taken into consideration when designing and locating a fermentation plant. This organism also dies when the butanol content of whatever it is fermenting rises to 2%.[9] For comparison, yeast dies when the ethanol content of its feedstock hits 14%. Specialized strains can tolerate even greater ethanol concentrations - so-called turbo yeast can withstand up to 16% ethanol.[10] However, if ordinary Saccharomyces yeast can be modified to improve its ethanol resistance, scientists may yet one day produce a strain of the Weizmann organism with a butanol resistance higher than the natural boundary of 7%. This would be useful because butanol has a higher combustion energy density than ethanol, and because waste fibre left over from sugar crops used to make ethanol could be made into butanol, raising the alcohol yield of fuel crops without requiring more crops to be planted.
Despite these drawbacks, DuPont and BP have recently announced that they are jointly to build a small scale butanol fuel demonstration plant [11] alongside the large bioethanol plant they are jointly developing with Associated British Foods.
The company Energy Environment International developed a method for producing butanol from biomass, which involves the use of two separate micro-organisms in sequence to minimize production of acetone and ethanol byproducts.[12]
The Swiss company Butalco GmbH uses a special technology to modify yeasts in order to produce butanol instead of ethanol. Yeasts as production organisms for butanol have decisive advantages compared to bacteria.[13]
The 3-carbon alcohol, propanol (C3H7OH), is not often used as a direct fuel source for petrol engines (unlike ethanol, methanol and butanol), with most being directed into use as a solvent. However, it is used as a source of hydrogen in some types of fuel cell; it can generate a higher voltage than methanol, which is the fuel of choice for most alcohol-based fuel cells. However, since propanol is harder to produce than methanol (biologically or from oil), methanol-utilizing fuel cells are preferred over those that utilize propanol.
Historical trend of Brazilian production of light vehicles by type of fuel, neat ethanol (alcohol), flex fuel, and gasoline vehicles from 1979 to 2017.
Brazil was until recently the largest producer of alcohol fuel in the world, typically fermenting ethanol from sugarcane.
The country produces a total of 18 billion litres (4.8 billion gallons) annually, of which 3.5 billion liters are exported, 2 billion of them to the U.S.[15] Alcohol cars debuted in the Brazilian market in 1979 and became quite popular because of a heavy subsidy, but in the 1980s prices rose and gasoline regained the leading market share.[16]
However, from 2003 on, alcohol has rapidly increased its market share once again because of new technologies involving flexible-fuel engines,[17] called "Flex" or "Total Flex" by all major car manufacturers (Volkswagen, General Motors, Fiat, etc.). "Flex" engines work with gasoline, alcohol or any mixture of both fuels. As of May 2009, more than 88% of new vehicles sold in Brazil are flex fuel.[18]
Because of the Brazilian leading production and technology, many countries became very interested in importing alcohol fuel and adopting the "Flex" vehicle concept.[17] On March 7 of 2007, US president George W. Bush visited the city of São Paulo to sign agreements with Brazilian president Luiz Inácio Lula da Silva on importing alcohol and its technology as an alternative fuel.[19]
As early as 1935, China has made alcohol fuel powered cars.[20]China has reported with a 70% methanol use to conventional gasoline an independence from crude oil.
National Committee of Planning and Action Coordination for Clean Automobile had listed key technologies related to alcohol/ether fuel and accelerated industrialization into its main agenda. Alcohol fuels had become part of five main alternative fuels: Two of which were alcohols; methanol and ethanol[21]
The United States at the end of 2007 was producing 26.9 billion litres (7 billion gallons) per year.[22] E10 or Gasohol is commonly marketed in Delaware and E85 is found in many states, particularly in the Midwest where ethanol from corn is produced locally.
Many states and municipalities have mandated that all gasoline fuel be blended with 10 percent alcohol (usually ethanol) during some or all of the year. This is to reduce pollution and allows these areas to comply with federal pollution limits. Because alcohol is partially oxygenated, it produces less overall pollution, including ozone. In some areas (California in particular) the regulations may also require other formulations or added chemicals that reduce pollution, but add complexity to the fuel distribution and increase the cost of the fuel.
The first alcohol fuel in Japan began with GAIAX in 1999. GAIAX was developed in South Korea, and imported by Japan. The principal ingredient was methanol.
Because GAIAX was not gasoline, it was a tax-free object of the gas tax of Japan. However, as a result, the use of GAIAX came to be considered an act of smuggling in Japan by the government and the petroleum industry. Retailing of GAIAX was done to avoid the tax evasion criticism by independently paying the diesel fuel tax in the legal system regulations.
Accidental vehicle fires where GAIAX was being refueled began to be reported in around 2000 when the tax evasion discussion had almost ended. The car industry in Japan criticized GAIAX, saying that "fires broke out because high density alcohol had corroded the fuel pipes". GAIAX was named a "high density alcohol fuel", and a campaign was executed to exclude it from the market long term. Finally, the Ministry of Economy, Trade and Industry also joined this campaign.[26]
The gasoline quality method was revised under the pretext of safety concerns in 2003. This prohibited the manufacturing and sale of "High density alcohol fuel", and added a substantial GAIAX sales ban. By revising the law, fuel manufacturers are prohibited from adding 3% or more alcohol to gasoline. This revision to the law is grounds not to be able to sell alcohol fuel greater than E3 in Japan.
The petroleum industry in Japan is now proceeding with research and development of an original alcohol fuel that differs from GAIAX. However, the commercial manufacture and sale of any new fuel may be barred by existing laws that currently exclude GAIAX from the market. Moreover, the strong aversion by the Japanese consumer to a high density alcohol fuel of any type may prevent commercial success of any new fuel.
Butanol (also called butyl alcohol) is a four-carbon alcohol with a formula of C4H9OH, which occurs in five isomeric structures (four structural isomers), from a straight-chain primary alcohol to a branched-chain tertiary alcohol; all are a butyl or isobutyl group linked to a hydroxyl group (sometimes represented as BuOH, sec-BuOH, i-BuOH, and t-BuOH). These are 1-butanol, two stereoisomers of sec-butyl alcohol, isobutanol and tert-butyl alcohol. Butanol is primarily used as a solvent and as an intermediate in chemical synthesis, and may be used as a fuel. Biologically produced butanol is called biobutanol, which may be n-butanol or isobutanol.
Biofuel is a fuel that is produced over a short time span from biomass, rather than by the very slow natural processes involved in the formation of fossil fuels such as oil. Biofuel can be produced from plants or from agricultural, domestic or industrial biowaste. Biofuels are mostly used for transportation, but can also be used for heating and electricity. Biofuels are regarded as a renewable energy source. The use of biofuel has been subject to criticism regarding the "food vs fuel" debate, varied assessments of their sustainability, and ongoing deforestation and biodiversity loss as a result of biofuel production.
Ethanol fuel is fuel containing ethyl alcohol, the same type of alcohol as found in alcoholic beverages. It is most often used as a motor fuel, mainly as a biofuel additive for gasoline.
Liquid fuels are combustible or energy-generating molecules that can be harnessed to create mechanical energy, usually producing kinetic energy; they also must take the shape of their container. It is the fumes of liquid fuels that are flammable instead of the fluid. Most liquid fuels in widespread use are derived from fossil fuels; however, there are several types, such as hydrogen fuel, ethanol, and biodiesel, which are also categorized as a liquid fuel. Many liquid fuels play a primary role in transportation and the economy.
Methanol fuel is an alternative biofuel for internal combustion and other engines, either in combination with gasoline or independently. Methanol (CH3OH) is less expensive to sustainably produce than ethanol fuel, although it is more toxic than ethanol and has a lower energy density than gasoline. Methanol is safer for the environment than gasoline, is an anti-freeze agent, prevents dirt and grime buildup within the engine, has a higher ignition temperature and can withstand compression equivalent to that of super high-octane gasoline. It can readily be used in most modern engines. To prevent vapor lock due to being a simple, pure fuel, a small percentage of other fuel or certain additives can be included. Methanol may be made from fossil fuels or renewable resources, in particular natural gas and coal, or biomass respectively. In the case of the latter, it can be synthesized from CO2 (carbon dioxide) and hydrogen. The vast majority of methanol produced globally is currently made with gas and coal. However, projects, investments, and the production of green-methanol has risen steadily into 2023. Methanol fuel is currently used by racing cars in many countries and has seen increasing adoption by the maritime industry.
Ethanol, an alcohol fuel, is an important fuel for the operation of internal combustion engines that are used in cars, trucks, and other kinds of machinery.
E85 is an abbreviation typically referring to an ethanol fuel blend of 85% ethanol fuel and 15% gasoline or other hydrocarbon by volume.
A flexible-fuel vehicle (FFV) or dual-fuel vehicle is 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, and both fuels are stored in the same common tank. Modern flex-fuel engines are capable of burning any proportion of the resulting blend in the combustion chamber as fuel injection and spark timing are adjusted automatically according to the actual blend detected by a fuel composition sensor. Flex-fuel vehicles are distinguished from bi-fuel vehicles, where two fuels are stored in separate tanks and the engine runs on one fuel at a time, for example, compressed natural gas (CNG), liquefied petroleum gas (LPG), or hydrogen.
Several common ethanol fuel mixtures are in use around the world. The use of pure hydrous or anhydrous ethanol in internal combustion engines (ICEs) is only possible if the engines are designed or modified for that purpose, and used only in automobiles, light-duty trucks and motorcycles. Anhydrous ethanol can be blended with gasoline (petrol) for use in gasoline engines, but with high ethanol content only after engine modifications to meter increased fuel volume since pure ethanol contains only 2/3 of the BTUs of an equivalent volume of pure gasoline. High percentage ethanol mixtures are used in some racing engine applications as the very high octane rating of ethanol is compatible with very high compression ratios.
In the liquid fuel industry, oxygenates are hydrocarbon-derived fuel additives containing at least one oxygen atom to promote complete combustion. Absent oxygenates, fuel combustion is usually incomplete, and the exhaust stream pollutes the air with carbon monoxide, soot particles, aromatic and polyaromatic hydrocarbons, and nitrated polyaromatic hydrocarbons.
The bioconversion of biomass to mixed alcohol fuels can be accomplished using the MixAlco process. Through bioconversion of biomass to a mixed alcohol fuel, more energy from the biomass will end up as liquid fuels than in converting biomass to ethanol by yeast fermentation.
The United States produces mainly biodiesel and ethanol fuel, which uses corn as the main feedstock. The US is the world's largest producer of ethanol, having produced nearly 16 billion gallons in 2017 alone. The United States, together with Brazil accounted for 85 percent of all ethanol production, with total world production of 27.05 billion gallons. Biodiesel is commercially available in most oilseed-producing states. As of 2005, it was somewhat more expensive than fossil diesel, though it is still commonly produced in relatively small quantities, in comparison to petroleum products and ethanol fuel.
Butanol may be used as a fuel in an internal combustion engine. It is more similar to gasoline than it is to ethanol. A C4-hydrocarbon, butanol is a drop-in fuel and thus works in vehicles designed for use with gasoline without modification. Both n-butanol and isobutanol have been studied as possible fuels. Both can be produced from biomass (as "biobutanol" ) as well as from fossil fuels (as "petrobutanol"). The chemical properties depend on the isomer (n-butanol or isobutanol), not on the production method.
An alternative fuel vehicle is a motor vehicle that runs on alternative fuel rather than traditional petroleum fuels. The term also refers to any technology powering an engine that does not solely involve petroleum. Because of a combination of factors, such as environmental and health concerns including climate change and air pollution, high oil-prices and the potential for peak oil, development of cleaner alternative fuels and advanced power systems for vehicles has become a high priority for many governments and vehicle manufacturers around the world.
Biofuel is fuel that is produced from organic matter (biomass), including plant materials and animal waste. It is considered a renewable source of energy that can assist in reducing carbon emissions. The two main types of biofuel currently being produced in Australia are biodiesel and bioethanol, used as replacements for diesel and petrol (gasoline) respectively. As of 2017 Australia is a relatively small producer of biofuels, accounting for 0.2% of world bioethanol production and 0.1% of world biodiesel production.
Biofuels are renewable fuels that are produced by living organisms (biomass). Biofuels can be solid, gaseous or liquid, which comes in two forms: ethanol and biodiesel and often replace fossil fuels. Many countries now use biofuels as energy sources, including Sweden. Sweden has one of the highest usages of biofuel in all of Europe, at 32%, primarily due to the widespread commitment to E85, bioheating and bioelectricity.
Second-generation biofuels, also known as advanced biofuels, are fuels that can be manufactured from various types of non-food biomass. Biomass in this context means plant materials and animal waste used especially as a source of fuel.
Biogasoline is a type of gasoline produced from biomass such as algae. Like traditionally produced gasoline, it is made up of hydrocarbons with 6 (hexane) to 12 (dodecane) carbon atoms per molecule and can be used in internal combustion engines. However, unlike traditional gasoline/petroleum based fuels, which are mainly composed from oil, biogasolines are made from plants such as beets and sugarcane or cellulosic biomass- substances normally referred to as plant waste.
The fleet of flexible-fuel vehicles in the United States is the second largest in the world after Brazil, and there were more than 21 million 85 flex-fuel vehicles registered in the country by the end of 2017. Despite the growing fleet of E85 flex-fuel vehicles, actual use of ethanol fuel is limited due to the lack of E85 refueling infrastructure and also because many North American flex-fuel car owners were not aware they owned an E85 flex-fuel vehicle. Flex-fuel vehicles are common in the Midwest, where corn is a major crop and is the primary feedstock for ethanol fuel production. Also the U.S. government has been using flex-fuel vehicles for many years.
The world's top ethanol fuel producers in 2011 were the United States with 13.9 billion U.S. liquid gallons (bg) and Brazil with 5.6 bg, accounting together for 87.1% of world production of 22.36 billion US gallons. Strong incentives, coupled with other industry development initiatives, are giving rise to fledgling ethanol industries in countries such as Germany, Spain, France, Sweden, India, China, Thailand, Canada, Colombia, Australia, and some Central American countries.
References
↑ ENZYMATIC CONVERSION OF CARBON DIOXIDE TO METHANOL "Archived copy"(PDF). Archived from the original(PDF) on 2012-03-15. Retrieved 2010-11-28.{{cite web}}: CS1 maint: archived copy as title (link)
↑ Non-Methane HydroCarbons "NMHC". Archived from the original on 2011-07-27. Retrieved 2010-11-27.
↑ Kelly, K.J., Bailey, B.K., Coburn, T.C., Clark, W., Lissiuk, P. "Federal Test Procedure Emissions Test Results from Ethanol Variable-Fuel Vehicle Chevrolet Luminas", SAE Technical Paper 961092
↑ Brinkman, N., Halsall, R., Jorgensen, S.W., & Kirwan, J.E., "The Development Of Improved Fuel Specifications for Methanol (M85) and Ethanol (Ed85), SAE Technical Paper 940764
↑ "Alcohol Ether Fuel in China"(PDF). University of California Riverside Environmental Research Institute. 13 Nov 2005. Archived from the original(PDF) on 2011-10-09. Retrieved 2011-12-04.
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