Alternate fuels Alcohol (Methanol; Ethanol)

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Isaac Prem Kumar (1126003)

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Naresh Joseph Chrisrty (1126005)

Alternate Fuels- Alcohols (Methanol and ethanol)

Methanol: Methanol, also known as methyl alcohol, wood alcohol, wood naphtha or wood spirits, is a chemical with the formula CH3OH (often abbreviated MeOH). It is the simplest alcohol, and is a light, volatile, colorless, flammable liquid with a distinctive odor very similar to, but slightly sweeter than, ethanol (drinking alcohol).[4] At room temperature, it is a polar liquid, and is used as an antifreeze, solvent, fuel, and as a denaturant for ethanol.It is also usedproducing biodiesel via transesterification reaction.

Source:
.Methanol may be made from fossil or renewable resources, in particular natural

gas and biomass respectively. Methanol is produced naturall the anaerobic metabolism of many varieties of bacteria, and is ubiquitous in the environment. As a result, there is a small fraction of methanol vapor in the atmosphere. Over the course of several days, atmospheric methanol is oxidized with the help of sunlight to carbon dioxide and water. Methanol burns in air, forming carbon dioxide and water: 2 CH3OH + 3 O2 2 CO2 + 4 H2O

Methanol was first produced by destructive distillation (pyrolysis) of wood, resulting in its common English name of wood alcohol. At present, methanol is usually produced using methane (the chief constituent of natural gas) as a raw material. In China, methanol is made for fuel from coal. "Biomethanol" may be produced by gasification of organic materials to synthesis gas followed by conventional methanol synthesis. This route can offer methanol production from biomass at efficiencies up to 75%.[citation needed] Widespread

production by this route has a proposed potential (see Hagen, SABD & Olah references below) to offer methanol fuel at a low cost and with benefits to the environment. These production methods, however, are not suitable for small-scale production Production: Today, synthesis gas is most commonly produced from the methane component in natural gas rather than from coal. Three processes are commercially practiced. At moderate pressures of 4 MPa (40 atm) a and nickel high catalyst temperatures to (around 850 C), to

methane reacts with steam on the chemical equation: CH4 + H2O CO + 3 H2

produce syngas according

This reaction, commonly called steam-methane reforming or SMR, is endothermic, and the heat transfer limitations place limits on the size of and pressure in the catalytic reactors used. Methane can also undergo partial oxidation with molecular oxygen to produce syngas, as the following equation shows: 2 CH4 + O2 2 CO + 4 H2

This reaction is exothermic, and the heat given off can be used in-situ to drive the steammethane reforming reaction. When the two processes are combined, it is referred to as autothermal reforming. The ratio of CO and H2 can be adjusted to some extent by the water-gas shift reaction, CO + H2O CO2 + H2,

to provide the appropriate stoichiometry for methanol synthesis. The carbon monoxide and hydrogen then react on a second catalyst to produce methanol. Today, the most widely used catalyst is a mixture of copper, zinc oxide, and alumina first used by ICI in 1966. At 510 MPa (50100 atm) and 250 C, it can catalyze the production of methanol from carbon monoxide and hydrogen with high selectivity: CO + 2 H2 CH3OH

It is worth noting that the production of synthesis gas from methane produces three moles of hydrogen gas for every mole of carbon monoxide, while the methanol

synthesis consumes only two moles of hydrogen gas per mole of carbon monoxide. One way of dealing with the excess hydrogen is to inject carbon dioxide into the methanol synthesis reactor, where it, too, reacts to form methanol according to the equation: CO2 + 3 H2 CH3OH + H2O

Although natural gas is the most economical and widely used feedstock for methanol production, many other feedstocks can be used to produce syngas via steam reforming. Coal is increasingly being used as a feedstock for methanol production, particularly in China. In addition, mature technologies available for biomass gasification are being used for methanol production. For instance, woody biomass can be gasified to water gas (a hydrogen-rich syngas), by introducing a blast of steam in a blast furnace. The water-gas / syngas can then be synthesized to methanol using standard methods. The net process is carbon neutral, since the CO2 byproduct is required to produce biomass via photosynthesis. 2 C16H23O11 + 19 H2O + O2 Performance: Methanol and methanol blends have higher octane ratings than gasoline,which reduces engine knock and can produce in a higher engine efficiency. The higher octane also gives methanol-fueled vehicles more power and quicker acceleration. M100 vehicles have difficulty starting in cold weather, but this is not a problem for M85 vehicles because of the presence of gasoline. Furthermore, because of methanols corrosive nature, a specialized fuel system is needed to handle the fuel. 42 H2 + 21 CO + 11 CO2 21 CH3OH + 11 CO2

Merits: y Methanol has superior fire safety characteristics given that it does not ignite as easily as gasoline,burns with 1/8th the heat of gasoline, and is less likely to cause deadly fires. The U.S. EnvironmentalProtection Agency estimated that because of methanols low volatility and inherent fire safetyadvantages, a switch to methanol fuel could save hundreds of lives each year, and millions of dollars in property losses. y Both methanol and ethanol burn at lower temperatures than gasoline, and both are less volatile, making engine starting in cold weather more difficult. Using methanol as a fuel in spark-ignition engines can offer an increased thermal efficiency and increased power output (as compared to gasoline) due to its high octane rating (114[8]) and high heat of vaporization. However, its low energy content of 19.7 MJ/kg andstoichiometric air-to-fuel ratio of 6.42:1 mean that fuel consumption (on volume or mass bases) will be higher than hydrocarbon fuels. The extra water produced also makes the charge rather wet (similar to hydrogen/oxygen combustion engines) and with the formation of acidic products during combustion, the wearing of valves, valve seats and cylinder might be higher than with hydrocarbon burning. Certain additives may be added to the fuel in order to neutralize these acids. y Methanol, just like ethanol, contains soluble and insoluble contaminants.[9] These soluble contaminants, halide ions 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 electric, 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. y Methanol is hygroscopic, meaning it will absorb water vapor directly from the atmosphere.[1] Because absorbed water dilutes the fuel value of the methanol (although it suppresses engine knock), and may cause phase separation of

methanol-gasoline blends, containers of methanol fuels must be kept tightly sealed. Demerits: y There are some safety concerns with methanol because it burns with a nearly invisible flame, making flame detection difficult for vehicle owners and operators. y A few teaspoons of methanol consumed orally can cause blindness and a few tablespoons can be fatal, if not treated. Antidotes can be effective if administered within hours of intake. For safety reasons, denaturants are added to M100 to give the fuel an unpleasant taste and odor. y As with other alternative fuel vehicles, adequate training is required to operate and maintain methanol based vehicles. Application: Methanol, a common laboratory solvent, is especially useful for HPLC, UV/VIS spectroscopy, and LCMS due to its low UV cutoff.

Ethanol : Ethanol fuel is ethanol (ethyl alcohol), the same type of alcohol found in alcoholic beverages. It is most often used as a motor fuel, mainly as a biofuel additive for gasoline. Bioethanol is a form of renewable energy that can be produced from

agricultural feedstocks. It can be made from very common crops such as sugar cane, potato, manioc and corn. There has been considerable debate about how useful bioethanol will be in replacing gasoline. Concerns about its production and use relate to increased food prices due to the large amount of arable land required for crops,[10] as well as the energy and pollution balance of the whole cycle of ethanol production, especially from corn. Recent developments with cellulosic ethanol production and commercialization may allay some of these concerns. Source: Ethanol is a renewable energy source because the energy is generated by using a resource, sunlight, which cannot be depleted. Creation of ethanol starts

with photosynthesis causing a feedstock, such as sugar cane, grain, or corn, to grow. These feedstocks are processed into ethanol. About 5% of the ethanol produced in the world in 2003 was actually a petroleum product] It is made by the catalytic hydration of ethylene with sulfuric acid as the catalyst. It can also be obtained via ethylene or acetylene, from calcium carbide, coal, oil gas, and other sources. Two million tons of petroleum-derived ethanol are produced annually. The principal suppliers are plants in the United States, Europe, and South Africa. Petroleum derived ethanol (synthetic ethanol) is chemically identical to bioethanol and can be differentiated only by radiocarbon dating Bio-ethanol is usually obtained from the conversion of carbon based feedstock. Agricultural feedstocks are considered renewable because they get energy from the sun using photosynthesis, provided that all minerals required for growth (such as nitrogen and phosphorus) are returned to the land. Ethanol can be produced from a variety of feed stocks such as sugar cane, bagasse,miscanthus, sugar beet, sorghum, grain, switch grass, barley, hemp, kenaf, potatoes, sweet potatoes, cassava, sunflower, fruit, molasses, corn, stover, grain, wheat, straw, cotton,

other biomass, as well as many types of cellulose waste and harvestings, whichever has the best well-to-wheel assessment. An alternative process to produce bio-ethanol from algae is being developed by the company Algenol. Rather than grow algae and then harvest and ferment it the algae grow in sunlight and produce ethanol directly which is removed without killing the algae. It is claimed the process can produce 6,000 US gallons per acre (56,000 litres per ha) per year compared with 400 US gallons per acre (3,750 l/ha) for corn production. Currently, the first generation processes for the production of ethanol from corn use only a small part of the corn plant: the corn kernels are taken from the corn plant and only the starch, which represents about 50% of the dry kernel mass, is transformed into ethanol. Two types of second generation processes are under development. The first type uses enzymes and yeast fermentation to convert the plant cellulose into ethanol while the second type uses pyrolysis to convert the whole plant to either a liquid bio-oil or asyngas. Second generation processes can also be used with plants such as grasses, wood or agricultural waste material such as straw.

Production process The basic steps for large scale production of ethanol are: microbial (yeast) fermentation of sugars,distillation, dehydration (requirements vary, see Ethanol fuel mixtures, below), and denaturing (optional). Prior to fermentation, some crops require saccharification or hydrolysis of carbohydrates such as cellulose and starch into sugars. Saccharification of cellulose is called cellulolysis (see cellulosic ethanol). Enzymes are used to convert starch into sugar.[21] Fermentation: Ethanol is produced by microbial fermentation of the sugar. Microbial fermentation will currently only work directly with sugars. Two major components of plants, starch and cellulose, are both made up of sugars, and can in principle be converted to sugars for fermentation. Currently, only the sugar (e.g. sugar cane) and starch (e.g. corn) portions can be economically converted. There is much activity in the area of cellulosic ethanol,

where the cellulose part of a plant is broken down to sugars and subsequently converted to ethanol. Distillation For the ethanol to be usable as a fuel, the majority of the water must be removed. Most of the water is removed by distillation, but the purity is limited to 95-96% due to the formation of a low-boiling water-ethanol azeotrope with maximum (95.6% m/m (96.5% v/v) ethanol and 4.4% m/m (3.5% v/v) water). This mixture is called hydrous ethanol and can be used as a fuel alone, but unlike anhydrous ethanol, hydrous ethanol is not miscible in all ratios with gasoline, so the water fraction is typically removed in further treatment in order to burn in combination with gasoline in gasoline engines. Dehydration: There are basically five dehydration processes to remove the water from an azeotropicethanol/water mixture. The first process, used in many early fuel ethanol plants, is calledazeotropic distillation and consists of adding benzene or cyclohexane to the mixture. When these components are added to the mixture, it forms a heterogeneous azeotropic mixture in vapor-liquid-liquid equilibrium, which when distilled produces anhydrous ethanol in the column bottom, and a vapor mixture of water and cyclohexane/benzene. When condensed, this becomes a two-phase liquid mixture. Another early method, called extractive distillation, consists of adding a ternary component which will increase ethanol's relative volatility. When the ternary mixture is distilled, it will produce anhydrous ethanol on the top stream of the column. With increasing attention being paid to saving energy, many methods have been proposed that avoid distillation altogether for dehydration. Of these methods, a third method has emerged and has been adopted by the majority of modern ethanol plants. This new process uses molecular sieves to remove water from fuel ethanol. In this process, ethanol vapor under pressure passes through a bed of molecular sieve beads. The bead's pores are sized to allow absorption of water while excluding ethanol. After a period of time, the bed is regenerated under vacuum or in the flow of inert atmosphere (e.g. N2) to remove the absorbed water. Two beds are often used so that one is available to absorb water

while the other is being regenerated. This dehydration technology can account for energy saving of 3,000 btus/gallon (840 kJ/L) compared to earlier azeotropic distillation.

Performance: The effect of speed on power output, brake specific heat consumption (BSHC) and thermal efficiency of a engine using ethanol is compared with gasoline engine. y The power output of ethanol engine is higher compared to gasoline engine at all speeds. y The brake specific heat consumption is improved with ethanol engine compared with petrol engine y The maximum thermal efficiency of ethanol engine is higher than petrol engine, The efficiency curve of the ethanol engine is flat for a wide range of speed which indicates that the part load efficiency is much better compared with petrol engine. y The engine torque is considerable higher for ethanol as compared to petrol engine.

Advantages of alcohol: Some of the advantages of alcohol fueled engines compared with gasoline engines are listed below: y The alcohols (both) have higher heat of vapourisation. As the liquid fuel evaporates in the air stream being charged to the engine, a higher heat of vapouristion cools the air allowing more mass to be drawn into the cylinder.This increases the power produced from the given engine size>High Latent Heat of vapourisation leads to higher volumetric efficiency and provides good internal cooling. y The high octane number of alcohols compared to petrol means higher compression ratios can be used, which results in higher engine efficiencies and higher power from the engine. y Ethanol burns faster than petrol allowing more uniform and efficient torque development. Both alcohols have wider flammability limits which results into rich A:F ratio being used when needed to maximize power by injecting more fuel per cycle. y Alcohols also have lower exhaust emissions than gasolineengine except for aldehydes.Both alcohols have lower carbon to hydrogen ratio than petrol and diesel and they produce less CO2.For the same power output, the CO2 produced by ethanol fired engine is about 80% of the petrol engine. Because of the high heat of vapourisation , the fuels burn with lower flame temperature than petrol and less NOx formation occurs. The CO percentage in both cases (alcohol &petrol) more or less remains the same. y Also contamination of water in alcohols is less dangerous than petrol or diesel because alcohols are less toxic to humans and has a recognizable taste. y The alcohols can also be blended with gasoline to form the so called Gashol(80% petrol and 20% alcohol) and widely used in USA. y Ethyl alcohol as a fuel offers the advantages of great safety by the properties of its low degree of volatility and higher flash point (17 degree celcius)

Even its thermal value is lower than petrol(60% only), it shows equally good thermal efficiency and lower fuel consumption. This is because, the air required for petrol and alcohol are the ratio 15:9 by weight and this is same as their calorific value which follows that the same heat is developed per cylinder charge in petrol, ethanol and methanol are very closely similar.

In many hot countries, more precautions are often taken for the use of more volatile spirit based fuels while alcohol is perfectly safe in hottest climate also.

The major problem faced with ethanol is the corrosion and special metals should be used for the engine part to avoid corrosion.