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FUEL SOURCES
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Methanol is the lowest molecular weight and simplest alcohol, produced from the natural gas component methane It is also called methyl alcohol or wood alcohol, the latter because it was formerly produced from the distillation of wood Ethanol, also known as grain alcohol or ethyl alcohol, is most commonly used in alcoholic beverages However, it may also be used as a fuel, most often in combination with gasoline For the most part, it is used in a gasoline-to-ethanol ratio of 9:1 to reduce the negative environmental effects of gasoline Ethanol can be readily produced by fermentation of simple sugars that are converted from starch crops Feedstocks for such fermentation ethanol include corn, barley, potato, rice, and wheat This type of ethanol may be called grain ethanol, whereas ethanol produced from cellulose biomass such as trees and grasses is called bioethanol or biomass ethanol Both grain ethanol and bioethanol are produced via biochemical processes, while chemical ethanol is synthesized by chemical synthesis routes that do not involve fermentation There is increasing interest in the use of a blend of 85 percent fuel ethanol with 15 percent gasoline This fuel blend called E85 has a higher fuel octane than premium gasoline allowing in properly optimized engines increase both power and fuel economy over gasoline Butanol, also known as butyl alcohol, may be used as a fuel with the normal combustion engine, typically as a product of the ferment of biomass with the bacterium Clostridium acetobutylicum The advantages of butanol are the high octane rating (over 100) and high energy content, only about 10 percent lower than gasoline, and subsequently about 50 percent more energy-dense than ethanol, 100 percent more so than methanol The major disadvantage of butanol is the high flashpoint (35 C, 95 F)
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13 SYNTHETIC FUELS
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The production of synthetic fuels is essentially a hydrogen-addition process Fuels such as gasoline and natural gas have an atomic hydrogen/carbon ratio on the order of 20 while the fuel sources have lower atomic hydrogen/carbon ratio (on the order of 10 to 15) The source of hydrogen can be intramolecular in which a carbonaceous low-hydrogen residue (eg, coke) is produced or intermolecular in which hydrogen is added from an external source On the one hand, that is, intramolecular hydrogenation, pyrolysis of the feedstock in the absence of any added agent produces volatile (high-hydrogen) products and a nonvolatile (low-hydrogen) coke In pyrolysis the carbon content is reduced by heating the raw hydrocarbon until it thermally decomposes to yield solid carbon, together with gases and liquids having higher fractions of hydrogen than the original material On the other hand, that is, hydrogenation from an external source, the hydrogenation is either direct or indirect Direct hydrogenation involves exposing the raw material to hydrogen at high pressure Indirect hydrogenation involves reaction of the feedstock with steam, and the hydrogen is generated within the system Thus, gaseous or liquid synthetic fuels are obtained by converting a carbonaceous material to a gaseous or liquid form, respectively In the United States and many other countries, the most abundant naturally occurring materials suitable for this purpose are coal and oil shale Tar sands are also suitable, and large deposits are located in Canada The conversion of these raw materials is carried out to produce synthetic fuels to replace depleted, unavailable, or costly supplies of natural fuels However, the conversion may also be undertaken to remove sulfur or nitrogen that would otherwise be burned, giving rise to undesirable air pollutants Another reason for conversion is to increase the calorific value of the original raw fuel by
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CHAPTER ONE
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removing unwanted constituents such as ash, and thereby to produce a fuel which is cheaper to transport and handle Although most of the emphasis for the production of synthetic fuels is on synthetic fuels from coal, oil shale, and tar sands, biomass can also be converted to synthetic fuels and the fermentation of grain to produce alcohol is a well known example However, in many countries, grain is an expensive product which is generally thought to be more useful for its food value Wood is an abundant and accessible source of bioenergy but it is not known whether its use to produce synthetic fuels is economic The procedures for the gasification of cellulosecontaining materials have much in common with the conversion of coal to gas Most of the conversion principles to be discussed are, however, applicable to the spectrum of carbonaceous or cellulosic materials which occur naturally, are grown, or are waste Synthetic fuel or synfuel is any liquid fuel obtained from any of the aforementioned fuel sources (ie, tar sand, coal, oil shale, natural gas, natural gas hydrates, and biomass) as well as biologic alcohol and through the agency of the Fischer-Tropsch synthesis For the purposes of this text, the term synthetic fuel also includes liquid fuels derived from crops, wood, waste plastics, and landfill materials In a similar manner, synthetic gaseous fuel (syngas) and synthetic solid fuel can also (but less often) refer to gaseous fuels and solid fuels produced from the same sources In fact, synthesis gas (syngas) is the name given to a gas mixture that contains varying amounts of carbon monoxide and hydrogen generated by the gasification of a carbon containing fuel to a gaseous product with a heating value Examples include steam reforming of natural gas or liquid hydrocarbons to produce hydrogen, the gasification of coal and in some types of waste-to-energy gasification facilities The name comes from their use as intermediates in creating synthetic natural gas (SNG) and for producing ammonia or methanol Syngas is also used as an intermediate in producing synthetic petroleum for use as a fuel or lubricant via Fischer-Tropsch synthesis and previously the Mobil methanol to gasoline process Syngas consists primarily of carbon monoxide, carbon dioxide, and hydrogen, and has less than half the energy density of natural gas It is combustible and often used as a fuel source or as an intermediate for the production of other chemicals Syngas for use as a fuel is most often produced by gasification of coal or municipal waste: C + O2 CO2 CO2 + C 2CO C + H2O CO + H2 When used as an intermediate in the large-scale, industrial synthesis of hydrogen and ammonia, it is also produced from natural gas (via the steam reforming reaction): CH4 + H2O CO + 3H2 The syngas produced in large waste-to-energy gasification facilities is used as fuel to generate electricity Coal gasification processes (Chap 5) are reasonably efficient and were used for many years to manufacture illuminating gas (coal gas) for gas lighting, before electric lighting became widely available When syngas contains a significant amount of nitrogen, the nitrogen must be removed Cryogenic processing has great difficulty in recovering pure carbon monoxide when relatively large volumes of nitrogen are present, as carbon monoxide and nitrogen have very similar boiling points (ie, 1915 C and 19579 C, respectively) Instead there is technology that selectively removes carbon monoxide by complexation/decomplexation
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