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FUELS FROM CROPS
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and 10 years in the Corn Belt, Lake States, Northeast, and Northern Plains regions Thus, if it were planted in the spring of 2000, switchgrass could be harvested in 2000 or 2001, willow could be harvested in 2004, and poplars could be harvested in 2006, 2008, or 2010, depending on the region The use of cellulosic biomass in the production of ethanol also has environmental benefits Converting cellulose to ethanol increases the net energy balance of ethanol compared to converting corn to ethanol The net energy balance is calculated by subtracting the energy required to produce a gallon of ethanol from the energy contained in a gallon of ethanol (approximately 76,000 Btu) Corn-based ethanol has a net energy balance of 20,000 to 25,000 Btu/gal, whereas cellulosic ethanol has a net energy balance of more than 60,000 Btu/gal In addition, cellulosic ethanol use can reduce greenhouse gas emissions Cellulosic ethanol can produce an 8 to 10 percent reduction in greenhouse gas emissions when used in E10 and a 68 to 91 percent reduction when used in E85
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94 OTHER ALCOHOLS
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941 Methanol Methanol is a colorless, odorless, and nearly tasteless alcohol and is also produced from crops and is also used as a fuel Methanol, like ethanol, burns more completely but releases as much or more carbon dioxide than its gasoline counterpart The balance is often seen as the various biprocesses that draw carbon dioxide from the atmosphere so there is no net modern release, as there is for fossil fuels Methanol and other chemicals were routinely extracted from wood in the nineteenth and early twentieth centuries However, the original route for methanol recovery from biomass was quite different to current routes Methanol was originally recovered from wood as a by-product of charcoal manufacture, and was often called wood alcohol Pyrolysis (heating wood in the absence of air) to above 270 C in a retort causes thermal cracking or breakdown of the wood and allows much of the wood to be recovered as charcoal The watery condensate leaving the retort contained methanol, amongst other compounds In 1923, commercial production of methanol from synthesis gas by a catalytic process was commenced Now almost all of the methanol used worldwide comes from the processing of natural gas In general, methanol production from natural gas feed consists of three steps: (a) synthesis gas (syngas) generation in the case of natural gas feed, syngas production consists of converting methane (CH4) into carbon monoxide (CO) and hydrogen (H2) via steam reforming; (b) synthesis gas upgrading primarily removal of CO2, plus any contaminants such as sulfur; and (c) methanol synthesis and purification reacting the carbon monoxide, hydrogen, and steam over a catalyst in the presence of a small amount of CO2 and at elevated temperature and pressure The methanol synthesis is an equilibrium reaction and excess reactants must be recycled to optimize yields Modern methods proposed for the production of methanol from biomass involve the conversion of the biomass to a suitable synthesis gas, after which processing steps are very similar to those developed for methanol production from natural gas However, the gasification techniques proposed are still at a relatively early stage of development using biomass feed and the methods are based on similar techniques used widely already with natural gas as feed Before biomass can be gasified it must be pretreated to meet the processing constraints of the gasifier This typically involves size reduction, and drying to keep moisture contents below specific levels Thereafter, biomass gasification involves heating biomass in the
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CHAPTER NINE
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presence of low levels of oxygen (ie, less than required for complete combustion to carbon dioxide and water) Above certain temperatures the biomass will break down into a gas stream and a solid residue The composition of the gas stream is influenced by the operating conditions for the gasifier, with some gasification processes more suited than others to producing a gas for methanol production In particular, simple gasification with air creates a synthesis gas stream that is diluted with large quantities of nitrogen This nitrogen is detrimental to subsequent processing to methanol and so techniques using indirect gasification or an oxygen feed are preferred For large-scale gasification, pressurized systems are considered to be more economic than atmospheric systems Once the economic optimum synthesis gas is available the methanol synthesis takes place This typically uses a copper-zinc catalyst at temperatures of 200 to 280 C and pressures of 50 to 100 atm The crude methanol from the synthesis loop contains water produced during synthesis as well as other minor by-products Purification is achieved in multistage distillation, with the complexity of distillation dictated by the final methanol purity required
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942 Propanol and Butanol Propanol and butanol are considerably less toxic and less volatile than methanol In particular, butanol has a high flash point of 35 C (95 F), which is a benefit for fire safety, but may be a difficulty for starting engines in cold weather The fermentation processes to produce propanol and butanol from cellulose are fairly tricky to execute, and the 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 7 percent For comparison, yeast dies when the ethanol content of its feedstock hits 14 percent Specialized strains can tolerate even greater ethanol concentrations so-called turbo yeast can withstand up to 16 percent ethanol 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 percent This would be useful because butanol has a higher energy density than ethanol, and because waste fiber left over from sugar crops used to make ethanol could be made into butanol, raising the alcohol yield of fuel crops without there being a need for more crops to be planted
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