Tuesday, March 17, 2009

Ethanol fuel

Ethanol fuel is ethanol (ethyl alcohol), the same type of alcohol found in alcoholic beverages. It can be used as a fuel, mainly as a bio fuel alternative to gasoline, and is widely used in cars in Brazil. Because it is easy to manufacture and process and can be made from very common crops such as sugar cane and corn, it is an increasingly common alternative to gasoline in some parts of the world. This is a renewable resource (can be produced, unlike petroleum which cannot be produced and in time will be gone).

Anhydrous ethanol (ethanol with less than 1% water) can be blended with gasoline in varying quantities up to pure ethanol (E100), and most spark-ignited gasoline style engines will operate well with mixtures of 10% ethanol (E10). Most cars on the road today in the U.S. can run on blends of up to 10% ethanol, and the use of 10% ethanol gasoline is mandated in some cities where harmful levels of auto emissions are possible.

Ethanol can be mass-produced by fermentation of sugar or by hydration of ethylene (ethene CH2=CH2) from petroleum and other sources. Current interest in ethanol mainly lies in bio-ethanol, produced from the starch or sugar in a wide variety of crops, but there has been considerable debate about how useful bio-ethanol will be in replacing fossil fuels in vehicles. Concerns relate to the large amount of arable land required for crops, as well as the energy and pollution balance of the whole cycle of ethanol production. Recent developments with cellulosic ethanol production and commercialization may allay some of these concerns.

According to the International Energy Agency, cellulosic ethanol could allow ethanol fuels to play a much bigger role in the future than previously thought. Cellulosic ethanol offers promise as resistant cellulose fibers, a major and universal component in plant cells walls, can be used to generate ethanol. Dedicated energy crops such as switchgrass are also promising cellulose sources that can be produced in many regions of the United States.

Chemistry

Glucose (a simple sugar) is created in the plant by photosynthesis.

6CO2 + 6H2O + light → C6H12O6 + 6O2

During ethanol fermentation, glucose is decomposed into ethanol and carbon dioxide.

C6H12O6 → 2C2H6O + 2CO2 + heat

During combustion ethanol reacts with oxygen to produce carbon dioxide, water, and heat:

C2H6O + 3O2 → 2CO2 + 3H2O + heat

After doubling the ethanol combustion reaction because two molecules of ethanol are produced for each glucose molecule, there are equal numbers of each type of molecule on each side of the equation, and the net reaction for the overall production and consumption of ethanol is just:

light → heat

The heat of the combustion of ethanol is used to drive the piston in the engine by expanding heated gases. It can be said that sunlight is used to run the engine.

Glucose itself is not the only substance in the plant that is fermented. The simple sugar fructose also undergoes fermentation. Three other compounds in the plant can be fermented after breaking them up by hydrolysis into the glucose or fructose molecules that compose them. Starch and cellulose are molecules that are strings of glucose molecules, and sucrose (ordinary table sugar) is a molecule of glucose bonded to a molecule of fructose. The energy to create fructose in the plant ultimately comes from the metabolism of glucose created by photosynthesis, and so sunlight also provides the energy generated by the fermentation of these other molecules.

Ethanol may also be produced industrially from ethene (ethylene). Addition of water to the double bond converts ethene to ethanol:.

CH2=CH2 + H2O → CH3CH2OH

This is done in the presence of an acid which catalyzes the reaction, but is not consumed.

When ethanol is burned in the atmosphere rather than in pure oxygen, other chemical reactions occur with different components of the atmosphere such as N2. This leads to the production of nitrous oxides NOx , a major air pollutant.

Sources

Ethanol is a "renewable" because it is primarily the result of conversion of the sun's energy into usable energy. Creation of ethanol starts with photosynthesis causing the feedstocks such as switchgrass, sugar cane, 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 bio-ethanol and can be differentiated only by radiocarbon dating.

Bio-ethanol is 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 feedstocks such as sugar cane, bagasse, miscanthus, sugar beet, sorghum, grain sorghum, switchgrass, 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.

Current, 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 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 a syngas. Second generation processes can also be used with plants such as grasses, wood or agricultural waste material such as straw.

Technology

Ethanol-based engines

Ethanol is most commonly used to power automobiles, though it may be used to power other vehicles, such as farm tractors and airplanes. Ethanol (E100) consumption in an engine is approximately 51% higher than for gasoline since the energy per unit volume of ethanol is 34% lower than for gasoline. However, the higher compression ratios in an ethanol-only engine allow for increased power output and better fuel economy than could be obtained with lower compression ratios. In general, ethanol-only engines are tuned to give slightly better power and torque output to gasoline-powered engines. In flexible fuel vehicles, the lower compression ratio requires tunings that give the same output when using either gasoline or hydrated ethanol. For maximum use of ethanol's benefits, a much higher compression ratio should be used, which would render that engine unsuitable for gasoline use. When ethanol fuel availability allows high-compression ethanol-only vehicles to be practical, the fuel efficiency of such engines should be equal or greater than current gasoline engines. However, since the energy content (by volume) of ethanol fuel is less than gasoline, a larger volume of ethanol fuel (151%) would still be required to produce the same amount of energy. In spite of that, as the ethanol-only vehicle wastes less energy, it yields the same or higher mileage.

A 2004 MIT study and an earlier paper published by the Society of Automotive Engineersidentify a method to exploit the characteristics of fuel ethanol substantially better than mixing it with gasoline. The method presents the possibility of leveraging the use of alcohol to even achieve definite improvement over the cost-effectiveness of hybrid electric. The improvement consists of using dual-fuel direct-injection of pure alcohol (or the azeotrope or E85) and gasoline, in any ratio up to 100% of either, in a turbocharged, high compression-ratio, small-displacement engine having performance similar to an engine having twice the displacement. Each fuel is carried separately, with a much smaller tank for alcohol. The high-compression (which increases efficiency) engine will run on ordinary gasoline under low-power cruise conditions. Alcohol is directly injected into the cylinders (and the gasoline injection simultaneously reduced) only when necessary to suppress ‘knock’ such as when significantly accelerating. Direct cylinder injection raises the already high octane rating of ethanol up to an effective 130. The calculated over-all reduction of gasoline use and CO2 emission is 30%. The consumer cost payback time shows a 4:1 improvement over turbo-diesel and a 5:1 improvement over hybrid. In addition, the problems of water absorption into pre-mixed gasoline (causing phase separation), supply issues of multiple mix ratios and cold-weather starting are avoided.

Ethanol's higher octane rating allows an increase of an engine's compression ratio for increased thermal efficiency. In one study, complex engine controls and increased exhaust gas recirculation allowed a compression ratio of 19.5 with fuels ranging from neat ethanol to E50. Thermal efficiency up to approximately that for a diesel was achieved. This would result in the MPG (miles per gallon) of a dedicated ethanol vehicle to be about the same as one burning gasoline.

Since 1986 there have also been ethanol engines based on the diesel principle operating in Sweden.[citation needed] They are used primarily in city buses, but also in distribution trucks, and waste collectors use this technology. The engines have a modified compression ratio, and the fuel (known as ED95) used is a mix of 95 % hydrous ethanol and 5 % ignition improver.[citation needed] The ignition improver makes it possible for the fuel to ignite in the diesel combustion cycle. It is then also possible to use the energy efficiency of the diesel principle with ethanol.

Engine cold start during the winter

High ethanol blends present a problem to achieve enough vapor pressure for the fuel to evaporate and spark the ignition during cold weather. When vapor pressure is below 45 kPa starting a cold engine becomes difficult. In order to avoid this problem at temperatures below 11 ° Celsius (59 °F), and to reduce ethanol higher emissions during cold weather, both the US and the European markets adopted E85 as the maximum blend to be used in their flexible fuel vehicles, and they are optimized to run at such a blend. At places with harsh cold weather, the ethanol blend in the US has a seasonal reduction to E70 for these very cold regions, though it is still sold as E85. At places where temperatures fall below -12 °C (10 °F) during the winter, it is recommended to install an engine heater system, both for gasoline and E85 vehicles. Sweden has a similar seasonal reduction, but the ethanol content in the blend is reduced to E75 during the winter months.

Brazilian flex fuel vehicles can operate with ethanol mixtures up to E100, which is hydrous ethanol (alcohol with up to 4% water), which causes vapor pressure to drop faster as compared to E85 vehicles, and as a result, Brazilian flex vehicles are built with a small secondary gasoline reservoir located near the engine to avoid starting problems in cold weather. The cold start with pure gasoline is particularly necessary for users of Brazil's southern and central regions, where temperatures normally drop below 15 ° Celsius (59 °F) during the winter. An improved flex motor generation that will be launched in 2009 will eliminate the need for this secondary gas storage tank.

Ethanol fuel mixtures

To avoid engine stall due to "slugs" of water in the fuel lines interrupting fuel flow, the fuel must exist as a single phase. The fraction of water that an ethanol-gasoline fuel can contain without phase separation increases with the percentage of ethanol.. This shows, for example, that E30 can have up to about 2% water. If there is more than about 71% ethanol, the remainder can be any proportion of water or gasoline and phase separation will not occur. However, the fuel mileage declines with increased water content. The increased solubility of water with higher ethanol content permits E30 and hydrated ethanol to be put in the same tank since any combination of them always results in a single phase. Somewhat less water is tolerated at lower temperatures. For E10 it is about 0.5% v/v at 70 F and decreases to about 0.23% v/v at -30 F.

In many countries cars are mandated to run on mixtures of ethanol. Brazil requires cars be suitable for a 25% ethanol blend, and has required various mixtures between 22% and 25% ethanol, since of July 2007 25% is required. The United States allows up to 10% blends, and some states require this (or a smaller amount) in all gasoline sold. Other countries have adopted their own requirements. Beginning with the model year 1999, an increasing number of vehicles in the world are manufactured with engines which can run on any fuel from 0% ethanol up to 100% ethanol without modification. Many cars and light trucks (a class containing minivans, SUVs and pickup trucks) are designed to be flexible-fuel vehicles (also called dual-fuel vehicles). In older model years, their engine systems contained alcohol sensors in the fuel and/or oxygen sensors in the exhaust that provide input to the engine control computer to adjust the fuel injection to achieve stochiometric (no residual fuel or free oxygen in the exhaust) air-to-fuel ratio for any fuel mix. In newer models, the alcohol sensors have been removed, with the computer using only oxygen and airflow sensor feedback to estimate alcohol content. The engine control computer can also adjust (advance) the ignition timing to achieve a higher output without pre-ignition when it predicts that higher alcohol percentages are present in the fuel being burned. This method is backed up by advanced knock sensors - used in most high performance gasoline engines regardless of whether they're designed to use ethanol or not - that detect pre-ignition and detonation.

Environment

Energy balance

All biomass goes through at least some of these steps: it needs to be grown, collected, dried, fermented, and burned. All of these steps require resources and an infrastructure. The total amount of energy input into the process compared to the energy released by burning the resulting ethanol fuel is known as the energy balance (or "Net energy gain"). Figures compiled in a 2007 by National Geographic Magazine point to modest results for corn ethanol produced in the US: one unit of fossil-fuel energy is required to create 1.3 energy units from the resulting ethanol. The energy balance for sugarcane ethanol produced in Brazil is more favorable, 1:8. Energy balance estimates are not easily produced, thus numerous such reports have been generated that are contradictory. For instance, a separate survey reports that production of ethanol from sugarcane, which requires a tropical climate to grow productively, returns from 8 to 9 units of energy for each unit expended, as compared to corn which only returns about 1.34 units of fuel energy for each unit of energy expended.

Carbon dioxide, a greenhouse gas, is emitted during fermentation and combustion. However, this is canceled out by the greater uptake of carbon dioxide by the plants as they grow to produce the biomass. When compared to gasoline, depending on the production method, ethanol releases less greenhouse gases.

Air pollution

Compared with conventional unleaded gasoline, ethanol is a particulate-free burning fuel source that combusts with oxygen to form carbon dioxide, water and aldehydes (a contraction of alcohol dehydrogenated). Gasoline produces 2.44 CO2 equivalent kg/l and ethanol 1.94 (this is -21% CO2)[citation needed]. The Clean Air Act requires the addition of oxygenates to reduce carbon monoxide emissions in the United States. The additive MTBE is currently being phased out due to ground water contamination, hence ethanol becomes an attractive alternative additive. Current production methods include air pollution from the manufacturer of macronutrient fertilizers such as ammonia.

A study by atmospheric scientists at Stanford University found that E85 fuel would increase the risk of air pollution deaths relative to gasoline. Ozone levels are significantly increased, thereby increasing photochemical smog and aggravating medical problems such as asthma.

Carbon dioxide

The calculation of exactly how much carbon dioxide is produced in the manufacture of bioethanol is a complex and inexact process, and is highly dependent on the method by which the ethanol is produced and the assumptions made in the calculation. A calculation should include:

  • The cost of growing the feedstock
  • The cost of transporting the feedstock to the factory
  • The cost of processing the feedstock into bioethanol

Such a calculation may or may not consider the following effects:

  • The cost of the change in land use of the area where the fuel feedstock is grown.
  • The cost of transportation of the bioethanol from the factory to its point of use
  • The efficiency of the bioethanol compared with standard gasoline
  • The amount of Carbon Dioxide produced at the tail pipe.
  • The benefits due to the production of useful bi-products, such as cattle feed or electricity.

The graph on the right shows figures calculated by the UK government for the purposes of the Renewable transport fuel obligation.

The January 2006 Science article from UC Berkeley's ERG, estimated reduction from corn ethanol in GHG to be 13% after reviewing a large number of studies. However, in a correction to that article released shortly after publication, they reduce the estimated value to 7.4%. A National Geographic Magazine overview article (2007) puts the figures at 22% less CO2 emissions in production and use for corn ethanol compared to gasoline and a 56% reduction for cane ethanol. Carmaker Ford reports a 70% reduction in CO2 emissions with bioethanol compared to petrol for one of their flexible-fuel vehicles.

An additional complication is that production requires tilling new soil which produces a one-off release of GHG that it can take decades or centuries of production reductions in GHG emissions to equalize. As an example, converting grass lands to corn production for ethanol takes about a century of annual savings to make up for the GHG released from the initial tilling.

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