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Energy Sources, Part A: Recovery, Utilization, and Environmental Effects

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Bioalcohols as Alternatives to Gasoline

A. Demirbas
a a

Sila Science, Trabzon, Turkey

Available online: 23 Apr 2009

To cite this article: A. Demirbas (2009): Bioalcohols as Alternatives to Gasoline, Energy Sources, Part A: Recovery, Utilization, and Environmental Effects, 31:12, 1056-1062 To link to this article: http://dx.doi.org/10.1080/15567030801909748

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Energy Sources, Part A, 31:10561062, 2009 Copyright Taylor & Francis Group, LLC ISSN: 1556-7036 print/1556-7230 online DOI: 10.1080/15567030801909748

Bioalcohols as Alternatives to Gasoline

A. DEMIRBAS1
1

Sila Science, Trabzon, Turkey

Abstract Gasoline is a blend of hydrocarbons with some contaminants, including sulfur, nitrogen, oxygen, and certain metals. The four major constituent groups of gasoline are olens, aromatics, parafns, and napthenes. The main alternative fuels include alcohol, liqueed petroleum gas, compressed natural gas, hydrogen, and electricity for operation gasoline-type vehicles. Ethanol and methanol are biofuels that provide alternatives to gasoline. Bioethanol is a fuel produced by processing familiar and renewable crops such as cereals, sugar beet, and maize using natural fermentation. Blended with petrol at 10%, bioethanol can be used in vehicles without the need to change fuel or engine specications. Keywords ethanol, gasoline, methanol, Otto engine

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Introduction
Crude oil is a mixture of gasoline, kerosene, light-weight lubricating oil, engine oil, gear oil, tars, parafns, aromatics, waxes, asphalt, and sand. Crude oil can be rened into its component parts by a series of separation processes. Crude oil constituents are tabulated in Table 1. Crude oil is not used directly as a fuel but as a feedstuff for the petrochemical industry to produce commercial transportation fuels, synthetic rubbers, plastics, and additional chemicals. Oil reneries were originally placed near the oil elds, in part because natural gas, which could not then be economically transported long distances, was available to fuel the highly energy-intensive rening process, but since 1950, for strategic reasons crude oil was transported by tankers to local reneries. Gasoline is obtained from crude oil, which is made of up various hydrocarbons. Only a few of these are used to make gasoline. Through a rening process called fractional distillation, the different hydrocarbons are separated by taking advantage of their different boiling points. Following this rening, crude oil is separated into its various parts, one of which is gasoline, which consists of approximately 6% crude oil (Demirbas, 2007). One of the ways to accomplish increasing the yield of gasoline from crude oil is through cracking. Cracking is a petroleum-rening process. which breaks or cracks the heavier, higher boiling-point petroleum fractions into more valuable products such as unnished gasoline, kerosene, fuel oil, and gas oils. Various technologies exist for cracking waste oils for use as automotive or gaseous fuels. The main drawback is that it is an energy intensive process requiring more sophisticated, and thus costly, equipment. The process can rarely compete directly with the direct use of waste oil as a fuel. The most common type of cracking is catalytic cracking (Redwan and Ali, 1992).
Address correspondence to Professor Ayhan Demirbas, P. K. 216, TR-61035 Trabzon, Turkey. E-mail: ayhandemirbas@hotmail.com

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Bioalcohols as Alternatives to Gasoline Table 1 Crude oil constituents Fraction Gas Petroleum ether Ligroin (light naphtha) Natural gasoline Kerosene Gas oil Lubricating oil Asphalt or petroleum coke Distillation range, K Below 293 293333 333373 313478 448598 Above 548 Non-volatile liquids Non-volatile solids Carbon number

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C1 C4 C5 C6 C6 C7 C5 C10, and cycloalkanes C12 C18 , and aromatics C12 and higher Long chains and cyclic structures Polycyclic structures

The most common process is uid catalytic cracking, in which the oil is cracked in the presence of a nely divided catalyst, which is maintained in an aerated or uidized state by the oil vapors. Fluid catalytic cracking is one of the major processes that effectively contributes to the gasoline pool (Demirbas, 2008). The catalysts used in renery cracking units are typically solid materials (zeolite, aluminum hydrosilicate, treated bentonite clay, fullers earth, bauxite, and silica-alumina) that come in the form of powders, beads, pellets, or shaped materials called extradites. Gasoline is a blend of hydrocarbons with some contaminants, including sulfur, nitrogen, oxygen, and certain metals. Gasoline is a mixture of about 150 chemicals rened from crude oil. It is usually a colorless, light brown or pink liquid. The four major constituent groups of gasoline are olens, aromatics, parafns, and napthenes. The important characteristics of gasoline are density, vapor pressure, distillation range, octane, and chemical composition. To be attractive, a motor gasoline must have (a) desirable volatility, (b) anti-knock resistance (related to octane rating), (c) good fuel economy, (d) minimal deposition on engine component surfaces, and (e) complete combustion and low pollutant emissions (Chigier, 1981).

Use of Gasoline in Otto Engines

What is the car and fuel of the future? In the near-term, by far the most cost-effective strategy for reducing emissions and fuel use is efciency. The car of the near future is the hybrid gasolineelectric vehicle, because it can reduce gasoline consumption and greenhouse gas emissions 3050% with no change in vehicle class and hence no loss of jobs or compromise on safety or performance. It will likely become the dominant vehicle platform by the year 2020 (Romm, 2006). Electricity can be used as a transportation fuel to power battery, electric, and fuel-cell vehicles. Electric fuel is electricity that is used to directly power the vehicle. The power is created by batteries and other electricity sources. Batteries are energy storage devices, but unlike batteries, fuel cells convert chemical energy to electricity. Fuel cell vehicles use electricity produced from an electrochemical reaction that takes place when hydrogen and oxygen are combined in the fuel cell stack. The production of electricity using fuel cells takes place without combustion or pollution and leaves only two byproducts, heat and water. Batteries are energy storage devices, but unlike batteries, fuel cells convert chemical

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A. Demirbas Table 2 Available motor fuels

Fuel type Traditional fuels Oxygenated fuels

Available motor fuel Diesel and gasoline Ethanol, methanol, methyl tertiary butyl ether (MTBE), ethyl tertiary butyl ether (ETBE), tertiary butyl alcohol (TBA), and tertiary amyl methyl ether (TAME) Liqueed petroleum gases (LPG), ethanol, 85% (E85), ethanol, 95% (E95), methanol, 85% (M85), methanol, neat (M100), compressed natural gas (CNG), liqueed natural gas (LNG), bio-diesel (BD), hydrogen, and electricity

Alternative fuels

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Source: Hacisalihoglu, 2009.

energy to electricity. Benets include no emissions and fewer parts to be serviced and replaced. Electricity is also cheaper than gasoline. Alternative fuels for Otto engines or light-duty vehicles (LDVs; cars and light trucks) contain (1) reformulated gasoline, (2) compressed natural gas, (3) methanol and ethanol, (4) liquid petroleum gas, (5) liqueed natural gas, (6) Fischer-Tropsch liquids from natural gas, (7) hydrogen, and (8) electricity (MacLean and Lave, 2003). Table 2 shows available motor fuels. Gasoline qualities are usually measured in terms of volatility and octane number of the hydrocarbons. Adequate volatility is required for smooth operation of petrol engines. Light hydrocarbons (LHs) have higher volatilities than those of heavy hydrocarbons (HHs). LHs may cause vapor lock when the engine is hot. HHs may not be volatile enough to start the engine when the engine is cold. Suitable hydrocarbons are in the C5 C8 range. Octane number is a measure of the gasoline quality for prevention of early ignition, which leads to cylinder knocks. Higher octane numbers are preferred in internal combustion engines. For gasoline production, aromatics, naphthenes, and isoalkanes are highly desirable, whereas olens and n-parafns are less desired. The population of automobiles is currently dominated by vehicles burning gasoline. The main alternative fuels include alcohol, liqueed petroleum gas, compressed natural gas, hydrogen, and electricity for operation of gasoline-type vehicles. Figure 1 shows the wholesale prices of a number of possible alternative fuels on an energy equivalent basis compared to conventional gasoline (Demirbas, 2009). Only compressed natural gas (CNG) and liquid petroleum gas (LPG) appear to have some economic advantage relative to gasoline while ethanol, methanol, and electricity are at a severe economic disadvantage (Piel, 2001).

Bioalcohols as Gasoline Alternatives

The alcohols are oxygenated fuels. Any alcohol molecule has one or more oxygen atom. The heating value of any substance decreases with increasing its oxygen content. Practically any of the organic molecules of the alcohol family can be used as a fuel. The alcohols that can be used for motor fuels are methanol (CH3 OH), ethanol (C2 H5 OH),

Bioalcohols as Alternatives to Gasoline

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Figure 1. Economics of gasoline alternative fuels. (Source: AICHE, 1997.)

propanol (C3 H7 OH), and butanol (C4 H9 OH). However, only methanol and ethanol fuels are technically and economically suitable for internal combustion engines (ICEs) (Bala, 2005). Ethanol (ethyl alcohol, CH3 -CH2 -OH) is a clear, colorless liquid with a characteristic, agreeable odor. Two higher blends of ethanol, E-85 and E-95, are being explored as alternative fuels in demonstration programs. Ethanol can be blended with gasoline to create E85, a blend of 85% ethanol and 15% gasoline. E85 and blends with even higher concentrations of ethanol create E95. Ethanol has a higher octane number (108), broader ammability limits, higher ame speeds, and higher heats of vaporization than gasoline. These properties allow for a higher compression ratio, shorter burn time, and leaner burn engine, which lead to theoretical efciency advantages over gasoline in an ICE. Disadvantages of ethanol include its lower energy density than gasoline, its corrosiveness, low ame luminosity, lower vapor pressure, miscibility with water, and toxicity to ecosystems. Currently, ethanol is produced from sugar beets and from molasses. A typical yield is 72.5 liters of ethanol per ton of sugar cane. Modern crops yield 60 tons of sugar cane per hector of land. Production of ethanol from biomass is one way to reduce both the consumption of crude oil and environmental pollution (Lang et al., 2001). Domestic production and use of ethanol for fuel can decrease dependence on foreign oil, reduce trade decits, create jobs in rural areas, reduce air pollution, and reduce global climate change carbon dioxide buildup (Demirbas, 2005). Figure 2 shows obtaining of bioethanol from cellulosic biomass materials. Bioethanol is made from cellulosic biomass materials instead of from more expensive traditional feedstock such as starch crops. Processing steps in bioethanol production are: milling, saccharication, fermentation, distillation, dehydration, and denaturing. Methanol is mainly manufactured from natural gas, but biomass can also be gasied to methanol. Methanol can be made with any renewable resource containing carbon such as seaweed, waste wood, and garbage. This is a promising alternative, with a diversity of fuel applications with proven environmental, economic, and consumer benets. Problems occurred early in the development of gasoline-methanol blends. As a result of its low price, some gasoline marketers over blended. Many tests have shown promising results using 85100% by volume methanol as a transportation fuel in automobiles, trucks, and buses.

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Figure 2. Bioethanol from cellulosic biomass materials.

Methanol can be used as one possible replacement for conventional motor fuels. Methanol has been seen as a possible large-volume motor fuel substitute at various times during gasoline shortages. It was often used in the early part of the century to power automobiles before inexpensive gasoline was widely introduced. Methanol is poisonous and burns with an invisible ame. Just like ethyl alcohol, methanol has a high octane rating and hence an Otto engine is preferable. If an ignition booster is used, methanol can be used in a diesel engine. P-Series fuel is a unique blend of natural gas liquids, ethanol, hydrocarbons, and methyltetrahydrofuran (MeTHF). MeTHF is a biomass-derived co-solvent. P-Series is made primarily from renewable resources and provides signicant emissions benets over reformulated gasoline. The other gasoline substitute ether, MTBE (methanol tertiary butyl ether) is a full petroleum derivate (65% isobutene, 35% methanol). P-series fuels are blends of ethanol, methyltetrahydrofuran (MeTHF), natural gas liquids and butane. It is expected that ethanol and MeTHF are to be derived from renewable domestic feedstocks, such as corn, waste paper, cellulosic biomass, agricultural waste, and wood waste from construction. The P-series fuels emissions are generally below those for reformulated gasoline and are well below federal emissions standards. P-series fuels join the list of alternatives to gasoline that includes ethanol (E85), methanol (M85), natural gas, propane, and electricity. P-Series fuels are clear, colorless, 89-93 octane number, liquid blends that are formulated to be used in exible fuel vehicles. Like gasoline, low vapor pressure formulations are produced to prevent excessive evaporation during summer and high vapor pressure formulations are used for easy starting in the winter. P-series is at least 60% nonpetroleum. Because a majority of the components that make up P-series fuels come

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from domestically produced renewable resources, this alternative fuel promotes both energy security and environmental quality. P-series could be 96% derived from domestic resources. P-series fuels could reduce fossil energy use by 49% to 57% and petroleum use by 80% relative to gasoline. Greenhouse gas emissions of the P-series fuels are 4550% below those of reformulated gasoline. P-Series would be used in severe cold-weather conditions to meet cold start requirements. P-series also has many environmental benets. Emissions from the production and use of P-Series are substantially better than those from gasoline. Each unit of P-series fuel emits approximately 50% less carbon dioxide, 35% less hydrocarbons, and 15% less carbon monoxide than gasoline. It also has 40% less ozone-forming potential. Ethanol can be produced by synthesis from the chemical compound ethylene, which is derived from crude oil or natural gas, or by the fermentation of carbohydrates. Methanol is stored and handled like gasoline because it is produced as a liquid. Most methanol is currently made from natural gas, but it can also be made from a wide range of renewable biomass sources, such as wood or waste paper. Bioethanol is a bio-fuel substitute of gasoline; i.e., it is ethanol obtained from biomass (not from fossil fuels), and used as a gasoline blend, usually after transformation to ETBE (ethanol tertiary butyl ether). Pure bioethanol (E100-fuel) has been used mainly in Brazil. More widespread practice has been to add up to 20% to gasoline (E20-fuel or gasohol) to avoid engine changes.

Comparison of Alcohols to Gasoline

Ethanol contains 35% oxygen by weight; gasoline contains none. Oxygen promotes more complete combustion, which results in fewer tailpipe emissions. Compared to the combustion of gasoline, the combustion of ethanol substantially reduces the emission of carbon monoxide, volatile organic compounds, particulate matter, and greenhouse gases. A liter of ethanol contains about 32% less energy than a liter of gasoline. One of the best qualities of ethanol is its octane rating. Methanol and methanol blends have higher octane ratings than gasoline, which reduces engine knock and can produce higher engine efciency. The higher octane also gives methanol-fueled vehicles more power and quicker acceleration. A higher octane rating allows certain engine design parameters, such as compression ratio, and valve timing, to be altered in such ways that fuel economy and power are increased. Methanol also offers important emissions benets compared with gasoline. It can reduce hydrocarbon emissions by 3040% with M85 and up to 80% with M100 fuels. Methanol costs less than gasoline, but has lower energy content. Taking this into account, costs for methanol in a conventional vehicle are slightly higher than those for gasoline. When used in fuel cells, which are considerably more efcient, fuel costs will be lower. Three important points of comparison are emissions, fuel economy, and octane quality. E100 and M100 vehicles have difculty starting in cold weather, but this is not a problem for E85 and M85 vehicles because of the presence of gasoline.

Conclusion
Gasoline is obtained from crude oil, which is made of up various hydrocarbons. Ethanol and methanol are biofuels that provide alternatives to gasoline. Biofuels are generally more environmentally benign than traditional fuels and are further dened as being renewable, meaning that the feedstock used to make a particular

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biofuel can be replenished at a rate equal to or faster than the rate at which the biofuel is consumed. Alternative fuels are substitute fuel sources to petroleum. These fuels are important because they replace petroleum fuels; however, some still include a small amount of petroleum in the mixture.

References
Bala, B. K. 2005. Studies on biodiesels from transformation of vegetable oils for diesel engines. Energy Edu. Sci. Technol. 15:145. Chigier, N. A. 1981. Energy, Combustion and the Environment. New York: McGraw Hill. Demirbas, A. 2005. Bioethanol from cellulosic materials: A renewable motor fuel from biomass. Energy Sources 27:327337. Demirbas, A. 2007. Gasoline and diesel fuel blends with alcohols. Energy Edu. Sci. Technol. 19:8792. Demirbas, A. 2008. New liquid biofuels from vegetable oils via catalytic pyrolysis. Energy Educ. Sci. Technol. 21:159. Demirbas, T. 2009. Overview of bioethanol from biorenewable feedstocks: technology, economics, policy and impacts. Energy Educ. Sci. Technol. A 22:163177. Gerritsen, L. A. 1988. Recent development in catalytic reforming. Paper #G-2. Proceedings of the Akzo Catalysts Symposium 88, The Netherlands. Hacisalihoglu, S. 2009. Ethanol-gasoline and ethanol-diesel fuel blends. Energy Educ. Sci. Technol. A 22:133-146. Lang, X., Macdonald, D. G., and Hill, G. A. 2001. Recycle bioreactor for bioethanol production from wheat starch II. Fermentation and economics. Energy Sources 23:427436. MacLean, H. L., and Lave, L. B. 2003. Evaluating automobile fuel/propulsion system technologies. Progress Energy Combus. Sci. 29:169. Piel, W. J. 2001. Transportation fuels of the future?. Fuel Proces. Technol. 71:167179. Redwan, D. S., and Ali, S. A. 1992. Recent advances in uid catalytic cracking process. Fuel Sci. Technol. Intl. 10:141172. Romm, J. 2006. The car and fuel of the future. Energy 34:26092614.

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