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close this book Alcohol fuels: Options for Developing Countries
View the document Acknowledgments
View the document Preface
View the document Overview
View the document 1 Production and Use
View the document 2 Biomass Sources
View the document 3 Ethanol Production
View the document 4 Methanol Production
View the document 5 Social, Economic, and Environmental Implications
View the document 6 Conclusions and Recommendations
View the document Advisory Committee on Technology Innovation
View the document Board on Science and Technology for International Development

1 Production and Use

Among the lower alcohols, the two prime candidates for replacing petroleum fuels are methanol and ethanol. Although both are now manufactured largely from petroleum sources, processes for their production from biomass are available.

Butanol, a four-carbon alcohol, can also be produced from nonpetroleum sources. It is, however, a less likely contender for broad use as a fuel because of its comparatively high cost.

In Table 3, some characteristics of these alcohols are compared with those of gasoline and diesel oil. Several differences are obvious:

· Alcohols are essentially pure chemicals, boiling at one temperature, while the petroleum fuels are mixtures of many different chemicals with wide boiling ranges.

· Alcohols contain oxygen, whereas the petroleum fuels do not.

· Heating values for the alcohols are significantly lower than for the petroleum fuels.

Each of these differences has its consequences in the use of the fuels. The wide boiling range of gasoline is an advantage; the lower boiling components are sufficiently volatile to allow engine starting even at low temperatures. Unmodified engines powered by pure methanol or ethanol will not start below 10°-15°C.

The presence of oxygen in the alcohols gives them compatibility with water. Neither gasoline nor diesel fuel has any significant solubility in water, but methanol and ethanol are completely miscible with it. These two alcohols have an affinity for water sufficient to draw it from the air, a characteristic that can cause problems in their unprotected use and storage.

TABLE 3 Liquid Fuel Characteristics



















Boiling point














Lower heating valuea














a Lower heating value = heat of combustion at 25° C and constant pressure to form H2O (gas) and CO2 (gas).


TABLE 4 Alcohol and Hydrocarbon Heating Values



Lower Heating Value (MJ/kg)













The energy produced when any of these fuels are burned depends on the heat-generating reaction of oxygen with carbon and hydrogen Since the alcohols already contain oxygen, their heating values are less than their parent oxygen-free hydrocarbons. Table 4 illustrates this point for methanol and ethanol.

The oxygen content of the alcohols means that less air is required for their combustion. Compared with gasoline, methanol requires only 44 percent as much air for combustion and ethanol only 66 percent as much.

Each of these differences affects the ways in which alcohol fuels can be used or substituted for petroleum fuels.


Ethanol, methanol, and butanol can all be produced from biomass. The manufacturing methods used, however, are quite different for each and are described below.


One of mankind's first biochemical activities was the preparation of wine. The earliest records of many societies describe the fermentation of grains and fruit juices for beverages. In time, the technique of distillation was developed to increase the ethanol concentration, and ultimately almost pure ethanol was produced.

Currently, both fermentative and synthetic methods are used to produce ethanol. The primary synthetic route is the catalytic hydrolysis of ethylene derived from petroleum:

CH2 = CH2 + H2O ———> CH3CH2OH

ethylene........water....à ........ethanol

Synthetic ethanol plants range in size from 40 million lifers to 450 million lifers per year.

A wide variety of crops have been used for the production of ethanol by fermentation. These include sugar-containing raw materials such as sugarcane; starch-containing raw materials such as cassava, potatoes, maize, and barley; and cellulosic materials such as wood and crop residues.

For crops like sugarcane, sugar beet, and sweet sorghum, the juice is expressed and fermented directly. The primary sugars converted to ethanol are glucose and fructose (from sucrose):

C2H12O6 ————>2CH3CH2OH + 2CO2

glucose..................ethanol.......... carbon dioxide

Starch-containing crops must be pretreated with acid or enzymes to convert their starch to glucose. Enzymatic pretreatment of potato starch and various grain starches is routinely practiced in alcoholic beverage manufacture.

Like starch, cellulose is a polymeric form of glucose, but cellulose containing raw materials are not as readily degraded to glucose, principally because of cellulose crystallinity and the naturally occurring binding material, lignin, which gives wood its structural strength. Since cellulose comprises almost 50 percent of all biomass, it is an almost universally available, renewable, and inexpensive raw material. Throughout the world, a great deal of research is under way to find economic ways to convert cellulose to glucose. Although there are wood-to-glucose acid process plants operating in the Soviet Union, data on economics are unavailable.

The technologies for producing ethanol from sugar and starch are well known and widely practiced. In contrast to methanol production, small-scale ethanol manufacture (I ton per day) from sugars or starches (but not from cellulose) is feasible.

A process for converting cassava to 95 percent alcohol is shown in Figure 3. Typically, the raw material is ground to a paste, slurried in water, and heated. Enzymes are then added to convert the starch to sugars. The mix is transferred to a fermentation tower, and nutrients and yeast cultures added. The yeasts convert the sugars to ethanol and carbon dioxide. Fermentation are usually run to give a 10-15 percent ethanol concentration. In addition, solids consisting of yeast cells, undissolved or unconverted starch, and fiber and protein from the raw material are present.

Generally, this complete mix is passed down through a stripping column, counter current to steam. A solution of approximately 50 percent ethanol in water is taken from the top of the column and the spent solids from the bottom.

The alcohol stream is next distilled, first to give a 95:5 ethanol: water mix and, if required, redistilled with a water-entraining agent such as benzene or cyclohexane to give anhydrous ethanol.

Figure 3. Conversion of cassava to 95 percent alcohol.



The original process for the production of methanol was from the dry distillation (pyrolysis) of wood. The process was expensive, the yields poor (about 30 kg per ton of hardwood), and the product impure. Synthetic methods have completely replaced this route to methanol. Current processes use synthesis gas, a mixture of carbon monoxide (CO) and hydrogen (H2) usually derived from natural gas.

This mixture is reacted under pressure at high temperatures to yield methanol:

CO.............. + 2H2 ————>CH3OH

carbon.......... hydrogen..........methanol


Although natural gas is the predominant source of carbon monoxide and hydrogen for this reaction, it is possible to generate this mixture from coal, wood (including wood wastes), peat, or urban solid wastes, although no commercial plants use this process. Several countries, however, including Australia, Brazil, Canada, the United States, and New Zealand, have done extensive engineering and economic studies on wood-to-methanol processes.

A drawback to any biomass-to-methanol scheme is the size of the plant required and, therefore, the amount of raw materials needed to keep it operating. The minimum practical plant size (about 200 tons per day of methanol) requires about 500 tons per day of ovendry wood or equivalent biomass. Such volumes of biomass are not usually available at a given site without extensive gathering and transportation costs.

Whether biomass, natural gas, coal, or peat are used as a source of carbon monoxide and hydrogen, the final reaction is the same. The gases are mixed and compressed to 50-100 atmospheres and reacted over a catalyst at about 250°C.

The methanol-containing gases leaving the converter are cooled to condense the methanol and the unreacted gases are recycled. The methanol is then purified by distillation. Only a small amount of byproducts are obtained, including dimethyl ether and higher alcohols.


Butanol-acetone mixtures can also be produced by fermentation of starch- and sugar-containing raw materials. At one time second only to ethanol production by fermentation, the commercial use of the butanol-acetone process diminished sharply with the increased availability of petroleum raw materials.

The process, based on molasses, is still used in South Africa. In a 90,000-liter fermenter, about 5,850 kg of sugars yield approximately the following amounts:


1,050 kg


525 kg


175 kg


2,900 kg


117 kg

Unlike ethanol fermentations, which can yield a 10-15 percent product concentration, the butanol-acetone fermentation gives only about a 2 percent product concentration because the organism used, Clostridium acetobutylicum, cannot tolerate higher levels of the products. Recovery of the butanol and acetone is therefore more energy intensive. Clostridial fermentations are also more susceptible to bacteriophage contamination, requiring scrupulous plant hygiene.

If some of the innovative techniques for ethanol concentration that are currently in development could be applied to butanol-acetone, the process could gain greater use. In addition, clostridial fermentations will be particularly useful for the conversion of sugars from cellulose hydrolysis. In this process, both C5 and C6 sugars are produced. While organisms used for ethanol production can utilize only the C6 sugars, clostridia can convert both C5 and C6 sugars.


For any biomass-to-fuel project to be viable, the energy in the fuel produced (and the attendant by-products) should exceed the nonrenewable energy required to produce and convert the biomass.

Energy inputs can be divided into those needed for crop production and those needed for crop conversion. Crop production includes the energy required for machinery, fertilizer, herbicides, and insecticides involved in culture, harvest, and transportation of the biomass. Crop conversion involves the energy consumed in equipment manufacture and the chemical or biochemical processes, separations, and purifications required to generate the fuel.

One calculation of the distribution of energy required in crop production for ethanol is summarized in Table 5.

Clearly, the machinery, transportation, and fertilizer components are controlling factors for crop production energy.

Total energy requirements for both production and conversion to ethanol for these same crops are shown in Table 6.

Although each of these crops shows a positive energy return, many other factors must be considered. These include the amount of water required for high crop yields, the length of growing and harvesting seasons, the practicality of storage, capital and processing costs, and the potential for yield improvements. Energy balances alone do not provide the basis for investment decisions. The reasons for using alcohol fuels may include increasing rural employment and stimulating agricultural development as well as replacing imported petroleum fuels.

Energy form and versatility are also important. No amount of wind energy, for example, will help propel a farmer's tractor. Electricity probably has the most versatile range of applications, and liquid fuels are usually more readily transported, stored, and used than solid or gaseous fuels.

The Brazilian national oil company, Petrobras, has a 60,000-literper-day cassava-to-ethanol plant in Minas Gerais. This plant, in its first 3 years of operation, produced alcohol on a stop-and-go basis, since deliveries of cassava were not sufficient to keep the plant in operation. A technical team in Brazil concluded that cassava alcohol would only be economic if the cassava were plantation grown and mechanically harvested. The cost of collecting cassava from small growers is probably too expensive.

TABLE 5 Approximate Distribution of Total Energy Required in Ethanol Crop Production (Percent)




























Sweet sorghum






SOURCE: DaSilva et al., 1978.


TABLE 6 Energy Balance for Ethanol Production



Energy (Mcal/ha/yr)


Crop Yield,



























+ 1,815

Sweet sorghum








SOURCE: DaSilva et al., 1978.


The use of alcohol and alcohol-gasoline blends in motor transport is almost as old as the automobile itself. In England before 1900, an internal combustion engine was designed to run on ethanol. Alcohol powered vehicles were common in Europe during World Wars I and II. Alcohols, particularly ethanol, have been used in many other countries as motor fuel.

Considerable applied research on the use of alcohols and alcoholgasoline blends is being conducted both by major automobile manufacturers and government agencies in the United States, Europe, the Philippines, arid Brazil. Past experience shows that few performance problems are encountered with blends of up to about 20 percent alcohol in gasoline. The most efficient use of straight methanol or ethanol requires significant engine modification, including replacement of alcohol-sensitive components. Problems of retrofitting cars to use alcohol fuel and the cost and subsidy of the fuel production have been the subject of intense debate in the Brazilian press.

Automobiles will operate satisfactorily on alcohol-gasoline blends or on pure methanol and ethanol. Currently, the cost per mile traveled is higher than gasoline using these alternatives, but benefits in terms of balance of payments, local employment generation, and use of renewable resources must be included in decision making.


Cooking and Lighting

Ethanol and methanol can be used for cooking and lighting. A variety of simple stoves are commercially available or can be easily fabricated for use with alcohols. The flame is clean, relatively smoke- and odorfree, easily controlled, and readily ignited and extinguished.

For lighting, neither alcohol has a luminous flame when burned with a wick. This can be overcome by adding a small amount of an illuminant such as kerosine, vegetable oil, or animal fat. Use of alcohols in thorium mantle lamps is also a possibility.

Utility Boiler Fuel

In Brazil, Jones has examined the use of ethanol as a utility boiler fuel. Because the Brazilian government is committed to purchase all ethanol produced, its use as a boiler fuel could be an equalizing factor in balancing increasing production with automotive use; electrical generation is an alternative that avoids the necessity of new storage facilities for temporary surpluses.

Further, oil-fired boiler conversion costs for ethanol are modes compared with those required for coal or charcoal, and ethanol ha a low atmospheric pollution factor.

The boiler used in the Brazilian trial was a 135-MW unit in the Piratininga Power Station in Sao Paulo. After atomizing tests, burne modifications, and combustion trials, boiler load tests were conducted A maximum load of 110 MW was reached. This limit was impose by the capacity of the fuel pump, however, rather than any inherer problem with ethanol use. Flue gas analysis showed traces (1.8 ppm of aldehydes, but lower levels of nitrogen oxides than would be found foul fuel oil.

Duhl and Boylan tested methanol and fuel oil in a utility boiled designed for use with natural gas. The test was conducted at the' Patterson Station of the New Orleans Public Service Company in, boiler delivering steam to a 50-MW generator. Methanol use resulted in a loss of boiler efficiency of about 3 percent compared with nature gas, while maintaining the rated load and final steam temperature Nitrogen oxide emissions from methanol were less than those from natural gas and much less than those from fuel oil.

Von Kleinsmid et al. have compared methanol and distillate fuel use in gas turbines for Southern California Edison. A 26-MW gas turbine was run for 523 hours using methanol, and a second turbine' using distillate fuel was run in parallel. Lower nitrogen oxide emis signs as well as fewer internal deposits were found with methanol.

Fuel Cells

Methanol has also been used in fuel cells, devices in which the chemical energy of the fuel is converted directly to electrical power. Fuel cell are capable of high efficiencies because they are not limited to the efficiency of the Carnot Cycle, as are heat engines. Fuel cells, however are still in the development stage. If proved practicable they could provide a significant market for methanol.


Johnston has outlined some of the uses of ethanol as a solvent and as a basic building block for chemical production, the potential for these uses is included here because it affects ethanol's cost and avail ability for fuel use.

About half of the ethanol sold in the United States is used as a solvent. Printing inks, shellacs, varnishes, nitrocellulose coatings, cosmetics, pharmaceuticals, and foods all utilize ethanol in varying amounts. Paints, brake fluids, lubricants, herbicides, pesticides, and explosives all consume ethanol at some point in their manufacture.

For use as a chemical building block, ethanol can be readily dehydrated to ethylene. By using a fixed or fluidized catalyst bed at about 300°C, a yield of 85-90 percent can be obtained—about 1.7-2.0 tons of ethanol per ton of ethylene are required. Some of the simple derivatives of ethylene are shown in Table 7. Ethanol has also been used to produce acetaldehyde, which is a precursor for acetic acid, acetic anhydride, butanol, DDT, ethylhexanol, and butadiene. The bulk of Indian production of several of these chemicals is now based on ethanol. In Brazil, facilities are being planned to produce lowdensity polyethylene and vinyl acetate from ethanol.

Palsson and coworkers have suggested that the raw materials and technology exist for basing a major fraction of the United States chemical industry on four biomass-derived fermentation products: ethanol, isopropanol, butanol, and 2,3 butanediol. The route for introduction of these fermentation products is through their dehydration to olefins. Existing processing facilities can then be used to convert these olefins to other commercial chemicals. Figure 4 illustrates some of the possible routes and chemicals. Figure 5 compares the costs of ethanol, ethylene, and butanol from sugar and petroleum.

TABLE 7 Ethylene Derivatives and Uses








Ethylene oxide

Intermediate for solvents,


plastics, surfactants, synthetic


fibers, textile chemicals,


corrosion inhibitors


Ethylene dichloride

Intermediate for plastics,


lacquers, explosives, rubber


Ethanol and methanol can both be produced from biomass and can be used as transportation fuels as well as for heating, lighting, and electricity generation.

In addition, both alcohols can be used as chemical intermediates. Ethanol is particularly versatile. It can be used to produce a wide variety of chemical derivatives, including solvents, plastics, and detergents.

Figure 4. Some of many possible chemical and biochemical derivatives of glucose.

Figure 5. Break-even costs between petrochemistry.



Alcohol Fuels for Motor Vehicles


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Spark Ignition

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Compression Ignition

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Energy Balance

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Other Uses for Alcohols

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Duhl, R.W., and Boylan, J.W. 1976. Use of Methanol as a Boiler Fuel. Symposium of the Swedish Academy of Engineering Sciences, March 23, 1976, Stockholm, Sweden.

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Jones, E.C. 1980. The utilization of ethanol as a fuel in utility size boilers. In: IV International Symposium on Alcohol Fuels Technology. Guaruja, Sao Paulo, Brazil.

Palsson, B.O., Fathi-Afshar, S., Rudd, D.F., Lightfoot, E.N. 1981. Biomass as a source of chemical feedstocks: an economic evaluation. Science 213:513-517.

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