Alcohols

The Alcohols – Methanol and Ethanol

 Alcohols have been popular alternative fuels for many years. In fact, Henry Ford's
first car was fuelled with alcohol.
 Both ethanol and methanol are now used as transportation fuels and will likely play an
increasingly important role in the future.
 The Ford Model T was the first commercial flex-fuel vehicle. The engine was capable
of running on gasoline or ethanol, or a mix of both.
 The 2003 VW Gol 1.6 Total Flex was the first commercial flexible-fuel vehicle in the
Brazilian market, capable of running on any mixture of gasoline ( E20 to E25 blend)
and ethanol (E100).
Methanol (wood alcohol)
 Methanol (sometimes called wood alcohol) can be made from various biomass
resources like wood), as well as from coal.
 However, today nearly all methanol is made from natural gas, because it is cheaper.
 Methanol is also very poisonous and very harmful if swallowed. Methanol must not
be confused with ethanol.
 it is also wise to avoid skin contact with methanol, as it can pass through the skin.
Alcohol-fueled vehicles Race Cars
 Since the 1960s, methanol has been the required fuel for the Indianapolis 500 and
other types of racing. The reason for this is that methanol is made of a single
chemical.
 Gasoline, on the other hand, contains many different chemicals, and can vary greatly
from one batch to another.
Fire Safety
 Methanol is safer in case of accidental fire than gasoline, because it burns cooler.
 One problem is that the flame from a methanol fire is difficult to see in bright
sunlight.
 Sometimes accidental fires are not detected immediately, because the fire is hard to
see.
 Methanol contains about half the energy of gasoline per gallon.
 Lower energy per gallon means fewer miles per gallon of fuel, not less power.
 The decrease in range with methanol is not a problem for racing cars though, since all
of the cars are using exactly the same fuel.
Flexible fuel vehicles
 Flexible fuel vehicles (FFVs) are specially designed vehicles that can operate on
alcohol, gasoline or any combination of the two.
 FFVs have become quite popular with California fleets.
 Although some vehicles run on pure alcohol, FFVs operate on alcohol blends for two
main reasons.
 Adding a small amount of gasoline improves the engine starting in cold weather and
improves flame visibility in daylight.
 Pure alcohols burn with a nearly invisible flame in daylight. By adding gasoline, the
flame is easier to see and therefore safer.
 The alcohols used in FFVs are E85 (85 percent ethanol with 15 percent gasoline, like
in the Ford Taurus ) or M85 (85 percent methanol and 15 percent gasoline).
 FFVs are specially designed to tolerate the corrosive nature of alcohols.
 FFVs can run on gasoline when needed.

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 The amount of energy in alcohol fuels is different than gasoline.

 A gallon of gasoline in California contains approximately 111,500 Btu (which stands
for British thermal units).
 By comparison, M85 contains approximately 65,000 Btu/gallon and E85 contains
approximately 81,000 Btu/gallon.
 The lower energy content of these fuels will result in fewer miles per gallon or a
shorter driving range.
 Still, with larger fuel tanks, FFVs often have driving ranges equivalent to
conventional gasoline cars.
 Currently, the Ford Ranger ethanol FFV, beginning with the 1999 model, is the only
vehicle available in the U.S. that can run on an alcohol fuel.
Fuel cell cars
Some experts feel that methanol may be a good fuel for fuel cell cars.
Methanol
Methanol, also known as methyl alcohol, carbinol, wood alcohol, wood naphtha
or wood spirits, is a chemical compound with chemical formula CH3OH (often
abbreviated MeOH).
It is the simplest alcohol, and is a light, volatile, colourless, flammable, toxic liquid
with a distinctive odor that is somewhat milder and sweeter than ethanol.
At room temperature it is a polar liquid and is used as an antifreeze, solvent, fuel,
and as a denaturant for ethanol.
It is also used for producing biodiesel via transesterification reaction.
Molecular formula CH3OH,Molar mass 32.04 g/mol,Appearance colorless liquid,Density
0.7918 g/cm³, Melting point –97 °C, -142.9 °F (176 K),Boiling point 64.7 °C, 148.4 °F
(337.8 K),Solubility in water Fully miscible ,Viscosity 0.59 mPa·s at 20 °C ,Flash point 11
°C ,Flammable (F),Toxic (T)
Methanol is produced naturally in the anaerobic metabolism of many varieties of bacteria,
and is ubiquitous in the environment.
As a result, there is a small fraction of methanol vapor in the atmosphere.
Over the course of several days, atmospheric methanol is oxidized by oxygen with the help of
sunlight to carbon dioxide and water.
Burning of Methanol
Methanol burns in air forming carbon dioxide and water:
2 CH3OH + 3 O2 → 2 CO2 + 4 H2O
A methanol flame is almost colorless in bright sunlight conditions, causing an additional
safety hazard around open methanol flames.
Methanol: A denaturant additive of Ethanol
Because of its toxic properties, methanol is frequently used as a additive for ethanol
manufactured for industrial uses— this addition of methanol economically exempts industrial
ethanol from the rather significant 'liquor' taxes that would otherwise be levied as it is the
essence of all potable alcoholic beverages.

History
 In their embalming process, the ancient Egyptians used a mixture of substances, including
methanol, which they obtained from the pyrolysis of wood.
 Pure methanol, however, was first isolated in 1661 by Robert Boyle, who called it spirit
of box, because he produced it via the distillation of boxwood. It later became known as
pyroxylic spirit.

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 In 1923, the German chemists Matthias and Pier, working for BASF developed a means
to convert synthesis gas (a mixture of carbon monoxide, carbon dioxide, and hydrogen)
into methanol.
 This process used a chromium and manganese oxide catalyst, and required extremely
vigorous conditions
 Modern methanol production has been made more efficient through use of catalysts
(commonly copper) capable of operating at lower pressures, the modern low pressure
methanol (LPM) was developed by ICI in the late 1960's with the technology now owned
by Johnson Matthey who are a leading licensor of methanol technology.

 The use of methanol as a motor fuel received attention during the oil crises of the 1970s
due to its availability, low cost, and environmental benefits.
 By the mid-1990s, over 20,000 methanol "flexible fuel vehices" capable of operating on
methanol or gasoline were introduced in the U.S.
 In addition, low levels of methanol were blending in gasoline fuels sold in Europe during
much of the 1980s and early-1990s.
 Automakers stopped building methanol FFVs by the late-1990s, switching their attention
to ethanol fueled vehicles.
 While the Methanol FFV program was a technical success, rising methanol pricing in the
mid- to late-1990s during a period of slumping gasoline pump prices diminished the
interest in methanol fuels.
 In 2006 astronomers using the MERLIN array of radio telescopes at Jodrell Bank
Observatory discovered a large cloud of methanol in space, 300 billion miles across.
Production
 Today, synthesis gas is most commonly produced from the methane component in natural
gas rather than from coal.
 Three processes are commercially practiced.
 At moderate pressures of 1 to 2 MPa (10–20 atm) and high temperatures (around 850 °C),
methane reacts with steam on a nickel catalyst to produce syngas according to the
chemical equation:
 CH4 + H2O → CO + 3 H2
 This reaction, commonly called steam-methane reforming or SMR is endothermic and the
heat transfer limitations place limits on the size of and pressure in the catalytic reactors
used.
 Methane can also undergo partial oxidation with molecular oxygen to produce syngas, as
the following equation shows:
 2 CH4 + O2 → 2 CO + 4 H2
 This reaction is exothermic and the heat given off can be used in-situ to drive the steam-
methane reforming reaction.
 When the two processes are combined, it is referred to as autothermal reforming. The
ratio of CO and H2 can be adjusted to some extent by the water-gas shift reaction,
 CO + H2O → CO2 + H2, to provide the appropriate stoichiometry for methanol synthesis.
 The carbon monoxide and hydrogen then react on a second catalyst to produce methanol.
Today, the most widely used catalyst is a mixture of copper, zinc oxide, and alumina first
used by ICI (Imperial Chemical Industries)in 1966.
 At 5–10 MPa (50–100 atm) and 250 °C, it can catalyze the production of methanol from
carbon monoxide and hydrogen
 CO + 2 H2 → CH3OH

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 It is worth noting that the production of synthesis gas from methane produces 3 moles of
hydrogen for every mole of carbon monoxide, while the methanol synthesis consumes
only 2 moles of hydrogen for every mole of carbon monoxide.
 One way of dealing with the excess hydrogen is to inject carbon dioxide into the
methanol synthesis reactor, where it, too, reacts to form methanol according to the
chemical equation
 CO2 + 3 H2 → CH3OH + H2O
 Although natural gas is the most economical and widely used feedstock for methanol
production, other feedstocks can be used.
 Coal is increasingly being used as a feedstock for methanol production, particularly in
China.
 In addition, mature technologies available for biomass gasification are being utlized for
methanol production.
Applications of Methonol
 The largest use of methanol by far, is in making other chemicals. About 40% of methanol
is converted to formaldehyde, and from there into products as diverse as plastics,
plywood, paints, explosives, and permanent press textiles.
 Also in the early 1970s, a Methanol to gasoline process was developed by Mobil for
producing gasoline ready for use in vehicles.
 One such industrial facility was built at Motunui in New Zealand in the 1980s.
 In the 1990s, large amounts of methanol were used in the United States to produce the
gasoline additive methyl tert-butyl ether (MTBE), while MTBE is not longer marketed in
the U.S., it is still widely used in other parts of the world.
 In addition to direct use as a fuel, methanol (or less commonly, ethanol) is used as a
component in the transesterification of triglycerides to yield a form of biodiesel.
 Other chemical derivatives of methanol include dimethyl ether, which has replaced
chlorofluorocarbons
 Dimethyl ether, or "DME" also can be blended with liquified petroleum gas (LPG) for
home heating and cooking, and can be used as a diesel replacement transportation fuel.
Fuel for vehicles
 Methanol is used on a limited basis to fuel internal combustion engines, mainly by virtue
of the fact that it is not nearly as flammable as gasoline.
 Methanol is harder to ignite than gasoline.
Methanol: A corrosive
 One of the drawbacks of methanol as a fuel is its corrosivity to some metals, including
aluminum.
 Methanol, although a weak acid, attacks the oxide coating that normally protects the
aluminium from corrosion:
 6 CH3OH + Al2O3 → 2 Al(OCH3)3 + 3 H2O
 The resulting methoxide salts are soluble in methanol, resulting in clean aluminum
surface, which is readily oxidized by some dissolved oxygen.
 Also the methanol can act as an oxidizer:
 6 CH3OH + 2 Al → 2 Al(OCH3)3 + 3 H2
 This reciprocal process effectively fuels corrosion until either the metal is eaten away or
the concentration of CH3OH is negligible.
 Concerns with methanol's corrosivity have been addressed by using methanol compatible
materials, and fuel additives that serve as corrosion inhibitors.
BIOALCOHOL
Renewable alternative Fuel

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 When produced from wood or other organic materials, the resulting organic methanol
(bioalcohol) has been suggested as renewable alternative to petroleum-based
hydrocarbons.
 Low levels of methanol can be used in existing vehicles, with the use of proper cosolvents
and corrosion inhibitors.
 The European Fuel Quality Directive allows up to 3% methanol with an equal amount of
cosolvent to be blending in gasoline sold in Europe.
 Today, China uses more than one billion gallons of methanol per year as a transportation
fuel in both low level blends used in existing vehicles, and as high level blends in
vehicles designed to accommodate the use of methanol fuels.
Health and safety
 methanol (whether it enters the body by ingestion, inhalation, or absorption through the
skin) can be fatal due to its CNS depressant properties in the same manner as ethanol
poisoning.
 The initial symptoms of methanol intoxication are those of central nervous system
depression: headache, dizziness, nausea, lack of coordination, confusion, drowsiness, and
with sufficiently large doses, unconsciousness and death.
 The initial symptoms of methanol exposure are usually less severe than the symptoms
resulting from the ingestion of a similar quantity of ethanol.
 Once the initial symptoms have passed, a second set of symptoms arises, 10 to as much as
30 hours after the initial exposure to methanol, including blurring or complete loss of
vision and acidosis.
 These symptoms result from the accumulation of toxic levels of formate in the
bloodstream, and may progress to death by respiratory failure.
 The ester derivatives of methanol do not share this toxicity.
 Ethanol is sometimes denatured (adulterated), and thus made undrinkable, by the addition
of methanol. The result is known as methylated spirit
Safety in automotive fuels
 Pure methanol has been used in open wheel auto racing since the mid-1960s.
 Unlike petroleum fires, methanol fires can be extinguished with plain water.
 A methanol-based fire burns invisibly, unlike gasoline, which burns with visible smoke.
 If a fire occurs on the track, there is no smoke to obstruct the view of fast approaching
drivers, but this can also delay visual detection of the fire and the initiation of fire
suppression actions.
 One concern with the addition of methanol to automotive fuels is highlighted by recent
groundwater impacts from the fuel additive methyl tert-butyl ether (MTBE).
 Leaking underground gasoline storage tanks created MTBE plumes in groundwater that
eventually contaminated well water.
 However, since methanol is readily biodegradable in both aerobic (oxygen present) and
anaerobic (oxygen absent) environments, methanol will not persist in the environment.
 The "half-life" for methanol in groundwater is just one to seven days, while many
common gasoline components have half-lives in the hundreds of days (such as benzene at
10-730 days).
 Since methanol is infinitely soluble in water and biodegradable, methanol is unlikely to
accumulate in groundwater, surface water, air or soil.
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 biofuel alternative to gasoline, and is widely used
in cars in Brazil.

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 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 fuel - production
 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.
Cellulosic Ethanol fuel
 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.
 Another simple sugar in the plant is also fermented, fructose.
 Three other compounds in the plant may 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. Sucrose, or table
sugar, is a molecule of glucose bonded to a molecule of fructose.

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 The energy to create fructose comes from the metabolism of glucose created by
photosynthesis.
 When ethanol is burned in the atmosphere rather than in pure oxygen, other chemical
reactions occur with different components of the atmosphere such as N 2. This leads to the
production of nitrous oxides NOx , a major air pollutant.
Sources
 Ethanol is considered "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 feedstock's 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.
Production of Ethanol
first generation processes
 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.
Second generation processes
 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.
Production process
 The basic steps for large scale production of ethanol are: microbial (yeast)
fermentation of sugars, distillation, dehydration (requirements vary, see Ethanol fuel
mixtures, below), and denaturing (optional).
 Prior to fermentation, some crops require saccharification or hydrolysis of
carbohydrates such as cellulose and starch into sugars.
 Saccharification of cellulose is called cellulolysis. Enzymes are used to convert starch
into sugar.
Fermentation
 Ethanol is produced by microbial fermentation of the sugar.
 Microbial fermentation will currently only work directly with sugars.

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 Two major components of plants, starch and cellulose, are both made up of sugars,
and can in principle be converted to sugars for fermentation.
 Currently, only the sugar (e.g. sugar cane) and starch (e.g. corn) portions can be
economically converted.
 However, there is much activity in the area of cellulosic ethanol, where the cellulose
part of a plant is broken down to sugars and subsequently converted to ethanol.
Distillation
 For the ethanol to be usable as a fuel, water must be removed.
 Most of the water is removed by distillation, but the purity is limited to 95-96% due to
the formation of a low-boiling water-ethanol azeotrope.
 The 95.6% m/m (96.5% v/v) ethanol, 4.4% m/m (3.5% v/v) water mixture may be
used as a fuel alone, but unlike anhydrous ethanol, is immiscible in gasoline, so the
water fraction is typically removed in further treatment in order to burn with in
combination with gasoline in gasoline engines.
Dehydration
 There are basically five dehydration processes to remove the water from an azeotropic
ethanol/water mixture.
 The first process, used in many early fuel ethanol plants, is called azeotropic
distillation and consists of adding benzene or cyclohexane to the mixture.
 When these components are added to the mixture, it forms a heterogeneous azeotropic
mixture in vapor-liquid-liquid equilibrium, which when distilled produces anhydrous
ethanol in the column bottom, and a vapor mixture of water and cyclohexane/benzene.
 When condensed, this becomes a two-phase liquid mixture.
 Another early method, called extractive distillation, consists of adding a ternary
component which will increase ethanol relative volatility. When the ternary mixture is
distilled, it will produce anhydrous ethanol on the top stream of the column.
 With increasing attention being paid to saving energy, many methods have been
proposed that avoid distillation all together for dehydration.
 Of these methods, a third method has emerged and has been adopted by the majority
of modern ethanol plants. This new process uses molecular sieves to remove water
from fuel ethanol.
 In this process, ethanol vapor under pressure passes through a bed of molecular sieve
beads. The bead's pores are sized to allow absorption of water while excluding
ethanol.
 After a period of time, the bed is regenerated under vacuum to remove the absorbed
water.
 Two beds are used so that one is available to absorb water while the other is being
regenerated. This dehydration technology can account for energy saving of 3,000
btus/gallon compared to earlier azeotropic distillation.

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