PROSES INDUSTRI

KIMIA

DOSEN : PAHLIZATRA
MATERI 8 : ALCOHOL INDUSTRY

ALCOHOL DAN KLASIFIKASINYA

METHANOL
ETHANOL
PENGGUNAAN ALCOHOL
TREND DAN PERTUMBUHAN INDUSTRI
ALCOHOL

Alcohol merupakan senyawa yang terdiri dari rantai

carbon yang terikat dengan gugus hydroxy (-OH)

Methanol

Ethanol

Propanol

Phenol

3
Alkohol juga dapat diklasifikasikan menjadi :
1. Monohidrat : hanya mempunyai satu gugus OH per molekul
2. Dihidrat : mempunyai dua gugus OH per molekul
3. Trihidrat : mempunyai tiga gugus OH per molekul

Contoh
Nama IUPAC Rumus Td (oC)
Metanol CH3OH 65.0
Etanol CH3CH2OH 78.5
1 Propanol CH3CH2CH2OH 97.0
1 - Butanol CH3CH2CH2CH2OH 117.0
PENAMAAN DAN PENGGAMBARAN MOLEKUL

Penamaan Alcohol :
a) Alcohol dinamai dengan menggantikan nama a atau e
dari nama alkana dan menggantikannya dengan ol.
Gugus OH dapat juga digunakan sebagai pengganti
menggunakan nama gugus, hydroxy. (contoh : methane
-> methanol, ethane -> ethanol, propane -> propanol)
b) Penamaan yang lain bisa juga dilakukan dengan
memberikan nama gugus alkyl dan diikuti dengan kata
alcohol (contoh : methanol = methyl alcohol , ethanol =
ethyl alcohol)
Formula Umum Alcohols : CnH(2n+2)O

Unsur pertama adalah Methanol

a) Penggambaran formula :
H
|
H-C-O-H
|
H
b) Nama systematic : methanol (dari : methan + ol)
c) Structural formula : CH3OH
d) Molecular formula : CH4O
NAMA DAN RUMUS BANGUN ALCOHOL

Contoh :
CH3OH Methanol
CH3CH2OH Ethanol

CH3-CH2-CH2-OH dinamakan propan-1-ol atau 1-propanol

CH3-CH(OH)-CH3 dinamakan propan-2-ol atau 2-propanol

Jika terdapat lebih dari 1 unsur hydroxyl, imbuhan di-, tri-, tetra-
biasanya digunakan di akhir "e" yang terdapat pada unsur alkane
CH2OHCH(OH)CH2OH -> Glycerol atau 1,2,3-propanetriol
Alkohol
Struktur molekul alkohol sama dengan molekul air

O O
Hilang 1 H, tambah 1 gugus R R H
H H
H OH R OH

Alkohol atau gugus hidroksil (OH) merupakan gugus

fungsional alkohol

COH
Tempat umumnya reaksi terjadi

Karbon alkohol Gugus alkohol

KLASIFIKASI ALCOHOL

Alcohol dapat dikelompokkan menjadi :

- Primary
- Secondary
- Tertiary

Tergantung pada apakah unsur carbon yang berikatan dengan

gugus OH dikelilingi oleh satu, dua, atau tiga atom carbon
lainnya.

9
Klasifikasi alkohol
Alkohol primer (1o) : hanya mempunyai satu karbon yang
terikat pada karbon alkohol
Alkohol sekunder (2o) : mempunyai dua karbon yang terikat
pada karbon alkohol

Alkohol tersier (3o) : mempunyai tiga karbon yang terikat

pada karbon alkohol

I I
H R R
R C OH R C OH R C OH
H H R II

1O 2O 3O
Primary Alcohol

Primary alcohol is bonded to carbon atom that is

bonded also to one or no carbon atom carbon atom.

11
SECONDARY ALCOHOLS

A secondary alcohol is attached to a carbon atom that

is bonded also to 2 carbon atoms.

12
TERTIARY ALCOHOLS

13
POLYHYDROXY ALCOHOLS

Alcohols that have more than one OH group are

known as polyhydroxyl alcohols. Two examples
are shown below

14
PROPERTIES ALCOHOL

The physical properties of alcohols are similar to those of both

water and hydrocarbons

The shorter chain alcohols such as methanol and ethanol are

similar to water, in general they
-- have higher boiling points than hydrocarbons
but lower than water
-- dissolve in water to some degree
-- are more polar than hydrocarbons but less
polar than water

15
PHYSICAL PROPERTIES

Boiling point is higher than hydrocarbon. (Due to

intermolecular H-bond)
Spirituous odour with burning taste.
Short chain alcohols, up till 4 carbon atoms are soluble in
water.

Extra info:
Phenol (at room temperature) is colourless liquid but tinged
with pink oxidation product. It is moderately soluble in water.
It is corrosive.
REACTIONS OF ALCOHOLS

Alcohols undergo several types of reactions including:

Oxidation
Dehydration
Reactions with active metals
Esterification
Substitution

17
CHEMICAL REACTIONS OF ALCOHOLS

1. Alcohol with alkali metals alkoxide (strong base!)

2 Na + 2 CH3OH H2(g) + 2 CH3O- + 2 Na+
(sodium methoxide)

2. Alcohol substitution
CH3CH2CH2OH + HCl CH3CH2CH2Cl + H2O

CH3CH2OH + PCl5 CH3CH2Cl + HCl + POCl3

3. Alcohol dehydration
CH3-CH2-OH CH2=CH2 + H2O
CHEMICAL REACTIONS OF ALCOHOLS

4. Alcohol oxidation (burning)

* primary alcohols aldehydes
* secondary alcohols ketones
* tertiary alcohols no reaction

5. Alcohol with caboxylic acid for Esterification reaction

alcohol + acid ester + H20
OXIDATION

Alcohols are oxidized to alkanals (aldehydes) or

alkanones (ketones) and even carboxylic acids.

20
OXIDATION

Primary Alcohols are Oxidized to Alkanals/Aldehyde

The most common oxidizing agents are acidic KMnO4 soultion

or , acidic K2Cr2O7 or even oxygen from the air(very very slow).
The mechanisms of such reactions are usually complex

21
OXIDATION
Secondary Alcohols are oxidized to Alkanones/Ketones

Example

22
OXIDATION

Tertiary Alcohols are not easily oxidized

There is no hydrogen attached to the tertiary carbon. It is

not possible for a carbonyl group on the tertiary carbon to
be oxidixed.

23
OXIDATION

Tertiary Alcohols are not easily oxidized

Furthermore the large R groups on the tertiary carbon,
prevent reacting groups. Hence tertiary alcohols are rather
unreactive.

24
OXIDATION

H O
excess [O] O
R C O H + [O] R C H R C

H + H2O OH
Aldehyde / Alkanal Carboxylic acid
Primary alcohol

H O Common O.A. :
K2Cr2O7/ H+,
R C O H + [O] R C R' KMnO4/ H+
R' Ketone
Secondary alcohol
DEHYDRATION

Many alcohols undergo intramolecular dehydration,

removing water to form alkenes.

26
REACTIONS WITH METALS

Alcohols are far less acidic than water but they react with
highly reactive metals such as potassium and sodium.
The metal replaces the hydrogen atom in the alcohol
group forming a salt and hydrogen gas

27
ESTERIFICATION

An alcohol reacts with an alkanoic acid to form an ester

and water.

28
Konsumsi alkohol

Etanol digunakan sebagai minuman, obat-obatan, dan

pelarut dalam sejumlah bahan farmasetikal, padahal etanol
adalah racun. Etanol dapat menyebabkan liver mengeras,
kematian sel-sel otak, dan kecanduan.
Konsumsi alkohol oleh ibu hamil akan menyebabkan Fetal
Alcohol Syndrome (FAS), bayi yang terkena FAS tumbuh
tidak normal, mental terbelakang, dan bentuk muka cacat.
Kadar alkohol dalam darah 0,05-0,15%, menghambat
koordinasi, di atas 0,01% bersifat racun, 0,3-0,5%
menghilangkan kesadaran dengan resiko kematian.
Methanol
SUITABILITY FOR USE IN ROAD TRANSPORT

Methanol burns cleanly in a car engine. Its combustion is

more complete than that of petrol so levels of carbon
monoxide are reduced. Also it does not release
carcinogenic benzene vapor or other aromatic
hydrocarbons into the air. It has a high octane number and
would require only small changes to the engine and petrol
pump design of any vehicle.
AVAILABILITY AND COST OF SUPPLY

Methanol is produced from the distillation of wood.

It is manufactured from synthesis gas, a mixture of carbon
monoxide and hydrogen.
In turn synthesis gas can be made from natural gas, so
there is plenty of it around as it can be produced in
industry and does not take as long to make as other
sources of energy like oil and coal. Another thing is that it
is very cheap.
 ENERGY DENSITY
One of the big problems
with methanol is that it
produces about 40% less
than 1 litre of petrol. This
means more refueling trips
and larger and heavier fuel
tanks.
The theoretical energy
density of methanol is 4780
watt-hour/litre. This is
higher than the raw
materials and the effective
density of methanol is 1673
watt-hour/litre which is less
than petrol.
SAFETY

Another good thing about methanol is that it is less volatile

than petrol and is less likely to explode in an accident,
which is why it is used in cars in the CART championship
world series.

One other problem with methanol is that it is toxic. Long-

term exposure can cause blindness and brain damage,
which is the reason why meths drinkers generally go
blind. This can raise a concern on the effects on mechanics
and petrol-pump attendants at filling stations.
STORAGE AND DISTRIBUTION

A good thing about methanol is that very little would have

to be done to vehicles petrol tank or filling station tanks.
Petrol tanks would not really need changing at all except
that the tanks would have to be larger and heavier as
methanol produces less energy than fuel, so more would
need to be pumped into the vehicle. Storage tanks would
not really have to change at all, which would save money.
WHAT ABOUT THE ENGINE

A few differences would have to be made to the engine.

One thing is that the engine would have to be bigger and
more powerful, so really it is best used on bigger vehicles
and cars. Overall really not a lot would have to be done to
the engine as methanol is quite similar to petrol and
diesel. Several car companies in the USA are already
making methanol ran cars.
IMPACT ON ENVIRONMENT

Methanol is more environmentally friendly. It does not

release carbon monoxide, nor does it emit carcinogenic
benzene vapor or other aromatic hydrocarbons as its
combustion is more complete. It is also less volatile than
fuel and is less explosive.
Synthesis of Methanol using Steam
Reforming of Natural Gas
Introduction
Methanol is a new future alternative fuels and
it also widely uses as a raw material for
MTBE and other materials.
The demand of this fuel is increasing in the
world.
History of the methanol

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.
In 1834, the French chemists Jean-Baptiste Dumas and
Eugene Peligot determined its elemental composition.
This was shortened to methanol in 1892 by the
International Conference on Chemical Nomenclature.
 In 1923, the German chemist Matthias Pier, working for
BASF developed a means to convert synthesis gas (a mixture
of carbon monoxide and hydrogen derived from coke and
used as the source of hydrogen in synthetic
ammonia production) into methanol.
Pressures 3001000 atm,
Temperatures of about 400C.
USES OF THE METHANOL

Fuel internal combustion engines, flammable as gasoline.

As a solvent and as an antifreeze in pipelines.
About 40% of methanol is converted to formaldehyde, and
from there into products as diverse as plastics, plywood,
paints, explosives, and permanent press textiles.
In the 1990s, large amounts of methanol were used in the
United States to produce the gasoline additive methyl tert-
butyl ether (MTBE).
Other chemical derivatives of methanol include dimethyl
ether, which has replaced chlorofluorocarbons as the
propellant in aerosol sprays, and acetic acid.
PROPERTIES OF THE METHANOL
 DEMAND OF THE METHANOL

4.3E+04
4.1E+04
3.9E+04
3.7E+04
Ton / day

3.5E+04
3.3E+04
3.1E+04
2.9E+04
CAPACITY AVAILABLE
2.7E+04 TOTAL DEMAND
2.5E+04 PRODUCTION
1996 1998 2000 2002Year 2004 2006 2008
DEMAND OF THE METHANOL

The demand of methanol is increased and the production

of the methanol is also increased.
Methanol project in the Port of Salalah Free Zone in Oman
will be planned to produce 3,000 metric ton per day and
the Completion of the project is expected in late 2008
The worlds largest methanol plant (Vivas Methanol)
planned to build a 7,500-metric ton./day and it Scheduled
to start up in 2006
METHANOL PRODUCTION PROCESSES

Methanol is made using the Low Pressure Methanol

Synthesis Process.
The main raw materials
The plants production process that can be divided into
four main stages:
Feed Purification.
Reforming.
Methanol Synthesis.
Methanol Purification.
Feed Purification and Reforming
Methanol Synthesis
Methanol Purification
Methanol Production Processes
Feed gas Preparation
NG is compressed to about 45 bar
sulphur removed by desulphurization
cooled contacts with hot water
Additional steam to achieve 3:1 steam to carbon
ratio for reforming.
The total feed stream is then heated in the gas
heated reformer preheater.
Synthesis Gas Generation
There are three main chemical reactions which occur in
this process step :
Steam reforming CH4 + H2O = CO + 3H2
Shift reaction CO + H2O = CO2 + H2
Combustion 2H2 + O2 = 2H2O
Preheated gas flows from the preheater to the tube
side of the advanced gas heated reformer (AGHR).
As it passed down through the catalyst the reforming
reactions start.
Oxygen About 0.50 tones per tones of methanol.
The oxygen is completely consumed
 Reforming reactions continue and the gas leaves 1000C with less
than 0.5% methane slip.

The process condensate which condenses out of the reformed gas

is recycled back to the saturator.

After heat recovery the reformed gas is finally cooled and then
compressed to about 70 barg in the synthesis gas compressor to be
fed as synthesis gas to the synthesis loop.
Methanol Synthesis
There are two main chemical reactions which occur in this process
step :
CO + 2H2 = CH3OH
CO2 +3H2 = CH3OH + H2O

Production of a crude methanol stream which is about 80%

methanol and 20% water, carried out over a catalyst.

Crude methanol is separated from the uncondensed gases and the

gases recirculated back to the converter via the circulator.
Methanol distillation
This section consists :
Topping column
Refining column
HEALTH EFFECTS

Short Term Effects

Small amount

Nausea, headache, abdominal pain, vomiting and

visual disturbances ranging from blurred vision to light
sensitivity.
High concentrations

Irritate mucous membranes, cause headaches,

sleepiness, nausea, confusion, loss of consciousness,
digestive and visual disturbances and death.
HEALTH EFFECTS

Long Term Effects

Repeated exposure
Systemic poisoning
Brain disorders
Impaired vision
Blindness.
FIRE AND EXPLOSION HAZARD

Small fires
Dry Chemical
CO2
water spray.
Large fire
Water spray
AFFF(R) (Aqueous Film Forming Foam (alcohol
resistant)).

Methanol burns with a clean clear flame that is almost

invisible in daylight
REACTIVITY DATA

Chemically Stable
Incompatible with other substances
Strong oxidizers, strong acids, strong bases.

Conditions of Reactivity
Presence of incompatible materials and ignition
sources

Hazardous Decomposition Products

Formaldehyde, carbon dioxide and carbon monoxide
 Storage
In totally enclosed equipment

Avoid ignition and human contact

Tanks must be grounded and vented and should

have vapor emission controls.
Avoid storage with incompatible materials.
MATERIAL SELECTION FOR STORAGE TANK

Anhydrous methanol is non-corrosive except:

Lead

Magnesium

Methanol is non-corrosive except:

lead

Aluminum

Mild steel is the recommended construction material.

Environnemental Protection
Biodegradation / Aquatic Toxicity:
Methanol biodegrades easily in
Water.
Soil.
Methanol in high concentrations (>1%) in
fresh or salt water can have short-term
harmful effects on aquatic life within the
immediate spill area.
A Methanol Based
Economy
Search for Alternative Fuels

Peak Oil is approaching or already

passed.
Oil market is becoming more and more
volatile.
Need for immediate change without an
infrastructure overhaul.
Slow down greenhouse gas emission.
 Production of Methanol

Syn-Gas method is use for almost all

production of Methanol
CO + 2H2 CH3OH
CO2 + 3H2 CH3OH + H2O
CO2 + H2 CO + H2O
Natural gas incompletely burned
(preferred fuel over coal).
Methanol can be produced directly from
CO2 and H2.
Methanol Based Economy
Production of Methanol
 Methanol as a Fuel
Half the energy density of gasoline.
Octane rating of 100 higher
compression ratios higher efficiency.
Higher flame speed results in more
complete fuel combustion.
Burns at lower temperatures use air-
cooling instead of liquid-cooling lighter
vehicles.
 Price of Methanol
Most of methanol produced comes from
natural gas.
Average wholesale price has been about
$175 per ton.
Methanol could be produced for less than
30 cents a gallon.
Crude oil costs $1.20 to $1.80 per gallon.
Price of Methanol
Methanol and the Environment

Less CO, NOx, SOx, and VOCs.

Onboard Methanol Reformer emissions
are less than SULEV standard.
DMFC emissions are virtually zero.
Readily degraded through photooxidation
and biodegradation.
Degrades in almost all environments.
No evidence of bioaccumlation.
 Methanol as Feedstock
Methanol is used largely as feedstock for
many chemicals.
Formaldehyde, acetic acid, polymers,
paints, adhesives, construction materials.
More chemicals could be produced from
methanol.
Methanol could become more readily
available (Methanol economy).
Ethanol
WHAT IS ETHANOL?

CH3CH2OH
Ethanol is a clean-burning, high-octane fuel that is
produced from renewable sources.
At its most basic, ethanol is grain alcohol, produced
from crops such as corn.
Since pure 100% ethanol is not generally used as a
motor fuel, a percentage of ethanol is combined with
unleaded gasoline, to form E10 and E85
E10: 10% ethanol and 90% unleaded gasoline, is
approved for use in any US vehicle
E85: 85% ethanol and 15% unleaded gasoline, is an
alternative fuel for use in flexible fuel vehicles (FFVs).
HOW IS IT MADE?

Ethanol can be made by fermenting almost any material that

contains starch.
Most of the ethanol in the U.S. is made using a dry mill
process.
In the dry mill process, the starch portion of the corn is
fermented into sugar then distilled into alcohol
Prior to fermentation, high-value chemicals are removed from
the biomass. These include fragrances, flavoring agents,
food-related products, and high value nutraceuticals with
health and medical benefits.
There are two main valuable co-products created in the
production of ethanol: distillers grain and carbon dioxide.
Distillers grain is used as a highly nutritious livestock feed
while carbon dioxide is collected, compressed, and sold for
use in other industries.
PROPERTIES

Physical properties:

Colorless liquid.
Pleasant alcoholic odor detectable at 49 to 716 ppm.
Miscible with water and most organic solvents.
Melting Point (C): -114.1
Boiling Point (C): 78.3
Specific Gravity: 0.789
Vapor Density: 1.6
PROPERTIES

When released into water it will volatilize and probably

biodegrade.

It would not be expected to adsorb into sediment or bio-

accumulate in fish.

Although no data on its biodegradation in natural waters

could be found, laboratory tests suggest that it may
readily biodegrade and its detection in water systems may
be due in part to its extensive use in industry with
possible relatively steady and large levels of discharges.
PROPERTIES

When released to the atmosphere it will photodegrade to

carbon dioxide and water in hours (polluted urban
atmosphere) to an estimated range of 4 to 6 days in less
polluted areas.

At low concentrations and amounts, ethanol is rapidly

metabolised without apparent harm. At high concentrations,
such as in leaks or spills, ethanol can have substantial acute
effects on a wide range of biota, while it can cause death to
many microbes. ETHANOL is used as both a food and a
disinfectant
FLAMMABILITY ???

Gasoline -40 F (1.4 7.4 %),

Ethanol 55 F (3.3 - 24.5 %)
Ethanol, in general, has a higher flash point than gasoline,
thus posing less risk, but
At low temperatures (< 32 degrees), E85 vapor is more
flammable than gasoline vapor
E85 vapor is less flammable than gasoline at higher temps.
The lower vapor pressure and lower heat of combustion of
E85 reduce risk of fire compared to gasoline. In the event of
a fire, the flame is less bright than a gasoline flame, but is
visible in daylight.
What is the difference in putting out an
ethanol fire versus putting out a gasoline fire?

NFPA 30 and 30A recommend that the same form of fire

fighting chemicals and techniques be used on E85 as is
used to fight fires fueled with unleaded gasoline.

The NFPA does not require different fire fighting for

ethanol in comparison to gasoline.
Energy Balance of Ethanol
Energy Balance

Although CO2 is released during ethanol production and combustion,

it is recaptured as a nutrient to the crops that are used in its
production.
Unlike fossil fuel combustion, which unlocks carbon that has been
stored for millions of years, use of ethanol results in comparatively
lower increases to the carbon cycle.
Ethanol also degrades quickly in water and, therefore, poses a
smaller risk to the environment than an oil or gasoline spill.
Research studies from a variety of sources have found ethanol to
have a positive net energy balance. The most recent, by the U.S.
Department of Agriculture, shows that ethanol provides an average
net energy gain of at least 77%.
It takes less than 35,000 BTUs of energy to turn corn into ethanol,
while the ethanol offers at least 77,000 BTUs of energy. Thus
ethanol has a positive energy balancemeaning the ethanol yields
more energy than it takes to produce it.
Impact on air quality
Using ethanol-blended fuel has a positive impact on air
quality. By adding oxygen to the combustion process
which reduces exhaust emissionsresulting in a cleaner
fuel for cleaner air.
Ethanol reduces the emissions of carbon monoxide,
VOX, and toxic air emissions:
Since ethanol is an alcohol based product, it does not produce
hydrocarbons when being burned or during evaporation thus
decreasing the rate of ground level ozone formation.
Ethanol reduces pollution through the volumetric displacement of
gasoline. The use of ethanol results in reductions in every
pollutant regulated by the EPA, including ozone, air toxins,
carbon monoxide, particulate matter, and NOX.
Impact on energy
independence
Since it is domestically produced, ethanol helps reduce
America's dependence upon foreign sources of energy.
U.S. ethanol production provides more than 4 billion
gallons of renewable fuel for our country.
Current U.S. ethanol production capacity can reduce
gasoline imports by more than one-third and effectively
extend gasoline supplies at a time when refining capacity
is at its maximum.
According to the Energy Information Administration, the
7.5 billion gallon ethanol production level in the recently
enacted Renewable Fuels Standard could reduce oil
consumption by 80,000 barrels per day.
 Impact on economy
In a 1997 study The Economic Impact of the Demand for Ethanol,
Northwestern Universitys Kellogg School of Management found that:
During ethanol plant construction, approximately 370 local jobs are created.
During ethanol plant operation, up to 4,000 local jobs are created.
Ethanol plant construction creates $60 million to $130 million in additional
income.
Ethanol plant operation creates $47 million to $100 million in additional
income.
American-made, renewable ethanol directly displaces crude oil we would
need to import, offering our country critically needed independence and
security from foreign sources of energy.

The U.S. Department of Agriculture has concluded that a 100 million

gallon ethanol facility could create 2,250 local jobs for a single
community. Ethanol production creates domestic markets for corn and
adds 4-6 cents a bushel for each 100 million bushels used. Better
prices mean less reliance on government subsidy programs not to
mention higher income and greater independence for farmers.
Impact on auto industry
Ethanol could be the alternative fuel source that
catapults sales of American auto manufacturers.
GM and Ford are looking for environmental fixes that are
quicker and cheaper than the more costly hybrids and
futuristic fuel cells. Both companies started promoting
flexible-fuel vehicles (FFVs) aggressively this year.
General Motors tied their new campaign "Live Green, Go
Yellow.'' to not only Super Bowl Sunday but the opening
of the Winter Olympics as well.
Since only about 600 of the nation's 170,000 filling
stations sell E85, both companies
have begun programs to install
E85 pumps at more stations.
Problems with Ethanol
Odors as a public nuisance, ex: New Energy Ethanol
Plant here in South Bend
Green house gas emissions have sometimes shown to
be equivalent to those of gasoline (data is often
inconclusive)
Environmental performance of ethanol varies greatly
depending on the production process
Costs involved with building new facilities for ethanol
production
New ways to maximize crop production are necessary
Research is needed to refine the chemical processes
to separate, purify and transform biomass into usable
fuel
Problems with Ethanol
Soil erosion from increased agriculture
Conversion of forests into agricultural landwhich
could lead to future environmental dilemmas
.
 Ethanol (ethyl alcohol, grain alcohol) is a clear, colorless liquid
with a characteristic, agreeable odor.

In dilute aqueous solution, it has a somewhat sweet flavor, but

in more concentrated solutions it has a burning taste.

Ethanol, the word, alcohol derives from Arabic al-kuhul, which

denotes a fine powder of antimony used as an eye makeup.
Alcohol originally referred to any fine powder, but medieval
alchemists later applied the term to the refined products of
distillation, and this led to the current usage.
 Ethanol can enter the environment as emissions
from its manufacture, use as a solvent and
chemical intermediate, and release in
fermentation and alcoholic beverage
preparation.
It naturally occurs as a plant volatile, microbial
degradation product of animal wastes, and in
natural fermentation of carbohydrates. Produced
naturally from a wide range of microbiological
processes (by fungi, bacteria, etc), and possibly
some plants.
When spilled on land it is apt to volatilize,
biodegrade, and leach into the ground water, but
no data on the rates of these processes could be
found. Its fate in ground water is unknown.
Ethanol is a clean-burning, high-
octane fuel that is produced from
renewable sources.

At its most basic, ethanol is grain

alcohol, produced from crops
such as corn.
 Ethanol can be made by a dry mill process or
a wet mill process.

Most of the ethanol in the U.S. is made using

the dry mill method. In the dry mill process,
the starch portion of the corn is fermented
into sugar then distilled into alcohol.
 The major steps in the dry mill process are:

1. Milling. The feedstock passes through a

hammer mill which grinds it into a fine powder
called meal.

2. Liquefaction. The meal is mixed with water

and alpha-amylase, then passed through cookers
where the starch is liquefied. Heat is applied at
this stage to enable liquefaction. Cookers with a
high temperature stage (120-150 degrees
Celsius) and a lower temperature holding period
(95 degrees Celsius) are used. High temperatures
reduce bacteria levels in the mash.
3. Saccharification. The mash from the cookers
is cooled and the secondary enzyme (gluco-
amylase) is added to convert the liquefied starch
to fermentable sugars (dextrose).

4. Fermentation. Yeast is added to the mash to

ferment the sugars to ethanol and carbon
dioxide. Using a continuous process, the
fermenting mash is allowed to flow through
several fermenters until it is fully fermented and
leaves the final tank. In a batch process, the
mash stays in one fermenter for about 48 hours
before the distillation process is started.
5. Distillation. The fermented mash, now called beer, contains
about 10% alcohol plus all the non-fermentable solids from the
corn and yeast cells. The mash is pumped to the continuous
flow, multi-column distillation system where the alcohol is
removed from the solids and the water. The alcohol leaves the
top of the final column at about 96% strength, and the residue
mash, called stillage, is transferred from the base of the
column to the co-product processing area.

6. Dehydration. The alcohol from the top of the column

passes through a dehydration system where the remaining
water will be removed. Most ethanol plants use a molecular
sieve to capture the last bit of water in the ethanol. The alcohol
product at this stage is called anhydrous ethanol (pure, without
water) and is approximately 200 proof.
7. Denaturing. Ethanol that will be used for fuel
must be denatured, or made unfit for human
consumption, with a small amount of gasoline (2-
5%). This is done at the ethanol plant.

8. Co-Products. There are two main co-products

created in the production of ethanol: distillers grain
and carbon dioxide. Distillers grain, used wet or
dry, is a highly nutritious livestock feed. Carbon
dioxide is given off in great quantities during
fermentation and many ethanol plants collect,
compress, and sell it for use in other industries.
Distillers grain can be fed to livestock wet or
dry. Dried distillers grain (DDG) is the most
common variety. Drying the distillers grain
increases its shelf life and improves its ability
to be transported over longer distances. If a
consistent nearby market can be secured,
ethanol producers can supply the feed as wet
distillers grain (WDG). The wet form is not
as easily transportable, but the cost of drying
the product is removed.
 Dried distillers grain with solubles (DDGS) is
the form available to the feed industry. The liquid
that is separated from the mash during the
distilling process is partially dehydrated into a
syrup, then added back onto the dried distillers
grain to create DDGS.

DDGS is a high quality feedstuff ration for dairy

cattle, beef cattle, swine, poultry, and
aquaculture. The feed is an economical partial
replacement for corn, soybean meal, and
dicalcium phosphate in livestock and poultry
feeds. Historically, over 85% of DDGS has been
fed to dairy and beef cattle, and DDGS
continues to be an excellent, economical feed
ingredient for use in ruminant diets.
The personal care products industry is one of
the largest users of industrial ethanol, or ethyl
alcohol.

Check the labels hairspray, mouthwash,

aftershave, cologne, and perfume all contain
large amounts of alcohol by volume. Ethanol is
also used in many deodorants, lotions, hand
sanitizers, soaps, and shampoos.
 Carbon dioxide is used to carbonate
beverages, to manufacture dry ice, and to
flash freeze meat. CO2 is also used by paper
mills and other food processors.

A project is underway in Kansas to use carbon

dioxide to recover oil from marginal oil fields.
Using this miscible CO2 flooding, carbon
dioxide from a nearby ethanol plant is injected
into oil-producing rocks about 3,000 feet
underground. The carbon dioxide mixed with
oil that has collected in hard-to-reach spots in
the rock, forcing it into nearby production wells.
 Ethanol melts at 114.1C, boils at
78.5C, and has a density of 0.789
g/mL at 20C.

Its low freezing point has made it

useful as the fluid in thermometers for
temperatures below 40C, the
freezing point of mercury, and for other
low-temperature purposes.
 Pure, 100% ethanol is not generally used as
a motor fuel; instead, a percentage of ethanol
is combined with unleaded gasoline. This is
beneficial because the ethanol:

decreases the fuel's cost

increases the fuel's octane rating
decreases gasoline's harmful emissions
BLENDING WITH GASOLINE
Any amount of ethanol can be combined with
gasoline, but the most common blends are:
 E10 - 10% ethanol and 90% unleaded
gasoline

E10 is approved for use in any make or

model of vehicle sold in the U.S. Many
automakers recommend its use because of
its high performance, clean-burning
characteristics. In 2004, about one-third of
America's gasoline was blended with ethanol,
most in this 10% variety.
 E85 - 85% ethanol and 15% unleaded
gasoline

E85 is an alternative fuel for use in flexible fuel

vehicles (FFVs). There are currently more than 4
million FFVs on America's roads today, and
automakers are rolling out more each year. In
conjunction with more flexible fuel vehicles,
more E85 pumps are being installed across the
country. When E85 is not availible, these FFVs
can operate on straight gasoline or any ethanol
blend up to 85%.
 Impact of Ethanol on
the Hereford Industry
 World Ethanol Production, 2006

19%
36%
U.S.A.

4% Brazil
China
8%
India
others
33%

Source: Renewable Fuels

Association
Basics of Ethanol
Production
Ethanol is an alcohol made by
fermenting grain and other
carbohydrates
This is an old process which traditionally
has been used to produce ethanol for
use as a beverage
97% of U.S. ethanol is made from corn

Rest: milo, wheat, brewery waste, whey,

etc
Economics of BioFuels
The economics of biofuels is
confusing, in part, because we
measure gasoline and diesel in
gallons and corn and soybeans in
bushels
Measuring everything in pounds
makes the economics easier to
understand
Economics of Ethanol
Corn is worth 6 per pound
Gasoline is worth 27 per pound
DDGS is worth 5.5 cents per pound
The cost of conversion is 3.5 per pound
There is a federal government subsidy of
2.5 for each pound of corn converted to
ethanol and DGS
U.S. Gasoline Usage, 1986-
06
160
140
120
Billion Gallons

100
80
60
40
20
0
1986

1988

1990

1992

1994

1996

1998

2000

2002

2004

2006
Source: U.S. Energy Information Administration
Gasoline & Ethanol Production,
1986-06
160
ethanol gasoline
140
120
Billion Gallons

100
80
60
40
20
0
1986

1988

1990

1992

1994

1996

1998

2000

2002

2004

2006
Source: U.S. Energy Information Administration
U.S. Gasoline Usage

141 billion gallons gasoline used per year

Mandating 10% ethanol in all gasoline would
require that nearly half of the U.S. corn crop
be processed into ethanol
If all U.S. corn were made into ethanol, it
would produce 31 billion gallons per year
To replace all U.S. gasoline would require
78.6 billion bushels of corn annually
Corn Milling Options

Wet Milling
Dry Milling
Wet Milling Process
Corn Starch
Germ Ethanol
Bran
HFCS
Gluten Steepwate
Corn Oil r solubles

Corn Gluten Meal

Germ
Meal

Corn Germ Meal Corn Gluten

Feed
Dry Milling Process
Stillage Corn Ethanol

Thin Stillage
Wet Distillers
Grain Condensed
Distillers Solubles
Wet Distillers Grain
with Solubles A bushel of corn will
produce ~2.75
DDGS gallons of ethanol, 17
lbs of CO2 and 17 lbs
of DDGS
Wet & Dry Milled Corn for Ethanol
4,5 Foreca
4,0 Wet Dry st
3,5
Billion Bushels

3,0
2,5
2,0
1,5
1,0
0,5
0,0
90-91

92-93

94-95

96-97

98-99

00-01

02-03

04-05

06-07

08-09

10-11

12-13

14-15

16-17
Source: FAPRI
Ethanol Capacity Growth
12

10
billion gallons

0
2001 2003 2005 2007

Jan. 1 capacity Under construction

Source: Renewable Fuel Association website http://www.ethanolrfa.org/industry/statistics/#B

 Ethanol Plant Statistics, 8/1/07
124 plants operating in 26 states with
capacity to produce 6.4844 billion gallons of
ethanol per year (49 plants farmer owned)
76 new plants under construction and 7
expansions with capacity to produce 6.3989
billion gallons of ethanol per year
~100 plants being planned

Source: Renewable Fuels

Association
 Corn Milled for Ethanol
6,0 Foreca
5,0 % corn for ethanol: st
Billion Bushels

4,0 2000-01: 6%
2005-06: 14%
3,0
2006-07: 20%
2,0
2007-08: 26%
1,0

0,0
90-91

92-93

94-95

96-97

98-99

00-01

02-03

04-05

06-07

08-09
Ethanol as Fuel
Over 90% of U.S. ethanol is used as fuel
Although ethanol and gasoline can be
blended in any proportion, in the U.S. it is
largely:
10% ethanol & 90% gasoline
85% ethanol & 15% gasoline (E85)
Blends with high ethanol content require
modifications in the automobile (flexible fuel
vehicle)
Sensor to detect ethanol/gasoline ratio
Corrosion resistant fuel tank & lines
Formulation of Alcohols

H H H H
O O O O
H-C-H H-C-H H-C-H H-C-H
H H-C-H H-C-H H-C-H
Methanol H H-C-H H-C-H
CH3OH Ethanol H H-C-H
62,800 BTU C2H5OH Propanol H
84,400 BTU C3H7OH Butanol
100,000 C4H9OH
Gasoline is mostly C8H18 BTU
110,000 BTU
Gasoline has 125,000 BTU/gallon
Approximate Energy Content

Gasoline has 125,000 BTUs per gallon

10% ethanol has 120,940 BTUs per gallon
E85 averages 92,500 BTUs per gallon
100% ethanol has 84,400 BTUs per gallon

Less energy means fewer miles per gallon

But,
ethanol has a higher octane rating than
gasoline
Reasons Ethanol Production Is
Increasing
Legislation
Production Subsidies
Mandated use
Phase-out of MTBE as oxygenate
Ethanol production is profitable
High cost of crude oil
Cheap corn
Reasons Ethanol Production Is
Increasing
Legislation
Production Subsidies
Mandated use
Phase-out of MTBE as oxygenate
Ethanol production is profitable
High cost of crude oil
Cheap corn
Mandated Ethanol Use
2005 federal energy bill mandates use of 7.5
billion gallons of renewable fuels by 2012
0.25 billion gallons of cellulosic derived
ethanol by 2013
Missouri mandate: minimum 10% blend if
conditions met (if price = or less than regular
gasoline), effective Jan. 1, 2008
Ethanol Production & Renewable Fuels
Mandate

9,0
Ethanol Production Mandate
8,0
7,0
Billion Gallons

6,0
5,0
4,0
3,0
2,0
1,0
0,0
1998

2000

2002

2004

2006

2008

2010

2012

2014
Source: FAPRI
Ethanol Production & Renewable Fuels
Mandate

14
Ethanol Production Mandate
12
Billion Gallons

10
8
6
4
2
0
1998

2000

2002

2004

2006

2008

2010

2012

2014

2016
Ethanol Production & Renewable Fuels
Mandate

40
Ethanol Production Mandate Proposed
35
30
Billion Gallons

25
20
15
10
5
0
1998

2000

2002

2004

2006

2008

2010

2012

2014

2016
Reasons Ethanol Production Is
Increasing
Legislation
Production Subsidies
Mandated use
Phase-out of MTBE as oxygenate
Ethanol production is profitable
High cost of crude oil
Cheap corn
Reasons Ethanol Production Is
Increasing
Legislation
Production Subsidies
Mandated use
Phase-out of MTBE as oxygenate
Ethanol production is profitable
High cost of crude oil
Cheap corn
Gasoline-ethanol Price
Relationship
Mandated use
Skys the limit
Octane enhancer
Equal retail prices
Slightly higher rack price for ethanol
Gasoline substitute
Retail price 2/3 that of gasoline
Rack price 75% that of gasoline
 Ethanol & Unleaded Gasoline
Average Rack Price FOB Omaha
4,00
ethanol gasoline
3,50
3,00
$/gallon

2,50
2,00
1,50
1,00
0,50
Mar

Mar

Mar
Jan 05

Jul

Jan 06

Jul

Jan 07

Jul
Sep

Sep
Nov

Nov
May

May

May
Source: http://www.neo.ne.gov/statshtml/66.html
 Ethanol & Unleaded Gasoline
Average Rack Price FOB Omaha
3,00
ethanol gasoline
2,50

2,00
$/gallon

1,50
Forecas
1,00
t
0,50

0,00
1982

1985

1988

1991

1994

1997

2000

2003

2006

2009

2012

2015
Source: FAPRI
 Ethanol Production, 1980-06
5,0
4,5
4,0 Only 1 dip in ethanol
Billion Gallons

3,5
production
3,0
2,5
2,0
1,5
1,0
0,5
0,0
1980

1982

1984

1986

1988

1990

1992

1994

1996

1998

2000

2002

2004

2006
Source: Renewable Fuels Association
Cellulosic
Ethanol
CELLULOSIC ETHANOL

Cellulosic ethanol is ethanol made from cellulose. It is the

same as grain ethanol: C2H5OH. The only difference is the
source material
The interest in cellulosic ethanol comes from the huge supply
of low-value source material
Wood trees, limbs, paper, cardboard
Grass - switchgrass, corn stalks, straw, fescue
Distillers Grains
Cellulosic Ethanol
Producing ethanol from cellulose is
something weve known how to do for
over 100 years
Doing it in a cost-competitive manner is
something we have yet to learn
However, there are many people seeking
research grants who claim to be close to
solving the cost problem
Biodiesel Production

Vegetable Oil Methanol + Catalyst

Alcohol Reactor Alcohol

recover recover
y y
Washing Settler Neutralization

Purification Settler Evaporation

Fatty acids
Biodiese Glycerin
l e