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I.

Introduction

Increased concerns for sustainability of the oil supply and the negative impact of fossil
fuels on the environment, particularly greenhouse gas emissions, have put pressure on society to
find renewable fuel alternatives. The most common renewable fuel today is ethanol produced by
fermentation. Currently the United States consumes approximately 20 million barrels of crude oil
daily of which about 60% is imported [1]. Liquid transportation fuels including gasoline, diesel
and jet fuel account for almost 70% of the total. The US Energy Policy Act of 2005 states that
the oil industry is required to blend 7.5 billion gal of renewable fuels into gasoline by 2012. In
addition, many states have passed renewable fuels standards that require the sale of 10% and
20% blends (E10 and E20) by certain dates [2].The annual ethanol production in the United
States recently surpassed 4 billion gal, with global produc1tion twice that[3]. Unlike petroleum
products, ethanol is a form of renewable energy that can be made from very common crops such
as sugarcane, switch grass, wheat, corn stover and corn.

II. History of the fuel grade ethanol industry

The ethanol industry's history goes back to the oil embargo in the 1970s and the concern at that
time was about a lack of reliable energy sources. Since then, the technology used in the ethanol
dry milling process has evolved and the newer plants generally are more efficient processing
facilities. As a result, the costs to produce ethanol from corn starch and the capital cost of dry
mill ethanol plants have decreased. In 1978, the cost of ethanol was $2.47 per gallon. By 1994
this price had dropped to $1.43 per gallon and current fuel ethanol production costs are estimated
by the authors to be about $0.88 per gallon for dry mill operations [4]. The cost reductions may
be traced to various factors. The production of ethanol has become less energy intensive due to
new techniques in energy integration and the use of molecular sieves for ethanol dehydration.
The amount of pure ethanol produced from a bushel of corn has increased from 2.5 gallons to
more than 2.7 gallons. The capital costs of dry mill ethanol plants have also decreased
[5]. In 1978 Katzen reported costs for a 50 million annual gallon plant to be about
$2.07 per annual gallon in current dollars. Today new ethanol plants with the
necessary utilities are estimated to cost between $1.25 and $1.50 per annual gallon
[6].

III. Production process

1 Industrial processes

Ethanol is produced as a petrochemical product through the hydration of ethylene.


The chemical equation is:
C2H4 + H2O → CH3CH2OH ∆H = -45kj/mol

This is done in the presence of an acid which catalyses the reaction. The catalyst is most
commonly phosphoric acid, adsorbed onto a porous support such as silica gel or earth. This
catalyst was first used for large-scale ethanol production by the Shell Oil Company in 1947[7].
The reaction is carried out with an excess of high pressure steam at 572 °F. In the U.S., this
process was used on an industrial scale by Union Carbide Corporation and others; but now only
LyondellBasell uses it commercially [8].

2 Fermentation

Ethanol fermentation, also referred to as alcoholic fermentation, is a biological process in


which sugars such as glucose, fructose, and sucrose are converted into cellular energy and
thereby produces ethanol and carbon dioxide as metabolic waste products [9]. It can be done
quite simply from many forms of agricultural feed stocks. The most five commonly used or
considered in this project are sugarcane, switch grass, wheat, corn stover and corn.

Feedstock Key Process Component Percent Composition


Corn Starch 74%
Wheat Starch 65%
Corn Stover Cellulose/Hemicellulose 66%
Switch grass Cellulose 39%
Sugarcane Sucrose 30%

2.1 Wheat
Wheat is the third most common used feedstock for ethanol production and
the primary feedstock in Europe and Australia. The proteins are insoluble in water
and may cause problems in ethanol production. Wheat protein has better quality for
food and feed applications than corn protein because it contains the essential amino
acid lysine. Because of these reasons it is not used as feedstock in this process. It is
currently used only in two plants in the United States as feed stock. The chemical
process is:

(C6H10O5)n + nH2O  (C6H12O6)n

C6H12O6  2C2H5OH + 2CO2

C6H10O5 + H20  2C2H5OH + 2CO2


2.2 Switch grass

Switch grass is a summer perennial grass that is native to North America. Large acre of land will
be required to grow switch grass to use in plant. It is a high energy herbaceous crop and the
technology is complex, leading to higher ethanol production cost. Therefore, it is not considered
in this process. The chemical reaction is:

C6H10O5 + H20 C6H12O6

C6H12O6  2C2H5OH + 2CO2

C6H10O5 + H20  2C2H5OH + 2CO2

2.3 Sugarcane

Sugarcane contains sucrose which is a molecular compound formed of glucose


and fructose. The chemical process is:

C12H22O11 + H2O  2(C2H12O6)

2C2H12O6  C2H5OH + 2CO2

C12H22O11 + H2O  C2H5OH + 2CO2

The uses of sugarcane ethanol are very apparent, especially when compared to corn-based
ethanol. Sugarcane is able, pound to pound, to produce much more energy than corn. Corn
requires additional enzymes, adding more steps and cost to the process. Sugarcane offers more
benefits as well. However, the production of sugarcane is not high in the United States;
sugarcane production requires a tropical climate, which is found only in a few states of the
United States. Therefore, it is not considered in this process.

2.4 Corn Stover


Corn Stover is a very good ethanol feedstock. It is very abundant in the United
States and has a yield high ethanol output. The current ethanol yield from corn
stover is approximately .23 ethanol/lb of dry corn stover. However, according to a
capital investment analysis of the process, it has been proven that the cost of
ethanol production using corn stover is more expensive than using other
feedstocks such as corn[9]. For that reason it is not considered as a feasible
alternative in this process. The chemical reaction is the same as switch grass.

2.5 Corn

Corn is the most widely grown crop in the United States with 332 million metric ton grown
annually. It is currently the least -cost feedstock available for ethanol production. The capital
investment cost of using corn as feedstock is less than any of the choices mentioned above.

Based on the constraints and availability of the raw materials, corn seems to be the most
bearable feed stocks at to this present study for ethanol production in the United States.

IV. Process Description

The production of fuel-grade ethanol will take place by starch fermentation from dry-
milled corn grain. A detailed description of the process is as follows.

4.1 Feedstock Preparation

Preparation of the corn grain involves cleaning and conditioning steps, as well as
generating an aqueous solution high in simple sugars. Generally, enough grain is stored on site in
bins to meet facility needs for 8-12 days of operation [10]. Broken corn kernels and foreign
materials (metal, dirt, cobs, etc.) are removed by blowers and screens. The cleaned corn is then
ground in hammer mills fitted with screens with openings (sieves or mesh) ranging between 0.13
and 0.19 in. in diameter (mesh size 4 and 6), which provides grain particles of a more uniform
size of a diameter between 0.02 to 0.08 in. [11]. Grinding serves to break the tough outer coating
of the corn kernel and increases the surface area of exposed starch. The fineness of the ground
material should be such that the maximum possible amount of ethanol is obtained, yet not so fine
as to cause downstream separation problems. At the same time, the viscosity of the mash
obtained prior to hydrolysis must allow good mixing with the enzyme, or pumping, if needed
[12].

4.2 Cooking and Liquefaction/Saccharification

The ground feed leaving the milling process must undergo a cooking stage in which
water is added to the corn to create slurry of approximately 21% starch. It is then heated to a
temperature of 248°F by directly injected steam to form a gelatinized mixture. After cooking, the
slurry temperature is reduced to an ideal temperature of 185°F and prepared for liquefaction [13].
In order to convert starch to glucose, the starch must first be broken down into smaller, more
workable chains of sugar. More specifically, upon the addition of alpha-amylase to the cooked
slurry, the reaction should produce a product of maltose and dextrins that will continue to the
saccharification stage of the process. The alpha-amylase solution should be added at 0.05% per
lb of entering starch [14]. After the addition of the enzyme for liquefaction, the mixture is to be
held in a holding tank for 20 minutes in order for the reaction to take place.

2(C6H10O5)n +nH2O  nC12H22O11

Following the liquefaction stage is saccharification, in which 12% of the enzyme


glucoamylase is added to the slurry at a temperature of 149°F [14]. The process is carried out at a
pH of 4.5. The stream leaving the saccharification stage consists of 27% glucose. The equation
takes place according to the following reaction:

C12H22O11 + H2O  2C6H12O6

4.3 Fermentation

Fermentation is the conversion of glucose to ethanol and carbon dioxide using yeast. The
fermentation in this process is a batch process with three fermenters of approximately 504,400
gal each. The residence time is set at 68 h, with a working volume of 83% in the fermenters[15].
This is the heart of the process. The corn mash passes from the saccharification tank into a heat
exchanger to cool down the temperature and then into a mixer where the mash is mixed with the
yeast, and urea. The temperature of the slurry entering the fermentor is 90°F [15]. In the
fermentor, yeast of the type Saccharomyces cerevisiae is used to convert glucose into ethanol.
The most often used form is active dry yeast. The main metabolic pathway involved in the
production is glycolysis (Embden–Meyerhof–Parnas or EMP pathway), through which one
molecule of glucose is metabolized, and two molecules of pyruvate are produced (Madigan et al
2000).The amount of yeast used in the fermentor is a function of the amount of corn feed
(2.765×10-4 pound yeast per pound corn feed processed)[16]. The process is anaerobic (without
oxygen) under which, the pyruvate is further reduced to ethanol with the release of CO2.
Theoretically, the yield is 0.511 for ethanol and 0.489 for CO2 on a mass basis of glucose
metabolized. Two ATPs produced in the glycolysis are used to drive the biosynthesis of yeast
cells which involves a variety of energy-requiring bioreactions making the production tightly
coupled with yeast cell growth, which means yeast must be produced as a co-product. Without
the continuous consumption of ATPs by the growth of yeast cells, the glycolytic metabolism of
glucose will be interrupted immediately, because of the intracellular accumulation of ATP,
which inhibits phosphofructokinase (PFK), one of the most important regulation enzymes in the
glycolysis[17]. In addition to ethanol and CO2, various by-products are also produced during
fermentation. The compositions are shown in the table below.

Product Fraction of glucose that gets


converted to product
Ethanol 0.92
Glycerol 0.043
Succinic acid 0.01
Lactic acid 0.002
Acetic acid 0.0024
Cell mass 0.0316

The reactions pertaining to the fermentation are as follows:

1. Glucose to ethanol

C6H1206 = 2C2H60 + CO2


1lb 0.5114lb 0.4885lb
2. Glucose to glycerol

C6H12O6 + 2H2O = 2C3H8O3 + O2

3. Glucose to Succinic acid

C6H12O6 + 2CO2 = 2C4H6O4 + O2


1lb 0.4885lb 1.3191lb 0.1776lb

4. Glucose to acetic acid

C6H12O6 = 3C2H4O2
1lb 1lb

5. Glucose to lactic acid

C6H1206 = 2C3H603
1lb 1lb

6. Glucose to cell mass

C6H12O6 + 1.2NH3 = 6CH1.8 O0.5 N0.2 + 2.4H2O + 0.3 O2


1lb 0.1135lb 0.8202lb 0.2400lb 0.0533lb

In the last reaction, ammonia is one of the reactants. This reaction is indicative of the anaerobic
growth of the yeast, where the cell mass of the yeast is increased. The ammonia comes from the
following reaction that is also assumed to take place inside the fermentor.

Urea + Water = 2 Ammonia + Carbon Dioxide


C0 (NH2)2 + H2O = 2NH3 + CO2
1lb 0.2999lb 0.5672lb 0.7327lb

The urea that is required for the reaction is fed into a mixer, from where it goes into a storage
tank and finally to the fermentor. In order to avoid nitrogen limited growth inside the fermentor,
it is assumed that there is a 10% feed more urea than what is stoichiometrically required in the
fermentor. The carbon dioxide that is produced is constantly vented out to a sink from where it
can be sequestered. The slurry from the fermentor containing corn solids is sent to a storage tank.
Further, the fermentation of glucose to ethanol by yeast is an exothermic reaction. Therefore,
heat must be removed in order to keep the temperature in the fermentor constant at the
recommended value of 90°F and pH is maintained to be 4.5[15]. Cooling is continuous as the
conversion of glucose to ethanol produces 516 Btu of heat per pound of ethanol [15].Yeast stress
factors, including bacterial infection, high temperatures, high alcohol levels, and high acid levels
inhibit ethanol production. Bacterial infection will reduce the ethanol yield drastically as the
bacteria compete with the yeast for the substrates. Bacteria under anaerobic conditions also
produce relatively large amounts of acetic and lactic acid, which further stress the yeast [17].
Ethanol in too high concentration is also toxic for the yeast. The recommended temperature for
fermentation for S. cerevisiae is between 86–95°F [18]. If the temperature rises or falls too
much, the yeast will produce less ethanol and more of other by-products. Furthermore, higher
temperature favors bacterial growth. Also, the amount of solids must be limited to about 36% in the
fermentor. After the fermentation, the slurry coming out has ethanol content over 23%-v/v (10.8%
w/w), lactic acid 0.8%-w/v, and acetic acid 0.05%-w/v.

4.4 Distillation

The slurry coming out of the fermentor has to be separated into a liquid
(ethanol + water mixture + solubles) and solid component. The solid-liquid
separation can either be achieved by a centrifuge, or by a mechanical press, or
by a distillation column known as a beer column. Since a centrifuge and a
mechanical press do the same separation job, only one separation technology is
used in this process. The maintenance cost and power requirements of a
centrifuge are usually higher compared to a mechanical press, and hence a
mechanical press is considered in the process [17]

The beer column has a set of 19 trays and it is the first column in the
distillation system. Before the beer reaches the distillation system it passes
through the beer/mash heat exchanger. The beer is fed to the beer column.
As the column is heated, the vapor rises and the beer falls through the trays
and the heat causes the alcohol to evaporate. The tray – by- tray
vaporization/condensation continues moving the concentration lower at each
descending tray. At the bottom of the column, the soluble and solids are sent
to the whole stillage tank for centrifugation. The top column is round 160-
165 F. The temperature at the bottom of the column is about 185-190 F with
a vapor pressure of about 8.4psig. Water and non fermentable materials
from the beer cascade to the bottom of the column. A vapor mixture of water
and alcohol called low proof (80-100) leaves the top of the beer column.

The rectifier has four tray and 20feet packing which serves as a similar
purpose as the trays. The alcohols from the top of the beer column, now in
vapor form, is pull into the bottom of the rectifier column, providing the heat
source for the rectifying column. The alcohol continues to rise and more
water is removed, increase to about 190 proof out of the top of the rectifying
column. The concentration of ethanol leaving the rectification column is 95%.
Two- third of the 190 proof alcohol produced is return to the top of the
rectifying column as reflux. The remaining one- third is kept as distillate
(product) and sent to a storage tank. The top of the column is about 155-
165F with a 6-7psia. The temperature at the bottom is about 185- 190F with
a vacuum pressure of 4.5psia. It is not possible for the distillation process to
completely separate the ethanol from the water. An azeotropic
concentration forms at 95% ethanol to volume, in addition the
condensation/vaporization cycle cannot further the materials, requiring a
dehydration process [18].

4.5 Dehydration

The dehydration of ethanol can be done by using molecular sieves to avoid the azeotropic
distillation. The ethanol-water mixture leaving the top of the rectification column will enter in a
molecular sieve. Because molecular sieve dehydration units are based on adsorption and
diffusion processes to separate ethanol from water, rather than a thermal process, it is
considerably more energy efficient [19]. A molecular sieve selectively adsorbs water from an
ethanol-water mixture closed to 99.9% pure ethanol is obtained at the outlet. It is a bed of zeolite
that operates in semi-continuous mode. The bed gets saturated with water after a period of time
and is then regenerated. Hence, there are two sieves operated in parallel in this process – one
being saturated with water while the other is being regenerated (or dehydrated). The molecular
sieves switch every time the hydrating bed gets saturated with water. For dehydrating the
molecular sieve we employ dry air because it is cheaper than any other alternatives [15].
Adsorption takes place at 203°F and at atmospheric pressure. A Heat exchanger brings the inlet
stream from the mixer Mix6 up to 203°F. The heat of adsorption is assumed to be stored in the
bed and provides the heat of desorption while regenerating. Air dehydrates the regenerating
molecular sieve under vacuum. A Heat exchanger heats air with an assumed relative humidity of
70% at 68°F to 203°F [14]. The hot moisture laden air at the outlet of the dehydrating molecular
sieve is then cooled to 77°F in heat exchanger and this stream leaves this exchanger saturated
with water at a temperature of 77°F.

4.6 Ethanol Recovery

The purified ethanol vapor streams coming from the rectifier and the molecular sieves are mixed
in a mixer, condensed in a condenser, and then cool to final product temperature (room
temperature). The condensation is assumed to take place at the boiling point of ethanol as the
outlet stream is almost pure ethanol. This nearly pure ethanol stream is then cooled to room
temperature in a heat exchanger from where it goes to storage.

5 Conclusions /Discussion

As you can see, making alcohol is easy and hard - easy if everything goes right, hard if
something goes wrong. And, if something does go wrong, it is experience that makes the
difference between a batch you can save, or a batch that you must throw out.
The future is very exciting in power alcohol production. Technology is moving very fast. Soon
yeast will probably be replaced by bacteria or a genetically engineered microbes which can
withstand higher alcohol concentration, distilling columns may be replaced by reverse osmosis,
and new low temperature enzymes will be developed. Future works in this project are in the
aspects of equipment selection, cost analysis, optimizing process to increase efficiency, kinetics
and developing a model.