You are on page 1of 104

Manufacturing of Ethyl Alcohol from Fruit Waste

INTRODUCTION
In general, alcohol means colorless volatile inflammable liquid especially
intoxicant in wire, beer, spirits etc. and as a solvent, fuel etc. Depending on the
interest of the person involved, for alcohols are many things to many people. To
most non technical people, "alcohol" in the broad sense is used to describe any
intoxicating beverage; thus, a heavy or habitual drinker is called "alcoholic" the case
is some what different in the industrial manufacturing fields which produce finished
goods, intermediates, or raw materials, alcohols play a key role as important
organic solvents and rank second only to water in terms of their almost universal
application. Hence to these people alcohols mean solvents.
Take a spoonful of medicine; feel the smoothness of the lacquer on the pine
pralines in the play room ; look at the tyres of your car, smell the window cleaner
spray, make use of a hair spray, deodorant stick, or are antiperspiral; carry your
water proof cloth covered books to school etc. Alcohols play their solvent role in all
these personal events. Alcohols can be regarded as hydroxyl derivatives of
hydrocarbons, one the basis of several types of classification, di-hydric. There are
various types of alcohol belonging to the homologues series of alcohols, of like
methanol, ethanol, propanol etc. teach member in the series have its own specific
property and most active member of the series is "Ethanol".
Here the fig. Below shows the chemicals from ethanol.

Acetaldehyde
Diethyl Ether
Ethylene

Mixed ether
Alkylated
Aeromatics Ethanol

Butadiene Ethoxides

Organic Esters Halides

Esters

C.O.E.& T.,Akola 1
Manufacturing of Ethyl Alcohol from Fruit Waste

Now, in this project we have made an attempt to prey prepare the alcohol
from waste fruits and for it we have chosen Sapota (Hindi Name:Chiku ). (Botanical
Name : Acharas Sapota, Mallinkara Acaras. Sopota the sweetest fruit second to
banana, is chiefly grown in moist coastal tracts of peninsular India, but in recent
years it has spread in the zones of plateau and also sub-mountains tracts of North
India. In India, the main centers of its cultivation are the coastal tract and
Maharashtra, coastal areas of Andhra Pradesh, Tamil Nadu, Karnataka, Saurashtra
and submountain and sumountain areas of H.P. and Bengal. In Maharashtra it is
grown over the areas of too hectares mainly concentrated in Thana, Pune,
Ahmednagar and Aurangabad districts. More than 70% of the area is in Thana
district. In India, it is mainly grown for fruits, but in outer countries the milky latex
from the bank of the "tree" , yields an important commercial product, which fours the
base for manufacture of chewing gums.
TREE CHARACTERS :
One of the definitions of alcohol refer to the occurrence or preparation of
alcohol by known methods such as fermentation of carbohydrates, or synthesis by
hydration of ethylene.
Alcoholic fermentation " a process in which certain kinds of sugar (glucose)
are converted in to alcohols and carbon dioxide by the action of various yields,
moulds of Bacteria on carbohydrate materials. Some of which do not themselves
undergo fermentation but can be hydrolysed in to fermentation substances. ( as in
the production alcohol and alcoholic beverages.)
HISTORY :
The knowledge of fermentation goes back about 6000 years, long before any
written records of history. Archeological studies of relics from due old tombs of
Egypt have uncovered vessels that contained residues of starch and yeasts. During
these ancient times, man originated alcohol which was accepted and celebrated
among puritive and civilized people for thousands of years. All the accident
references discuss alcohol in the form of beverage. But distillation was not known
in Europe until the twelfth a thirteenth century, A.D. Gradually, the concept of

C.O.E.& T.,Akola 2
Manufacturing of Ethyl Alcohol from Fruit Waste

distillation came into the mind of the people workers over the put of alcohol for
India.
In India, the concept of fermentation was commercialized in 1900 to 1910
after the discovery of Louis Pastern and the process came in to use before 1930 to
about 1948 saw the development of indirect Hydration process to manufacture
Ethanol synthetically.
OBJECTIVE :
Growth in potable alcohol industries in liked with the demand for the
consumption of the people and the chemical products in industries in which alcohol
plays an impatant role.
Fruits ripe within 4-5 days, the unripe fruits can be stored at 50% 52 F for
five weeks while ripe fruits can be stored at 320 to 350F.
Yield up to 10 years – 750 fruits/ha.
Field up to 5 years – 1000 – 1500 fruits/ha.
After 15 years, yield was – 2000 – 2500 fruits or 18 – 20 tons /ha.
Especially, in Maharashtra, Sapota was grown in area of 3900ha and the
production was obtained 10,920.
HANDLING AND STORAGE :
Unripe Sapota is kept into the large capacity containers and the containers
are packed with the straw. So, that the surface of the two fruits could not touch with
each other. It should be stored away from all ignition sources and also from high
and low temp. The temp is kept moderate ( depending upon the atmosphere
conditions of the place ).
Under these conditions, the unripe Sapota gets ripen and ready to eat.
All the sources for ethanol production
The three types of sources of ethanol production –
1) SACCHARINE ( Sugar containing ) materials in which the carbohydrate ( the
actual substance from which the alcohol is made ) is present in the form of simple,
directly fermentable six and twelve carbon sugar cane, sugar beets, fruit ( Fresh or
dried ), citrus molasses, cane sorghum why and skim milk.

C.O.E.& T.,Akola 3
Manufacturing of Ethyl Alcohol from Fruit Waste

2) STARCHY MATERIALS : That contain more complex carbohydrates such as


starch and insulin that can be broken down into the simplex sex and twelve carbon
sugars by hydrolysis with acid or by the action of enzymes in a process called
malting. Such materials includes corn, grain sorghum, barley, wheat, potatoes,
sweet potatoes, Jerusalem artichokes, cacti manioc, arrowroot and so in.
3) CELLULOSE MATERIALS :- Such as wood, wood waste, paper, straw, corn
stalks, corn cobs, cotton, etc. which contain material that can be hydrolyzed with
acid, enzymes or otherwise converted into fermentable sugars called glucose.
Different type of fruits likely to produce ethanol.
Fruit composition in Municipal solid waste :-
The fruit pertaining to solid.
The Municipal solid waste pertaining to fruit waste in Akola City is 25%.
Now, the composition of waste, in Hampshire waste the energy content
cones from :
Articles % total of energy content
Paper/Card 46%
Plastics 22%
Putrescibles 11%
Fires 5%
Textiles 3%
Misc. 13%
Table for carbohydrate content in other fruits.

Fruit production and Acreage in Maharashtra :


The fruit production and acreage in Maharashtra State is given below in table form
as.

C.O.E.& T.,Akola 4
Manufacturing of Ethyl Alcohol from Fruit Waste

FRUIT CHOSEN FOR EXPERIMENTATION


We have chosen the Chiku for experimentation. Botanical Name of Chiku is
Acharas sapota and the Family name is Mallinkara acaracs.
Chiku is called sapota. It is cheafly grown in moist coastal tracts of
paninsular India, but in recent years it has spread in zones of the Deccan Plateau
and also in sub mountain tracts of North India. In India the main centers of its
cultivation are coastal tract and Maharashtra, coastal areas of Andhra Pradesh,
Tamil Nadu, Karnataka, Saurashtra and sub-mountain areas of U.P. and Bengal. In
Maharashtra it is grown over the area of 100 hectares mainly concentrated in
Thana, Poona, Ahmednagar and Aurangabad districts. More than 70% of the area
is is in Thana district. In India, it is mainly grown for fruits, but in other countries the
milky latex from the bark of the tree yields an important commercial product, which
forms the base for manufacture of Chewing-gum. It has very attractive shape and
used as decorative tree.
Origin:- It is a native of Maxico in Tropica, America, like that of guava. It is so
established in India, that one can hardly believe that it is foreign to India.
Tree characters:- It is slow growing evergreen tree, forms a good grown does not
require any training and pruning, height of the tree is 8-12 m bears terminaly.
Climate:- It is a tropical fruit crop which likes strictly tropical climate warm and moist
weather with high annual rainfall of 250 cms (80"-100"). It thrives in places where
maximum and minimum temperatures do not go beyond 340C and 110C. It does not
very hot and dry summers and temperature below 50C. If temperature go above
430C. dropping of blossom and scortching of fruits takes place in dry zones. Rain
cloudy weather is not any way harmful to the plant. It can be grown from sea level
to an elevation of 1000 m, but does not do well above 500 m. The best chiku
plantations are found within a short distance from sea shore ( in heavy rainfall area).
It can also be grown in drier tracts, chiku flowers all the year round in June-July,
Oct-Nov, and Jan.Feb. While under Poona conditions it flowers in June-July and
crops harvested in Dec-January.
Soil :- Chiku can be grown in soils having a minimum depth of 1 m. having water
table below 3-4 m. Chiku requires wall drained soils, alluvial loams on the river

C.O.E.& T.,Akola 5
Manufacturing of Ethyl Alcohol from Fruit Waste

banks, sandy loans sea, red lateritic soils of high rainfall area and well drained
medium black soils are suitable for its cultivation. Chiku will not thrife well on ill
drained soils, soils having hard pan below, loamy soils very deep and stickly soils,
soils containing high per cent of lime are not suitable. The pH range should be 5.5
to 7.5.
Propagation:- Chiku is commercially propagated by vegetative methods like are
layering or inarch grafting, Inarch grafts are prepared on the root stock seedlings of
Rayans(Khirni) or chiku itself. In India, Khirni is very commonly used as root stock
for chiku. The gooti is shallow rooted the majority of roots concentrating in upper
30-40 cms. Of soils while roots of graft go as deep as 90 cms so gooti can thrive
well in both light and deep soils while grafts are suitable for planting only in soils
having 1 m depth, gooti is reported to hear sweeter and mellower pulp, Grafts on
Khirni bear havily than on layers.
Planting:- In drier part planting is done on the onset of monsoon where as in heavy
rainfall areas it is planted after the heavy showers are over. Before planting the
land should be ploughed harrowed and brought to a fine tilth. The pits of size 1 x 1
x 1 m. are opened at a distance of 10 x 10 m. or 12 x 12 m. The pits should be
filled in with 2 kg phosphate, FYM and good soil. After planting the plant should be
supported with bamboo.
Varieties:- There are three main varieties grown in Maharashtra.
1. Kalipatti:- Leaves are dark green, leading variety of the state level shaped fruits,
or excedant spreading branches. The quality is best, pulp is very sweet, mellowing,
yields heavily. It contains one-two seeds, does well in climate of Konkan.
2. Pillipatti:- Next best variety of the State. It is also called as 'Chatri' due to
peculiar habit of growth in whorls, leaves lighter green, fruits are oval and round
small fruits. It is less sweet as compared to Kalipatti. Does best in humid climate.
3.Cricket ball :- Fruits large sized, round variety having granular flesh of market
sweetness grown away from the see coast in drier areas. Bears heavily as
compared to above two varieties.
Manuring:- When the plants are one year old it should receive about 5 kg of FYM
and about 150 gm of nitrogen. The doses should be increased with the

C.O.E.& T.,Akola 6
Manufacturing of Ethyl Alcohol from Fruit Waste

advancement in age. At the age of 7th years it starts bearing fruits. There are two
main seasons Oct-Nov. and Jan-Feb, so far each flowering the tree should receive
50 kg FYM + 1 kg N, 0.5 kg P 2O5 and 0.5 kg of K2O. In drier areas the flowering will
be mostly at beginning of monsoon, so manuring should be done in the month of
May. In case of Chiku there is not bahar treatment (i.e. with holding of water
practices are followed ). However, immediately after harvest orchard hygienic
practices are followed.
Training and Pruning:- Naturally chiku trees assumes a very attractive shape. It is
an ever green tree and requires hardly and pruning, training is done by allowing the
plant to grow upto and height of 1 m above which 3-4 well spaced branches are
allowed to arise.
Harvesting and Yield:- Fruits are ready for harvest in about 4 months i.e. Oct-Nov.
flowering fruits matures by Jan-Feb. or flower matures fruits by April-May.
Harvesting is done when fruits is fully developed matured fruit are not allowed to
ripe on the fruit. At maturity it develop deep chocolate color. If you take a streak on
the fruit immature fruit shown a green below while matured fruit shows yellow colour
below the skin.
Fruits ripe within 4-5 days. The unripe fruits can be stored at 50 0-520F for
five weeks while ripe fruits can be stored at 320-350F.
Yield up to 10 years - 750 fruits/ha.
Yield 15 years - 1000 – 1500 fruits/ha.
After 15 years yield - 2000-2500 fruits or 18-20 tons/ha.
Highly susceptible to water logging and very densative to stagnation. It
however tolerates considerable drought. The plant can tolerate extremes but the
yield goes down as shadding of flowers occurs above 390C. Fair distribution or
rains with mild summer helps in increasing the set. Ramphal cannot withstand
severe summers or cold as that of sustard apple.

C.O.E.& T.,Akola 7
Manufacturing of Ethyl Alcohol from Fruit Waste

Fruit carbohydrates table:


Fruit Carbohydrates Calories per piece
Apple 10.5 grams 44
Apple cooking 9 grams 35
Apricot 6.7 grams 30
Avocado 2 grams 150
Banana 26 grams 107
Blackberries each 0.2 grams 1
Blackcurrant each 0.25 grams 1.1
Cherry each 0.6 grams 2.4
Clementine 7.5 grams 30
Currants 1.4 grams 5
Damson 7.2 grams 28
Dates 3.3 grams 12.5
Gooseberries 0.65 grams 2.6
Grapes each 0.6 grams 2.4
Grapefruit whole 23 grams 100
Guava 4.4 grams 24
Kiwi 8 grams 34
Lemon 3.4 grams 20
Lychees 0.7 grams 3
Mango 9.5 grams 40
Melon 26 grams 110
Nectarines 9 grams 42
Olives trace 6.8
Orange 8.5 grams 35
Passion Fruit 3 grams 30
Paw Paw 6 grams 28
Peach 7 grams 35

C.O.E.& T.,Akola 8
Manufacturing of Ethyl Alcohol from Fruit Waste

Pear 12 grams 45
Pineapple 12 grams 50
Plum 6 grams 25
Prunes 2.2 grams 9
Raisins 1.4 grams 5
Raspberries each 0.2 grams 1.1
Rhubarb 0.8 grams 8
Satsumas 8.5 grams 35
Strawberries (1 average) 0.6 grams 2.7
Sultanas 1.4 grams 5
Tangerine 6 grams 26

Values for carbohydrates in fruit may vary between different sized pieces!

Fruit Production and Acreage in Maharashtra


Sr. Fruit Area Production
No.
1 Grapes 10,000 79,000
2 Banana 53,800 14,18,700
3 Mango 35,400 1,45,140
4 Sweet orange 5,700 20,520
5 Mandarin orange 33,600 1,51,200
6 Kagzi lime 13,200 29,040
7 Other citrus fruits 800 1,600
8 Pomegranate 7,700 40,040
9 Guava 8,500 39,950
10 Custard apple 2,800 6,720
11 Fig 200 160
12 Jackfruit 300 326
13 Papaya 1,500 11,250
14 Sapota 3,900 10,920
15 Cashew nut 19,000 5,890
16 Others 23,700 18,480
Total 2,20,100 19,78,936

C.O.E.& T.,Akola 9
Manufacturing of Ethyl Alcohol from Fruit Waste

Physical Properties of Ethanol


Constants Absolute 95% (by
vol)
0
Boiling point, C 78.3 78.0
Electrical conductivity at 250C, Ohm-1/cm 1.35 x 10-9 -
Explosive limits in air, vol % 4.3-19.0 -
Flash point ( ASTM Tag Open Cup ), 0C 21 22
Freezing point, 0C 114.1 -
Heat of combustion of liquid, Kcal/mole 328 -
Heat of fusion, cal/g 25.0 -
Heat of vaporization at bp and 1 atm, cal/g 204.3 -
Ignition temp.(apparent) in air, 0C 371-427 -
Refractive index, n2D0 1.3614 1.3651
Specific gravity at 20/20 0C 0.7905 0.8038
Specific tension at 200C, dynes/cm 0.579 0.618
Surface tension at 200C, dynes/cm 22.3 22.8
Vapour pressure at 200C, mm Hg 44 43
Viscosity at 20 0C, cps 1.22 1.41

Chemical Properties : The chemical properties of ethanol are typical of n-


saturated monohydric alcohols, especially in reactions which are concerned with the
hydroxyl group. The ethyl group, however, does undergo several unique reactions,
(as was previously noted for the methyl group of methanol).
Alkylation. Ethanol is an important alkylating agent, especially with ammonia
and the amines. This particular unit process is known ammonolysis and aminolysis,
and the reaction with ammonia is shown below :
CH3 CH2OH + NH3 CH3 CH2NH2 + H2O
ethyl amine

Sulfuric acid is known to dehydrate ethanol to ether in the manufacturing


process which is based on hydration. Hydrochloric acid and alumina get are also
commonly used as dehydratic catalysts.
The aromatic nucleus may be alkylated with ethanol in the presence of a
Friedel-Crafts catalyst :

CH2 CH3+ H2O


+ CH3 CH2OH

C.O.E.& T.,Akola 10
Manufacturing of Ethyl Alcohol from Fruit Waste

ethyl benzene

Concentrated sulfuric acid may from ethyl hydrogen sulfate if added slowly to
ethanol :
CH3 CH2OH + H2SO4 CH3 CH2 H2SO4 + H2O

Slow distillation at reduced pressure will then form diethyl sulfate, an


ethylating agent :
2CH3 CH2 H2SO4 (CH3 CH2 )2SO4 + H2SO4

Sulfur trioxide adds to ethanol and forms carbyl sulfate :


CH3 CH2OH + 2SO3 CH2 – CH2 – O
| | |
SO2 O SO2
Carbyl sulfate

Complex Formation. Ethanol behaves like water of crystallization and forms


complexes with various inorganic compounds. The alcohol combines with calcium,
magnesium, and platinum chlorides to form crystalline products.
Dehydration. This reaction may proceed in two directions with ethanol. The
intramolecular route to ethylene is favored when high temperatures and large
catalyst ratios are employee :

CH3 CH2OH CH2 = CH2 + H2O

Intermolecular dehydration forms diethyl ether :

2CH3 CH2OH CH3 CH2 O CH2 CH3 + H2O

Ester Formation. Both inorganic and organic acids will form esters with
ethanol :
CH3 CH2OH + HNO3 CH3 CH2 NO3 + H2O
ethyl nitrate

Organic acids form organic esters and water :

C.O.E.& T.,Akola 11
Manufacturing of Ethyl Alcohol from Fruit Waste

CH3 CH2OH + RCOOH RCOOCH2 CH3 + H2O


ester

Since esterification is an equilibrium reaction, completion is favored by a


large excess of alcohol, by a large excess of acid, or by removal of water, Ethanol is
quite low in cost; therefore, it is ordinarily the compound used in excess. Acid
derivatives (such as acid chlorides, acid anhydrides, and simple alkyl esters of
acids) will also form esters.
Ethanol condenses with the carbonyl group of aldehydes and ketones at
about 1000C to form acetals :
2CH3 CH2OH + RCHO RCH(OCH2 CH3)2+ H2O

The process of ester interchange is used to prepare ethyl esters from natural
fats and oils :
CH2OOCR CH2OH
| |
2CH3 CH2OH + CH2OOCR CH2OH + 3 RCOOCH2CH3
| | ethyl esters
CH2OOCR CH2OH
glycerol

Ethers. Ethyl ether formation is the result of an intermolecular catalytic


dehydration of ethanol at low temperature :
2CH3 CH2OH CH3 CH2OCH2 CH3 + H2O

Vinyl ethyl ether or diethyl acetal are formed by the addition of ethanol to
acetylene, the final product being dependent on whether an alkaline or acid catalyst
is used :
NaOC2H5
CH3 CH2OH + CH ≡CH CH3 CH2OCH2 =CH2
Vinyl ethyl ether
acid
CH3 CH2OH + CH3 CH2OCH ≡CH2 CH3 CH(OCH2CH3)2
catalyst diethyl acetal

C.O.E.& T.,Akola 12
Manufacturing of Ethyl Alcohol from Fruit Waste

Haloform Reaction, Ethanol may be oxidized by hypohalites to acetaldehyde


and will then undergo the "haloform" reaction :
CH3 CH2OH + NaOCl CH3 CHO + NaCl + H2O

CH3 CHO + 3NaOCl CCl3 CHO + 3NaOH


CCl3 CHO + NaOH CHCl3 + HCOONa
Halogenation. Ethanol may undergo a typical reaction in which hydrogen
halides, phosphorous halides, and similar reagents replace the hydroxyl group by
halogen :
3CH3 CH2OH + PCl 3CH3 CH2Cl + P(OH)3
Oxidation. Conversion of ethanol to acetaldehyde can be accomplished by
oxidation or dehydration. Air oxidation is carried out in the presence of copper and
silver wire catalysts:
Cu, Ag
CH3 CH2OH + (O) CH3 CHO + H2O
Dehydrogenation of ethanol is catalyzed by chromium-activated copper :
Cu
CH3 CH2OH CH3 CHO + H2
Further oxidation of acetaldehyde leads to acetic acid :
Cu
CH3 CHO+ (O) CH3 COOH
Direct chemical oxidation of ethanol to acetic acid in one step is not carried
out commercially because of appreciable decomposition to carbon dioxide, carbon
monoxide, methane and other low molecular weight compounds. However, one
step oxidation to acetic acid is achieved industrially by fermentation.
Reaction with Metals. Sodium, potassium and calcium may replace the
hydroxyl hydrogen in ethanol to form a metal alkoxide (alcoholate):
Cu, Ag
2CH3 CH2OH + 2N 2CH3 CH2 ONa + H2
Sodium ethoxide

Sodium and aluminum ethoxide are valuable agents in the field of organic
synthesis.

C.O.E.& T.,Akola 13
Manufacturing of Ethyl Alcohol from Fruit Waste

Thermal Decomposition. Hearing ethanol above 800 C forms ethylene,


acetaldehyde, water, and hydrogen. The use of a finely divided catalyst (such as
alumina or metals) will cause decomposition at lower temperatures.

FERMENTATION

Fermenting fruits and vegetables can bring many benefits to people in


developing countries. Fermented foods play an important role in providing food
security, enhancing livelihoods and improving the nutrition and social well being of
millions of people around the world, particularly the marginalised and vulnerable.

Improving food security

Eight hundred million people do not have enough food to eat. If we include those
not free from hunger the figure rises to 1.2 billion people. This is one fifth of the
World's population. A further two billion people are deficient in one or more micro-
nutrients (Anon, 1996). In the seventies, food security was viewed mainly in terms
of food supply at the global and national levels. Since then there has been a major
shift in understanding of food security with more emphasis on access to food rather
than purely on production. The Food and Agriculture Organisation of the United
Nations (FAO), amongst other influential organisations, has recognised that the
problem of food security cannot be tackled in isolation. Moreover that it is an
integral component of other development issues. FAO highlights the fact that the
world food insecurity problem is a result of undemocratic and inequitable distribution
of and access to resources rather than a problem of global food production (Anon,
1995), (Anon, 1996).

Fermentation technologies play an important role in ensuring the food security of


millions of people around the world, particularly marginalised and vulnerable
groups. This is achieved through improved food preservation, increasing the range

C.O.E.& T.,Akola 14
Manufacturing of Ethyl Alcohol from Fruit Waste

of raw materials that can be used to produce edible food products and removing
anti- nutritional factors to make food safe to eat.

Food preservation

Fermentation is a cheap and energy efficient means of preserving perishable raw


materials. When harvested, fruit and vegetables, undergo rapid deterioration,
especially in the humid tropics where the prevailing environmental conditions
accelerate the process of decomposition. There are several options for preserving
fresh fruit and vegetables including drying, freezing, canning and pickling. However
many of these are inappropriate for use on the small-scale in developing countries.
For instance the canning of vegetables at the small-scale has serious food safety
implications and contamination with botulism is a possibility. Freezing of fruits and
vegetables is not economically viable at the small-scale. Fermentation requires very
little sophisticated equipment, either to carry out the fermentation or for subsequent
storage of the fermented product. It is a technique that has been employed for
generations to preserve food for consumption at a later date and to improve food
security. There are examples from around the world of the role fermented foods
have played in preserving food to enhance food security.

Increasing income and employment

The production of fermented fruit and vegetable products provides income and
employment to millions of people around the world.

Food processing is probably the most important source of income and employment
in Africa, Asia and Latin America. The Food and Agriculture Organisation of the
United Nations has stated that value added through marketing and processing raw
products can be much greater than the value of primary production (Anon, 1995).
For instance in sub-Saharan Africa more than 60% of the workforce is employed in
the small scale food processing sector, and between one third and two thirds of
value added manufacturing is based on agricultural raw materials (World Bank,

C.O.E.& T.,Akola 15
Manufacturing of Ethyl Alcohol from Fruit Waste

1989), (Conroy et al, 1995). This is particularly important as agriculture and the
formal sector are unable to absorb the growing labour force in many countries.

Fermented foods are popular throughout the world and the production of fermented
food products is important in many countries in providing income and employment.

In Africa, fermented cassava products (like Gari and Fufu) are a major component
of the diet of more than 800 million people and in some parts of Africa it constitutes
over 50% of the diet (Oyewole, 1992). In Asia the preparation of fermented foods is
a widespread tradition. Kimchi (a fermented cabbage product) is the major food
product of Korea. Soy sauce (a fermented legume product) is economically
important from Indonesia to Japan. Over a billion litres are produced each year in
Japan alone. Over 2000 million litres are produced each year in Korea and over 150
million litres in Taiwan. Miso (a fermented legume product) is also very important in
Asia with over 560,000 tons produced a year in Japan alone (Anon, 1982). In Latin
America, fermented cereal products, alcoholic drinks and fermented milk products
are three of the most important sectors of the economy.

Improving nutrition

The optimum health and nutrition of individuals is dependent upon a regular supply
of food and a balanced diet. When diets are sub-optimal, the individual's capacity
for work and achievements are greatly reduced. The most vulnerable groups are
women, children and weaning infants. Availability of food, dietary restrictions and
taboos, misconceptions, limited time available for feeding or eating compound to
create a group of individuals who are nutritionally disadvantaged. Approximately
30% of women consume less than their daily requirements of energy and at least
40% of women world-wide suffer from iron-deficiency anaemia. Fermentation can
enhance the nutritional value of a food product though increased vitamin levels and
improved digestibility.

Vitamins

C.O.E.& T.,Akola 16
Manufacturing of Ethyl Alcohol from Fruit Waste

Fermentation processes can result in increased levels of vitamins in the final


product. Saccharomyces cerevisiae is able to concentrate large quantities of
thiamin, nicotinic acid and biotin and thus form enriched products.

• Sorghum beer in Southern Africa contains relatively high levels of riboflavin


and nicotinic acid, which are important for people consuming a high maize
diet. Pellagra (a vitamin deficiency disease associated with high maize diets)
is unusual in communities in which sorghum beer is consumed. Even
children benefit from consuming the dregs which contain relatively little
alcohol but are rich in vitamins.
• Palm wine in West Africa is high in vitamin B12, which is very important for
people with low meat intake, and who subsist primarily on a vegetarian diet.
• Pulque (a fermented plant sap) is an important source of vitamins for the
economically deprived in Mexico. The fermentation process involved in
Pulque production increases its vitamin content. For instance the vitamin
content (milligrams of vitamins per 100g of product) of pulque increases from
5 to 29 for thiamine, 54 to 515 for niacin and 18 to 33 for riboflavin
(Steinkraus, 1992) during fermentation.
• Idli (a lactic acid bacteria fermented product consumed in India) is high in
thiamine and riboflavin.

Digestibility

Micro-organisms contain certain enzymes, such as cellulases, which are incapable


of being synthesised by humans. Microbial cellulases hydrolyse cellulose into
sugars which are then readily digestible by humans. Similarly pectinases soften the
texture of foods and liberates sugars for digestion. Fermented foods are often more
easily digestible than unfermented foods (Kovac, 1997), (Parades-Lopez, 1992).

Lactic acid fermented weaning foods are traditionally produced in developing


countries, both to improve the safety of the food and to improve its digestibility.
Starchy porridges are commonly fed to weaning infants in developing countries. The

C.O.E.& T.,Akola 17
Manufacturing of Ethyl Alcohol from Fruit Waste

consistency of these gruels, combined with the small capacity of the infants
stomach, means that it is physically impossible for the child to consume adequate
energy to meet its high demands. By acidifying the porridge through lactic acid
fermentation, starch is hydrolysed into shorter chains of glucose and dextrose,
which reduce the viscosity of the porridge and increase its energy density. Thus the
child is more able to meet its energy requirements.

Medicinal benefits

There are many traditional beliefs about the medicinal properties of fermented food
products. The Fur ethnic group in Sudan strongly believe that the consumption of
fermented foods protects them from disease (Dirar, 1992). Koumiss (a fermented
milk product in Russia) has been used to treat tuberculosis. Pulque (a fermented
fruit sap) is felt to have medicinal properties in Mexico.

There is a sound scientific basis to these assertions:

• The lowering of the pH inhibits the growth of food spoiling or poisoning


bacteria and destroys certain pathogens (Hammes, and Tichaczek, 1994).
• Certain lactic acid bacteria (e.g. Lactobacillus acidophilus) and moulds have
been found to produce antibiotics and bacteriocins (Wood and Hodge, 1985)
(Matususaki et al, 1997) (Adams and Nicolaides, 1997), (Gourama and
Bullerman, 1995), (Nout, 1995)..
• The beneficial health effects of lactic acid bacteria on the intestinal flora are
well documented (Ottogalli and Galli, 1997), (Motarjemi et al, 1996).
• Substances in fermented foods have been found to have a protective effect
against the development of cancer (Frohlich et al, 1997).

Fermentation is a traditional method of reducing the microbial contamination of


porridges in Kenya (Watson, Ngesa, Onyang, Alnwick and Tomkins, 1996) A study

C.O.E.& T.,Akola 18
Manufacturing of Ethyl Alcohol from Fruit Waste

in Tanzania has shown that children fed with fermented gruels had a 33% lower
incidence of diarrhoea than those fed unfermented gruels, owing to the inhibition of
pathogenic bacteria by lactic acid forming bacteria (Svanberg, 1992).

Improving cultural and social well being

Fermentation can improve the flavour and appearance of food. One important area
is the creation of meat-like flavour. Over the years, Sudanese women have
developed products to replace meat in their diets. These include "kawal", fermented
wild legume leaves, "sigda" (fermented sesame press-cake) and "furundu"
(fermented red sorrel seeds). The strong flavours of fermented food products can
enhance a dull diet. Fermented vegetables such as pickles, gundruk and sauerkraut
are used as condiments to enhance the overall flavour of the meal. A small amount
of pickle can make a bland starchy diet (like dahl and rice in Asia) much more
appealing (Battcock, 1992).

The diversity of fermented foods

Numerous fermented foods are consumed around the world. Each nation has its
own types of fermented food, representing the staple diet and the raw ingredients
available in that particular place. Although the products are well know to the
individual, they may not be associated with fermentation. Indeed, it is likely that the
methods of producing many of the worlds fermented foods are unknown and came
about by chance. Some of the more obvious fermented fruit and vegetable products
are the alcoholic beverages - beers and wines. However, several more fermented
fruit and vegetable products arise from lactic acid fermentation and are extremely
important in meeting the nutritional requirements of a large proportion of the worlds
population. Table 2.1 contains examples of fermented fruit and vegetable products
from around the world.

Organisms responsible for food fermentations

The most common groups of micro-organisms involved in food fermentations are:

C.O.E.& T.,Akola 19
Manufacturing of Ethyl Alcohol from Fruit Waste

• Bacteria
• Yeasts
• Moulds

1 Bacteria

Several bacterial families are present in foods, the majority of which are concerned
with food spoilage. As a result, the important role of bacteria in the fermentation of
foods is often overlooked. The most important bacteria in desirable food
fermentations are the lactobacillaceae which have the ability to produce lactic acid
from carbohydrates. Other important bacteria, especially in the fermentation of fruits
and vegetables, are the acetic acid producing acetobacter species.

2 Yeasts

Yeasts and yeast-like fungi are widely distributed in nature. They are present in
orchards and vineyards, in the air, the soil and in the intestinal tract of animals. Like
bacteria and moulds, yeasts can have beneficial and non-beneficial effects in foods.
The most beneficial yeasts in terms of desirable food fermentation are from the
Saccharomyces family, especially S. cerevisiae. Yeasts are unicellular organisms
that reproduce asexually by budding. In general, yeasts are larger than most
bacteria. Yeasts play an important role in the food industry as they produce
enzymes that favour desirable chemical reactions such as the leavening of bread
and the production of alcohol and invert sugar.

Table 1 : Fermented foods from around the world.

Name and region Type of product

Indian sub-continent

Acar, Achar, Tandal achar, Garam nimboo achar Pickled fruit and vegetables

Gundruk Fermented dried vegetable

C.O.E.& T.,Akola 20
Manufacturing of Ethyl Alcohol from Fruit Waste

Lemon pickle, Lime pickle, Mango pickle

South East Asia

Asinan, Burong mangga, Dalok, Jeruk, Kiam-chai, Pickled fruit and vegetables
Kiam-cheyi, Kong-chai, Naw-mai-dong, Pak-siam-
dong, Paw-tsay, Phak-dong, Phonlami-dong,
Sajur asin, Sambal tempo-jak, Santol, Si-sek-chai,
Sunki, Tang-chai, Tempoyak, Vanilla,

Bai-ming, Leppet-so, Miang Fermented tea leaves

Nata de coco, Nata de pina Fermented fruit juice

East Asia

Bossam-kimchi, Chonggak-kimchi, Dan moogi, Fermented in brine


Dongchimi, Kachdoo kigactuki, Kakduggi, Kimchi,
Mootsanji, Muchung-kimchi, Oigee, Oiji, Oiso
baegi, Tongbaechu-kimchi, Tongkimchi, Totkal
kimchi,

Cha-ts’ai, Hiroshimana, Jangagee, Nara senkei, Pickled fruit and vegetables


Narazuke, Nozawana, Nukamiso-zuke, Omizuke,
Pow tsai, Red in snow, Seokbakji, Shiozuke,
Szechwan cabbage, Tai-tan tsoi, Takana, Takuan,
Tsa Tzai, Tsu, Umeboshi, Wasabi-zuke, Yen tsai

Hot pepper sauce

Africa

Fruit vinegar Vinegar

Hot pepper sauce

Lamoun makbouss, Mauoloh, Msir, Mslalla, Olive Pickled fruit and vegetables

Oilseeds, Ogili, Ogiri, Hibiscus seed Fermented fruit and vegetable

C.O.E.& T.,Akola 21
Manufacturing of Ethyl Alcohol from Fruit Waste

seeds

Wines Fermented fruits

Americas

Cucumber pickles, Dill pickles, Olives, Sauerkraut, Pickled fruit and vegetables

Lupin seed, Oilseeds, Pickled oilseed

Vanilla, Wines Fermented fruit and vegetable

Middle East

Kushuk Fermented fruit and


vegetables

Lamoun makbouss, Mekhalel, Olives, Torshi, Pickled fruit and vegetables


Tursu

Wines Fermented fruits

Europe and World

Mushrooms, Yeast Moulds

Olives, Sauerkohl, Sauerruben Pickled fruit and vegetables

Grape vinegar, Wine vinegar Vinegar

Wines, Citron Fermented fruits

(Taken from G Campbell-Platt (1987))

Moulds

Moulds are also important organisms in the food industry, both as spoilers and
preservers of foods. Certain moulds produce undesirable toxins and contribute to
the spoilage of foods. The Aspergillus species are often responsible for undesirable
changes in foods. These moulds are frequently found in foods and can tolerate high

C.O.E.& T.,Akola 22
Manufacturing of Ethyl Alcohol from Fruit Waste

concentrations of salt and sugar. However, others impart characteristic flavours to


foods and others produce enzymes, such as amylase for bread making. Moulds
from the genus Penicillium are associated with the ripening and flavour of cheeses.
Moulds are aerobic and therefore require oxygen for growth. They also have the
greatest array of enzymes, and can colonise and grow on most types of food.
Moulds do not play a significant role in the desirable fermentation of fruit and
vegetable products.

When micro-organisms metabolise and grow they release by-products. In food


fermentations the by-products play a beneficial role in preserving and changing the
texture and flavour of the food substrate. For example, acetic acid is the by-product
of the fermentations of some fruits. This acid not only affects the flavour of the final
product, but more importantly has a preservative effect on the food. For food
fermentations, micro-organisms are often classified according to these by-products.
The fermentation of milk to yoghurt involves a specific group of bacteria called the
lactic acid bacteria (Lactobacillus species). This is a general name attributed to
those bacteria which produce lactic acid as they grow. Acidic foods are less
susceptible to spoilage than neutral or alkaline foods and hence the acid helps to
preserve the product. Fermentations also result in a change in texture. In the case
of milk, the acid causes the precipitation of milk protein to a solid curd.

Enzymes

The changes that occur during fermentation of foods are the result of enzymic
activity. Enzymes are complex proteins produced by living cells to carry out specific
biochemical reactions. They are known as catalysts since their role is to initiate and
control reactions, rather than being used in a reaction. Because they are
proteinaceous in nature, they are sensitive to fluctuations in temperature, pH,
moisture content, ionic strength and concentrations of substrate and inhibitors. Each
enzyme has requirements at which it will operate most efficiently. Extremes of
temperature and pH will denature the protein and destroy enzyme activity. Because
they are so sensitive, enzymic reactions can easily be controlled by slight

C.O.E.& T.,Akola 23
Manufacturing of Ethyl Alcohol from Fruit Waste

adjustments to temperature, pH or other reaction conditions. In the food industry,


enzymes have several roles - the liquefaction and saccharification of starch, the
conversion of sugars and the modification of proteins. Microbial enzymes play a role
in the fermentation of fruits and vegetables.

Nearly all food fermentations are the result of more than one micro-organism, either
working together or in a sequence. For example, vinegar production is a joint effort
between yeast and acetic acid forming bacteria. The yeast convert sugars to
alcohol, which is the substrate required by the acetobacter to produce acetic acid.
Bacteria from different species and the various micro-organisms - yeast and moulds
-all have their own preferences for growing conditions, which are set within narrow
limits. There are very few pure culture fermentations. An organism that initiates
fermentation will grow there until it’s by-products inhibit further growth and activity.
During this initial growth period, other organisms develop which are ready to take
over when the conditions become intolerable for the former ones.

In general, growth will be initiated by bacteria, followed by yeasts and then moulds.
There are definite reasons for this type of sequence. The smaller micro-organisms
are the ones that multiply and take up nutrients from the surrounding area most
rapidly. Bacteria are the smallest of micro-organisms, followed by yeasts and
moulds. The smaller bacteria, such as Leuconostoc and Streptococcus grow and
ferment more rapidly than their close relations and are therefore often the first
species to colonise a substrate (Mountney and Gould, 1988).

Table 2 : Micro-organisms commonly found in fermenting fruit and vegetables

Organism Type Optimum Reactions


conditions

C.O.E.& T.,Akola 24
Manufacturing of Ethyl Alcohol from Fruit Waste

Acetobacter genus Aerobic aw > =0.9 Oxidise organic compounds


rods (alcohol) to organic acids
A. aceti
(acetic acid). Important in
A. pasteurianus
vinegar production.
A. peroxydans

Streptococcaceae Gram Acid


Family positive tolerant
cocci aw > =0.9

Streptococcus genus Homofermentative. Most


S. faecalis common in dairy
S. bovis fermentations, but S. Faecalis
S. thermophilus is common in vegetable
products. Tolerate salt and can
grow in high pH media.

Leuconostoc genus Gram Heterofermentative. Produce


L. mesenteroides positive lactic acid, plus acetic acid,
L. dextranicum cocci ethanol and carbon dioxide
L. from glucose. Small bacteria,
paramesenteroides therefore have an important
L. oenos role in initiating fermentations.
L. oenos is often present in
wine. It can utilise malic acid
and other organic acids.

Pediococcus genus Saprophytic organisms found


in fermenting vegetables,
P. cerevisiae
mashes, beer and wort.
P. acidilactici
Produce inactive lactic acid.
P. pentosaceus

Lactobacillaceae Gram Acid Metabolise sugars to lactic

C.O.E.& T.,Akola 25
Manufacturing of Ethyl Alcohol from Fruit Waste

Family positive tolerant acid, acetic acid, ethyl alcohol


rods. Non- aw > =0.9 and carbon dioxide.
motile

Lactobacillus genus The genus is split into two


types – homo- and hetero-
fermenters. Saprophytic
organisms. Produce greater
amounts of acid than the cocci

Homofermentative Produce only lactic acid. L.


Lactobacillus spp. plantarum important in fruit
L. delbrueckii and vegetable fermentation.
L. leichmannii Tolerates high salt
L. plantarum concentration.
L. lactis
L. acidophilus

Heterofermentative Produce lactic acid (50%) plus


Spp. acetic acid (25%), ethyl
L. brevis alcohol and carbon dioxide
L. fermentum (25%). L. brevis is the most
L. buchneri common. Widely distributed in
plants and animals. Partially
reduces fructose to mannitol.

Yeasts Tolerate
acid, 40%
sugar
aw > =0.85

Saccharomyces Many pH 4-4.5 S. cerevisiae can shift its


Cerevisiae aerobic, 20-30 C metabolism from a

C.O.E.& T.,Akola 26
Manufacturing of Ethyl Alcohol from Fruit Waste

S. pombe some fermentative to an oxidative


anaerobes pathway, depending on
oxygen availability. Most
yeasts produce alcohol and
carbon dioxide from sugars.

Debaromyces Tolerant of high salt


Zygosaccharomyces concentrations
rouxii Tolerates high salt
Candida species concentration and low aw
Geotrichum
candidum

Desirable fermentation

It is essential with any fermentation to ensure that only the desired bacteria, yeasts
or moulds start to multiply and grow on the substrate. This has the effect of
suppressing other micro-organisms which may be either pathogenic and cause food
poisoning or will generally spoil the fermentation process, resulting in an end-
product which is neither expected or desired. An everyday example used to
illustrate this point is the differences in spoilage between pasteurised and
unpasteurised milk. Unpasteurised milk will spoil naturally to produce a sour tasting
product which can be used in baking to improve the texture of certain breads.
Pasteurised milk, however, spoils (non-desirable fermentation) to produce an
unpleasant product which has to be disposed of. The reason for this difference is
that pasteurisation (despite being a very important process to destroy pathogenic
micro-organisms) changes the micro-organism environment and if pasteurised milk
is kept unrefrigerated for some time, undesirable micro-organisms start to grow and
multiply before the desirable ones. In the case of unpasteurised milk, the non-
pathogenic lactic acid bacteria start to grow and multiply at a greater rate that any
pathogenic bacteria. Not only do the larger numbers of lactic acid bacteria compete

C.O.E.& T.,Akola 27
Manufacturing of Ethyl Alcohol from Fruit Waste

more successfully for the available nutrients, but as they grow they produce lactic
acid which increases the acidity of the substrate and further suppresses the bacteria
which cannot tolerate an acid environment.

Most food spoilage organisms cannot survive in either alcoholic or acidic


environments. Therefore, the production of both these end products can prevent a
food from spoilage and extend the shelf life. Alcoholic and acidic fermentations
generally offer cost effective methods of preserving food for people in developing
countries, where more sophisticated means of preservation are unaffordable and
therefore not an option.

The principles of microbial action are identical both in the use of micro-organisms in
food preservation, such as through desirable fermentations, and also as agents of
destruction via food spoilage. The type of organisms present and the environmental
conditions will determine the nature of the reaction and the ultimate products. By
manipulating the external reaction conditions, microbial reactions can be controlled
to produce desirable results. There are several means of altering the reaction
environment to encourage the growth of desirable organisms. These are discussed
below.

Manipulation of microbial growth and activity

There are six major factors that influence the growth and activity of micro-organisms
in foods. These are moisture, oxygen concentration, temperature, nutrients, pH and
inhibitors (Mountney and Gould, 1988). The food supply available to the micro-
organisms depends on the composition of the food on which they grow. All micro-
organisms differ in their ability to metabolise proteins, carbohydrates and fats.
Obviously, by manipulating any of these six factors, the activity of micro-organisms
within foods can be controlled.

Moisture

C.O.E.& T.,Akola 28
Manufacturing of Ethyl Alcohol from Fruit Waste

Water is essential for the growth and metabolism of all cells. If it is reduced or
removed, cellular activity is decreased. For example, the removal of water from cells
by drying or the change in state of water (from liquid to solid) affected by freezing,
reduces the availability of water to cells (including microbial cells) for metabolic
activity. The form in which water exists within the food is important as far as
microbial activity is concerned. There are two types of water - free and bound.
Bound water is present within the tissue and is vital to all the physiological
processes within the cell. Free water exists in and around the tissues and can be
removed from cells without seriously interfering with the vital processes. Free water
is essential for the survival and activity of micro-organisms. Therefore, by removing
free water, the level of microbial activity can be controlled. The amount of water
available for micro-organisms is referred to as the water activity (aw). Pure water
has a water activity of 1.0. Bacteria require more water than yeasts, which require
more water than moulds to carry out their metabolic activities. Almost all microbial
activity is inhibited below aw of 0.6. Most fungi are inhibited below aw of 0.7, most
yeasts are inhibited below aw of 0.8 and most bacteria below aw 0.9. Naturally, there
are exceptions to these guidelines and several species of micro-organism can exist
outside the stated range. See table for further information on water activity and
microbial action. The water activity of foods can be changed by altering the amount
of free water available. There are several ways to achieve this – drying to remove
water; freezing to change the state of water from liquid to solid; increasing or
decreasing the concentration of solutes by adding salt or sugar or other hydrophylic
compounds (salt and sugar are the two common additives used for food
preservation). Addition of salt or sugar to a food will bind free water and so
decrease the aw. Alternatively, decreasing the concentration will increase the
amount of free water and in turn the aw. Manipulation of the aw in this manner can be
used to encourage the growth of favourable micro-organisms and discourage the
growth of spoilage ones.

Table 3: Water activity for microbial reactions

C.O.E.& T.,Akola 29
Manufacturing of Ethyl Alcohol from Fruit Waste

Aw Phenomenon Examples

1.00 Highly perishable foods

0.95 Pseudomonas, Bacillus, Foods with 40% sucrose or 7%


Clostridium perfringens and some salt
yeasts inhibited

0.90 Lower limit for bacterial growth. Foods with 55% sucrose, 12% salt.
Salmonella, Vibrio
Intermediate-moisture foods (aw =
parahaemolyticus, Clostridium
0.90-0.55)
botulinum, Lactobacillus and some
yeasts and fungi inhibited

0.85 Many yeasts inhibited Foods with 65% sucrose, 15% salt

0.80 Lower limit for most enzyme Fruit syrups


activity and growth of most fungi.
Staphylococcus aureus inhibited

0.75 Lower limit for halophilic bacteria Fruit jams

0.70 Lower limit for growth of most


xerophilic fungi

0.65 Maximum velocity of Maillard


reactions

0.60 Lower limt for growth of osmophilic Dried fruits (15-20% water)
or xerophilic yeasts and fungi

0.55 Deoxyribose nucleic acid (DNA)


becomes disordered (lower limit
for life to continue)

0.50 Dried foods (aw=0-0.55)

0.40 Maximum oxidation velocity

C.O.E.& T.,Akola 30
Manufacturing of Ethyl Alcohol from Fruit Waste

0.25 Maximum heat resistance of


bacterial spores

Taken from Fellows (1988).

Oxidation-Reduction potential

Oxygen is essential to carry out metabolic activities that support all forms of life.
Free atmospheric oxygen is utilised by some groups of micro-organisms, while
others are able to metabolise the oxygen which is bound to other compounds such
as carbohydrates. This bound oxygen is in a reduced form.

Micro-organisms can be broadly classified into two groups - aerobic and anaerobic.
Aerobes grow in the presence of atmospheric oxygen while anaerobes grow in the
absence of atmospheric oxygen. In the middle of these two extremes are the
facultative anaerobes which can adapt to the prevailing conditions and grow in
either the absence or presence of atmospheric oxygen. Microaerophilic organisms
grow in the presence of reduced amounts of atmospheric oxygen. Thus, controlling
the availability of free oxygen is one means of controlling microbial activity within a
food. In aerobic fermentations, the amount of oxygen present is one of the limiting
factors. It determines the type and amount of biological product obtained, the
amount of substrate consumed and the energy released from the reaction.

Moulds do not grow well in anaerobic conditions, therefore they are not important in
terms of food spoilage or beneficial fermentation, in conditions of low oxygen
availability.

Temperature

Temperature affects the growth and activity of all living cells. At high temperatures,
organisms are destroyed, while at low temperatures, their rate of activity is
decreased or suspended. Micro-organisms can be classified into three distinct
categories according to their temperature preference (see table2.4).

C.O.E.& T.,Akola 31
Manufacturing of Ethyl Alcohol from Fruit Waste

Table 4 Classification of bacteria according to temperature requirements.

Temperature required for growth 0C

Type of Minimum optimum maximum General sources of


bacteria bacteria

Psychrophilic 0 to 5 15 to 20 30 Water and frozen foods

Mesophilic 10 to 25 30 to 40 35 to 50 Pathogenic and non-


pathogenic bacteria

Thermophilic 25 to 45 50 to 55 70 to 90 Spore forming bacteria


from soil and water

(Taken from Mountney and Gould, (1988).

Nutritional requirements

The majority of organisms are dependent on nutrients for both energy and growth.
Organisms vary in their specificity towards different substrates and usually only
colonise foods which contain the substrates they require. Sources of energy vary
from simple sugars to complex carbohydrates and proteins. The energy
requirements of micro-organisms are very high. Limiting the amount of substrate
available can check their growth.

Hydrogen ion concentration (pH)

The pH of a substrate is a measure of the hydrogen ion concentration. A food with a


pH of 4.6 or less is termed a high acid or acid food and will not permit the growth of
bacterial spores. Foods with a pH above 4.6. are termed low acid and will not inhibit
the growth of bacterial spores. By acidifying foods and achieving a final pH of less
than 4.6, most foods are resistant to bacterial spoilage.

The optimum pH for most micro-organisms is near the neutral point (pH 7.0).
Certain bacteria are acid tolerant and will survive at reduced pH levels. Notable

C.O.E.& T.,Akola 32
Manufacturing of Ethyl Alcohol from Fruit Waste

acid-tolerant bacteria include the Lactobacillus and Streptococcus species, which


play a role in the fermentation of dairy and vegetable products. Moulds and yeasts
are usually acid tolerant and are therefore associated with spoilage of acidic foods.

Micro-organisms vary in their optimal pH requirements for growth. Most bacteria


favour conditions with a near neutral pH (7). Yeasts can grow in a pH range of 4 to
4.5 and moulds can grow from pH 2 to 8.5, but favour an acid pH. The varied pH
requirements of different groups of micro-organisms is used to good effect in
fermented foods where successions of micro-organisms take over from each other
as the pH of the environment changes. For instance, some groups of micro-
organisms ferment sugars so that the pH becomes too low for the survival of those
microbes. The acidophilic micro-organisms then take over and continue the
reaction. The affinity for different pH can also be used to good effect to occlude
spoilage organisms.

Inhibitors

Many chemical compounds can inhibit the growth and activity of micro-organisms.
They do so by preventing metabolism, denaturation of the protein or by causing
physical damage to the cell. The production of substrates as part of the metabolic
reaction also acts to inhibit microbial action.

Controlled fermentation

Controlled fermentations are used to produce a range of fermented foods, including


sauerkraut, pickles, olives, vinegar, dairy and other products. Controlled
fermentation is a form of food preservation since it generally results in a reduction of
acidity of the food, thus preventing the growth of spoilage micro-organisms. The two
most common acids produced are lactic acid and acetic acid, although small
amounts of other acids such as propionic, fumaric and malic acid are also formed
during fermentation.

C.O.E.& T.,Akola 33
Manufacturing of Ethyl Alcohol from Fruit Waste

It is highly probable that the first controlled food fermentations came into existence
through trial and error and a need to preserve foods for consumption later in the
season. It is possible that the initial attempts at preservation involved the addition of
salt or seawater. During the removal of the salt prior to consumption, the foods
would pass through stages favourable to acid fermentation. Although the process
worked, it is likely that the causative agents were unknown. Today, there are
numerous examples of controlled fermentation for the preservation and processing
of foods. However, only a few of these have been studied in any detail - these
include sauerkraut, pickles, kimchi, beer, wine and vinegar production. Although the
general principles and processes for many of the fermented fruit and vegetable
products are the same -relying mainly on lactic acid and acetic acid forming
bacteria, yeasts and moulds, the reactions have not been quantified for each
product. The reactions are usually very complex and involve a series of micro-
organisms, either working together or in succession to achieve the final product.

What are yeasts?

A yeast is a unicellular fungus which reproduces asexually by budding or division,


especially the genus Saccharomyces which is important in food fermentations
(Walker, 1988). Yeasts and yeast-like fungi are widely distributed in nature. They are
present in orchards and vineyards, in the air, the soil and the intestinal tract of
animals. Like bacteria and moulds, they can have beneficial and non-beneficial
effects in foods. Most yeasts are larger than most bacteria. The most well known
examples of yeast fermentation are in the production of alcoholic drinks and the
leavening of bread. For their participation in these two processes, yeasts are of
major importance in the food industry.

Some yeasts are chromogenic and produce a variety of pigments, including green,
yellow and black. Others are capable of synthesising essential B group vitamins.

C.O.E.& T.,Akola 34
Manufacturing of Ethyl Alcohol from Fruit Waste

Although there is a large diversity of yeasts and yeast-like fungi, (about 500
species), only a few are commonly associated with the production of fermented
foods. They are all either ascomycetous yeasts or members of the genus Candida.
Varieties of the Saccharomyces cervisiae genus are the most common yeasts in
fermented foods and beverages based on fruit and vegetables. All strains of this
genus ferment glucose and many ferment other plant derived carbohydrates such
as sucrose, maltose and raffinose. In the tropics, Saccharomyces pombe is the
dominant yeast in the production of traditional fermented beverages, especially
those derived from maize and millet (Adams and Moss, 1995).

Conditions necessary for fermentation

Most yeasts require an abundance of oxygen for growth, therefore by controlling the
supply of oxygen, their growth can be checked. In addition to oxygen, they require a
basic substrate such as sugar. Some yeasts can ferment sugars to alcohol and
carbon dioxide in the absence of air but require oxygen for growth. They produce
ethyl alcohol and carbon dioxide from simple sugars such as glucose and fructose.

CH O
6 12 6  2C H OH
2 5 + 2CO 2

Glucose yeast ethyl alcohol carbon dioxide

In conditions of excess oxygen (and in the presence of acetobacter) the alcohol can
be oxidised to form acetic acid. This is undesirable if the end product is a fruit
alcohol, but is a technique employed for the production of fruit vinegars (see later
section on mixed fermentations).

Yeasts are active in a very broad temperature range - from 0 to 500 C, with an
optimum temperature range of 200 to 300 C.

The optimum pH for most micro-organisms is near the neutral point (pH 7.0).
Moulds and yeasts are usually acid tolerant and are therefore associated with the
spoilage of acidic foods. Yeasts can grow in a pH range of 4 to 4.5 and moulds can
grow from pH 2 to 8.5, but favour an acid pH (Mountney and Gould, 1988).

C.O.E.& T.,Akola 35
Manufacturing of Ethyl Alcohol from Fruit Waste

In terms of water requirements, yeasts are intermediate between bacteria and


moulds. Bacteria have the highest demands for water, while moulds have the least
need. Normal yeasts require a minimum water activity of 0.85 or a relative humidity
of 88%.

Yeasts are fairly tolerant of high concentrations of sugar and grow well in solutions
containing 40% sugar. At concentrations higher than this, only a certain group of
yeasts – the osmophilic type – can survive. There are only a few yeasts that can
tolerate sugar concentrations of 65-70% and these grow very slowly in these
conditions (Board, 1983). Some yeasts – for example the Debaromyces - can
tolerate high salt concentrations. Another group which can tolerate high salt
concentrations and low water activity is Zygosaccharomyces rouxii, which is
associated with fermentations in which salting is an integral part of the process.

Production of fruit alcohol


Alcohol and acids are two primary products of fermentation, both used to good
effect in the preservation of foods. Several alcohol-fermented foods are preceded
by an acid fermentation and in the presence of oxygen and acetobacter, alcohol can
be fermented to produce acetic acid. Most food spoilage organisms cannot survive
in either alcoholic or acidic environments. Therefore, the production of both these
end products can prevent a food from undergoing spoilage and extend its shelf life.
Primitive wines and beers have been produced, with the aid of yeasts, for
thousands of years, although it was not until about four hundred years ago that
micro-organisms associated with the fermentation were observed and identified. It
was not until the 1850’s that Louis Pasteur demonstrated unequivocally the
involvement of yeasts in the production of wines and beers (Fleet, 1998). Since
then, the knowledge of yeasts and the conditions necessary for fermentation of wine
and beer has increased to the point where pure culture fermentations are now used

C.O.E.& T.,Akola 36
Manufacturing of Ethyl Alcohol from Fruit Waste

to ensure consistent product quality. Originally, alcoholic fermentations would have


been spontaneous events that resulted from the activity of micro-organisms
naturally present. These non-scientific methods are still used today for the home
preparation of many of the worlds traditional beers and wines.
Alcoholic drinks fall into two broad categories: wines and beers. Wines are made
from the juice of fruits and beers from cereal grains. The principal carbohydrates in
fruit juices are soluble sugars; the principal carbohydrate in grains is starch, an
insoluble polysaccharide. The yeasts that bring about alcoholic fermentation can
attack soluble sugars but do not produce starch-splitting enzymes. Wines can
therefore be made by the direct fermentation of the raw material, while the
production of beer requires the hydrolysis of starch to yield sugars fermentable by
yeast, as a preliminary step (Stanier, Dourdoff and Adelberg, 1972).
Raw fruit juice is usually a strongly acidic solution, containing from 10 to 25 percent
soluble sugars. Its acidity and high sugar concentration make it an unfavourable
medium for the growth of bacteria but highly suitable for yeasts and moulds. Raw
fruit juice naturally contains many yeasts, moulds, and bacteria, derived from the
surface of the fruit. Normally the yeast used in alcoholic fermentation is a strain of
the species Saccharomyces cerevisiae (Adams, 1985).
The fermentation may be allowed to proceed spontaneously, or can be "started" by
inoculation with a must that has been previously successfully fermented by S.
cerevisiae var. ellipsoideus. Many modern wineries eliminate the original microbial
population of the must by pasteurisation or by treatment with sulphur dioxide. The
must is then inoculated with a starter culture derived from a pure culture of a
suitable strain of wine yeast. This procedure eliminates many of the uncertainties
and difficulties of older methods. At the start of the fermentation, the must is aerated
slightly to build up a large and vigorous yeast population; once fermentation sets in,
the rapid production of carbon dioxide maintains anaerobic conditions, which
prevent the growth of undesirable aerobic organisms, such as bacteria and moulds.
The temperature of fermentation is usually from 25 to 30oC, and the duration of the
fermentation process may extend from a few days to two weeks. As soon as the
desired degree of sugar disappearance and alcohol production has been attained,

C.O.E.& T.,Akola 37
Manufacturing of Ethyl Alcohol from Fruit Waste

the microbiological phase of wine making is over. Thereafter, the quality and stability
of the wine depend very largely on preventing further microbial activity, both during
the "aging" in wooden casks and after bottling (Stanier et al, 1972).
At all stages during its manufacture, fruit juice alcohol is subject to spoilage by
undesirable microorganisms. Pasteur, whose descriptions of the organisms
responsible and recommendations for overcoming them are still valid today, first
scientifically explored the problem of the "diseases" of wines. The most serious
aerobic spoilage processes are brought about by film-forming yeasts and acetic
acid bacteria, both of which grow at the expense of the alcohol, converting it to
acetic acid or to carbon dioxide and water. The chief danger from these organisms
arises when access of air is not carefully regulated during aging. Much more serious
are the diseases caused by fermentative bacteria, particularly rod-shaped lactic acid
bacteria, which utilise any residual sugar and impart a mousy taste to the wine.
Such wines are known as turned wines. Since oxygen is unnecessary for the growth
of lactic acid bacteria, wine spoilage of this kind can occur even after bottling. These
risks of spoilage can be minimised by pasteurisation after bottling.
Fermentation pathways

The initial steps are identical to those of respiration. For example, for
carbohydrate fermentation, the pathway begins with glycolysis. In EM glycolytic
pathway, there are generated two pyruvate molecules, two reduced coenzyme
NADH molecules, and two ATP molecules for each molecule of glucose. The
remainder of the fermentation pathway is concerned with reoxidising the coenzyme.
In fermentation, reoxidation of NADH to NAD+ depends on the reduction of
pyruvate molecules formed during glycolysis. Different microorganisms have
developed different pathways for utilising the pyruvate for reoxidising the reduced
coenzyme with different terminal sequences of the various fermentation pathways
resulting in the formation of various end products (Fig). The different fermentation
pathways are named for the characteristic end products that are formed. The most
common ones are as follows :

C.O.E.& T.,Akola 38
Manufacturing of Ethyl Alcohol from Fruit Waste

C.O.E.& T.,Akola 39
Manufacturing of Ethyl Alcohol from Fruit Waste

Fig. The ethanolic Fig. The homolactic acid fermentation


fermentation pathway pathway End product is lactic acid (lactate)

Batch Growth of Micro-Organism


The batch growth of micro-organisms involves adding a small quantity of the
micro-organisms or their spores (the seed culture or inoculum) to a quantity of
nutrient material in a suitable vessel. In the case of an aerobic fermentation (i.e. a
growth process requiring the presence of molecular oxygen) the contents of the
vessel (or fermenter) are aerated and the growth of the micro-organism allowed to
proceed. For convenience, the case where the feed material is present in aqueous
solution is considered and, furthermore, it is assumed that in the feed there is
contained a carbon and energy source which is the limiting substrate for the growth
of the culture. Whilst for an aerobic culture aeration is of prime importance, the fact
that air enters the vessel and leaves enriched in carbon dioxide will be ignored in
this discussion and the analysis focused on the changes occurring in the liquid
phase.

C.O.E.& T.,Akola 40
Manufacturing of Ethyl Alcohol from Fruit Waste

After inoculation, assuming no lag phase, the resultant growth can be


analysed by considering the unsteady-state material balances for the substrate and
biomass. The general form of this balance for a fermenter is :

Flow of Formation by Flow of


material in + – material out = Accumulation
biochemical
Since a batch process is being considered, the flow in and out of the fermenter are
reaction
both zero and the expression reduces to:

Formation by
= Accumulation
biochemical
So, for the case of the biomass:
reaction
dx
R xV = µVX = V (1)
dT
where µ is the specific growth rate, V is the volume of the vessel and X is the
instantaneous concentration of the biomass. If Y is the overall yield coefficient for
the formation of biomass and the limiting substrate concentration is 5, then the
equivalent expression for substrate is:
dS
RS V = V (2)
dT
where Rs is the rate of conversion of substrate per unit volume of the reactor.
Equation 5.116 makes no assumptions regarding the uniformity of the yield
coefficient Yx/s, but if that can be taken to be constant then equation may be used to
relate equations (1) and (2). This condition is met when µ is large in comparison
with m so that, dispensing with the subscript, the differential form of equation can be
written:
dS dX
Y =− (3)
dt dt
which gives:
YRs = - µ X (4)
Equation 2 thus becomes:

C.O.E.& T.,Akola 41
Manufacturing of Ethyl Alcohol from Fruit Waste

1 dS
− µX = (5)
Y dt
The yield coefficient may also be expressed in its integral form as:
X − X0
Y= (6)
S0 − S
which can be re-arranged:
X − X0
S = S0 − (6)
Y
If the growth follows the Monod kinetic model, then equation may be substituted into
equation 1 to give:
dX µ SX
= m (7)
dt Ks + S
The condition of the fermentation after any time / would then be given by:
X
K s + S dX t
∫ µ m S X =∫0 dt
X0
(8)

However, S is a. function of X and substitution using equation 6 must be made


before carrying out the integration. The result is:
K S Y + S 0Y + X 0  X  K SY  YS 0 
ln  + ln  (9)
µ m ( YS 0 + X 0 )  X 0  µ m ( YS 0 + X 0 )  ( YS 0 + X 0 − X ) 

A similar expression can be obtained for the substrate concentration:

K S Y + S 0Y + X 0  Y ( S 0 − S )  K SY  S 
ln1 +  − ln  = t (10)
µ m ( YS 0 + X 0 )  X0  µ m ( X 0 + YS 0 )  S 0 
These rather unwieldy equations can be used to generate a graph showing the
changes in biomass and substrate concentrations during the course of a batch
fermentation (fig). Their main disadvantage is that they are not explicit in X and S so
that a trial and error technique has to be used to determine their values at a
particular value of t.

C.O.E.& T.,Akola 42
Manufacturing of Ethyl Alcohol from Fruit Waste

Fig. The time couse of a batch fermentation as predicted by equations 9 and 10. The parameters
used in the calculation were : KS= 0.015 g/l, µm=0.35 h-1, Y = 0.5, X0 = 0.1 g/l, S0= 2 g/l

It is worth noting that the curves obtained in Fig. show an inflexion towards
the final stages of the fermentation, whereas the broken line showing the values of
X generated by equation shows no such characteristic and predicts that the growth
would proceed to give an infinite value of X.

DIFFERENT PROCESS FOR ETHANOL PRODUCTION


Classification of process
A) Fermentation -
i) From sucrose substrate.
ii) From waste sulfite substrate paper mills/Cellulose material such as wood waste,
paper, straw cotton etc.
iii) From starch substrate.
B) Petroleum processing
i) Catalytic hydration of ethylene.
ii) Etherification and hydrolysis of ethylene
iii) Oxidation of petroleum.
Ethyl Alcohol by Fermentation
Chemical reactions

C.O.E.& T.,Akola 43
Manufacturing of Ethyl Alcohol from Fruit Waste

(a) Main reaction


Invertase
C12H22O11 + H2O 2C6H12O6
Zymase
C6H12O6 2C2H5OH + 2CO2
(b) Side reactions

2C6H12O6 + H2O ROH + R' CHO


higher mol. Wt. Alcohols

Quantitative requirements
(a) Basis : 1 ton of 100% alcohol (1.26 kiloliters) and 90%
yield from total sugar
Molasses (50-55% total sugar) 5.6 tons
Sulfuric acid (600 Be) 27 kg
Ammonium sulfate 2.5 kg
Coal 0.7-1.5 tons
Process water 12 tons
Cooling water 50 tons
Electricity 35 KWH
By-products : CO2 0.76 ton
Fusel oil (higher mol. wt. Alcohols )
Residual cattle feed or fertilizer 0.20 – 0.60 ton
(b) Plant capacities : 10-100 tons/day of ethyl alcohol
Process description
Molasses is diluted to a 10-15% sugar concentration and adjusted to a pH of
4-5 to support yeast growth which furnishes invertase and zymase catalytic
enzymes. Nutrients such as ammonium and magnesium sulfate or phosphate is
added when lacking in the molasses. This diluted mixture called mash is run into
large wooden or steel fermentation tanks.
Yeast solution, grown by inoculating sterile mash, is added and fermentation
ensues with evolution of heat which is removed via cooling coils. The temperature
is kept at 20-300C over a 30-70 hr period, rising near the end of 350C. Carbon

C.O.E.& T.,Akola 44
Manufacturing of Ethyl Alcohol from Fruit Waste

dioxide may be utilized as a by-product by water scrubbing and compressing;


otherwise it is vented after water scrubbing.
Separation of the 8-10% alcohol in the fermented liquor called beer is
accomplished by a series of distillations. In the beer still, alcohol (50-60% conc.)
and undesirable volatiles such as aldehydes are taken off the top and fed to the
aldehyde still. Alcohol is pulled off as a side-stream split to the rectifying column. In
this final column, the azeotropic alcohol-water mixture of 95% cannot is taken off as
a top side streams conde and run to storage where it is split into three parts :
(1) direct sale as potable, government controlled alcohol
(2) denatured by small additions of mildly toxic ingredients and sold for industrial
uses
(3) made anhydrous by ternary azeotropic distillation using benzene or
extractive distillation using ethylene glycol
When fusel oil recovery is practiced, side-streams are drawn off near the bottom of
the aldehyde and rectifying columns and are separated by decantation. These
higher molecular weight alcohols are sold directly for solvents or are fractionated to
give predominantly amyl alcohol.
The bottoms from the beer still, known as slops, are either discharged as
waste or concentrated by evaporation to cattle feed depending on fuel and by-
product sales economics.

C.O.E.& T.,Akola 45
Manufacturing of Ethyl Alcohol from Fruit Waste

Major engineering problems


 Collection and storage of molasses
 Maintenance of sterile and specific yeast culture conditions.
 Batch versus continuous operation; continuous molasses dilution in the head
end of the process and continuous distillation are incorporated to save
space, equipment and operating costs
 Waste disposal problem : if uneconomic to concentrate for cattle feed, must
use trickling filters, activated sludge or anaerobic digestion to lower the
biological oxygen demand (BOD) before discharging to water run-off
 Fuel economy in the series of distillations : use of preheat exchangers
 Development of methods to produce anhydrous alcohol from the 95% alcohol
azeotrope.

C.O.E.& T.,Akola 46
Manufacturing of Ethyl Alcohol from Fruit Waste

PRODUCTION FROM SULFITE WASTE LIQUIOR


Alcohol may be obtained by fermenting the waste liquors from the sulfite
pulping process; in this case the source of the alcohol, ultimately, is wood, but it is
obtained as a by-product of the process for producing paper pulp. The pulping
process aims at separating lighin and some hemicellulose from the usable cellulose
fiber. Derivatives of these separated compounds, together with fermentable sugar
from the less-resident fractions of cellulose, appear in the waste liquor. While
alcohol recovery from this source has been commercially successful abroad,
particularly in Sweden, the first commercial attempt in the U.S., at Mechanics ville,
New York, was unsuccessful and was abandoned because of various uneconomical
conditions. An admixture of molasses is believed to have been used in this plant to
improve the alcohol recovery.
The waste liquor from the sulfite process contains from 2 to 3.5% of sugar, of
which about 65% is fermentable to alcohol. Before such a liquor can be fermented,
however, the sulfur dioxide, as well as the acetic and formic acids present in the
solution, must be neutralized, usually with lime. The sulfur dioxide gas used for the
original pulping action can be largely removed by aeration, before neutralization, if
desired. Special types of yeast may be required. Alcohol yields are about 1% of
the volume of liquid fermented; hence relatively large distillation capacities are
required.
During World War II two commercial plants operating on sulfite liquor were
operated in North America, one in Thorold, Ontario, in 1943 and the other in
Bellingham, Washington, in 1945. Yields of 18.22 gal of alcohol per ton of pulp
produced are claimed; a distinctive feature of the process is the re-use of the yeast.
The alcohol yield may be raised to 27 gal. Per ton of pulp, if all sugars are
recovered. Previous difficulties of the process were the extreme dilution of the
solutions, the expense of pre-purification of the liquors, and the waste of
nonfermentable sugars. It is claimed that future costs based on large operations
may be as low as 12c per gal. Although 20c would probably be a safer estimate.

C.O.E.& T.,Akola 47
Manufacturing of Ethyl Alcohol from Fruit Waste

Alcohol from waste sulfite liquior.


Figure gives a flow sheet of the Bellingham, Washington, plant. Removal of
sulfur dioxide from the waste sulfite liquor is accomplished by stripping the liquor
with stream, by countercurrent flow in a column, approximately 8 ft. in diameter by
45 ft. tall, fabricated of stainless steel to the general pattern of a distillation column
having 20 plates. Liquor enters at the top and steam at the bottom. Sulfur dioxide
and steam are discharged out the top and are salvaged by injection into the digester
cooking acid. The sulfur recovery amounts to about 20 lb.of sulfur per ton of pulp
and offsets the cost of the steam required. The composition of the sulfite waste
liquor discharged at the bottom varies depending on the stream input. Stripping
results in complete removal of the free sulfur dioxide and part of the loosely
combined sulfur dioxide. The pH of the stripped liquor varies between 3.8 and 4.2
depending upon the grade of pulp being cooked. Although the column is equipped
with control instruments to deliver automatically a product of constant pH, it is
normally operated at a fixed steam liquor ratio of 1 lb of stream per 2 gal.of liquor
feed. Part of the heat input is recovered in the digester cooking acid. The sulfite
waste liquor from the base of the stripping column is pumped to the alcohol-plant
building for continuation of liquor preparation.

C.O.E.& T.,Akola 48
Manufacturing of Ethyl Alcohol from Fruit Waste

The acidity of the sulfite waste liquor can be sufficiently reduced by stripping
alone to make further treatment unnecessary, but for best economy it usually proves
desirable to add lime. The lime is added as a 10% water slurry injected into the
sulfite waste liquor at a point just ahead of the coolers. The equipment consists of
an outside lime-storage bin, two agitated lime-slurry tanks, and the necessary
pump. A pH controller regulates the amount of lime addition. The sulfite waste
liquor is adjusted to a pH of 4.5 for fermentation. The quantity of lime average
about 3 lb.of lime per 1000 gal.of sulfite waste liquor treated.
After lime addition, the liquor is cooled to a temperature of 32 0C. Cooling is
accomplished by two-stage flash evaporation under high vacuum, as this method
has the advantage of concentrating the liquor at the same time that it is being
cooled and also of eliminating additional amounts of sulfur dioxide. Concentration is
in the order of 12% which results in proportional reduction of costs during the
subsequent steps of processing.
The essential feature of this process is that after fermentation, the fermented
work is run through a centrifugal separator to remove the yeast. This yeast is then
re-used in a following fermentation in the operating cycle. The basis of this process
is that when yeast is present in a suitable medium containing sugar, the course of
the resulting fermentation tends to divide into two stages. In the first stage, the
yeast cells multiply, using sugar for food, until they become crowded. During this
stage there is maximum growth of yeast and minimum production of alcohol. In the
second stage, the yeast reduces its rate of budding, or division, and continues to
feed on the remaining sugar present. During this stage there is minimum growth of
yeast and maximum production of alcohol. The purpose of re-using the yeast is to
establish at once in each new fermentation the same high concentration of yeast
cells that was present at the end of the previous fermentation. In this way the
fermentation is limited to the second stage and the alcohol yield, therefore, is
improved.
Under any given set of conditions there is a fairly narrow concentration range
of yeast cells per unit volume above which the rate of yeast growth diminishes every
rapidly. Operation throughout the entire fermenting cycle at yeast concentration in

C.O.E.& T.,Akola 49
Manufacturing of Ethyl Alcohol from Fruit Waste

excess of such critical value offers important advantages in the case of waste sulfite
liquor. Since large volumes of fermenting liquor are involved, profile yeast growths
must ensue before the critical concentration is reached if the initial inoculum is
small. This yeast growth is obtained at the expense of sugar, which would
otherwise produce alcohol. At the same time, because waste sulfite liquor is, at
best, a dilute sugar solution, the sugar required for yeast growth represents a
greater proportion of the total than in the case of more concentrated sugar solutions
from molasses or grain. The advantages of the yeast re-use process in increasing
alcohol yields are, therefore, much greater in the case of waste sulfite liquor than in
application to the more conventional raw materials.
Fermentation is carried out in eight interconnected fomenter of 90,000 gal
capacity each. To the liquor being pumped from storage is injected measured
proportionate amounts of urea and yeast. The liquor enters the first fomenter,
overflows into the second and so on through to the last fomenter whereupon
fermentation is complete. From 70 to 80% of the fermentable sugars are fermented
in the first two fomenters and about 95% of the fermentable sugars are converted to
alcohol in the complete cycle. Fermentation time has been varied between 12 and
20 hours. This short fermentation time, principally due to the elimination of the
yeast-multiplication stage, can also be attributed partly to the adequate mixing
provided in the fermenters, which keeps the yeast cells in suspension and partly to
the fact that the yeast is acclimatized through re-use.
Control of fermentation consists of regular measurement of the sugar
concentration of the liquor entering and leaving the fermented and the alcohol
content of the fermented liquor. The yeast is examined daily under the microscope
for viability and cell count.

From starch substrate


Technology for manufacturing alcohol from starch based raw materials such
as grains (sorghum grains) on laboratory scale which is scaled up to 15,000 LPD
pilot plant, the process involved in brief is as follows: The chemical equation which
takes place is as follows:

C.O.E.& T.,Akola 50
Manufacturing of Ethyl Alcohol from Fruit Waste

(C6H10O5)n + H2O ——————> n(C6H1206)


Starch glucose water Free glucose
C6H12O6 ——————> 2(C2H5OH) + 2CO2
Glucose Ethanol Carbon dioxide

A) Milling and Gelatinization


The starch containing amylaceous material is first cleaned, purified, dried
and milled/ground in small particle and then charged into a steam chest where it is
cooled by steam at 140°C and then enzymes are added. The steam injection breaks
down the starch and make it more water soluble. The starch swells to many times
the original size and become gelatinized. A liquefying enzyme also breaks the
starch into smaller molecular chain.
B ) Hydrolysis and saccharification
The mash is then blown into a flash tank and cooled at around 90°C. The
sudden expansion dissolves the starch out of it bond and disengages it so that it
can be decomposed more quickly and more completely. It is now ready for
fermentation in mash tabs. Here the addition of appropriate enzymes i.e. α -
amylaze carries out composition of polysaccarides to the extent required under
controlled condition.
C) Fermentation
The fermented mash of saccharides is then charged to pre-fermenter where
yeast is added, (yeast is cultivated in a separate yeast culture vessel) The function
of pre-fermenter is to allow the yeast cells to multiply and reduce the chances of
bacterial contamination from the pre-fermenterr, the mash is transferred to
fermenters where it is set to optimum condition for saccharides fermentation. The
process of fermentation takes about 60 hours at a temp, of 30 - 32°C. The
fermentised mash is ready for distillation. The fermented mash contains 8 - 9% V/V
ethanol.
D) CO2 recovery
CO2 evolved during the fermentation is collected in balloon, washed, purified,
liquefied and stored.
E) Filtration

C.O.E.& T.,Akola 51
Manufacturing of Ethyl Alcohol from Fruit Waste

Fermented mash should be filter to remove suspended solids through filter


press and then this filtrate will send to distillation for obtaining distillate.
F) Distillation
The distillation section consists of six number of column viz. analyzer cum
degasifying column, aldehyde column, rectifying column, exhaust and methanol
column.
The fermented mash after preheating is passed to the primary distillation
column. Where rectified spirit is recovered. Rectified spirit is further distilled in
successive columns to remove aldehydes, ketones, methanol etc. to obtain extra
neutral alcohol. The spent wash generated in distillation section is centrifuge and
concentration is dried to generate cattle food as by product (DDG).

Salient Features
Quality of yeast creature
The flocculating yeast culture must having fermentation efficiency of over
90%. Fermentation temp.
The performance of yeast towards alcohol production depends on
temperature. The efficiency is highest at and below 32°C and hence maintaining
section temp, is very important.
The salt content of diluted molasses should be such that the osmotic
pressure generated will not destroy the yeast functioning. Apart from this, the
problem of salting out on dissolved inorganics is also reduced by reducing the salts.
The typical detrimental problem is that almost all other continuous
fermentation lies in the fact that any effect to separate yeast from salt (precipitated)

C.O.E.& T.,Akola 52
Manufacturing of Ethyl Alcohol from Fruit Waste

for recycle of yeast is not successful. Salt recycle along with yeast should not be
avoided.
In the process, the yeast is denser than the precipitating salt and hence the
salt and yeast separation is easy and complete.

C.O.E.& T.,Akola 53
Manufacturing of Ethyl Alcohol from Fruit Waste

Synthetic Alcohol from Hydrocarbon gases


Direct Hydration Process. The reaction C2H4 + H2O C2H6OH is exothermic, H =
10.964 cal. At 150C. Aston (6) gives values for the free-energy change, which lead
to values for log K as follows; at 300 0 K., 1.119; at 4000 K., - 0.81; at 5000 K, - 2.02;
at 6000 K., - 2.80. The equilibrium is favored by low temperature and high pressure
and the conversion to ethylene is favored by having a high ratio of ethylene to
water, so far as it is economical to do this. At the lower temperatures the pressure
cannot be increased indefinitely because the water would condense, thereby uging
the equilibrium unfavorably and at higher temperature in crease of pressure tends to
cause polymerization of the ethylene. At 2000 C. and with the water to ethylene ratio
at 2 to 1, the equilibrium reaches 20% conversion at 300 p.s.i., but at 3000 C., and
with 5 to 1 water-to-ethylene, equilibrium conversion is only 15% at 1200 p.s.i.

C.O.E.& T.,Akola 54
Manufacturing of Ethyl Alcohol from Fruit Waste

At the low temperatures necessary for favourable equilibrium the reaction


rate is slow and therefore catalysts must be used. Commercial utilization of the
process has been proposed, presumably with efficient catalysts, although published
data indicate on the low conversions. At 2000C, and 1500 p.s.i. (conditions under
which the equilibrium conversion is only 8%), conversions of 2-4% were obtained
with a contact time of 60 seconds. British investigators have used, as catalysts,
complex phosphates, of many metals, including iron, nickel, calcium, strontium,
barium and magnesium (2). Dodge and co-workers (13.27) found aluminum oxide
the most active catalyst of about twenty materials, including oxides and phosphates
of aluminum, thorium, and tungsten.
Side reactions are not important at moderate temperatures and pressures.
Dodge found polymerization at 3500C., but not at 3200 C. or below. The British
workers did not mention polymerization or ether formation at 150-3000 C and
pressures up to 1500 p.s.i.
Since the conversion per pass is necessarily low, recycling is required, and a
comparatively concentrated source of ethylene must be used to prevent the inerts
from building up to too high a concentration readily available from the ethylene-
producing plants of the petrochemical industry which operate to supply feed
material for polyethylene and ethylene oxide.

C.O.E.& T.,Akola 55
Manufacturing of Ethyl Alcohol from Fruit Waste

Alcohol from ethylene

Preparation of ethanol by esterification and hydrolysis is a three-step process :


(1) Absorption of ethylene in concentrated (about 95% by weight) sulfuric acid.

CH2 + CH2 + H2SO4 CH3 CH2 OSO3 H


Ethyl hydrogen sulfate

2CH2 = CH2 + H2SO4 (CH3 CH2 )2 SO4


diethyl sulfate

Figure shows a generalized flow diagram of the indirect hydration process as


practiced in the United States.

Flow diagram for the manufacture of ethyl alcohol by esterification and hydrolysis

C.O.E.& T.,Akola 56
Manufacturing of Ethyl Alcohol from Fruit Waste

Ethylene gas is absorbed in 5-98% sulfuric acid at reaction temperatures of


50-800 C and pressures of 150-200 psig. Process conditions in the USSR are
generally at higher temperature (70-800C) and higher pressure (374-400 psig).
Absorption of ethylene is exothermic and cooling is required. Increased absorption
is favored by stronger acid concentrations, higher temperature and pressure, and
good agitation.
(2) Hydrolysis of ethyl sulfates :
CH3 CH2 OSO3 H + H2O CH3 CH2 OH + H2SO4
(CH3 CH2 )2 SO4 +2 H2O 2CH3 CH2 OH + H2SO4

The mixed esters (ethyl hydrogen sulfate and diethyl sulfate) in the absorbate
are hydrolyzed with 1-2 volumes of water. The equivalent practice in the USSR is to
hydrolyze with 0.8 volume of water per volume of absorbate. In the United States a
residence time of 1.5-2 hr at 700 C hydrolyzes the sulfates to ethyl alcohol and dilute
sulfuric acid.
The hydrolysis mixture contains ethyl alcohol, ethyl ether, sulfuric acid and
water. Diethyl ether tends to form as the main by-product of the reaction between
ethanol and diethyl sulfate :
CH3 CH2 OH + (CH3 CH2 )2 SO4 CH3 CH2 OSO3 H + CH3CH2OCH2 CH2

The crude hydrolyzate is separated in a stripping column and forms bottoms


which contain dilute sulfuric acid and a gasous overhead which includes alcohol,
ether and water. After washing with a countercurrent flow of water or dilute caustic,
the gaseous mixture is condensed and further purified by distillation. Ether is first
removed by steam stripping and 950 alcohol is then obtained by a second column.
Yields of ethanol from ethylene are about 86 880 by weight. A rule of thumb
is that about 1 gallon of 95% ethanol is produced from every 4 lb of ethylene.
(3) Reconcentration of dilute sulfuric acid : Dilute sulfuric acid (50-60%) is
concentrated for reuse by vacuum evaporation and represents one of the more
costly steps in the indirect hydration process. Weak acid is first passed through a
reboiler where the acid strength is raised to about 70%. The most common method

C.O.E.& T.,Akola 57
Manufacturing of Ethyl Alcohol from Fruit Waste

of concentration is by the Simonson-Mantius process which yields 90% acid from a


two-stage vacuum evaporator operating at pressures of 2.5 and 0.4 in Hg absolute,
respectively. The 90% acid is brought back to a 96-98% strength by fortification
with 103% olcum. Dowtherm A at about 3000C, is the usual heat transfer medium
and maintains an acid temperature of up to 1900 C during re-concentration.
Buildup of carbonaceous materials in sulfuric acid is one of the more serious
problems of acid re-concentration. Insoluble (elemental) carbon and liquid organic
compounds are both present. Carbonaceous materials may be removed by heating
at 175-3150 C for about 2 hours, or by extraction with kerosene or ethyl ether. Oils
and tars can be separated by cooling the dilute (60%) acid. Foaming of dilute
sulfuric acid may be reduced by the addition of low-molecular-weight aliphatic alkyl
sulfates. Foaming of 90% acid is decreased by heat soaking at 150-2800 C for 2-24
hr.

SELECTION OF PROCESS
a) PROCESS SELECTION :
As seen previously the different processes used in ethanol manufacture are
basically of two types only synthetically from petroleum or by fermentation of sugar
i.e. biochemical process.
Considering the economics, the cost of ethanol from petroleum derivatives is
favorable even today ( outside India ) as the 86 prices in the U.S. candidate (8)
Alcohol from ethylene 0.3706$/Kg. And that from fermentation of molasses
0.4012$/Kg. Indian alcohol without tax costs Rs.3/ht., which at the present dollar
rate works out about 0.15$/Kg.
b) Why synthetic Ethanol is not favorable ?

C.O.E.& T.,Akola 58
Manufacturing of Ethyl Alcohol from Fruit Waste

However, the cost of petroleum to India is very high. One reason for this is
that most of petroleum has to be imported for which costly foreign exchange is
needed. Also, the to the recent gulf wars the prices of crude have zone up. Thus
the synthetic ethanol manufacture is not favorable.
c) Why Synthetic Ethanol is not suitable ?
Almost 30% of the alcohol consumed in India is for potable purpose. That
alcohol desired from petroleum does not provide the special properties required
from liquor making. As a result fermentation alcohol is the best option from India's
point of view.
d) Why Sapota is suitable for alcohol production in India.
Also India produces large quantity of sugar ( 11 mt in 1989-90). Now 3 Kgs
of sugar produced also produce one kg of sapota such large quantity of sapota
would be wasted of not used. Then, it is suitable for alcohol production such me
Sapota is having high carbohydrate content, cheaply having high carbohydrate
content, cheaply available, can be easily fermented. It is the cheapest product
compared to other fruits having much better yield. The present price of tax paid
alcohol is Rs.5.60/lit, which at present price of dollar works out to be 18/lit, which is
quite competitive internationally.
India has got large production of fruits. Most of the fruits having high sugar
and carbohydrate content is exported from India. The fruits having high
carbohydrate content are Banana, Mango, Jackfruit, Grapes, Orange Sapota etc.
and a variety of fruits are available inthenantent. But we have chosen the Sapota
for our project because of the following reasons –
1. It is easily perishable.
2. It is having high carbohydrate and sugar content.
3. It can be fermented easily.
4. It is cheaply available in the market.
5. Its storage cost is cheap.

C.O.E.& T.,Akola 59
Manufacturing of Ethyl Alcohol from Fruit Waste

ACTUAL PROCESS AT EXPERIMENTAL SITE


Practical process involving chiker in dudes following steps :
1. Grinding
2. Dilution and Sterilization
3. Culture Development.
4. Pre fermenter stage
5. Fermentation
6. Separation and recovery of alcohol.
7. Rectifying column
8. Waste treatment.
1. Grinding : - First take the sported Spota, $ clean and grindo 10 kg of Sapota into
a fine meal of about the size needed for live stock feed, in a grinder.

C.O.E.& T.,Akola 60
Manufacturing of Ethyl Alcohol from Fruit Waste

2. Dilution and Sterilization :- As seen before Sapota contains about 50% sugar
and also that nearest cannot sustain in sugar concentration of about 15-20 %
depending upon strain quality. As such dilution of the Sapota to between 10-15 %
Sugar is done.
Also, nearest cannot complete with other micro organizers such as bacteria,
which are even present. Thus, the Sapota must be sterilized by heating to about
700C. Both these procedures can be simultaneous achieved in a continuous dilutes
in which water are fed so that detection and sterilization is done.
Culture Development :- Yeast strains are usually proprietary and energy distillery
maintains a culture of its own that's suitable to the molasses and environment found
there. This culture must be grown to a size useful for industrial scale production.
This involves many difficulties such as control over temperature, pH, nutrient level,
sterile and ascetics conditions.
Single strain of yeast from the laboratory refrigerator is first grown in small
flask and the size doubled energy eight hours until 20ht stage. Then the operation
shifts from the laboratory to plant shed where it is grown up to the 200 lit. size and
then used for fermentation, in the pre-fomenters at about 5-10% w/w of the diluted
Sapota. At each stage, sterilized diluted Sapota is used. Nutrients such as ammonia
sulphate, urea, diammonium phosphate are added and also sulphuric acid.

C.O.E.& T.,Akola 61
Manufacturing of Ethyl Alcohol from Fruit Waste

Pre-fermenter Stage :- The diluted Sapota & developed yeast culture are fed to
the fomenter tanks, which are provided with heating coils and air sparkers. The
idea here is not to produce alcohol but to allow the yeast to grow to a high
concentration i.e. the part of life cycle of yeast involving the exponential growth
stage is completed here. Oxygen is required in this stage and to air sparing is
required this also helps in agitation. The exothermic reactions are aided by cooling
water calculated through the cells. Generally, 2-4 pre fomenters are used and
residence time is between 6-8 hours.
Fermenters :- The work from the prefer mentors is prepared to the fomenters.
These are not provided with air spanners since here only the anaerobic stage of the
life cycle of yeast is to be allowed since alcohol is produced only during this stage.
The sugar is converted according to the following equation.
C6H12O6 2 C2H5OH + 2CO2 + 130KJ
It is observe that a lot of heat is generated during the reaction and hence
inter cooling is required. The froth is pumped through a plate type exchanger and
maintained at around 30-320c. At high temperature, not only is the alcohol
productivity low but also the amount of alcohol cost as a result of evaporation and is
entrained along with carbon dioxide formed is high.
Hence the maintenance of low temp. is must. The fomenters have closed
heads and the carbon dioxide formed is easily collected. It is bubbled through a tank
of water so that any alcohol entranced is it is recovered the gas may then be
compressed and stored. These are usually between? 4-8 fomenters and residence
time 28-32 hours.
Separation and Recovery of alcohol - : The resulting solution from the fomenters is
known as wash. This wash contains between 8-10% alcohol, unfermented sugar,
ash from the Sapota and water. The costtrest of all and the price determining stage
of the process is the recovery of the alcohol from the wash not only in high purity
but also economically.

C.O.E.& T.,Akola 62
Manufacturing of Ethyl Alcohol from Fruit Waste

Distillation of Ethanol
Whatever method of preparation is used, the ethanol is initially obtained in
admixture with water. The ethanol is then extracted from this solution by simple or
steam distillation.
Although the boiling of ethanol, 78.3°C, is significantly lower than the boiling
point of water, 100°C, these material cannot be separated completely by distillation.
Instead, an azeotropic mixture (i.e. a mixture of 95% ethanol and 5% water) is
obtained, and the boiling point of the azeotrope is 78.15°C. In the distillation, the
most volatile material (i.e. the material that the has the lowest boiling point) is the
first material to distill from the boiling point. If flask, and this material is the
azeotrope of 95% ethanol which has the lowest boiling point. If an efficient
fractionating column is used, there is obtained first 95% alcohol, then a small
intermediate fraction of lower concentration and then water. But no matter how
efficient the fractionating column used, 95% alcohol cannot be further concentrated
by distillation.
The separation of mixture by simple distillation occurs because the vapour
has a different composition from the liquid from which it distills (i.e. the vapour is
richer in the more volatile component). We cannot separate 95% alcohol into its
components by distillation, because here the vapour has exactly the same
composition as the liquid, towards distillation, then 95% alcohol behaves exactly like
a pure compound.
A liquid mixture that has the peculiar property of giving a vapour of the same
composition is called an azeotrope (i.e. constant - boiling mixture). Since it contains
two components 95% alcohol, have boiling points lower than those of their
components, and are known as minimum - boiling mixtures. Azeotrope having
boiling points higher than those of their components are known as maximum boiling
mixtures.

C.O.E.& T.,Akola 63
Manufacturing of Ethyl Alcohol from Fruit Waste

Actual Process of Experimentation Site

Manufacturing of Ethanol from Sapota

Confirmative Test

C.O.E.& T.,Akola 64
Manufacturing of Ethyl Alcohol from Fruit Waste

Sr.No. Test Observations Inference


1 Red litmus paper dipped in No Change Ethanol is present
ethanol
2. Ethanol + NaOH Solution No colour change Ethanol is present
3 Ethanol + Bromine Water No reaction C2H5OH is present
4 It's melting point is 392 °K No colour change Ethanol is present.
5. Burning Test When ignited, it Ethanol is present
catches fire.
Idoform Test
Idoform is prepared by treating an aqueous solution of ethyl alcohol (Ethano!)
with NaOH and iodine and heating the mixture and a water bath to about 80 °C. the
Solution on cooling gives the crystals of Idoform which are filtered, washed and
dried they have found lemon yellow coloured, lustrous solid with typical odour.
2 NaOH + I2 NaOl + Nal + H2O
Oxidation
CH3-CH2-OH + NaOl CH3CHO + Nal + H2O
CH3CHO + 3NaOl CI3-CHO + 3NaOH
Hydrolysis
NaOH + Cl3 -CHO CHI3 + HCOONA
Lodoform

Specific Gravity Test


a. Weight of empty specific gravity bottle = X gms
b Weight of empty specific gravity bottle + distilled water = Y gms
c. Weight of empty specific gravity bottle + Ethanol Sample = Z gms
∴Weight of distilled water = A = Y - X gm
∴Weight of distilled water = B = Z - X gm
∴ Specific gravity of Ethanol = B/A = (Z - X) / (Y - X)
Density of Ethanol Sample
1) Take 1000 ml of ethanol sample in bottle and weigh it (X gm)
∴weight of ethanol sample = W = X - Y gm
where, Y - weight of empty bottle
∴density of ethanol = ρ = W /1000 gm / ml

C.O.E.& T.,Akola 65
Manufacturing of Ethyl Alcohol from Fruit Waste

PLANT LAYOUT

Sapota

C.O.E.& T.,Akola 66
Manufacturing of Ethyl Alcohol from Fruit Waste

PROCESS
LAYOUT

RESULTS OF EXPERIMENTATION
C.O.E.& T.,Akola 67
Manufacturing of Ethyl Alcohol from Fruit Waste

By the experimentation we have found the following results :-


i) Ethanol yield = 3.5 Kg
ii) Specific gravity = 0.9720
iii) Specific gravity = 18 %
iv) Density = 0.9720 gm/ml.
Chiku has good potential as a raw material for ethanol production. The
process for Alcohol production using chiku, although a little expensive, is still
preferable as it is environment friendly compared to molasses. Use of Chiku for
ethanol fermentation will use up to 10-15% of the mold – damaged chiku (Sapota)
which will help farmers realize a good price for their product. Ethanol producing
companies, research institutions and the Government can coordinate with farmers
to strategically develop value added utilization of Chiku.
Yield of ethanol from 10 kg of Chiku should be 3.5 to 4 lit. but we got 3-5
liters of 8% ethanol.

MATERIAL BALANCE

C.O.E.& T.,Akola 68
Manufacturing of Ethyl Alcohol from Fruit Waste

Basic  1000 kg of sapota.


Invertese
C12H22O11 + H2O C6H12O6 + C6H12O6 ,
d-glucose d-fructose
zymase
C6H12O6 2 C2H5OH +2 CO2
Alcohol
Glucose in Sapota = 0.22 x 1000 = 220 kg

From reaction we have

1 kmol C12H22O11 = 4 Kmol C2H5OH

342 kg C12H22O11 = 184 kg C2H5OH

Theoretical production of rectified spirit.

184
= × 220kg = 118.36kg
342

Density of rectifying spirit = 0.782 kg/wt

Theoretical production of rectifying spirit

118.36
= = 150.77 wt
0.785

1000 kg Sapata gives =.150.77 lit ethonal

1000
1 lit of ethonal = = 6.632 kg of Sapota.
150.77

Basis Production of 1000 lit/day of( 10% by weight ) ethanol.

Balance over mash preparation section

1 lit of ethanol required 6.632 Kg of Sapota.

∴ Sapota required = 6.632 × 1000

= 6632 Kg/day

Water added = 3 Part/Part of Sapota.

C.O.E.& T.,Akola 69
Manufacturing of Ethyl Alcohol from Fruit Waste

Water added = 3 × 6632 = 19δ96 Kg/day

∴ Mash produced = 6632 + 19δ96

= 26528 Kg/day

As Sapotal contain 22% sugar in the form of Glucose

∴It will contain = .22 × 6632

= 1459.04 Kg Glucose/day.

According to stochiometry for 18% efficiency

180 Kg of Glucose gives 180 Kg of ----- give

16.56 Kg of ethanol.

1459.04 × 16.56
∴ethanol produced =
180

= 134.23

Amt of sugar 1459.04


conc. Of Mash = =
Amt of Mash 26528

= 0.055

Balance on Fermenter

Feed to fermenter includes

1) Mash = 26528 Kg / day.

2) Yeast culture = 0.5 Kg / day.

3) Nutrients present =

Calcium carbonate = 1.66 Kg /day

HCL ( 31 % ) = 5 Kg / day

Fermentor output includes

C.O.E.& T.,Akola 70
Manufacturing of Ethyl Alcohol from Fruit Waste

1)Ethanol = 134.23 Kg.

2) CO2 gas

3) Residue with Biomass ( It also have some quantity of glucose )

4) Distillers dried grain and soluble.

5) Un converted sugar.

6) Waste water.

Now water required for reaction pure Alcohol is --

18
= × 26528 = 2652. Kg / day
180

i.e. water consumed = 26528 Kg./day.

Initially water added = 19896 Kg / day.

Water coming outside fermenter = 19896 – 2652.8

= 17243.2 Kg./ day.

As we are using 5 Kg of 31% HCL solution it also contain. 1.05 Kg of water

∴Total water coming out of fermenter

= 17243.2 + 1.05

= 17244.95 Kg / day

2) From reaction stomchiometry moles of CO2

= Moles of ethanol produced

= 134.23 / 46.07 = 2.91 K mole/day

∴CO2 produced will be = 2.91 × 44

= 128 .04 Kg / day.

C.O.E.& T.,Akola 71
Manufacturing of Ethyl Alcohol from Fruit Waste

3) Biomass produced :- Material balance over the fermanter with respect to yeast

mass is –

[ Change within the vessel ] = [ increase due to feed ] + [ increase due to growth ] –

[ decrease due to loss in effluent ] – [ decrease due to deth ]

Dx x − xo
it can be given as = K = 0.5
Ds So − s

For ethanol system value of K is 0.5 value taken from book wasteless chemical

processing where X, Xo = Dry cell mass finally and initially.

S,So = Substrate mass finally and initially

We have Xo = 0.5 Kg. / day.

So = 1459.04 Kg sugar

S = finally wt. Of substrate left.

We have ethanol produced = 134.23 Kg / day

Mole of ethanol = 2.91 Kmol / day.

From Stochiometry of reaction

2.91
Moles of Glucose converted =
2

= 1.45 K mole / day

1459.04
initial moles of glucose =
180

= 8.105 K. moles

∴Moles unconverted = 8.105 – 1.45 = 6.655 K moles

∴Kg of substrate at the end = 6.655 × 18

S = 119.79 Kg / day

C.O.E.& T.,Akola 72
Manufacturing of Ethyl Alcohol from Fruit Waste

X − Xo
Now = 0.5
So − S

X − .5
= 0.5
1459.04 − 119.79

X = 670.125 Kg of cells.

Along will all goes out about 50% water

∴water with cell = 50 % by wt. Of cells.

= 0.5 × 670.125

= 335.0625 Kg water

∴wt. Of biomas = 670.125 + 335.0625

= 1005. 1875 Kg.

3) Glucose contain 78 % solid material, it will come out of fermentor as it is –

∴D D G S = 0 .78× 6632 = 5172.96 Kg / day

∴We obtain

1) ethanol = 134.23 Kg./ day.

2) Water = 17243.2 – 335 . 0625

= 16908 . 1375 Kg / day.

3) biomass = 1363.02 Kg/ day.

4) DDGS = 5172.96 / day.

Calculation for percentage of ethanol in the whole liquid in fermenter.

Spent wash = Total product from fermenter

C.O.E.& T.,Akola 73
Manufacturing of Ethyl Alcohol from Fruit Waste

- Bio Mass - DDGS

= 23578.3.75 - 1005.1875 – 5172.96

= 17400.2 Kg / day

134.23
% of ethanol in spent wash = × 100 = 17
17400.2

Spent wash is liquid in fermenter which have to be sent to column.

Material balance on distillation column.

In put = pure alcohol + water + impurities

= 17400.2 Kg / day

From balance on distillation column we get

F=D+R ………… .…. (1)

F Xc = D × d + R Xf ………………………. (2)

Where Xf , Xd , XF are the weight fractions in feed distillate and residue.

From equation 2 we can write

Kg of ethanol in feed = Kg of ethanol in distillate + Kg of ethanol in residue

We required distillate = 1000 lit / day ( 18 % . by wt.)

XD = .18

∴ Kg of ethanol in distillate = Volume × density

= 1000 × 0.9720

= 972 Kg

972
Kg of water in distillation = × 100 − 972
18

= 4428 Kg.

Equation 2 gives
C.O.E.& T.,Akola 74
Manufacturing of Ethyl Alcohol from Fruit Waste

17400.2 X .17 = 972 + RXr

R Xr = 1986.034

Now water in distillate = 4428 Kg

Residue will be (R) = Spent wash – distillate

= 17400.2 – ( 972 + 4428 )

= 12000.2 Kg

R = 12000.2 Kg

1986.034
Xr = × 100 = 16.55%
12000.2

From above data we calculate

XF = 0.17 % = 0.0017

Xd = 18 % ( deried ) = 0.18

Xw = 16.55 % = 0.1655

C.O.E.& T.,Akola 75
Manufacturing of Ethyl Alcohol from Fruit Waste

ENERGY BALANCE

Steps to follow in Energy Balance Calculations Across a piece of Equipment


1) Prepare a block diagram for the unit.
2) Write down the available information such as the flow rates of the incoming and
outgoing streams, their enthalpies, heat and work input, heat losses, etc.
3) Try to identify a tie substance.
4) Select a suitable basis for calculation.
5) If no chemical reaction takes place within the system, consider whether there is a
phase change such as vaporization and condensation, fusion and solidification,
sublimation, transition from one crystal structure to another, crystallization etc.
Consider enthalpy changes accompanying such a change, if any.
6) If chemical reactions occur, consider enthalpy changes accompanying the
reactions.
7) Tabulate all energy input items in one column and all output items in another. For
convenience, all entries in each column are arranged to be of positive sign. Thus,
any work done on the system will appear as an input item while work done by the
system will appear as an output item. Heat absorbed is an input item, and heat
evolved and/or losses are output items. The enthalpies of all entering streams are
entered as input items, and those of the outgoing streams as output items. Heats of
reaction, if negative, are input items, while they are considered to be output items if
positive.

C.O.E.& T.,Akola 76
Manufacturing of Ethyl Alcohol from Fruit Waste

EXAMPLES
Problems on y-x data prediction (binary azeotrope)
(1) The azeotrope of ethanol (1) - benzene (2) system has a composition of 44.8%
mole % ethanol with a boiling point of 68.2°C at 760 mm Hg. At 68.2°C the vapour
pressure of pure benzene is 517 mm Hg and that of ethanol is 506 mm Hg.
Calculate the Van Laar constants for the system and evaluate the activity
coefficients for a solution containing 10, 20, 70 and 90% (mole) of ethanol. Prepare
the plot of log γ1 – x1 and log γ2 – x2.
Ans. A = 0.870 B = 0.577
for 10% solution γ1= 4.19 γ2 = 1.026
(2) At atmospheric pressure ethyl acetate and ethanol form an azeotrope containing
53.9% (mole) of the former component with a boiling point of 71.8°C. Evaluate (a)
the values of the constants in the Van Laar equation and (b) the azeotropic
composition at 56.3°C if the Van Laar constants remain unchanged. The vapour
pressures in mm Hg of the pure liquids are as follows
71.8°C 56.3°C
ethanol 587 298
ethyl acetate 636 360
Problem on VLE
(1) The isobaric y-x data for the system ethanol (1) n-heptane (2) at 760 mm Hg pr
are as follows
x1 y1 rc
0.023 0.330 85.0
0.181 0.580 73.3
0.310 0.605 71.6
0.406 0.625 71.4
0.610 0.648 71.4
0.821 0.700 71.5
0.910 0.760 72.5
0.970 0.881 75.4

C.O.E.& T.,Akola 77
Manufacturing of Ethyl Alcohol from Fruit Waste

The temp, dependence of wilson's and R-K constants established from other
sources is given below. The model constants of R-K and wilson equations are
temperature sensitive for some systems.
Wilsons constants
Λ12 = 0.0366 + 0.000253 t + 0.0000143 t2
Λ21 = 0.1720 + 0.0006516 t (where t  °C)
R-K consts
B = 0.8525 + 0.00095 t
C = -0.1185-0 - 00025 t ( t  °C)
Evaluate the activity coefficient values at x, = 0.023 and x, = 0.610 by the wilson
and R-K equations by (i) by taking the average value of the constants between the
min & max temperatures, and (ii) taking into account their temperature dependence.
(3) The azeotrope of ethanol (1) 78.4°C b.pt. - benzene (2) 80.5°C b. pt, system has
a composition of 44.8 mole % ethanol with a boiling point of 68.24°C at 760mm Hg
pressure. At 68.24°C the v.p. of pure benzene is 507 mm Hg and that of ethanol is
516 mm Hg calculate the Van Laar constants for the system and the predict the y-x
data for this system for the entire molefraction range giving an increment of 0.1
molefraction in the x1 values Van Laar consts
A = 0.830, B = 0.575
The v.p. values for the two components are given below
ethanol
temperature °C V.p mm Hg
19.0°C 40 mm
26 60
35 100
48.4 200
63.5 400
78.4 760

For benzene, the Antoine constants are given


A = 6.9056, B= 1211.03 C = 220.8

C.O.E.& T.,Akola 78
Manufacturing of Ethyl Alcohol from Fruit Waste

B
The Antoine eqn. is log10 p = A −
C + t 0C

Illustration

Derive an expression for Ka as a function of temperature for the following reaction of


the ethanol process.
2CO (g) + 4H2 (g) = C2H5OH (g) + H2O (g)
The following data are available for ∆G° as a function of temperature
T°K ∆G° cal/gm mole
200 - 39,662
400 - 17,884
600 5168
Solution
The general expression for the heat capacity of each component can be
represented by the following general expression.
Cp = α+βT+γT2 +…
The heat capacity values for the reactants and products are, in cal/gm mole °K are

CO Cp = 6.60 + 0.00120 T
H2 Cp = 6.62 + 0.00081 T
C2 H5 OH Cp = 3.58 + 0.04985 T - 16.99x10-6 T2
H2O Cp = 8.22 + 0.00015 T + 1.34X10-6 T2
From these data the difference terms are obtained
∆α = 3.58 + 8.22 - 2 (6.60) - 4 (6.62) = - 27.88

400

C.O.E.& T.,Akola 79
Manufacturing of Ethyl Alcohol from Fruit Waste

300

200
y'
100

0
0.001 0.002 0.003 0.004 0.005

1
T
Similarly
∆β = 0.04436 and ∆γ = -15.65x10-6
By plotting y' as defined below versus 1/T, the values of ∆H00 and I may be
determined graphically.
 ∆β ∆γ 2  ∆H 00
 R ln K a − ∆α ln T - T− T  = y' = 1 −
 2 6  T

T°K R In K y' 1/T


200 198.4 341.9 0.005
400 44.7 203.2 0.0025
600 -8.60 157.5 0.00166

From the line on the graph, the slope is 55,400 cal/gm mole and is equal
to -∆H00. The intercept 65.0 and is equal to I. The equation for ∆G° is then
∆G° = - RT In Ka = -55400 + 27.88T lnT- 0.02218 T2 +2.61 x106T3 - 65.0 T

Illustration

C.O.E.& T.,Akola 80
Manufacturing of Ethyl Alcohol from Fruit Waste

Express the heat of reaction as a function of temperature for the reaction shown in
the above illustration. Calculate the heat of reaction as a function of pressure at
200°C and from 1 atm to 20 atm.
Solution
Referring to the above illustration, the values for the heat capacity constant
differences were as follows
∆α = - 27.88 ∆β = 0.04436 ∆γ = -15.65 x 106
By using heats of formation we may get an improved value of -∆H00. The heats of
formation are
Component -∆H0298 cal/gm mole
CO -26416
H2 0
C2H5OH - 56,625
H2O - 58,798
For the reaction
Cal
-∆H0298 = -61,591
gm mole of C 2 H 5 OH

By the equation
1 1
∆H 0 = ∆H 00 + ∆αT + ∆βT 2 + ∆γT 3 + ...
2 2
∆H00 = - 55,386
The equation for the heat of reaction as a function of temperature would be
∆H0 = - 55,386 – 27.88 T + 0.02218 T2 – 5.217 x 10-6 T3

C.O.E.& T.,Akola 81
Manufacturing of Ethyl Alcohol from Fruit Waste

COST ESTIMATION

Cost Estimation for 15,000Lpd rectified spirit plant at (A.P. D. R.C., P.K.V Akola)
1. Liquification section 20,00,000 (20 Lacs)
2.Saccharification section 20,00,000 ( 20 Lacs)
3. Weighing and fermentation and storage tank 1,10,00,00 ( 110 Lacs)
4. Instrumentation 5,00,000 ( 5 Lac )
5. Electrical 25,00,000 ( 25 lacs)
6. Utilization for fermentation plant 18,00,000 ( 18 lacs)
7. Distillation plant to produce rectified spirit/extra ± 65,00,000 (65 lacs )
neutral Alcohol for 10,000 L PD
8. Zero effluent discharge process
to get protein cattle feed 2,50,00,000 ( 25 lacs)
9. Inter connection pipelines,
valve and instrumentation 10,00,000 ( 10 lacs )
10. Reaction and commissioning 5,00,000 ( 5 lacs )
11. Building 75,00,000 ( 75 lacs )
12. Boiler for 11,000 1/day plant 40,00,000 (40 lacs )
-------------------------
6,43,00,000 (6.43 Crore )
The total price of equipment for 15,000 LPD Rectified spirit plant is Rs 6.43 crore.
(Rupees six crores forty three lacs only ). The above price is based on present
prevailing price of deonedized copper sheets and copper tubes ex-manufacturing
works at Rs 175/ per kg. For shut and tubes respectively.

C.O.E.& T.,Akola 82
Manufacturing of Ethyl Alcohol from Fruit Waste

Basis :-
No of working days = 300/ year
Glucose content in Sapota = 220 gm/Kg
Alcohol yield from Sapota = 150-170 lit lt
Fermantation efficiency = 92 – 95 %
Plant capacity = 15 KL / day
Consumption Rate Total cost /
year
Raw material Per day Per year Rs.
Waste Sapota 47 t 14100 4000 /t 564.00
Enzymes
-1 45 Kg 13.50 t 465 / kg 62.775
AMG 22.5 Kg 6.75 t 825 / kg 55.6875
Steam 52.5t 15750 t 1190 / t 187.425
Electricity 2400Kw 7.2 lack kw 7.5 / Kw 54.00
Water
Process water 300 m3 90000 m3 2.50 / m3 2.25
Cooling water 250m3 75000 m3 2.50 /m3 1.875
Acid 75 Kg 22500 Kg 4 / Kg 0.90
Antifoam 15 Kg 4500 Kg 20 / Kg 0.90
agent
CaCO3 25 Kg 7500 Kg 5 / Kg 0.375
Yeast Only during start up
Total variable cost = 930.1875
Less credit for spent Sapota
14100 t 3000 / t = 423.00
Net variable cost = 507.1875
Natural produced = 45 lacs liters.
Variable cost of alcohol / lit of alcohol = Rs.11.27 / lit

Basis:-

No.of working days = 300 days / year

Glucose content in Sapota = 220 gm / Kg.

Alcohol yield from Sapota = 150 – 170 lit / t

C.O.E.& T.,Akola 83
Manufacturing of Ethyl Alcohol from Fruit Waste

Fermentation efficiency = 92 – 95 %

Plant capacity = 15 kl / day

Raw material Consumption / Consumption Rate Total cost /


day per year Rs year
Sapota 47 t 14100 9000 / t 1269.00
Enzymes
-1 45 Kg 13.50 t 465 / kg 62.775
AMG 22.5 Kg 6.75 825 / kg 55.67
Steam 52.5 t 15750 t 1190 / t 187.425
Electricity 2400 Kw 7.2 Lack / Kw 7.5 / Kw 54.00
Water
Process water 300 m3 90000 m3 2.50 / m3 2.25
Cooling water 250m3 75000 m3 2.50 /m3 1.875
Acid 75 Kg 22500 Kg 24 / Kg 0.90
Antifoam 15 Kg 4500 Kg 20 / Kg 0.90
agent
CaCO3 25 Kg 7500 Kg 5 / Kg 0.375
Yeast Only during start up
Total variable cost = 1635.875

Less credit for spent Sapota

14100 t 7000 / t = 987.00

Net variable cost = 648.875

Variable cost of alcohol / lit of Alcohol = Rs. 14.4 / lit.

DISCUSSION
Chiku is called as Sapota. It is mostly grown in moist coastal tracts of
paninsular India, but in recent years it is seen that, it can be grown in zones of the
Deccan plateau and also in sub mountain traces of north India. Fruits are ready for
harvest in about 4 months i.e. oct-Nov, flowering fruits natures by Jan- Feb or
flowering natures fruits by April –May. Harvesting is done when the fruit is fully
malined. The sapota can be easily stored. It is that type of fruit which is easily
penshable , cheap in cost, having high sugar and carbohydrate content. It can be
fermented easily so its operating cost is very low.

C.O.E.& T.,Akola 84
Manufacturing of Ethyl Alcohol from Fruit Waste

Total municipal solid waste of Akola district is 150 mt/day. The organic waste
content in total waste is 29 %. Out of total organic waste 50 % will be available for
the alcohol Production ( 37.5 mt/day). Since by the fermentation process we are
able to produce ethyl alcohol at the cost of 11.27 Rs/lit it will be feasible to develop
such plant in Akola.
Ethyl alcohol is an important feed stock for the manufacturer of various
chemicals. These chemicals are primarily the basic carbon based products like
acetic acid, butanol, butadiene, Acetic an hydride etc. Ethylene, Ethylene oxide are
also produced from Petrochemical route. However this requires plants of huge
scales and thus requires substantially high investments. The drug industry also
uses alcohol as a raw material for production of insulin, Antibiotics tonics and
several other essential bulk drugs and formulations.
The areas for future research and development activities are briefly listed
below :
To increase the substrate utilization ability of excellent ethanol producers like yeast
and 2 mobiles.
To enhance alcohol tolerance of yeast.
To increase the ethanol production ability of bacteria capable of utilizing cellulose,
hemicellulose, pentoses etc.
Practical exploitation of the superior capabilities of Z mobiles. This anaerobic
bacterium is a better producer of ethanol than yeast as it has a relatively slower
growth rate coupled with higher sugar conversion rate. Immobalized Z. mobilis
could be used to achieve high rate of ethanol production. Z mobilis production rates
can be as high as 60/9/11 hr as compared to only 309/1/hr for yeast.
Efficient and cost effective process of continuous recovery of ethanol needs to be
developed. Such a process would keep ethanol concentration in the bioreactor
growth to low levels and would avoid product inhibition of yeast cells.
More efficient and cheaper methods of ethanol recovery need to be developed to
reduce the cost of recovery. Some possible approaches may be reverse osmosis,
Selective absorption using solid absorbants and use of super critical CO2 to
selectively extract ethanol. The major upcoming user segments are cosmetics and

C.O.E.& T.,Akola 85
Manufacturing of Ethyl Alcohol from Fruit Waste

premium potable liquor. These segments require extra neutral alcohol (ENA) or
grain alcohol. Extra neutral alcohol is obtained from sugar molasses after it has
been re-distilled 3 to 4 times. Even after triple distillation, the alcohol has traces of
sulphur odour, as the base material has traces of sulphur. Fuel ethanol or
anhydrous alcohol is produced by dehydration of rectified spirit. Ethanol used as
part of the fuel by blending with petrol, for a motor vehicle is called fuel ethanol.
India produce 1.3 billion lit. of ethanol in world production of lit. over 35 billion litres.
Ethanol – General Demand.
The total Ethanol production in India was in order of 1200 million lit. for the
year 1993-94 of this 48% or 570 million lit. accounted for industrial sector 42% or
504 million lit. or potable sector, 3.5 % or 4.2 million lit. for other end use and 2.5%
or 3 million lit for exports. The percentage of growth rate observed between 15 to
20 % per annum.

Project demand for Alcohol for production of Chemicals in India.


Sr. Product Estimated demand for Alcohol requirement in
No. chemicals in MT million lit.
1. 2- Ethyl hexanol 67000.00 221.10
2. Acetic Acid 80000.00 112.00
3. Vinyl Acetate monomer 34000.00 069.70
4. N – Butanol 15000.00 028.50
5. Ethylin oxide 25000.00 055.00
6. Ethylene glycol 8000.00 141.60
7. S.B.R. 93000.00 306.90
8. Styrene 90000.00 82.08
9. Pharmaceuticals 300.00
Total Alcohol Requirement 1483.00

C.O.E.& T.,Akola 86
Manufacturing of Ethyl Alcohol from Fruit Waste

MARKET POTENTIAL
Alcohol finds its use in diverse applications ranging from potable liquor of life saving
drugs to paints and perfumery to renewable source of energy.
Future Demands
Fuel/motor spirit 68%
Industrial/Solvents 21%
Beverages 11%
Ethanol possibilities
 As potable hard drinks.
 As an extraction agent in the synthesis of medicine as a solvent and as
dilluant in liquors and paints.
 As an industrial raw material for valve added down stream.
 As disinfectant for cleaning.
 As an add mix in fuels.
 As an oxygenate reducing exhaust emission
 As anti-freezing agent in colder climate.
 As octane booster

SAFETY
General Safety Rules Followed In Chemical Process Plant Operation :
All process plant injuries even if they are minor has to be reported to the concerned
higher authority and medical data bank system.
'Strike any where' matches are prohibited on the process plant area.
Firearms, ammunition, explosives are prohibited within the process plant area.
Intoxicants or the persons under the influence of intoxicants are prohibited in the
process plant area.
Smoking is permitted in designated areas only, Matches, lighters are not permitted
in the areas marked strictly prohibited'.
All employees must follow the rules for any area they enter. This is strictly
necessary when they are exposed to hazardous area.

C.O.E.& T.,Akola 87
Manufacturing of Ethyl Alcohol from Fruit Waste

The use, operation of machinery/equipment is permitted only by authorization and


under supervision.
Machinery, equipment, piping system shutdown for repair, maintenance must be in
accordance with the display of tag, clear or other mark.
For equipments, whose operation is a 'danger' should be marked, 'Do not operate'.
Climbing, standing on machinery, equipment is prohibited unless authorised by
senior supervisor.
Compressed air is not to be applied to the person or clothing of self or other
persons.
Approved eye protection must be worn in designated areas.
Finger rings, loose clothing, other loose accessories and long free hair are not to
be, when within arms reach of unguarded operating machinery or moving belt.
Approved foot protection is required as specified for the work assignment.
Use of defective tools or equipments is prohibited.
Scissors and knieves are to be sheathed when not in use.
While picking up broken glass, use gloves, dust pan and brush and dispose off the
broken glass in a specified contour.
Fire alarm boxes, fire extinguishers, fire doors, eye wash station, safety showers
and emergency equipments must be kept clear of obstruction.
Permission must be obtained while entering the restricted area
Discarded match stems and contents of ash trays are not to be placed in waste
baskets.
Keep all four chair legs on the floor when seated in a straight back chair.
Drawers and doors in desks and cabinets are to be kept closed when they are not in
use.
Running on process plant property is prohibited except in case of an emergency.
When ascending or descending stairways keep to the left, use handrail and take
only one step at a time.
Only approved chemicals must be brought on process plant site.
Steel taps on shoes are prohibited
Spills and leakages must be attended immediately.

C.O.E.& T.,Akola 88
Manufacturing of Ethyl Alcohol from Fruit Waste

Never wipe face with a shop towel.


An approved work permit is required for work on plant services such as steam, air,
water inert gas, sewers etc. when alternation or changes in use of service are
required.
Importance Of Plant Layout In Safety:
Large process plants like petroleum refineries, petrochemical plants, fertilizer, heavy
chemicals etc. require special attention in plant layout due to the nature of material
handled and products lied. The following information is required for the development
of a plant layout.
1) Capacity of the process plant and equipments required to be installed.
2) Process flow diagram and the process flow sequence.
3) Utility requirements.
4) Number of storage tanks
5) Raw material receiving section, product dispatch section.
6) Open storage area, covered storage area.
7) Flare system and their number.
Administrative buildings, laboratory, security, workshop, R and D, fire station,
canteen, first air unit, change rooms, parking place etc. While selecting a site for
plant layout the following information necessary.:
i) Site location map and geographical, meterorlogical conditions and soil conditions,
source of water supply and its location.
ii) Environmental conditions, transport facilities, proximity to railway stations, airport
etc.
iii) Electric supply to the plot site.
iv) Waste disposal location and other drainages.
v) Material transport facilities, approach roads etc.
vi) Wind velocity, temperature, annual rainfall, susceptible to earth quakes etc.
It is necessary to develop economical plant layout, so that interconnecting
pipeline network, steel structures requirement is reduced plot layout will differ if the
process has single stream flow pattern or multi stream flow pattern. Plant layout is
considerably affected by interconnecting pipeline network, thickness of insulation,

C.O.E.& T.,Akola 89
Manufacturing of Ethyl Alcohol from Fruit Waste

location of pumps, hazardous operation, statutory rules and regulations, tenance,


safety and ease of erection. Ail these factors can be grouped as --
i) Economics consideration ii) Safety considerations iii) Operational considerations
iv) Maintenance considerations v) Constructional consideration
vi) Aesthetic considerations vii) Further expansion.
Concept Of Plant Layout: .
The entire plot is divided into blocks, representing different sections. The size
of blocks depend upon the equipments or facilities to be accommodated while
locating the blocks or subclocks the following points should be considered:
Layout planning should be in sequential process flow order so that piping required is
minimum.
The bocks representing flammable gases should be located in such away that the
inflammable gases are not carried by wind to the source of ignition.
The main process unit block should be centrally located.
Storage tanks should be grouped according to product classification. As far as
possible storage tanks should be located in lower elevations.
Safety Needs During Construction And Start Up :
It is necessary to adhere to safety regulations during construction and start
up facilities. This helps to provide maximum protection to operating personnel,
equipments as well as contractor personnel throughout all phases of a project.
Safety checklist and regulations shall depend upon the possibility of accident
rate. Well in advance of actual construction, the project engineer should hold safety
planning meeting operating personnel in areas in which work is to be carried out
and discuss the hazards of work areas and the special protective measures
needed. If the special hazards exist, it is necessary have safety manager present
for this planning.
The details of safety measures have to be given to contractors and his
personnel for acquaintance. To ensure, the adherance to process plant safety
standards, the work contract should include a clause which calls for concellation of
contract in the event of willful violation of safety rules. The contractor must obtain
daily permits for welding and other spark producing operation. Similarly, the

C.O.E.& T.,Akola 90
Manufacturing of Ethyl Alcohol from Fruit Waste

operating personnel must have the authority to stop construction work in evern of a
production hazard or the violation of standard safety rules. The project engineer
should visit the work site at least once during each working day to observe whether
the work is accomplished on schedule and safely. If extra hazardous work is to be
carried out, he should be personally present to guide and direct these efforts.

Personal Safety:
In a process plant operation personal safety has high importance. It can be
achieved by i) hazard removal, ii) hazard control, iii) personal protection.
Personal safety can be achieved by thorough training and effective
supervision, training should be aimed at providing the ability to use the process
equipment and perform its function and motivate to do the operation property and
safety. Many of the problems arise due to some training insufficiency. It is also
necessary to have continuous supervision so that any procedure is not violated and
malpractices are stopped. Supervision helps to enforce strict discipline. Human
factors need to be considered to design the work place. It helps to reduce the
accidents. Human factors should be considered from the beginning of the project.
Proper allocation of functions between man and machine can help for accident
prevention.
Human factors are mainly considered in terms of human errors. Human error,
to a large extent is a function of the work situation and can be reduced by good
design of the work situation. Some errors can be attributed to individuals and there
can be variations in error rates between individuals. From management point of
view human errors have to be considered in the areas of.
i) equipment design, ii) working methods, iii) motivation, iv) stress/tension
In environmental conditions proper illumination, fresh air, temperature
conditions and noise I are important parameters. However, it is wrong to say that all
the stresses are harmful. There is generally an optimum stress level for any
individual in any particular work assignment.
Common kind of stresses can be due to:

C.O.E.& T.,Akola 91
Manufacturing of Ethyl Alcohol from Fruit Waste

i) Lot of works to be done at a time (reading instructions from manual, listening to


boss, recording the Instrument reading etc.
ii) feeling of insecurity or being personally threatened.
iii) Excessive noise level in work area.
iv) Excessive body temperature.
v) Inadequate sleep/rest
vi) Influence of drugs/liquor
vii) Physically not fit, feeling tired or some illness.
A stress may either increase or decrease arousal to or from the optimum, for
example, over stressed person may behave like an over loaded computer or
overloaded computer system. Some experts say that continuous noise increases
person's alertness, (but it is doubtful how far it is true), increases his speed or
efficiency for simple operations. High noise level exposure and over stressed
person cannot be accurate at complex work. The stresses under which workers can
operate needs to be studied thoroughly by all those responsible for an industrial
safety. Ultimately industrial safety and personal safety has to go hand in hand.

SAFETY IN HANDLING LIQUIDS


Flammable Liquid Storage:
Liquids received at process plant are usually in drums, carboys, tank cars,
trucks or pipelines. While dealing with flammable liquids, it needs to be considered
that, vapours from the evaporation liquid or liquid itself can burn or explode when
mixed with air in the presence of a source of ignition. Liquids with flash point below
32°C give off ignitable vapours at normal ambient temperatures. Such liquids can
be stored in closed containers and in limited quantities in rooms of fire resisting
construction, such storage should be above ground and isolated from the remainder
of the building by fire walls and self closing fire doors.
Large quantities of flammable liquids are stored in isolated areas of fire
resisting construction. Such liquids can be stored underground also. The rooms
used for storage should not have openings covered with glass or transparent
material which can allow the direct rays of the sun to pass, in stored in rooms.

C.O.E.& T.,Akola 92
Manufacturing of Ethyl Alcohol from Fruit Waste

Through ventilation should be provided at the floor as well as at the ceiling level to
remove accumualted vapours. .
Solvents should not be stored along with chemicals with which they are likely
to react violently, in confined spaces, solvent vapours can cause oxygen deficiency.
In flammable liquid storage area, electrical fittings should be flame proof and
vapour proof type.

USES AND APPLICATIONS


The most important application of ethanol; because of which it is having a
great demand in our day to day life; are
1. In the preparation of hair spray.
2. In the manufacturing of deodorant strip stick, on an anti per spirant.
3. As components of saturated and unsaturated polyester resins and allayed
resins. These resins, which are known for their excellent stability.
4. In a wide range varnishes and coatings.
5. The addition of poly isocynates to polyetherpolyols and polyesterpolyols derimed
from polyhydric alcohols leads to polyurethanes, which are used in production of
elastomers and various types of foams.
6. Used as synthetic lubricants, plasticizers, dispersants and additives to poly
(Vinyl chloride ) to improve adhesion.
7. Diols are used in the production of pharmaceuticals and fragrances.
C.O.E.& T.,Akola 93
Manufacturing of Ethyl Alcohol from Fruit Waste

8. Used as the starting material for the production of formaldehyde and antifreeze
in autonecatine cooling systems.
9. Used as a nersotile compound used as a solvent for fats, oils, varnishes and
lacquers and plastic fibre such as cellulose nitrate.
10. Used as a fuel.
11. It is approved as denaturant for industries and chemical intermediate for the
manufacture of many organic compounds including dyes, esters, plastics etc.
12. Used for the extraction of aromatic portions from petroleum.
13. Used as solvent to recover tars from ignite deposits; for removing acid impurities
from vegetable oils, denaxing guns, extracting organic salts, purifying harmones
and steroids etc.
14. Used as cleaner of steel, metal and plastic surfaces; as a component in glass
cleaners and special dry cleaners; as a reducing agent in copper clearing brass
annealing and soldering fluxes.
15. Formation of gas hydrates & ice in natural gas pipelines is inherited by this
alcohol.

CONCLUSION
Ethyl /Alcohol is widely used in chemical industries. Growth in potable
alcohol industries is likely to be increase with the demand and consumption of the
people and the chemical products in industries in which alcohol plays an important
role. In this project we have selected Sapota as raw material for the Ethyl Alcohol
production, as it contains high carbohydrate percentage and is widely grown in
Maharashtra State.
From the experiments it was found that Ethyl alcohol can be obtained
conveniently with simple fermentation process. Economically the project is feasible
as the cost required for the overall project is less and the product price is
considerably less than the market price. Hence the production of Ethyl alcohol from
fruit waste like Sapota, is feasible in region like Maharashtra.

C.O.E.& T.,Akola 94
Manufacturing of Ethyl Alcohol from Fruit Waste

REFERENCES
1. Ullman's Encydopedia of Industrial Chemistry Vol : A1 ( Fifth edition )
2. Encyclopedia of Chemical technology Vol.1.
3. ALCOHOLS : By John. A. Monick.
4. Outlines of Chemical Technology : By G. RAO & Dryden.
5. Agro Product Development Research Center. : Dr.P.D.K.V.Akola
6. Stoichiometry IIIrd Edition By : B. I. Bhatt.
7. Handbook of Chemical Engineering. 5th Edition J. H. Perrys.
8. Plant Design & Economics for Chemical Engg.
3rd Edition By : Max. 5 Peters & Klaus Timmerhaus.
9. Handbook of Horticulture Vol. 12
10. Introduction of Bio technology : By R. A. Singh.
11. Pollution Control In Process Industries. : By : S. P. Mahajan.
12. Project Report on " Production of 15 KL Per Day

C.O.E.& T.,Akola 95
Manufacturing of Ethyl Alcohol from Fruit Waste

"Ethanol from Blackned Sorghum"


13. Principal of horticulture and fruit growing tenth revised edition by Y.N. Kunte,
M.P. Kawthalkar,K.S.Yawalkar.
14. Process Design of Equipments Volume 2 By S.D Dawande.
15. Microbiology By. P.D. Sharma
16. Chemical Engineering Vol. 3 By Coulson & Richardson's.
17. Introduction to Chemical Engineering
By : Salil K. Ghosal
Shyamal K Sanyal
Siddhartha Datta
18. Chemical Engineering Thermodynamics By D. Srinivasan.
Websites :-
www.ethylalcohol.com
www.ethanolmt.org
www.Fineprint.com
www.Maharashtra Pollution Control dept.org.in

APPENDIX

C.O.E.& T.,Akola 96
Manufacturing of Ethyl Alcohol from Fruit Waste

C.O.E.& T.,Akola 97
Manufacturing of Ethyl Alcohol from Fruit Waste

C.O.E.& T.,Akola 98
Manufacturing of Ethyl Alcohol from Fruit Waste

C.O.E.& T.,Akola 99
Manufacturing of Ethyl Alcohol from Fruit Waste

C.O.E.& T.,Akola 100


Manufacturing of Ethyl Alcohol from Fruit Waste

C.O.E.& T.,Akola 101


Manufacturing of Ethyl Alcohol from Fruit Waste

C.O.E.& T.,Akola 102


Manufacturing of Ethyl Alcohol from Fruit Waste

INDEX

Sr. Particulars Page


No. No.
1 Introduction 1
2 Fermentation 15
3 Different Processes for ethyl alcohol production 40
4 Process Selection 55
5 Actual Process at Experimentation site. 57
6 Plant Layout 62
7 Results of Experimentation 64
8 Material Balance 65
9 Energy Balance
10 Examples
11 Cost Estimation 72
12 Discussion 75
13 Safety 78
14 Uses and application 84
15 Conclusion
References
Appendix

C.O.E.& T.,Akola 103


Manufacturing of Ethyl Alcohol from Fruit Waste

C.O.E.& T.,Akola 104

You might also like