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 Ethylene Alkylated Aeromatics Butadiene Organic Esters Esters Diethyl Ether Mixed ether Ethanol Ethoxides Halides

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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. in Europe until the twelfth a thirteenth century, A.D. All the accident references discuss alcohol in the form of beverage. But distillation was not known Gradually, the concept of

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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.

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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 Paper/Card Plastics Putrescibles Fires Textiles Misc. % total of energy content 46% 22% 11% 5% 3% 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.

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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
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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. 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.
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Bears heavily as

The doses should be increased with the 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 However, immediately after harvest orchard hygienic practices are followed ). 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 Yield 15 years After 15 years yield 750 fruits/ha. 1000 – 1500 fruits/ha. It 2000-2500 fruits or 18-20 tons/ha.

Highly susceptible to water logging and very densative to stagnation.

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.

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Manufacturing of Ethyl Alcohol from Fruit Waste

Fruit carbohydrates table: Fruit Apple Apple cooking Apricot Avocado Banana Blackberries each Blackcurrant each Cherry each Clementine Currants Damson Dates Gooseberries Grapes each Grapefruit whole Guava Kiwi Lemon Lychees Mango Melon Nectarines Olives Orange Passion Fruit Paw Paw Peach
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Carbohydrates 10.5 grams 9 grams 6.7 grams 2 grams 26 grams 0.2 grams 0.25 grams 0.6 grams 7.5 grams 1.4 grams 7.2 grams 3.3 grams 0.65 grams 0.6 grams 23 grams 4.4 grams 8 grams 3.4 grams 0.7 grams 9.5 grams 26 grams 9 grams trace 8.5 grams 3 grams 6 grams 7 grams

Calories per piece 44 35 30 150 107 1 1.1 2.4 30 5 28 12.5 2.6 2.4 100 24 34 20 3 40 110 42 6.8 35 30 28 35 8

Manufacturing of Ethyl Alcohol from Fruit Waste

Pear Pineapple Plum Prunes Raisins Raspberries each Rhubarb Satsumas Strawberries (1 average) Sultanas Tangerine

12 grams 12 grams 6 grams 2.2 grams 1.4 grams 0.2 grams 0.8 grams 8.5 grams 0.6 grams 1.4 grams 6 grams

45 50 25 9 5 1.1 8 35 2.7 5 26

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

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

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Manufacturing of Ethyl Alcohol from Fruit Waste

Physical Properties of Ethanol Constants Boiling point, C Electrical conductivity at 250C, Ohm-1/cm Explosive limits in air, vol % Flash point ( ASTM Tag Open Cup ), 0C Freezing point, 0C Heat of combustion of liquid, Kcal/mole Heat of fusion, cal/g Heat of vaporization at bp and 1 atm, cal/g Ignition temp.(apparent) in air, 0C Refractive index, n2D0 Specific gravity at 20/20 0C Specific tension at 200C, dynes/cm Surface tension at 200C, dynes/cm Vapour pressure at 200C, mm Hg Viscosity at 20 0C, cps Chemical Properties :
0

Absolute 78.3 1.35 x 10-9 4.3-19.0 21 114.1 328 25.0 204.3 371-427 1.3614 0.7905 0.579 22.3 44 1.22

95% vol) 78.0 22 1.3651 0.8038 0.618 22.8 43 1.41

(by

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
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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 :
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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 | 2CH3 CH2OH + CH2OOCR | CH2OOCR Ethers. CH2OH | CH2OH | CH2OH
glycerol

+

3 RCOOCH2CH3
ethyl esters

Ethyl ether formation is the result of an intermolecular catalytic 2CH3 CH2OH CH3 CH2OCH2 CH3 + H2O

dehydration of ethanol at low temperature :

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 CH2OH + CH3 CH2OCH ≡CH2
acid

CH3 CH2OCH2 =CH2
Vinyl ethyl ether

CH3 CH(OCH2CH3)2
catalyst diethyl acetal

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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 + 3NaOCl CCl3 CHO + NaOH CH3 CHO + NaCl + H2O CCl3 CHO + 3NaOH 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)
Cu

CH3 CHO + H2O

Dehydrogenation of ethanol is catalyzed by chromium-activated copper : CH3 CH2OH
Cu

CH3 CHO + H2

Further oxidation of acetaldehyde leads to acetic acid : 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
Cu, Ag

hydroxyl hydrogen in ethanol to form a metal alkoxide (alcoholate): 2CH3 CH2OH + 2N 2CH3 CH2 ONa + H2
Sodium ethoxide

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

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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 micronutrients (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

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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,

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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

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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
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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
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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:
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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 Indian sub-continent Acar, Achar, Tandal achar, Garam nimboo achar Gundruk Pickled fruit and vegetables Fermented dried vegetable Type of product

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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-siamdong, 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 Nata de coco, Nata de pina 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 Hot pepper sauce Lamoun makbouss, Mauoloh, Msir, Mslalla, Olive Oilseeds, Ogili, Ogiri, Hibiscus seed Pickled fruit and vegetables Fermented fruit and vegetable Vinegar Fermented tea leaves Fermented fruit juice

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seeds Wines Americas Cucumber pickles, Dill pickles, Olives, Sauerkraut, Pickled fruit and vegetables Lupin seed, Oilseeds, Vanilla, Wines Middle East Kushuk Fermented vegetables Lamoun makbouss, Mekhalel, Olives, Torshi, Pickled fruit and vegetables Tursu Wines Europe and World Mushrooms, Yeast Olives, Sauerkohl, Sauerruben Grape vinegar, Wine vinegar Wines, Citron (Taken from G Campbell-Platt (1987)) Moulds Pickled fruit and vegetables Vinegar Fermented fruits Fermented fruits fruit and Pickled oilseed Fermented fruit and vegetable Fermented fruits

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
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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
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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 conditions
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Reactions

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Manufacturing of Ethyl Alcohol from Fruit Waste

Acetobacter genus A. A. A. peroxydans Streptococcaceae Family aceti pasteurianus

Aerobic rods

aw > =0.9

Oxidise organic compounds (alcohol) (acetic to acid). organic acids in Important

vinegar production. Gram positive cocci Acid tolerant aw > =0.9 Homofermentative. common is common in in Most dairy vegetable

Streptococcus genus S. S. S. thermophilus faecalis bovis

fermentations, but S. Faecalis products. Tolerate salt and can grow in high pH media.

Leuconostoc L. L. L.

genus

Gram positive cocci

Heterofermentative.

Produce

mesenteroides dextranicum

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

paramesenteroides L. oenos

Pediococcus genus P. P. cerevisiae acidilactici

Saprophytic organisms found in fermenting beer vegetables, and wort. mashes,

Produce inactive lactic acid. Gram Acid Metabolise sugars to lactic 25

P. pentosaceus Lactobacillaceae
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Manufacturing of Ethyl Alcohol from Fruit Waste

Family

positive rods. Nonmotile

tolerant aw > =0.9

acid, acetic acid, ethyl alcohol and carbon dioxide.

Lactobacillus genus

The genus is split into two types – homo- and heterofermenters. Saprophytic organisms. Produce greater amounts of acid than the cocci

Homofermentative Lactobacillus L. L. L. L. L. acidophilus Heterofermentative Spp. L. L. L. buchneri brevis fermentum spp. delbrueckii leichmannii plantarum lactis

Produce only lactic acid. L. plantarum important in fruit and vegetable fermentation. Tolerates concentration. high salt

Produce lactic acid (50%) plus acetic acid (25%), ethyl alcohol and carbon dioxide (25%). L. brevis is the most common. Widely distributed in plants and animals. Partially reduces fructose to mannitol.

Yeasts

Tolerate acid, sugar aw > =0.85 40%

Saccharomyces Cerevisiae

Many aerobic,

pH 20-30

4-4.5 C

S. cerevisiae can shift its metabolism from a

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S. pombe

some anaerobes

fermentative to an oxidative pathway, oxygen depending availability. on Most

yeasts produce alcohol and carbon dioxide from sugars. Debaromyces Zygosaccharomyces rouxii Candida Geotrichum candidum species Tolerant Tolerates of high high salt salt

concentrations concentration and low aw

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 endproduct 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 nonpathogenic 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
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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 microorganisms depends on the composition of the food on which they grow. All microorganisms 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

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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

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Aw 1.00 0.95

Phenomenon

Examples Highly perishable foods

Pseudomonas, yeasts inhibited

Bacillus, Foods with 40% sucrose or 7%

Clostridium perfringens and some salt

0.90

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

botulinum, Lactobacillus and some yeasts and fungi inhibited 0.85 0.80 Many yeasts inhibited Lower limit for most

Foods with 65% sucrose, 15% salt enzyme Fruit syrups

activity and growth of most fungi. Staphylococcus aureus inhibited 0.75 0.70 Lower limit for halophilic bacteria Lower limit for growth of most xerophilic fungi 0.65 Maximum 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 0.40 Maximum oxidation velocity Dried foods (aw=0-0.55) velocity of Maillard Fruit jams

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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).
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Table 4 Classification of bacteria according to temperature requirements. Temperature required for growth 0C Type bacteria Psychrophilic Mesophilic 0 to 5 10 to 25 15 to 20 30 to 40 30 35 to 50 of Minimum optimum maximum General bacteria Water and frozen foods Pathogenic and nonsources of

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
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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 microorganisms 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.

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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 microorganisms, 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.

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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).
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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
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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,
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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 :

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Manufacturing of Ethyl Alcohol from Fruit Waste

Fig. The ethanolic fermentation pathway

Fig. The homolactic acid fermentation 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.

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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 material in +

Formation by biochemical

Flow of material out

= Accumulation

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 biochemical So, for the case of the biomass: reaction dx R xV = µVX = V dT
= Accumulation

(1)

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: RS V = dS V dT (2)

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: Y which gives: YRs = - µ X Equation 2 thus becomes:
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dS dX =− dt dt

(3)

(4)

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1 dS µX = Y dt X − X0 S0 − S X − X0 Y

(5)

The yield coefficient may also be expressed in its integral form as: Y= (6)

which can be re-arranged: S = S0 − (6)

If the growth follows the Monod kinetic model, then equation may be substituted into equation 1 to give:

µ SX dX = m dt Ks + S
The condition of the fermentation after any time / would then be given by: K s + S dX t ∫ µ m S X =∫ dt X0 0
X

(7)

(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 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:   )  (9)

 S K S Y + S 0Y + X 0  Y ( S 0 − S )  K SY − ln1 +   µ ( X + YS ) ln S  µ m ( YS 0 + X 0 )  X0 m 0 0   0

 =t  

(10)

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.

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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
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Manufacturing of Ethyl Alcohol from Fruit Waste

(a) Main reaction
Invertase

C12H22O11 + H2O
Zymase

2C6H12O6 2C2H5OH + 2CO2

C6H12O6 (b) Side reactions 2C6H12O6 + H2O Quantitative requirements

ROH + R' CHO
higher mol. Wt. Alcohols

(a) Basis : 1 ton of 100% alcohol (1.26 kiloliters) and 90% yield from total sugar Molasses (50-55% total sugar) Sulfuric acid (600 Be) Ammonium sulfate Coal Process water Cooling water Electricity By-products : CO2 5.6 tons 27 kg 2.5 kg 0.7-1.5 tons 12 tons 50 tons 35 KWH 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

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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 byproduct sales economics.

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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.

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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.

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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.

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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
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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 The liquor enters the first fomenter, proportionate amounts of urea and yeast.

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:
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Manufacturing of Ethyl Alcohol from Fruit Waste

(C6H10O5)n + H2O ——————>
Starch glucose water

n(C6H1206)
Free glucose

C6H12O6
Glucose

——————>

2(C2H5OH)
Ethanol

+

2CO2
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
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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)
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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.

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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.
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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 ethyleneproducing plants of the petrochemical industry which operate to supply feed material for polyethylene and ethylene oxide.

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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

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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 )2 SO4 +2 H2O CH3 CH2 OH + H2SO4 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
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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 ?

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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.

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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.
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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.

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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.

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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.

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Manufacturing of Ethyl Alcohol from Fruit Waste

Actual Process of Experimentation Site

Manufacturing of Ethanol from Sapota

Confirmative Test
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Manufacturing of Ethyl Alcohol from Fruit Waste

Sr.No. 1 2. 3 4 5.

Test

Observations No Change No colour change No reaction No colour change When ignited, it catches fire.

Inference Ethanol is present Ethanol is present C2H5OH is present Ethanol is present. Ethanol is present

Red litmus paper dipped in ethanol Ethanol + NaOH Solution Ethanol + Bromine Water It's melting point is 392 °K Burning Test

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
Oxidation

NaOl + Nal + H2O CH3CHO + Nal + H2O CI3-CHO + 3NaOH
Hydrolysis

CH3-CH2-OH + NaOl CH3CHO + 3NaOl NaOH + Cl3 -CHO Specific Gravity Test

CHI3 + HCOONA
Lodoform

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
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Manufacturing of Ethyl Alcohol from Fruit Waste

PLANT LAYOUT

Sapota

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Manufacturing of Ethyl Alcohol from Fruit Waste

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PROCESS LAYOUT

RESULTS OF EXPERIMENTATION
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Manufacturing of Ethyl Alcohol from Fruit Waste

By the experimentation we have found the following results :i) Ethanol yield ii) Specific gravity iii) Specific gravity iv) Density = 3.5 Kg = 0.9720 = 18 % = 0.9720 gm/ml. The

Chiku has good potential as a raw material for ethanol production.

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
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Basic  1000 kg of sapota. C12H22O11 + H2O C6H12O6
zymase Invertese

C6H12O6 + C6H12O6 , d-glucose d-fructose

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 = 0.785 1000 kg Sapata gives =.150.77 lit ethonal 1 lit of ethonal = 1000 = 6.632 kg of Sapota. 150.77 = 150.77 wt

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.

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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 ----16.56 Kg of ethanol. ∴ethanol produced = 1459.04 × 16.56 180 give

= 134.23 conc. Of Mash = Amt of sugar 1459.04 = 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

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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.

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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 ] it can be given as Dx x − xo = 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 So S = 0.5 Kg. / day. = 1459.04 Kg sugar = finally wt. Of substrate left.

We have ethanol produced = 134.23 Kg / day Mole of ethanol = 2.91 Kmol / day.

From Stochiometry of reaction Moles of Glucose converted = 2.91 2

= 1.45 K mole / day initial moles of glucose = 1459.04 180

= 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
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Now

X − Xo = 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

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- Bio Mass - DDGS = 23578.3.75 - 1005.1875 – 5172.96 = 17400.2 Kg / day % of ethanol in spent wash = 134.23 × 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 Kg of water in distillation = 972 × 100 − 972 18 = 4428 Kg. Equation 2 gives
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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 Xr = 12000.2 Kg = 1986.034 × 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

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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.

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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 ethanol ethyl acetate 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 0.023 0.181 0.310 0.406 0.610 0.821 0.910 0.970 y1 0.330 0.580 0.605 0.625 0.648 0.700 0.760 0.881 rc 85.0 73.3 71.6 71.4 71.4 71.5 72.5 75.4 587 636 56.3°C 298 360

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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
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 19.0°C 26 35 48.4 63.5 78.4 V.p mm Hg 40 mm 60 100 200 400 760 (where t  °C)

For benzene, the Antoine constants are given A = 6.9056,
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B= 1211.03

C = 220.8 78

Manufacturing of Ethyl Alcohol from Fruit Waste

The Antoine eqn. is

log10 p = A −

B 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 200 400 600 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 H2 C2 H5 OH H2O Cp = 6.60 + 0.00120 T Cp = 6.62 + 0.00081 T Cp = 3.58 + 0.04985 T - 16.99x10-6 T2 Cp = 8.22 + 0.00015 T + 1.34X10-6 T2 ∆G° cal/gm mole - 39,662 - 17,884 5168

From these data the difference terms are obtained ∆α = 3.58 + 8.22 - 2 (6.60) - 4 (6.62) = - 27.88

400
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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.
0 ∆H 0 ∆β ∆γ 2   T− T  = y' = 1 −  R ln K a − ∆α ln T 2 6 T  

T°K 200 400 600

R In K 198.4 44.7 -8.60

y' 341.9 203.2 157.5

1/T 0.005 0.0025 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

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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 CO H2 C2H5OH H2O For the reaction -∆H0298 = -61,591 By the equation
0 ∆H 0 = ∆H 0 + ∆αT +

-∆H0298 cal/gm mole -26416 0 - 56,625 - 58,798 Cal gm mole of C 2 H 5 OH

1 1 ∆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

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COST ESTIMATION
Cost Estimation for 15,000Lpd rectified spirit plant at (A.P. D. R.C., P.K.V Akola) 1. Liquification section 2.Saccharification section 4. Instrumentation 5. Electrical 6. Utilization for fermentation plant 20,00,000 (20 Lacs) 20,00,000 ( 20 Lacs) 5,00,000 ( 5 Lac ) 25,00,000 ( 25 lacs) 18,00,000 ( 18 lacs)

3. Weighing and fermentation and storage tank 1,10,00,00 ( 110 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 9. Inter connection pipelines, valve and instrumentation 10. Reaction and commissioning 11. Building 12. Boiler for 11,000 1/day plant 10,00,000 ( 10 lacs ) 5,00,000 ( 5 lacs ) 75,00,000 ( 75 lacs ) 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. 2,50,00,000 ( 25 lacs)

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Basis :No of working days Glucose content in Sapota Fermantation efficiency Plant capacity = = 300/ year = 220 gm/Kg 92 – 95 % = 15 KL / day Rate Rs. 4000 /t 465 / kg 825 / kg 1190 / t 7.5 / Kw 2.50 / m3 2.50 /m3 4 / Kg 20 / Kg Total cost / year Raw material Waste Sapota Enzymes -1 AMG Steam Electricity Water Process water Cooling water Acid Antifoam Per day 47 t 45 Kg 22.5 Kg 52.5t 2400Kw 300 m3 250m3 75 Kg 15 Kg Per year 14100 13.50 t 6.75 t 15750 t 7.2 lack kw 90000 m3 75000 m3 22500 Kg 4500 Kg 564.00 62.775 55.6875 187.425 54.00 2.25 1.875 0.90 0.90 0.375

Alcohol yield from Sapota = 150-170 lit lt

Consumption

agent CaCO3 25 Kg Yeast Total variable cost = 930.1875 Less credit for spent Sapota 14100 t Net variable cost Natural produced 3000 / t

7500 Kg 5 / Kg Only during start up

= = = =

423.00 507.1875 45 lacs liters. Rs.11.27 / lit

Variable cost of alcohol / lit of alcohol

Basis:No.of working days = 300 days / year Glucose content in Sapota = 220 gm / Kg. Alcohol yield from Sapota = 150 – 170 lit / t
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Fermentation efficiency Plant capacity Raw material Sapota Enzymes -1 AMG Steam Electricity Water Process water Cooling water Acid Antifoam

= 92 – 95 % = 15 kl / day

Consumption / day 47 t 45 Kg 22.5 Kg 52.5 t 2400 Kw 300 m3 250m3 75 Kg 15 Kg

Consumption per year 14100 13.50 t 6.75 15750 t 7.2 Lack / Kw 90000 m3 75000 m3 22500 Kg 4500 Kg

Rate Rs 9000 / t 465 / kg 825 / kg 1190 / t 7.5 / Kw 2.50 / m3 2.50 /m3 24 / Kg 20 / Kg

Total cost / year 1269.00 62.775 55.67 187.425 54.00 2.25 1.875 0.90 0.90 0.375

agent CaCO3 25 Kg Yeast Total variable cost = 1635.875 Less credit for spent Sapota 14100 t Net variable cost 7000 / t

7500 Kg 5 / Kg Only during start up

= = =

987.00 648.875 Rs. 14.4 / lit.

Variable cost of alcohol / lit of Alcohol

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.
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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
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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. No. 1. 2. 3. 4. 5. 6. 7. 8. 9. Product 2- Ethyl hexanol Acetic Acid Vinyl Acetate monomer N – Butanol Ethylin oxide Ethylene glycol S.B.R. Styrene Pharmaceuticals Total Alcohol Requirement Estimated demand for chemicals in MT 67000.00 80000.00 34000.00 15000.00 25000.00 8000.00 93000.00 90000.00 Alcohol requirement in million lit. 221.10 112.00 069.70 028.50 055.00 141.60 306.90 82.08 300.00 1483.00 86

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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 Beverages 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 68% 11% Industrial/Solvents 21%

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.
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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.
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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,
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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.
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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:

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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.
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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.
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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.

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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. 5th Edition J. H. Perrys. 7. Handbook of Chemical Engineering.

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
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"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 : Salil K. Ghosal Shyamal K Sanyal Siddhartha Datta 18. Chemical Engineering Thermodynamics Websites :www.ethylalcohol.com www.ethanolmt.org www.Fineprint.com www.Maharashtra Pollution Control dept.org.in By D. Srinivasan. By Coulson & Richardson's. 17. Introduction to Chemical Engineering

APPENDIX

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

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