Natural Product Industries

7/28/2019 Natural Product Industries

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Natural Product Industries-I

Edible & Essential Oils

Soaps & Detergents; Glycerin

Carbohydrates & Fermentation


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Edible & Essential Oil

Oils are organic molecule of carbon, hydrogen, oxygen. It is composed of long chain fatty acids and esters

(glyceride ester) as well as derivative of glycerine, long

chain fatty alcohol.

Non-edible oils

caster oil, linseed oil.

Edible oils :

ground nut oil, coconut oil,soyabean oil .

Oil is used in producing vanaspati ghee, soaps anddetergents, cosmetics, medicines, polymers, paints andvarnishes and in many other applications.


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Edible & Essential Oil

COMPOSITION & STRUCTURE R1, R2 and R3 are not necessarily same.

Degree of saturation controls the melting point

and chemical reactivity

Name (R) Composition No. of =

bond

Melting

Point (0C)

Reactivity to

O2

Stearic C17

H35

0 69 Nil

Oleic C17H33 1 14 Fair

Linoleic C17H31 2 -5 Rapid

Lenolenic C17H29 3 -11 Highly Rapid

R1CO OCH2

R2CO OCH

R3CO OCH2


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Methods of Extracting Vegetable Oils(a) Cleaning and dehulling:

Mechanical cleaning is done to remove stones and other undesirable material.

Dehulling remove hulls, dry outer covering of seed.

(b) Cracking rolls:

Crushing rolls crush the oil seeds and gets flacked seeds.

(c) Digestion

100 parts of flaked seeds are thoroughly mixed with 5-10 parts of water byrotating blades.

Softening by means of heat and moisture is done here.

Steam is added for heating purpose.

Acid is formed by hydrolysis of ester.

The seeds get swollen up.(d) Expeller:

The swollen seeds are crushed under high pressure and cells of seeds getruptured and oil is released.

The tapering shape ensures more application of pressure on the seeds

The oil depleted cake is either sent for solvent extraction or used as animal feed

Oil is sent for purification.


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(e) Mix tank: The extracted oil is treated with alkali like NaOH or Na2CO3 to

remove fatty acids.

(f) Centrifuge: Acids are separated in centrifuge separator.

These separated acids are used as foots for soap manufacturing.

(g) Rotary filter: The clear oil is treated with some bleaching agent likeFullers Earth

Carbon in filter aid before rotary filter. Rotary drum filter is used for removal of seed particles which may be

present.

This finished oil is produced.

From this process around 1-2% oil content remains in the meal.

(h) Extraction: The flaked seeds or oil extracted seeds from crushing rolls & Oil

depleted cake is also added in extractor.

The solvent extracts oil from the seeds.

The wet meal is collected in the middle and is sent for solvent

removal.


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(i) Solvent removal:

Steam is used to extract solvent carried by the oil seeds.

The rotating blades ensure better exposure to steam.

The solvent free meal is sent to dryer and then used as animal feed.

Solvent is collected from top and is recycled after cooling it in heatexchanger.

(j) Flash film evaporator:

The solvent is preheated by steam.

Oil is concentrated here by evaporating the more volatile component

(hexane). The hexane is recycled back to extractor after heat recovery.

The use of flash evaporator reduces the cost of vacuum stripping column.

(k) Vacuum stripping column:

The oil from flash evaporator is fed here.

The stripping is done by steam i.e. steam carries away the hexane. And it is under vacuum for the reason that the boiling point of hexane and

oil are close to each other. Jet ejector is used here to generate vacuum.

The hexane is recycled again.

Oil produced here is either directly used or sent for purification.


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Solvent Extraction

Can be use alone or in combination withmechanical method

Solvent extraction + mechanical method

High yield : 98-99% of available oil Poor quality: dark color, odor, free acid content

Expeller + solvent extraction

Yield over 80% as prime quality oil

Only 18-20 % as the poorer gradeType of solvents used

Petroleum cuts in hexane range-flammable

Trichloroethylene - toxic


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Vegetable Oil Extraction Method


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Hydrogenation of Oils

Hydrogenation Hydrogenation process is used to remove double bonds and to

make fats and oil saturated.

It raises melting point and improves its stability and resistance torancid oxidation.

The most common end product of hydrogenation is Vanaspatighee. Other products include hardened industrial oils andpartially hydrogenated liquid oil.

The pressure temperature conditions are complicated forcertain types of double bond saturation. Ghee base oil is hydrogenated at (1-2 atmg; 135-180C) for

melting point similar to butter.

Vanaspati shortening is produced at (2-3.5 atmg; 120-160C) forhigher melting point fats.


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Chemical reactions

Hydrogenation

R1 (C = C)x R2 + (x-y) H2 R1 (C = C)y R2

Catalyst preparation

Nickel formate decomposition (finely divided catalyst)

Ni(HCOO)22H2O190 C Ni + 2CO2 + H2 + 2H2O

Reduced Ni on inert catalyst support (Nickel saltsprecipitated on inert porous carier e.g., kieselguhr, ditomceous

earth and reduced at high T)

NiCO3 Ni + H2O +CO2

Raney or spongy nickel method (produces spongy, highsurface area catalyst, sodium aluminate is washed out with water)

2Al Ni + 6 NaOH Ni + 2NaAlO3 + 3H2


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Hydrogenation of vegetable oils


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Process Description(a) Hydrogenator:

Oil is fed to the hydrogenator, where hydrogen, and steam areintroduced.

The catalyst oil slurry of concentration 5 to 15 kg per ton of oil isalso put.

The reaction is slightly exothermic so steam is sometimes turnedoff.

(b) Deodorizer: Deodorization of oil removes undesired smell and taste

subjecting oil in steam at high temperature and vacuum.

(c) Finishing & Cooling: Oil color is removed by treating with fullers earth or carbon.

It is then filtered, mixed with some vitamins.

Slow cooling is done for granular structure ghee. For non-granular products rapid chilling is done


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Major engineering problems

Heat of reaction (exothermic)

During hydrogenation cooling requires via cooling coils

T < 200 0C to avoid side rxn e.g., pyrolysis and prevent sintering

of porous catalyst

H2 handling problems

Wide explosive limit range Equipment should be leak-tested (with freon on He detector)

Carbon steel for oil hydrogenation (to avoid H2 embrittlement prob.)

Rancidity

The moisture and oxygen cause deterioration of fats. Thecombine action of both moisture and oxygen causes rancidity

which is characterised by bad smell, development of red color,

increase in acidity and increase in viscosity. Prolonged exposure

to air yield undesirable resinous products causing rancidity.


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Kinetic rate factor

Surface rxn andadsorption, control rxn

rate at 100 0C

Rates increased by

increasing H2pr (7 atm.gauge)

At 180 0C, mass transfer

for solution of H2 and

diffusion to and from

catalyst : rate controlling

steps

H2 Oil

Solution of H2 Diffusion

catalyst

Diffusion to cat Chemisorption

on catalyst

Chemisorption

on catalyst

Surface reaction on catalyst

Desorption of fat products from catalyst

Diffusion of fat products from catalyst to

liquid phase


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SOAP &

DETERGENT

Chemical process technologyCHE C322


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SOAPS

Soaps are the sodium and potassium salts of the

fatty acids (long chain carboxylic acid).

Common fatty acids used are oleic acid, stearic

acid, palmitic acid, lauric acid and myristic acid.

Sodium stearate ( C17H35COO-Na+)

Sodium palmitate ( C15H31COO-Na+)

Sodium oleate ( C17H33COO-Na+)

Soaps are used for human comfort, cleanliness

and for industrial use.


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CLEANSING ACTION OF SOAPS

Soap is a surface active agent or surfactant.

The soap molecules contain both hydrophilic part and

hydrophobic part. The hydrophilic part of soap is carboxylate

head group (COO-Na+) and hydrophobic part is aliphatic chain.

The dirt or grease is cleaned by key mechanism as shown.


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Agitation breaks the grease into micelles whose surfaces

are covered by the negatively charged carboxylate groups,

the hydrophilic -COO- groups of the embedded soapmolecules.

The grease droplets repel each other and remain

suspended in the wash water

In the end, the suspended droplets go down the drain

with the wash water.
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CHEMICAL RECTIONS

Fat splitting reaction: (Catalyst : Metal oxide, ZnO)

(RCOO)3C3H5+ 3H2O 3RCOOH + C3H5(OH)3

triglycerides water fatty acid glycerin

Saponification Reaction:

RCOOH + MOH RCOOM + H2O

fatty acid base soap water


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METHOD OF SOAP MAKING

BATCH SAPONIFICATION

This process includes acid

hydrolysis of glycerides followed

by alkali addition or direct

saponification using strong

caustic in batch process

operation

Are the oldest types of soap

manufacture.

CONTINUOUS HYDROLYSIS AND

SAPONIFICATION PROCESS

This method is greatly used

flexibility in control of product

distribution

Higher glycerin yield

Less off color production

Requires less space and

manpower.


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SOAP MANUFACTURING(Along with Fatty acid and Glycerin)


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ADVANTAGES & DISADVANTAGES

ADVANTAGES

Soaps are eco-friendly and bio degradable.

DISADVANTAGES Soaps are not suitable in the hard water.

They have weak cleansing properties than detergents.

DETERGENTS


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DETERGENTS

Detergents have better surface tension lowering

action than soaps. Due to excessive foaming, it is unable to reduce

organic content of sewage effluent.

Biodegradation of detergent is an important

environmental factor. Detergent compounds, which can be oxidized to

simple end-products, are known as biologically softsyndets and preferred in detergent compounding.

Detergents are of four types - anionic, cationic,non- ionic and amphoteric. Most common type is anionic which is generally made

up of sodium salts of an organic sulfate or sulfonate.


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Detergent Compounding

Anionic (give R- in water) Sulfate RO.SO3H and Sulfonate (aryl benzene sulfonate)

Sulfated compounds are quite stable compare to sulfonate The molecular structure of R is important in determining the

biological softness. Straight chain normal paraffin structure gives asoft ABS where as branched or isoparaffin structure resistsbiodegradation.

Cationic (give R+ in water) Quaternary ammonium compound : germicidal properties

Non-Ionic Alkyl-aryl ethylene oxide derivatives, fatty acids amide

Produce little foam, but enhance soil removal and greaseemulsification

Detergent Builders Fluorescent dies as brighteners; zeolite/phosphate builders to

extend foam; sodium carboxycellulose to improve soil and dirt

suspension


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EXAMPLES OF DETERGENTS

General method to make synthetic detergents:

Alkylbenzene + oleum alkylbenzene sulfonateTallow fatty alcohol + oleum fatty alcohol sulfate

Sulfonate + sulfate + NaOH sodium salts

R.CH2OH +H2SO4 R.CH2O.SO3H NaOH

R.CH2O.SO3Na

Sodium salts + builders Detergents


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1. Soaps cannot be used in hard

water

1. Synthetic detergents can be

used in hard water

2. Soap is made from vegetable oil

or edible oils

2. Synthetic detergents made from

byproducts of petroleum industry

( to conserve edible oil)

3. Soaps cannot be used in acidic

medium ( otherwise precipitatethe fatty acids)

3. Synthetic detergents can be

used in any medium includingacidic.

4. Soaps have weak cleansing

action

4. Synthetic detergents have

strong cleansing action.

5. Soaps are not very soluble inwater

5. Synthetic detergents are highlysoluble

6. Soaps are biodegradable and do

not cause pollution

6. Synthetic detergents are not

biodegradable and cause water

pollution

Comparison of Soaps and Detergents


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Sodium sulphate and sodium silicate - to keep the powder dry.

Sodium triphosphate or sodium carbonate - to make the solution alkaline. (

helps to remove dirt and also soften water.)

Carboxy methyl cellulose to keep the dirt particles removed are kept

suspended in the solution.

sodium perborate (bleaching agent) - for obtaining sparkling white

clothes,

Washing powders are a combination of soaps, detergents and other chemicals.

washing powders have about 15 to 30% of their weight in synthetic detergents

WASHING POWDERS


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Carbohydrates & Fermentation

Industries


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Carbohydrates

Naturally occurring combinations of C, H and O With H and O in 2:1 ratio (Hydrates of Carbon)

The most common types

Sucrose (ordinary sugar) Starch

Dextrose

Cellulose

Fermentation Industries

Use carbohydrates as a substrate for production of

various chemicals & biologicals.


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Sucrose Chemical formula : C12H22O11 (disaccharide)

Naturally in most fruits and vegetables. Sugar occurs in greatestquantities in sugarcane and sugar beets from which sugar isseparated economically and commercially.

Structural formula : (Glucose + Fructose)

Molecular weight 342

Density = 1.58 kg/m

3

Sucrose is soluble in water but

slightly soluble in methyl alcohol

and ethyl alcohol.


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Production Process

India is the homeland of sugarcane and sugar. Process : Extraction of sugarcane

Crystalline white sugar

Gur, a dark brown sugar concentrate

Raw Material : Sugarcane

composition of sugarcane juice differences betweenvarieties and location. It is a solution, containing

soluble and insoluble impurities (i.e non sucrosespecies).

Its is also slightly acid with the pH between 4.5- 5.5,TSS 15-25 and sucrose 10 20 % w/w.


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Process Flowsheet

Juice extraction pressingPurification of juiceClarification evaporation

Crystallization Centrifugation Drying and screening

Activate

Carbon Filter


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Process Description Juice extraction pressing

Two or three heavily grooved crusher rollers break the cane and extract a

large part of the juice. Revolving knives cutting the stalks into chips aresupplementary to the crushers.

As the cane is crushed, hot water (or a combination of hot water andrecovered impure juice) is sprayed onto the crushed cane counter currently.

Clarification

The juice from the mills, a dark green color, is acid and turbid.

The clarification (or defecation) process is designed to remove both solubleand insoluble impurities (such as sand, soil, and ground rock)

The process employs lime and heat as the clarifying agents. Milk of limeneutralizes the natural acidity of the juice, forming insoluble lime salts.

Heating the lime juice to boiling coagulates the albumin and some of the

fats, waxes, and gums, and the precipitate formed entraps suspended solidsas well as the minute particles.

The muds separate from the clear juice through sedimentation. The non-sugar impurities are removed by continuous filtration. The final clarifiedjuice contains about 85 percent water and has the same composition as theraw extracted juice except for the removed impurities.


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Evaporation

To concentrate this clarified juice, about two-thirds of the water isremoved through vacuum evaporation.

Generally, four vacuum-boiling cells or bodies are arranged in series so

that each succeeding body has a higher vacuum (and therefore boils ata lower temperature). The vapors from one body can thus boil thejuice in the next onethe steam introduced into the first cell doeswhat is called multiple-effect evaporation. The vapor from the last cellgoes to a condenser. The syrup leaves the last body continuously withabout 65 percent solids and 35 percent water.

Crystallization Crystallization is the next step that takes place in a single-stage

vacuum pan. The syrup is evaporated until saturated with sugar. Assoon as the saturation point has been exceeded, small grains of sugarare added to the pan. These small grains, called seed, serve as nucleifor the formation of sugar crystals. Additional syrup is added and

evaporated so that the original crystals that were formed are allowedto grow in size.

The growth of the crystals continues until the pan is full. When sucroseconcentration reaches the desired level, the dense mixture of syrupand sugar crystals, called massecuite, is discharged into largecontainers known as crystallizers. Crystallization continues in thecrystallizers as the massecuite is slowly stirred and cooled.


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Centrifugation

Massecuite from the mixers is allowed to flow into centrifugals,where the thick syrup, or molasses, is separated from the raw sugarby centrifugal force.

The high-speed centrifugal action used to separate the massecuiteinto raw sugar crystals and molasses. A centrifugal machine has acylindrical basket suspended on a spindle, with perforated sideslined with wire cloth, inside which are metal sheets containing 400to 600 perforations per square inch.

The basket revolves at speeds from 1,000 to 1,800 RPM. The raw

sugar is retained in the centrifuge basket because the perforatedlining retains the sugar crystals. The mother liquor, or molasses,passes through the lining (due to the centrifugal force exerted). Thefinal molasses (blackstrap molasses) containing sucrose, reducingsugars, organic non-sugars, ash, and water, is sent to large storagetanks.

Drying and packaging

Damp sugar crystals are dried by being tumbled through heated airin a granulator. The dry sugar crystals are then sorted by sizethrough vibrating screens and placed into storage bins. Sugar isthen sent to be packed in the familiar packaging we see in grocery

stores, in bulk packaging, or in liquid form for industrial use.


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Plant Economy


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Major engineering problems Extraction of juice from cane

Optimization : design of rolls, temperature, time ofoperation

Use of ultrasonic vibration

Choice of flocculation agents

High magnesia lime is old but best choice CO2 in carbonation step : reduce alkalinity ; improved

filterability and decolorization

Evaporation & Crystallization Difficult crystallization, Calendria type evaporators are

used Crystallization : batch-wise in 4th or last effect

Measurement of supersaturation : boiling point rise,vacuum measurement and control


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Critical zone of supersaturation

Transition region- pulverized sugar seeds are added

and new nuclei are produced at highest point ofsaturation (graining)

Metastable region- degree of supersaturation is

reduced by decreasing vacuum and crystal will grow

Simultaneous feed liquor addition and evaporation can

raise the total quantity of crystal.

Separation of crystal from syrup

Improved centrifugal machine design (high speed1800-2400 rpm)

Control of viscosity and surface tension of syrup give

clean and rapid separation


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Inversion of sugar

Acid hydrolysis of sugar in glucose and fructose

The extent of inversion is measured by

polarimeter. The non inverted sugar has +97

polarization and completely inverted sugar has -20 polarization.

Minimized by : making quick delivery to the

sugarcane presses less than 2 days

Low temperature short time conditions : to

reduce inversion


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Extraction from sugarcane for Gur

production

Low cost product made by simple evaporation process.

Cane juice extraction Clarification

Concentration

Occurs in open pan evaporators until (80-85%solidification).

The product run out of the bottom of pan.

The product is dark brown solidifies paste at roomtemperature and invert partially to mono-saccarides on

storage. It contains neutritionally desirable minerals, particularly

iron.


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Starch

High polymer carbohydrate

Occur in grains and roots in

form of granules (3-100 )

Chemical formula : C6H10O5

n varies 200-500

Major source : Maize kernel n


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Process Description

Cleaning & screening

Steeping

Coarse grinding &

degermination

Fine grinding &

extraction

Gluten separation

Starch refining

Dehydration & drying


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Manufacture of Ethanol from Molasses

Ethanol is a volatile, flammable, clear, colorless

liquid. A good solvent. It is also used as a germicide,

beverage, antifreeze, fuel, depressant and chemicalintermediate.

Molecular formula- C2H5OH

Molecular weight- 46.07

Density- 0.791 at 20C

Boiling Point- 78.3C It can be made by the fermentation process of

material that contains sugar or from the compoundwhich can be converted to sugar.


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Methods of Production

Fermentation From sucrose substrate

Yeast enzyme readily ferment sucrose to ethanol.

From waste sulfite substrate of paper mills

From starch substrate

Petroleum Processing

Catalytic hydration of ethylene

Esterification and hydrolysis of ethylene

Oxidation of petroleum


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Fermentation Fermentation applies to both the aerobic and anaerobic metabolic

activities of micro-organisms in which specific chemical changes are

brought about in an organic substrate due to the enzymes produced bythose microbes.

Fermentation is the core part of distillery which is carried out in largecylindrical vessel generally made of stainless steel is called as fermenter.

The media which has been prepared is introduced in the prefermenterand after 7 - 8 hours it is transferred into fermenter where fermentation

is carried out. Here batch fermentation is carried out without maintenance of complete

sterility of equipment. However, this pre supposes a rapid start of theyeast fermentation. This fermentation inhibits the growth of othermicrobes by depleting the available nutrients, by lowering the pH andmost importantly by the formation of ethanol. To reduce the pH H

2SO

4is

usually added.

As we know molasses contain approximately 50% invert sugar i.e.sucrose. It is converted into glucose and fructose in the presence of yeastand invertase enzyme.


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Ethyl alcohol by fermentation

Enzymatic reactions

Enzymes (bio-catalyst)are produced by living organism (bacteria)

Mild Condition : pH 4 -9 and T 30 to 70 C.

Raw material requirements: Molasses (50-55% total sugar);

Sulfuric acid; Ammonium sulfate.


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Eff f i f h l


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Effect of various factors on ethanol

conversion

[1] Effect of pH (Fermentation Process)


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Effect of Temperature

Effect of molasses concentration


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Effect of yeast concentration

Effect of time

Process Description


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Process Description

F i l l f i i


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Functional role of various units

(a) Molasses storage tank: Molasses (liquor obtained as by product of

sugar industries) is a heavy viscous material, which contains sucrose,fructose and glucose (invert sugar) at a concentration of 50-60(wt%).

(b) Sterlization tank: Yeast is sterilized under pressure and then cooled.

(c) Yeast cultivation tank: Yeast grows in the presence of oxygen by

budding. Yeast is cultivated in advance.(d) Yeast storage tank: Yeast are unicellular, oval and 0.004 to 0.010mm in

diameter. PH is adjusted to 4.8 to 5 and temperature up to 32C.

(e) Fermentation tank: Chemical changes are brought by the action of

enzymes invertase and zymase secreted by yeast in molasses.

Fermentation is anaerobic. Heat is evolved which is removed by

cooling coils. Residence time is 30-70 hours and temperature is

maintained at 20-30C. 8 -10%alcohol by volume(beer) is produced by

fermentation process. HCl or sulfuric acid is added to obtain pH 4.5

(f)Diluter: H l i dil t d t 10 t 15% l ti


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(f)Diluter: Here molasses is diluted to 10 to 15% sugar solution.

(g)Scrubber: Carbondioxide is released and utilized as by product. By-product CO2contains some ethanol due to Vapor liquid evaporation and can be recovered by

water scrubbing. Water is sent back to continuous diluter stream.

(h)Beer still: 50-60% concentration alcohol and aldehyde is produced. Slops areremoved as bottom product. Slop is concentrated by evaporation for cattle feed

or discharged as waste. Slop contains proteins, sugar and vitamins.

(i)Aldehyde still: Undesirable volatile liquid; aldehyde is taken off from the top of

the still. From the side stream alcohol is feed to the decanter.

(j)Decanter : Fusel oil which is high molecular weight alcohol is recovered bydecantation. The principle behind extraction of fusel oil from ethanol is that

higher alcohols are more volatile than ethanol in solution containing a high

concentration of water.

(k)Rectifying column: In the column, azeotropic alcohol- water mixture of 95%ethanol is withdrawn as side product. This 95% ethanol is condensed in

condenser and stored in storage tank. Side stream is withdrawn and sent to

decanter. At the bottom, water is discharged. Here, alcohol water mixtures are

rectified to increase the strength of alcohol.


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(l)Storage tank: From storage tank, three streams are evolved:

Direct sale as potable alcohol

Denatured by small addition of mildly toxic agent for industrial use. To anhydrous still to produce 100% ethanol.

(m)Mix tank: For producing denatured alcohol, denaturant is

mixed with the 95% ethanol produced from rectifying column.

Denaturant is normally methanol/naphtha (10vol%)

(n)Ternary Azeotropic distillation: The product from rectifying

column is a ternary minimum boiling azeotrope of ethanol,

water and benzene. Benzene is an azeotropic agent.

Main units present are: anhydrous still, decanter, stripper and few heat

exchangers.

Anhydrous motor fuel grade ethanol (100% ethanol) is produced as

product.

Heat integration and energy recovery plays a vital role in reducing

energy requirements.

E i i P bl


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Engineering Problems

Collection and storage of molasses

Maintenance of sterile and specific yeast

culture conditions.

Batch versus continuation operation Waste disposal problem

Development of methods to produce

anhydrous alcohol from the 95% alcoholazeotrope

S d ti th l d ti


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Second generation ethanol production

technology


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Assignment-1 [08/03/13]

[1] Draw a block diagram of Productionprocess: Fig. IIID-4 : Ethyl alcohol by

Fermentation.

Show all input and output species from eachunit.

Get operating T and P for all units.

Note- Work should be neat.

Submission date : 15/03/13

Date post:	14-Apr-2018
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