2008
Fermentation & Distillation
Er. Raghvendra Sachan RVS 1/1/2008
2008 Fermentation & Distillation
Er. Raghvendra Sachan RVS 1/1/2008
Raghvendra Sachan
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CONTENTS 1.
INTRODUCATION.................................................... .............................................................................................. .......................................... ....... .............. .......4 5
3.
ALCOHOLIC BEVERAGES: ................................................. ...................... ............................. .............. .............. ....... 5 DISTILLED LIQUORS:........................................................ ........................................................................ ........................ ............... ......... ..6
5.
MANUFACTURE OF ALCOHOL ALCOHOL ...................................................... ........ ............... .............. .............. ....... 7 RAW MATERIAL FOR ALCOHOL INDUSTRY:.................................... ........ ........... ...7
2.
4.
6. 7.
ALCOHOL YIELD.................................................. .................................. ....... ............. ......8
8.
PRODUCTION OF ETHANOL BY FERMENTATION OF SUGAR:........... ................. ......9 9
9.
BY PRODUCTS OF ALCOHOL MANUFACTURE .........................................10 .........................................10
10. 11. 12. 13. 14.
FERMENTATION...................................................... .............................................................................................. ........................................ ....... .............. .......11 11 DISTILLERY..................................................... ..................................................................................................... ................................................ ....... .............. ........13 1. 3 DISTILLATION....................................................... .............................................................................................................. ......................................................... ..14 14 EFFLUENT TREATMENT PLANT...................................................... ...................................................................... ....................... .......... ...15 15 CALCULATION OF COD.................................................. ................... .......................... .............. ....... 18
15.
ENVIRONMENTAL SIGNIFICANCE OF DO........................................... ....... .........19 19
16.
BIOCHEMICAL OXYGEN DEMAND.................................................. ....... ............. ......19 19
17. 18.
EXPERIMENTAL DETAILS...................................................... ..................................................................................... ..................................... ......20 20 BOTTLING UNIT .................................................. ....................................................... ........................................................... ....22 22
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INTRODUCATION An alcoholic ethanol. alcoholic beverage is a drink containing ethanol. Ethanol is a drug, drug, and depressant, and even though alcohol is a legal drug in most parts of the world, many societies regulate or restrict the sale and use of it. Ethanol (CH3CH2OH), the active ingredient in alcoholic
beverages, is almost always produced by fermentation - the metabolism of carbohydrates of carbohydrates by certain species of yeast of yeast in the absence of oxygen of oxygen.. The process of culturing yeast under alcohol alcohol-pr -produc oducing ing condit condition ionss is referr referred ed to as brewing. brewing. Spir Spirit itss are are prod produc uced ed by distillation of a fermented product, concentrating the alcohol and eliminating some of the by-products. Alco Alcoho holi licc
beve bevera rage gess
incl includ udee
lowlow-al alco coho holl-co cont nten entt
beverages produced by fermentation of sugar - or starch-containing starch-containing products, and highalcohol-content beverages produced by distillation of the low-alcohol-content beverages. Sometimes, the alcohol content of low-alcohol-content beverages is increased by adding distilled products, particularly in the case of wines.
Most yeast cannot grow when the concentration of alcohol is higher than about 18% by volume, so that is a practical limit for the strength of fermented beverages such as wine, beer wine, beer , and sake. sake. Strains of yeast have been developed that can survive in solutions of up to 25% alcohol by volume, but these were bred for ethanol fuel production, not beverage production. Spirits are produced by distillation of a fermented product, concentrating the alcohol and eliminating some of the by-products.
In many many countri countries, es, alcohol alcoholic ic beverag beverages es are common commonly ly consumed at the major daily meals (lunch and dinner). Most early beers were in fact highly nutritional and served as a means of calorie distribution
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ALCOHOLIC BEVERAGES: Alcoho Alcoholic lic beverag beverages es vary vary conside considerab rably ly in their their ethanol ethanol content and in the foodstuffs from which they are produced. Most alcoholic beverages can be broadly classified as fermented beverages, beverages, beverages made by the action of yeast on sugary foodstuffs, or as distilled beverages, beverages, beverages whose preparation involves concentrating the ethanol in fermented beverages by distillation. distillation. The ethanol content of a beverage is usually measured in terms of the volume fraction of ethanol in the beverage, expressed either as a percentage or in alcoholic proof units. proof units.
•
Undistilled Beverages: These are produced by fermentation process from fruit juice or
grains. The beverages prepared from grape juice are called wines. Wines contain 18-20% alcohol alcohol and produced by natural natural fermentation fermentation are called called “Natural “Natural wines”. Weak natural wines are made stronger by addition of pure alcohol from outside and are named as Fortified wines. e.g. beer, champaigne.
•
Distilled Beverages: If the fermented liquids are distilled, most of the alcohol along
with other volatile products like flavor, essential oils, esters and higher alcohol pass over as distillate. The distiller liquors have a high alcohol content that may go up to 50% or more. e.g. whisky, brandy, rum, gin etc. It implies that pure brandy, whisky will be made strictly from from their their raw material materials, s, which which are cherri cherries, es, malt malt respect respective ively. ly. But in the case case of blended, some part of alcohol is supplied by genuine raw material while the rest is supplied through the spirit manufactured. While in the case of essence, only the essence of brandy or whisky is mixed in rectified spirit. This is usually cheap and low in quality.
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DISTILLED LIQUORS: COUNTRY LIQUOR : - Single distilled spirit FOREIGN LIQUOR : - Double distilled spirit
COUNTRY LIQUOR is of two types
a) Plane country liquor: It is produced by mixing alcohol (80-90%) strengthened with DM water on a volume basis such that final strength of alcohol is 25%.
b) Spice (masala) country liquor : It is made by mixing alcohol with water such that alcohol is around 42.8%. Along with this, malt essence and caramel, which gives it the unique brownish color, is also added.
FOREIGN LIQUOR is of following types:
Whisky: Made from malt spirit (malt is the technical name of germinated and dried barley), has 40-50% alcohol.
Brandy: Made from grapes, litchis, cherries, apple has 40-50%alcohol.
Rum: Made from molasses spirit has 45-55% alcohol.
Gin: Made from maize, barley has 40-45% alcohol.
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MANUFACTURE MANUFACTURE OF ALCOHOL In Moha Mohan n Meak Meakin in Ltd. Ltd. the the bulk bulk of alco alcoho holl is bein being g produced from sugar cane molasses. Molasses is a thick viscous bye-product of the sugar industry which is acidic in nature, rich in salts, dark brown in colour and it also contains sugar which could not be crystallized. For manufacturing alcohol, the Molasses is diluted with water into a solution containing 15-16 % of sugars. This solution is then inoculated with yeast strain and is allowed to ferment ferment at room temperature. temperature. The fermented fermented wash is distil distilled led in a series series of distil distillat lation ion column columnss to obtain obtain alcoho alcoholl of adequat adequate/ e/ requis requisite ite strength and quality/ specification. This alcohol is used for various purposes including potab potable le and indust industria rial. l. For manufa manufactu cture re of alcohol alcoholic ic beverag beverages, es, the alcohol alcohol is, if required, matured and blended with malt alcohol (for manufacture of whisky) and diluted to requisite strength to obtain the desired type of liquor/ Indian Made Foreign Liquor (IMFL). This is bottled in bottles of various sizes for the convenience of consumers.
RAW MATERIAL MAT ERIAL FOR ALCOHO AL COHOL L INDUSTRY INDU STRY: In alcoh alcohol ol ferm fermen enta tati tion, on, gluc glucos osee or sugar sugar cane cane is the the fermentation materials. Therefore any natural product which contain this sugar can be easily transformed into them, is a potential source of ethyl alcohol.
The raw material for alcohol industries are:
stuff containing fermentable sugars: e.g. Sugarcane juice, dry date molasses, fruit juice etc.
Material containing starch or cellulose: e.g. potato, e.g. potato, Rice, barley, maize or wood
They are first treated to convert the starch or cellulose into the sugar’s that are then fermented by yeast.
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ALCOHOL YIELD
If spirit= X (bulk liters) and it has Y% of alcohol in it then
ALCOHOL YIELD = (XY)/100 BASIS
For the manufacture of 1000 liters of 94.5% ethyl alcohol Molasses
5000 g
Water
20000 lit
Yeast
2.5 kg
Sulphuric acid
0.125 lit
Urea
0.25 kg
Coal
500 kg
Plant capacity
20000 lit/day
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PRODUCTION OF ETHANOL BY FERMENTATION OF SUGAR:
Ethyl alcohol is produced from sugar-containing material such as molasses by fermentation process utilizing yeast enzymes to convert the sugar into alcohol. alcoholic fermentation is the conversion of sugar into carbon dioxide gas (CO2) and ethyl alcohol. This process is carried out by yeast enzymes. This is in fact a complex series of conversions that bring about the conversion of sugar to CO2 and alcohol The most widely used molasses is obtained as a by product in the sugar mill and contain glucose and fructose.
CHEMICAL REACTIONS : invertase
C12H22O11 + H2O
2C6H12O6
invertase
C6H12O6
2C2H5OH + 2CO 2
Side reaction
2C6H12O6 + H2O
ROH + RCHO (High mol. wt.)
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BY PRODUCTS OF ALCOHOL MANUFACTURE
i) Carbon-dioxide: large quantities are evolved during the fermentation process. This is used in the solid form as ice.
ii) Fused oil: is a liquid with nauseating odour. It is used in confectionary and fruit essences.
iii)
Acetaldehyde: obtained during the alcohol distillation
iv) Spent wash: the residual liquor from which ethyl alcohol has been removed by distillation. It contains nitrogenous matter which can be used as manure and fodder.
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FERMENTATION It involves slow decomposition of big molecules of ce rtain organic compounds into simpler ones under the catalytic influence of non living complex substances called ferments. The majority of process requires oxygen and is c lassified as aerobic. A few processes carried out in the absence of oxygen are called anaerobic. Fermentation is in two parts. Part 1
Aerobic (Oxygen is present) This is the initial rapid process where the yeast is doubling its colony size every 4 hours. (Usually 24-48 hours) Part 2
Anaerobic. (No oxygen present) Slower activity and the yeast focus on converting sugar to alcohol rather that increasing the number of yeast cells.
ALCOHOLIC FERMENTATION : The chief ethanol producers are fungi especially strain of Saccharomyces cerevisiae. The yeast respires aerobically but in the absence of air they ferment carbohydrates to ethanol and CO2. The by-product, CO2, bubbles through the liquid and dissipates into the air. The other by-product alcohol, remains in the liquid which is great for us but not for the yeast, as the yeast dies when the alcohol exceeds its tolerance level. The The ferm fermen enta tati tion on proc proces esss has has othe otherr limi limits ts such such as temperatur temperature. e. Greater Greater than 27C kills the yeast less and than 15C results results in yeast activity activity which is too slow. The conversion of glucose to ethanol can be represented as:
C6H12O6 Raghvendra Sachan
2CO2 + 2C2H5OH 11
The abilit ability y of yeast yeast cells cells to conver convertt sugar sugar into into Carbon Carbon dioxide and Alcohol is down to enzymes. Several enzymes are involved each does its step in the process. The final step is Zymase reduction which takes the end product of the other enzymes (acetaldehyde/glycerol), and turns this into good old ethyl alcohol. Sadly alcohol actually destroys enzymes and kills the yeast cell if in high concentrations. This happens at different levels for different strains of yeast.. Brewers yeast cannot withstand much beyond 5 or 6% Alcohol by volume. Wine yeast is more tolerant at a range of 1015%. Specially cultured strains of yeast with the correct environment can withstand alcohol levels up to 21% alcohol.
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DISTILLERY
THERE ARE TWO TYPES OF DISTILLERISES:
1) Potable is prepared from raw material containing sugar. Firstly the alcohol is produced from raw material and then liquor is prepared from alcohol.
2)
Non potable alcohol is manufactured in the form of spirit.
The distillery industry today consists broadly of two parts, one potable liquor and the industrial alcohol. The potable distillery producing Indian Made Foreign Liquor and Country Liquor has a steady but limited demand with a growth rate of about 8 per cent per annum. The industrial alcohol industry, on the other hand, is showing a declining trend because of high price of Molasses which is invariantly used as substrate for production of alcohol. The alcohol produced is now being utilized in the ratio of approximately 52 per cent for potable and the balance 48 percent for industrial use. Over the years the potable liquor industry has shown remarkable results in the production of quality spirits.
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DISTILLATION Distillation is the process of separation of two miscible volatile liquids by vaporization, given that both the liquids exist in both the phases. Distillation of raw alcoholic brews concentrates the alcohol and leaves behind many chemicals that are not volatile at distillation temperatures In practices distillation can be carried out by either of two principle methods. The liquid mixture to be separated and condensing the vapor without allowing any liquid to return to the still, and then there be no reflux. The second method is based on the return of the part of the condense to the still under such conditioned that this returning liquid is brought into the condenser. Either of these methods can be conducted as a continuous or batch process. Distillation unit consist of an analyzer (23 plates), aldehyde column and rectifier (56 plates). The analyzer and the rectifier are connected via the 13th plate called the adjust plate. In the rectifier section the heat is provided from the bottom to the condens condenser er heat exchange exchange takes takes place place betwee between n the vapors entering entering the water flowing through condenser.
PROCESS PRO CESS DESCRIPT DESC RIPTION ION: In it the condensed liquid from the rectifier enters the purification column. The steam is added to the condensed liquid and the alcohol rich vapor is sent to the condenser that is further processed to the silent column. The silent spirit produced from the silent column is also called E.N.A. or extra neutral alcohol, which is double distilled alcohol generally used for making whisky.
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EFFLUENT TREATMENT PLANT The main raw material of distillery molasses and when it is distilled after fermentation to get alcohol, produce large q uantity of liquid effluent called “ spent wash”. wash”. This spent wash contains organic matter in the effluent is therefore required to be remove so that it can be discharged safely into the environment. In the effluent treatment plant, set up by Mohan Meakin ltd in March 1988, the treatment of the effluent takes place in the following steps: 1.
Anaerobic treatment i.e., biogas generation, two stage
2.
Aer Aerobi obic tre treat atme ment nt i.e., .e., secon econda dary ry treat reatme ment nt
3.
Clar Clarif ifiicati cation on uni unit wi with chem chemiical cal tr treatm eatmen entt
4.
Seco Second nd stag stagee aera aerati tion on unit unit with with chem chemic ical al trea treatm tmen entt
5.
Sludge decanter machine
6.
Clar Clarif ific icat atio ion n by two two meth methan anee sep separ arat ator or clar clarif ifie ier r
7.
Fer Ferti irrig rrigat atiion in the the zeal zeal of zer zero di discha scharrge
8.
Fountain wi with at atomization technique
9.
Floc Floccul culat atio ion n uni unitt with with R.C. R.C.C. C. clar clarif ifie ierr for for chem chemic ical al trea treatm tmen entt
10.
Recyc Recycli ling ng of of tre treat ated ed tra trade de effl effluen uentt for for cool coolin ing g purp purpos osee Spen Spentt wash wash rich rich in orga organi nicc matt matter er from from the the dist distil ille lery ry
having a temperature of 100-1020C, is cooled through heat exchangers to bring the required temperature of 400C. This effluent is fed into METHANE REACTOR. Methane reactor is the heart of effluent treatment plant. The biological process which includes the degradation of higher organic compounds and reduction of BOD take place in this zone. The methane (8, 000-9,000 NM 3/day) is recovered as a by product during the course of BOD reduction. reduction. The methane reactor has been designed for 90% reduction in BOD. The The over overfl flow ow of the the meth methan anee dige digest ster er is sent sent to the the anaerobic filter clarifiers and then to aeration basin having 3 surface aerators of 50 HP each, to provide sufficient oxygen for the growth of aerobic bacteria responsible for furthe furtherr decompo decomposit sition ion of pollut pollutant ants. s. The efflue effluent nt of the brewer brewery y direct directly ly comes comes to
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aeration basin along with the anaerobic stream. This basin has been designed for 90% reduction in BOD. Effl Efflue uent nt is then then sent sent to clar clarif ifie ierr where where the the sludg sludgee is separated and dewatered through sludge decanter machine previously, sludge was been dried by press deg dewatering machine and sludge drying beds. A part of sludge as required is recirculated to the aeration basin. Separated sludge is used as manure in the lawns lawns and agricu agricult ltural ural farms. farms. The overflo overflow w efflue effluent nt from from the seconda secondary ry clari clarifie fierr is further taken to the secondary stage aeration unit and clarifiers for further reduction of the BOD the BOD value. value. In this, chemical treatment is also added for the further reduction reduction in BOD value. value. The superna supernatan tantt treatm treatment ent trade trade efflue effluent nt coming coming out from from methan methanee separa separator tor clarif clarifier ierss is parti partiall ally y sent sent to the founta fountain in having having an atomiz atomizati ation on technique fro more natural aeration and it is used for ferti irrigation partially. The F.L.D. and brewery bottle washing water of low BOD value is mixed in second stage aeration for treatment with the help of chemicals, i.e., flocculants and polyelectrolyte. The The trea treate ted d trade trade effl effluen uentt thus thus comi coming ng out out from from the the clarifiers or flocculation unit is taken into the cooling tower and used for cooling purpose in distil distiller lery y condens condenser er before before being being discha discharge rged. d. Ultima Ultimatel tely y treate treated d efflue effluent nt being being discharged top river Gomti is within the norms (i.e., 30pm) values led down by the pollution control board. Not only this, Mohan Meakins has a substantial saving of coal in the form of biogas and reduced the coal consumption consumption which is in the tune of 8590%.
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P.I Diagram of E.T. Plant
Mohan Meakin Ltd. Lucknow Air Compressor Spent Wash Vat Washing, Distillery & Vat washing brewery
P.H.E Digester
1
2
2
4
3
7(a) 7(b)
5
6
Secondary treatment i.e. two stages Bottle Washing of I.M.F.L Anaerobic treatment i.e. two stage followed by Clarifier Bottle Washing of Country Liquor Bottling
15
14
12
11
10
8
9
Tertiary treatment i.e. chemical treatment
C.O.D. mg/L Spent wash 60000-65000 1. New Digester 21000-22000 2. Old Digester Clarifier 16000-17000 3. Aeration Tank no. 1 13000-5000 4. Degassing Tank ..... ….. 5. Secondary Clarifier 8000-10000 6. Aeration Tank no. 2 3000-4000 7. M.S. clarifier 7(a)-7(b) ….. ….. 8. Atomization Tank ….. ….. 9. Chemical Tank ….. ….. 10. Final Clarifier 300-350 11. Cooling Tower ….. ….. 12. Discharge Point 200-250 13. Sl Sludge Centrifuges & Sludge Beds….. 14. Gas Holder ….. ….. 15. Gas boiler ….. …..
B.O.D mg/L 25000-30000 3500-4000 2000-2500 600-700 ….. ….. 150-200 100-150 ….. ….. ….. ….. ….. ….. 50-55 ….. ….. 30 ….. ….. ….. ….. ….. …..
T.S.S. mg/L 4000-5000 11000-12000 1500-2000 2500-3000 ….. ….. 1200-1500 120-150 ….. ….. ….. ….. ….. ….. 100-120 ….. ….. 60-90 ….. ….. ….. ….. ….. …..
Flow 300-350M 3/D
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150-200M 3/D
250-300M3/D
800-900M 3/D
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CALCULATION OF COD
FOUR SAMPLES FROM THE DIFFERENT STAGES OF E.T.P ARE TO BE TAKEN:
0.25ml of spent wash , make volume up to 50 ml with DM water and transfer to the conical flask, added 75ml conc. Sulphuric acid, transferred the contents to the condenser heat exchanger for about 2-6 hours and after that 150ml DM water added followed by cooling for about an hour.
0.5ml from digester P1, make volume to 50ml with DM water and transfer to the conical flask, added 75ml conc. Sulphuric acid,
CALCULATION OF COD
FOUR SAMPLES FROM THE DIFFERENT STAGES OF E.T.P ARE TO BE TAKEN:
0.25ml of spent wash , make volume up to 50 ml with DM water and transfer to the conical flask, added 75ml conc. Sulphuric acid, transferred the contents to the condenser heat exchanger for about 2-6 hours and after that 150ml DM water added followed by cooling for about an hour.
0.5ml from digester P1, make volume to 50ml with DM water and transfer to the conical flask, added 75ml conc. Sulphuric acid, transferred the contents to the condenser heat exchanger for about 2-6 hours and after that 150ml DM water added followed by cooling for about an hour.
0.5ml from digester outlet, make volume to 50 ml with DM water and transfer to the conical flask, added 75ml conc. Sulphuric acid, transferred the contents to the condenser heat exchanger for about 2-6 hours and after that 150ml DM water added followed by cooling for about an hour.
1ml from aeration tank, make volume to 50 ml with DM water and transfer to the conical flask, added 75ml conc. Sulphuric acid, transferred the contents to the condenser heat exchanger for about 2-6 hours and after that 150ml DM water added followed by cooling for about an hour.
Titrate all the 4 samples against ferrous ammonium sulphate with ferroin as an indicator.
8000(Blank titration – Sample titration) * Normality of Ferrous ammonium sulphate COD = ml Sample
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ENVIRONMENTAL ENVIRONMENTAL SIGNIFICANCE OF DO
In liquid waste, DO is the factor that determine weather the biological change are brought by anaerobic organism. It is used for oxidation of organic and inorganic matter and produces innoculus end product.
CALCULAT CALC ULATING ING DO COLLECTION OF SAMPLE - entry of air should be avoided. STANDARED REAGENTS FOR MEASURING DOReducing agent used is 0.025N sodium thiosulphate. Starch solution determines end point. Standard reagent used is iodine. End point-blue turns colorless.
BIOCHEMICAL OXYGEN DEMAND
Amount of oxygen required by bacteria while stabilizing decomposable organic matter under aerobic condition. BOD test is used to determine the pollutional strength of domestic and industrial waste in terms of oxygen that will require if discharged into natural water. How to find BOD
Adjust the sample to about 200c and aerate with diffused air to increase or decrease the dissolved gas content of the sample to near saturation. 2 or more BOD bottles are then filled with the samples, at least one is analyzed for DO immediately and then other one incubated for 5 days at 200C After 5 days the amount of DO remaining in the incubated samples is determined and the 5 days BOD is calculated by subtracting 5 da ys results for those on day 0.
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EXPERIMENTAL DETAILS Sugar testing :
In sugar testing two things are find out: 1)
Brix: It is the percentage of molasses solution in water by weight. Normally available molasses has a brix is briolette. it consists of two parts, the u pper part is used to find brix, the bottom part gives the temperature, which is thus used to find the correction to brix.
100gm molasses
900ml water
Mix
Check brix
Check the temperature
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2)
Total reducing sugar (TRS) 100gm molasses
900ml water
Mix
Check brix
Check the temperature
Take 10ml solution in a pipette
Add HCl (2ml)
Boil to 70oC
Cool
Add sodium bicarbonate (neutralizer)
Titrate against fehling solution with methyl blue as indicator
Noted the reading
Formula for calculating the glucose in 100gm molasses: Fehling factor * 100*100 Glucose in 100gm molasses =
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Burette reading
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BOTTLING UNIT The rectified spirit that is obtained from the distillation plant is stored in the storage tank and taken out according to the demand. The flavor and essence are according the product nature. At the time of bottling strength decreases to 42.8 % then after labeling they are packed and delivered.
Rectified spirit Addition of essence and flavor Filtration Filling in the bottle capping Sealing Checking any particle impurity Labeling security hologram Packaging in cartons Transportation unit
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