OVERVIEW OF ALCOHOL PRODUCTION

• By
• Dr Seema Paroha
• Professor , Biochemistry
• National Sugar Institute , Kanpur.U.P
Use of different raw materials/feed
stocks For ethanol production
Raw Material - Determinants & Imperatives

Price • Multi Feed Stock Option

• Simultaneous Sugary and Starchy feed Stock

Availability • Multi feed Stock options in close vicinity

• Best in Class (high sugar & low inhibitors)

Yield • Hygiene and Sanitation (to control infection)
• Co-Products (for revenue generation)
Raw Materials for Bioethanol
 Raw Material Selection Criteria

 Availability & Cost of Raw Material

 Storage, Handling & Transportation Cost
 Pre-Processing & Capital Cost
 Utility Cost
 Technology Availability
 Plant Location
 Plant Capacity & Annual Operation
 Revenue from Co-products
 Effluent Treatment & Discharge
 The feed stocks raw materials are of 3 types

1. Saccharine – containing Sugar

2. Starchy - Containing Starch

3. Cellulosic - Containing Cellulose

Saccharine
All saccharine material can be converted to ethanol after their conversion to glucose.
Sucrose + H2O Glucose + fructose
Lactose + H2O Glucose + Galactose
Maltose + H2O 2Glucose
Cellobiose + H2O 2Glucose
 Classes of Carbohydrates

Monosaccharides contain a single polyhydroxy aldehyde or

ketone unit (e.g., glucose, fructose).
●
Disaccharides consist of two monosaccharide units linked
together by a covalent bond (e.g., sucrose).
●●
Oligosaccharides contain from 3 to 10 monosaccharide units
(e.g., raffinose).
●●●●●●●●
Polysaccharides contain very long chains of hundreds or
thousands of monosaccharide units, which may be either in
straight or branched chains (e.g., cellulose, glycogen, starch).
 1
CHO 6 CH2OH 6 CH2OH

H C OH 5 O 5 O H
2 H H H
HO C H H H
3 D-glucose 4 H 1 4 H 1
OH OH
H C OH (linear form) O
4 OH 2
OH
3 2 3
H C OH
5 H OH H OH
maltose
CH2OH
6

6 CH2OH 6 CH2OH 6 CH2OH 6 CH2OH

5 5 5 O 5
H O H H O OH H H O OH
H H H H
4 H 1 4 H 1 4 1 O 4 1
OH OH OH H OH H
OH OH OH H H
3 2 3 2 OH H
3 2 3 2
H OH H OH
H OH H OH
-D-glucose -D-glucose cellobiose

CH2OH CH2OH
H O H H O H amylopectin
H H
OH H OH H 1
O
OH
O
H OH H OH

CH2OH CH2OH 6 CH2 CH2OH CH2OH

H O H H O H H 5 O H H O H H O H
H H H H H
OH H OH H OH H 1 4 OH H OH H
4 O O
O O OH
OH
3 2
H OH H OH H OH H OH H OH
 Simple

Sucrose
Single Stage Hydrolysis

Raw Moderate Stacrh

Complex
Material Two Stage Hydrolysis

Most Complex
Cellulose

Lignin

Pretreatment Followed by Liquefaction

12
Hemicellulose
 Saccharine Raw Materials

Sugarcane Juice Sugar beet Juice Sugarcane Black strap

molasses molasses

Cashew apple Mahua Flowers Whey Beet molasses

All saccharine material can be converted to ethanol after their conversion to glucose.
Sucrose + H2O Glucose + fructose
Lactose + H2O Glucose + Galactose
Maltose + H2O Glucose + Glucose
Cellobiose + H2O Glucose + Glucose
S.No. Saccharine Content Sugar Content Yield (Litres/Ton)
(%)

1 Sugarcane Juice 35-45 70-80

2 Sugar beet Juice 12-13 60-65

3 Sugarcane molasses 48-49 230-270

4 Beet molasses 48-49 250

5 Black strap molasses 50-51 250

7 Cashew apple 7-8 60-62

9 Mahua Flowers 50-67 225-250

 Typical characteristics of Indian cane
molasses
S. No. Particulars Test values

1 Brix 86.00-90.00
2 Moisture content (%) 15.00-21.50
3 Total suspended solids (%) 3.50-7.00
4 Total dissolved solids (%) 72.00-82.00
5 pH of molasses 4.20-4.50
6 Total reducing sugars (%) by mass 42.00-52.00
7 Total fermentable sugars (%) by mass 40.00-48.00
8 Calcium content (gms/1000 brix) 1.80-2.75
9 Fermentable/Non fermentable ratio 1.50-2.00
(F/N)
10 Carbonated ash (%) 8.00-12.00
11 Sulphated ash (%) 11.00-15.00
12 Nitrogen (% of molasses) 0.700-1.200
13 Potassium (% of ash) 15.00-16.50
14 Sodium (% of ash) 0.90-0.95
15 Chlorides (% of ash) 13.00-14.00
16 Phosphates (% of ash) 0.25-0.35
17 Total organic volatile acids (mg/lit.) 2500-7000
 Starchy Raw Materials

Corn
Wheat
Rice Sorghum

Barley
Sweet potato

Tapioca Rice Bran cake Potato

Starchy substance too are needed to be converted to
glucose after gelatinization, liquefaction and Scarification.

cooking
Starch gelatinized starch

α – amylase
enzyme

Glucose liquefied starch

glucoamylase
S.No. Starch Content Starch Content Yield
% Kg/Ton

1 Corn 74 491

2 Wheat 65 431

3 Rice 80 531

4 Sorghum 75 497

5 Millets 70 464

6 Barley 64 425

7 Tapioca 35 190

8 Potato 20 130

9 Sweet potato 25 150

10 Rice bran cake. 45 230

 Cellulosic Raw Materials

Bagasse

Rice Husk

Wheat Husk

grasses
Corn cobs
 Plant Part used for Ethanol Production
Cassava Root
Sweet potato Root
Sugar Beet Root ( Juice/ molasses )
Sugar Cane Stalk (Juice/Molasses/Bagasse)
Sweet Sorghum Stalk
Paddy Grain (Husk/Rice Bran Cake)
Corn Grain/Residue
Sorghum Grain
Wheat Grain/Straw
Millets Grain
Barley Grain
Rice Grain/Husk
Mahua Flowers
Cashew apple; Juice
Forest plants Wood waste
 Raw material
Mostly Broken Rice, Kinki, Millet and Sorghum or mixed grains are being used
as raw material in these distillery units. Under table is about the starch
percentage & alcohol yield from various grains.

Raw material Fermentable Alcohol yield

Carbohydrate (Lit. of alcohol/MT)
(Starch %)
Rice 62-67 380-418
Sorghum 62-65 380-410
Wheat 62-65 380-410
Potato 19-20 127-134
Malt 58-59 389-395
Maize 62-65 380-410
Grain Quality
Starch is present as granules which are embedded in a protein matrix. This matrix is
surrounded by cell walls containing a gum called -glucan. The starch granules are
therefore inaccessible and protected from attack by the amylase enzymes that are
produced during germination.
During the process however, the cell walls and the protein will be dissolved by other
enzymes which are produced naturally as the seed grows.
It must have a low proportion of protein. The lower the protein, the higher the amount
of carbohydrate. (Protein levels are measured by measuring nitrogen content, a typical
spec being less than 1.8%.)
The grains should be of an even size. That way they are more likely to grow evenly.
The grains should be consistent colour, helping indicate the same variety and lack of
damage due to for instance moisture.
The grains should be large. Large are easier to process .
They must be undamaged, free of split or pre-germinated grains and free of disease or
pests such as beetles or moths.
They must be free of other cereals or other varieties.
The moisture level must be suitable. If freshly harvested, not more than 18%, and
suitable for drying to 12% prior to storage.
 Molasses
Composition and classification
• The third boiling of the sugar syrup yields dark, viscous fluid known as
molasses.
• The majority of sucrose from the original juice has crystallized and been
removed.
• The quality of Indian molasses is inferior as compared to the molasses
available in countries such as Brazil and Australia and also varies widely
within the country. The quality of Indian molasses is inferior as in India
sugar is produced by double sulphitation method that involves three and
half boiling and use of SO2 for sulphitation.
• Sugarcane molasses is agreeable in taste and aroma, and is primarily used
for sweetening and flavoring foods.
• It is a defining component of fine commercial brown sugar.
• Unlike highly refined sugars, it contains significant amounts of vitamin
B6 and minerals, including calcium, magnesium, iron, and manganese.
• It is a major raw material for the production of ethyl alcohol, bakers’ yeast
and citric acid.
 Characteristics* of Indian cane
molasses

Sr. No. Particulars Test values

1 oBrix 86.0-88.0
2 Moisture content (%) 15.0-21.5
3 Total suspended solids (%) 3.5-7.0
4 Total dissolved solids (%) 72.0-82.0
5 pH of molasses 4.20-4.50
6 Total reducing sugars (%) by mass 42.0-44.0
7 Total fermentable sugars (%) by mass 35.0-40.0

Characteristics/ properties - How substance appears and behave both chemically

and physically
 Composition
Particulars %
Total solids 83 to 85
Invert/Reducing sugar 12 to 18
Sucrose 30 to 40
Fermentable sugar 50 to 55
Non-sugar organic compounds* 20 to 25
Ash 7 to 10
Moisture 12 to 14

*includes nitrogenous substances, cane wax, vitamins, etc.

Note-Composition of a substance is what the substance is made of
 Classification
Grade ˚Brix TRS (% w/w) Ash (% w/w)
A 88 to 90 50 and above 12 to 13
B 85 to 88 44 to < 50 14 to 15
C* 83 to 85 40 to < 44 17 to 18

Molasses containing TRS less than that of ‘C’ grade are considered to be of ‘Below’ grade.
What is good quality molasses?:
As far as Indian molasses is concerned the quality of molasses is usually judged on the
basis of
1. Fermentable to Non-fermentable (F/NF) ratio. This should be as high as possible but
not less than 1,

2. The level of contaminants in molasses. On and average the contamination level in

molasses is about 103 CFU/g of molasses. Higher level than this results in poor
fermentability of molasses,

3. Total organic volatile acidity of molasses. For good quality molasses the TOVA should
be in the range of 3000-3500 ppm. Higher volatile acidity is an indication of
contamination of the molasses and the volatile acids generated retards the
fermentation rates,

4. Sludge content of molasses- The normal range of sludge content of molasses is 8.0-
12.0% (v/v). Higher sludge content results in lowering the effective volume of
fermenters and scaling problems in equipment’s and distillation columns.
Types of Fermentation
 Fermentation

Batch Continuous Fed-batch

1) Alcon and Tate & Lyle

2) Melle Bionet
3) Semi-continuous
4) Biostil
5) Cascade
6) Encillium
 Batch fermentation
 All necessary medium components and the inoculum are added at the
beginning.

 The products of fermentation, whether intracellular or extracellular, are

harvested only at the end of the run.

 The concentration of medium components are not controlled during the

process.

 As the living cells consume nutrients and yield product(s), their

concentrations in the medium vary along the process.

 The affecting factors, such as pH and temperature, are normally kept

constant during the process.

 The optimum concentration of raw materials can be decided only according

to the initial concentration.
 Continuous fermentation

 One or more feed streams containing the necessary nutrients are fed
continuously.

 The output stream containing the cells, products and residues is

continuously withdrawn.

 A steady state is established for the process.

 The culture volume is kept continuous by maintaining an equal volumetric

flow rate of feed and output.

 Need for cleaning is minimized as a continuous culture concentration is

maintained in the fermenter.
 Fed-batch fermentation

 Nutrient or raw material is fed intermittently.

 After the first filling, the inoculum is added.

 After a small retention time, filling is continued.

 Fermentation starts right after the first filling and continues along the
process.

 At the end of the process, fermenter is emptied and the product is obtained.

 It is currently the most popular mode of fermentation amongst the

distilleries in India.
 Commercial fermentation processes

Alcon process and Tate & Lyle process

 Both the processes are nearly the same and in these processes feed is

sterilized only once during the first filling in the fermenter.

 Feed is given without sterilization.

 The contents of the fermenter are mixed by pumped recirculation.

 The settled yeast is recycled and supernatant is sent for distillation.

 Yeast cell concentration is 10 to 45 g/l.

Commercial fermentation processes

Alcon process and Tate & Lyle process

 Commercial fermentation processes

Melle Bionet process

 Achieves a reduced fermentation time and increased yield by yeast recycling.

 The yeast cells from the previous batch are centrifuged and 80% are recycled back
increasing cell density to 80 billion cells/liter which initiates fermentation
immediately.

 The productivity is high and reduced growth makes more sugar available for
conversion to ethanol (2 to 7% more).

 Centrifugation is done at pH 2.0 to remove lactic acid bacteria (non-sporulating).

 Mainly used for ethanol production from sulphite waste liquor.

Commercial fermentation processes

Melle Bionet process

 Commercial fermentation processes

Semi-continuous process

 Carried out initially as batch, but, afterwards 25% of fermented wash is retained as
seed for next cycle.
 The process was described by K.H.K., Japan and has a fermentation efficiency of
88%.
 Yeast cells can be reused without any mechanical device.
 Reduction in frequency of fresh yeast propagation, thus,
 Low process water utilization.
 No increase in fermentation temperature.
 Prevention of microbial control without any energy output.
 Can be worked out on.
 Fermentation efficiency and ethanol recovery are more than conventional batch
fermentation.
Commercial fermentation processes

Semi-continuous process
 Commercial fermentation processes

Biostil process

 A continuous fermentation system providing high yield of alcohol and reduces

effluent volume.

 An excess amount of yeast instantaneously converts sugar into alcohol.

 Yeast is constantly separated from the fermented wash and recycled in the
fermenter.

 It converts almost all sugar that is put into the fermenter through molasses into
alcohol.

 Conversion of minimum 90% of fermentable sugars.

 Yield is 286 litres containing 47.5% fermentable sugars at distillation efficiency of

98.5%.
 Commercial fermentation processes

Biostil process

 A special feature of biostil is the recycle of weak wash which has been passed
through distillation column and exhausted of most of the alcohol.

 Recycling of weak wash reduces the requirement of water needed to dilute the
molasses being pumped into the fermenter.

 Schizosaccharomyces pombe yeast is used which tolerates high amount of dissolved

solid increased due to the recycling of weak wash.

 About 60% of wash is recycled, thus, total effluent output is 5 to 6 l/l of ethanol.

 It uses only one fermenter, thus, drastically reduces the space requirement.

 It is an infection free process.

 Commercial fermentation processes

Biostil process

 Formation of glycerol, higher alcohols and fusel oils is suppressed.

 Yeast propagation is required only during start of the process.

 No DAP and urea is added.

 No spent wash, but, only weak beer is recycled.

 Process water is 25% less than cascade.

 Cost of ETP is reduced by half.

Commercial fermentation processes

Biostil process
 Commercial fermentation processes

Cascade process (HiFerm)

 It utilizes three to five fermenters in series.

 Wash flows from one fermenter to other.

 The first fermenter is used partly for growth and the remaining exclusively for
alcohol production.

 This is done by adding part of substrate in first fermenter and sparging it with air.

 Sugar concentration is maintained at relatively low level and oxygen is provided via
air.

 In the other fermenters, remaining substrate is added and carbon dioxide sparged.
 Commercial fermentation processes

Cascade process (HiFerm)

 It raises sugar content and ensures that no oxygen is present, thus,

providing ideal conditions for ethanol production.

 Ethanol content of wash is 8.5 to 9.0%.

 It provides low steam consumption, reduced effluent volume and

suppression of microbial activities.

 Since, fermentation is distributed over several fermenters, gas evolved per

fermenter as well as foaming is reduced.

 Lot of time is saved in filling the fermenters, cleaning, etc.

Commercial fermentation processes

Cascade process (HiFerm)

 Commercial fermentation processes

Encillium process

 Molasses is diluted in a mixer tank and pasteurized by heating to 90°C.

 Now it is cooled at 30°C and introduced into the first of the few fermenters.

 Air is constantly supplied to the fermenter.

 The overflow from the first fermenter along with some additional molasses
is fed to the next fermenter.

 The broth from the second fermenter is distilled to separate ethanol.

 The yeast is retained in the fermenters and overflow stream from the end
fermenter is totally free from yeast.
 Commercial fermentation processes

Encillium process

 The temperature is maintained at 30 to 32°C.

 The process includes molasses treatment and clarification plant consisting

of primary clarifier, a secondary clarifier and heat exchangers, etc.

 The process of clarification involves diluting the molasses with hot water at

90°C in 1:1 proportion.

 This diluted molasses is then preheated by outgoing wort.

 It is further heated to 85°C by live steam and clarified in primary clarifier.

Commercial fermentation processes

Encillium process
 DIFFERENT TYPES OF COLUMNS
USED FOR DISTILLATION PROCESS
 Distillation
1. Analyzer Column
2. Degasifying Column
3. Pre Rectification cum stripper column
4. Extractive distillation column
5. Recovery Column
6. Rectifier cum Exhaust Column
7. Simmering Column
8. MSDH column
 Analyzer Column
Alcohol – water vapour

Wash
•In this column preheated fermented wash is stripped off from all

volatile components, including ethyl alcohol.

•From bottom, spent wash is drained and sent to ETP.

•This column generally has a degasser section on the top, which

removes all dissolved gases in the fermented wash.

•This column is generally operated under vacuum to eliminate the

chance of scaling and reduce energy requirement.

•The vapors (45% to 55% ethanol vapors) of this column are

condensed and fed to prerectifier column.

Spent wash
 Pre-rectifier Column
Vapour

•In this column the heavier alcohols (fusel oil) are

FO

Feed separated and collected from top middle draw.

•It is operated under vacuum.

•The main product is drawn off from the top side of

the column.

•Bottom product of the column is called spent lees.

Spent lees
 Vapour
Rectifier Column

RS
•This column operates under elevated pressure.
•Rectified spirit, the first alcoholic product, is drawn
FO
from this column.
Feed
•The bottom product, spent lees, is used in the process
of fermentation.
•Fusel oil and technical alcohol are also drawn from
this column.

Spent lees
 Vapour
Extractive Distillation Column

•In this column DM water is used as an extractant to

Water
dilute the rectified spirit.
RS •Water is added to change the relative volatility of the
undesirable components to obtain a product clear of
smell.
•Water is added in the ratio of 1:9.
•It is operated at atmospheric pressure.
•Bottom product is fed to the simmering column for
further concentration.
Dilute alcohol
 Vapour
Simmering Column

•This column is operated under high reflux and vaccum

•Methanol, diacetyl and mercaptans are separated from

Feed

the top of the column.

•The final product, i.e., extraneutral alcohol (ENA) is

obtained as bottom product.

ENA
 Recovery Column

TA
•Fusel oils along with the condensates of analyzer and

FO ED column are fed to this column for concentration.

Feed •A technical alcohol is taken out from the top of the

column.

•Fusel oils are drawn off from upper trays

•Bottom lees is drained off.

•It is operated at atmospheric pressure.

Spent lees
 Molecular Sieve Dehydration System

•Consists of a simple column and two sieve columns packed with zeolite.

•RS is fed to the column for concentration and heating.

•The superheated vapour is fed to one of the sieve columns for adsorption of

moisture.

•When the first sieve column gets saturated, the second is under operation.

•The first sieve column is cleared of the accumulated moisture by vacuum.

•Ethanol (99.6%) is obtained from the sieve column and is cooled.

Contd…
 Molecular Sieve Dehydration System

Steam

Sieve Sieve

Steam
 Flow diagrams Related to
Process, Distillation and MSDH
 Molasses from sugar section Process water

Molasses pit

Molasses Bulk Storage Molasses day tank

Air Laboratory yeast culture wort

Air sparging system Yeast vessel series

Pre-fermentors

Fermented wash tank Fermentors

Sludge settling tank CO2 Scrubber

Fermented wash Yeast sludge CO2

Compressed/solidified for sale

To distillation section Recycled or sent to poultry feed/bio-
or released into the atmosphere
compost
 Soft water Impure spirit vapours*
Soft water

Aldehyde column
Extractive distillation column Vapours
Steam through re-boiler Vapours

Fermented wash Analyser Pre-rectifier Spent lees Rectifier

Steam through re-boiler

Spent wash Vapours

Spent lees Fusel oil

To evaporator section

Rectified spirit vapours

Steam through re-boiler Fusel oil column

Simmering column
Spent lees

Fusel oil tank Fusel oil Extra neutral alcohol

vapours

Impure spirit vapours*

Impure spirit tank Impure spirit

ENA receivers Extra neutral alcohol Condensers
RS receivers Rectified spirit

Rectified spirit re-drawn To Ethanol section

 Steam through re-boiler

Rectified spirit Rectified spirit vapours Super-heated vapours

Super-heater

Molecular Sieve bed 1

Steam through re-boiler Evaporator
column
Molecular Sieve bed 2

Vacuum pump

Ethanol vapour

Weak spirit Condenser Regeneration Drum

Condenser

Ethanol receivers Ethanol