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Process Overview
Starch To Alcohol conversion
By Praveen Kumar
Pioneer Distilleries Nanded
(Diageo India)
Basic Process
Raw Material receipt Preparation for Fermentation
Distillation Fermentation
Co products & effluent handling
Basic Process
This effectively remains the same for all processes
Feedstock preparation
Fermentation
Distillation
•However there are significant differences which are
addressed at a high level in this presentation but dealt
with in some detail in the rest of the course
Carbohydrates and Fermentable Sugars
• Carbohydrates, or “hydrates of carbon,” are an important group of
naturally occurring organic compounds.
•Commonly these are formed by green plants through photosynthesis
• Carbohydrates are any of the various compounds comprised of
• carbon, hydrogen and oxygen, general formula Cx(H20)y
• Carbohydrates are used to store energy until required by the organism
– Sugars, starches, cellulose, glycogen and related substances
• Saccharides, the simplest form of carbohydrates, consist of single
sugar units with five or six carbon atoms in ring form
– They are commonly called “sugars” or “sweeteners”
Carbohydrates and Fermentable Sugars
•Starch and cellulosic compounds are polymeric molecules
•– Made up of basic unit called monomers
•– These monomers are joined together by a chemical bond
called a glycosidic link
•Carbohydrates can be divided into four basic classes
•– Monosaccharide's
•– Disaccharides
•– Oligosaccharides
•– Polysaccharides
•Each of these comprises of successively more of the
same basic unit or units
Carbohydrates and Fermentable Sugars
1.Monosaccharide:
– Glucose and Fructose
Can be fermented to ethanol by yeast, only under anaerobic conditions
2.Disaccharides :
– Sucrose and Maltose
– Sucrose is fructose and glucose molecule linked together
– Sucrose is obtained from sugar cane and sugar beets
– Commonly known as table sugar
– Maltose comprises of two molecules of glucose linked together
– Both maltose and sucrose are fermentable to ethanol by yeast
3.Oligosaccharides:
– Are Saccharides with more than three but less than eight units
– Oligosaccharides can not be fermented by yeast to produce ethanol
4.Polysaccharides:
– Polymeric carbohydrates of many thousand of monomeric sugar units linked
together through glycosidic linkages
– Starch, glycogen or cellulose
– Neither starch or cellulose can be directly fermented by yeast to produce
ethanol
– Must be hydrolyzed to fermentable sugars
STARCH
(Polysaccharides )
STARCH (A LITTLE MORE COMPLICATED)
Good well understood feedstock.
•Long chains of glucose molecules.
•Consists of: Grains
Tubers (potato, cassava)
Rice
Starch chains need to be broken down before fermentation.
Starch (a little more complicated)
• The basic chemical formula of starch
• (C₆ H₁₀O₅)n is similar to glucose, C₆H₁₂O₆, where
'n' is the number of Glucose molecules present.
There are two forms of starch:
• Amylose, the branchless form
• Amylopectin, the branched form.
• The main function of starch is as way to store
energy for plants
DEGREE OF POLYMERIZATION (DP)
Glucose = DP1
These can
Maltose = DP2 be fermented
by yeast
Maltotriose = DP3
Four or more glucose molecules = DP4+
Dextin
Malto-dextrin
Oligosaccharide
Maltose
Glucose
1000
100
10
1
Amylose and amylopectin
Conversion Of starch to Glucose
Fermentation Starch
• Maintain correct sugar
balance
• Most common method is
Simultaneous
Saccharification and
Fermentation (SSF)
• Very high alcohols
possible but good cooling
is essential.
Enzymes
•Enzymes are a type of protein present in, and essential to, all
living things
•Enzymes act as biological catalysts
They increase the rate of chemical reactions without
undergoing any permanent change themselves
•Enzyme are not consumed in the reaction Can continue to
catalyze a reaction as long as the proper reactants
are available
•The surface of each enzyme contains various chemical groups
that can react with small molecules
Enzyme
•Comparison of enzymatic and nonenzymatic reaction kinetics
Starch Process
Liquefaction
Dextrinswollen starch molecules
Liquefaction is the process of turning starches, into smaller molecules
called dextrins
– Alpha amylase (AA) enzyme is need for Liquefaction
– Granular structure of starch needs to be broken before AA can bring
about hydrolysis of starch to dextrins
– AA breaks randomly breaks alpha 1,4 glucosidic linkages but not alpha
1,6 linkages
Saccharification
•New dry grind ethanol plants do
Simultaneous Saccharification and Fermentation (SSF)
•Some plants still have separate saccharification process
Saccharification versus SSF
Starch Advantages
• If dried can be stored easily between harvest.
• Uses conventional well understood process.
• Cooking process kills most bacteria.
• With grains a high protein feedstock is a by-product.
• High fermentation alcohols and high yields are
obtainable.
• Possibility of other valuable by-products.
Disadvantages
• Feed stock is often also a food or grown on the same land
• Lower yield of alcohol per acre than sugar.
• Lower overall net energy gain compared with sugar. Due to
the gelatinization requirement of the starch (cooking)
• Higher chemical costs compared to sugar Due to the
addition of commercial enzymes or the use of malted
grains
Sugar
• SUGAR FERMENTATIONS
Types of Cane Sugar Feedstock
• Juice
• High Test
• Blackstrap
Cane Juice
• JUICE FERMENTATION
Juice (Beet or cane)
• Advantages
• Rapid fermentation
• Extra nutrients not usually required
• No up front energy needed for concentration
• Effluent easy to treat or recycle
• Disadvantages
• Low alcohol fermentations
• Cannot be stored
• Usually contaminated (low pH or antimicrobials)
• Molasses or concentrated juice often added to increase sugar content.
Distillation Juice
• Distillation is straight forward and not high fouling.
• Beverage: Generally a highly flavoured product
• Batch and continuous distillation to produce Cachaça in
Brazil also rum in Haiti and Dominican Republic.
• Fuel Common to use juice during the campaign, often
fortified with molasses or syrup to reduce the amount
of water that needs to be removed.
• HIGH TEST MOLASSES (CANE)
What is High Test?
• Juice concentrated to
60 to 70% sugar
• No sugar is removed
Why use it?
• Advantages:
• Vinasse can be used
• Little sugar lost to Maillard reaction
• Can be stored
• Can be diluted to optimum strength for fermentation
• High alcohols possible
• Disadvantages:
• Extra energy to remove water
• Nutritional supplements, minerals and FAN needed
• Blackstrap Molasses
Points to Remember
• No one makes Blackstrap Molasses as a product. It is a
waste product of sugar production. As such, the alcohol
plant receives all the molasses plant upsets, poor storage
conditions, added chemicals and efficiency improvements.
Even previously used molasses can be added.
• Very high mineral content
• And as such it is a very variable product and its overall
distilling quality is constantly declining.
• You need to account for this in plant design and operations.
Types of molasses
• A Type one crystallization
step rare but good feed
stock if handled properly.
• B Type two crystallization
steps
• C Type three crystallization
steps. Most common form
of blackstrap
• Refiners From the cleanup
of the raw sugar. Lower
minerals higher sugar. May
contain alpha-amylase.
Minerals: beet thick juice vs. molasses
• Component (mg/kg) Thick Juice Molasses
• Calcium 48 1000-5000
• Magnesium 3.6 1000-1500
• Manganese <1.2 3
• Phosphorus 20 200-700
• Potassium 2260 20,000-70,000
• Sodium 409 5000-10,000
• Zinc 2.4 40
• Sulphur 1500-5000
• Biotin .04-.13
• Folic Acid 0.04
• Copper 2.5
They vary a lot!
• 2 Cane Molasses Assays
• #1 #2
• Brix 84.9 88.32
• Silica 0.22
• Total Sugar 51.30 58.39
• Reducing Sugars 18.97 23.58
• Non fermentable Sugars 4.96 6.5
• Ash 13.40 11.08
• Calcium 0.41 0.35
• Sucrose 32.36 33.31
Fermentation
Sucrose structure
• Invertase: is an enzyme produced by the yeast which
breaks down sucrose into glucose and fructose. This allows
the two sugars to be transported through the cell
membrane. High test molasses is sometimes treated with
invertase to prevent the crystallization of the sucrose.
.
Fermentation
• Fermentation allows Glycolysis to continue making
ATP when oxygen is unavailable.
• Anaerobic process
• Glycolysis will happen the same way it does at the
beginning of cellular respiration
– Glycolysis splits glucose into two pyruvic acid molecules
– Pyruvic acid and NADH enter Fermentation
Fermentation
• Fermentation will occur instead of cellular respiration
due to the lack of oxygen
• Occurs in the cytoplasm of cells
• Fermentation does not produce ATP
Two Types of Fermentation
• Lactic Acid
• Alcoholic
Alcoholic Fermentation
• Alcoholic fermentation
– Yeast and certain bacteria
– Pyruvate is broken into alcohol and carbon dioxide
– Used in the production of beer, wine and bread
Different product from fermentation
Points in Fermentation
• Stress can be high
• Incremental feed reduces
stress
• Once dilution water is
added becomes very
susceptible to bacterial
action
• High solids can result in
sludge in fermenter and
wash column
DISTILLATION
Distilling
Molecular Sieves
Co product / Effluent handling
• This varies dependant on
• Feedstock
• Country (regulatory and permissible)
• Plant design
Starch based
• Because of the “high solids content” and the
analysis of the remaining product a valuable
animal feed is possible
• In some countries “zero discharge” is required,
which can require significant recycling of
material
• Generally can produce a High COD / BOD
effluent that can be treated or discharged
with permission
Sugar Based
• Here the remaining solids are much lower value
and are generally used in co-generation systems
supplying both heat and power for the plant
• Liquid discharge is either treated and discharged
or simply discharged. In some areas it can be land
applied as a mineral fertilizer
• Molasses based production generally produced a
very dark and very low value and hard to dispose
of effluent. Recent methods of incineration are
showing reasonable success
• Thank You

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Presentation on Grain and Molasses fermentation

  • 1. Process Overview Starch To Alcohol conversion By Praveen Kumar Pioneer Distilleries Nanded (Diageo India)
  • 2. Basic Process Raw Material receipt Preparation for Fermentation Distillation Fermentation Co products & effluent handling
  • 3. Basic Process This effectively remains the same for all processes Feedstock preparation Fermentation Distillation •However there are significant differences which are addressed at a high level in this presentation but dealt with in some detail in the rest of the course
  • 4. Carbohydrates and Fermentable Sugars • Carbohydrates, or “hydrates of carbon,” are an important group of naturally occurring organic compounds. •Commonly these are formed by green plants through photosynthesis • Carbohydrates are any of the various compounds comprised of • carbon, hydrogen and oxygen, general formula Cx(H20)y • Carbohydrates are used to store energy until required by the organism – Sugars, starches, cellulose, glycogen and related substances • Saccharides, the simplest form of carbohydrates, consist of single sugar units with five or six carbon atoms in ring form – They are commonly called “sugars” or “sweeteners”
  • 5. Carbohydrates and Fermentable Sugars •Starch and cellulosic compounds are polymeric molecules •– Made up of basic unit called monomers •– These monomers are joined together by a chemical bond called a glycosidic link •Carbohydrates can be divided into four basic classes •– Monosaccharide's •– Disaccharides •– Oligosaccharides •– Polysaccharides •Each of these comprises of successively more of the same basic unit or units
  • 6. Carbohydrates and Fermentable Sugars 1.Monosaccharide: – Glucose and Fructose Can be fermented to ethanol by yeast, only under anaerobic conditions 2.Disaccharides : – Sucrose and Maltose – Sucrose is fructose and glucose molecule linked together – Sucrose is obtained from sugar cane and sugar beets – Commonly known as table sugar – Maltose comprises of two molecules of glucose linked together – Both maltose and sucrose are fermentable to ethanol by yeast 3.Oligosaccharides: – Are Saccharides with more than three but less than eight units – Oligosaccharides can not be fermented by yeast to produce ethanol 4.Polysaccharides: – Polymeric carbohydrates of many thousand of monomeric sugar units linked together through glycosidic linkages – Starch, glycogen or cellulose – Neither starch or cellulose can be directly fermented by yeast to produce ethanol – Must be hydrolyzed to fermentable sugars
  • 8. STARCH (A LITTLE MORE COMPLICATED) Good well understood feedstock. •Long chains of glucose molecules. •Consists of: Grains Tubers (potato, cassava) Rice Starch chains need to be broken down before fermentation.
  • 9. Starch (a little more complicated) • The basic chemical formula of starch • (C₆ H₁₀O₅)n is similar to glucose, C₆H₁₂O₆, where 'n' is the number of Glucose molecules present. There are two forms of starch: • Amylose, the branchless form • Amylopectin, the branched form. • The main function of starch is as way to store energy for plants
  • 10. DEGREE OF POLYMERIZATION (DP) Glucose = DP1 These can Maltose = DP2 be fermented by yeast Maltotriose = DP3 Four or more glucose molecules = DP4+ Dextin Malto-dextrin Oligosaccharide Maltose Glucose 1000 100 10 1
  • 12. Conversion Of starch to Glucose
  • 13. Fermentation Starch • Maintain correct sugar balance • Most common method is Simultaneous Saccharification and Fermentation (SSF) • Very high alcohols possible but good cooling is essential.
  • 14. Enzymes •Enzymes are a type of protein present in, and essential to, all living things •Enzymes act as biological catalysts They increase the rate of chemical reactions without undergoing any permanent change themselves •Enzyme are not consumed in the reaction Can continue to catalyze a reaction as long as the proper reactants are available •The surface of each enzyme contains various chemical groups that can react with small molecules
  • 15. Enzyme •Comparison of enzymatic and nonenzymatic reaction kinetics
  • 17. Liquefaction Dextrinswollen starch molecules Liquefaction is the process of turning starches, into smaller molecules called dextrins – Alpha amylase (AA) enzyme is need for Liquefaction – Granular structure of starch needs to be broken before AA can bring about hydrolysis of starch to dextrins – AA breaks randomly breaks alpha 1,4 glucosidic linkages but not alpha 1,6 linkages
  • 18. Saccharification •New dry grind ethanol plants do Simultaneous Saccharification and Fermentation (SSF) •Some plants still have separate saccharification process
  • 20. Starch Advantages • If dried can be stored easily between harvest. • Uses conventional well understood process. • Cooking process kills most bacteria. • With grains a high protein feedstock is a by-product. • High fermentation alcohols and high yields are obtainable. • Possibility of other valuable by-products.
  • 21. Disadvantages • Feed stock is often also a food or grown on the same land • Lower yield of alcohol per acre than sugar. • Lower overall net energy gain compared with sugar. Due to the gelatinization requirement of the starch (cooking) • Higher chemical costs compared to sugar Due to the addition of commercial enzymes or the use of malted grains
  • 23. Types of Cane Sugar Feedstock • Juice • High Test • Blackstrap
  • 24. Cane Juice • JUICE FERMENTATION
  • 25. Juice (Beet or cane) • Advantages • Rapid fermentation • Extra nutrients not usually required • No up front energy needed for concentration • Effluent easy to treat or recycle • Disadvantages • Low alcohol fermentations • Cannot be stored • Usually contaminated (low pH or antimicrobials) • Molasses or concentrated juice often added to increase sugar content.
  • 26. Distillation Juice • Distillation is straight forward and not high fouling. • Beverage: Generally a highly flavoured product • Batch and continuous distillation to produce Cachaça in Brazil also rum in Haiti and Dominican Republic. • Fuel Common to use juice during the campaign, often fortified with molasses or syrup to reduce the amount of water that needs to be removed.
  • 27. • HIGH TEST MOLASSES (CANE)
  • 28. What is High Test? • Juice concentrated to 60 to 70% sugar • No sugar is removed
  • 29. Why use it? • Advantages: • Vinasse can be used • Little sugar lost to Maillard reaction • Can be stored • Can be diluted to optimum strength for fermentation • High alcohols possible • Disadvantages: • Extra energy to remove water • Nutritional supplements, minerals and FAN needed
  • 31. Points to Remember • No one makes Blackstrap Molasses as a product. It is a waste product of sugar production. As such, the alcohol plant receives all the molasses plant upsets, poor storage conditions, added chemicals and efficiency improvements. Even previously used molasses can be added. • Very high mineral content • And as such it is a very variable product and its overall distilling quality is constantly declining. • You need to account for this in plant design and operations.
  • 32. Types of molasses • A Type one crystallization step rare but good feed stock if handled properly. • B Type two crystallization steps • C Type three crystallization steps. Most common form of blackstrap • Refiners From the cleanup of the raw sugar. Lower minerals higher sugar. May contain alpha-amylase.
  • 33. Minerals: beet thick juice vs. molasses • Component (mg/kg) Thick Juice Molasses • Calcium 48 1000-5000 • Magnesium 3.6 1000-1500 • Manganese <1.2 3 • Phosphorus 20 200-700 • Potassium 2260 20,000-70,000 • Sodium 409 5000-10,000 • Zinc 2.4 40 • Sulphur 1500-5000 • Biotin .04-.13 • Folic Acid 0.04 • Copper 2.5
  • 34. They vary a lot! • 2 Cane Molasses Assays • #1 #2 • Brix 84.9 88.32 • Silica 0.22 • Total Sugar 51.30 58.39 • Reducing Sugars 18.97 23.58 • Non fermentable Sugars 4.96 6.5 • Ash 13.40 11.08 • Calcium 0.41 0.35 • Sucrose 32.36 33.31
  • 36. Sucrose structure • Invertase: is an enzyme produced by the yeast which breaks down sucrose into glucose and fructose. This allows the two sugars to be transported through the cell membrane. High test molasses is sometimes treated with invertase to prevent the crystallization of the sucrose. .
  • 37. Fermentation • Fermentation allows Glycolysis to continue making ATP when oxygen is unavailable. • Anaerobic process • Glycolysis will happen the same way it does at the beginning of cellular respiration – Glycolysis splits glucose into two pyruvic acid molecules – Pyruvic acid and NADH enter Fermentation
  • 38. Fermentation • Fermentation will occur instead of cellular respiration due to the lack of oxygen • Occurs in the cytoplasm of cells • Fermentation does not produce ATP
  • 39. Two Types of Fermentation • Lactic Acid • Alcoholic
  • 40. Alcoholic Fermentation • Alcoholic fermentation – Yeast and certain bacteria – Pyruvate is broken into alcohol and carbon dioxide – Used in the production of beer, wine and bread
  • 41. Different product from fermentation
  • 42. Points in Fermentation • Stress can be high • Incremental feed reduces stress • Once dilution water is added becomes very susceptible to bacterial action • High solids can result in sludge in fermenter and wash column
  • 46. Co product / Effluent handling • This varies dependant on • Feedstock • Country (regulatory and permissible) • Plant design
  • 47. Starch based • Because of the “high solids content” and the analysis of the remaining product a valuable animal feed is possible • In some countries “zero discharge” is required, which can require significant recycling of material • Generally can produce a High COD / BOD effluent that can be treated or discharged with permission
  • 48. Sugar Based • Here the remaining solids are much lower value and are generally used in co-generation systems supplying both heat and power for the plant • Liquid discharge is either treated and discharged or simply discharged. In some areas it can be land applied as a mineral fertilizer • Molasses based production generally produced a very dark and very low value and hard to dispose of effluent. Recent methods of incineration are showing reasonable success