Biorefinery Products and Applications Guide
Biorefinery Products and Applications Guide
INTRODUCTION
➢ Raw Sugar
➢ First generation bioethanol from blackstrap molasses obtained as the byproduct of
the sugar manufacturing process
➢ Second generation Bioethanol from the sugarcane bagasse obtained as the by-product
of the sugar manufacturing process
➢ Biofertilizers like vinasse
➢ Energy obtained by using bagasse as a fuel, generation of electricity etc
➢ Bulk organic chemicals: acetic acid, butanol, ethyl acetate etc
➢ Specialty Chemicals: ethyl lactate, cinnamic alcohol, cinnamic acid etc
Sucrose:
• It is found naturally in many food plants along with the monosaccharide fructose.
• In many fruits, such as pineapple and apricot, sucrose is the main sugar.
Ethanol:
• It is a byproduct of the metabolic process of yeast
1
• It is present in any yeast habitat
• It is commonly found in an overripe fruit
• It is also produced during the germination of many plants as a result of natural
anaerobiosis.
• Ethanol produced by symbiotic yeast can be found in Betram Palms blossoms.
• Ethanol has been detected in outer space, forming an icy coating around dust grains
in interstellar clouds.
1.3 Manufacturers
Its history begins with the discovery of sugarcane in the South Pacific, probably New
Guinea and as the time passed, the plant was grown in Southeast Asia and India, eventually
making its way to China.
2
• Sugar was relatively rare in Europe until the 13th century, when trading with Asia
expanded. The cultivation of sugar cane in the New World also increased its
availability. In Europe, the use of sugar beets for making sugar also increased
during the 1800s.
Bioethanol:
3
CHAPTER-2
Sucrose:
➢ Granulated sugars are used at the table to sprinkle on foods and to sweeten hot drinks
and in home baking to add sweetness and texture to cooked products.
➢ Milled sugars are ground to a fine powder. They are used as icing sugar, for dusting
foods and in baking and confectionery.
➢ Screened sugars are crystalline products separated according to the size of the grains.
They are used for decorative table sugars, for blending in dry mixes and in baking
and confectionery.
➢ Brown sugars are granulated sugars with the grains coated in molasses to produce a
light, dark or Demerara sugar. They are used in baked goods, confectionery and
toffees.
➢ Sugar cubes are white or brown granulated sugars pressed together in block shape.
They are used to sweeten drinks.
➢ Liquid sugars are strong syrups consisting of 67% granulated sugar dissolved in
water. They are used in the food processing of a wide range of products including
beverages, ice cream and jams.
➢ Invert sugars and syrups are blended to manufacturer’s specifications and are used in
breads, cakes and beverages for adjusting sweetness, aiding moisture retention and
avoiding crystallization of sugars
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primarily in the amount of impurities present. Generally, as you move down the
chain to a lower quality ethanol, higher amounts of impurities are present.
➢ The Purest: “GNS” or grain neutral spirits. The highest level of ethanol purity is
“GNS” or grain neutral spirits, beverage quality. This is only domestically produced
from fermentation grain sources, typically corn or wheat. In addition to meeting all
of the quality requirements for USP and FCC grade materials, GPC beverage alcohol
must pass stringent organoleptic analysis. Since GNS is intended for human
consumption, this test is the most important screening tool. Organoleptics are
normally run at 40 proofs (20% by volume).
➢ Purer: “FCC Grade” ethanol (Food Chemical Codex) adds heavy metal specification
limits to the grades below since most FCC grade materials are used in food
applications. This can be either of fermentation or synthetic origin.
➢ “USP Grade” ethanol (U.S. Pharmacopoeia) has specific tests that measure impurities
present, setting limits on each type.
➢ “NF Grade” ethanol (National Formulary) lowers the amount of impurities further to
the 20 to 25 ppm levels.
Not-as-pure: The highest impurity levels are found in “fuel grade” ethanol that is produced
via the fermentation process. It is added to gasoline as an octane enhancer/extender and to
reduce carbon monoxide and nitrous oxide pollution. Manufacturers of this grade don’t take
great care in removing the impurities produced in the process because they “burn” easily in
a combustion engine.
5
CHAPTER-3
ECONOMIC SCENARIO
Indian Scenario:
India's bioethanol production is on the rise, with the country aiming to triple its biofuel
use and accelerate global deployment. The Indian ethanol market reached 3200 million
liters in FY2023 and is expected to grow at a CAGR of 5.67% until FY2035, reaching
approximately 6300 million liters.² This growth is driven by increased ethanol
consumption in fuel additives and beverages, as well as government initiatives to
convert excess sugar into ethanol.
- Increased Ethanol Blending: The National Biofuel Polic.y 2018 aims to achieve 10%
ethanol blending by 2022 and 20% by 2025.
- Growing Demand for Fuel Additives: Ethanol is used as a fuel additive to improve
octane ratings and reduce emissions.
- Expanding Beverage Industry: Ethanol is used in the production of beer, cider, wine,
and spirits.
Regional Demand:
- West India dominates the ethanol market, driven by demand from industries in
Gujarat, Maharashtra, and Rajasthan.
- Other regions, such as North, South, and East India, are also expected to contribute to
the growth of the ethanol market.
Government Initiatives:
6
World Scenario :
On the basis of data projected on demand and supply of ethanol in 2015 and 2020 it
can be clearly seen that from 2015 to 2020 in just a time period of 5 years, a gap between
demand and supply increases from about 10000 million litres in 2015 to 20000 million litres
in 2020 which is a sign of danger for the world community.
It’s a global matter of concern as gap between demand and supply is continuously
increasing. Demand is going high and high and our production rate is going down. As
petroleum and crude are depleting at a faster rate there is a need to produce bioethanol from
biomass to fill the gap between demand and supply.
Fig 3.1 Current and Projected Demand and Supply of Bioethanol Worldwide
Application wise Consumption pattern: Of the total ethanol world demand 28% is for the
blending purpose to be used as a fuel and the remaining 50% and 22% by the portable and
industrial sector in year 2011. Future demand analysis shows that demand for industrial and
portable sector is increasing that means ethanol consumption in this sector is more than that
for fuel purpose. Thus we should lay more emphasis on the production of ethanol from
lignocellulosic material specially sugarcane bagasse to meet heavily growing demand.
7
CHAPTER – 4
4.1 Properties
Sucrose:
➢ Sucrose is the organic compound commonly known as table sugar and sometimes
called saccharose. A white, odorless, crystalline powder with a sweet taste, it is best
known for its nutritional role.
➢ Sucrose is a molecule with five stereo centers and many sites that are reactive or
can be reactive. The molecule exists as a single isomer.
Structure:
α-D-glucopyranosyl-β-D-
fructofuranoside
8
Chemical Properties:
➢ Sucrose is readily soluble in aqueous protic solvents such as methanol and ethanol.
It is insoluble in ether and chloroform and anhydrous ethanol and glycerol. It is
moderately soluble in DMF, pyridine, and dimethyl sulphoxide.
➢ Under mild acid catalysis, usually dilute HCl, sucrose is easily hydrolysed and
inversion occurs (change in the sign of polarization from +66.5 to a negative value,
owing to the large negative rotation of fructose). A small amount of the fructose
formed is converted to D-fructose di- anhydrides. A small degree of inversion is
detectable under alkaline conditions.
➢ Sucrose is hydrogenated with Raney nickel to a mixture of sorbitol and mannitol;
under more drastic conditions, glycerol and propylene glycol are produced. Mild
oxidation gives oxalic and tartaric acids, as well as acidic materials designated as
saccharic acids.
Bioethanol:
Chemical Properties:
Combustion of Ethanol:
Ethanol burns with a pale blue, non luminous flame to form carbon dioxide and steam.
9
C2H5OH + 3O2→2CO2 + 3H2O
Dehydration of Ethanol:
When ethanol is mixed with concentrated sulphuric acid with the acid in excess and
heated to 170oC, ethylene is formed. (One mole of ethanol loses one mole of water)
C2H5OH→C2H4 + H2O
Sucrose:
Diabetes: It is a disease that causes the body to metabolize sugar poorly, occurs when either:
The body attacks the cells producing insulin, the hormone that allows the metabolizing of
sugar (Type 1 diabetes).The body's cells exhibit impaired responses to insulin (Type 2
diabetes).
Obesity: The National Health and Nutrition Examination Survey I along implies that obesity
may correlate better with sugar consumption than with fat consumption, and that reducing
fat consumption while increasing sugar consumption actually increases the level of obesity
Bioethanol:
Ethanol contains 35% oxygen, is non-toxic, water-soluble and quickly biodegradable. These
properties make it an ideal substance to formulate fuel blends the use of which will mean a
cleaner and less polluted environment and, as a consequence, a healthy planet for us all and
for future generations. Compared to petroleum-based fossil fuels, Ethanol blends contribute
significantly towards the safety and conservation of the environment.
10
• In 2005, Ethanol use in the US reduced CO2 -greenhouse gas emissions by about
7.8 million tons.
• According to the American Lung Association of Metropolitan Chicago, Ethanol-
blended, reformulated gasoline reduces smog-forming emissions by 25% since 1990.
• Ethanol brings down tailpipe emissions by 30%, toxic content by 13% (mass) and
21% (potency), and tailpipe fine particulate matter (PM) emissions by 50%.
• Ethanol has a positive energy balance, for it generates more energy than is
consumed during production. It yields 67% more fossil energy than is used to grow,
harvests and process the grain.
• Ethanol reduces formaldehyde emissions.
The first and foremost concern for public health is its carcinogenic effects, as there is
unambiguous evidence for the carcinogenicity of ethanol orally consumed in the form of
alcoholic beverages. Limited and conflicting epidemiological evidence is available on the
link between the use of ethanol in the oral cavity in the form of mouthwashes or mouth
rinses and oral cancer.
11
CHAPTER – 5
MANUFACTURING PROCESSES
We have selected the location of our proposed integrated sugarcane based biorefinery in
SOLAPUR, MAHARASHTRA.
Uttar Pradesh and Maharashtra are the 2 leading sugarcane producing states of India. We
have preferred Maharashtra over Uttar Pradesh because:
Near Maharashtra, seaport is there which helps in transportation of raw materials from
abroad and export of our products to other countries i.e. helps in reducing transportation
cost.
➢ Security is good.
➢ Product market.
Manufacturing Process
Micro-organism used:
Selected strains of the yeast Saccharomyces cerevisiae are commonly employed for
fermentation. This is because (a) they grow vigorously, (b) they have high tolerance for
alcohol and (c) they have a high capacity for producing a large yield of alcohol.
The basic Steps involved in the process are:
12
CHAPTER- 6
Advantages:
Renewable energy source from biomass. Reduced greenhouse gas emissions (70-90% less
than gasoline). Energy security through domestic production. Job creation in agriculture,
manufacturing, and transportation. Low sulfur content reduces sulfur dioxide emissions.
High octane rating improves engine efficiency. Biodegradable and non-toxic. Can be
produced from various sugar-rich feedstocks (sugarcane, corn, beet). Supports rural
development and agriculture growth. Diversifies energy matrix, reducing dependence on
fossil fuels.
Disadvantages:
Land use competition with food crops (food vs. fuel debate).Water consumption for
irrigation and processing (2,500 liters per liter ethanol).High production costs (double those
of fossil fuels).Energy intensity (1.5 units energy input per unit ethanol).Limited scalability
due to feedstock availability and transportation costs.
13
Advantages Over Bioethanol from Corn Maize:
Higher ethanol yield (90-100 liters/ton sugar vs. 70-80 liters/ton corn). Lower production
costs (sugar fermentation is more efficient). Water conservation (sugarcane requires less
irrigation than corn). Reduced fertilizer usage (sugarcane is more nutrient-efficient). Lower
land requirements (sugarcane yields more ethanol per hectare). Diversified feedstock
options (multiple sugar-rich crops). Existing infrastructure (sugar mills, distilleries). Faster
fermentation rates (24-48 hours vs. 72 hours). Simplified pretreatment process (no starch
gelatinization needed). Reduced energy consumption (fewer processing steps).
14
15
Fig2.Flow sheet for the Production of Bioethanol from Sugar Syrup
1. Preparation of the medium: Water is added to the molasses to bring down the
sugar concentration to the desired level (usually 30 to 40 percent). A measured
quantity of acid is then added so as to adjust the pH on the acidic side.
Water: Molasses when introduced into the fermenter is first diluted because
molasses is basically a thick syrup which cannot be fermented easily as choking of
materials takes place and this thick liquid may stick to the walls of the reactor and disturbs
the entire section. To avoid this molasses is first diluted hence water also takes a
part among raw materials
6.2 Process:
As it was already mentioned that molasses is the by-product of sugar industry,
molasses is first diluted with water. For the sugar content of nearly20-25% (w), 75-80
%( w) is added and will be sent into fermenter and allow them to react or ferment for 1-
3days. In the fermenter, the formation of ethyl alcohol takes place. In
brewing, alcoholic fermentation is the conversion of sugar into carbon dioxide gas
16
(CO2) and ethyl alcohol. This process is carried out by yeast cells using a range of
enzymes. This is in fact a complex series of conversions that brings about the
conversion of sugar to CO2 and alcohol. To be specific yeast is a eukaryotic
micro-organism. Not all yeasts are suitable for brewing. In brewing we use the
sugar fungi form of yeast. These yeast cells gain energy from the conversion of the
sugar into carbon dioxide and alcohol. The carbon dioxide by-product bubbles
through the liquid and dissipates into the air. In confined spaces the carbon dioxide
dissolves in the liquid making it fizzy. The pressure buildup can be quite immense.
Certainly enough to cause the explosion of a sealed glass bottle. 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. Wine yeast is more
tolerant at a range of 10- 15%. Especially cultured strains of yeast with the correct
environment can withstand alcohol levels up to 21% alcohol. Then the beer
stream which consists of alcohol (10- 15%) and water mixture and CO2 will be
separated into two different streams where CO2 will be sent into the beer column
where the CO2 stream will be separated by varying temperature or pressure
conditions. In general pressure would be increased to separate the gas stream because
if temperature is increased, the quality of alcohol is affected. Much of the CO2 that is
generated during the fermentation process can be captured and converted into
marketable products, such as dry ice, liquid CO2 for soft drinks, fire-fighting foams,
filtration products and various industrial uses. After separating CO2, the ethanol-
water mixture will be sent into distillation column and the ethanol will separated.
In practice, maximum of 95% of ethanol can be recovered.This mixture is often
referred to as hydrous sugarcane ethanol´ because it contains 5% water. Hydrous
alcohol is preheated, vaporized and superheated before being admitted to the vessels
containing molecular sieve material. In this superheated, excited and vapor phase at
controlled temperature and pressure, adsorption of water molecules by sieve is optimized
while the alcohol molecules pass through Water accumulated on sieve is removed by
means of vacuum applied to column, reducing partial pressure of H2O, making it
evaporate again and allowing molecular sieve to be reused in next cycle.It is repeated for
continuous operation and referred to as pressure sieving mechanism. By further
dehydration, absolute or anhydrous ethanol is obtained with 99.5%.
17
CHAPTER-7
MATERIAL BALANCE
BASIS: 23 tons per hour of bio ethanol from the rectification column (95% by
weight)
7.1 FERMENTER
Overall Reaction:
C12H 22O 11+H 2O→2C 6 H 12 O 6→4C2H 5 OH+4CO2
Assumptions:
. Sugar syrup contain 52% fermentable sugar in the form of sucrose and 48% water
. 1 kg=2.1544*10^-3 kg H2 SO4
. 1 kg H2SO4 =0.2 kg H2 O
Streams:
3. CO2
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Mol. Weight of sucrose= 342
➢ CO2-1517.28kg/hr
Losses:
Feed + yeast + Sulphuric acid CO2 + Mixture of ethanol, water and biomass
7.2 CENTRIFUGE:
Streams:
• Mixture of ethanol, water, biomass and sucrose
• Mixture of ethanol, water and sucrose
• Biomass recycled
.
Kg/hr(inlet) Components Kg/hr(outlet)
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7.3 DISTILLATION COLUMN:
Assumptions:
• 80% by weight of ethanol in distillate
• % by weight of ethanol in bottom product
Streams:
F=D+R
18450 = D + R
Component balance over distillation column for ethanol:
F*f=D*d + R*r
18450*0.072 = D*0.8 + R*0.0
By solving above equations we get, D=1230kg/hr & R=17220kg/hr
Assumptions:
• 95% by weight of ethanol in the distillate
• . 1% by weight of ethanol in residue
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R+1197.7=x+1230
Component balance:
0.01*R+0.95*1197.7=0.97*x+0.8*1230
Therefore, R=164.7 kg/hr
x=131.7 kg/hr
Streams:
Feed: Hydrous Ethanol (95% by weight of ethanol)
Top Product: Recycle stream to the rectification column( E )
Bottom Product: Anhydrous ethanol (99.5% by weight of ethanol)( W )
D=x +E+W
1197.7=131.7+E+W
0.95*1197.7=131.7+0.96*W+0.995E
Therefore, E=78.95kg/hr, W=986.25
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CHAPTER-8
ENERGY BALANCE
Energy Balance Reactions:
For Non-reaction processes:
∆H=∑miHi(outlet)-∑miHi(inlet)
Q-WS=∆H+∆EK+∆EP
WS=0 (when no moving parts)
Q=∆U (for closed systems)
Q=∆H (for open systems)
8.1 FERMENTER:
Stoichiometric Equation:
C12H22O11+H2O→2C6H12O6→4C2H5OH+4CO2
T=298K (assuming isothermal conditions)
P=1atm
Energy Balance in fermenter:
∆H=4(∆Hformation Ethanol) +4(∆Hformation CO2)-2(∆Hformation glucose)
ENTHALPIES OF FORMATION
∆Hformation (Ethanol) =-276.5kJ/mol
∆Hformation (CO2) =-393.5kJ/mol
∆Hformation H2O (l) = -285.8 kJ/mol
∆Hformation H2O (g) = -241.8 kJ/mol
∆Hformation (glucose) (g) =-1250 kJ/mol
∆Hformation (sucrose) (g) =-2220kJ/mol
Therefore, ∆H= [4(-276.5) +4(-393.5)-2(-1250)] =-180kJ/mol
From the stoichiometric reaction,
Sucrose balance:
Min of sugar solution=20,000kg/hr
22
But, sucrose content in sugar solution=88%
Sucrose=0.88*20,000=17,600kg/hr
Moles of sucrose=17,600/342=51.46 mol
Water balance:
Water content in solution =12%
Water=0.12*20,000=2400 kg/hr
Moles of water=2400/18=133.33 mol
H2SO4 added=30.24kg/hr
CO2 balance:
Moles of CO2 out =723.25/44=40.180mol
Yeast inlet=711.24+177.8=889.01 kg/hr
C2H5OH balance:
Nout= 20102/184=109.25 moles
Now, energy Balance:
Q-WS=∆H+∆EK+∆EP
Now, ∆EK=0 (Kinetic changes)
∆EP=0(horizontal unit)
Q-WS=∆H
Assumption:
Power input=1.6 watt/kg of input
Total input=20919.25kg/hr
Power Input=WS=440.341
∆H° =793.126 KW
Q=∆H+WS=793.126+440.341= 1233.47kw/hr
• Temperature of distillate=82°C
23
• Feed enters at 25°C
For ethanol in distillate:
∆H=∆HV+ ∫CpdT=38.58 + dT =38.58+5.516
= 44.034 kJ/mol
For water in distillate:
100 78.5
∆H=∆HV +∫25 Cp dT + ∫100 Cp dT
=40.656+5.655-1.6211=44.69 kJ/mol
Ethanol in residue:
∆H =∆HV+ =38.58+103.1*10^-3(100-25) =46.3125kJ/mol
Water in residue:
∆H =∆Hv+ =40.656+75.4*10^-3(100-25) =46.311 kJ/mol
∆H=475455.042 kJ
Q=mCp∆T=∆H
Cp=43.99kJ/kg°C
∆T=75°C ,Therefore, Steam required, m=144.11 kg/hr
8.3 RECTIFICATION COLUMN:
Assumptions:
Feed Temperature- 78.5°C
Distillate Temperature-78.5°C
Residue-100°C
∆H=14246.71kJ/mol
Q=mCp∆T=∆H therefore, m= 4.32kg of steam/hr
8.4 DEHYDRATION COLUMN:
∆H=10,000 KJ
Therefore, steam requirement is, m=10.571kg of steam/hr
24
CHAPTER 9
CONCLUSION
25
CHAPTER-11
BIBLIOGRAPHY
26
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