GREEN GENES- A PROMISING FUEL SOURCE FOR FUTURE Narasimha Reddy Palicherlu
Graduation Presentation_CeylanpinarATAY_2
1. PRODUCTION OF BIOETHANOL
Graduation Project Presentation
Ceylanpınar ATAY
18.06.2013
Advisor:
Prof. Dr. Filiz KARAOSMANOĞLU
Jury Members:
Prof. Dr. Sadriye KÜÇÜKBAYRAK OSKAY
Dr. Hikmet İSKENDER
2. Content
Aim of the Project
Introduction
Theoretical Study
Plant Examination Visit
Conclusion
2
3. Aim of the Project
• To examine the production and utilization of bioethanol
• To analyze the current status and the future of bioethanol
in Turkey, the EU, and the world
Literature Search
Plant Examination Visit
Biofuels and
Biorefinery
Definition
Bioethanol in
Turkey, the EU,
and the world
Production of
Bioethanol
Konya Sugar
Industry and
Trade Inc. 3
11. Bioethanol (Fuel Ethanol)
Properties Values
Formula C2H5OH
Molecular Weight (g/mol) 46.1
Carbon (w/w, %) 52.1
Hydrogen (w/w, %) 13.1
Oxygen (w/w, %) 34.7
C/H ratio (wt) 4
Specific Weight (kg/L) 0.79
Vapor Pressure (at 38 oC)
(mmHg)
50
Boiling Temperature (oC) 78.5
Solubility in Water ∞
Stoichiometric (air/EtOH) 9
Lower Heating Value (kcal/kg) 6400
Ignition Temperature (oC) 35
Specific Heat (kcal/kg oC) 0.6
Melting Point (oC) -115
Sugar-based
Feedstocks
(sugar beet, sugar
cane, sweet
sorghum)
Starch -based
Feedstocks
(corn, wheat,
patato, cassava,
sorghum)
Lignocellulose-
based Feedstocks
(stalk, straw,
branch, root )
Bioethanol
11
An alternative fuel for internal combustion engines
The most preferred biofuel
12. Bioethanol
Applications:
• Alternative engine fuel,
• A contribution to the fuel
• A fuel cell fuel
• A raw material for the production of
bioethyl tertiary buthyl ether and biodiesel
As a substitute of gasoline or diesel:
• Gasoline with additive alcohol: 5% ethanol + 95% gasoline
• Gasohol: 10% ethanol + 90% gasoline
• E20: 20% ethanol + 80% gasoline
• E25: 25% ethanol + 75% gasoline
• E85: 85% ethanol + 15% gasoline
• E-Diesel (Oxydiesel, Diesohol): Diesel fuel containing max.
15% ethanol
12
14. Turkey
Compulsory to use E2
without special
consumption tax
Compulsory to use E3
without special
consumption tax
Legal
Regulation
of EMRA
2013
2014
2013 2014
Blending % 2 3
Bioethanol
Demand
(m3)
50000 75000
14
15. Turkey
Plant
Annual
Capacity
Feedstock(s) City
Çumra
84 million
liters
Sugar Beet Konya
Tezkim
40 million
liters
Wheat
Corn
Adana
Tarkim
40 million
liters
Corn Bursa
Eskişehir
20 million
liters
Sugar Beet Eskişehir
Total Established Capacity of
Bioethanol Production
190 million liters
Bioethanol Production in
2012
< 30 million liters
15
Bioethanol plants established in Turkey:
16. The European Union
• A minor bioethanol
producer compared
to the US and Brazil
• 28% of the total biofuel
market in the road
transport in 2011
Calender
Year
2006r 2007r 2008r 2009r 2010r 2011e 2012f 2013f
Benelux 19 37 76 143 380 696 1,013 1,013
France 294 539 746 906 942 949 949 949
Germany 430 397 580 752 765 730 759 823
United
Kingdom
0 44 70 70 278 190 253 316
Spain 405 359 346 465 471 465 465 465
Poland 162 120 114 165 194 171 203 228
Other 323 310 655 970 1,147 1,419 1,295 1,396
Total 1,633 1,806 2,587 3,471 4,177 4,620 5,000 5,380
Bioethanol Production Capacity in the EU (million liters)
Wheat
Corn
Rye
Barley
Sugar Beet
16
17. World
COUNTRIES 2008 2009 2010 2011
USA 36,388 42,177 49,440 54,000
BRAZIL 27,146 26,075 28,680 21,000
CHINA 6,900 7,300 7,000 2,100
INDIA 2,063 1,588 1,938 1,681
FRANCE 1,545 1,790 1,850 1,100
CANADA 950 1,320 1,500 1,800
GERMANY 815 1,015 1,120 800
ENGLAND 350 390 650 -
RUSSIA 535 513 544 -
SPAIN 417 540 620 -
THAILAND 574 662 795 -
UKRAINE 370 360 370 -
COLOMBIA 270 342 342 -
POLAND 186 216 270 -
ARGENTINA 236 244 345 -
INDONESIA 200 220 250 -
SOUTH KOREA 160 169 172 -
ITALY 111 115 110 -
OTHER
COUNTRIES
4,338 4,865 5,374 -
WORLD (Total) 83,554 89,901 101,370 109,573
Bioethanol Production of the World (billion liters)
Largest Bioethanol Producer
204 Bioethanol Production Plants
Corn ethanol
USABRAZIL
Second Bioethanol Producer
335 Bioethanol Production Plants
Sugar Cane
CHINA
Third Bioethanol Producer
Asia’s Largest
Corn, Cassava, Sweet Patato
17
18. World
Country Mandates [M] or
Usages
Country Mandates [M] or
Usages
Argentine E5 [M] Peru E8 [M]
Australia E10 The Phillippines E10 [M]
Brazil E20-E25 [M], E85 Austria E10
Canada E5 [M] Denmark E5
China E10 Finland E5-E10 [M]
Colombia E10 [M] France E5-E10
Costa rica E7 [M] Germany E5-E10
India E5 [M] Ireland E4 [M]
Jamaica E10 [M] Romania E4 [M]
New Zealand E10 Sweden E5 [M], E85-E95
Pakistan E10 USA E15 [M], E10-E85
Paraguay E18-E24 [M]
The Global Bioethanol Blending Mandates and Common Usages
18
19. Production Methods of Bioethanol
Sugar-based
Bioethanol
Production
Starch-based
Bioethanol
Production
Lignocellulose-
based
Bioethanol
Production
Cellulose
Platform
Starch
Platform
Sugar
Platform
Sugars
Cellulose
Fermented
Mash
>90%
Ethanol
>99%
Ethanol
Extraction
Saccharification
Pretreatment
Hydrolysis
Fermentation Distillation
Dehydration
19
21. Starch-based Bioethanol Production
Corn
Wheat
Patato
Dry Milling
The whole grain is
directly included to
the production
Corn
21
Wet Milling
Starch is separated
from all other corn
kernel components
such as fiber, gluten,
germ, oil
25. Lignocellulose-based Bioethanol
Production
Pretreatment
Dehydration
Distillation
Fermentation
Hydrolysis
Lignocellulose-based
Feedstocks
Bioethanol
Physical
Pretreatment
Chemical
Pretreatment
Physicochemical
Pretreatment
Biological
Pretreatment
Mechanical Comminution
A combination of chipping,
grindling, and milling
Pyrolysis
The heating the biomass in the
absence of oxygen or with a
small amount of oxygen
Commonly carried out at high
temperatures (400-700 ℃ )
Steam Explosion (Autohydrolysis)
Biomass is heated using high pressure steam (20-
50 bar, 160-290 ℃ ) and decompressed to the
atmospheric pressure
Ammonia Fiber Explosion (AFEX)
Biomass is exposed by high temperature and
pressure
Carbon Dioxide Explosion
It does not cause to the formation of inhibitors
compared to AFEX and steam explosion
Microorganisms such as brown-, white-, and
soft-rot fungi are used
Acidic Hydrolysis
• Dilute Acid Hydrolysis: 1-3% of H2SO4 at 200-240 ℃
• Concentrated Acid Hydrolysis: provide high yield of free
sugars (90%)
Enzymatic Hydrolysis
25
Ozonolysis
Ozone to degrade the lignin and hemicellulose
Dilute /Concentrated Acid Hydrolysis
Sulfuric acid, nitric acid, hydrochloric acid, phosphoric
acid and peracetic acid to increase the porosity
Alkaline Hydrolysis
Sodium hydroxide, ammonia, calcium hydroxide and
oxidative alkali (NaOH + H2O2 or O3)
Organosolv Pretreatment
An organic solvent mixture with inorganic acid
catalysts to remove lignin
Ionic Liquids Pretreatment (ILs)
To dissolve the cellulose and lignin
27. Konya Sugar Industry and Trade Inc.
Cumra Integrated Sugar Plant
Bioethanol Production Plant
Established in 2007
Totally located on the land of 53.000
m3
Closed area is 11.600 m3
280.00 L/day bioethanol
84 million liters annual capacity
Raw Material Storage
Fermentation
Distillation and Evaporation
MSDH (Dehydration)
D type Ethanol Plant
Organic Fertilizer Plant
Filling and Handling Plant 27
30. Conclusion
30
• clean alternatives to fossil fuels
• could help to reduce the world’s depence on oil
• domestic resource
• an important alternative fuel for internal combustion engines in
Turkey, the EU and the world
• Bioethanol production is successfully applicable to the biorefinery
concept
Biofuels produced from biomass
Bioethanol
34. Bioethanol
Blending bioethanol with gasoline and diesel fuel
• decreases the cost and emissions of the
fuel
• increases the octane rating
Compared with gasoline, ethanol has a higher octane number,
broader flammibility limits, higher flame speeds, and higher
heats of vaporization.
These properties provide higher compression ratio, shorter burn
time, leaner burn engine and higher efficiency.
Combustion properties of ethanol such as higher autoignition
temperature and flash point than those of gasoline ensure safer
transportation and storage.
38. Product Stream
Pretreatment
Technique
Fermentation Strategies
Cellulose, hemicellulose, and lignin
in one product stream
Mechanical
communition,
irradiation, biological
pretreatments, and
ionic liquids
Co-fermentation or sequential fermentation of pentose and
hexose if no further pretreatments are used.
Solubilized lignin and hemicellulose
sugars in liquid phase and cellulose
in solid phase
Alkali, organosolv,
AFEX, ARP, wet
oxidation
With liquid and solid separation, fermentation of pentose or
co-fermentation of hexose and pentose depending on the
substrate. The solid stream will go through hydrolysis and
sequential or co-fermentation.
Without liquid and solid separation, solubilized oligomeric
hemicellulose sugars in the liquid might need
depolymerization.The solid cellulose portion will need
hydrolysis. Then, the pentose and hexose will undergo co-
fermentation or sequential fermentation.
Solubilized hemicellulose sugars in
liquid phase and lignin and
cellulose in solid phase
Uncatalyzed and
catalyzed (SO2, CO2)
steam explosion,
liquid hot water, pH-
controlled liquid hot
water, dilute acid
pretreatment, wet
oxidation
With liquid and solid separation, liquid might need pentose or
both pentose and hexose fermentation. The solid cellulose
will be hydrolyzed and fermented into ethanol
straightforward.
Without liquid and solid seperation, solid hydrolysis is need
first. Depending on the pretreatment severity, the solubilized
hemicellulose oligomeric sugars might need depolymerizaiton
first. And then mixture of pentose and hexose need
sequential or co-fermentation.
Hinweis der Redaktion
Good evening, my Dear advisor and jury members/ Professors and guests/my friends/students. I’m Ceylanpınar Atay. Today, I’m glad to explain my graduation project «Production of Bioethanol» to you. I wish you all an enjoyable presentation.
I would like to start with the content. First, I will explain the aim of the project and then introduction, theoretical study and plant examination visit parts will come. At the end, my presentation will close with conclusion.
In literature search, relevant definitions, production of bioethanol, bifuels and biorefinery concepts will be presented. Also a brief look of bioethanol in Turkey, the EU, and the world will be held. In plant Examination Visit Part, Konya sugar industry and the bioethanol production from sugar beet will ve focused.
Biomass is a general term for materials derived from growing plants and animal manure. It refers to woody residues and energy forests, oil seed plants (sunflower, rapeseed,soybean), carbohydrate plants (potato, wheat, corn, beet), fiber plants (linseed, hemp plant,sorghum), vegetal wastes (stalk, straw, branch, root, husk).Biomass is an important renewable energy resource and also environmentally strategic resource. Biomass energy technologies capture the energy stored in biomass and make it available in useful forms (biofuels and electricity, heat & cold). Traditionally biomass has been utilized through direct combustion, and this process is still widely used in many parts of the world. Another means of utilizing it is realized through conversion technologies. From these technologies many solid, liquid, and gaseous biofuels can be obtained as alternative fuel candidates.
Biofuels are key components for energy sector, because biofuels are clean alternatived to the fossil fuels. They could reduce the dependence on oil all around the world. Biofuels produced from renewable resources reduce the carbon dioxide emissions compared to fossil fuels. They are environmental friendly. Bofuels are produced from agricultural products and wastes, so biofuel production and utilization offer both the employment opportunities and the new incomes for rural areas. Each country use its own domestic sources. Eventually it supports the agro-economy.
Biofuels are basically classified into four groups considering their production methods and feedstocks. First generation biofuels are produced from agricultural feedstocks. Especially bioethanol is obtained from sugar- and starch-based feedstocks. Second generation biofuels are…..Production of these fuels targets the usage of non-food feedstocks and is converted from lignocellulose-based feedstocks. Third generation biofuels are fuels obtained from algae, or liquid or solid biofuels obtained by integrated biorefinery technology from trees, grass, weeds, wastes, residues, and new oilseeds, or biofuels produced from genetically modified vegetables containing less lignin and more cellulose. Fourth generation biofuels, also known as carbon negative biofuels, are obtained from genetically modified raw materials. It is mainly aimed to provide lower carbon dioxide (CO2) emissions released to the atmosphere with the developed technologies. It is unknown how soon after 2030 they will be used commercially.
Biorefinery is an integrated and multifunctional overall concept that uses biomass as a diverse source of raw materials for the sustainable and simultaneous generation of a spectrum of different intermediates and products. All biomass components could be utilized in biorefineries. First, pretreatment and conditioning are applied to biomass. Primary refining involves the separation of biomass components into intermediates such as cellulose, starch, sugar, lignin etc. Secondary refining defines the conversion and processing of these intermediates to many finished or semi-finished products. These technologies alter depending on biomass characteristics. New processes and methods are classified into four groups: chemical processes (milling, extraction, sieving etc.), Physical processes, thermochemical processes, and biological processes (enzymatically catalysed conversions, fermentation etc.). Currently a flexible product mixture that involves biochemicals, biomaterials, and biofuels, as well as the production of heat, cold, and electricity can be obtained by using different conversion technologies.
Biorefineries are similar to oil refineries.They are used to produce chemicals, materials and fuels. While biorefineries use biomass (sugar based, starch-based, lignocellulose-based feedstock, oil crops, aquatic biomass (algaes and seaweeds), organic residues and wastes; oil rafineries use petroleum or natural gas as a source.The co-products can also be food or feed.
Bioethanol, also known as fuel ethanol, is the most important internal combustion engine fuel among other biofuels and it is the most preferred biofuel in the world. Bioethanol is produced from sugar-based feedstocks (such as sugar beet, sugar cane and sweet sorghum), from starch-based feedstocks (such as corn, wheat, cassava, patato and sorghum).Finally it is produced from lignocellulosic feedstocks such as stalk, straw, branch and root. When it is produced from sugar- or starch-based feedstocks, it is defined as first generation bioethanol. When it is produced from lignocellulose-based feedstocks, it is defined as second generation bioethanol. The properties of bioethanol is shown in Table.
At the present, bioethanol is utilized in different proportions as a substitute of gasoline and diesel (E-Gasoline: gasoline including a maximum of 5% alcohol). Gasohol including 20% ethanol and 80%gasoline. E20, E25, E85 including 20, 25,85% ethanol and E-diesel, also known as oxydiesel and diesehol, refers to diesel fuel containing maximum fifteen percent ethanol. Gasohol is the primary alternative for gasoline with its high performance and clean burning characteristics and E-Diesel is the alternative for diesel. Blending bioethanol with gasoline or diesel fuel decreases the cost and emissions and increases the octane rating.
I would like to mention about the Current Situation and the Future of Bioethanol in Turkey, the EU and the World
According to the declaration of EMRA (Energy Market Regulatory Authority of Turkey) in 2011, today it is compulsory to use 2% ethanol blends (2 percent ethanol 98 percent petroleum) without special consumption tax in Turkey and this ratio will be 3% in 2014. According to the ethanol blends, bioethanol demand will increase simultaneously.
There are three bioethanol plants established in Turkey: Tarkim, which is the first E2 (2 percent ethanol and 98 percent petroleum) supplier in the liquid fuel sector, Tezkim and Cumra. Tarkim and Tezkim have severally 40 million liters of annual bioethanol production capacity [1]. Cumra annually supplys 84 million litres bioethanol, which is 56% of the bioethanol production in Turkey. Also, Eskisehir Sugar Plant has an annual capacity of 20 million liters. While Cumra produces bioethanol from sugar beet, Tarkim produce from corn and Tezkim produce from wheat and corn. Total established capacity of bioethanol production is 190 million liters. However in 2012, less than 30 million liters bioethanol is produced in Turkey.
The European Union is only a minor producer of bioethanol compared to the United States and Brazil. In the EU, bioethanol represented about 28 percent of the total biofuels market in the road transport sector on volume basis in 2011. The main feedstocks are wheat, corn, rye, barley, sugar, and beet.
Looking the bioethanol production statistics, all around the world the largest producer is USA. The country has two hundred and four bioethanol plants and produces bioethanol from corn.
Brazil the second bioethanol producer, it has three hundred thirty five bioethanol plants. Brazil produced bioethanol from sugar cane.
And the third producer is China, produces from corn. Also cassava and sweet patato are competitive feedstocks for China.
All over the world the bioethanol blends are commonly used in the transportation sector. A lot of countries mandate the usage of bioethanol to increase their greenhouse gas emissions. For example, Brazil mandate to use E20-E25 and also the flexi-fuel cars could use E85. In USA, E15 is mandated in 10 states.
Production method of bioethanol differs according to the feedstock used. Here is the production diagram of the bioethanol. Extraction for sugar based feedstock, saccharification for starch-based feedstock are applied. For cellulose-based feedstock, first pretreatment and hydrolysis is applied to convert fermentable sugars. After fermentation, fermented mash is distilled and dehydrated to produce bioethanol with 99% purity.
At the beginning of the process, sugar cane is washed, crushed, and milled to extract the juice and produce bagasse. In the clarifier, the pH of the juice is adjusted, impuruties are removed and press mude is separated and used commercially as a component of animal feed. The stream is fed to the fermentor. Yeast is added. The fermentation is carried out at 30-32 and pH is between 4-4.5. Subsequently fermented mash (fermented wort, beer, wine) is fed to the concentration column, the rectification column for distillation and to molecular sieves for dehydration. Yeasts are centrifuged and sent back to the fermentor. The stillage (the bottom product of the concentration column) is sent to the evaporator to generate concentrated stillage, which is used as fertilizer. 1. washing tank 2. mill 3. clarifier 4. rotary drum 7. absorber12.combustor 13. turbogenerator
Bioethanol could be produced from starch-based feedstocks such as corn, wheat and patato. The most used feedstock is corn, I try explain the production from corn. The process is divided by dry milling and wet milling. In dry milling, the whole grain is directly included to the production.In wet milling, Starch is separated from all other corn kernel components such as fiber, gluten, germ, oil.
After cleaning, water, germ meal, fiber and gluten is separated from starch. All defined as corn gluten meal could be used as feed supplement. Also starch could be employed as syrup. In mashing step, starch is dissolved in water with temperature effect. In liquefaction, alfa amylase degrade starch into oligosaccharides and dextrin and in saccharification glucoamylase convert these small molecules into sugars. After fermentation, distillation and dehydration, bioethanol is obtained.
The initial steps of dry milling are cleaning, milling and mashing. The impurities are cleaned and corn kernels are crushed by mechanical mills. Same as wet milling liquefaction, sacharification, fermentation and distillation are carried out. While distillate is dehydrated to obtain bioethanol. Residues are centrifuged and dryed to obtain Dried Distillers Grains and Solubles.
Lignocellulose-based bioethanol depends on pretreatment, hydrolysis, fermentation, distillation and dehydration steps. Plant cell microfibrils are composed of cellulose, hemicellulose and lignin. To release the pentose and hexose sugars for fermentation, this structure should be broke down.
Because of the robust structure of plant wall cell, it requires pretreatment to improve enzyme accessibility in enzymatic hydrolysis. In brief, pretreatment is essential
For this project, I’ve visited Konya Sugar Industry and Trade Inc operates under the umbrella of pankobirlik (Sugar Beet Producers’ Cooperative of Turkey) . Bioethanol production plant takes part in Cumra Integrated Sugar Plant, which is established in 2007. It is totally located on the land of 53.000 m2 and 11.600 m2 of the area is closed area, 280.000 Litres/day of bioethanol is produced in the plant. Also, the annual capacity of bioethanol production of the plant is 84.000.000 Litres. The Bioethanol Production Plant is divided by seven parts. D type ethanol refers to the ethanol which is used in the chemical industry as a raw material.
The sugar beet is first extracted in the Sugar Production Plant. Thick juice including 60-62% of sugar or the molasses including 48% sugar are feedstocks of bioethanol production. The co-product is vinnasse (stillage) which is nonvolatile substances and suspended solids along with the culture broth. Vinasse is sold commercially as fertilizer and animal feed additive.
Thick juice is fed from thick juice tanks and mollesses is fed directly to the feedstock tank. In dilution tank, water and vinasse is addedd according to the sugar and dry matter content of feedstock. At the start, yeast culture is in a small tube and cultivated in the laboratory. The yeast cultivation is carried out in three different sized aerated bioreactor. They are cultivated gradually for 8 hours.The goal is to achieve the desired amount of the yeast in a controlled manner. Yeast culture and molesses are mixed in fourth yeast cultivation tank, then transferred to y.activation tanks. In 4 fermenters, fermentation is carried out and ethanol is obtained by 10%. BATCH. Fermented mash is pumped to yeast sedimentation tank in which yeast are sedimented and sent back to y. Act.tanks. These condensed yeasts and inactive bacterias acidify the medium in the yeast activation tanks. The intermediate tank balance the batch and continuous regimes. In the degasser column above the conct.c., fermented mash is condensed to 25%. In cont. To 40-45 %. In rectification column, 96%. The anhydrous ethanol next enters to the molecular sieves that adsorb the remaining water to produce pure (99.9%) ethanol.
