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PRODUCTION OF BIOETHANOLGraduation Project Presentation
Ceylanpınar ATAY18.06.2013
Advisor: Prof. Dr. Filiz KARAOSMANOĞLU
Jury Members:Prof. Dr. Sadriye KÜÇÜKBAYRAK OSKAY
Dr. Hikmet İSKENDER
Content Aim of the Project
Introduction
Theoretical Study
Plant Examination Visit
Conclusion 2
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 worldLiterature 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
Introduction
4
Biomass
Woody Residues and Energy Forests
Oil Seed Plants
Carbo-hydrate Plants
Fiber Plants Algaes
Industrial and Municipal Wastes
Animal Wastes
Vegetal Wastes
Biofuels 5
ElectricityHeat & Cold
Biomass
Biomass
• Alternative to the Fossil Fuels
• Environmental Friendly
• Agro-economy
6
Biofuels
1st Generation Biofuels (2000-2010)
2nd Generation Biofuels (2010-2030)
3rd Generation Biofuels (2030- )
4th Generation Biofuels (2030- )
Biofuels
Bioethanol Biodiesel, Bio-ethyl tertiary butyl ether and Biogas
Bioethanol, Biodiesel, Biomethyl, Biobuthyl,
Biomethyl tertiary buthyl ether and
Biomethane, Biohydrogen etc.
Biofuels from Algaes or Genetically
Modified Vegetables and by Integrated
Biorefinery Technology
Biofuels from Genetically
Consummated Vegetables
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Biorefineries
Pretreatment and
Conditioning
Chemical, Physical,
Thermochemical and Biological
Processes
BiofuelsBiomaterialsBiochemicals
BIOMASS
SugarStarchCellulose Lignin
Primary Refining
Secondary Refining
Heat & Cold, Electricity
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Biorefineries
Petroleum & Natural Gas
Sugar-basedStarch-based Lignocellulose-basedOil CropsAquatic Biomass Organic Residues Wastes
Petrochemical Process Biorefining
End Products
Food & Feed
Oil Refineries Biorefineries
9
Theoretical Study
10
Bioethanol (Fuel Ethanol)
Properties ValuesFormula C2H5OHMolecular Weight (g/mol) 46.1Carbon (w/w, %) 52.1Hydrogen (w/w, %) 13.1Oxygen (w/w, %) 34.7C/H ratio (wt) 4Specific Weight (kg/L) 0.79Vapor Pressure (at 38 oC) (mmHg)
50
Boiling Temperature (oC) 78.5Solubility in Water ∞Stoichiometric (air/EtOH) 9Lower Heating Value (kcal/kg) 6400Ignition Temperature (oC) 35Specific Heat (kcal/kg oC) 0.6Melting 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
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
The Current Situation & the Future of Bioethanol
in Turkey, the EU and the World
13
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
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:
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)
WheatCornRye
BarleySugar Beet
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WorldCOUNTRIES 2008 2009 2010 2011
USA 36,388 42,177 49,440 54,000BRAZIL 27,146 26,075 28,680 21,000CHINA 6,900 7,300 7,000 2,100INDIA 2,063 1,588 1,938 1,681
FRANCE 1,545 1,790 1,850 1,100CANADA 950 1,320 1,500 1,800
GERMANY 815 1,015 1,120 800ENGLAND 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
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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
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Production Methods of Bioethanol
Sugar-basedBioethanol Production
Starch-basedBioethanolProduction
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
Sugar-based Bioethanol Production
Saccharomyces Cerevisiae Sugar Beet
Sugar Cane
Sweet Sorghum
Fermentation30-32
pH 4.0-4.548 h
• Batch • Semicontinuous• Continuous
20
1 Washing tank 8 Concentration Column
23
MillClarifier
9 Rectification Column
4 Rotary Drum 10 Molecular Sieves
5 Fermentor 11 Evaporator
6 Centrifuge 12 Combustor
7 Absorber 13 Turbogenerator
Ethanol-water separation methods,• Pressure-swing distillation• Azeotropic distillation• Extractive distillation• Adsorption• Pervaporation
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
Starch-based Bioethanol Production
Mashing
Starch
Gluten Separation
Defiber
Degermination
Steeping
Cleaning
Corn
Corn
Wheat
Patato
Syrup
GlucoamylaseSaccharification
Liquefaction
Bioethanol
YeastFermentation
22
Distillation
Dehydration
Water
Germ Meal
Fiber
Gluten
Corn Gluten Feed
α-amylase
CO2
Wet Milling
Starch-based Bioethanol Production
Distillation
Fermentation Saccharification Liquefaction
MashingMillingCleaningCorn Corn
Wheat
Patato
Distillate
Residues
Centrifugation
Dehydration Bioethanol
Distillers Grains and Solubles
Drying
DDGS(Dried Distillers Grains and Solubles)
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Dry Milling
Lignocellulose-based Bioethanol Production
Pretreatment
Dehydration
Distillation
Fermentation
Hydrolysis
Lignocellulose-basedFeedstocks
Bioethanol
To decrease cellulose crystallinity
To increase the porosity of the lignocellulosic biomass
To release or partially degrade the lignin
To provide the enzyme accessibility
To ensure the formation of sugars
24
Lignocellulose-based Bioethanol Production
Pretreatment
Dehydration
Distillation
Fermentation
Hydrolysis
Lignocellulose-basedFeedstocks
Bioethanol
Physical Pretreatment
Chemical Pretreatment
Physicochemical Pretreatment
Biological Pretreatment
Mechanical ComminutionA combination of chipping, grindling, and milling
PyrolysisThe heating the biomass in the absence of oxygen or with a small amount of oxygenCommonly 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
Plant Examination Visit
26
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
Bioethanol Production from Sugar Beet
Sugar Beet
Vinasse
Bioethanol
Thick Juice
Molasses
Animal Feed AdditiveFertilizer
28
Thick Juice Tanks
Yeast Culture Tubes
Bioethanol Production from Sugar Beet
29
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
Special thanks to Prof. Dr. Filiz KARAOSMANOĞLU,
Prof. Dr. Sadriye KÜÇÜKBAYRAK OSKAY Prof. Dr. Hikmet İSKENDER
Dr. Aslı İşlerResearch and Training Assistant Nazlı ERDÖNMEZ BORAND
The Union of Sugar Beet Growers CooperativesDr. Figen AR
Executive Assistant Melek Tongur
Konya Sugar Industry and Trade Inc.Bioethanol Production Manager Muammer Alşan
Bioethanol Production Chief Alparslan V. Dereli
Back-up Slides
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.
Bioethanol
Ethylene
Hydrogen
Glycol ether
Ethyl Acrylate
Acetic Acid
Ethyl Acetate
Ether
Ethyl Chloride
Bioethanol
Biorefineries
Biorefineries
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.