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

7

Biorefineries

Pretreatment and

Conditioning

Chemical, Physical,

Thermochemical and Biological

Processes

BiofuelsBiomaterialsBiochemicals

BIOMASS

SugarStarchCellulose Lignin

Primary Refining

Secondary Refining

Heat & Cold, Electricity

8

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

16

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

17

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

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)

23

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.