PRODUCTION OF

BIOETHANOL
Graduation Project Presentation
Ceylanpnar ATAY
18.06.2013
Advisor:
Prof. Dr. Filiz
KARAOSMANOLU
Jury Members:
Prof. Dr. Sadriye
KKBAYRAK OSKAY

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 world
Literature Search
Definition

Production
of
Bioethanol

Biofuels and
Biorefinery

Bioethanol
in Turkey,
the EU, and
the world

Plant Examination
Visit
Konya Sugar
Industry and
Trade Inc.

Introduction

Woody Residues
and Energy
Forests

Oil Seed Plants

Carbo-hydrate
Plants

Biomass
Electricit
y
Heat &
Cold

Bioma
ss

Vegetal Wastes

Animal Wastes

Industrial and
Municipal Wastes

Algaes

Fiber Plants

Biofuels

Biofuels

Alternative to the Fossil

Fuels
Environmental Friendly

Biom
ass

Agro-economy

Biofuels
Bioethanol
Biodiesel,
Bio-ethyl
tertiary
butyl ether
and Biogas

Biofuels from
Algaes or
Genetically
Modified
Vegetables and
by Integrated
Biorefinery
Technology

Bioethanol,
Biodiesel,
Biomethyl,
Biobuthyl,
Biomethyl
tertiary buthyl
ether and
Biomethane,
Biohydrogen etc.

Biofuels from
Genetically
Consummate
d Vegetables

Biorefineries

Heat &
Cold,
Electricity

BIOMA
SS

Pretreatme
nt and
Conditioni
ng
Primary
Refining

Sugar
Starch
Cellulose
Lignin

Chemical,
Physical,
Thermochemi
cal and
Biological
Processes
Secondary

Biofuels
Biomaterials
Biochemicals

Biorefineries
Oil
Refineries

Petroleum
& Natural
Gas

Petrochemi
cal Process

Biorefine
ries

End Products

Sugar-based
Biorefini Starch-based
Lignocelluloseng
based
Oil Crops
Aquatic Biomass
Organic Residues
Food & Wastes
Feed

Theoretical Study

10

Bioethanol (Fuel Ethanol)

An alternative fuel for internal combustion
engines
The most preferred biofuel
Properties
Formula

Bioethanol

Molecular Weight
(g/mol)
Carbon (w/w, %)
Hydrogen (w/w, %)
Oxygen (w/w, %)
C/H ratio (wt)
Specific Weight (kg/L)
Vapor Pressure (at 38
o
C) (mmHg)
Boiling Temperature
(oC)
Solubility in Water
Stoichiometric
(air/EtOH)
Lower Heating Value
(kcal/kg)
Ignition Temperature
(oC)
Specific Heat (kcal/kg
o

Value
s
C2H5O
H
46.1
52.1
13.1
34.7
4
0.79
5
0
78.5

9
6400
3
5
0.

11

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

The Current Situation & the Future

of Bioethanol
in Turkey, the EU and the World

Turkey

201
4
201
3

Legal
Regulati
on of
EMRA

Blending
%
Bioethan
ol
Demand
(m3)

2013

2014

50000

75000

Turkey
Bioethanol plants established in Turkey:
Plant
umra
Tezkim
Tarkim
Eskiehir

Annual
Capacity

Feedstock
(s)

Total Established
84 Capacity
million
Sugar
of
liters
Beet
Bioethanol
40 million
Wheat
Production
liters
Corn
190
million liters
40 million
liters
20 million
liters

Corn

Sugar
Beet

City
Konya
Adana
Bursa

Bioethanol
Eskiehir
Production
in 2012
< 30 million liters

15

The European Union

Bioethanol Production Capacity in the EU (million
liters)
Calend

A minor bioethanol
er
producer compared
Year
to the US and Brazil Benelu

2006 2007 2008 2009 2010 2011 2012 2013

r

19

37

76

143

380

696

294

539

746

906

942

430

397

580

752

Kingdo

44

70

m
Spain
Poland

405
162

359
120

323
1,63
3

28% of the total

France
biofuel market in the Germa
road transport in 2011 ny

1,01

1,01

949

3
949

3
949

765

730

759

823

70

278

190

253

316

346
114

465
165

471
194
1,14

465
171
1,41

465
203
1,29

465
228
1,39

310
1,80

655
2,58

970
3,47

7
4,17

9
4,62

5
5,00

6
5,38

United

Wheat
Corn
Rye
Barley
Sugar
Beet

Other
Total

16

World
Bioethanol Production of the World (billion
COUNTRIES
2009
2010
2011
liters) 2008
54,00
USA
36,388 42,177 49,440
0
21,00
BRAZIL
27,146 26,075 28,680
0
CHINA
6,900
7,300
7,000
2,100
INDIA
2,063
1,588
1,938
1,681
BRAZIL
USA
CHINA
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
Third
Largest
Second
Bioethanol
Bioethanol
Bioethanol
Producer
Producer
Producer
INDONESIA
200
220
250
SOUTH
160
169
172
Asias
204 Bioethanol
335
Largest Production
KOREA
Plants
ITALY
111
115
110
Corn, Cassava, Sweet PatatoOTHER
4,338
4,865
5,374
Corn ethanol
Sugar
Cane
COUNTRIES
WORLD
83,554 89,901 101,37 109,5

17

World
The Global Bioethanol Blending Mandates and Common
Usages
Country
Mandates
Country
Mandates

Argentine
Australia
Brazil
Canada
China
Colombia
Costa rica
India
Jamaica
New
Zealand
Pakistan
Paraguay

[M] or

[M] or

Usages
E5 [M]
E10

Usages
E8 [M]
E10 [M]

E20-E25 [M],
E85
E5 [M]
E10
E10 [M]
E7 [M]
E5 [M]
E10 [M]
E10
E10
E18-E24 [M]

Peru
The
Phillippines
Austria

E10

Denmark
Finland
France
Germany
Ireland
Romania
Sweden

E5
E5-E10 [M]
E5-E10
E5-E10
E4 [M]
E4 [M]
E5 [M], E85E95
E15 [M], E10E85

USA

18

Production Methods of Bioethanol

Sugar Extraction
Platfor
m

Starch Saccharifica
Ferment Distillation >90%
Sugars Fermentati
Platfor tion
ed Mash
Ethanol
m
on
Hydrolysis
Cellulo
Pretreatm
se
ent
Platfor
m

Cellulose

Dehydrati
on
>99%
Ethanol
19

Sugar-based Bioethanol Production

Saccharomyc
es Cerevisiae

Fermentation
30-32
Ethanol-water pH 4.0-4.5
separation methods,
48 h
Pressure-swing
distillation Batch
Azeotropic
distillation
Semicontinuo
Extractive distillation
us
Adsorption
Continuous
Pervaporation

Sugar
Beet

Sugar Cane

Sweet
Sorghum
1

Washing
tank

Concentration
Column

2
3

Mill
Clarifier

Rectification
Column

Rotary
Drum

10

Molecular Sieves

Fermentor

11

Evaporator

Centrifuge

12

Combustor

20

Starch-based Bioethanol
Production
Corn
Corn

Wet Milling
Starch is
separated from all
other corn kernel
components such
as fiber, gluten,
germ, oil

Dry Milling

Wheat

The whole grain is

directly included
to the production
Patato

21

Starch-based Bioethanol
Production
Wet
Milling
Corn
Mashing

Steeping

Liquefaction

Germ
Meal

Degerminati
on

Saccharificat
ion

Glucoamylase

Fiber

Defiber

Fermentatio
n

Yeast

Water

CO

Glute
n
Syrup

Gluten
Separation
Starch

amylase

Wheat

Patato

Corn
Glut
en
Feed

Corn

Cleaning

Distillation
Dehydration

Bioethano
l

22

Starch-based Bioethanol
Production
Dry
Milling
Corn

Cleaning

Milling

Mashing

Fermentation

Saccharification

Liquefaction

Distillation

Distillate

Dehydration

Wheat

Bioetha
nol
Patato

Residues
Centrifugation

Corn

Distillers
Grains and
Solubles

Drying
DDGS
(Dried Distillers
Grains and
Solubles)

23

Lignocellulose-based Bioethanol
Production
Lignocellulosebased
Feedstocks
Pretreatmen
t
Hydrolysis
Fermentatio
n
Distillation
Dehydration
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

Lignocellulose-based Bioethanol
Production
Ozonolysis
Lignocellulosebased
Feedstocks
Pretreatmen
t
Hydrolysis
Fermentatio
n
Distillation
Dehydration
Bioethanol

Ozone to degrade the lignin and

Acidic Hydrolysis
Mechanical
hemicellulose

Steam
Explosion (Autohydrolysis)
Comminution

Dilute Acid Hydrolysis:

1-3%
of H2SO4 atAcid
200-Hydrolysis
Physical
Dilute
/Concentrated
A combination
of
chipping,
Biomass is heated using high pressure
Pretreatment
240
grindling,
andnitric
milling
Sulfuric acid,
acid, hydrochloric acid,
steam (20-50 bar, 160-290 ) and
Chemical
Concentrated Acid
Hydrolysis:
high acid to
phosphoric
acidprovide
and peracetic
Pyrolysis
decompressed to the atmospheric
Pretreatment
yield of free sugars
(90%)
The
heating
the biomass
increase
the porosity
Alkaline Hydrolysis
pressure
in the absence of oxygen
PhysicochemicalSodium hydroxide, ammonia, calcium
or with
a smallFiber
amount
of
Ammonia
Explosion
(AFEX)
Pretreatment
Enzymatic Hydrolysis
oxygen
hydroxide and oxidative alkali (NaOH +
Biomass carried
is exposed
Commonly
outby
athigh temperature
Microorganisms
such
as brown-,
Biological
H
O3)
2O2 or
high
(400andtemperatures
pressure
white-,
fungi are used
Pretreatment 700
) and soft-rot
Organosolv
Pretreatment
Carbon Dioxide Explosion
An organic
solvent
mixture
with inorganic
It does not
cause
to the formation
of
acidinhibitors
catalystscompared
to removetolignin
AFEX and steam
Ionic
Liquids Pretreatment (ILs)
explosion
To dissolve the cellulose and lignin

25

Plant Examination Visit

26

Konya Sugar Industry and Trade

Inc.

Established
in 2007
Raw Material
Storage
Totally
located on the land of
Fermentation
53.000
m3 and Evaporation
Distillation

Cumra Integrated Sugar Plant

Bioethanol Production Plant

Closed
is 11.600 m3
MSDHarea
(Dehydration)
280.00
bioethanol
D typeL/day
Ethanol
Plant
84
millionFertilizer
liters annual
Organic
Plant
capacity
Filling and Handling Plant

27

Bioethanol Production from Sugar

Beet

Sugar Beet

Molasses

Bioethanol
Thick Juice

Vinasse

Fertilizer

Animal
Feed
Additive
28

Bioethanol Production from Sugar

Beet
Yeast Culture
Thick Juice TanksTubes

Conclusion
Biofuels produced from
biomass
clean alternatives to fossil fuels
could help to reduce the worlds depence on oil
domestic resource

Bioethanol
an important alternative fuel for internal
combustion engines in Turkey, the EU and the
world
Bioethanol production is successfully applicable to
the biorefinery concept

Special thanks to

Prof. Dr. Filiz KARAOSMANOLU,

Prof. Dr. Sadriye KKBAYRAK OSKAY
Prof. Dr. Hikmet SKENDER
Dr. Asl ler
Research and Training Assistant Nazl
ERDNMEZ BORAND
The Union of Sugar Beet Growers
Cooperatives
Dr. Figen AR
Executive Assistant Melek Tongur
Konya Sugar Industry and Trade Inc.
Bioethanol Production Manager Muammer
Alan
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

Bioethanol
Bioethanol

Ethylene
Hydrogen
Glycol ether
Ethyl Acrylate
Acetic Acid
Ethyl Acetate
Ether
Ethyl Chloride

Biorefineries

Biorefineries

Product Stream

Cellulose, hemicellulose,
and lignin in one product
stream

Pretreatment
Technique
Mechanical
communition,
irradiation,
biological
pretreatments,
and ionic liquids

Fermentation Strategies

Co-fermentation or sequential fermentation of

pentose and hexose if no further pretreatments
are used.

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
Solubilized lignin and
Alkali,
or co-fermentation.
hemicellulose sugars in organosolv, AFEX,
Without liquid and solid separation, solubilized
liquid phase and cellulose
ARP, wet
oligomeric hemicellulose sugars in the liquid
in solid phase
oxidation
might need depolymerization.The solid cellulose
portion will need hydrolysis. Then, the pentose
and hexose will undergo co-fermentation or
sequential fermentation.
With liquid and solid separation, liquid might
Uncatalyzed and
need pentose or both pentose and hexose
catalyzed (SO2,
fermentation. The solid cellulose will be
CO2) steam
hydrolyzed and fermented into ethanol
Solubilized hemicellulose explosion, liquid
straightforward.
Without liquid and solid seperation, solid
sugars in liquid phase
hot water, pHhydrolysis is need first. Depending on the
and lignin and cellulose
controlled liquid
pretreatment severity, the solubilized
in solid phase
hot water, dilute
hemicellulose oligomeric sugars might need
acid
depolymerizaiton first. And then mixture of
pretreatment, wet