Nikos Papayannakos, Professor National Technical University of Athens School of Chemical Engineering Unit of Hydrocarbons and Biofuels Processing

UGent Francqui Chair 2013 | Inauguration Lecture

PRODUCTION ROUTES OF BIODIESEL FROM VEGETABLE OILS AND FATS

Nikos Papayannakos, Professor National Technical University of Athens

School of Chemical Engineering

Unit of Hydrocarbons and Biofuels Processing

14 February 2013

• Our University – School

• Introduction

Energy - Biodiesel

• Production Processes

• Thermal Process

• Catalytic Process Homogenous Heterogenous

• Enzymatic Process

• Biodiesel Characteristics

• Conclusions

PRESENTATION OUTLINE UGent/FCh13/IL

NATIONAL TECHNICAL UNIVERSITY OF ATHENS

• Oldest and most famous T. U. in Greece

• Founded in 1836

• Comprises the Schools of : - Chemical Engineering

- Civil Engineering - Architecture

- Mechanical Engineering - Electrical Engineering

- Mining and Metallurgical Engineering - Naval Architecture and Marine

Engineering - Rural and Surveying Engineering

UGent/FCh13/IL

14 February 2013

Founded in 1917

Consists of the Sections :

 Chemical Science

 Process Analysis and Plant Design

 Material Science and Engineering

 Synthesis and Development of Industrial processes

Incoming students : 140 per year 5 years studies

Courses : 9 Semesters Diploma Dissertation : 1 Semester

SCHOOL OF CHEMICAL ENGINEERING UGent/FCh13/IL

Academic Field

Chemical Reaction Engineering and Reactor Design Fields of applications

Environmental Friendly Conventional Fuels VGO/HVGO Hydrotreatment

Naphtha - Diesel Hydrodesulphurization Benzene Hydrogenation

Environmental Protection

Automotive Exhaust Gas Treatment Flue Gas Desulphurization

Waste / By products Upgrading

Refinery by-products / Used lubricants HDT Acidic Oils / Oleins TRE/HDT

Biofuels Production

Biodiesel production processes Green Diesel production

Renewable Diesel from HDT of Bio Oils

Research Topics

Simulation of the operation of :

• Laboratory Reactors

• Pilot Reactors

• Industrial reactors

Scale up / Scale down studies

• Hydrodynamics

• Mass transfer

• Reaction Kinetics

Reactor miniaturization

• String Bed Reactors UGent/FCh13/IL

14 February 2013

UNIT OF HYDROCARBON AND BIOFUELS PROCESSING

Basic Needs for Life

- Shelter/Accommodation - Food - Water

- Medicines

- Energy (Heating, cooking, lighting etc. ) - Basic commodities (Clothing, etc. )

Additional Needs of Modern Life

-

Transport

- Entertainment

- Various Commodities – Special Materials

UGent/FCh13/IL

-

Direct - One step Use (Heating space and water

-

Multiple steps

Photovoltaics and Concentrated Solar power (Solar Energy to Electric Energy to Final Form) Conversion into Chemical Energy

Solid : Coal, Lignite, Turf Fossil fuels - Liquid : Oils

Gas : Natural Gas

Renewable fuels - Biomass

Special Chemical transformations/circles - Photocatalysis

14 February 2013

The ways we use the Solar Energy UGent/FCh13/IL

Solid Biomass Liquid Biomass

Cellulose Glycerolipids Hemi cellulose

Lignin

Starch/Sugars

Biofuels

Conventional Bioethanol Biodiesel

New BTL-FT/Synthetic-fuels Green/Renewable Diesel Biofuels from Bio-Oils

Development of Biofuels

- Environmental Protection - Depletion of fossil feeds - Supply security

- Increase of energy demand

BIOMASS UGent/FCh13/IL

Consumption 2000 = 4.4 x Consumption 1950 Population 2000 = 2.2 x Population 1950

14 February 2013

World Population and Energy Consumption UGent/FCh13/IL

Source:

http://epp.eurostat.ec.europa.eu/cache/ITY_OFFPUB/KS-SF-10-043/EN/KS-SF-10-043-EN.PDF

EU-27 Gross Inland Consumption 2009

% of Total Consumption

UGent/FCh13/IL

The contribution of renewables in gross final energy consumption in EU-27

Source :

http://epp.eurostat.ec.europa.eu/cache/ITY_PUBLIC/8-18062012-AP/EN/8-18062012-AP-EN.PDF

% of Total Energy Consumption

Year

14 February 2013

UGent/FCh13/IL

Source :

http://epp.eurostat.ec.europa.eu/statistics_explained/index.php?title=File:Final_energy_consumption,_EU27,_2010_(1)_(%25_of_total,_based_on_tonnes_of_oil_equivalent).png

&filetimestamp=20121012130317

Energy Consumption by Sector in EU-27, 2010 (tn of oil equivalent)

UGent/FCh13/IL

EU-27 Total Energy Consumption for Transport

Source : http://epp.eurostat.ec.europa.eu/portal/page/portal/energy/data/database

14 February 2013

UGent/FCh13/IL

Evolution of Diesel/Kerosene/Gasoline Demand in EU

Gasoline Kero/Jet fuel

Total Light Duty Vehicles

Diesel to Vans and Trucks Diesel to Light Duty Vehicles

Milion Tonnes per year

1995 2000 2005 2010 2015 2020

Source : EBB : 916/COM/08

UGent/FCh13/IL

Fuel Energy content by weight

(lower calorific value, MJ/kg)

Energy content by volume

(lower calorific value, MJ/l)

Bioethanol (from biomass) 27 21

Bio-ETBE 36 (37 % from renewable sources) 27 ( 37 % from renewable sources)

Biomethanol (from biomass) 20 16

Bio-MTBE 35 (22 % from renewable sources) 26 (22 % from renewable sources)

Bio-DME (from biomassl) 28 19

Bio-TAEE 38 (29% from renewable sources) 29 (29 % from renewable sources)

Biobutanol (from biomassl) 33 27

Biodiesel 37 33

Fischer-Tropsch diesel (from biomass)

44 34

Hydrotreated vegetable oil 44 34

Pure vegetable oil 37 34

Biogas (a fuel gas produced from biomass and/or from the

biodegradable fraction of waste, that can be purified to natural gas quality, to be used as biofuel, or wood gas)

50 —

Petrol 43 32

Diesel 43 36

THE EUROPEAN PARLIAMENT AND OF THE COUNCIL DIRECTIVE 2009/28/EC-2009 14 February 2013

Transportation Fuels UGent/FCh13/IL

Benefits from the use of Biodiesel

1. Environmental : Closed CO₂ Cycle

2. Emissions : Low HC, CO, PM in exhaust gas 3. Biodegradability : 98 % in 21 days

4. Non-toxic

5. Low production and transportation cost 6. Miscibility with conventional Diesel

An ISSUE related to biofuel production

The competition of the raw materials for Biofuels with FOOD uses But, the TRUE DILEMMA

For our Society is the sharing of the available land for production of food and Energy either cultivating plants that can produce food or not

BIODIESEL was introduced to the market in Germany, France and Austria about 20 years ago and now it is the most widely used biofuel worldwide

for blends with petrodiesel to fuel Diesel engines.

BIODIESEL UGent/FCh13/IL

Source: LBST for EHA/DWV, Hydrogen & Renewables, 2008

Algae : x 10 - 50

14 February 2013

Driving Distance from one Hectare of Land UGent/FCh13/IL

U.S.

(National Biodiesel Board / http://www.biodiesel.org )

A fuel comprised of mono-alkyl esters of long-chain fatty acids derived from vegetable oils or animal fats, designated B100, and meeting the requirements of the American Society for Testing and Materials ( ASTM International ) D6751

What is Biodiesel?

UGent/FCh13/IL

European Union

DIRECTIVE 2009/28/EC OF THE EUROPEAN PARLIAMENT AND OF THE COUNCIL of 23 April 2009

Methyl-esters produced from vegetable or animal oil, of diesel quality, to be used as biofuel. (comply with EN 14214).

B I O D I E S E L

B a s i c S t a r t i n g M a t e r i a l s

 Vegetable Oils

 Animal Fats

Vegetable Oils

More than 98 % TG

BIODIESEL

Methylesters

Animal Fats

C₂H₅

(CH₂)₇COOH₃C

COOH₃C CH₃(CH₂)₇ (CH₂)₁₁COOH₃C

OILY SEEDS

(Cotton, Sunflower, Soya, Rapeseed etc.)

ALCOHOL MeOH

14 February 2013

From Flowers to Biodiesel UGent/FCh13/IL

Total EU

12000 10000 8000

6000

4000 2000 6000

0

EU Production ( in ‘000 tonnes ) ¹²⁰⁰⁰

10000 8000

6000 4000

2000

0 1998 2000 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011

Germany France Spain Italy Others EU

Total EU 500

3500

3000 2500

2000 1500 1000

Countries

Note : 2011 figures are only estimations

EU and Member States’ Biodiesel Production

Source :

European Biodiesl Board site : http://www.ebb-eu.org/studies.php

Biodiesel Production UGent/FCh13/IL

Transesterification Reactions

CH₂O

CH₂O CHO

CR₁ O

CR₂ O

CR₃ O

CH₂O

CH₂O CHO

CR₁ O

CR₂ O

H

CR₃ O O R

CH₂O

CH₂O CHO

CR₁ O

CR₂ O

H

+ ROH +

CH₂O

CH₂O CHO

CR₁ O

H

H

CR₂ O O R

CH₂O

CH₂O CHO

CR₁ O

H

H

CR₁ O O R

+

+ CH₂O

CH₂O CHO

H

H

H + ROH

+ ROH

OIL

Glycerine

(CH₃OH)

Biodiesel

14 February 2013

Transesterification Reactions UGent/FCh13/IL

1 Oil or Fat 1 Triglyceride

Catalyst

+ 3 Μethanols + 3 Alcohols

3 Μethyl-esters + 1 Glycerine H

H C C

O R₁ O

H C C

O R₂ O

H C C

O R₃ O

H

Transesterification

Catalyst + 3 CH₃OH

+

C O

R₁ O C H₃ C

O

R₂ O C H₃ C

O

R₃ O C H₃

+

H H C H O

H C H O

H C H O

H Ester Group

1 Free Fatty Acid + Catalyst 1 Soap + 1 Water RCOOH + NaOH RCOONa + H₂O Saponification

R1, R2, R3 : C16, C18, C20 (85 – 95% ) Saturated, Mono-, Di- and Tri- double bond unsaturated HC chains

Transesterification Reaction UGent/FCh13/IL

N.T.U.A.

CATALYTIC PROCESSES

Homogeneous Catalysis

a. Bases ( NaOH , KOH , CH₃ONa) b. Acids ( H₂SO₄, HCl, HNO₃ )

Methanol / Oil = 6 /1(mol / mol); Reaction Temperature : 61 – 64 ^oC Methanol / Oil = 30 / 1 (mol / mol); Reaction Temperature : 61 – 90 ^oC

Heterogenous Catalysis

a. Base catalysts b. Acid catalysts

Methanol / Oil = 6 /1 (mol / mol); Reaction Temperature 120 – 210 ^oC Methanol / Oil = 6 /1 (mol / mol); Reaction Temperature 120 – 210 ^oC

THERMAL PROCESS

ENZYMATIC PROCESS

Methanol / Oil = 6 /1 (mol / mol); Reaction Temperature 150 – 210 ^oC

Methanol / Oil = 3 / 1 (mol / mol); Reaction Temperature 30 – 45 ^oC

14 February 2013

Biodiesel Production Technologies UGent/FCh13/IL

• Advantages

– Treatment of acidic oils and feeds with high FFAs and water content

• Disadvantages

– Methanol excess – Long Reaction Time

– Severe Corrosion Effects from the Catalyst (strong acids )

– High Reaction Temperature

Production of Biodiesel by Acid Homogenous Catalysis UGent/FCh13/IL

O

R’ OR’’

H +

OR’’

OH R’

+

OR’’

OH R’ +

OH

R’ + OR’’

+

R O

H

R’

OH

OR’’

O R

H

+ ^-H+/R”OH O

R’ OR

C 1 C 2

C 3 Oil

Product

OH OH

R” = O-C-R_B

O-C-R_A O O OH

O-C-R_A O

OR OR

N.T.U.A.

Source:

Schouchardt U., Sercheli R., Vargas M., J. Braz. Chem. Soc., 1998, 9:199-210

14 February 2013

Mechanism of Acid Catalysis UGent/FCh13/IL

• Advantages

– Low methanol excess – Short reaction time

– Not high reaction temperature

• Disadvantages

– The treatment of acidic oils and feeds with high FFAs and water content is Problematic

Production of Biodiesel by Base Homogeneous Catalysis UGent/FCh13/IL

CH₂ CH R''COO

CH₂ O CR''' O R'COO

OR

R'COO

CH₂ CH R''COO

CH₂ O R''' OR

O R'COO

CH₂ CH R''COO

CH₂ O R'COO

BH

CH₂ CH R''COO

CH₂ OH R'COO

B

ROH B RO BH

ROOCR'''

CH₂ CH R''COO

CH₂ O R'COO

CH₂ CH R''COO

CH₂ O R''' OR

O

+

- -

(2)

-

+ ⁽³⁾

-

+ ⁺ + ⁽⁴⁾

+ - + + (1)

-

Source :

Schouchardt U., Sercheli R., Vargas M., J. Braz. Chem. Soc., 1998, 9:199-210

N.T.U.A.

14 February 2013

Mechanism of Base Catalysis UGent/FCh13/IL

Homogeneous Base Catalysis

Production of soaps from FFAs and water in Oil Loss of Oil Mass and Post-treatment

Catalyst consumption

Biodiesel, Glycerine need Post-treatment Homogeneous Acid Catalysis

High Methanol / Oil ratios Prolonged reaction time

Corrosive environment due to the presence of acid Biodiesel, Glycerine need Post-treatment

Thermal Process

High Reaction Temperature, Pressure Enzymatic Process

High Biocatalyst Cost / Low reaction rates Heterogeneous Catalysis

High Reaction Temperature, Pressure

Main Characteristics of Production Technologies UGent/FCh13/IL

Feedstocks

Rape seed Oil Sun flower Oil

Palm Oil Soya bean Oil Cotton seed Oil Acid Cotton Seed Oil

Jatropha seed oil Corn Oil

Used cooking Oils ( Olive Oil etc ) Waste Animal Fats

Rice bran oil Babassu oil

Developed Process

Homogeneous Base Catalysis

Processes

Under Development

Thermal

Heterogeneous Catalysis Enzymatic

14 February 2013

Technologies and Feedstocks UGent/FCh13/IL

EXPERIMENTATION

• Batch Reactor

• Sampling during operation

• Reaction Temperature : 150 – 210

C

• Reaction Pressure : 12 – 40 bar

Thermal and Heterogeneous Catalytic Processes UGent/FCh13/IL

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

0 200 400 600 800 1000 1200 1400 1600

Time (min)

Mass ratio (gr/gr)

Triglycerides Diglycerides Monoglycerides

T = 200 ^oC, MeOH / Oil = 6 / 1

Refined Cotton seed Oil

14 February 2013

Results of the Thermal Process UGent/FCh13/IL

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

0 200 400 600 800 1000 1200 1400 1600

Time (min)

Mass ratio (gr/gr)

Triglycerides Diglycerides Monoglycerides Acidity

T = 200 ^oC, MeOH / Oil = 6 / 1

Initial Acidity : 9.5 % wt Final Acidity : 2.9 % wt

Results of the Thermal Process UGent/FCh13/IL

Acidic Cotton seed Oil

1. Batch reactor

◊ Homogeneous mixture with constant density (d _mixture = constant)

◊ Isothermal – single phase mixture, apparent constant rates

2. Three reactions first order with respect to each reacting component

◊ Irreversible Triglycerides reaction TG + MeOH ME + DG

◊ Reversible Di- and Mono-glycerides reactions DG + MeOH ME + MG

MG + MeOH ME + GL

−

= = ⋅

⋅ ^ME

MG

eq,2 22 DG MeOH

K K C C

K C C

, −

= = ⋅

⋅

3 GL ME

eq 3 3 MG MeOH

K K C C

K C C

3. Equilibrium

14 February 2013

Kinetic Model for the Homogeneous Process UGent/FCh13/IL

Refined oils 1. Triglycerides

Acid oils (High FFAs)

= − ₁ ⋅ ⋅

TG TG MeOH

dC K C C dt

1 2 2

DG TG MeOH MG ME DG MeOH

dC K C C K C C K C C

dt = ⋅ ⋅ + ⁻ ⋅ ⋅ − ⋅ ⋅

2 3 2 3

MG DG MeOH GL ME MG ME MG MeOH

dC K C C K C C K C C K C C

dt = ⋅ ⋅ + ⁻ ⋅ ⋅ − ⁻ ⋅ ⋅ − ⋅ ⋅

2. Diglycerides

3. Monoglycerides

1ox TG MeOH ox

K C C C

− ⋅ ⋅ ⋅

1ox TG MeOH ox 2ox DG MeOH ox

K C C C K C C C

+ ⋅ ⋅ ⋅ − ⋅ ⋅ ⋅

2ox DG MeOH ox 3ox MG MeOH ox

K C C C K C C C

+ ⋅ ⋅ − ⋅ ⋅ ⋅

4 4 2

OX ox OX MeOH ox ME H O

dC K C C K C C

dt = − ⋅ ⋅ + ⁻ ⋅ ⋅

4. Acidity

UGent/FCh13/IL Kinetic Model for the Homogeneous Process

Solid Catalytic Systems for Biodiesel Production

Carriers / Catalysts Supported Active Phase Mesoporous Zeolites Occluded

X, Y, HY, H-ZSM-5, and H-Beta KOH, NaOH, MCM-41 CaO, SrO,

ETS-4 and ETS-10 KF, KI, K₂CO₃, KNO₃ ETS-10 (H) (Acidic form) CaMnO₃, Ca₂Fe₂O₅, Mesoporous Silicates CaZrO₃, CaCeO₃ SBA – 15

Oxides/Salts Ion-exchanged

Singe metal oxides Li, Na, K, Fe, Cs, Ba, Mg Basic Oxides MgO, CaO, ZnO, La2O3, BaO

Acidic Oxide Al₂O₃ Neutral Oxide SiO₄ Mixed metal oxides Al₂O₃–SnO, Al₂O₃–ZnO

Mg–La oxides, Mg–Al, and Li–Al oxides CaMnO₃, Ca₂Fe₂O₅, CaZrO₃, and CaCeO₃ Mesoporous MgAl2O4

Hydrotalcites

Mg–Al LDH lattices Acidic resins

Amberlyst-15, Nafion-NR50, Relite CFS Sulphonated Zirconia

Basic Requirements

1. No surface ( sites ) deactivation

2. No leaching

3. Robust activity in the presence of H₂O and FFAs

Application

1. Formulation into particles

2. Long term testing in a pilot

14 February 2013

Catalytic Process UGent/FCh13/IL

• Basic solid catalyst, consisting of magnesium (Mg) and aluminum (Al) in any molecular ratio Mg : Al ≥ 1 (1:1, 2:1, 3:1, 4:1)

• E.g. for molar ratio Mg:Al = 2:1 we have HT-2

• Thermal analysis

– The water content (12%) is removed after 180 ^oC up to 300 ^oC.

– The crystal structure remains unchanged up to 350 ^oC.

– The crystal begins to degrade at 350 ^oC by removing H₂O and CO₂, thereby forming MgO-Al₂O₃ solid that remains stable up to 800 ^oC.

– At 900 ^oC formed MgO and MgAl₂O₄.

( )

4 2 2 3

Mg Al OH CO mH O⋅

Η κρυσταλλική δομή του:

OH^- Mg²⁺, Al³⁺

OH^-

CO32-

, H2O 7,63 Å

OH^-

Mg²⁺, Al³⁺ 4,77 Å OH^-

CO32-

, H2O

Catalyst : Hydrotalcite

Catalytic Process UGent/FCh13/IL

( )

( ) (

)

( )

Mg Al OH CO mH O με

0 ≤x≤0,5

⋅

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

0 200 400 600 800 1000 1200 1400 1600

Time (min)

Mass ratio (gr/gr)

Triglycerides Diglycerides Monoglycerides

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

0 200 400 600 800 1000 1200 1400 1600

Time (min)

Mass ratio (gr/gr)

Triglycerides Diglycerides Monoglycerides Acidity

Refined Cotton seed Oil

Test Conditions :

Τ=200^oC, methanol / oil 6:1 , 1wt.% Catalyst (HAS)

Acidic Cotton seed Oil

Initial Acidity : 9.5 % wt Final Acidity : 2.9 % wt

14 February 2013

Results of the Catalytic Process UGent/FCh13/IL

Catalytic Kinetics and Mass Balances

( )

TGs

TGs,c TGs MeOH cat

dN k C C m

dt = − ×

( )

DGs

TGs,c TGs MeOH DGs,c MGs MEs DGs,c DGs MeOH cat

dN k C C k C C k C C m

dt = + ⁻ − ×

( )

MGs

DGs,c DGs MeOH MGs,c GL MEs DGs,c MGs MEs MGs,c MGs MeOH cat

dN k C C k C C k C C k C C m

dt = + ⁻ − ⁻ − ×

(

)

FFAs

FFAs,c FFAs MeOH FFAs,c MEs H O cat

dN k C C k C C m

dt = − + ×

( ) ( ) ( )

i

i thermal mi x i acid FFAs mix i cat cat.

dN r M r C M r m

dt = − − × − − × × − − ×

Thermal FFAs Catalysis Solid Catalyst

Kinetic Modeling of the Catalytic Experiments UGent/FCh13/IL

Total transesterification reaction rates

EXTRUDATES PRODUCTION

• HT2 treatment at 350 ^oC for a period of 6 h.

– Celite 545 (15 %wt) was used as adhesive material .

– The catalyst mixture HT2 - Celite was homogenized with the aid of water.

– The extrudates were dried for 24 h at room temperature and 24 h at 100 ^oC before the final heat treatment at 550 ^oC for 6 h.

– The final extrudates size : 5 - 6 mm length and 2 mm diameter

EXPERIMENTS USING THE CATALYST EXTRUDATES

• Reaction temperature : 180 ^oC and 200 ^oC.

• HT2 Catalyst mass : 2.5 wt. % of the initial oil.

• The extrudates were placed in a special metal basket protection.

• Raw materials :

– refined cottonseed with acidity less than 1 wt. %

– laboratory produced acidic cottonseed (with acidity 9.5 wt. %) – refined palm oil with acidity less than 1 wt. %

– Fried coconut oil with acidity 2.7 wt. %.

14 February 2013

Catalytic Extrudates from HAS (HT2) UGent/FCh13/IL

Catalytic Effect of Extrudates vs Thermal at 200 ^oC

Thermal

Thermal with basket Extrudates in basket

Reaction Time (h)

Mass fraction (gr/gr)

Deactivation study of HT2 extrudates at 200 ^oC

Experiment Experiment Experiment Experiment

Reaction Time (h) (h)

Mass fraction (gr/gr)

TGs consumption at 200 ^oC with different HT2 forms

Powder HT-2 Reused HT-2 Powder Calcined HT-2 powder at 350 ^oC Extrudates HT-2

Crushed HT-2 extrudates

Reaction Time (h)

Mass fraction (gr/gr)

Triglycerides Conversion with HAS Extrudates UGent/FCh13/IL

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

0 200 400 600 800 1000

Time (min)

Mass ratio (gr/gr)

TG DG MG

ACIDITY

0 0.05 0.1 0.15 0.2 0.25

0 200 400 600 800 1000

Time (min)

Mass ratio (gr/gr)

TG DG MG

ACIDITY

2

Removal

Equilibrium C_TG = 0.0wt.%

C_DG = 1.8wt.%

C_MG = 10.0wt.%

Acidity = 2.9wt.%

1^st removal C_TG = 0.0wt.%

C_DG = 0.5wt.%

C_MG = 4.5wt.%

Acidity = 1.4wt.%

2^nd Removal C_TG = 0.0wt.%

C_DG = 0.2wt.%

C_MG = 2.0wt.%

Acidity = 1.0wt.%

Τ= 200^oC Acid Cottonseed oil

Solid Catalyst (HAS)

1st Removal

14 February 2013

Glycerol Removal UGent/FCh13/IL

0 0.2 0.4 0.6 0.8 1

0 2 4 6 8 10

Time (h)

Mass fraction (g/g) Methanol

Ethanol

Ethanol Transesterification with HAS

Results with Various Feeds



 Refined - Cooked Palm oil

 Crude Animal Fat



 C_DG = 2.0 - 2.5 wt. %

 C_MG = 10.0 - 11.0 wt. %

HAS Extrudates Performance UGent/FCh13/IL

Typical Example

Process Conditions :

System: Semi - Batch reactor

Oil : Refined cottonseed oil Alcohol : Methanol / Gradual Addition

Methanol / Oil = 3 / 1 Batch size : 10 g

Temperature : 35 ^oC;

Biocatalyst : 4 %w/w Novozym 435

refined cottonseed oil

0 0.05 0.1 0.15 0.2 0.25 0.3

0 10 20 30 40 50

reaction time (h)

mass ratio (g/g) _{DG MG}

N.T.U.A.

refined cottonseed oil

0 0.2 0.4 0.6 0.8 1

0 10 20 30 40 50

reaction time (h)

mass ratio (g/g) _TGMethanol Addition

Methanol Addition

System Characteristics :

• Catalyst : Immobilized Lipases

• Lipase Acitivation

• No direct contact of methanol with Biocatalyst

• Temperature : 25 – 50 ⁰C

14 February 2013

Enzymatic Process UGent/FCh13/IL

Batch - Recycle System N.T.U.A.

Feed Tank

Reactor

Glycerin

Methanol Oil

Biocatalyst Stability and Deactivation Studies

• Biocatalyst – glycerin separation using solvents

Main Disadvantages:

• Rapidly contaminated by Oil Impurities and lose activity

• High Cost

Enzymatic Process UGent/FCh13/IL

Property Unit min max Biodiesel

Ester content %(m/m) 96.5 - 98.58

Density at 15^oC kg/m³ 860 900 883

Viscosity at 40^oC mm²/s 3.5 5 4.2

Flash point ^oC 120 - 172

Sulfur content mg/kg - 10 7

Cetane number 51 - 52.03

Water content mg/kg - 500 335

Copper strip corrosion (3h at 50^oC) Rating Class1 Class 1 1a Oxidation stability 110^oC Hours 6 - 6.9

Acid value mg_KOH/g - 0.5 0.15

Iodine value gr_iodine/100gr - 120 105.6

Linolenic acid methyl ester % (m/m) - 12 0.2

Polyunsaturated methyl esters % (m/m) - 1 0

Monoglyceride content % (m/m) - 0.8 0.6

Diglyceride content % (m/m) - 0.2 0.07

Triglyceride content % (m/m) - 0.2 0

Group metals (Ca, Mg) mg/kg - 5 < 0.6 / <

0.05

Group metals (Na, K) mg/kg - 5 0.08 / 0.15

Phosphorus content mg/kg - 10 0.5

S T A N D A R D S EN 14 214

Properties of Biodiesel from Cotton Seed Oil UGent/FCh13/IL

SAMPLE N.A. Additive 1 Additive 2 Additive 3 Biodiesel from Sunflower oil 1.63 h

≈ 0.03 % 2.12 h. 3.60 h. -

≈ 0.06 % 1.48 h. 5.45 h. 1.7 h.

≈ 0.25 % 3.55 h. 15.5 h. 3.15 h.

≈ 0.60 % 4.97 h. 23.8 h. 5.38 h.

Biodiesel from Cottonseed oil 6.03 h

≈ 0.03 % 6.15 h. 8.62 h. -

≈ 0.06 % 6.85 h. 11.8 h. 3.62 h.

≈ 0.25 % 8.63 h. 22.4 h. 6.50 h.

≈ 0.60 % 11.1 h. 38.6 h. 8.02 h.

Oxidation Stability according to ΕΝ-14214 Oxidation Stability Limit : 6.00 h (min)

N.T.U.A.

UGent/FCh13/IL

Sample Lubricity

(wear scar )

• Reference diesel ^* 551

• Diesel + 2% CME (v/v) 195

• Diesel + 5% CME (v/v) 153

• Pure Biodiesel (CME) 144

Deeply desulphurized diesel fuel that does not contain biodiesel has a lower lubricity and requires lubricity improving additives to prevent excessive engine wear.

Effect of Biodiesel addition on final fuel lubricity

14 February 2013

Sample

• ADO (Diesel) 54.3

• CME (Biodiesel ) 52.3

• ADO + 2% CME 53.9

• ADO + 5% CME 57.7

• ADO + 10% CME 58.0

Properties of Biodiesel – Diesel Mixtures UGent/FCh13/IL

Effect of Biodiesel addition on final fuel Cetane Number

* Max 460 : EN ISO 12156-1

N.T.U.A.



Biodiesel is produced by a rebuilding process of the molecular chains of the main constituent of the oils and fats, triglycerides

 Apart from the native vegetable oils, used-waste vegetable oils and fats as well as algal oils are important starting materials for biodiesel production

 The new processes being developed for Biodiesel production concern either the feed pretreatment or the transesterification reaction

 Feed acidity acts catalytically to transesterification reactions

 Thermal, non-catalytic reaction is an effective way to pretreat acidic feeds and produce methyl-esters

Conclusions 1/2 UGent/FCh13/IL



Solid catalysts will simplify the production process and produce clean glycerin

 Processes based on solid catalysts can be flexible and treat both acidic and refined vegetable oils and fats

 Enzymatic transesterification is a very attractive process but enzymes with better characteristics and lower price must be developed

 The major advantage of biodiesel among its rival biofuels is the relevant simplicity of its production processes while all of them originate from wells that will never dry.

14 February 2013

Conclusions 2/2 UGent/FCh13/IL

Contributors for this presentation :

Collaborators Companies

Diasakou M. Hellenic Petroleum Co.

Bikou E. Motor Oil

Louloudi A. Public Power Corporation

Barakos N. MINERVA

Pasias S. Soya Mills

Mitsios M. GF Energy

Aggelogiannaki E.

Acknowledgments UGent/FCh13/IL