Analysis of Political, Economical and Technical Aspects of Biodiesel

Analysis of Political, Economical and Technical Aspects of Biodiesel

- Effect of Additives to Improve the Performance at Low Temperatures -

Pedro Miguel Moura Lopes

Dissertation for obtaining a Master of Science degree in

Chemical Engineering

Coordinator (IST): Professor Dr. João Carlos Moura Bordado Coordinator (AZC): Dr. Robin Harrison

September 2007

Analysis of the Political, Economical and Technical Aspects of Biodiesel Fuel

Arizona Chemical Confidential Information 2

“Sometimes it takes darkness and the sweet confinement of your loneliness,

to learn that anything or anyone that does not bring you alive,

is too small for you.”

David Whyte,

Poet, Marine Zoologist (1955 - )



Fig. 1- Detail of the original US 608,845 patent filled by Rudolf Diesel in 1898 (Source: [1])



Foreword

The initial files used in the elaboration of the present document date back to July 2005, when I first

joined Arizona Chemical after my eight months internship period. Two years have passed ever since and there

has been an incredible amount of research conducted in the area of sustainable energy sources. As Dr. Rudolf

Diesel stated in 1912 “… there have been so many publications recently… on the construction of the Diesel

engine… it is hardly possible to give any fresh information on the subject. “ (Source: [12]). The exact same words

can be used regarding the overwhelming amount of technical literature currently available on biodiesel, such as

scientific and other type of publications covering multiple aspects, from new techniques to improve farming yields,

new and optimized transesterification methods, economical projections, energetic life cycle analysis, mechanical

modifications to the fuel injection system, etc. So, one may wonder what the relevance of this work is, i.e., why

another review of biodiesel? Truth is, almost without exception, the published literature mentioned above is

somewhat compartmented, covering in isolation one particular aspect: update of technical breakthroughs,

summary of political decisions or analysis of the vegetable oil market dynamics. It is, therefore, the intention of

the present work to establish an integrated approach to the biodiesel theme and to demonstrate the close

relationship that exists between political, economical and technical aspects. It is also the intention, based on the

information captured in the following pages, to present the disadvantages resulting from the use of biodiesel and

other first generation biofuels. If renewability is the end goal, other alternatives must urgently be investigated.

I intended with this document to present a detailed overview of the biodiesel theme, covering the state of

the art knowledge in the area and additionally provide a strong insight in future trends and energy scenarios.

Structurally, this document is divided in two main parts. Part one aims at discussing the reasons why the global

scale implementation of biofuels is a challenge that stands in a (delicate) equilibrium of three major parameters:

economical, political and technical. Reaching the European biofuels target utilization of 5.75% by 2010 implies a

significant increase in the current usage of renewable material, and presently the only two biofuels candidates to

achieve such quota in Europe, as well as globally, are bioethanol and biodiesel. Bioethanol, even though not

presented with the same depth of biodiesel, is mentioned throughout this first part. The second part is dedicated

to the behaviour of biodiesel at low temperatures, with emphasis on establishing the applicability of cold flow

improver additives. A patent was produced (WO 2006/105306) as an outcome of the experimental work and the

additive obtained has properties unique for a cold flow improver additive.

This document is to be presented and defended to a jury of professors in the Instituto Superior Técnico,

part of the Technical University of Lisbon, for obtaining a Master of Science Degree in Chemical Engineering.



Acknowledgements The completion of the present document was only possible to achieve with the guidance, support and patience of

a number of people that I have the privilege to interact, work and learn from.

I would like to express my gratitude to Dr. Robin Harrison, European Group Leader Oleochemicals, who enabled

me to verify that my concept of leadership by example is accurate and that is in fact the only true kind of

management style. Thank you for your continuous support and development opportunities, ever since my

internship period.

My sincere appreciation goes to Professor Dr. João César Bordado, for the knowledge and guidance provided,

both throughout my degree and during the preparation of this work.

I am deeply grateful to Dr. Robert Kaiser, European Marketing Manager for Fuels Additives, for all the leaning

and development opportunities that were given to me outside the direct scope of technology projects. Your

continuous support and encouragement have contributed undoubtly to my professional development.

I would like to express my gratitude to Dr. Roy Lofthouse, European Business Unit Manager Oleochemicals, for

the recognition of my dedication and work in Arizona, summon up by the 2006´s “I am Arizona” award that I was

granted with.

To Dr. Dries Muller, I would like to thank the numerous conversations and discussions held, regarding a great

number of subjects, some of which related with biofuels. They have enabled me to realise the long road that I still

need to travel in order reach your level of understanding and “dot connecting” ability. Godspeed my friend!

I would like give my most profound gratitude to my parents, Ana and Cristiano, for so many reasons…

And to Dr. Ana Paula Ferreira, a very special thank you, for forever being part of my train.



List of Abbreviations AGQM- Arbeitsgemeinschaft Qualitätsmanagement Biodiesel e.V. TME – Tallow Methyl Esters ATPA – Amine Terminated Polyamide TOFA – Tall Oil Fatty Acids

BLT – Bundesanstalt für Landtechnick SPF – Single Form Payment

BP – British Petroleum SVO – Straight Vegetable Oil

CAP – Common Agricultural Policy toe – Tonnes of oil equivalent, equivalent to 107 kilocalories or 41.86 GJ

CFI – Cold Flow Improver TG – Triglyceride

CI – Compression ignition UFOP - Union zur Förderung von Oel- und Proteinpflanzen”

CO Carbon monoxide ULSD – Ultra Low Sulphur Diesel

CO2 Carbon dioxide U.S. – United States of America

DSC – Differential Scanning Calorimetry UN – United Nations

DT – Developing and Threshold (countries) UK- United Kingdom

EBB – European Biodiesel Board UVO – Used Vegetable Oil

EDA – Ethylene Dialkylamine VOC - Volatile Organic Compounds

ETPA – Ester Terminated Polyamide

EU – Europe / European Union

EU-15 – European Union before the enlargement of 2004

EU-25 – Current and enlarged European Union

EVA – Ethylene Vinylacetate

FA – Fatty Acids

FCCC – Framework Convention on Climate Change

FFA – Free Fatty Acids

FOB – Free on Board

GC – Gas Chromatography

GDP – Growth Domestic Product

GHG - Green house gases

GJ – Giga Joule (1 x 109 Joules)

GToe – Giga tonnes of oil equivalent

HFRR - High Frequency Reciprocating Rig

IPCC – Intergovernmental Panel on Climate Change

IEA – International Energy Agency

IS – Injection System

IV – Iodine Value

J - Joule

km - kilometre

kWh - kilowatt/hour

LNG - Liquefied Natural Gas

LPG - Liquefied petroleum gas

LTP – Low Temperature Performance / Properties

Mtce - million tonnes of coal equivalent (1 Mtce = 0.7 Mtoe)

Mtoe - Million tonnes of oil equivalent

MW - megawatt = 1 watt x 106

NGO – Non Governmental Organization

NORDEN – Nordic Innovation Centre

NOx - Nitrogen oxides

NREL – National Renewable Energy Laboratory

OECD – Organization for Economic and Co-operation development

OPEC – Organization of Petroleum Exporting Countries

PROALCOOL – National Ethanol Program (Brazil)

RME – Rapeseed Methyl Esters

SI – Spark Ignition

SME – Soybean Methyl Esters



Index

Part I – Analysis of the Political, Economical and Technical Aspects of Biodiesel Fuel

1- Historical Introduction………………………………………………………………………………………....11 2- Political overview of Biofuels in Europe……………………………………………………………………..18 2.1- Energy Systems……………………………………………………………………………………..…18

2.2- Worldwide Reserves of Fossil Fuels and Demographic Growth………………………………………..…22

2.3- Emission of Green House Gases…………………………………………………………………….…34

2.4- European Policy on the Utilization of Renewable fuels……………………………………………...……40

3- Overview of the European Diesel and Biodiesel Market …………………………………………….……49

3.1- European Diesel Market Dynamics………………………………………………………………......…49

3.2- European Biodiesel Market Dynamics………………………………………………………………..…53

3.3- United-States Biodiesel Market…………………………………………………………………………60

3.4- Global Biodiesel Market……………………………………………………………………………...…61

4- Technical aspects of Biodiesel……………………………………………………………………………….66

4.1- Biodiesel definition……………………………………………………………..………………………66

4.2- Chemical Nature of Vegetable Oils and Animal Fats…………………………………………………..…67

4.3- Conventional Feedstocks for Biodiesel Production……………………………………………..….…….71

4.4 –Alternative Feedstock for Biodiesel Production……………………………………….…………………81

5- Straight vegetable oil…………………………………………………………………..………………...……85

5.1- Mechanical Modifications ……………………………………………………………..…………….…90

5.2- Microemulsifications……………………………………………………………..………………..……92

5.3- Pyrolysis/ Thermal Cracking……………………………………………………………..………..……93

5.4- Blends with Diesel………………………………………………..………………………………….…95

5.5- Transesterification……………………………………………………………..……………….………97



6- Transesterification……………………………………………………………..………………………………97

6.1- Homogeneous Basic Catalysis…………………………………………….…………………..……...101

6.2- Homogeneous Acid Catalysis…………………………………………………………………..……..103

6.3- The Integrated Process…………….…………………………………………………………..…..…104

6.4- Alternative Transesterification Processes………………………………...………………..…………..105

7- Overview of the Diesel Engine………………...………………………………………………..……….…109

8- Biodiesel Properties………………………………………………….…………………………..………….114

8.1- Foam Formation………….……………………………………………………………..……………115

8.2- Viscosity………….…………………………..………………………………………………….…..116

8.3- Electrical Conductivity………….…………………………..…………………………………………116

8.4- Presence of Water………….…………………………..………………………………………....…117

8.5- Corrosive Properties………….…………………………..………………………………………..…117

8.6- Lubricity………….…………………………..……………………………………………………....117

8.7- Cetane Number………….…………………………..…………………………………………....…118

8.8- Particle Contamination………….…………………………..………………………………..……….119

8.9- Elastomer Compatibility………….………………………………………………………..……….…120

8.10- Storage and Oxidative Stability………….…………………………..………………………...…..…120

8.11- Emissions ………….………………………………………………………….………..……….…124

8.12- Effect of Chemicals Derived from the Transesterification Process………….………..…….…………..131

8.13- Energy Life Cycle Assessment – Well to Wheel Analysis ………….…………………………..…...…133

8.14- Carbon Life Cycle Assessment – Well to Wheel Analysis………….…………………………..…..….136

Part II – Effect of Additives to Improve the Performance of Biodiesel at Low Temperatures

1- Introduction to the Theory of Crystallization………….…………………………..…..…………………...142



2- Performance of Fuels at Low Temperatures………….…………………………..…………………...….144

3- Methods to Improve the Performance of Biodiesel at Low Temperatures………….………………….148

4- Experimental Protocol, Results and Discussion ………………………..…………………………….….157

4.1- Initial Screening of Polyamide Material as Cold Flow Improver Additive………….…………………..….157

4.2- Second Round of Polyamide Screening………….…………………………..…..…………………....159

4.3- Determination of the Optimal Carrier Solvent………….…………………………..………………..….160

4.4- Comparison of the Prototype Additive Performance vs. the Industry Standard………….…………..….161

4.5- Effect of the Prototype Additive in Diesel Fuel and Bxx blends………….…………………………..…...162

5- Final Discussions and Conclusions………….……………………………………………………..…..….170

6.1- Discussion of the Political and Market Aspects of Biodiesel………….…………………………..….….170

6.2- Discussion of the Technical Aspects of Biodiesel………….…………………………..…..…….

6.3- Connecting the Dots………….…………………………..………………………………..….

6- References………….…………………………..…..………………………………………………..

Appendix A- Diesel and Biodiesel Fuel Specifications………….…………………………..…..….136



Part I

“Analysis of the Political, Economical and Technical Aspects of Biodiesel Fuel”

Confidential Information Contact Author



Part II

“Effect of Additives to Improve the Performance of Biodiesel

at Low Temperatures”

Confidential Information Contact Author



1. References

The list of references used for the elaboration of the present document is presented next. It should be noted that

the references aren’t indicated following the conventional alphabetical order, instead they are presented following

the order they are mentioned in the main document. The reason for this is related with the amount of documents

researched and to facilitate the consultation.

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