Technical Guide - FAME in Diesel - Storage & Handling: Version 3 (January 2009)

GS.07.
50614
CONFIDENTIAL
Technical guide - FAME in diesel –

Storage & Handling
Version 3 (January 2009)

GS.07.50614
CONFIDENTIAL
Technical guide - Use of FAME in Automotive

Gas Oil (AGO)
Version 3 (Dec 2008)
by
Ed. de Saegher
Mark Brewer
Wai-Yin Wong
Siri Sivalingam
Karlheinz Arnecke
Paul van Oers
CONFIDENTIAL
This document is made available subject to the condition that the recipient will neither use nor disclose the contents except as agreed in
writing with the copyright owner. Copyright is vested in Shell Global Solutions International B.V., The Hague.
© Shell Global Solutions International B.V., 2006. All rights reserved.
Neither the whole nor any part of this document may be reproduced or distributed in any form or by any means (electronic, mechanical,
reprographic, recording or otherwise) without the prior written consent of the copyright owner.
Shell Global Solutions is a trading style used by a network of technology companies of the Shell Group.
GS.07.50614 1 CONFIDENTIAL
Document History
Date Issue Reason for Change Author Approved by

M Brewer GSMR
Wai-Yin Wong GSLM
Peter de Kleine
Ed De Saegher GSLM
GSLM
15/03/2007 1 1st issue Siri Sivalingam GSLM
Jim Cooke
Karlheinz Arnecke
GSMR
GSLM
Several updates on the following:

• Chlorine and Oxygen content of
FAME
• Biodegradability and Ecotoxicity
• Microbial Contamination
• Precipitation above cloud point in M Brewer GSMR
AGO blends Wai-Yin Wong GSRSD
• Maximum allowable skin Siri Sivalingam
Kevin Buijs
20/12/2007 2 temperature in heating system to GSRSD
GSRSD
avoid thermal degradation of FAME Karlheinz Arnecke
• MPP in transporting FAME GSRSD
• Reprocessing (slops)
• Spontaneous Combustion of Neat
FAME
• QAG reference list
• Change of departmental indicators
Several updates on the following:

• ASTM spec for bio-diesel blend was
introduced (Chapter 5.2)
• Sampling of FAME and biodiesel
blends. (Chapter 5.5)
• Microbial contamination (Chapter
7.2)
• Cold flow properties/Low
temperature operability – AGO
blends (Chapter 10.1)
• Blending Properties: Neat FAME
(Chapter 11)
• Added Impurities (Chapter 8.1.9) Paul van Oers Joseph
18/12/2008 3 • Non-metallic materials compatibility (GSDM) Kurczycki
(Chapter 8.1.10) Mark Brewer (GSRM) GSDM
• Tank classification and construction
(Chapter 8.1.11)
• MPP in transporting FAME (Chapter
12.5)
• Added Regulatory compliance
FAMES (Chapter 18.3)
• GTL blending component (Chapter
21)
• Change of departmental indicators
• Sensitivity of gasoline cars for small
contaminations of FAME in the fuel
(chapter14.2)
Next review date December 2009
Summary
This document provides technical guidance for an implementation team on the key issues to
be considered when introducing Fatty Acid Methyl Esters (FAME) into automotive gas oil
(AGO) in a market. The report specifically considers FAME contents up to 5%v in AGO (B5)
and would apply to 10% v/v in most of the case and considers the full fuel supply chain
starting from the supply of FAME through to blending at refinery and depot storage, as well
as retail sites and use by the final customer.
The key issues relate to those aspects of FAME that differ from conventional AGO. These
are principally their cold properties, their poorer oxidation stability and their tendency to pick
up water and dirt in the supply chain to a greater extent than conventional AGO. This has
implications, in particular for the handling and blending of neat FAME. Blends with AGO can
be treated in a similar manner to conventional AGO. The need for the maintenance of a good
housekeeping regime becomes even more critical when FAME is introduced into the diesel
fuel.
The presence of FAME can alter the properties of AGO, in particular in terms of the low
temperature properties and increased water solubility and solvency. Because of this, specific
actions need to be taken to prepare storage tank farms for the introduction of FAME-
containing fuels. Storage tanks require checking, assessment and cleaning to remove water
and dirt. Furthermore material compatibility issues with materials used through the supply
chain should be looked at.
Refinery blending is the favoured way for FAME addition, although local circumstances might
favour terminal blending. For terminal blending “side stream gantry blending” is the
distribution standard, and deviation from this standard requires derogation via the distribution
biofuels team.
The table below summarises all the highlighted red () key points and recommendations
made in this report.
Chapter KEY POINTS & RECOMMENDATIONS
3.1 The properties and performances of FAME depend on the fatty acids
compositions, chain length and number of double bonds C=C in the molecules.
4 All requests and enquiries about FAME supply are handled through Shell
Trading contacts.
5 Compliance to FAME standards and quality specifications is important to ensure
good performance of the final AGO blend.
5.4 Local FAME specifications must be met by the FAME suppliers.
5.5 If a metal sample can is used for products containing FAME the sample can
shall be made from stainless steel. Only opaque bottles should be used for
storing samples as light can also affect the results.
7 Good housekeeping standards are of primary importance to minimize the
ingress of water into the neat FAME or AGO blends and ensure the products
remain within specification. Water and sediment contamination are the two main
housekeeping issues for FAME.
7.1 Good housekeeping to eliminate free water, proper material compatibility and
FAME that meets the quality specifications, are all measures to prevent
corrosion.
7.1 Copper, brass, bronze and galvanised materials should be avoided for fuel
systems where FAME is used.
7.2 FAME-containing fuels are more susceptible to microbial growth than

hydrocarbon-based fuels. Maintenance of good housekeeping practices to keep
the fuel dry is therefore important to avoid microbial contaminations.
8.1 In general many of the storage and handling aspects for neat FAME are similar
to standard diesel (AGO).
8.1.4 As FAME is prone to oxidation the blending operator (refinery or terminal)
should ensure that the FAME supplier delivers on spec quality FAME.
8.1.4 FAME being stored for longer than 1 month should be checked regularly and
treated with antioxidant to avoid stability problems.
8.1.6 Neat FAME viscosity increases rapidly at lower temperatures
8.1.7 The cold properties of FAME depend on their degree of saturation, with more
saturated FAME, such as TME and POME having the worse properties.
Additives are only currently available that can lower the pour point and CFPP of
RME. The Shell recommendation is that these Additives should not be used.
8.1.8 It is recommended that FAME should be stored at temperatures at least 6 °C
above its cloud point.
8.1.11 It is recommended to store FAME in fixed roof tanks.
8.1.11 Copper and copper containing alloys lead such as tin and zinc should be
avoided as they can significantly increase sediment and deposit formation from
FAME
8.2.1 The standard storage and handling procedures used for conventional AGO can
be used for AGO-FAME blends.
9.1 FAME is a fuel for AGO applications only and FAME is not to be blended with
gasoline.
9.2.1 There is a clear preference for blending of FAME at refinery. Significant
advantages are to be gained from blending FAME at the refinery as the refinery
is in a better position to take full advantage of both the financial and
environmental benefits that may be gained from large scale FAME blending.
9.2.2 For terminal blending side-stream gantry blending is the standard within
Distribution and deviation from this standard requires derogation via the
distribution biofuels team.
9.3 Due to the chemical nature of FAME it can be used and handled in the blending
process like any other common HC blend component for AGO.
9.3.2 Batch blending can be done at refineries and terminals. For homogeneity
reasons and in the absence of tank mixers gantry side stream blending is the
Distribution standard for terminal blending.
9.3.3 Inline blending systems are preferred systems in refineries to blend big volumes
and to minimize product quality give away.
9.3.4 Sequential blending at terminals is not recommended, due to product
homogeneity and safety issues during loading operations.
9.4 Pre-blends of FAME can be used to improve low temperature storage
characteristics.
9.5 During the blending process the fuel temperature should be 6°C above the
Cloud point of the FAME and has to be in a range that assures that cold-flow
additives are dissolved completely. The blending temperature has to comply
with the standard safety requirements for AGO.
9.6 There is no difference in additive handling whether the AGO contains FAME or
not.
10 Most of the AGO blend properties do not show a different behaviour compared
to conventional diesel blending. Most blend issues can easily be addressed by
adjusting the additive levels and are therefore unlikely to be obstacles to FAME
introduction. Cold-flow is an exception and needs special attention.
10.1 The addition of FAME to AGO can have a large impact on the cold properties
(CP and CFPP) of the fuel that can, in many cases, make meeting the
specifications difficult using current cold flow additives. FAME derived from
highly saturated, high melting point materials such as TME and POME can be
particularly problematical.
10.4 Neat FAME normally has a higher viscosity than standard AGO.
10.6 Existing blend rules apply to FAME blends up to 20%v.
12.1 In areas of cold climates refineries and depots receiving FAME should consider
whether heating of transfer lines and storage tanks are necessary.
12.4 The supplier must provide a Certificate of Analysis (CoA) for every batch of
FAME delivered. Prior to accepting a delivery of FAME product, it is important to
inspect the CoA to ensure that the properties reported lie within the allowable
range of the supply specification. Guidelines on ensuring and maintaining
product quality from FAME suppliers (GS.06.52356 V2) are to be followed.
12.5 In Europe the transportation of B5 (5%v/v FAME) in multi product pipelines that
is also used for Jet-A1 is acceptable by using a combination of minimum batch
size, modified interface cutting, product sequencing and buffers to ensure the
average level of FAME in a batch of jet fuel is below the maximum level of 5ppm
as defined in DEF STAN 91-91 for Jet-A1. This however is subject to the
approval of pipeline operators.
12.6 Colonial Pipeline has decided not to permit shipments of fuels containing bio-
components at this time. Any FAME blending into AGO will therefore have to be
carried out at terminals.
13.1.1 It is preferred that FAME does not contain any cold flow improvers, to minimize,
risk of interactions with other fuel additives and supply chain costs.
13.1.2 The recommended antioxidants for FAME are generally described as hindered
phenols, like BHT. These chemistries can be used up to 1000mg/L in a B100
FAME based on the acceptable levels in AGO and Jet fuel
13.2.1 Care should be taken to ensure B5 does not become overdosed with
Antioxidant.
13.2.2 Conventional AGO cold flow improvers are effective in B5 fuels produced from
FAME containing a low saturated fatty ester content, such as RME. Up treating
with current CFI cannot always prevent significant increases in CFPP for B5
fuels produced from FAME containing high-saturated fatty ester content.
13.2.3 There is no evidence from studies done to date that FAME has any detrimental
impact on either ester-based or acid-based lubricity additives. If the FAME
content is above 2%v in the final blend, optimisation of the dosing of a lubricity
additive should be considered.
13.2.3 If the FAME content is below 2%v in the final blend, dosing of a lubricity additive
should be considered.
13.2.4 FAME can cause a loss in static dissipater additive (SDA) activity.
13.2.5 B5 does not appear to affect the performance of cetane improvers in base fuels.
Normally, no additional boost is provided by high cetane FAME when added to
fuels containing 2-EHN (high cetane)
13.2.6 Use of FAME in V Power Diesel, is generally NOT recommended and should be
reviewed for individual cases and be subject to separate QAG assessments.
14.1 Reprocessing 5 to 10% slops containing 1-5% FAME on intake via CDU and
HDS is possible and will pose no significant risks on HDS catalyst performance.
If all product streams are fully hydro-treated at all time, there will be no risks on
product contamination. It is recommended that the refineries investigate the
origin of the slops and its process unit configurations before deciding on the
reprocessing route back to the refineries.
14.2 FAME containing gasolines (as a result of cross-contamination) should not be

deliberately re-blended into gasoline.
15 The risks associated with FAME contamination of heating oil due to shared
logistics will be accepted by the Commercial Fuels Business. An individual
case-by-case evaluation should be performed before the downgrading of
FAME-containing diesel for use as heating oil.
16 Introduction of B5 should not require any special cleaning or flushing of retail
tanks. It is recommended that it is handled in a similar manner to AGO
containing a mid or top tier performance additive package.
17 Generic QARs have been developed to cover use of FAME conforming to
standard specifications in main grade fuels in both Europe and the US.
18 For AGO blends (up to 20%v), the fuel should be treated as conventional AGO
in all HSE aspects. FAME meeting EN14214 or equivalent, is generally
classified as non-hazardous.
18.2 Neat FAME can self-ignite when soaked into porous material, e.g. rags, textiles,
insulations and inorganic materials, therefore materials saturated with FAME
should be disposed of correctly.
19 There is growing pressure from governments in several parts of the world to
increase the amount of FAME included in AGO from the B5 level covered in this
guide.
20 Implementation-related knowledge on higher alkyl esters is currently very limited
and will be further developed.
21 GTL blending in diesel up to a level of 5 % will not cause interaction with FAME
(change in solvency characteristics). Higher concentrations up to a level of 30%
have shown to be compatible but local testing is recommended before blending
of GTL is started
Table of Contents
Summary 2
1 Introduction 9
2 Definitions/Glossary 10
3 Fatty Acid Methyl Ester FAME 11
3.1 Types 11
3.2 Common Sources of FAME 11
3.2.1 Rapeseed Methyl Ester, RME 11
3.2.2 Soybean Methyl Ester, SME 11
3.2.3 Palm Oil Methyl Ester, POME 11
3.2.4 Coconut Oil Methyl Ester, CME 11
3.2.5 Tallow Methyl Ester, TME 12
3.2.6 Used Vegetable Oil Methyl Ester, UVOME or Used Cooking Oil Methyl Ester,
UCOME 12
3.2.7 Jatropha 12
3.3 FAME (B100) properties 12
3.4 Non specification characteristics of FAME compared to AGO 12
4 Suppliers 14
5 Quality & Standards 15
5.1 Germany (representing EU) – Biodiesel Quality Management Association
AGQM 15
5.2 USA - National Biodiesel Accreditation Commission (NBAC) BQ-9000 15
5.3 Australia – Biodiesel Association of Australia (BAA) 16
5.4 Shell Quality Assurance Process 16
5.5 Sampling of FAME and biodiesel blends 17
6 FAME Specification Items 18
6.1 Density 18
6.2 Kinematic Viscosity 18
6.3 Flash Point 18
6.4 Sulphur Content 18
6.5 Carbon Residue 18
6.6 Distillation (T90) 18
6.7 Cetane Number 19
6.8 Ash Content 19
6.9 Water Content 19
6.10 Total Contamination 19
6.11 Copper Strip Corrosion 20
6.12 Ester Content 20
6.13 Free Glycerol 20
6.14 Mono-, Di- and Triglycerides and Total Glycerol 20
6.15 Methanol 20
6.16 Iodine Number 20
6.17 Linolenic Acid Methyl Ester 21
6.18 Polyunsaturated FAME 21
6.19 Acid Number 21
6.20 Phosphorus Content 21
6.21 Content of alkali and alkaline-earth metals 21
6.22 Oxidation Stability 21
6.23 Low Temperature Behaviour 21
7 Housekeeping of neat FAME and AGO blends 23

7.1 Corrosion behaviour: Neat FAME 24
7.2 Microbial contamination: Neat FAME and AGO Blends 24
8 Storage 27
8.1 Neat FAME 27
8.1.1 General 27
8.1.2 Water classification 27
8.1.3 Water contamination 27
8.1.4 Oxidation stability 27
8.1.5 Solvent properties 28
8.1.6 Viscosity - Temperature behaviour 28
8.1.7 Low temperature properties 30
8.1.8 Low Temperature Operability 31
8.1.9 Impurities 32
8.1.10 Non-metallic materials compatibility 32
8.1.11 Tank classification and construction 33
8.1.12 Tank cleanliness 34
8.2 AGO-FAME Blends 34
8.2.1 General 34
8.2.2 Tank classification 34
8.2.3 Tank cleaning 34
8.2.4 Elastomer Material compatibility – AGO Blends 34
9 Blending 35
9.1 Introduction 35
9.2 Location 35
9.2.1 Refinery Blending 35
9.2.2 Terminal Blending 35
9.3 Type 36
9.3.1 Side Stream Blending at Terminals 36
9.3.2 Batch Blending 37
9.3.3 Inline Blending. 37
9.3.4 Sequential blending at Terminals 39
9.3.5 Mixing time 40
9.4 Pre-Blending 40
9.5 Temperature of Blending 40
9.6 Additives 41
9.7 Blend analysis –NIR 41
9.8 Blend experiences from refineries 41
10 Blending properties: AGO Blends 42
10.1 Cold flow properties/Low temperature operability - AGO Blends 42
10.2 Density 43
10.3 Cetane 44
10.4 Viscosity 44
10.5 Distillation characteristics 44
10.6 Blending rules for FAME into diesel 44
11 Blending properties: Neat FAME 45
12 Transportation 46
12.1 Introduction 46
12.2 Tankers 46
12.3 Trucks and rail cars 46
12.4 Certificates of Analysis 48
12.5 Multi product pipelines (MPP) - Europe 48
12.6 Multi product pipelines - US 49
13 Additives 50
13.1 Additives for FAME B100 50
13.1.1 Cold flow improvers 50
13.1.2 Antioxidants 50
13.2 Effect of FAME on AGO Additives 51
13.2.1 Anti oxidant 51
13.2.2 Cold flow additives 51
13.2.3 Lubricity 51
13.2.4 SDA – Conductivity 51
13.2.5 2-EHN – Cetane Improvers 52
13.2.6 Impact on performance additives 52
14 Reprocessing Fuels containing FAME (including Slops) 53
14.1 Reprocessing slops via CDU and HDS 53
14.2 Blending into main grade fuels. 54
15 FAME in Industrial Gas oil and Domestic Heating Oil 55
16 B5 in Retail. 56
17 Risk Management in the introduction of FAME in Shell AGO products
– the Quality Assurance Group (QAG) 57
18 HSE Issues 58
18.1 Static risks, electrical conductivity: Neat FAME and AGO Blends 58
18.2 Spontaneous Combustion – Neat FAME 58
18.3 Regulatory Compliance 59
19 Higher FAME content blends (B7, B10/B20) 60
20 Fatty acid ethyl/alkyl esters FAEE 61
21 GTL blending component 62
22 Additional General References 64
Appendix A. Common Fatty Acids 65
Appendix B. Typical FAME properties 66
Appendix C. Fats and oil composition 77
Appendix D. Trans-esterification process 78
Appendix E. Iodine number 79
Appendix F. FAME structures 81
Appendix G. EN 14112 Oxidation stability – Rancimat test 82
Appendix H. Blend experiences from refineries 84
Appendix I. FAME CAS & EINECS list 87
Appendix J. Grouping and Mapping of FAME 88
Bibliographic Information 89
Report distribution 90
1 Introduction
There is growing pressure around the world to increase the use of bio-components such as
FAME in automotive fuels as they offer governments opportunities to increase domestic
energy security, support their agriculture industry, develop renewable energy and reduce
carbon dioxide emissions. In this context many Shell Operating Companies are looking to
introduce FAME into AGO. Storage and handling issues at refineries and distribution sites,
are often not as straight forward as for conventional AGO alone. FAME is already present in
some countries in AGO blends of up to 5%v (designated as B5), although 7%v (B7), 10%v
(B10) and 20%v (B20) blends are also available.
The aim of this document is to provide guidance on the additional measures that are required
when introducing FAME into a refinery tank farm or distribution depot based upon the
experiences of the Shell companies and non-Shell parties. The intended audience for this
guide include personnel who are involved with the introduction and implementation of FAME.
It should be noted that this Technical Guide forms part of a group of documents from Global
Solutions related to FAME implementation into a market. Other Guides cover Quality
Assurance, and Specific property issues, while an overall Implementation Guide is available
to provide a summary of the key technical issues that should be considered by the business
implementation team responsible for FAME introduction.
This FAME Technical guide will be updated as new information or experiences become
available. Your views and learning’s are welcomed for this next issue. Please send your
comments to the author: Paul.vanOers@Shell.com
2 Definitions/Glossary
The following nomenclature and definitions will be used in this document.
AGO Automotive Gas Oil or Diesel

AOME Animal Oils Methyl Esters
ASTM American Society for Testing and Materials
CEN Comité Européen de Normalisation (European Committee for Standardisation)
CFI Cold flow improver
CME Coconut Oil Methyl Ester
CoA Certificate of Analysis
EI Energy Institute
FAME Fatty Acid Methyl Ester
MDFI Middle distillate flow improver
NIR Near Infra Red
OEM Original Equipment Manufacturer
POME Palm Oil Methyl Ester
RME Rapeseed Methyl Ester
ROME Recycled Oil Methyl Esters
SME Soybean Methyl Ester
SunME Sunflower Methyl Ester
TME Tallow Methyl Ester
UCOME Used Cooking Oils Methyl Esters
UVOME Used Vegetable Oils Methyl Esters
Additionally (W) and (S) refer to Winter or Summer grades respectively
In this guide:
The convention used to denote FAME types or AGO blends is as follows:
RME, SME, POME, CME, UCOME, AOME or FAME is used to refer to neat methyl esters
Bxx refers to a specific blend of xx% of an ester in AGO.
B100 is also used to refer to 100% methyl esters
The convention used to denote specific FAME types are normally written as Cxx:n;
where xx = number of carbon atoms in the fatty acid
n = number of double bonds
when n = 0, it is saturated
when n > 0, it is unsaturated
Further details of the chemistry are given in Chapter3

3 Fatty Acid Methyl Ester FAME

3.1 Types
The most common types of biomass derived diesel (bio-diesel) are known as Fatty Acid
Methyl Esters (FAME) which are defined as the methyl esters of long chain fatty acids (e.g.
from C12 to C18) derived from natural oils.
The properties and performances of FAME depend on the fatty acids

compositions, chain length and number of double bonds C=C in the
molecules.
FAME is produced via a chemical process called trans-esterification with methanol in the
presence of an alkaline or acidic catalyst to yield methyl esters. Glycerol is formed as a co-
product of the reaction. See Appendix D for a chart showing the trans-esterification process.
FAME can be produced from various oil-derived feedstock such as soybean, rapeseed,
sunflower seed, jatropha, coconut, palm and used vegetable oils, as well as tallow (animal
fats), although the most common types of FAME produced are:
Rapeseed Methyl Ester, RME (Europe – France, Austria, Germany)

Soybean Methyl Ester, SME (USA, South America)
Palm Oil Methyl Ester, POME (Malaysia, Indonesia, Thailand)
Coconut Oil Methyl Ester, CME (Philippines)
Tallow Methyl Ester, TME (UK, Oceania)
The choice of biomass source is determined by the availability of feedstock in a specific

region.
3.2 Common Sources of FAME
3.2.1 Rapeseed Methyl Ester, RME

Rapeseed oil, also known as canola oil, is derived from various mustard species. Rapeseed
oil has been used in Europe since the 13th century as fuel for lamps, as a raw material for
soaps and paint production, and as cheap cooking oil. RME remains the feedstock of choice
in most European countries, with France and Germany as the main producers.
3.2.2 Soybean Methyl Ester, SME

Soybean oil is the most common FAME feedstock used in the USA.
3.2.3 Palm Oil Methyl Ester, POME

Palm oil is currently produced in great quantities in the Far East, especially in Malaysia and
Indonesia. The high hectare yields and moderate cost of POME make it potentially an
attractive FAME. The production of POME from palm oil not only yields glycerol but also
yields vitamin E and carotene, which are valuable co-products for the pharmaceutical
companies. Shell only considers the use of POME from sustainable origin.
3.2.4 Coconut Oil Methyl Ester, CME

CME is a coconut oil derived methyl ester and is widely produced in the Philippines where
there is considerable interest in developing CME as an alternative fuel. It has a very different
fatty acid distribution compared to other FAME.
3.2.5 Tallow Methyl Ester, TME

Tallow is derived from animal fats, a by-product of the meat industry and is relatively cheaper
than vegetable oil esters. Tallow is largely available in Australia and New Zealand.
Less common FAME include:
3.2.6 Used Vegetable Oil Methyl Ester, UVOME or Used Cooking Oil Methyl Ester, UCOME
There is increasing interest in using recycle oils, which include UVOME - most commonly
derived from used frying oil. Recycled oils come from a variety of sources and the
composition may vary. They are chemically and physically degraded and often contaminated,
hence have to be treated to remove impurities. The recycled oils are already in used in
Europe and Japan.
3.2.7 Jatropha
Jatropha oil is extracted from Jatropha curcas (physic nut). This non-edible oil is particularly
attractive as a feedstock for FAME as it tends to be considerably cheaper than edible
vegetable oils. It is largely grown in India and has already been blended into diesel for
fuelling trains but is not widely available at present.
A list of most common fatty acids can be found in Appendix A
3.3 FAME (B100) properties

The properties of FAME are determined by the composition of the fats and oils. The fatty
acids composition is also dependent on the processing of the raw material. A chart showing
the composition of various fats and oils is shown in Appendix C
There are two main types of fatty acid esters, saturated or unsaturated: see Appendix F
• Saturated fatty acid esters do not contain any double bonds
• Unsaturated fatty acid esters do contain double bonds. They can contain 1 or more
double bonds. If they have 1 double bond, then they are called mono unsaturated,
and for more than 1 double bond, they are called poly unsaturated
In general, the properties of FAME can be linked to its fatty acid compositions.
A high content of Saturated fatty acids (e.g. CME, POME, TME) is associated with:
• Higher CFPP, cloud point & pour point
• Higher cetane number
• Better oxidation stability
A high content of unsaturated fatty acids (e.g. RME, SME) is associated with:
• Lower CFPP, cloud point & pour point
• Lower cetane number
• Poorer oxidation stability
3.4 Non specification characteristics of FAME compared to AGO
• AGO fuel typically consists of about 30-35% aromatics and 65-70% paraffin’s and
traces of olefins and sulphur. Most of the paraffin’s in AGO fuel are in the range from
C10 to C16. FAME derived from rapeseed or soybean oil contains primarily C16 and C18
fatty acid methyl esters with one up to three C=C double bonds per molecule.
• Oxygen: Higher oxygen content than AGO and this reduces black smoke. Typically,
oxygen content in FAME amounts to between 10 to 12 % m/m, as shown in Figure 1.
Calculated Oxygen Content of FAME molecules
16
15
14
13
Oxygen content %
12
Typical Oxygen content of FAME ester types are between 10-12%
11
10
6
C12:0 C14:0 C16:0 C18:0 C20:0 C22:0 C24:0 C18:1 C18:2 C18:3
Fatty acid ester type
Figure 1: Calculated Oxygen content of FAME molecules
• Chlorine: Chlorine analysis showed typical levels of <20mg/kg. The UCOME results were
not significantly different from other FAME tested. High chlorine levels in UCOME have
been linked to increased dioxin exhaust emissions. These results suggest the UCOME
tested is likely to be no worse for this than other FAME types.
• Lubricity: Excellent lubricity improver and can eliminate the use of a separate lubricity
improver in low sulphur AGO. Bio-degradability: FAME is classified as “readily bio-
degradable”. .
• Eco-toxicity: Relative to conventional AGO, FAME can show significantly less eco-toxicity
to a range of micro-organism.
• Solvency: FAME is an effective solvent, hence tends to loosen and mobilise existing
deposits in pipes and tanks during distribution. If not carefully managed, this may lead to
problems with filter blockage further downstream.
• Conductivity: Whilst neat FAME components are expected to have higher conductivity
than AGO, the effect of introducing low concentrations of FAME into AGO on the overall
conductivity is small and not sufficient to ensure safe handling. On the contrary,
unexpected and large reductions in conductivity have been observed upon blending 5%
SME into base fuel containing static dissipater. Hence, the standard advice on the use of
conductivity additives is still applied, and to be verified on a case-by-case basis.
• Calorific value: FAME has lower calorific value compared to AGO, which increases fuel
consumption.
• Micro-organism: Neat FAME could be a potential source for micro-organism to enter the
supply chain. Advice is to monitor the microbial activity of FAME (see also chapter 7.2).
4 Suppliers
All requests and enquiries about FAME supply are handled through Shell
Trading contacts.
FAME supply is handled through Shell Trading. The focal points are:
• STR Shell Trading Rotterdam (Europe and World),
• SIETCO Shell Trading Singapore (for East and World).
• STUSCO Shell Trading Houston (for US)
• SCAPSA Shell Trading Latin America
If suppliers approach sites directly, they should be forwarded to the Shell Trading contacts as
appropriate. This will enable maintenance of a consistent position with suppliers. It will also
ensure QA is maintained, avoid un-necessary risks and help to develop global opportunities.
5 Quality & Standards

Compliance to FAME standards and quality specifications is important to
ensure good performance of the final AGO blend.
There are standards and quality accreditation schemes to provide quality control and
assurance in order to ensure that bio diesel in the marketplace meets the quality
specifications. Latest versions of local FAME and diesel blend specifications should be
obtained from the local Product Quality Focal Points.
5.1 Germany (representing EU) – Biodiesel Quality Management Association

AGQM
Over the past decade, Germany has put policies in place to create the most extensive
biofuels market in Europe and the largest biodiesel production capacity worldwide.
Throughout Germany, the Biodiesel Quality Management Association (AGQM) provides
quality assurance via its accreditation scheme, which covers raw material selection,
production processes and storage, loading and transportation, as well as quality measures at
the retail stations. AGQM has developed a system of measures for quality management.
In Europe product specifications exist for AGO and biodiesel: Namely:
EN 590 - describes the physical properties that all AGO fuel must meet if it is to be sold in the
EU, Iceland, Norway or Switzerland. It allows the blending of up to 5%v FAME with
conventional AGO. Only FAME meeting the EN 14214 specification can be used for blending
into AGO.
EN 14214 is currently the standard for neat biodiesel, developed by the European Standards
organisation CEN. The EN 14214 specification is broadly based on DIN 51606, a previous
German standard for Biodiesel. EN 14214 specifies properties and the test methods needed
to determine compliance. This standard allows any feedstock to be used, however its
specifications are most easily met by rapeseed methyl esters (RME). It only covers the use of
Fatty Acid Methyl esters (FAME).
5.2 USA - National Biodiesel Accreditation Commission (NBAC) BQ-9000

The National Biodiesel Board (NBB) of the US is the trade association for the biodiesel
industry. It has formed the National Biodiesel Accreditation Commission (NBAC) to audit fuel
producers and marketers in order to enforce fuel quality standards in the US. This
accreditation program BQ-9000 is a combination of the ASTM D6751 and a quality system
program that includes storage, sampling, fuel testing, blending, shipping, distribution and fuel
management practices. This accreditation process is comprehensive and includes a detailed
review of the applicant’s quality system documentation, followed by a formal audit of
conformance to its system, leading to recognition in Accredited Producer and Certified
Marketer.
Also in the US (like Europe) separate specifications for neat biodiesel and diesel blends
exist.
ASTM D 975 –08a: Standard Specification for Diesel Fuel Oils – this standard applies to
petroleum-derived AGO and allows the blending of max 5 % v/v bio diesel (not limited to
FAME) in No. 1 and No. 2 diesel fuels without the need for labelling at the pump. The
biodiesel blend stock used in these blends is required to meet ASTM D6751
ASTM D7467-08a: Standard Specification for Diesel Fuel Oils – this standard applies to
petroleum derived AGO and allows the blending of biodiesel (not limited to FAME) in
concentrations between 5 and 20% v/v. B20 was a request from the US military through
DESC. The Defense Energy Support Center asked for the B6-B20 specification to make the
need for product quality data cascade to the supplier in a mandatory sense. Without the
ASTM specification, DESC and/or the local consuming arm of the military, state of federal
government was responsible for confirming product quality if the supplier was hesitant. Now
that the specification exists, suppliers can be pointed to it for contract compliance, and free
up the government from the responsibility to fund their own QA/QC programs. The biodiesel
blend stock used in these blends is required to meet ASTM D6751
ASTM D 6751-08a – is currently the standard specification for neat FAME (B100) intended
for blending with AGO fuel (15 to 500 ppm Sulphur).
5.3 Australia – Biodiesel Association of Australia (BAA)

BAA was founded in late 2000 to ensure that the biodiesel industry is established in
Australia. Among other responsibilities, BAA trained and certified FAME and biodiesel
producers and farmers to ensure the quality of product is met.
The Fuel Standard (Biodiesel) Determination 2003 sets out the physical and chemical
parameters of neat FAME. It also sets out the associated test methods that the Australian
government will use to determine compliance. In general, industry members are in
agreement with the proposed standards, which will form the basis of the Australian Standard
for biodiesel.
5.4 Shell Quality Assurance Process

Local FAME specifications must be met by the FAME suppliers.
One of the key issues in ensuring the trouble free use of AGO blends is the quality of the
neat FAME. It is essential that the neat FAME should comply with the local FAME
specification prior to blending with AGO. Additional specifications can be included if required
to ensure the FAME meets local operating unit requirements.
A set of Quality Control protocols has been developed (GS.06.52356 - Process for Ensuring
and Maintaining Product Quality from FAME (Fatty Acid Methyl Ester) Suppliers). The main
principles underpinning these protocols are:
• Responsibility for the quality of the FAME product lies with the supplier, and this will be
stated clearly in the supply contract.
• FAME should only be purchased from a reputable supplier. When assessing potential
FAME suppliers, Shell Operating Units should follow the guidance given by Contracts
and Procurement within Shell Trading or the local Supply organisation.
• The contract will include inter alia clauses to define the specification to which the product
must conform, (ii) how conformance will be demonstrated (scope and frequency of
testing, reporting of results), and (iii) the arrangements in the event that product does not
meet the specification.
• Laboratories providing data to demonstrate product conformity must be either (1)
accredited to a relevant internationally recognised standard, or (2) audited by a Shell
technical focal point prior to the establishment of a supply contract.
• In addition to the quality assurance provided by the supplier, a rapid quality control test
must be run on every delivery to check for error or contamination. This includes check of
the CoQ and a rapid QC check on density, water content, flashpoint and appearance
before discharging the product. Oxidation stability of the product is managed by
monitoring the storage tank frequently (see 8.1.4).
5.5 Sampling of FAME and biodiesel blends
When sampling neat FAME or diesel containing FAME the usage of traditional copper
sample cans should be avoided as this might affect the oxidation stability result. Stainless
steel or glass are preferred materials for the sample cans. The sample cans should be kept
clean and dry. For storing the samples only opaque bottles should be used as light can also
affect the results. If the sample is being taken for measuring the oxidation stability then the
sample should be analyzed promptly. (<3 days)
If a metal sample can is used for products containing FAME the sample
can shall be made from stainless steel. Only opaque bottles should be
used for storing samples as light can also affect the results.
6 FAME Specification Items

This chapter gives a brief description of the significance of the key properties normally
specified for neat FAME (B100) in EN14214 and ASTM D6751. .
6.1 Density
FAME densities are generally higher than those of conventional AGO although changes in
density with temperature are very similar. The density of FAME depends not only on the fatty
acid composition but also on purity. Density increases with decreasing chain length and
increasing number of double bonds present in the fatty acid esters. Density can be
decreased by the presence of low-density contaminants, such as methanol and is therefore a
useful quick check for gross contamination in transit.
6.2 Kinematic Viscosity

Kinematic viscosity at 40°C is higher for FAME than for conventional AGO (see 8.1.6) and
will increase with higher contents of high molecular compounds such as un-reacted
glycerides or polymers. Viscosity can be decreased by the presence of low viscosity
contaminants, such as methanol and water.
6.3 Flash Point

Flash Point is a measure of flammability of fuels and thus an important safety criterion in
transport and storage. The Flash Point of FAME are normally well above 100°C but can
rapidly decrease with increasing amounts of residual alcohol present. The flash point is
therefore used as the mechanism to limit the level of un-reacted alcohol remaining in the
finished fuel.
6.4 Sulphur Content

The preferred sulphur test method for FAME is ASTM D 5453. FAME is typically sulphur-free,
however FAME derived from recycled oils may contain some sulphur.
6.5 Carbon Residue

This parameter is considered a measure of the tendency of a fuel sample to produce
deposits on injectors and inside the combustion chamber when used in an engine though this
relationship is not confirmed. It is suggested to correlate with the respective amounts of
glycerides, free fatty acids, soaps and remaining catalyst from the FAME processing. It is
also influenced by high concentrations of polyunsaturated FAME and polymers that may be
present.
6.6 Distillation (T90)

This specification was incorporated (only in ASTM D 6751) as an added precaution to ensure
the fuel had not been adulterated with high boiling contaminants. As FAME is a mixture of
different components (Appendix C) it does not have a single boiling point but a (small range)
distillation curve. At atmospheric pressure boiling points of the individual FAME components
generally ranges from 330 to 360°C.
6.7 Cetane Number

In general FAME has slightly higher cetane numbers than conventional AGO, see Table 1.
Cetane number increases with increasing length of both fatty acid chain and ester group,
while it is inversely related to the number of double bonds, see Figure 2.
FAME type Cetane number

Sunflower ME 49
Rapeseed ME 54
Soybean ME 46
Palm oil ME 62
Tallow ME 58
Coconut ME 62
Table 1: Cetane numbers of typical FAME
Cetane number for fatty acid types
80
70
60
Cetane number
50
40
30
20
10
0
C12:0 C14:0 C16:0 C18:0 C18:1 C18:2 C18:3
Fatty acid type
Figure 2: Variation in Cetane number for a series of single component FAME
6.8 Ash Content

Ash content describes the amount of inorganic contaminants, such as abrasive solids and
catalyst residues, and the concentration of soluble metal soaps contained in a fuel sample.
These compounds are oxidised during the combustion process to form ash, which is
connected with engine deposits and particulate filter plugging.
6.9 Water Content

The typical FAME specification limits water content to 500 ppmw whereas the corresponding
maximum concentration for conventional AGO is less than half this value (200 ppmw). Water
content should be managed to a low level in order to prevent microbial contamination in the
FAME and the diesel.
6.10 Total Contamination

FAME meeting the specifications regarding ash content will show sufficiently low values for
total contamination. Total contamination tends to be of minor relevance in conventional AGO,
as distillation steps during production reduce the content of insolubles. FAME with a high
concentration of insoluble impurities tends to cause blockage of fuel filters and may cause
damage of injection pumps. High concentrations of soaps and sediments are mainly
associated with these phenomena. Care should be taken with high cloud point FAME that
FAME residues do not remain on the filter, the use of warm solvent and filtering equipment is
recommended.
6.11 Copper Strip Corrosion

Assesses the tendency of a fuel to cause corrosion to copper, zinc and bronze parts of the
engine and the storage tank. The presence of acids or sulphur-containing compounds in
FAME can tarnish the copper strip, thus indicating the possibility for corrosion.
6.12 Ester Content

The parameter is an important tool for assessing the illegal admixture of other substances,
such as AGO or solvent in the FAME. Low values for pure FAME may originate from
inappropriate reaction conditions or from various minor components within the original fat or
oil source.
6.13 Free Glycerol

The content of free glycerol in FAME solely depends on the production process and is
therefore one major criterion of FAME quality. Values out of specification may stem from
insufficient washing of the ester product, which leads to glycerol separation on storage.
Glycerol may also form from hydrolysis of remaining mono, di and triglycerides in stored
FAME. Free glycerol separates within the fuel tank, collecting at the bottom and attracting
other polar compounds, such as water, mono-glycerides and soaps, and can cause damage
to storage and vehicle systems.
6.14 Mono-, Di- and Triglycerides and Total Glycerol

As for free glycerol, the amount of glycerides depends on the production process. Low
concentrations of mono-, di- and triglycerides can only be achieved by selecting optimum
reaction conditions and/or by distillation of the final ester product. FAME with high levels of
mono-, di-, and triglycerides may cause coking and the formation of deposits on injection
nozzles, pistons and valves. They may also adversely affect cold weather operation and
cause filter plugging.
6.15 Methanol
High methanol contents pose safety risks in FAME transport and storage due to lowering of
flash points. Residual methanol in the ester product is removed by distillation or by repeated
aqueous washing steps. Flashpoint values higher than 100°C guarantee that the maximum
limit of 0.2% methanol is not exceeded.
6.16 Iodine Number

Iodine number is a measure of total un-saturation within FAME. FAME with higher iodine
numbers has a tendency to polymerise and form deposits on injector nozzles, piston rings
and piston ring grooves. See Appendix E.
6.17 Linolenic Acid Methyl Ester

This is a polyunsaturated FAME (a methyl ester with 3 double bonds) that is more prone to
undergo polymerization reactions, potentially causing increased engine deposits and lube oil
thickening. Limiting its content is therefore aimed at limiting such undesirable reactions.
6.18 Polyunsaturated FAME

See above, 6.17.
6.19 Acid Number

High fuel acidity can contribute to increased corrosion and the formation of deposits within
the engine. The acid number is used to determine the level of free fatty acids or processing
acids that may be present in FAME. High acid values indicate poor process control of the
manufacturing process. Acid number can also increase during FAME storage due to fuel
aging.
6.20 Phosphorus Content

Phosphorus in fuel is suspected of decreasing the efficiency of oxidation catalytic converters
and of causing higher particulate matter emissions. Phosphorus is either a residual
contaminant from the raw material (as phospholipids) or is introduced during the production
process (acid catalysis or acidic washing). Higher levels indicate poor raw material quality or
process controls.
6.21 Content of alkali and alkaline-earth metals

Alkali and alkaline-earth metals such as sodium and potassium are associated with the
formation of ash within the engine while calcium soaps can be responsible for injection pump
sticking These metals are introduced into FAME during the production process. Alkali metals
stem from catalyst residues, while alkaline-earth metals may originate from hard washing
water. Sodium may be present in used cooking oils for salt.
6.22 Oxidation Stability

Due to their chemical composition, FAME is more sensitive to oxidative degradation than
conventional AGO fuel. This is especially true for FAME with a high content of poly
unsaturated esters, which may polymerise to form insoluble sediments and gums, that can
be associated with fuel filter plugging and deposits within the injection system, the
combustion chamber and sump. Oxidation stability of a fuel can be influenced by adding anti-
oxidants to the fuel (see chapter 13.1.2)
Customer report GS08.54630 “AGO and biodiesel oxidation stability” gives a good overview
of the issues related to oxidation stability. See Appendix G for details on the Rancimat
method.
6.23 Low Temperature Behaviour

The behaviour of fuels under low ambient temperatures is an important quality criterion in
regions of temperate and arctic climates. Partial solidification in cold weather may cause
blockages of fuel lines and filters, leading to distribution and blending problems for neat
FAME and operability issues in AGO blends.
The same cold-temperature property measurements (cloud point, pour point and CFPP) are
used for FAME and AGO, however, FAME generally have poorer low temperature properties
than conventional AGO. This is covered in more detail in later chapter 8.1.6.
The “cold soak filterability” test is recently being introduced in the ASTM D 6751. This is an
attempt to identify high risk FAME where usage could potentially result in precipitation at
temperatures above the cloud point.
7 Housekeeping of neat FAME and AGO blends

Good housekeeping standards are of primary importance to minimize the
ingress of water into the neat FAME or AGO blends and ensure the products
remain within specification. Water and sediment contamination are the two
main housekeeping issues for FAME.
The solubility of water in FAME (around 1500 ppmw) is higher than in AGO (50-80 ppmw).
As the specification for the water content of neat FAME is usually below this limit (e.g. 500
ppmw in EN14214) it is thus important to keep neat FAME dry.
As for diesel water bottoms should not be maintained in FAME storage tanks, since water
can cause internal corrosion of tank bottoms and lower shell plates and encourages microbial
growth.
It is recommended to drain the water bottoms of neat FAME storage tanks on a weekly basis,
prior to blending with AGO and before every new FAME delivery.
Water that has been introduced into tanks from ships, or if pipelines are cleaned by a water
plug, should be kept to a minimum, and drained as soon as possible.
During the first few months following FAME introduction, the water content of the neat FAME
should be assessed regularly to ensure that the housekeeping measures are working
effectively and the water content of the FAME is not significantly increased during storage. It
is recommended to record the water content in the FAME, estimated quantity of water
drained and any abnormal observation during water draining activities. This will help to
monitor the effectiveness of the housekeeping in place.
No FAME shall be used for blending purpose and no AGO blends shall be dispatched as
product from tanks where settled water may be drawn into the suction line. It is essential to
take every precaution to ensure a customer never receives any free or entrained water from
a refinery or terminal through any mode of transportation.
Tank vent pipes should be inspected periodically as they can allow rainwater to seep into the
system.
There are refineries where the haze point is reached in AGO despite the fact of on-
specification water content. Care should be taken in case of FAME blending containing
relatively high water concentrations (ref EN14214 spec) to ensure the AGO blend remains
within the water specification and clear and bright.
The time taken for water phase separation to occur is normally increased when FAME is
present. This can influence the daily operations in Oil Movement, thus the required settling
time of a tank should be considered.
If water contents become too high, check that the correct housekeeping procedures are
being followed.
7.1 Corrosion behaviour: Neat FAME

Good housekeeping to eliminate free water, proper material compatibility and
FAME that meets the quality specifications, are all measures to prevent
corrosion.
Corrosion originates from a combination of several factors, for example, the presence of free
water, incompatible material use and the presence of corrosive acids (together with the
presence of water) and free methanol in the FAME.
FAME is more susceptible to water contamination than petroleum diesel. As in standard

diesel, the presence of free water, apart from sustaining bacterial growth, can also promote
corrosion of fuel system components. The formation of corrosive (weak) acids (for example
formic and acetic acids) in the presence of water will effectively corrode all metallic parts.
However, if the water content spec for FAME is met ( max 500 ppmw in EN 590), there
should be no corrosion problem.
The presence of excess free methanol is likely to corrode materials like aluminium and zinc.
However, since the specification for methanol content in FAME is low (max 0.2% m/m, in EN
590) it is unlikely that methanol stress corrosion cracking of carbon steel piping will happen in
any FAME applications. Therefore, an additional stress relief heat treatment on the piping is
not necessary.
Material compatibility should be looked at when dealing with neat FAME (and the AGO
blends). Any installed or attached parts made of non-ferrous metals (for example copper,
brass, bronze) and galvanised materials must be replaced with equivalent parts made of
steel. This measure serves to prevent corrosion effects, which results in the formation of
metallic soaps and could impair the quality of FAME.
The limit specified for FAME is the same as that for petroleum AGO fuel. As the presence of
free fatty acids or residual acids will mask the true value of the copper strip corrosion, tests
like EN 14104 – Acid value is used to ensure that FAME does not contain those components.
Copper, brass, bronze and galvanised materials should be avoided for fuel
systems where FAME is used.
7.2 Microbial contamination: Neat FAME and AGO Blends

FAME-containing fuels are more susceptible to microbial growth than pure
hydrocarbon-based fuels. Maintenance of good housekeeping practices to
keep the fuel dry is therefore important to avoid microbial contaminations.
The presence of contaminating micro-organisms in middle distillate fuels, including FAME

containing fuels, can cause problems such as filter blockages in vehicles and dispenser
pumps, corrosion problems in storage tanks and pipe work and deterioration of product
quality (increased water entrainment into the fuel resulting from the production of
biosurfactants).
Microbial contamination occurs when micro-organisms grow and multiply in water, which
comes into contact with the fuel. Growth is most commonly found in water bottoms of fuel
storage tanks but can also occur in water droplets entrained into the fuel, e.g. mixed-in during
tank filling and emptying operations. Growth may also occur as bio-film on the internal
surfaces of tanks, which are exposed to water periodically, causing microbiological corrosion.
The most common sources of water within fuel distribution and storage systems are:
• Settling from fuel on immediate cooling following manufacture
• Condensation within tanks associated with humidity and temperature changes
• Contamination with water during marine distribution operations
• Leaking tank roof seal, manhole covers, etc. allowing ingress of rainwater.
A systematic approach of preventative maintenance and treatment should be taken to

maintain good housekeeping. Keeping the fuel as dry as possible is essential, e.g. draining
and cleaning of fuel storage tanks and handling systems throughout the distribution chain.
Regular microbial testing of water bottoms to determine trends in contamination is also good
practice.
Storage tank housekeeping (post-introduction of FAME)
B100
• Twice per month water check (visible and total) and microbiological testing of rag
layer1.
• All free settled water and/or emulsion layer removed.
B5
• Monthly water check (visible and total) and microbiological testing of rag layer.
• All free-settled water and/or emulsion layer removed.
Table 2 Storage tank housekeeping
Evidence of microbial growth in water samples includes discolouration, turbidity (i.e.

cloudiness) or the presence of particulate matter. There may also be a layer of microbial
biomass at the fuel/water interface. The industry standard laboratory method for determining
level of microbial contamination in fuels/water is IP385/99, which is equivalent to ASTM
D6984-04 Determination Practice for Enumeration of Viable Bacteria and Fungi in Liquid
Fuels - Filtration and Culture Procedures. Optical microscopy can also be performed. There
are on-site testing options available, e.g. MicrobMonitor2, Dip-slide and ATP photometry,
which provide its practicality for, use within certain limitations. Microb Monitor is the preferred
method for routine monitoring of microbial contamination.
There are no standard agreed microbiological limits for acceptable contamination levels
in fuels. Low numbers can cause operational problems and high numbers do not
necessarily cause operational problems.
It is reasonable to assume that if there is no evidence of significant microbial proliferation

in the water associated with the fuel, then the fuel is not significantly contaminated.
Studies have shown that when contaminated FAME is used as a blending component, it
can lead to microbial proliferation when blended into diesel fuel.
Treatment of contaminated fuels can be done with biocides.
1
This is the fuel/water interface layer.
2
The MicrobMonitor method
Biocides are chemical agents capable of killing micro-organisms in fuel. They can be
used in a low dosage as a preventative or in a high dosage as a disinfectant or shock
treatment. Two chemistries that are in widespread use are (Table 2 Storage tank
housekeeping)
• Isothiazolinone (trade names: Kathon FP1.5, Spec-Aid 8Q700).
• Oxazolidine (trade name: Grotamar 71).
Trade name Manufacturer Preventative Disinfectant Contact time

treat rate treat rate for
(ppm) (ppm) decontaminat
ion (hrs)
Kathon FP 1.5 Rohm & Haas 50-100 100-200 12
Spec-Aid GE Water 50 100 48-72
8Q700
Grotamar 71 Schulke & 200 1000 15-24
Mayr
Table 3 Recommended treat rates and contact times
The preferred treatment is a disinfectants (high dosage) to kill micro-organisms responsible

for fuel degradation. Preventative concentrations of these biocides may cause microbial
resistance and so are not recommended at present
Treatment with high dosages should be done in a careful manner as

a) Operators may be exposed to large concentrations of biocide at any one time. The
recommended handling procedures and dose rate from biocide suppliers should
always be followed.
b) Operational problems (e.g. filter blockages) can be caused further downstream
due to increased levels of biomass at that point.
Careful consideration of health, safety and environment impact of biocide use

should be given before a biocide treatment. A risk assessment must be carried out
before biocide-contaminated water can be disposed of to assure compliance with
environmental regulations.
Maintenance of good housekeeping practices is thus important to avoid microbial problems in

FAME-containing fuels. If microbial contamination is suspected then test and treat as
recommended in GS.08.51095v2. Recent learnings on the field problems in France and the
Netherlands have also been summarised in this report
8 Storage
8.1 Neat FAME
This section describes the storage and handling requirements of neat FAME.
In general many of the storage and handling aspects for neat FAME are
similar to standard (AGO).
8.1.1 General
There are a number of issues associated with neat FAME which mean that additional rules
and precautions are required for its storage and handling, over and above those that would
be normally be applied for handling conventional AGO. These issues are summarised below:
8.1.2 Water classification

Due to its high biological degradability FAME is graded water hazard class 1, i.e. however it
should be treated in the same way as diesel.
8.1.3 Water contamination

FAME are hygroscopic and they increase the solubility of water in AGO, thereby interfering
with the water-shedding properties of the fuel. FAME that is stored in its neat form is
particularly prone to excessive water retention. Water contamination in a fuel can be a
problem as it can increase the risk of corrosion in tanks and vehicles’ fuel injection systems
and encourage microbial growth which can lead to blocked filters at retail sites or in vehicles.
See also in chapter 7.
8.1.4 Oxidation stability

FAME is reported to have poorer oxidation stability than conventional AGO due largely to the
differences in chemical structure. The oxidation stability of FAME is dependent on the degree
of un-saturation of the fatty acid esters present in the material: those with a higher content of
unsaturated compounds are more likely to have poorer oxidation stability. Thus FAME such
as POME, which has a high-saturated fatty acid content, is normally more stable to oxidation.
Heat and sunlight will accelerate the oxidation process, as will the presence of certain metals
such as copper, brass, bronze, lead, tin, and zinc. The manufacturing process will also affect
the stability of the FAME. Bleaching, deodorizing or distilling oils and fats before or as a part
of the FAME production process can remove natural antioxidants, which will lessen the
FAME stability.
Poor oxidation stability can result in long-term storage problems and may accelerate fuel
oxidation, leading to gumming and deterioration of fuel injection systems. The use of anti-
oxidant additives is likely to be required in most cases, and should usually be added to the
bio-component by the FAME manufacturer rather than by the end-user. These additives are
most effective when added as soon as possible after FAME production. The type and
concentrations of additives are described in chapter 13.1.2.
As FAME is prone to oxidation the blending operator (refinery or terminal)

should ensure that the FAME supplier delivers on spec quality FAME.
Stability of FAME can be prolonged by limiting the fuel’s exposure to oxygen and, most
importantly, by use of antioxidant additives. The storage life and stability of FAME are
contingent on the FAME being stored properly but as a general guideline short-term storage
(<1month) of FAME should be possible without addition of antioxidant with little or no stability
problems. Any fuel stored for longer than 1 month, however, may warrant the use of
antioxidants and should be tested regularly for oxidation stability, acid number, viscosity, and
sediments. The trend in these properties should be monitored. The recommended frequency
of testing is: monthly if Rancimat result is >8hrs and bi-weekly if result is <8hrs. Storage
periods, for FAME, longer than 1 month have been reported in the market.
FAME being stored for longer than 1 month should be checked regularly and
treated with antioxidant to avoid stability problems.
If long term storage is required FAME should also have a high oxidation stability (Rancimat)
value (>10 hr), contain a lower level of unsaturated fatty acid esters, and minimal levels of
poly unsaturated fatty acid esters. The FAME should also be checked regularly and stored
under controlled conditions.
8.1.5 Solvent properties

FAME and AGO blends have good solvent properties and so have the potential to mobilise
dirt and gums formed in older AGO tanks, leading to problems with filter blockage further
downstream. Again this effect is worse for neat FAME than AGO blends.
8.1.6 Viscosity - Temperature behaviour
Neat FAME viscosity increases rapidly at lower temperatures
Neat FAME has a higher viscosity than standard AGO as shown in Figure 3 Neat FAME
viscosity showing viscosity is normally higher than standard AGO (Viscosity of standard AGO
2-4.5cSt) The typical kinematic viscosity for standard AGO is between 2 to 4.5 cSt and this is
relatively lower than that of neat FAME (between 3 to 5.5 cSt as shown in Figure 4 Pure
Fatty acid ester viscosities, showing that viscosity is inversely proportional to the number of
double bonds and directly proportional to the chain length.. This behaviour is particularly
noticeable at lower temperatures. For instance, the effect of temperature on the viscosity of
RME and samples of UCOME are shown in Figure 5 shows the increase in viscosity at lower
temperatures. while the relationship between shear rate and dynamic viscosity of UCOME at
-10°C is illustrated in Figure 6 shows the increase in Viscosity at lower shear rates
The viscosity of FAME is related to the fatty acid composition. The viscosity of FAME is
inversely proportional to the number of double bonds and directly proportional to the chain
length. Figure 4 demonstrates how the viscosity varies with fatty acid and the impact this has
on the viscosity of the different FAME types.
Production impurities can also significantly affect the viscosity. The presence of
glycerol/glycerides and oxidation polymers, for example can increase the viscosity while
residual alcohol can reduce the viscosity.
Viscosity increases rapidly below the cloud point of the FAME.

Kinematic Viscosity 40C
7
6
Viscosity cSt
5
4
3
2
1
0
POME RME SME SUNME CME
FAME type
Figure 3 Neat FAME viscosity showing viscosity is normally higher than standard AGO
(Viscosity of standard AGO 2-4.5cSt)
Kinematic viscosity 40C
6
5
Viscosity cSt
4
3
2
1
0
C14:0 C16:0 C18:0 C18:1 C18:2 C18:3
Fatty acid type
Figure 4 Pure Fatty acid ester viscosities, showing that viscosity is inversely proportional to
the number of double bonds and directly proportional to the chain length.
Viscosity Temperature Profile (constant shear rate 1169 1/s)

100
90
80
70
Viscosity mPas
60
50
40
30
20
10
0
-20 -15 -10 -5 0 5 10 15 20 25 30 35
Temperature C
Ref: Kerschbaum, S., Rinke, G. Measurement of the temperature dependent
UCOME A UCOME B RME B RME A viscosity of biodiesel fuels (2004) Fuel, 83 (3), pp. 287-291
Figure 5 shows the increase in viscosity at lower temperatures.

RMEA contains a CFI additive that improves the Viscosity below the Cloud point.
Dyn viscosity of UCOME at -10C
700
600
500
Dyn Viscosity mPas
400
300
200
100
0
0 200 400 600 800 1000 1200 1400
Shear rate 1/s Ref: Kerschbaum, S., Rinke, G. Measurement of the temperature
dependent viscosity of biodiesel fuels (2004) Fuel, 83 (3), pp. 287-
291
Figure 6 shows the increase in Viscosity at lower shear rates
8.1.7 Low temperature properties
The cold properties of FAME depend on their degree of saturation, with more
saturated FAME, such as TME and POME having the worse properties.
Additives are only currently available that can lower the pour point and CFPP
of RME. The Shell recommendation is that these Additives should not be
used.
Cold flow properties of FAME are one of the main operational issues to consider. More
saturated FAME, (such as TME and POME) have poor cold properties and will pose more
handling issues than less saturated FAME (such as RME or SME). This is shown in Figure 7,
which gives the Pour Point, Cloud point and CFPP of a number of FAME types.
20
10
0
Temperature ( C) TME POME RME (S) RME (W) SME
o
-10
-20
-30
Cloud Point
-40 CFPP
Pour Point
-50
Figure 7 shows the range of low temperature properties for a selection of FAME types.
Additives are currently available that can lower the Pour Point and CFPP of neat RME,
although they have minimal effect on Cloud Point. This is shown in Figure 7, where the RME
(W) contains such an additive. RME containing cold flow additives has been used in
Germany without reported incidents, however the current Shell recommendation is to prohibit
the use of such additives. The reason for this is to minimize the risk of interaction between
these cold flow additives with other types of fuel additives, for example performance
additives. It will also maintain supply flexibility and minimise supply chain costs.
8.1.8 Low Temperature Operability
It is recommended that FAME should be stored at temperatures at least 6 °C

above its cloud point.
Low temperature can cause FAME to solidify, but on warming it liquefies quickly. Pure FAME
can be stored underground in most cold climates, but above ground fuel systems should be
protected with insulation, agitation, heating systems, or other measures if ambient
temperatures regularly fall below the cloud point of the FAME l. This precaution includes
piping, tanks and pumping equipment. Heating can be by any of the common heating
mechanisms, but should be designed to minimise hotspots and prolonged storage at
temperatures above 50°C to minimise oxidation. Preferred system should be based on
tempered water, as steam will be to extreme and cause hotspots and accelerate product
degradation. The thermal degradation of FAME can occur even at relatively low
temperatures. The maximum allowable skin temperature of 80 –100 degC is the guideline
used to reflect the maximum design freedom.
8.1.9 Impurities
Precipitation can also be affected by other impurities. Low temperature precipitation can be
increased by the presence of Sterol esters and increased water content. Other very low level
impurities (Fatty acid soaps and Fatty waxes) have also been associated with precipitation.
8.1.9.1 What are Sterol glucosides?

Sterol glucosides are very low-level impurities; they are common in SME and POME.
Precipitation issues have been reported in N America attributed to Sterol glycosides. These
deposits are normally found in B100 fuels and appear as fine (salt/sugar like) white or brown
crystals. If they are not removed during production they will cause issues with filterability
further down stream. They can act as seed crystals for glyceride or methyl ester precipitation
at lower temperatures.
They are very insoluble in B100 and often precipitate after production of B100. They are only
found in plant-derived material. Levels in B100 are raw material and process specific. With
correct processing SG should not be an issue.
8.1.9.2 What is the appropriate test method?

The only current test method is the cold soak filtration test an annex to ASTM D6751 ( US
FAME spec) –suggested specification limits are included but will be reviewed after trial
period. Other tests are being developed by EI and DGMK in Europe to detect these
materials they are also based on cold soak filtration tests.
8.1.9.3 What should we be doing?

Purchasers of FAME should engage with suppliers, in particular where Soy is involved, to
understand what steps they are taking to manage the sterol glucosides. Purchasers of
FAME should ensure QA procedures include a cold soak test for 100%SME loads or where
the percentage of SME is greater than 50% of the ester.
8.1.10 Non-metallic materials compatibility

In this section recommendations are given for the initial selection of non-metallic materials,
resistant against 100% FAME and mixtures of FAME and diesel, Non-metallic materials
include:
• Thermoplastic materials (linings, tanks, pump internals, filters, valve seats, etc);
• Elastomer materials (gaskets, seals, O-rings, hoses, etc);
Selection of non-metallic materials to be used in 100% FAME and/or mixtures of FAME and
diesel should be based on long-term compatibility of the material under fully immersed
conditions, from either laboratory testing (according to ASTM C 581 or equivalent), or from
field service experience.
Non-metallic materials should comply with DEP 30.10.02.13-Gen “Non-metallic materials –

selection and application”.
Chemical classification Abbreviation

(High-density) Polyethylene (HD)PE
Polypropylene PP
Polyvinylchloride PVC
Polyetheretherketone PEEK
Polyvinylidenefluoride PVDF
Polytetrafluoridethylene PTFE (Teflon)
Table 4 Suitable polymers

Chemical classification Abbreviation Trade name

Nitrile butadiene rubber NBR Buna-N
Fluoroelastomer FKM Viton, type B or F
Perfluoro elastomer FFKM Kalrez
Polychloroprene rubber CR Neoprene
Table 5 Suitable elastomer materials
8.1.11 Tank classification and construction
It is recommended to store FAME in fixed roof tanks.
The flash point property of the stored product determines the storage tank type according to
the rules as set by Energy institute (IP - Institute of Petroleum).
Neat FAME has a flashpoint above 100°C and therefore is categorized as "unclassified"
according to the IP flash point class definition (reference: IP guide - Area classification code
for handling flammable liquids, July 2005). Further details are also given in Shell Design
Engineering Practice (DEP) 34.51.01.31- VERTICAL CARBON STEEL STORAGE TANKS –
based on EN 14015).
The experience of FAME users (suppliers, refineries, etc) has shown that the most effective
way to prevent water ingress is to store neat FAME in a tank with a fixed roof, keeping the
tank as full as possible.
Conical-bottom designed tanks for FAME and AGO blend storage are recommended, as they
are easier to drain.
Floating- roof tanks can be effective provided good housekeeping practices are strictly
maintained and the turnover of FAME in the tank is high, since they are more prone to water
ingress via the roof rim seal.
It is recommended that FAME should be stored in dedicated tanks constructed from mild
steel. Alternative tank materials, suitable for FAME storage, are the following:
• Stainless steel
• Aluminium
• Polymer materials (see 8.1.10).
Copper and copper containing alloys lead such as tin and zinc should be
avoided as they can significantly increase sediment and deposit formation
from FAME.
It is not recommended to install desiccators on FAME tanks due to potential risk of having
vent blockage.
If heating should be applied for storage reasons heat transfer calculation shall be performed
in order to define the heating coil length and possible insulation requirements.
8.1.12 Tank cleanliness

Good housekeeping practices are essential to avoid debris or deposit problems in storage
tanks.
The requirement of tank cleaning prior to introducing FAME into a tank is based on these
good housekeeping standards. Therefore it is important to identify the condition of the
storage tanks before introduction of FAME. See also chapter 8.1.5 on solvent properties of
FAME.
In general if no deposit problems exist in current AGO blending activities there is no

requirement for a tank cleaning exercise.
8.2 AGO-FAME Blends
8.2.1 General
The standard storage and handling procedures used for conventional AGO
can be used for AGO-FAME blends.
AGO blends of up to 20% (B20) should be treated as conventional AGO. It is advised to store
AGO blends in fixed roof tanks.
It is stressed that B5 is “just diesel”, which meets all the requirements of the diesel
specification. The term biodiesel is used for the 100% FAME and is also referred to as B100.
This statement is considered key to minimising confusion and/or concerns in the
marketplace.
8.2.2 Tank classification

The flash point property of the stored product determines the storage tank type according to
the rules as set by the Energy Institute EI (previously IP (Institute of Petroleum))
AGO blends have a flashpoint between 55 to 100°C and are stored at ambient temperature,
which meets a class III type of product.
Further details are also given in Shell Design Engineering Practice (DEP) 34.51.01.31
8.2.3 Tank cleaning

FAME molecules have good solvent properties and so have the potential to mobilise dirt and
gums formed in older tanks, leading to problems with filter blockage further downstream. The
cleaning effect phenomenon has not been observed for B5 and lower blends. It did occur for
B20 blends incidentally. This resulted in a 2 or 3 times additional filter change after first
introduction. It is believed that the cleaning effect may occur faster if the concentration of
FAME is higher.
8.2.4 Elastomer Material compatibility – AGO Blends
Use of Nitrile Butadiene Rubber (NBR) with 40% acrylonitrile, which are commonly found in
fuel systems, can also be sufficient for AGO blends up to 20%v (B20).
9 Blending
9.1 Introduction
FAME blending depends on a variety of factors, including the volume of FAME required to
make the blend, the finished blend level, the volume of blended products being sold, tankage
and space availability, equipment and operational costs, and customer requirements for
blends, both now and in the future. It should be noted that
FAME is a fuel for AGO applications only and FAME is not to be blended with
gasoline.
FAME blending into AGO is not necessarily difficult. There are some ‘rules’ and ‘occurrences’
which should be considered to not run into operational or product quality difficulties. In the
following sections the options on how to blend FAME (B100) into base AGO are described
and recommendations are presented.
9.2 Location
As the market matures and volumes continue to increase, it is very likely that the actual point
of blending will occur further and further upstream in the distribution system where it is most
efficient and economical.
9.2.1 Refinery Blending
There is a clear preference for blending of FAME at the refinery. Significant

advantages are to be gained from blending FAME at the refinery as the
refinery is in a better position to take full advantage of both the financial and
environmental benefits that may be gained from large scale FAME blending.
Blending FAME in a refinery allows for the correction of certain base fuel parameters (e.g.
density, T95 and cold flow parameters). It also enables the blender to take advantage of the
natural lubricity properties of FAME especially in low sulphur base fuels in which the lubricity
additive can be reduced or removed.
Quality assurance of feedstocks and finished products can be easily achieved in a refinery
rather than in a depot or terminal. Product blending is a daily business in a refinery where
knowledge and suitable equipment are in place. The volumes blended in a refinery give more
flexibility and is much more suited to establish a robust blend process.
Cold flow additives to adjust cold flow properties in finished AGO are not normally available
at terminals in EU. Additional investment for additive storage and injection has to be
accounted for or the base AGO for FAME blending has to have enough quality reserves to
compensate for possible adverse effect of the FAME blending on cold flow properties.
Cold flow additives are normally available at terminals in the US, but additional investment for
additional additive storage and injection may need to be accounted for.
9.2.2 Terminal Blending

In certain circumstances, it might be reasonable to go for terminal blending. Reasons can be
limitations in logistics, for example the prohibition on pumping FAME containing AGO through
a multi product pipeline or due to some specific restrictions throughout the supply chain
where major investment in extending the existing blending, transport and/or storage facilities
is not justified.
For terminal blending side-stream gantry blending is the standard within

Distribution and deviation from this standard requires derogation via the
distribution biofuels team.
9.3 Type
Regardless the types of blending the following sections are based on blending FAME into
AGO basefuel. The FAME used should meet the local specification required for blending.
Due to the chemical nature of FAME it can be used and handled in the
blending process like any other common HC blend component for AGO.
Existing equipment like tanks, pipes, mixers, sample points, measurements and process
control equipment of the blending system shall be used. If the existing equipment does not
allow the use of FAME, e.g. lack of tanks, then an upgrade of the system has to be done.
The tie-in to existing pipe work has to be realized in a way that the blending system retains
its basic character. An inline blending system should not be extended with a sequencing
batch blending process. In cases where the inline blending is done upfront of a HDS unit, the
tie-in of the FAME line has to be done down stream of the HDS unit. The blending remains a
continuous process and is not of batch character.
9.3.1 Side Stream Blending at Terminals
Side stream blending is ratio blending of FAME to a base AGO stream.
The control algorithms required for true continuous ratio blending of components into the tank
truck compartment is inherently more complex than a sequential load mode. Each blend
component must have a correctly tuned flow rate control valve in order to correctly adjust its
own injection rate in accordance with the overall blend recipe during the blending activities.
Maintaining the ratio of the low percentage component during low flow start-up can be
difficult. Therefore it is important to ensure that calibration of rack meters covering the lower
and higher range are carried out in order to have reliable and accurate blending
performance.
There is no homogeneity problem in a compartment with ratio blending mode. The actual
component ratio during the load is representative of the final ratio. The number of
occurrences of off spec blends tends to be less by ratio blending mode. The blending into the
compartment can be stopped at any point during the loading activities without affecting the
target blend recipe. The truck loading time is less for ratio blend mode compared to
sequential blending mode.
By ratio blending the AGO and FAME into the truck, there are two points of custody transfer,
AGO and FAME (Figure 8 AGO/FAME injection line up and metering – ratio blending (side
stream blending) It is noted that there are no volume gain or shrinkage effects taking place
while blending FAME into AGO. Hence metering position is less critical compared to e.g.
ethanol in gasoline gantry blending set-ups.
M M
AGO FAM E
Figure 8 AGO/FAME injection line up and metering – ratio blending (side stream blending)
9.3.2 Batch Blending

In batch blending the blend components are typically stored in predefined pools. During
blending predefined quantities from these pools are transferred to a product tank, according
to target recipe. There is no flow ratio control. Components are rundown or pumped either
simultaneously or sequentially into a batch tank. This tank is then homogenized, sampled
and tested.
Batch blending can be done at refineries and terminals. For homogeneity
reasons and in the absence of tank mixers gantry side stream blending is the
Distribution standard for terminal blending.
If big volumes have to be blended the slow process of batch blending should not be the first
choice.
If batch blending is used some basics have to be considered:

• FAME has a relative high density in the order of 880 kg/m3 (vs. maximum density of
AGO of 845 kg/m3) when tank connections are close to the tank bottom, FAME
should be added first to the tank then AGO should be added. This should minimise
layering in finished product tank.
• Prior to implementation of FAME blending, a check on effectiveness of available
mixing equipment has to be done and suitable mixing times for proper
homogenization of finished product have to be defined. Checks should be in place to
ensure tank homogeneity. Density checks of the top, middle, and bottom of tanks are
required.
9.3.3 Inline Blending.

For inline blending components are rundown to predefined pools. From these pools the inline
blender draws components according to a recipe. Components are rundown or pumped
simultaneously under individual flow ratio control into the blend header. The blend header
then feeds a batch tank. The inline blending could be designed with Blend Ratio Controller
(BRC) and Blend Property Controller (BPC). Qualities can be monitored on-line usually
through use of an on-line Quality Measuring Instruments (QMIs).
Inline blending systems are preferred systems in refineries to blend large

volumes and to minimize product quality give away.
The blend itself is closely monitored by QMIs and/or by lab analyses. The blend components
are blended in a fixed ratio given by a recipe (Blend Ratio Control - BRC). The recipe and
hereafter the blend ratios can be adjusted based on the feedback of measured product
qualities in the blend line.
FAME as an AGO blend component should be and can be tied-in to an existing inline
blending system.
Basic requirements are:

• Tie-in of FAME lines should be upstream of the static mixer of the blend line. If this is
not possible e.g. for engineering reasons, a second static mixer should be
considered. It is not recommended to blend FAME downstream of the static mixer. If a
static mixer is not present then the blend header design and flow rate window should
be designed to generate sufficient mixing. In these cases the mixing has to take place
in the turbulence flow of the mixing line and by the mixing equipment of the blend
tank. The knowledge of the effectiveness of the mixing is essential to define proper
procedures for tank settling and draining and homogenization.
• Additive injection, e.g. cold flow additives should be upstream of the static mixer.
• Tie-in of suction line of fast loop for QMIs and for lab sampling has to be downstream
of tie-in of FAME component line to the blend line, ideally downstream of the static
mixer. It should be noted that additives injected into the blend need some time to act.
Inline Blending of B5
Components Additives Products Shipment
2EHN MDFI WASA

Kero
T-201
Process Units
LGO-1 Pipeline
Refinery
T-202 B5
QMI T-301
LGO-2
T-203 B5
T-302
HGO
T-204 B5
T-303
B100
T-205
Figure 9 Basic set-up of an inline blending system in a refinery

Inline Blending of B5 with Gasoil Blending up- and downstream of HDS Unit
Components Additives Products Shipment
2EHN MDFI WASA

Kero
Process Units
T-201 Pipeline
B5
QMI T-301
LGO
T-202
B5
HDS
T-302
HGO
T-203
B5
T-303
B100
T-205
Figure 10 Inline blending system where base fuel is blended upstream of a HDS unit and Fame
blending is downstream. A similar system is operated at Harburg Refinery line blending is also
done at terminal level where at some locations the FAME in blended into the diesel during the
discharge of barge or delivery of the product through a pipeline.
9.3.4 Sequential blending at Terminals

Sequential blending is an operation where FAME and AGO are loaded into a compartment
separately with no or little mixing occurring as the fuels are loaded into the compartment of a
truck or ship.
Sequential blending at terminals is not recommended, due to product

Homogeneity and safety issues during loading operations.
The FAME has to be loaded first for bottom loading truck followed by the lower density AGO
fuel. This loading method and sequence provides some mixing mechanism. The mixing
mechanism is further enhanced during transfer activities. This is generally enough mixing
except in cold weather.
It is not recommended to load FAME into a cold empty tank truck as this can cause the
FAME to solidify. In cold weather, it is better to load the tank truck with half AGO fuel
followed by FAME before final loading of AGO fuel. This will help to prevent the FAME from
freezing to the internal parts of the tank truck.
FAME injection at the terminal can be arranged in a similar fashion as the Ethanol side
stream blending approach (chapter 9.3.1).
9.3.5 Mixing time

Mixing time between the FAME and AGO in a Terminal loading gantry should be maximised
in the design. There should be enough line length between the point of FAME injection and
the loading flange.
Estimate of required line length according to a rule of thumb at turbulent flow is:
- L/D ~ 100 for co annular injection

- L/D ~ 65 for a T injection
- Using a pipe bend in line work takes another L/D ~ 15 of,
- An overall L/D ~ 50 results to an 99% mixing quality
The application of a static mixer should be considered, albeit this goes at an extra pressure
drop, which the system should be able to handle. The need for good hydraulics is a prime
factor to assure good and consistent blending under all flow conditions.
9.4 Pre-Blending
The chemical nature of FAME allows it to be blended with any kind of hydrocarbon distillates.
It is recommended not to use pre-blends (e.g. B90 or B80) to get a higher oxidation stability
blend component. Even B80 or B90 blends can be degraded quite quickly resulting in an off-
spec blend component. B20 or even lower pre-blends can be used to improve low
temperature storage and product handling characteristics.
Pre-blends of FAME can be used to improve low temperature storage

characteristics
9.5 Temperature of Blending

Temperature can be a crucial item in the whole production system. Operation, safety and the
product quality may suffer if the product or the components are either too hot or too cold.
FAME that is stored in a tank without heating may cool down in wintertime and crystal
formations take place. During blending and mixing with components with higher temperatures
the crystals will dissolve. This applies for inline blender and for batch blender.
The temperature during the blending process and thus in the finished product is determined
by the following conditions:
I) The dissolving of cold flow additives in AGO has to be assured using a specific
temperature range. This temperature range depends strongly on the cold flow
additives, which are injected. A typical range is between 25°C and 40°C. The
additive supplier should be contacted to get the specific temperatures.
II) The individual temperature of each blend component should be at least 6°C
above the highest cloud point of individual components. For refinery blending this
is not a constraint as FAME blending is usually done in the (relatively hot)
rundown. For terminal blending the temperature of the fuel should be at least 6
deg C above the cloud point of the FAME used. .
III) The blender temperature has to be below the Flashpoint of the finished AGO.
Specification in EN 590 is above 55°C.
During the blending process the fuel temperature should be 6°C above the
Cloud point of the FAME and has to be in a range that assures that cold-flow
additives are dissolved completely.
The blending temperature has to comply with the standard safety requirements for AGO.
9.6 Additives
There is no difference in additive handling whether AGO blending is with or
without FAME.
Additives are usually stored in heated vessels. If the storage vessel is unheated a dilution of
the additive with a hydrocarbon distillate (e.g. Kerosene) may help to maintain ability of
additive dosing and responsiveness of the additive itself. The additive suppliers give advice
on how to handle specific products.
9.7 Blend analysis –NIR

Near Infra-Red NIR models will be developed to measure AGO blend properties. Contact
NIR focal point in GSEA for the latest information.
9.8 Blend experiences from refineries

The learning and observations from some European refineries has been summarised and
attached in Appendix H. Please note that the described experiences are not necessarily
regarded as best practice.
10 Blending properties: AGO Blends
The cold flow property is an exception and needs special attention.
Most of the AGO blend properties do not show a different behaviour compared
to conventional AGO blending. Most issues can easily be addressed by
adjusting the additive levels and are therefore unlikely to be obstacles to
FAME introduction. Cold flow property is an exception and needs special
attention.
10.1 Cold flow properties/Low temperature operability - AGO Blends

The addition of FAME to AGO can have a large impact on the cold properties
(CP and CFPP) of the fuel that can, in many cases, make meeting the
specifications difficult using current cold flow additives. FAME derived from
highly saturated, high melting point materials such as TME and POME can be
particularly problematical.
The addition of FAME to diesel fuel can have a considerable impact on the low temperature
properties (cloud point and CFPP) of the fuel (whether cold flow additives are used in the
base diesel fuel or not) and understanding this impact is one of the key aspects of ensuring
fuel fitness for purpose. This report aims to describe the various ways in which FAME can
affect fuel cold properties, discuss the reason why these occur and present advice for
minimising the effects. It is based on work carried out as part of the Fuels Product
Management programme underpinned by more fundamental understanding gained from a
Manufacturing and Supply R&D product quality project.
The low temperature properties of diesel fuel can be influenced by both the methyl ester type
and composition of the FAME and by the presence of impurities in the FAME. Methyl esters
are the main components of FAME and the low temperature properties of the blended fuel
are mainly influenced by the saturated methyl ester content of the FAME, which is directly
proportional to the cloud point, pour point and CFPP of the FAME. Of the common FAME
types, RME has a low saturated methyl ester content and thus has less influence on fuel cold
properties than FAME such as POME, which has a high-saturated methyl ester content.
Work has shown that, for EN590-type fuels with cloud points above –10 °C, the CFPP of the
fuel will be affected if the level of saturated FAME in the blend exceeds 1%. As a general
guideline, however, the original CFPP should be recoverable by up-treating the fuel with a
suitable cold flow additive. Once the saturated FAME level exceeds ca 2%, however, the
cloud point of the fuel will also be measurably affected and the original CFPP will be
unattainable without excessive addition of cold flow additive.
Threshold levels for use of common FAME types in diesel fuel can be set based on these
guidelines. Thus TME/POME use is limited to ca 4.5% levels before the cloud point is
influenced and CFPP becomes unrecoverable. By contrast RME can be used at
concentrations of up to 10% without changing the CFPP or cloud point while the level for
SME is somewhat below 7%.
The presence of impurities in FAME can also influence the cold properties of the blended
diesel fuel. In this case the issue is predominantly precipitation of the impurities at
temperatures above the cloud point of the fuel, which can lead to potential blockage of fuel
filters. Saturated mono-glycerides have been identified as one of the main problem species
for blended fuels.
When B5 biodiesel blends were introduced to the Swedish market, during winter 2006/7
there was an industry-wide issue of precipitate appearing in fuel at temperatures well above
its cloud point. This caused operability problems for some commercial customers and
significant precipitated material was observed during inspection of depot storage tanks in the
spring of 2007. As an interim solution to the problem the industry has reverted to B2, which
had been successfully used in the Swedish market previously. The FAME used to produce
the B5 blend met the EN 14214 FAME specification and was an RME/SME mixture. An
investigation has identified the precipitates as saturated mono-glycerides. This is un-reacted
material from the FAME manufacturing process. Monoglyceride content is primarily a function
of the processing steps applied in manufacture and will vary by supply point. Perhaps
counter intuitively, perceived “heavy” or difficult FAME such as TME could often have low
mono-glyceride content because it will have undergone extra processing. Laboratory tests
have shown that precipitation of such partial glycerides can be expected from B5 blends at
typical Swedish winter temperatures due to their low solubility in diesel
These impurities have poor solubility in diesel fuel, which is temperature dependent. FAME
specifications only contain limits on total mono-glycerides and the proportion of these in a
particular FAME that are saturated will depend on the FAME type. However, for FAME types
ranging from RME to POME, a total mono-glyceride specification of 0.2% should prevent
saturated mono-glyceride precipitation in fuels with cloud points above –5 °C, while higher
levels (0.3 to 0.4%) could be tolerated in FAME such as RME that have low saturated methyl
ester contents. The effect of saturated mono-glyceride precipitation can be mitigated to some
degree by use of specific cold flow additives designed to keep the precipitate in suspension
as a finer suspended particle. These additives are still in the development phase, however it
is important to note that they will not prevent saturated mono-glyceride precipitation.
Other impurities that can impact cold properties of FAME include sterol glucosides (only
present in plant-derived FAME and most common in SME and POME). Sterol glucosides can
precipitate from the FAME itself (as opposed to the saturated mono-glycerides which
precipitate from the blended diesel fuel). Sterol glucosides have been a particular issue with
SME in the USA but correct FAME processing would be expected to prevent or minimise
their impact.
More details are given in GS.07.53836: Customer Report (S&D) - Precipitation above the
cloud point from Gas-oils containing FAME and in GS.08.54767: Customer Report (S&D) –
Understanding Biodiesel Low Temperature Issues.
10.2 Density
FAME have a relatively high density (about 880 kg/m3) compared to AGO and when blended
with AGO could lead to a product blend with a density higher than the maximum limit given
by the AGO specification (EN 590 is 845 kg/m3). This is of particular concern if the density of
the base AGO is already close to the upper limit even before blended with FAME. Especially
when the FAME is blended at the terminal the maximum density specification of the diesel
supplied should be defined in order to ensure density remains within specification after
blending the FAME into the diesel. The effect on density of blending FAME in AGO is linear,
i.e. the blend density is proportional to the concentration of FAME.
FAME and its blends demonstrate a temperature-dependent behaviour of the specific gravity
that is qualitatively similar to AGO fuels2.
2
Reference AOCS Press, Paper Number 9143 in JAOCS 77, 115-119, February 2000.
10.3 Cetane
FAME has intrinsically higher or equivalent cetane compared to the AGO. FAME with higher
cetane (i.e. POME) can improve the cetane of base fuels. With only 5%v FAME, the
magnitude of improvement is close to the accuracy of the test method. It is recommended not
to rely upon FAME at low concentration to provide cetane quality to meet specifications.
Instead, they should preferably be blended into spec-compliant base fuel.
10.4 Viscosity
Neat FAME normally has a higher viscosity than standard AGO.
EN 14214 specifies a maximum viscosity of 5 mm2/s at 40 deg C, which is slightly more than
the maximum viscosity given by EN 590 for AGO i.e. max 4.5 mm2/s. If the base AGO and
the FAME are close to their maximum viscosity specification, this have to be taken into
account as this may lead to possible off-specification product. See also 8.1.6.
10.5 Distillation characteristics

No foreseeable issues with distillation when blending FAME with AGO. As FAME is a mixture
of different components (Appendix C) it does not have a single boiling point but a (small
range) distillation curve. At atmospheric pressure boiling points of the individual FAME
components generally ranges from 330 to 360°C.
10.6 Blending rules for FAME into diesel

Existing blend rules apply to FAME blends up to 20%v.
The properties and rules investigated are given in the table below. The full details are in
report OG0330932 - Investigation into existing blend rules for FAME.
Property Blend rule Validity

Density Linear by volume Valid
Flash point Linear by volume (Wickey Valid
Chittenden Index)
Cetane number Linear by volume Still valid though data set is
limited
Viscosity Linear by weight (V50 index) Valid
Cloud point Linear by volume (Pauillac Valid with local experience to
index) determine small offsets
T90/T95 distillation Linear by volume (on% Valid
recovery at 90 and 95%)
Table 6 Blending rules for FAME into diesel
Not all FAME are the same and have different properties. It is recommended that refinery will
test the available FAME in the local region and perform laboratory trial blends to gain
confidence.
11 Blending properties: Neat FAME

Assume all properties blend linearly in EN14214 except items in the table 7 below
Property Blend Rule

Viscosity @ 40°C
Density @ 15°C Assume linear but check, certain
Cetane Number blends have shown unusual behavior.
Cloud Point "linear by volume"
CFPP "Ethyl"
Pour Point "Paulliac" or "Harburg"
Flash Point
Oxidation Stability Use lowest result
Copper Strip Corrosion
Table 7 Neat FAME blending properties
Application of “Cold Flow Property Blend Rules for FAME-to-FAME Blending” was assessed
by comparing predicted results with laboratory results. The comparison is based on POME-
RME blends with different ratios. (see report GS.08.53285)
The recommended blend rules for Cloud Point, CFPP and Pour Point are given in “Figure
12”. These blend rules had been originally developed for AGO and IGO blends and need a
small correction for bias if used for neat FAME blending.
These correction factors are within the repeatability of the reference test methods, but may
be different (likely to be larger) if using different FAME types (other than RME and POME)
and if FAME is already pre-additivated with cold flow improver additives.
Correction factors to be used for RME-POME blends:

Cloud Point: calculated result – 0.5 °C
CFPP: calculated result + 1 °C
Pour point: calculated result - 1 °C
12 Transportation
12.1 Introduction
FAME must be stored and handled using procedures that do not allow the temperature to
drop below 6 C above the cloud point of the FAME. . The cloud point of the FAME, the FAME
temperature, the ambient temperature, and the time the fuel is in transit are all factors that
must be taken into consideration. All handling procedures should be discussed and agreed to
by both the supplier and receiver.
FAME should be transported in a way that avoids contamination. The following guidelines are
recommended and are similar to those used by distributors and transporters of middle
distillate fuels. Therefore, in order to protect product integrity, the supplier and receiver
should agree to adhere to the guidelines.
The delivery of FAME to refinery or terminal happens either by trucks (e.g. Heide refinery) or
by barge (e.g. Harburg refinery). In case of truck delivery FAME may cool down to ambient
temperature and in case of barge delivery it may cool down to river water temperature.
In areas of cold climates refineries and depots receiving FAME should

consider whether heating of transfer lines and storage tanks are necessary.
Specification agreements about cold flow properties of FAME is a question of cold flow
performance in B5 or B10 but also of site-specific logistics, their capabilities for handling the
product and local climate conditions.
12.2 Tankers
Tankers dedicated to FAME should be used. If dedicated tankers are not available, non-
dedicated tankers can be considered taking into account the pre cargo. Depending on the
pre cargo adequate measures have to be taken before loading with FAME.
An example of using non-dedicated tankers in consideration of the pre cargo is shown in the
“pre cargo matrix” from ‘Rhine Supply’. The matrix is accessible on the home page of ‘Rhine
Supply’
http://sww.shell.com/downstream/supply_distribution/supply/rhine/qhse_ms/procedures/trans
port_operation.html
Example: If the pre cargo has been automotive diesel (10 ppm for Europe) the tanker has to
be “well drained” before loading with FAME. In cases the pre cargo has been Gasoil with a
high Sulphur content, e.g. IGO with 1000 ppm Sulphur, the tankers have to be “well drained”
and “stripped” before loading with FAME.
Dedicated hoses that are compatible with FAME should be used to avoid cross
contamination from residue left in the hoses. Hoses should be capped or shielded during
transportation. Tankers that have been used for heavy fuel oils or asphalt should never be
used to carry FAME fuel.
12.3 Trucks and rail cars

The guidelines below should be adapted to meet any unique need of the facility.
Trucks and rail cars should be made of aluminium, carbon steel, or stainless steel. Proper
inspection and washout certificates should arrive with the tank or rail car or be faxed to the
receiver prior to cargo arrival. Check composition of the last 3 previous loads for any residual
materials present.
The receiver, at their discretion, may determine that AGO fuel, kerosene or jet fuel is
acceptable as a residual. A closed cup flash point test (ASTM D93) should be performed if
light hydrocarbon material was in the transport as residual material. Certain residuals may
not be acceptable.
These residuals could include, but are not limited to:

• Food products or raw vegetable oils
• Gasoline
• Light solvents
• Lubricants
• Chemical surfactants
• Caustics
• Residual water
• Surfactants/detergents
• Heavy fuel oils
• Asphalts/bitumen
It should be assured that the used hoses and seals are clean and compatible with B100.
Viton or Teflon-lined hoses are recommended. Cold climate conditions may impose product
transfer difficulties. In this case it should be determined whether there is a need for insulation
or for methods to heat truck or rail car contents.
Neat FAME is generally shipped in one of the following ways during cold climate conditions:
• Hot in trucks for immediate delivery (27°C to 45°C);

• Hot (49°C to 54°C) in rail cars for delivery within 7-8 days (will still arrive warm if only
about 1 week has passed since loading)
• Unheated in rail cars that are equipped with steam coils. The fuel in the tank car can
be re-liquefied at the final destination with steam or hot oil - this is not the preferred
approach;
• Pre-blended with AGO fuel, kerosene, or other low cloud point fuel in either rail cars
or trucks.
Key Points for transporting neat FAME (B100):

• Aluminium, carbon steel, or stainless steel containers during transport
• Proper inspection and/or washout of transport
• Check for previous load carried and residual
• Food products or raw vegetable oil, gasoline, and lubricants are not acceptable
residuals
• No residual water in transport
• Hoses and seals are clean and compatible with B100
• Determine need for insulation or method of heating the transport if shipped during
cold weather conditions
12.4 Certificates of Analysis

The supplier must provide a Certificate of Analysis (CoA) for every batch of
FAME delivered. Prior to accepting a delivery of FAME product, it is important
to inspect the CoA to ensure that the properties reported lie within the
allowable range of the supply specification. Guidelines on ensuring and
maintaining product quality from FAME suppliers (GS.06.52356 V2) are to be
followed.
Standard off loading procedures should be followed along with specific guidelines in
GS.06.52356 V2 - Process for Ensuring and Maintaining Product Quality from FAME (Fatty
Acid Methyl Ester) Suppliers.
The tests recommended in the above report are a minimum requirement, further tests can be
carried out if required.
12.5 Multi product pipelines (MPP) - Europe

Multi product pipelines (MPP) may contain several grades of diesel, mogas, Jet fuel, heating
oil and other refinery intermediates such as naphtha, isomerate etc. Pipelines are the most
efficient way to transport liquid fuels but require careful management to avoid cross
contamination of products. Jet fuel is a particularly sensitive product and all contamination is
to be avoided. Cross contamination is managed in a variety of different ways depending on
the pipeline operator and the hardware available.
In Europe the transportation of B5 (5 %v/v FAME) in multi product pipelines

that is also used for Jet-A1 is acceptable by using a combination of minimum
batch size, modified interface cutting, product sequencing and buffers to
ensure the average level of FAME in a batch of jet fuel is below the maximum
level of 5ppm as specified in DEF STAN 91-91 for Jet-A1. This is however
subject to the approval of pipeline operators.
When biodiesel containing FAME was first introduced into Multi Product Pipelines (MPPs) co-
transporting jet fuel in 1995, trials conducted using the best available analytical methods at
that time indicated no detectable trail back of the FAME component into following jet fuel
batches. Pipeline sequencing operations were not altered based on these data. However,
with significant advances in experimental analytical techniques, some evidence of very low-
level FAME was detected in interface samples in 2006 prompting both refinement of the
analytical methods and a further controlled pipeline trial in 2007. This controlled trial
demonstrated that low level trail back of the FAME component from biodiesel into a following
jet fuel batch can occur at detectable levels. In the absence of reliable data on historical trace
level FAME carryover in MPPs, the initial fuel supply industry advice required revision of the
sequencing of batches of biodiesel and jet fuel by employing a non-aviation buffer material
between the products.
The widespread mandatory introduction of bio-materials in automotive fuels during 2008 has
presented a significant challenge to the operators of fuel supply and distribution systems.
Whilst the use of non-aviation buffer materials between diesel fuel containing FAME and jet
fuel should still be followed whenever possible, it is acknowledged that this places a
significant operational constraint on the pipeline operator and may not be practical to
maintain the required supply integrity. Following discussions with the engine and airframe
OEM's in 2007, the approval of an effective “non-detection” limit of FAME using the latest
analytical technique was agreed. The Joint Inspection Group Ltd. (JIG) issued a detailed
guidance bulletin (Number 15) (www.jointinspectiongroup.org) in November 2007 for the fuel
supply and distribution industry. Careful control of a combination of sequencing, batch size
and interface management can be used to ensure the level of FAME trail back into jet fuel is
below this detection limit Operators of multiproduct handling systems should also verify that
bulk contamination, even at very low levels (e.g. 0.01%), cannot occur.
Whilst pipeline operators and fuel distributors will need to go through a management of
change activity that will involve some testing for low level FAME using the new analytical
tests, it is not envisaged that routine testing of every batch will be required for two primary
reasons. Firstly, the general consistency of bulk fuel distribution operations provides surety
that once initial conditions have been tested and shown to provide the necessary control of
FAME, only periodic confirmatory testing should be needed. Secondly, management of
change systems shall be employed to ensure that any significant alteration to the distribution
operation is appropriately controlled and further FAME testing is triggered to verify the new
mode of operation. The sophisticated analytical techniques used to detect the low levels of
FAME are neither simple to run and interpret nor readily available. There are currently no
precision data for these methods.
Based on learning from an incident in the UK, it is important to note that testing activities
conducted to verify the effectiveness of QA procedures should focus on the final batch tanks
where jet fuel leaves a multi-product handling system. The handling system downstream of
the tested tank should be completely segregated from diesel containing FAME and there
must be no risk of any other contamination mechanism. If this is not the case and
downstream segregation cannot be guaranteed then FAME testing to verify downstream
operations should be performed. See JIG Bulletin 16 for further details and guidance.
The less than 5 mg/kg approval is granted on the basis that the aviation petroleum industry is
working towards an approval of 100 mg/kg FAME in jet fuel under the guidance of the engine
and airframe OEMs and that the ASTM protocol for additive and alternative fuel approval
shall be followed.
12.6 Multi product pipelines - US

In the US, the Colonial Pipeline System shippers (and owners) have voted against shipping
biodiesel on the main artery supplying petroleum products to the U.S. East Coast. A
statement was released by the company in October 2006 stating that, based on a survey of
our customers.
Colonial Pipeline has decided not to permit shipments of l fuels containing bio-
components at this time. Any FAME blending into AGO will therefore have to
be carried out at terminals.
The reasoning behind this decision is the fungible character of the system in combination
with the fear of liability. No technical evidence is available that there would be a problem.
13 Additives
13.1 Additives for FAME B100
13.1.1 Cold flow improvers

FAME (RME) containing additives has been used in Harburg in the past, without reported
incidents. In spite of this;
It is preferred that FAME does not contain any cold flow improvers, to
minimize, risk of interactions with other fuel additives.
Conventional AGO cold flow improvers can improve the Pour point and CFPP of B100 FAME
containing a low saturated fatty ester content. The low temperature properties of FAME with
a high-saturated fatty acid ester content cannot be significantly influenced by the introduction
of current additive technology.
Any unusual low temperature properties of FAME should be investigated further to ensure
fitness for purpose.
13.1.2 Antioxidants
The supplier needs to ensure the product will meet the specification on receipt at the Shell
location. The oxidation test in EN14214 is the EN 14112 Rancimat test, with a pass level of
>6 hours. Antioxidants can be used to achieve this result
The recommended antioxidants are generally described as hindered phenols,

like BHT. These chemistries can be used up to 1000mg/L in a B100 FAME
based on the acceptable levels in AGO and Jet fuel
The full list is shown below. Alternative antioxidants will need to be QAG assessed if the
market needs require further alternatives.
Recommended Antioxidant list:

• 2,6-di-tertiary-butyl-4-methyl-phenol (BHT)
• 2,4-dimethyl-6-tertiary-butyl-phenol
• 55% min. 2,4-dimethyl-6-tertiary-butyl-phenol, 15% min. 4 methyl-2, 6-ditertiary-butyl-
phenol with the remainder, 30% maximum, as a mixture of mono-methyl and di-
methyl-tertiary-butyl-phenols
• 72%min. 2,4-dimethyl-6-tertiary-butyl-phenol, 28% max. mixture of tertiary-butyl-
methyl-phenols and tertiary-butyl di-methyl phenols
• 2,6-di-tertiary-butyl-phenol
Alternative antioxidants are available and have been risk assessed for use in the supply
system. Contact GSMR or DSX for current assessments.
13.2 Effect of FAME on AGO Additives
13.2.1 Anti oxidant
As FAME may already contain antioxidant to ensure the Oxidation stability requirements are
met for EN14214.
Care should be taken to ensure B5 does not become overdosed with
Antioxidant.
13.2.2 Cold flow additives
Conventional AGO cold flow improvers are effective in B5 fuels produced from
FAME containing a low saturated fatty ester content, such as RME. Up
treating with current MDFI cannot always prevent significant increases in
CFPP for B5 fuels produced from FAME containing high-saturated fatty ester
content.
New additives, when available, will be needed to ensure high saturated FAME can be used
successfully. Until than we need to carefully consider the type of FAME that can be used in a
country, depending on the climate conditions (chapter 10.1).
Ideally before the introduction of FAME the additive supplier should be consulted to ensure
the system is robust enough to ensure low temperature operability is maintained.
13.2.3 Lubricity
There is no evidence from studies done to date that FAME has any
detrimental impact on either ester-based or acid-based lubricity additives.
FAME exhibit good lubricating properties when blended into AGO, both in the absence or
presence of lubricity additives. The extent of this effect is dependant on the FAME type.
Optimization of the level of FAME required to meet the lubricity specification needs to be
done on a case-by-case basis.
The extent of lubricity improvement varies across different FAME types (as it depends on
different raw materials and type of processing).
If the FAME content is below 2%v in the final blend, dosing of a lubricity
additive should be considered.
It is recommended that the operating unit carry out HFRR tests in the local base fuel, using
FAME from potential suppliers, to check that the particular FAME / AGO / lubricity additive
combination they intend to use will give sufficient lubricity performance in their market
( GSMR can provide advice if required).
13.2.4 SDA – Conductivity
Unexpected and large reductions in conductivity have been observed upon blending 5%
conductivity additives is still applied, and to be verified on a case-by-case basis
FAME can cause a loss in static dissipater additive (SDA) activity.
This should be checked for the FAME/SDA combination being used and the SDA dose rate
increased as necessary to ensure the finished fuel meets the required conductivity level to
satisfy local safety standards.
13.2.5 2-EHN – Cetane Improvers
B5 does not appear to affect the performance of cetane improvers in base

fuels.
Normally, no additional boost is provided by high cetane FAME when added to fuels
containing 2-EHN (high cetane), therefore fuels need to meet local cetane requirements
before FAME is added.
13.2.6 Impact on performance additives

Provided the FAME used is compliant with the local applicable specification when blended
into the fuel, and that the finished fuel is also on spec, the presence of the FAME in AGO is
not expected to have any detrimental impact on the antifoam or antirust performance aspects
of the NEMO 2000 family of AGO performance additives. In terms of injector cleanliness
performance, there is some evidence that FAME can impair the detergency action of the
additive to a limited extent; work is ongoing to investigate this in more detail.
Use of FAME in V Power Diesel is generally NOT recommended and should

be reviewed for individual cases and be subject to separate QAG
assessments.
.
14 Reprocessing Fuels containing FAME (including Slops)
14.1 Reprocessing slops via CDU and HDS

Reprocessing 5 to 10% slops containing 1-5% FAME on intake via CDU and
HDS is possible and will pose no significant risks on HDS catalyst
performance If all product streams are fully hydro treated at all times, there will
be no risks on product contamination. It is recommended that the refineries
investigate the origin of the slops and its process unit configurations before
deciding on the reprocessing route back to the refineries.
A number of refineries expressed concerns about re-processing of slops material that

contains FAME. Two aspects of consideration include the impact on HDS catalyst
performance as well as other process units, and the impact on product quality especially Jet.
The specific reprocessing route chosen will largely depend on how the slops containing non-
FAME are currently processed in the refinery. Potential routes from current practice include:
• Downgrading to IGO/DHO (chapter 15)

• Collection and recycling at low rate through the refinery
• Collection and disposal externally
• Blending away in product (14.2)
It is also important to understand the characteristics of FAME when it is exposed and

reprocessed via the different stages of the refinery process. It has been identified that the
most likely reactions that will occur are the hydrolysis and thermal decomposition of FAME.
Hence, the highest risk of potential FAME breakdown mechanisms happens in desalters and
pre-distillation furnaces in refineries, due to the presence of water and high temperature
exposure, respectively.
Hydrolysis, when in the presence of water in the desalter, will convert FAME into free fatty
acids and methanol. These components could remain in the organic phase representing a
potential corrosion risk in later refinery stages through the formation of methanoic acid.
Although these component are likely to be instantaneously hydrogenated and converted to
hydrocarbon and water in the HDS reactor (with increased partial hydrogen pressure), but
these corrosive mixtures could still be harmful to the upstream feed lines and vessels. For
example, free fatty acids in crude oil could lead to corrosion issues in the crude distiller but it
depends clearly on the concentration. Apart from corrosion, fatty acids can react with alkaline
salts in crude (saponification reaction) to form soaps and this increases the emulsion layer in
the desalter vessel.
• There should not be a corrosion issue if all organic acids in crude are below 0.3
mg KOH/100g.
Thermal decomposition of FAME breaks it down to shorter FAME molecules, and if distilled
into the kerosene stream may cause product contamination especially when kerosene is not
treated before sending to the Jet A1 pool.
• If all product streams are at all time hydro-processed, there is no risk of

product contamination.
It is recommended that the refineries investigate the origin of the slops and its process unit
configurations before deciding on the reprocessing route back to the refineries.
• HDS catalyst performance is not greatly affected by the reprocessing of a small

quantity of slops containing
FAME, for e.g. 10% slops containing 5% FAME gives only 0.5% FAME on the total HDS
feed. This will require only a small increase in HDS operating temperature, i.e. Weighted
Average Bed temperature, WABT (<2 degC) and continuous monitoring. The deactivation of
catalyst (if any) is reversible. It can be assumed that the esters are fully converted into water.
For instance, Petit Couroune reprocessed about 4% of slops on CDU feed containing
approximately 0.2% of esters, based on their best estimates. No issues on CDU operation
and product quality have been reported.
• Hence, from the HDS point of view, reprocessing of slops containing FAME
should not cause big issues for 5 to 10% of slops containing <5%v FAME.
14.2 Blending into main grade fuels.
As a result of cross-contamination at a retail station mixtures of gasoline and diesel

(containing FAME) are withdrawn from an underground storage tank. It is advised not to use
these streams for (re)-blending into gasoline as small amounts of FAME into gasoline may
cause problems. Issues with fatty acid based materials have been observed (by Shell and
OEMs) in gasoline vehicles including;
• Sodium soap formation leading to filter blocking

• Corrosion of lead in fuel storage tanks causing lead build up in lubricant and potential
exhaust catalyst poisoning.
• Faster oil aging affecting the lubricity of automotive oil and causing build-up of deposit
inside the engine.
These issues have been seen at levels of 100ppm and higher in gasoline.
FAME containing gasolines (as a result of cross-contamination) should

not be deliberately re-blended into gasoline.
15 FAME in Industrial Gas oil and Domestic Heating Oil

The risks associated with FAME contamination of heating oil due to shared
logistics will be accepted by the Commercial Fuels Business. An individual
case-by-case evaluation should be performed before the downgrading of
FAME-containing diesel for use as heating oil.
Introduction of FAME into a market can potentially lead to its introduction into the Industrial
gas oil or heating oil pool. This may be as contamination (at ppm levels) by the downgrading
of AGO fuel to industrial gas oil or by the deliberate introduction of FAME (at percentage
levels).
There are a number of issues (such as water contamination, oxidation stability and solvent
properties) associated with handling and storage of neat FAME, which could affect heating oil
properties if blended with FAME. Such issues have the potential to lead to problems such as
filter and pump blockage. However, use of RME in both France and Germany has revealed
no significant increase in problems or complaints in the heating oil market, despite the
potential for FAME contamination in both markets. A European-wide joint industry field trial
(EHI and Eurofuel) has been started in 2007 to investigate in fitness for purpose of heating
fuels containing 5 % FAME. No severe problems have been reported until today.
Based on this experience therefore, current recommendations are that:
• The risks associated with FAME contamination of heating oil due to shared logistics will
be accepted by the Commercial Fuels Business and further precautions are not needed.
The relevant customer service centre, however, should be fully informed to identify as
soon as possible any potential increase in customer complaints. Today, in Germany, a
contamination of heating fuel is allowed up to a level of 0,5 % FAME according to several
industry standards
• An individual case-by-case evaluation should be performed before the downgrading of
FAME-containing diesel for use as heating oil. This should identify market specific
potential risk and assure that local requirements are met. The decision to downgrade
AGO to heating oil should be supported by a positive business case. The Commercial
Fuels business should be consulted if a risk evaluation has to be carried out.
16 B5 in Retail.
Introduction of B5 should not require any special cleaning or flushing of retail
tanks. It is recommended that it is handled in a similar manner to AGO
containing a mid or top tier performance additive package.
Introduction of B5 into a retail network should not require any special cleaning or flushing of
retail tanks, and it is recommended that it be handled in a similar manner to AGO containing
a mid or top tier performance additive package (such as VPower Diesel). In particular, as far
as water & dirt pickup are concerned, B5 should not present any additional problems
compared to differentiated fuels.
As a precaution, however, water levels in retail tanks should be checked (either by automatic
gauge or manually) and any water removed before introducing FAME blends into the. During
normal operations, retail site staff should not be required to carry out any additional actions
beyond those that would normally be applied for the handling of AGO.
17 Risk Management in the introduction of FAME in Shell AGO

products – the Quality Assurance Group (QAG)
The Quality Assurance Group (QAG) Process provides a risk-based assessment of the
fitness for purpose of new or significantly changed fuel products prior to introduction into the
market. The output is a risk assessment for the business to enable informed decision making
on acceptance/mitigation/avoidance of fuels Product Quality (PQ) risk. The process is owned
by the Fuels Product Management Group in Supply (DSX/3) and documented in a detailed
process description on the Fuels Product Management website.
A key output of the QAG Process is a Quality Assessment Record (QAR) that documents the
risk assessment outcome together with any recommended operating or use constraints. .
Generic QARs have been developed to cover use of FAME conforming to
standard specifications in main grade fuels in both Europe and the US.
Use of FAME in premium grades (V-Power Diesel) requires a case-by-case assessment and
any Operating Unit intending to introduce differentiated fuels containing FAME into their
market should contact the QAG coordinator (DSX/36) to discuss QAG requirements as early
as possible.
18 HSE Issues
For AGO blends (up to 20%v), the fuel should be treated as conventional AGO
in all HSE aspects. FAME is generally classified as non-hazardous.
Full HSE details are provided in the Material Safety Data Sheet, contact suppliers for the
current version.
18.1 Static risks, electrical conductivity: Neat FAME and AGO Blends
Whilst neat RME shows a higher electrical conductivity than conventional AGO (250 pS/m at
20˚C as measured by the ASTM D2624-95), the effect of introducing up to 5%v RME (or
other FAME) in AGO on the overall conductivity of the blended fuel is small and not sufficient
to ensure safe handling.
Unexpected and large reductions in conductivity have been observed upon blending 5%
conductivity additives is still applied, and to be verified on a case-by-case basis.
According to Shell Guidelines, a minimum conductivity of 50 pS/m has to be assured at the

terminal gantry. Most refineries have defined an internal specification of min 100 pS/m to
compensate any conductivity losses that occur during handling and shipping of the product
The Terminal Operation Manual describes that the fuel should have a minimum conductivity
of 80 pS/m at arrival at the terminal
18.2 Spontaneous Combustion – Neat FAME
Neat FAME can self-ignite when soaked into porous material, e.g. rags,
textiles, insulations and inorganic materials, therefore materials saturated
with FAME should be disposed of correctly.
High Iodine value FAME when under high surface to air ratios, can oxidise rapidly and
generate excessive heat. When the temperature rises above its ignition point, combustion
then begins in the presence of sufficient oxygen. Therefore neat FAME soaked into porous
material, e.g. rags of a critical mass in an open container or drum can self-ignite and cause
spontaneous combustion. Recently two incidents were reported by US Independent Liquid
Terminals Association (ILTA) on the spontaneous combustion of saturated rags soaked with
biodiesel. To prevent such incidents from happening at terminals when handling neat FAME,
the following practices are recommended:
1. Conduct a facility audit for FAME exposure, locations of loading/unloading and the
proper location for the FAME disposal drums.
2. Proper signage at all loading and unloading points indicating FAME rags need to be
placed in the proper containers.
3. Containers are properly labelled FAME Rags Only and filled with enough water to
cover the saturated rags.
4. Before disposal, wash rags with soap and water, and dry in well-ventilated area.
5. Discuss the hazards of FAME with all staff and visitors to the facility that might be
working with this material.
Improve housekeeping at all facilities especially those areas where FAME might be present
to limit the exposure to fire and/or damage in the event of a fire.
18.3 Regulatory Compliance
Substance Identity & Registration
Many FAMEs are sold as the “source oil or fat”-methyl ester, and many of these are identified
by their CAS and EINECS numbers (Appendix I) There are, however, no specific substance
identities for used cooking oils or some of the newer oil sources, such as Jatropha.
There are, however, at least four (A-D below) generic descriptors for FAMEs, covering
slightly different ranges of fatty acid composition, which could be useful.
Descriptor CAS No EINECS No
Fatty acids, C16-18 and C18-unsatd., Me esters 67762-38-3 267-015-4 A
Fatty acids, C16-18 and C16-18-unsatd., Me 102047-28-9 310-005-2 B
esters
Fatty acids, C14-18 and C16-18-unsatd. Me 67762-26-9 267-007-0 C
esters
Fatty acids, vegetable oil, Me esters 68990-52-3 273-606-8 D
Fatty acids, rape-oil oil, Me esters 85586-25-0 287-828-8 R
Table 8 Generic descriptors for FAMEs
The first (A) is the most specific, and covers around 90% of the composition of most FAMEs
derived from both vegetable oils and animal fats. In consequence, we have used this
substance identity to pre-register most FAME imports into Europe for Shell Trading, under
the new REACH Legislation. Certain (high erucic acid) forms of Rape Methyl Ester (RME)
would only be covered by descriptions D & R, and we have also pre-registered using “R”.
In making the FAME pre-registrations, we have linked them to some of the individual fatty
acid methyl esters, such as methyl oleate, as they have been known for years and extensive
HSE information is available in the public domain. (Enter the CAS or EINECS No in the ESIS
database (http://ecb.jrc.ec.europa.eu/esis/) and click on “IUCLID Chemical Data Sheet”). The
mapping of CAS Numbers and typical fatty acid compositions and oil/fat sources is given in
Appendix J.
Shorter fatty acid chain length FAMEs form another family that are currently not imported into
Europe, although “Fatty acids, coco, Me esters” are used in fuels in the East. It is exempt
from Registration under REACH. The FAME from Palm Kernel oil is a similar substance but
not currently imported or exempt from REACH.
The chemical composition of FAMEs derived from other sources (fish, algae, etc) would need
to be checked to see if any of the generic descriptors was suitable, or it had already been
given a separate substance identity, otherwise the material needs to be registered as a new
substance.
Inclusion on the local Chemical Inventory, where it exists, is generally a requirement for
manufacture and sale in that country. This can be checked via the ARIEL database at
https://webinsight.arielresearch.com/ . Contact a business Product Steward or the Product
Regulatory Support Group to run a search or if you require access.
19 Higher FAME content blends (B7, B10/B20)

There is growing pressure from governments in several parts of the world to
increase the amount of FAME included in AGO from the B5 level.
In Europe, the current EN590 standard covers FAME contents of up to 5%v (B5). CEN have
been requested by the European Commission to recommend necessary changes to EN590
to cover B10 blends. Activities to investigate potential issues associated with B10 are also
ongoing in some national inter-industry organisations (such as the German DGMK).
Objections to the use of B10 are currently being voiced by some OEMs (particularly in
Germany). These revolve around issues of:
• Increased fouling of injectors from the higher FAME content and how this is related to the
oxidation stability of the B10. Some OEMs are pushing for changes in the EN590
oxidation stability test to account for this. Initial results suggest that B10 blends can lead
to loss of engine power with time compared to conventional AGO. This is associated with
increased injector fouling
• Non-compatibility of current elastomer seals with B10 blends
• Incompatibility with current methods of regeneration of particulate traps
• Accelerated dilution and degradation of the lube oil
In addition to these B10 blends are also likely to lead to:

• Higher water retention levels
• A greater impact on AGO cold flow properties than B5 (especially if TME / POME type
products are used)
• Increased difficulty in meeting T95 and density specs for refineries already constrained
for these parameters.
Based on discussion within CEN between the oil companies, OEMs, and biodiesel producers
the acceptance level of biodiesel in EN 590 is expected to increased to max 7% v/v. However
in order to make sure that the final blend still is “fit for purpose” an additional oxidation
stability specification (EN 15751) of min 20 hr will be introduced for blends containing more
than 2% v/v FAME (voting in CEN Jan 2009).
In the US, a new specification (ASTM D7467) for B6-B20 blends was approved at the ASTM
meeting.
In Europe France has introduced B7 in 2008 with some adjustments in the national diesel
specification (oxidation stability, mandated BHT level of 1000 ppm, limited increase TAN).
Higher concentrations of FAME are used by captive fleets with a high variety in specifications
often developed in close cooperation with the OEMs.
20 Fatty acid ethyl/alkyl esters FAEE

There is current activity to allow usage of other alkyl esters (in particular fatty acid ethyl
esters) in AGO, although manufacturing capacity of these is currently very limited. On the
specification side, work will begin within CEN to develop a similar specification to EN14214
for fatty acid ethyl esters. ASTM D6751 is more general and currently allows for all fatty acid
alkyl esters.
Implementation-related knowledge on higher alkyl esters is currently very

limited and will be further developed.
However, similar issues are expected as with FAME, although physical properties of the base
esters will be different, notably in viscosity, density and low temperature properties.
21 GTL blending component

Gas to Liquids (GTL) diesel has become one of the components to be mixed with
conventional AGO in view of its excellent cetane quality, low density, as well as negligible
sulphur and aromatics contents which make it potentially valuable for improved emissions
performance in diesel vehicles.
GTL blending in diesel up to a level of 5% will not cause interaction with FAME
(change in solvency characteristics). Higher concentrations up to a level of
30% have shown to be compatible but local testing is recommended before
blending of GTL is started.
Fleet tests with neat GTL have demonstrated “fit-for-purpose” fuel.

Laboratory blending tests with Diesel and GTL up to 30 % showed validity of current blend
rules.
Based on properties of Diesel base-fuel and GTL, potential blend constraints, in particular
Density, Cloud Point, CFPP and Pout Point need attention. CFPP and Pour Point may need
additional cold flow additives to get on spec. In case of GTL-Kerosene blending also
Viscosity may become a constraint.
An interaction with FAME in Diesel-GTL blends up to 5 % could not be observed.

The use of FAME in Diesel-GTL blends can compensate poor density of GTL and poor
lubricity of GTL.
One of the possible issues when blending high levels of GTL into diesel is the change in
solvency characteristics (no aromatics in GTL). This can change the solubility behaviour of
FAME contaminants like mono saturated glycerides and steroglucocides and result in
precipitation.
The following recommendations are included for local implementation of blends

containing FAME in combination with GTL blends above 5% v/v:
• Local S&D to consider the operational precautions for winter period storage and
handling of neat GTL in new markets.
• Local PQ Advisor to assess whether there are site-specific issues related to the
mixing of Bintulu and Sasol GTL in the case where separate storage is not available
(with help of QAG team if required).
• In addition to EN 590 tests (and tests in any additional local specifications) it is
recommended that prior to introduction of GTL into diesel the following tests are
carried out on lab blends
1. Filterability;
2. Cold Soak filterability (if FAME is present);
3. Appearance after 1 week at 5°C above cloud point (if FAME is present)
• It is essential that the local PQ lead ensures that the checks highlighted are fully
applied in order to confirm compatibility from a cold flow, additive compatibility and
general handling point of view.
• Local PQ lead to review the robustness of the CVP where maingrade claims fuel
economy benefits.
Further information on the QAG process can be found livelink:

https://sww-
knowledge.shell.com/knowhow/livelink.exe?func=ll&objId=36655370&objAction=browse&sort
=name&viewType=1 (restricted access, please the QAG-coordinator for more information
22 Additional General References

• Biodiesel the comprehensive handbook – Mittelback, 2004, ISBN 3-200-00249-2
• Review On Biodiesel Standardization World-Wide - IEA Bio energy Task 39, BLT
Wieselburg, www.blt.bmlfuw.gv.at
• A Fleet Managers Guide for the Handling, Receipt and Storage of Bio diesel Fuel -
Version 1, April 2005, Bio diesel Association of Canada
• Bio diesel Handling and Use Guidelines v2 2004- US DofE
• Business Management for Bio diesel Producers. National Renewable Energy Laboratory,
July 2004, NREL/SR-510-36242
• US National biodiesel board website; http://www.biodiesel.org/
• GS.08.54630 customer report: AGO and biodiesel oxidation stability
• GS.08.54767 customer report: Understanding biodiesel low temperature issues
• GS.07.53836: Customer Report (S&D) - Precipitation above the cloud point from Gas-oils
containing FAME.
• Report GS.07.53961 Customer Report: The reprocessing of slops containing FAME at
Stanlow Refinery.
• GS.06.52356 - Process for Ensuring and Maintaining Product Quality from FAME (Fatty
Acid Methyl Ester) Suppliers
• GS.06.53282 Microbial contamination, a technical guide
• GS.08.51095 V2: Microbial Contamination of Diesel Fuel, A Guidance Note
• Joint Inspection Group: Bulletin No 15 and 16 (on transport through multiproduct
pipelines), November 2007 and June 2008.
Appendix A. Common Fatty Acids

Chemical Names and Descriptions of some Common Fatty Acids
Carbon Double
Common Name Atoms Bonds Scientific Name Sources
Butyric acid 4 0 butanoic acid butterfat
Caproic Acid 6 0 hexanoic acid butterfat
Caprylic Acid 8 0 octanoic acid coconut oil
Capric Acid 10 0 decanoic acid coconut oil
Lauric Acid 12 0 dodecanoic acid coconut oil
Myristic Acid 14 0 tetradecanoic acid palm kernel oil
Palmitic Acid 16 0 hexadecanoic acid palm oil
Palmitoleic Acid 16 1 9-hexadecenoic acid animal fats
Stearic Acid 18 0 octadecanoic acid animal fats
Oleic Acid 18 1 9-octadecenoic acid olive oil
Vaccenic Acid 18 1 11-octadecenoic acid butterfat
Linoleic Acid 18 2 9,12-octadecadienoic acid grape seed oil
Flaxseed
Alpha-Linolenic Acid
18 3 9,12,15-octadecatrienoic acid (linseed)
(ALA)
oil
Gamma-Linolenic
Acid 18 3 6,9,12-octadecatrienoic acid borage oil
(GLA)
peanut oil,
Arachidic Acid 20 0 eicosanoic acid
fish oil
Gadoleic Acid 20 1 9-eicosenoic acid fish oil
Arachidonic Acid
20 4 5,8,11,14-eicosatetraenoic acid liver fats
(AA)
5,8,11,14,17-eicosapentaenoic
EPA 20 5 fish oil
acid
Behenic acid 22 0 docosanoic acid rapeseed oil
Erucic acid 22 1 13-docosenoic acid rapeseed oil
4,7,10,13,16,19-
DHA 22 6 docosahexaenoic fish oil
acid
Small amounts
Lignoceric acid 24 0 tetracosanoic acid
in most fats
Appendix B. Typical FAME properties

The following charts and tables show typical ranges of data for a selection of FAME types
available. The Harburg data is from their LIMS system and the Argent data their analysis.
The data gives a good indication of the range of values that can be expected for a selection
of FAME properties. Each new supplier should be asked to provide data on the typical
ranges for key FAME properties to ensure the blending location can effectively manage their
operations
HARBURG FAME (RME)
Oxidation
Density Viscosity Flash Water Cloud
Acid Value CFPP stability
15C KV40 point Content point
Rancimat
kg/m3 cSt mgKOH/g °C mg/kg °C °C Hrs
Average 883.3 4.434 0.28 151 235 -4.9 -15.5 7.1
Std Dev 0.25 0.067 0.08 14.9 55 1.2 3.6 0.7
Max 884.0 4.505 0.46 174 396 -3 -9 8.4
Min 870.3 3.966 0.13 80 128 -7 -22 4
Distillation profile °C
IBP 10% 50% 90% FBP

Average 317 327 335 344 348
Std Dev 4.8 7.0 1.3 2.4 2.9
Max 325 336 337 348 356
Min 301 279 329 337 343
FAME (RME) Distillation profile
360.0
350.0
340.0
Temperature C
330.0
320.0
310.0
300.0
0 10 20 30 40 50 60 70 80 90 100
- - - Error bars 3xStd Dev % distilled
Typical properties of Harburg deliveries of FAME

(RME)
30 100.%
Frequency
25 80.%
20 60.%
15
10 40.%
5 20.%
0 .%
e
4
8
2
or
2.
2.
3.
3.
4.
4.
88
88
88
88
88
88
88
88
M
Frequency Cumulative % Density 15C kg/m3

(RME)
14 100.%
12 80.%
Frequency
10
8 60.%
6 40.%
4
2 20.%
0 .%
0
0
0
0
0
0
0
0
0
0
0
10
14
18
22
26
30
34
38
42
46
50
Frequency Cumulative % Water Content mg/kg

Typical properties of Harburg deliveries of

FAME (RME)
15 100.%
Frequency 80.%
10 60.%
5 40.%
20.%
0 .%
-9
-7
-5
5
3
1
9
7
5
3
1
-2
-2
-2
-1
-1
-1
-1
-1
Frequency Cumulative % CFPP C

(RME)
25 100.%
Frequency
20 80.%
15 60.%
10 40.%
5 20.%
0 .%
0
e
M 0
-9
-8
-7
-6
-5
-4
-3
-2
-1
or
-1
Frequency Cumulative % Cloud point C

FAME (RME)
40 100.%
Frequency
30 80.%
60.%
20
40.%
10 20.%
0 .%
3 4 5 6 7 8 9 10 More
Oxidation Stability (Rancimat Hrs)
Frequency Cumulative %

FAME (RME)
Frequency 50 100.%
40 80.%
30 60.%
20 40.%
10 20.%
0 .%
1
2
3
4
5
6
7
8
9
1
e
0.
0.
0.
0.
0.
0.
0.
0.
0.
or
M
Frequency Cumulative % Acid value mgKOH/g
Typical properties of Harburg

deliveries of FAME (RME)
20 100.%
80.%
Frequency
15
60.%
10
40.%
5 20.%
0 .%
4
M 5
e
41
42
43
44
45
46
47
48
49
4.
4.
or
4.
4.
4.
4.
4.
4.
4.
4.
4.
Frequency Cumulative % Viscosity cSt


(RME)
30 100.%
25
Frequency
80.%
20 60.%
15
10 40.%
5 20.%
0 .%
0
0
0
0
0
0
0
0
0
0
M 0
e
10
11
12
13
14
15
16
17
18
19
20
or
Frequency Cumulative % Flashpoint C
Argent TME Data

Cold Filter
Plug Point Iodine Viscosity Linolenic Acid
Deg C Number Density kg/m3 mm2/s % (m/m)
Average 8.5 60 875.9 4.52 1.7
Std Dev 1.88 5.9 0.8 0.06 0.4
Max 13 72 877 4.6 2.6
Min 6 50 874 4.4 1.1
Typical CFPP values for TME

5 100.%
Fr 4 80.%
eq 3 60.%
ue
nc 2 40.%
y 1 20.%
0 .%
5 6 7 8 9 10 11 12 13 14 15
More
Frequency Cumulative CFPP
% deg C
Typical Density (15) values for TME

8 100.%
7
6 80.%
Frequency
5 60.%
4
3 40.%
2 20.%
1
0 .%
0
1
2
3
4
5
6
7
8
9
M 0
e
87
87
87
87
87
87
87
87
87
87
88
or
Frequency Cumulative % Density
Typical KV40 values for TME

12 100.%
10 80.%
Frequency
8
60.%
6
40.%
4
2 20.%
0 .%
1
2
3
4
5
6
7
8
9
4
M 5
e
4.
4.
4.
4.
4.
4.
4.
4.
4.
or
Frequency Cumulative % Viscosity

Typical Iodine values for TME

3.5 100.%
3
80.%
Frequency
2.5
2 60.%
1.5 40.%
1
20.%
0.5
0 .%
50
52
54
56
58
60
62
64
66
68
70
72
Frequency Cumulative % Iodine value
Typical C18:3 values for TME
4.5 100.%
4
3.5 80.%
Frequency
3
60.%
2.5
2
40.%
1.5
1 20.%
0.5
0 .%
e
2
4
6
8
2
4
6
8
1
3
1.
1.
1.
1.
2.
2.
2.
2.
or
M
Frequency Cumulative % C18:3 content

Argent UCOME Data
Typical Density (15) values for UCOME

10 100.%
Frequency
8 80.%
6 60.%
4 40.%
2 20.%
0 .%
e
5
6
7
8
9
0
1
2
or
87
87
87
87
87
88
88
88
M
Density
Typical KV40 values for UCOME
12 100.%
10 80.%
Frequency
8
60.%
6
40.%
4
2 20.%
0 .%
4 4.1 4.2 4.3 4.4 4.5 4.6 4.7 4.8 4.9 5 More
Viscosity
Typical CFPP values for UCOME
6 100.%
Frequency
80.%
4 60.%
2 40.%
20.%
0 .%
e
-4
-2
or
M
CFPP C
Typical Iodine value for UCOME
5 100.%
Frequency
4 80.%
3 60.%
2 40.%
1 20.%
0 .%
70
72
74
76
78
80
82
84
86
88
90
Iodine Value
Typical C18:3 values for UCOME

Frequency
8 100.%
6
4 50.%
2
0 .%
e
2
4
6
8
2
4
6
8
3
4
or
2.
2.
2.
2.
3.
3.
3.
3.
M
C18:3 Content %
Appendix C. Fats and oil composition
100%
90%
80%
70%
60%
50%
40%
30%
20%
10%
0%
Coconut
Soybean
Corn
Cottonseed
Sunflower
Lard
Rapeseed
Olive
Safflower
Palm
Peanut
Tallow
Butterfat
Beef
Saturated fatty acids Mono-unsaturated fatty acids Poly-unsaturated fatty acids
Appendix D. Trans-esterification process
General transesterification mechanism

Appendix E. Iodine number

Iodine number (or Iodine value) is a measure of total unsaturation within a mixture of fatty
material, regardless of the relative shares of mono-, di-, tri- and polyunsaturated compounds.
Saturated fatty acids do not contribute to the Iodine number. The Iodine number does not
take into consideration structural/reactivity factors of unsaturated fatty compounds.
It is expressed in g iodine, which reacts with 100g of the respective sample.
Two procedures for the determination of iodine value are provided by EN 14214.
EN14111 a titrimetric method using Wijs reagent is suggested. It can be calculated from the
relative methyl ester contents as determined by capillary gas chromatography according to
EN 14103. Here iodine values are obtained by adding up the respective contributions of each
unsaturated ester contained in the sample, multiplying the methyl ester mass per cents with
conversion factors characteristic of each compound. See below.
Annex B extract from EN14214

Calculation of Iodine Value
NOTE: This method is adapted for biodiesel from the AOCS recommended practice Cd 1c –
85 for the determination of the iodine value of edible oil from its fatty acid composition.
B.1 Scope
This method describes a procedure for calculating the iodine value of neat biodiesel or
biodiesel extracted from blends with diesel fuel. In case of dispute on the iodine value this
method shall not be used as a substitute for EN 14111.
B.2 Definition
This method is used to calculate the iodine value expressed in g I2 /100 g sample from the
percentage by mass of methyl esters as determined by either EN 14103 (neat biodiesel) or
EN 14331 [1] (biodiesel extracted from blends with diesel fuel).
B.3 Procedure
The methyl ester composition of the sample is checked using the appropriate method as
described in paragraph 2. NOTE: The total methyl esters thus revealed should equal 100
after the deduction of the methyl ester C17 used for internal standard in EN 14103.
The percentage by mass thus obtained is then used to calculate the sample’s iodine value,
being the sum of the individual contributions of each methyl ester, obtained by multiplying the
methyl ester percentage by its respective factor (Table B.1), as indicated in the example in
Table B.2.The factor for each constituent of biodiesel is given in Table B.1.
Table B.1
METHYL ESTER FACTORS
Methyl ester Factor
Methyl ester of saturated fatty acids 0
Methyl hexadecenoate (Methyl palmitoleate) C16:1 0,950
Methyl octadecenoate (Methyl oleate) C18:1 0,860
Methyl octadecadienoate (Methyl lineolate) C18:2 1,732
Methyl octadecatrienoate (Methyl linolenate) C18:3 2,616
Methyl eicosenoate C20:1 0,785
Methyl docasenoate (Methyl erucate) C22:1 0,723
An example of the calculation of iodine value from the percentage by mass of methyl esters
is given in Table B.2
Table B.2
CALCULATION EXAMPLE
Methyl ester of the Percentage % Factor Contribution
following acids m/m
Myristic C14:0 0,3 0 0
Palmitic C16:0 4,0 0 0
Palmitoleic C16:1 1,1 0,950 1,0
Stearic C18:0 2,0 0 0
Oleic C18:1 60,5 0,860 52,0
Linoleic C18:2 19,8 1,732 34,3
Linolenic C18:3 9,4 2,616 24,6
Eicosanoic C20:0 0,4 0 0
Eicosenoic C20:1 0,7 0,785 0,6
Docosanoic C22:0 0,7 0 0
Docosenoic C22:1 1,1 0,723 0,8
Calculated Iodine 113,3
Value
B.4 Expression of the result

Iodine value (calculated from the methyl ester composition) = X g iodine /100 g (B.1)
The result shall be reported to one decimal place.
NOTE 1: In 1994 the AOCS Uniform Methods Committee reviewed the coefficients used and
concluded that no changes were necessary at that time. The present procedure uses the
coefficients selected in the past for use in calculating the iodine value in triglyceride blends.
The reasoning behind that choice is that triple the molecular weight of a methyl ester is
almost identical to the molecular weight of the corresponding triglyceride.
NOTE 2: For samples with unsaponifiable content greater than 0.5% (m/m) or those
containing a significant additive content, the calculated value tends to be higher than the true
value.
NOTE 3: The calculated result tends to be lower than the true value in samples with a lower
iodine value.
Iodine value ranges of FAME

EN14214 specification limit
tallow
soybean
FAME type
rapeseed
palm
coco
0 20 40 60 80 100 120 140 160

Iodine value mgI2/100g
Figure 11: Ranges of Iodine value for FAME types
Appendix F. FAME structures

Appendix G. EN 14112 Oxidation stability – Rancimat test
The Rancimat test Figure 12 measures the induction period prior to the onset of rapid
oxidation.
Air is passed through the sample, at a specific temperature (110 ºC). The gases released,
are absorbed in water and the conductivity is measured. Figure 13 Determination of
Oxidation Stability Principle.
The time at which the conductivity begins to increase rapidly is defined as the induction time.
Figure 14 Typical Rancimat Trace
Acids produced during the oxidation process and are absorbed in the water causing the
conductivity to increase.
Figure 12 Rancimat equipment
Figure 13 Determination of Oxidation Stability Principle

Figure 14 Typical Rancimat Trace

Appendix H. Blend experiences from refineries
Refinery blending – Petit Couronne (Shell refinery until 2008)

• Neat RME is pumped from the barge in which it is delivered to the storage tank, and from
the storage tank to the RME-5 blending tank via multiple product pipelines that are also
used for pumping AGO, IGO and light marine fuel. No contamination or pump failure
issues have been reported as a result of this.
• Blending of the RME with AGO is carried out in the AGO tank when it is about 2/3 full.
The AGO tank is conical-bottomed and has a floating roof. The water bottom of the tank is
drained off, and then the full dose of RME is injected and blended into the AGO using
large stirrers.
• A potential problem of blending RME (and other FAME) into AGO is meeting the AGO
density specification. RME (and other FAME) has a relatively high density (~880 kg/m3)
compared to AGO and when blended with AGO could lead to a product blend density
higher than the maximum limit given in the local AGO specification (EU specification
EN590:2004 is 845 kg/m3). This is of particular concern if the density of the base AGO is
already close to the upper limit of the density specification before the RME (or other type
of FAME) is introduced. At the Petit-Couronne Refinery the density of the base fuel is
adjusted to 843 kg/m3 and a maximum of 5%v RME (usually 4% by volume) is blended
into the AGO to ensure that the density remains within specification.
• Whilst neat RME shows a higher electrical conductivity than conventional AGO (250pS/m
at 20°C as measured by the ASTM method D2624-95), the effect of introducing up to 5%
RME (or other FAME) in AGO on the overall conductivity of the blended fuel is small and
not sufficient to ensure safe handling. The standard advice on the use of conductivity
additives is still applied.
• The water content of the base AGO should be as low as possible prior to blending with
the FAME and should certainly lie within the local AGO specification. In those markets
where the base AGO is already at the upper limit of the water specification, addition of
even small volumes of FAME may take the fuel out of the specification set for AGO.
• The amount of RME incorporated into the AGO is systematically measured using the
method (EN 14078) specified in the EU AGO standard EN590-2004. This method has
also been found to be appropriate when the FAME present is sunflower methyl ester
(SunME), SME, CME and POME. However it is only suitable for FAME-AGO blends
containing up to 5% FAME.
• Once the RME has been blended into the AGO at Petit-Couronne, it is either transferred
to the truck loading facilities or sent by pipeline into the distribution system. In the vicinity
of the Petit-Couronne refinery, deliveries of RME-5 are made by road tanker.
• The tanks used to store RME at Petit Couronne, Heide and Harburg were previously
used for other products. The tanks were not cleaned before introducing RME; however
when RME was first introduced, it was diluted with AGO in order to reduce the solvency
effect and the potential for dirt pick up was significantly reduced. In the initial stages of
using RME blends in France, the RME addition rate was just 2%, hence the risk of filter
blocking in customers’ vehicles due to the solvency of RME was reduced further.
Level of RME in tank is Water falls on the floating roof

kept as high as possible to Floating roof
and is collected through a
minimise water ingress. If drainage tube from the floating
the level of RME is high, roof tank
water only really collects
on the floating roof. If the RME level – generally no
RME level is low, water problems encountered as
also collects on the walls a result of the oxidative
of the tank and runs down stability of RME as
into the RME below (larger turnover of product is high
surface exposed to water)
Roof feet, roof settles on
Desiccators not used bottom of tank when tank
is almost empty
No anti-oxidants required Tank made out of mild
(product turnover is high) steel – RME forms a
Drainage channel protective layer on tank
surface which prevents
rusting
Conical-bottomed tank for easy

drainage
Water
drainage
Water Water and HC
drainage drainage
Figure 15 is a schematic of the neat FAME floating roof storage tank as being used at Petit
Couronne by Shell France
Refinery Blending - Germany.

Procedures in Germany are broadly similar to those outlined above for Petit Couronne.
• So far the only FAME that has been used is RME.

• Deliveries of FAME arrive at Harburg by barge, and at Heide by truck.
• RME is stored in a dedicated, fixed roof tank prior to blending with AGO. Typical turnover
rate is ~4 days for a 430m3 tank (Heide).
• For economic reasons, the supply contract specifies RME that contains no flow improver.
Instead, heating is employed to ensure the RME remains fluid.
• Pre-delivery checks at Harburg are the responsibility of a surveyor appointed to oversee
the handover of cargo between shipper and customer. At Heide, truck deliveries are
subject to density and water checks at the laboratory prior to acceptance. These checks
are in addition to checking the data on the Certificate of Quality.
• In-line blending is employed at both locations.
• Finished blends are analysed by the refinery laboratory (Rancimat testing at PAE)
• Quality issues so far encountered are water content, contamination and filterability
(SEDAB) during winter, probably caused by water.
• RME-5 blends are stored in 9000 m3 fixed roof tank prior to dispatch by road, rail or barge.
Neither RME-100 nor RME-5 is distributed via pipeline in Germany.
• Typically AGO released from Shell refineries in Germany contains 4.6-4.7% RME. AGO
destined for export is released without RME
• Infrastructure changes were required at Heide to accommodate FAME blending, including
a revamp of the truck delivery area with a new line to the tank, installation of heated lines
and a new blender component loop.
• Operating Units have not reported any problems with oxidation or water pick up issues
due to the hygroscopic nature of neat FAME whilst in storage. Potentially the water pick
up risk is higher in case of low tank turnover rates.
Refinery blending – Pernis
FAME that is used is a mixture of RME, TME, UCOME, SME that is blended up to the EN
14214 specification at a third party location. From the third party location the FAME is
shipped to Pernis refinery where a separate line is used to fill the two storage tanks (content
10.000 m3) usage is 8kt.month. Stock level is kept below 6kt
The FAME doesn’t/t contain any flow improver, but in order to assure good pumpablity the
CFPP in winter is specified at max –10 C.
Oxidation stability of the FAME is tested every two weeks, no problems meeting the
specification have been reported up till now.
FAME storage at the third party supplier and at Pernis is checked for microbial contamination
every month. (sample from lowest sample point). No issues have been reported up till now.
Blending of the FAME at the refinery is done in line and blended into the final tank together
with the other diesel components (LGO, Kero and HCU-gasoil)
Conductivity additive is added to the mixture (Stadis 450) in a concentration of 2 ppm in order
to have a minimum conductivity of 100 pS/m.
Lubricity additive is not used anymore except for the blends that are moved via RMR
(pipeline to Germany) Infineum R655 at 120 ppm
For RMR blends dedicated blend tanks are used as the product should not contain FAME.
Type of cold flow additive that is used is Infineum R720 (wasa) and R591 (MDFI) and is
dosed at a concentration of 150 ppm, 300 ppm regardless whether the product contains
FAME. Responds up till was sufficient to meet the spec.
The amount of FAME blended in the AGO is measured via EN 14078
Tanks (fixed roof) at Pernis are drained for water after every discharge and minimum once
very week. Before blending Up till now the amount of water removed from the tank is
minimum. Typical water content of the FAME is 300-400 ppm.
Appendix I. FAME CAS & EINECS list
Substance Name CAS # EINECS #

Fatty acids, animal, unsatd., Me esters 85480-42-8 287-322-7
Fatty acids, butter, Me esters 85536-26-1 287-507-2
Fatty acids, castor-oil, Me esters 68390-63-6 269-908-4
Fatty acids, coco, Me esters 61788-59-8 262-988-1
Fatty acids, fish-oil, Me esters 68605-02-7 271-709-2
Fatty acids, Iris germanica, Me esters 95009-32-8 305-759-4
Fatty acids, Iris pallida, Me esters 95009-33-9 305-761-5
Fatty acids, lanolin, Me esters 85005-41-0 284-974-4
Fatty acids, linseed-oil, Me esters 91051-16-0 293-066-7
Fatty acids, mustard-oil, Me esters 84238-16-4 282-485-0
Fatty acids, olive-oil, Me esters 93572-01-1 297-429-0
Fatty acids, palm kernel-oil, Me esters 91051-32-0 293-084-5
Fatty acids, palm-oil, Me esters 91051-34-2 293-086-6
Fatty acids, peanut-oil, Me esters 93572-08-8 297-436-9
Fatty acids, rape-oil, Me esters 85586-25-0 287-828-8
Fatty acids, safflower-oil, Me esters 68605-14-1 271-715-5
Fatty acids, soya, Me esters 68919-53-9 272-898-4
Fatty acids, sperm-oil, Me esters 68440-46-0 270-457-0
Fatty acids, sunflower-oil, Me esters 68919-54-0 272-900-3
Fatty acids, tall-oil, Me esters 74499-22-2 277-893-0
Fatty acids, tallow, Me esters 61788-61-2 262-989-7
Fatty acids, vegetable-oil, Me esters 68990-52-3 273-606-8
Appendix J. Grouping and Mapping of FAME

CDS in
CAS EC ESIS Type 1 (Std) Type 2 (Low) Type 3 (High)
Soya bean, Rapeseed (Low

EA, Canola), Tallow, Lard,
Sunflower, Jatropha,
Cottonseed, Palm, Palm Coconut (Exempt
Oleine, Palm Stearin, Used Annex IV) & Palm
Cooking Oil, Corn, Olive, etc. Kernel Rapeseed (Hi EA)
Fatty Acids, C16-18 and C18- Fatty acids, coco, Fatty acids, rape-
CAS Description unsatd., Me esters Me esters oil, Me esters
61788-59-8 (Coco)
91051-32-0 (Palm
CAS 67762-38-3 Kernel) 85586-25-0
262-988-1 (Coco),
293-084-5 (Palm
EC 267-015-4 Kernel) 287-828-8
C8:0 111-11-5 203-835-0 Methyl Caprylate/Octanoate HPV Y <10
C10:0 110-42-9 203-766-6 Methyl Caprate/Decanoate HPV Y 4-6
C12:0 111-82-0 203-911-3 Methyl Laurate HPV Y <1 45-50
C14:0 124-10-7 204-680-1 Methyl myristate HPV Y <5 15-20
C16:0 112-39-0 203-966-3 Methyl palmitate HPV N 4-45 <10 <4
C18:0 112-61-8 203-990-4 Methyl Stearate LPV N 2-23 <5 <3
C18:1 112-62-9 203-992-5 Methyl Oleate HPV Y 15-61 6-16 21-34
C18:2 112-63-0 203-993-0 Methyl Linoleate N N 3-62 13-17
C18:3 301-00-8 206-102-3 Methyl Linolenate N N <10 8-9
C22:1 1120-34-9 214-305-3 Methyl Erucate N N 40-50
C8-C14 <5 68-78 <0.1

C16-C18 >90% 19-26 50-60
>C18 >40
Bibliographic Information
This report has been classified as Confidential and is not subject to US Export Control
regulations.
Report Number : GS.07.50614

Title : Technical guide - Use of FAME in Automotive Gas Oil (AGO)
Version 3
Author(s) : M Brewer GSMR
Wai-Yin Wong GSRM
Siri Sivalingam GSRM
Karlheinz Arnecke GSRM
Paul van Oers
Reviewed by : M Brewer GSMR
Andrew Smith GSRM
Approved by : Joseph Kurczycki GSRM
Content Owner : Rick Malpas GSMR
Peter de Kleine GSRM
Issue Date : January 2009
Activity Code : 54013718
Issuing Company : Shell Global Solutions International BV
P.O. Box 541, 2501 CM The Hague, The Netherlands.
Tel. +31 70 377 9111
Established at Carel van Bylandtlaan 30, 2596 HR
The Hague
Commercial Register, The Hague 27155370
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GS.07.

Technical guide - FAME in diesel –

Version 3 (January 2009)

Technical guide - Use of FAME in Automotive

© Shell Global Solutions International B.V., 2006. All rights reserved.

Date Issue Reason for Change Author Approved by

Several updates on the following:

Several updates on the following:

7.2 FAME-containing fuels are more susceptible to microbial growth than

14.2 FAME containing gasolines (as a result of cross-contamination) should not be

7 Housekeeping of neat FAME and AGO blends 23

AGO Automotive Gas Oil or Diesel

Additionally (W) and (S) refer to Winter or Summer grades respectively

Further details of the chemistry are given in Chapter3

3 Fatty Acid Methyl Ester FAME

The properties and performances of FAME depend on the fatty acids

Rapeseed Methyl Ester, RME (Europe – France, Austria, Germany)

The choice of biomass source is determined by the availability of feedstock in a specific

3.2 Common Sources of FAME

3.2.1 Rapeseed Methyl Ester, RME

3.2.2 Soybean Methyl Ester, SME

3.2.3 Palm Oil Methyl Ester, POME

3.2.4 Coconut Oil Methyl Ester, CME

3.2.5 Tallow Methyl Ester, TME

Less common FAME include:

A list of most common fatty acids can be found in Appendix A

3.3 FAME (B100) properties

3.4 Non specification characteristics of FAME compared to AGO

Calculated Oxygen Content of FAME molecules

Figure 1: Calculated Oxygen content of FAME molecules

5 Quality & Standards

5.1 Germany (representing EU) – Biodiesel Quality Management Association

In Europe product specifications exist for AGO and biodiesel: Namely:

5.2 USA - National Biodiesel Accreditation Commission (NBAC) BQ-9000

5.3 Australia – Biodiesel Association of Australia (BAA)

5.4 Shell Quality Assurance Process

5.5 Sampling of FAME and biodiesel blends

6 FAME Specification Items

6.2 Kinematic Viscosity

6.3 Flash Point

6.4 Sulphur Content

6.5 Carbon Residue

6.6 Distillation (T90)

6.7 Cetane Number

FAME type Cetane number

Cetane number for fatty acid types

Figure 2: Variation in Cetane number for a series of single component FAME

6.8 Ash Content

6.9 Water Content

6.10 Total Contamination

6.11 Copper Strip Corrosion

6.12 Ester Content

6.13 Free Glycerol

6.14 Mono-, Di- and Triglycerides and Total Glycerol

6.16 Iodine Number

6.17 Linolenic Acid Methyl Ester

6.18 Polyunsaturated FAME

6.19 Acid Number

6.20 Phosphorus Content

6.21 Content of alkali and alkaline-earth metals

6.22 Oxidation Stability

6.23 Low Temperature Behaviour

7 Housekeeping of neat FAME and AGO blends