REVIEW ON BIODIESEL STANDARDIZATION WORLD-WIDE
Prepared for
IEA Bioenergy Task 39, Subtask „Biodiesel“
Prepared by
BLT Wieselburg, www.blt.bmlfuw.gv.at
Heinrich Prankl Werner Körbitz Martin Mittelbach Manfred Wörgetter
IEA Bioenergy May 2004
REVIEW ON BIODIESEL STANDARDIZATION WORLD-WIDE
Prepared for
IEA Bioenergy Task 39, Subtask „Biodiesel“
Prepared by
BLT Wieselburg, www.blt.bmlfuw.gv.at
Heinrich PRANKL BLT – Federal Institute of Agricultural Engineering, Wieselburg, Austria Werner KÖRBITZ ABI – Austrian Biofuels Institute, Vienna, Austria
Martin MITTELBACH Institute of Chemistry – University Graz, Austria
Manfred WÖRGETTER BLT – Federal Institute of Agricultural Engineering, Wieselburg, Austria
With contributions from:
Steve HOWELL MARC IV, USA Daniel SHEEDY Australian Government Department of the Environment and Heritage Renè PIGEON Natural Resources Canada Luiz P. RAMOS Universidade Federal do Paraná Rua Francisco H. dos Santos, Brazil Claudia REMSCHMIDT Institute of Chemistry – University Graz, Austria
May 2004
Published by:
Manfred Wörgetter BLT – Bundesanstalt für Landtechnik Federal Institute of Agricultural Engineering Rottenhauserstr. 1, A 3250 Wieselburg [email protected]
Editorial
IEA Bioenergy, an international collaboration in Bioenergy, aims to accelerate the use of environmentally sound and cost-competitive bioenergy on a sustainable basis, and thereby achieve a substantial contribution to future energy demands. (www.ieabioenergy.com/).
The main objectives of Task 39 “Liquid Biofuels” are to work jointly with governments and industry to identify and eliminate non-technical environmental and institutional barriers which impede the use of liquid fuels from biomass in the transportation sector, and to identify remaining technological barriers to Liquid Biofuels technologies. IEA Bioenergy Task 39 "Liquid Biofuels" is currently composed of 10 countries (Austria, Canada, Denmark, European Union, Finland, Ireland, The Netherlands, Sweden, USA and UK) interested in working together to successfully introduce biofuels for transportation into the marketplace. This Task reviews both technical and policy/regulatory issues and provides participants with comprehensive information that will assist them with the development and deployment of biofuels for motor fuel use www.forestry.ubc.ca/task39/GT4/Frames/home.html). The extent to which biofuels have entered the marketplace varies significantly by country. The reasons for these differences are complex and include a variety of policy and market issues. While biofuels offer significant potential, the prices of biofuels are higher than their petroleum equivalents. As a result, biofuels have been successfully implemented only in those countries that have recognized the value of those benefits and have made appropriate policy decisions to support biofuels (www.liquid-biofuels.com/FinalReport1.html).
Standardization is one of the key issues in the development of new products and markets. For the producers and distributors of Biodiesel, standards are a vital necessity. Legislators and authorities need approved standards for the evaluation of safety and environmental risks. The development of engines, vehicles and equipment is based on the properties of the fuel; the range of the fuel parameters must be limited. The development of a new standard is complex and long-lasting task even on the national level. International standardization is the result of the co-operation of national standardization organization and enables the development international markets. In respect of this aspects BLT has initiated this review on Biodiesel Standardization worldwide. The study describes general aspects of the standardization process, important regulations and recommendations as well as and the state of the standardization in Europe, North America, Australia and Brazil. Thanks to the good contacts of the authors it reflects the actual state of the Biodiesel standardization worldwide. Standardization of biofuels is “work in progress”, and therefore the Liquid Biofuels Task will try to continue the monitoring of the development.
M. Wörgetter Wieselburg, 06 May. 04
Content Page 1
Content
1 General aspects of standardization...... 3
1.1 Introduction ...... 3 1.2 Standardization in CEN...... 3 1.2.1 Aims and principles of creating new standards ...... 4 1.2.2 Levels of standardization ...... 4 1.2.3 Types of European standards and technical specifications...... 5 1.2.4 European policy of standardization...... 5 1.2.5 The organization of CEN ...... 6 1.2.6 The CEN process ...... 8 1.3 Standardization in United States of America ...... 12 1.3.1 ASTM in general ...... 12 1.3.2 Development of standards...... 13 1.3.3 Mission Statement ...... 12 1.3.4 Principles ...... 13 1.4 Standardization at ISO...... 14 1.4.1 ISO in general...... 14 1.4.2 ISO standardization process...... 14 1.4.3 ISO strategies ...... 14
2 Important regulations and recommendations for transport fuels...... 16
2.1 European Directive on fuel quality ...... 16 2.2 The World-Wide Fuel Charter ...... 20 2.2.1 Overview...... 20 2.2.2 Members list ...... 21 2.2.3 Definition of categories and related diesel fuel properties: ...... 21 2.2.4 Technical background for harmonized diesel fuel recommendations...... 22 2.2.5 Fatty-acid-methyl-ester (FAME)...... 23
3 Development of Biodiesel standards...... 25
3.1 History of biodiesel standardization in Europe...... 25 3.1.1 Austria...... 25 3.1.2 Czech Republic...... 25 3.1.3 France...... 25 3.1.4 Germany ...... 25 3.1.5 Italy ...... 26 3.1.6 Sweden...... 26 3.2 Biodiesel standardization in CEN...... 26 3.2.1 CEN/TC19/WG24: Specification of automotive diesel / Task Force ‘Biodiesel’27 3.2.2 CEN/TC19/WG25: Specification of FAME used as fuel for heating ...... 28 3.2.3 CEN/TC19/WG26: Verification of FAME related fuel test methods ...... 28 3.2.4 CEN/TC307/WG1: Test methods on FAME ...... 28 3.3 Biodiesel standardization in United States...... 29 3.3.1 Introduction...... 29 3.3.2 Biodiesel Markets in the United States: Background and History...... 29 3.3.3 US Biodiesel standard history...... 30 3.3.4 Biodiesel standard ...... 31 3.3.5 Pure specification vs. blend specification ...... 33 3.3.6 Provisional ASTM biodiesel standard ...... 34
IEA Bioenergy – Liquid Biofuels May 2004 Page 2 Content
3.3.7 After ASTM PS 121 ...... 35 3.3.8 Future ASTM considerations ...... 37 3.3.9 US biodiesel quality programs ...... 37 3.3.10 Standard harmonization...... 38 3.4 Biodiesel standardization in Australia ...... 38 3.4.1 Introduction...... 38 3.4.2 General aspects...... 38 3.4.3 Standardization bodies and working groups...... 39 3.4.4 Mechanism for decision and approval ...... 39 3.4.5 Initiatives and driving forces ...... 40 3.4.6 Current state ...... 40 3.5 Biodiesel standardization in Canada...... 41 3.6 Biodiesel standardization in Brazil ...... 43 3.6.1 Introduction...... 43 3.6.2 National Biodiesel Program ...... 44 3.6.3 Biodiesel standardization...... 45 3.6.4 Future perspectives ...... 47 3.7 Further Biodiesel specification activities ...... 48
4 Biodiesel standard parameters and limits ...... 49
4.1 Comparison of the requirements...... 49 4.2 Comparison of parameters and limits ...... 54 4.2.1 Density...... 54 4.2.2 Kinematic viscosity ...... 54 4.2.3 Flash point ...... 55 4.2.4 Sulfur content...... 55 4.2.5 Carbon residue ...... 56 4.2.6 Cetane number ...... 57 4.2.7 Ash content...... 58 4.2.8 Water content ...... 58 4.2.9 Total contamination ...... 59 4.2.10 Copper strip corrosion ...... 59 4.2.11 Ester content...... 60 4.2.12 Free glycerol ...... 61 4.2.13 Mono-, di- and triglycerides and total glycerol ...... 61 4.2.14 Methanol ...... 62 4.2.15 Iodine number, linolenic acid methyl ester and polyunsaturated FAME ...... 63 4.2.16 Acid number...... 64 4.2.17 Content of phosphorus ...... 65 4.2.18 Content of alkali and alkaline-earth metals...... 65 4.2.19 Oxidation stability...... 66 4.2.20 Cold temperature behaviour ...... 67
5 Summary and Conclusions ...... 69
6 References...... 71
May 2004 IEA Bioenergy – Liquid Biofuels General aspects of standardization Page 3
1 GENERAL ASPECTS OF STANDARDIZATION
1.1 Introduction
Standards are technical specifications for products, processes or services. They should be approved by all parties involved and should reflect the current state of the art. Standards guarantee work on an orderly basis in all areas of economy and administration by fixing terms and requirements and by establishing criteria for quality control, safety and testing.
ISO defines 'standard' as follows:
'Technical specification or other document available to the public, drawn up with co-operation and consensus or general approval of all interests affected by it, based on the consolidated results of science, technology and experience, aimed at the promotion of optimum community benefits and approved by a body recognized on the national, regional or international level.'
ASTM defines a standard as a document being developed and established within the consensus principles of the organization and which meets the requirements of ASTM procedures and regulations. Full consensus standards are developed with the participation of all parties who have a stake in the standards' development and/or use [1].
Standards are drawn up in independent institutes of standardization and are available for the public. Basically standards are not binding but can become legally binding on a national as well as international level.
Standards are of vital importance for producers, distributors and users of biofuels. Authorities need approved standards for the evaluation of safety risks as well as environmental pollution. Independent lubrication oil producers are interested in a standardized fuel.
1.2 Standardization in CEN
Sources: NICOLAS, REPUSSARD [2], STAMPFL-BLAHA [3]
CEN, the European Committee for Standardization, was founded in 1961 by the national standards bodies in the European Economic Community and EFTA countries. Now CEN is contributing to the objectives of the European Union and European Economic Area with voluntary technical standards which promote free trade, the safety of workers and consumers, interoperability of networks, environmental protection, exploitation of research and development programs, and public procurement.
IEA Bioenergy – Liquid Biofuels May 2004 Page 4 General aspects of standardization
1.2.1 Aims and principles of creating new standards
According to the definition quoted above a standard is aimed at the 'promotion of optimum community benefits' [2]. The expected advantages of standardization are for instance: • The promotion of quality of products, processes and services, • The promotion of economy, • The promotion of international commerce by eliminating barriers And, following from the last aspect • The promotion of industrial efficiency.
To be sure that standards are generally accepted and suitable for the practical application there are some principles of standardization: [3]
• Neutrality of teamwork (access and transparency): All parties affected by the standard should participate at all levels of the standardization process by sending experts to the meetings. • Consensus: The process of standardization should definitely result in a consensus. But European standards do not have to be accepted unanimously. • Publicity: Every draft is subject to a public objection process. • Coherence: Standards have to be consistent and unified on a European as well as national level. This means that conflicting national standards have to be withdrawn as soon as a European standard is published.
Standards come from the voluntary work of participants representing all interests concerned: industry, authorities and civil society, contributing mainly through their national standards bodies. Draft standards are made public for consultation at large. The final, formal vote is binding for all members. The European Standards must be transposed into national standards and conflicting standards must be withdrawn.
1.2.2 Levels of standardization
National standards: Central institutes of standardization in the individual countries are responsible for standardization on a national level. These institutes, which are mostly organizations under civil law, provide the infrastructural and organizational framework for efficient standardization work.
European standards: CEN (Comité Européen de Normalisation), located in Brussels, is responsible for standardization on a European level. The 28 national institutes of standardization are members of CEN. The standards set up by CEN are basically binding in all member states. Technical Committees (TC), made up of representatives of the national Committees, elaborate these European standards and adapt them to the current state of the art. Basically European standards have to be included in all national standards. Conflicting national standards have to be withdrawn.
International standards: International standards are set up by the International Organization for Standardization (ISO) located in Geneva. In contrast to European standards, ISO standards do not have to be adapted as national standards.
The technical co-operation between ISO and CEN was approved in 1991 (Vienna Agreement ISO/CEN). The aim of this agreement is to avoid the duplication of standardization work and
May 2004 IEA Bioenergy – Liquid Biofuels General aspects of standardization Page 5 to secure the highest possible degree of identity between European and international standards.
1.2.3 Types of European standards and technical specifications
Standardization processes on a European level lead to the publication of one of the following documents:
• European standard (EN): Standardization work is always aimed at developing a European standard. An EN must be transposed and applied on a national level. Divergent national standards have to be removed.
• Harmonization document (HD): If an EN is not possible because national differences have to be considered, an HD will be made available. In this case, a member is free to retain or publish a national standard dealing with a subject covered by the HD, provided that it has a technically equivalent content.
• European pre-standard (prEN): This document is drawn up as a prospective standard for provisional application in fields with a high degree of innovation.
Apart from standards according to ISO there are a number of other technical specifications or standardizing documents. The following table 1 compares these types with regards to drafting, adoption and application [3].
Table 1: Comparison of several types of technical specification and standards
Company Codes of practice Standards Public contract Regulations standard or professional specifications specifications
Drafting Company Members of a All parties All interested Public profession interested parties authorities
Adoption Company Members of a Consensus and Public authorities Public profession validation authorities
Application Company/ Business Business Business companies interests interests (public interests (voluntary) contracts) (compulsorily)
Public authorities may make these documents compulsory or refer them
1.2.4 European policy of standardization
Source: NICOLAS, REPUSSARD [2]
Free trade (and the removal of technical trade barriers related to it) is one of the basic principles of the European Union. Directive 83/189/EEC [4] is the main regulation on preventing technical barriers to trade in the Community. The objectives of the Directive are to create transparency in the field of technical standards and regulations, to prevent the creation of new obstacles to trade and to promote European harmonization and the emergence of European standardization if required by the Community. The latter aspect is
IEA Bioenergy – Liquid Biofuels May 2004 Page 6 General aspects of standardization carried out by following the mandate procedure enabling Community authorities to invite European standards institutions to draw up European standards.
The Commission is responsible for the administration of Directive 83/189/EEC. A Standing Committee including representatives of the member states gives assistance. These representatives are officially responsible for standardization policy on a national level. The Standing Committee is chaired by a representative of the Commission.
The New Approach to technical harmonization and standards (85/C 136/01 [5]) is an essential tool of the Community's harmonization activities. This approach rests on the basic assumption that standards should be referred to in order to define the technical characteristics of products. This means that directives that have to be transposed into national regulations are only harmonizing the essential requirements of products (e.g. safety, health,). Technical specifications, which are used in order to comply with these essential requirements, will be developed in conjunction with the standardization process, taking into account the stage of technology.
Therefore the responsibilities of each economic partner are defined as follows: public authorities are responsible for legal aspects and sanctions; economic partners are responsible for technology (standards) and for introduction on the market.
1.2.5 The organization of CEN Sources: www.cennorm.be [6], NICOLAS, REPUSSARD [2]
CEN (Comité Européen de Normalisation) is the European Committee for Standardization. It is a non-profit-making international association of a scientific and technical nature registered in accordance with Belgian law and founded in 1961. The CEN Management Centre is located in Brussels and is responsible for promoting the activities of the association. CEN is a system of formal processes to produce standards, shared principally between 28 National Members, 8 Associate Members and two Counselors and the CEN Management Centre, Brussels. The national standardization institutes are the National Members of CEN. They make up the delegations to the technical committees, vote for and implement European Standards as national standards. Associate Members are broad-based European organizations, representing particular sectors of industry as well as consumers, environmentalists, workers, and small and medium-sized enterprises. They undertake to promote CEN and European standardization.
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Table 2: CEN members [6] Country Name Abbr. Austria Österreichisches Normungsinstitut ON Belgium Institut Belge de Normalisation IBN Cyprus Cyprus Organization for the Promotion of Quality CYS Czech Republic Czech Standards Institute (CSNI) CSNI Denmark Dansk Standardiseringsrad DS Estonia Estonian Centre for Standardisation (EVS) EVS Finnland Suomen Standardisoimisliitto t.y. SFS France Association francaise de Normalisation AFNOR Germany Deutsches Institut für Normung e.V. DIN Greece Ellinikos Organismos Typopoiiseos ELOT Hungary Hungarian Standards Institution MSZT Iceland Standardization Council of Iceland STRI Ireland National Standards Authority of Ireland NSAI Italy Ente Nazionale Italiano di Unificazione UNI Latvia Latvian Standards Ltd LVS Lithuania Lithuanian Standards Board LST Luxembourg Service de l'Energy de l'Etat Département Normalisation SEE Malta Malta Standards Authority MSA The Netherlands Nederlands Normalisatie - Instituut NNI Norway Norges Standardiseringsforbund NSF Poland Polish Committee for Standardization PKN Portugal Instituto Portugês da Qualidade IPQ Slovakia Slovak Standards Institute SUTN Slovenia Slovenian Institute for Standardization SIST Spain Asociación Española de Normalización y Certificación AENOR Sweden Standardiseringskommissionen i Sverige SIS Switzerland Schweizerische Normen-Vereinigung SNV United Kingdom British Standards Institution BSI
Table 3: CEN Associates [6] Associates Name Abbrev. Chemical Industry European Chemical Industry Council CEFIC Construction Industry European Construction Industry Federation FIEC Consumers European Association for the co-ordination of ANEC Consumer representation in standardization Environment European Environmental Citizens Organization for ECOS Standardization Machine tools European Committee for Co-operation of the CECIMO Machine Tool Industries Medical Technology European Medical Technology Industry EUCOMED Association Small and Medium- European Office of Craft/Trades and Small and NORMAPME sized Enterprises Medium-sized Enterprises for Standardization Trade Union European Trade Union Technical Bureau for TUTB Health and Safety
CEN is governed by the General Assembly of its National Members. The Assembly is responsible for the budget, membership and appointment of officers. The Administrative
IEA Bioenergy – Liquid Biofuels May 2004 Page 8 General aspects of standardization
Board is authorized to direct CEN's operations. It prepares the annual budget and membership applications. The Technical Board is primarily responsible for the co-ordination of CEN standardization work. It controls the standards program and promotes its execution by the Management Centre. The Management Centre assists the Secretary General in carrying out his statutory functions (maintenance of CEN's procedures, execution of Internal Regulations for standards work, management of the public enquiry, formal votes for European Standards,..). The Technical Committees (TC) are responsible for the drafting of European standards in well-defined sectors. The TC involve experts from all areas affected by the activities of CEN (industry, public administration, science, consumers, trade unions, etc.).
The structure of CEN Members (National & Associate)
Affiliates General Assembly (CEEC) EC, EFTA Administrative Board CENELEC, ETSI, ISO CEN Management Centre
Certification Board Technical Board
Technical European Committees organizations in liaison
Figure 1: The structure of CEN [6]
1.2.6 The CEN process
Because of the very large number of drafts that have to be processed within CEN an effective method of work and decision-making has to be applied. It also has to be ensured, that the work is quick and consistent and the basic principles of standardization (transparency, access for all interested parties,..) are maintained.
In each process three major phases can be distinguished: programming, drafting and adoption of standards. In figure 2 these phases are sketched.
Programming: Standardization processes can be initiated by four complementary channels:
1) National standardization institute: This channel is used for applications, which have generally been the subject of concerted consideration on a national level with the business interests concerned.
May 2004 IEA Bioenergy – Liquid Biofuels General aspects of standardization Page 9
2) European institutions (in practice mainly the European Commission, often supported by the EFTA): This channel is based on an agreement between CEN and the Commission; it is used for the application of standards, which come under certain European policies.
On demand the Commission works out a draft mandate for CEN. The Central Secretariat of CEN draws up a program, a precise draft timetable and also an estimation of costs. After consultations with the national institutions the draft mandate is validated as regards financial and human resources. The policy validation is done in the Standing Committee for Directive (83/189/EEC). After the validated draft has been accepted, a formal contract is concluded between CEN and the Commission committing CEN to carrying out the planned program.
3) Associated standardizing bodies: They have a high degree of independence in planning their own activities. CEN submits the draft standards resulting from these programs to an adoption procedure.
4) European trade associations: Only in certain cases.
Concerning channel 1 and 2 a process deciding the procedure for implementing the program follows. The decision is taken by the Technical Board or more and more delegated to the competent Technical Sector Board. One of the three complementary methods for preparing a draft European standard has to be chosen:
• Common work of CEN and ISO: Under certain conditions ISO can be entrusted with supervising the standardization work. • Adoption of a reference document: If a reference document exists (e.g. a finished ISO standard) which is probably acceptable, it can be adopted as a CEN standard. • Development of a standard in the Technical Committee: In most cases the responsibility for the development of a draft standard is entrusted to a Technical Committee of CEN.
It is important that the formal decision to start work on European standard is always accompanied by a status-quo decision: The members of CEN have to refrain from proceeding the work on the same subject done on a national level.
Drafting: The real standardization work is done in working groups by experts, mainly from the specific Committees of the members. Under the collective responsibility of the Technical Committee a draft standard is worked out in accordance with the rules for the formal presentation of standards. The draft standard has to be approved by the TC and is then passed on to the Central Secretariat. It is given a standard number and the document is called prEN No xx.
IEA Bioenergy – Liquid Biofuels May 2004 Page 10 General aspects of standardization
National members and Mandates proposed e European organisations (EC, EFTA) phas .
ogr Technical board pr decision . and ppl A IOS-IEC-ASB Questionnaire European technical subcontracting procedure committee proposal e as ph
g Reference prEN ftin DIS - prEN document a r D
6-month public-comment stage e
tion phas Final draft dop A
Formal vote ase
on ph EN/HD iti spos an
Tr National standards (NS) - EN..., HD...
Figure 2: Creation of a European standard [2]
Adoption of a European standard: The prEN is passed on to the member countries and is submitted to public comment for six months. Then the comments are collected and evaluated. The Technical Committee responsible works out a final draft reaching a broad consensus.
The paper is submitted to a 'formal vote' by the national members. For the formal vote the members of CEN have weighted majorities (see Table 4).
May 2004 IEA Bioenergy – Liquid Biofuels General aspects of standardization Page 11
Table 4: Weighed votes [7] Country Votes until Votes from Country Votes until Votes from Dec 2003 Jan 2004 Dec 2003 Jan 2004 Austria 4 10 Latvia 4 Belgium 5 12 Lithuania 7 Cyprus 3 4 Luxembourg 2 4 Czech Republic 12 Malta 2 3 Denmark 3 7 The Netherlands 5 13 Estonia 4 Norway 3 7 Finland 3 7 Poland 27 France 10 29 Portugal 5 12 Germany 10 29 Slovakia 2 7 Greece 5 12 Slovenia 4 Hungary 3 12 Spain 8 27 Iceland 1 3 Sweden 4 10 Ireland 3 7 Switzerland 5 10 Italy 10 29 United Kingdom 10 29
National transposition of a European standard: The full status of a European standard is only acquired if it has been transposed and made applicable on a national level. This is an essential element of the European standardization program because it ensures that European standards are automatically integrated in to national standards. It should be noted that an adopted European standard has to be transposed and applied also in those countries, which voted against it. To ensure technical consistency divergent national standards have to be withdrawn.
IEA Bioenergy – Liquid Biofuels May 2004 Page 12 General aspects of standardization
1.3 Standardization in the United States of America
Source: ASTM website [1]
1.3.1 ASTM in general
ASTM International was founded in 1898 and is a non-profit organization providing a global forum for the development and publication of voluntary consensus standards for materials, products, systems, and services. More than 30000 individuals (producers, users, consumers, and representatives of government and academia) from 100 nations are the members of ASTM International. ASTM standards serve as the basis for manufacturing, procurement, and regulatory activities in over 130 varied industry areas. Formerly known as the American Society for Testing and Materials, ASTM International provides standards that are accepted and used in research and development, product testing, quality systems, and commercial transactions around the globe. The ASTM headquarter is located in West Conshohocken, Pennsylvania, USA.
1.3.2 Mission statement and strategic objectives
The mission is to provide the value, strength, and respect of marketplace consensus.
To be the foremost developer and provider of voluntary consensus standards, related technical information, and services having internationally recognized quality and applicability that
• promote public health and safety, and the overall quality of life; • contribute to the reliability of materials, products, systems and services; and • facilitate national, regional, and international commerce.
Strategic objectives:
1. To provide the optimum environment and support for technical committees to develop needed standards and related information. 2. To ensure ASTM products and services are provided in a timely manner and meet current needs. 3. To increase the awareness of the ASTM consensus process, the benefits of participation, and the value of ASTM standards and services in the global marketplace. 4. To strengthen both the national and international acceptance and use of ASTM products and services. 5. To make the ASTM process, resources, skills, and facilities available to the marketplace to accommodate it’s changing needs. 6. To ensure the fair representation and participation of key stakeholders in ASTM activities to secure technically sound standards. 7. To maintain ASTM's fiscal stability in order to fulfill the Society's mission.
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1.3.3 Principles
The principles necessary for the development of standards to meet societal and market needs are:
• Decisions are reached through consensus among those affected. • Participation is open to all affected interests. • Balance is maintained among competing interests. • The process is transparent. Information on the process and progress is directly available. • Due process assures that all views will be considered and that appeals are possible. • The process is flexible, allowing the use of different methodologies to meet the needs of different technology and product sectors. • The process is timely; purely administrative matters do not slow down the work. • Standards activities are coherent, avoiding overlap or conflict. • Standards are relevant, meeting agreed criteria and satisfying real needs by providing added value. • Standards are responsive to the real world; they use available, current technology and do not unnecessarily invalidate existing products or processes. • Standards are performance-based, specifying essential characteristics rather than detailed designs.
1.3.4 Development of standards
Standards development work begins when members of an ASTM technical committee identify a need or other interested parties approach the committee. Task group members prepare a draft standard, which is reviewed by its parent subcommittee through a letter ballot. After the subcommittee approves the document, it is submitted concurrently to the main committee and the entire membership of ASTM.
All negative votes cast during the balloting process, which must include a written explanation of the voters’ objections, must be fully considered before the document can be submitted to the next level in the process. Final approval of a standard depends on concurrence by the ASTM Standing Committee on Standards that proper procedures were followed and due process was achieved.
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1.4 Standardization at ISO
Source: ISO website [8]
1.4.1 ISO in general
The International Organization for Standardization (ISO) is a network of national standards institutes from 148 countries with a Central Secretariat in Geneva, Switzerland. ISO is working in partnership with international organizations, governments, industry, business and consumer representatives. Only one body per country is accepted for membership of ISO.
Each member institution has the right to take part in the development of any standard, which is considered to be important. The activities are carried out in a democratic way. Each participating member in ISO has one vote independent from the size. The development of ISO standards is based on market requirements. The principal activity of ISO is the development of technical standards, but ISO standards also have important economic and social impacts.
ISO standards are voluntary but may become a market requirement like in the case of ISO 9000 quality management systems. In few cases (mainly in health, safety or environment issues) ISO standards are adopted as part of a regulatory framework. Main principle of development of ISO standards is based on consensus among the interested parties.
1.4.2 ISO standardization process
The work is distributed among approx. 3000 technical bodies (technical committees, subcommittees, working groups,..). The result of a drafting process carried out by national expert delegations after receiving a consensus is a Draft International Standard (DIS). The DIS is circulated for comment and balloting. Many members have public review procedures for making draft standards known and available to interested parties and to the general public. The ISO members then take account of any feedback they receive in formulating their position on the draft standard. If the voting is in favor, the document, with eventual modifications, is circulated to the ISO members as a Final Draft International Standard (FDIS). If that vote is positive, the document is then published as an International Standard.
1.4.3 ISO strategies
In the ISO strategies for 2002-2004 [9] the key concepts underlying ISO’s operational model and business stance are expressed as: Value – Partnership – Optimization. In pursuit of these strategic goals, ISO will strive to • understand, serve and possibly anticipate market needs (value); • ensure the maximum participation and collaboration of all the relevant parties during the various stages of work within the ISO system (partnership); • improve continuously the core business processes of the organization (optimization), by securing and effectively using the resources required to meet the standardization needs of
May 2004 IEA Bioenergy – Liquid Biofuels General aspects of standardization Page 15
the 21st century, while making substantial use of information and communication technologies.
ISO has five major strategies expressed as commitments to: • Increasing ISO’s market relevance; • Strengthening ISO’s international influence and institutional recognition; • Promoting the ISO system and its standards; • Optimizing the use of resources, and • Supporting national standards bodies in developing countries.
Figure 3: ISO-structure chart [8]
IEA Bioenergy – Liquid Biofuels May 2004 Page 16 Important regulations and recommendations for transport fuels
2 IMPORTANT REGULATIONS AND RECOMMENDATIONS FOR TRANSPORT FUELS
2.1 European Directive on fuel quality
Source: Gammeltoft, European Commission (2003) [10]
In the historical context one can observe early initiatives of the European Commission to improve air quality and reduce harmful exhaust emissions by regulating certain quality parameters of fuels for combustion engine driven vehicles. The following timetable shows the sequence of relevant Directives:
• 1975: Directive 75/716/EEC o Maximum sulfur content of gas oil 0,5 % from 1 October 1976, o Maximum sulfur content of gas oil 0,3 % from 1 October 1980.
• 1978: Directive 78/611/EEC o Maximum lead content in petrol of 0,4 % g/l.
• 1985: Directive 85/210/EEC o Obligation to reduce lead content to 0,15 g/l, o Benzene content of leaded & unleaded petrol 5 % max. (v/v), o Introduction of unleaded petrol from 1 October 1989.
• 1985: Directive 85/536/EEC o Maximum limits for oxygenates (ethanol, MTBE, etc.).
• 1987: Directive 87/416/EEC o Regular grade leaded petrol banned.
• 1993: Directive 93/12/EEC o Maximum sulfur content of diesel 0,2 % from 1 October 1994, o Maximum sulfur content of diesel 0,05 % from 1 October 1996.
In 1994 the so called “European Auto-Oil Programme” was initiated as a platform of the European Commission, the oil industry and the vehicle industry with the aim to establish an objective assessment of cost-effectives measures necessary to reduce road transport emissions to levels consistent with air quality objectives and to define a cost-effective vehicle & fuel quality package.
The political outcome of the “European Auto-Oil Programme” in 1998 was defined by
• 1998: Directive 98/70/EC relating to the quality of petrol and diesel fuels: o From 1 January 2000: Leaded petrol banned, Maximum sulfur content of petrol < 150 ppm,
May 2004 IEA Bioenergy – Liquid Biofuels Important regulations and recommendations for transport fuels Page 17
Maximum benzene in petrol < 1%, Maximum aromatics in petrol < 42%, Maximum sulfur content of diesel < 350 ppm. o From January 2005: Maximum sulfur content of petrol & diesel < 50 ppm, Maximum aromatics in petrol < 35%. o New emission limits for all vehicle types for year 2000 and 2005 (& 2008 for HDVs’ NOx).
The result of the “European Auto-Oil Programme” can be visualized as follows:
For petrol cars the emission reduction targets were defined for the category HC & NOx, for NOx and for CO in 4 steps (Euro I, II, III and IV):
Figure 4: Petrol cars emission reduction targets [10] Petrol cars
% reduction
100
80
60
40
20 CO 0 NOx 4 6 8 8 8 0 2 8 9 4 9 6 19 HC+NOx 9 19 8 9 0 19 19 2 19 0 4 19 6 19 8 199 0 0 20 200 200 20 200 201
Euro I Euro II Euro III Euro IV
6
For diesel cars the emission reduction targets were defined for the category HC & NOx and for PM in 4 steps (Euro I, II, III and IV):
IEA Bioenergy – Liquid Biofuels May 2004 Page 18 Important regulations and recommendations for transport fuels
Figure 5: Diesel cars emission reduction targets [10]
Diesel cars
% reduction
100 90 80 70 60 50 40 30 20 10 0 PM 4 6 8 8 0 8 2 4 6 198 9 HC+NOx 19 9 8 0 19 199 2 0 19 4 19 0 6 199 0 8 199 0 0 20 0 20 1 20 20 20 20 Euro I Euro II Euro III Euro IV
7
And for heavy duty vehicles (HDV) the emission reduction targets were defined for the category NOx and for PM in 5 steps (Euro I, II, III, IV and V):
Figure 6: HDV emission reduction targets [10]
Heavy-duty vehicles on ETC
% reduction
100 90 80 70 60 50 40 30 20 10 0 PM 80 82 84 86 88 19 90 19 92 19 NOx 94 19 96 19 98 19 19 00 02 19 19 04 19 06 20 08 20 10 20 20 20 20 Euro I Euro II Euro III Euro IV Eur o V 8
May 2004 IEA Bioenergy – Liquid Biofuels Important regulations and recommendations for transport fuels Page 19
The time horizon for reaching the defined goals for all 3 categories is set with the year 2010.
The expected result in reduction of road transport emissions in the European Union is illustrated by the following graph
The expected result in reduction of road transport emissions in the European Union is illustrated by the following graph:
Figure 7: Expected result in emissions reduction (Index: 1995 =100) [10]
140
120
100
80
60
40
20
0 1990 1995 2000 2005 2010 2015 2020
CO NOx PM-diesel VOC Benzene SO2 CO2
It can be seen that the continuous improvements in fuel quality as defined by fuel standard parameters played a key role in these significant reductions of 6 emission types and in the stabilisation of CO2-emissions.
The successfully completed “European Auto-Oil Programme” was continued in the “European Auto-Oil II Programme”, which aims were to make an assessment of the future trends in emissions and air quality and establish a consistent framework within which different policy options to reduce emissions can be assessed using the principles of cost- effectiveness, sound science and transparency and to provide a foundation for the transition towards longer term air quality studies covering all emission sources.
Recent amendments to the Directive 98/70/EC relating to the quality of petrol and diesel fuels can be summarised in the following
• “Sulphur-free” fuels with less than 10 ppm (Directive 2003/17/EC of 22.03.2003) : o phased introduction starting no later than 1 January 2005, o complete switch no later than 1 January 2009 (to be confirmed).
IEA Bioenergy – Liquid Biofuels May 2004 Page 20 Important regulations and recommendations for transport fuels
• Uniform fuel quality monitoring: Directives 98/70/EC and 2003/17/EC require monitoring the quality of fuels in Member States. For this purpose Member States have to deliver data in accordance with Commission Decision 2002/159. According to Directive 2003/17/EC the Commission has to publish annually, and for the first time by 31/12/2003 a report on actual fuel quality in the different Member States o with reference to new CEN standard, o with introduction of penalties and fines for non-compliance by Member States. • Review by 31 December 2005 at the latest o future requirements of Community vehicle emissions and air quality legislation, o proposal on captive fleets and the special fuels there are, o proposals of specifications applicable to LPG, natural gas and Biofuels (e.g. Biodiesel = EN 14214). • Listed subtasks of the review o end date for full introduction of 10 ppm sulphur diesel fuel, o implication of PAH air quality standards,
o progress towards the CO2 -Community target of 120 g/km after already having reached a voluntary agreement with ACEA of 140 g/km as a first step, o introduction of alternative fuels, including Biofuels, o alignment of appropriate fuel quality requirements for non-road applications with on-road requirements (97/68/EC).
More details on European legislation concerning automotive fuels quality can be found in: http://europa.eu.int/comm/environment/air/legis.htm#transport.
2.2 The World-Wide Fuel Charter
Literature source: World-Wide Fuel Charter, December 2002 [11].
2.2.1 Overview The World-Wide Fuel Charter was first established in 1998 with the intention to promote greater understanding of the fuel quality needs of motor vehicle technologies and to harmonize fuel quality world-wide in accordance with vehicle needs. The objective of the global fuels harmonization effort is to develop common, world-wide recommendations for quality fuels, taking into consideration customer requirements and vehicle emission technologies, which will in turn benefit our customers and all other affected parties. The development of these common recommendations will ensure that automotive and engine manufacturers provide consistent fuel quality advice world-wide.
The World-Wide Fuel Charter is mentioned in this study as
1. It has included a chapter on Fatty-acid-methyl-ester (FAME) for the first time and 2. Biodiesel has become a fuel of world-wide importance with increasing numbers of production sites and wide usage in major countries on all continents.
May 2004 IEA Bioenergy – Liquid Biofuels Important regulations and recommendations for transport fuels Page 21
The implementation of the World-Wide Fuel Charter recommendation will
• Reduce the impact of motor vehicles on environment through reduced vehicle fleet emissions;
• Consistently satisfy customer performance expectations; and
• Minimize vehicle equipment complexities with optimized fuels for each control category, which will reduce customer costs in purchase and operation and increase satisfaction.
2.2.2 Members list The following institutions are member of the World-Wide Fuel Charter:
• ACEA (European Automobile Manufacturers Association / www.acea.be / Brussels, Belgium;) representing: BMW, DAF Trucks, Fiat Auto, Ford of Europe, General Motors Europe, MAN Nutzfahrzeuge, DaimlerChrysler, Porsche, PSA Peugeot Citroen, Renault, Scania, Volkswagen, Volvo.
• Alliance of Automobile Manufacturers / www.autoalliance.org / Washington D.C., USA) representing: BMW of North America, DaimlerChrysler, Isuzu Motors America, Mazda North America, Mitsubishi Motor America, Nissan North America, Porsche Cars North America, Toyota Motor North America, Volkswagen of North America.
• EMA (Engine Manufacturers Association / www.enginemanufacturers.org / Chicago, USA) representing: Briggs & Stratton, Caterpillar, Cummins, DaimlerChrysler, Deere, Detroit Diesel, Deutz, Ford Motor, General Motors, Hino Motors, International Truck & Engine, Isuzu Motor, Kohler, Komatsu, Kubota, Mitsubishi Engine, Mitsubishi Fuso Truck, Onan- Cummins Power, Volvo Powertrain, Waukesha Engine, Dresser, Yamaha Motor, Yanmar Diesel.
• JAMA (Japan Automobile Manufacturers Association / www.japanauto.com / Tokyo, Japan) representing: Daihatsu Motor, Fuji Heavy Industries, General Motors Japan, Hito Motors, Honda Motor, Isuzu Motor, Kawasaki Heavy Industries, Mazda Motors, Mitsubishi Motors, Nissan Diesel Motor, Nissan, Motor, Suzuki Motor, Toyota Motor, Yamaha Motor.
Associated members are:
• AIAM (Association of International Automobile Manufacturers)
• AIAMC (Association of International Automobile Manufacturers of Canada)
• AMIA (Associacion Mexicana de la Industria Automotriz)
• ANFAVEA (Brazilian Association of Motor Vehicles)
• CVMA (Canadian Vehicle Manufacturers’ Association)
• CAMPI (Chamber of Automobile Manufacturers of the Philippines)
• CAAI (Chinese Association of Automotive Industry)
• KAMA (Korean Automobile Manufacturers Association)
• NAAMSA (National Association of Automobile Manufacturers of South Africa)
• TAIA (Thai Automotive Industry Association)
2.2.3 Definition of categories and related diesel fuel properties:
IEA Bioenergy – Liquid Biofuels May 2004 Page 22 Important regulations and recommendations for transport fuels
1. Category 1 fuels represent the lowest quality and can be found in markets with no or first level of emission control. A category 1 diesel fuel is characterized by a cetane number of min. 48.0 and a sulfur content of max. 3000 mg/kg.
2. Category 2 fuels represent an improved quality level and can be found in markets with stringent requirements for emission control (e.g. US Tier 0 or 1, EURO 1 and 2). A category 2 diesel fuel is characterized e.g. by a cetane number of min. 53.0 and a sulfur content of max. 300 mg/kg.
3. Category 3 fuels represent a further improved quality and can be found in markets with advanced requirements for emission control (e.g. US California LEV, ULEV and EURO 3 and 4). A category 3 diesel fuel is characterized by e.g. a cetane number of min. 55,0 and a Sulfur content of max. 30 mg/kg.
4. Category 4 fuels represent further advanced requirements for emission control, to enable sophisticated NOx and PM after-treatment technologies (e.g. US California LEV-II, US EPA Tier 2, EURO 4 in conjunction with increased fuel efficiency constraints). A category 4 diesel fuel is characterized by a sulfur content of max. 10 mg/kg. Each of the categories is defined with a detailed diesel fuel specification sheet.
2.2.4 Technical background for harmonized diesel fuel recommendations For the following properties very detailed descriptions of the criteria’s influence and sometimes quite complex significance is given. Although these descriptions do not yet refer to biodiesel’ influence on a number of properties it is recommended to analyze carefully the potential effect biodiesel pure or blends may have.
• Cetane number and index: The influence on cold start ability, on exhaust emissions, on fuel consumption and on combustion noise is described.
• Density and viscosity: The effect of density on emission, on fuel consumption and on emission control systems, and the effect of fuel viscosity on the injection system performance are discussed.
• Sulfur: The effect of sulfur on engine life, on PM emission, its contribution in formation of PM, the effect on diesel after-treatment and NOx absorbers, on continuously regenerating diesel particulate filters and diesel particulate filters is described. 1
• Aromatics: The influence of total aromatic content on NOx-emissions, of polyaromatic content on particulate emissions, and of polyaromatic content on PAH-emissions is discussed. 2
• Distillation: The influence of “heavy end” on PM emissions and of T95 on tailpipe emissions is described.
• Cold flow: The various cold flow performance tests are discussed as well as different cold flow limits.
• Foam: Methods for foam control are described.
• Lubricity: The influence of lubricity on pump wear and the relevant test method, the High Frequency Reciprocating Rig (HFRR) is described.
1 Authors comment: It can be expected that in the next issue of the Charter the low levels of sulfur of max. 10 mg/kg of biodiesel fuel and the related benefits are going to be mentioned. 2 It should be mentioned the biodiesel is free of aromatic compounds.
May 2004 IEA Bioenergy – Liquid Biofuels Important regulations and recommendations for transport fuels Page 23
2.2.5 Fatty-acid-methyl-ester (FAME) While the World-Wide Fuel Charter permits a content of max. 5 % v/v biodiesel according to standards EN 14214 or ASTM D6751 in the specification sheets for fuel categories 1, 2 and 3, but such permission has not yet been included the biodiesel-option for diesel fuel in category 4.3
In the sector “Background for Harmonized Fuel Recommendations” one specific chapter deals with FAME, describing Fatty-acid-methyl-esters (including vegetable derived esters) as extenders to or replacements of diesel fuel. The Charter is listing all the various potential feedstock sources (rapeseed, sunflower, palm, soybean, cooking oils and animal fats), and the typical characteristics for rapeseed oil methyl ester (RME) are given in the 3 following criteria:
• Cetane number = 51 3 • Density = 0.880 kg/m 2 • Viscosity at 40°C = 3.5 mm /sec
The technical advantages of methyl esters are seen in ensuring lubricity of injection equipment and in the reduction of exhaust particulate matter. The Charter lists however also some concerns specifically dealing with:
• Low temperatures: the use of additives is recommended “to avoid excessive rise in viscosity.” 4
• Hygroscopicity: it is recommended to apply “special care to prevent high water content and consequent risk of corrosion.” With a defined limit of max. 500 mg/kg water in the published CEN-standard EN 14214 for FAME and a voluntarily agreed level of max. 300 mg/kg water ex works of most of the industrial biodiesel plants this risk seems to be well under control.5
• Deposit formation: the assumption is made that “deposit formations tend to be higher than for fossil diesel, so detergent additive is strongly advisable.” 6
• Material compatibility: it is described that “seals and composite material in the fuel system are attacked unless they are specially chosen for their compatibility.” 7
3 This is in contradiction to real practice as by far the largest volumes of biodiesel are marketed today either as 100-% pure fuel or as a blend of max. 5 % in category-4 countries, i.e. countries within the European Union. 4 The following comment was received from the European Biodiesel Board as a letter to ACEA of 03.09.2002: “At low temperatures biodiesel performs very similar to mineral diesel. The use of additives is required exactly as it is the case for mineral diesel. These additives exist and are currently used during the whole winter period in Germany enabling biodiesel use until temperatures of -20°C. The biodiesel specifications about performances at low temperatures are the same as for mineral diesel. As a result low temperatures do not represent a specific problem for biodiesel.”
5 The European Biodiesel Board comment: “The term hygroscopic is inappropriate in the case of biodiesel as it gives an exaggerated and too absolute definition. It would be more precise to state that “Biodiesel can fix relatively higher quantities of water than mineral diesel”. EBB member companies guarantee very low levels of water content well inside the EN 14214 specifications.” 6 Authors comment: The observations of real practice in European countries lead to the conclusion that only biodiesel of very poor, substandard quality can lead to the mentioned symptoms, similarly with poor quality mineral diesel. With EN 14214 in place deposit formations represent no longer a critical symptom. The use of detergents has not been tested and appears to be questionable. 7 It has become state-of-the-art however, that vehicles of e.g. BMW, DaimlerChrysler, Volkswagen and Volvo with warranties are equipped with adequate materials and can be ordered under defined codes or that certain vehicles parts are exchanged for resistant ones, which are produced from fluorine-rubber or VITON.
IEA Bioenergy – Liquid Biofuels May 2004 Page 24 Important regulations and recommendations for transport fuels
The Charter’s conclusions: “Based on the technical effects of FAME, it is strongly advised that FAME content be restricted to less than or at 5%. As a pure fuel, or at higher levels in diesel fuel, the vehicles need to be adapted to the fuel, and particular care is needed to avoid problems.”
While the Charter is aware of the efforts of the European standards organization CEN in finishing the FAME specification EN 14214 soon it maintains a quite restrictive position: “Until this work is completed and based on the technical concerns raised by the introduction of FAME in diesel fuel, it should not be introduced into high quality fuels such as required in Category 4 markets. ASTM recently approved a standard specification (D6751) for biodiesel (B100) that is still under review by some automakers and engine manufacturers. Non- extended fatty acids are not acceptable for use as fuels.” 8
8 It has to be mentioned however that today biodiesel is used nearly exclusively in Category 4 markets either as a blend with up to 5 % (e.g. France, United Kingdom) or as 100 % pure fuel in those vehicles, for which a full warranty was issued (e.g. Austria, Germany).
May 2004 IEA Bioenergy – Liquid Biofuels Development of Biodiesel standards Page 25
3 DEVELOPMENT OF BIODIESEL STANDARDS
3.1 History of biodiesel standardization in Europe
3.1.1 Austria
Discussions about vegetable oil as a fuel for diesel engines first started after the energy crisis in 1973 resulting from the need to secure the energy supply of agriculture. After various tests with blends of fossil diesel fuel and vegetable oil the transesterification of vegetable oil into methyl ester was first considered by Austrian research institutes. Between 1980 and 1990 several research projects were carried out to investigate the production and utilization of rape oil methyl ester as a diesel fuel primarily for tractors.
In 1990 a working group was formed within the Austrian Standards Institute. In 1991 the world's first standard for rape oil methyl ester (ONORM C1190 [12]) could be published. This preliminary standard was reissued with several amendments on 1 January 1995 [13]. Besides a standard for fatty acid methyl ester in general was worked out and published as ONORM C1191 on 1 July 1997 [14].
3.1.2 Czech Republic
In 1990 investigations on biodiesel as transport fuel started with long term tests on tractors. The standardization work began in close co-operation with engine manufacturers and the Ministry of Transport. The standard for fatty acid methyl ester of rapeseed oil (CSN 65507) was published in 1994 [15]. In 1998 the standard was updated [16] and two further standards were published for diesel fuel containing fatty acid rape oil methyl ester above 5% (ČSN 65 6509 [17]) and diesel fuel containing fatty acid rape oil methyl ester above 30 % (ČSN 65 6508 [18]).
3.1.3 France
In France first activities started with experiments on captive fleets with blends of 20 % methyl ester and 80 % fossil diesel fuel in 1988. A joint program was established with the aim to offer rape oil methyl ester on the general diesel market. It was a basic requirement for the new fuel that it could be used in the same way as pure fossil fuel. As result of these considerations France decided to use biodiesel in 5 % blends so that no adjustments to engines or the distribution procedures were required.
In 1990 the Institute Francais du Pétrole started its work on a technical specification. In December 1993 the quality criteria were published first by ministerial order in the 'Gazette Officielle' of the French Republic [87], [88] and were updated in 1997 [19], [20].
3.1.4 Germany
In the early nineties a working group ‘Arbeitsgemeinschaft Biodiesel des Arbeitsaus- schusses 632’ was established within the DIN in Germany. The requirements and analysis methods were taken from the fossil fuel standard. Only a few parameters were adapted to the specific nature of biodiesel. A pre standard was published as DIN V 51606 in June 1994 [21]. In the following years the scope of the standard was extended to a broader basis of raw
IEA Bioenergy – Liquid Biofuels May 2004 Page 26 Development of Biodiesel standards materials. The DIN E 51606 [22] already being valid for fatty acid methyl ester was published as a draft in September 1997.
3.1.5 Italy
The ‘Commissione Tecnica di Certificazione nell Autoveicolo’ (CUNA) developed a specification for biodiesel which was published in May 1993 [23] and included in the ministerial decree for excise duty in December 1993. The standardization work concentrated on analysis methods, limits and engine tests. In the following years the CUNA specification was transferred into the standard UNI 10635 for vegetable oil methyl ester [24]. Because standardization of biodiesel started on a European level in 1999, national activities had to be stopped. The European activities took longer than expected. Italy requested for the permission to publish an update of the UNI standard. Thus, the UNI 10946 for biodiesel as automotive diesel fuel [25] and the UNI 10947 for biodiesel as heating fuel [26] were published in 2001.
3.1.6 Sweden
Around 1990 it was started to use rape oil methyl ester not only in blends of 20 to 50 %, but also in a pure form. Although in Sweden the production and use of biodiesel is low, a standardization group consisting of engine producers, oil companies and biodiesel producers began its work. The group looked at the standardization work already done in Europe and tried to follow the existing standards and recommendations. Country-specific requirements like winter operability and sulfur content had to be taken into account. The Swedish standard for vegetable oil methyl ester (SS 15 54 36, [29]) was published in 1996.
3.2 Biodiesel standardization in CEN
The European Commission has set itself the ambitious aim to increase the market share of renewable energy to 12% until 2010. The ways and means used for accomplishing this aim, i.e. establishing regulations concerning the creation of favorable conditions for renewable sources of energy, are summarized in the “White Paper on Renewable Sources of Energy” [30].
In May 2003 a Directive of the European Parliament and of the Council on the promotion of the use of biofuels for transport [31] was published. The objective is to provide for a Community framework to foster the use of biofuels for transport within the EU. Member States should ensure that a minimum proportion of biofuels and other renewable fuels are placed on their markets. A minimum share of 2% is proposed for 2005, which shall be increased by 0.75% per year up to 5.75 % for 2010.
Standards are of importance for the producers, suppliers and users of biodiesel. Authorities need approved standards for the evaluation of safety risks and environmental pollution. Standards are necessary for approvals of vehicles operated with biodiesel and are therefore a prerequisite for the market introduction and commercialization of biodiesel.
Consequently a mandate was given by the European Commission to CEN to develop standards for biodiesel as well as the necessary standards concerning the methods applied [32].
May 2004 IEA Bioenergy – Liquid Biofuels Development of Biodiesel standards Page 27
The proposed standards are aimed at the following targets: enabling a free movement of goods concerning biodiesel and providing guarantees for the use of biodiesel on the part of vehicle and plant producers. As a consequence an essential contribution to the accomplishment of the common aims - preserving the environment, guaranteeing the energy supply and preserving jobs - shall be made.
Biodiesel is used as a fuel for diesel engines and as fuel used for the production of heat. Therefore, the mandate provided for the development of the following standards: ∗ Biodiesel as sole diesel engine fuel (100%) ∗ Biodiesel as extender to diesel engine fuel according to EN590 ∗ Biodiesel sole or as extender to mineral oil products, in particular for the production of heat. It was decided by CEN to divide the work between two existing Technical Committees (TCs): • TC 19: Petroleum products, lubricants and related products • TC 307: Oilseeds, vegetable and animal fats and oils and their by-products - methods of sampling and analysis.
The following working groups (WGs) were involved:
CEN TC19 CEN TC307 | | WG24: Specification of automotive WG1: Test methods on FAME diesel / Task Force ‘Biodiesel’ WG25: Specification of FAME used as fuel for heating WG26: Verification of FAME related fuel test methods
Co-ordination group Figure 8: Structure of the Biodiesel standardization within CEN
A co-ordination group was installed where the Chairmen and Secretaries of TC19 and TC307 and the Conveners of the Working Groups were involved to ensure an overall co-ordination.
3.2.1 CEN/TC19/WG24: Specification of automotive diesel / Task Force ‘Biodiesel’
The task was to standardize requirements for 100% FAME and for mixtures of FAME to mineral oil based fuel for diesel engines and to verify the applicability of EN590 for blends of mineral oil based fuel with FAME (5% maximum). A task force was entrusted with the standardization work. First priority was given to work out drafts for 100% biodiesel and for biodiesel used as a 5% blend to mineral diesel fuel.
The difficulties consisted in the fact that so far most experience is concentrating on biodiesel produced from rapeseed oil. But it was aimed by the European Commission that the new standards should be valid for fatty acid methyl ester in general. The raw material is not pre- determined and thus the choice of the limiting values is attributed special importance. A ‘finger print’ system including limits for specific fatty acids was rejected.
IEA Bioenergy – Liquid Biofuels May 2004 Page 28 Development of Biodiesel standards
During the process it was decided to elaborate only one standard being valid for both, biodiesel as pure fuel and as a blending component to EN 590 diesel fuel. Therefore an amendment to EN 590 had to be issued to allow a 5% incorporation of FAME into diesel fuel.
The final standard EN 14214 [33] specifies the requirements and test methods for marketed and delivered fatty acid methyl esters (FAME) to be used either as automotive fuel for diesel engines (100%) or as an extender for automotive fuel for diesel engines in accordance with the requirements of EN 590.
3.2.2 CEN/TC19/WG25: Specification of FAME used as fuel for heating
The task of the working group was proposed as to specify requirements for FAME used as fuel for heating oil and as a blending component for the production of heating oil.
Heating oil has so far only been standardized on a national level, but not on a European level. Besides, the national requirements differ fundamentally. Thus, the instructions given to the WG have been altered. Henceforth, only one standard had to be developed, which determines the requirements for biodiesel as pure heating oil as well as the requirements for biodiesel used as mixing component for fossil heating oil. The resulting blends have to meet the requirements of the national standards for heating oil in the countries applying the standards.
The final standard EN 14213 [34] specifies requirements and test methods for marketed and delivered fatty acid methyl ester (FAME) to be used either as a heating fuel (100%) or as a blending component for the production of heating fuel.
3.2.3 CEN/TC19/WG26: Verification of FAME related fuel test methods
The task of the working group was to establish the applicability of already existing standards for petroleum test methods including precision data and to develop new standards for test methods. Round robin tests had to be carried out for each test method with sole biodiesel. Later the round robin tests were repeated with blends of biodiesel and fossil diesel fuel.
The precision data from this program are given in normative annexes of the standards EN 14213 and EN 14214, where these were found to be different from the precision data given in the test methods for petroleum products.
3.2.4 CEN/TC307/WG1: Test methods on FAME
The task was to standardize necessary test methods for the determination of the composition of 100% FAME, including the establishment of precision data. In some cases the precision level claimed by ISO 4259 (2R rule) could not be achieved with FAME. An improvement of the methods is still necessary.
May 2004 IEA Bioenergy – Liquid Biofuels Development of Biodiesel standards Page 29
3.3 Biodiesel standardization in the United States
Werner Koerbitz (ABI), Steve Howell (NBB)
3.3.1 Introduction
An ASTM Biodiesel Task Force was formed in 1994 to develop a US standard for biodiesel. Several iterations of the standard have occurred between biodiesel producers, engine manufacturers, and researchers and good agreement has been reached. The National Biodiesel Board and US biodiesel suppliers have adopted specifications based on the ASTM work. Recent approval was granted for the development of a provisional ASTM biodiesel standard which would be published by ASTM while additional data and approvals for a full ASTM standard (further field data, test method precision and bias information, and approval of the GC method for free and total glycerine) are occurring.
3.3.2 Biodiesel Markets in the United States: Background and History
Biodiesel, a renewable diesel fuel substitute or blending stock, is currently being commercialized in the US. Public interest in a cleaner environment, reduced dependence on foreign oil, and support for industrial products from agriculture has recently given rise to several pieces of nation wide legislation and government sponsored initiatives. These initiatives began with the passage of the Clean Air Act Amendments of 1990 and the Energy Policy Act of 1992. Embedded in this legislation are a variety of programs encouraging the use of clean burning fuel sources (Clean Air Act) and the development of alternative fueled vehicles (Energy Policy Act). Interest in a variety of cleaner burning alternative fuels increased, although many of these programs required the purchase of vehicles capable of running on alternatives fuels (over 75% of new vehicles purchased by federal, state or alternative fuel fleets must be alternative fueled vehicles) but it did not require the actual usage of alternative fuel in the vehicles. As a result of this, and the general lack of availability of alternative fuels, vehicle manufactures produced bi-fuel vehicles that could run on either conventional gasoline or diesel fuel as well as an alternative fuel, primarily natural gas or ethanol.
The Energy Conservation Re-Authorization Act (ECRA) of 1998 provided legislation that permitted the burning of B20 in existing diesel vehicles to receive the same credit as that of purchasing a new alternative fueled vehicle. This was the first piece of US legislation that actually required the use of fuel in order to receive a credit. This biodiesel specific legislation allows 450 gallons of pure biodiesel, B100, burned in existing diesel engines in a minimum of a B20 blend or higher to receive one alternative fuel vehicle purchase credit. These credits can then be used by federal, state and alternative fuel provider fleets to meet the Energy Policy Act vehicle purchase requirements or sold or traded to other fleets, under certain restrictions. This dramatically increased the usage of B20 in federal fleets (US Department Agriculture, Forest Service, General Administration Agency, etc.), state fleets (primarily Departments of Transportation road crews and school buses0, and alternative fuel provider fleets (primarily service vehicles of utility companies providing electricity and natural gas).
The US EPA also recently announced significant reductions in the required emissions certification levels of on road diesel engines. Beginning in model year 2007, NOx and PM certification levels for new diesel engines will be decreased over 90% compared to 2004 levels. This will make diesel engines cleaner than the cleanest natural gas burning engine available in the US today. In order to accomplish this dramatic reduction, fuel sulfur levels are being reduced to a maximum of 15 ppm in 2006, down from current levels of 500 ppm for
IEA Bioenergy – Liquid Biofuels May 2004 Page 30 Development of Biodiesel standards the on road market. This will enable sulfur sensitive after treatment technologies to be utilized for diesel engines. Similar reductions are being planned for the off road market in the 2010 to 2014.
This recent EPA legislation is changing the alternative fuel market in the United States. With such clean diesel engines available in the not too distant future, fleets are abandoning clean natural gas options that require different engines and fueling infrastructure for biodiesel blends and new Ultra Low Sulfur Diesel Fuel (S15 petrodiesel). Lowering the sulfur level to 15 ppm for the new S15 petrodiesel also removes other minor constituents that provide lubricity to the fuel, so a lubricity additive or fuel component will need to be added after removing the sulfur for most of the S15 petrodiesel. Biodiesel can be this lubricity component, even in blends of 2% biodiesel and lower, and B2 to B5 blends are also seeing an increasing amount of market penetration.
According to Mr. Steve Howell, MARC-IV Consulting Inc (2) and who serves as the Technical Director of the National Biodiesel Board and as well as Chairman of the ASTM Task Force on Biodiesel Standards, the biodiesel industry is targeting for large scale penetration of B2 into US diesel fuel with continued market penetration of B20 into government fleets and school buses, with use B100 only in certain niche markets. The biodiesel industry in the US is seeking incentives for biodiesel use, similar to that available for ethanol in the US, and as of the writing of this report passage of a $1 per gallon incentive for biodiesel appears very likely. According the Howell, the biodiesel industry believes this incentive will be sufficient to allow large scale penetration of biodiesel in the US.
3.3.3 US Biodiesel standard history
In June of 1994, a Task Force was formed within the American Society for Testing and Materials (ASTM) to begin development of a standard for biodiesel. The first step undertaken by the Task Force was the determination of the philosophy for the standard (1). Various options were considered from adding a section to the existing ASTM petrodiesel standard (ASTM D975), to development of a standard for a blend with petrodiesel, to a stand alone standard. The following was agreed upon by Biodiesel Task Force and subsequently by the membership of ASTM in the mid 1990’s:
1. Develop a stand alone specification for pure biodiesel, B100. 2. Work closely and cooperatively with petroleum, engine manufacturing, and biodiesel interests. 3. Base the development of the standard on the end product physical and chemical attributes needed for satisfactory operation, not on the source of the biodiesel or the manufacturing process. This is the same philosophy used for the development of the US petrodiesel specification, ASTM D 975. 4. Begin with existing D975 petrodiesel specification, eliminating items not applicable to biodiesel. 5. Extend it to new characteristics being considered for D975 as D975 is updated. 6. Extend it to address biodiesel specific properties needed for satisfactory engine operation.
This philosophy has formed the base by which the development of the Standard in the US has progressed. The reader will find many references to ‘biofuels’ and to ‘biodiesel’ fuels in the technical literature. Biodiesel has been referred to as a coal slurry, a pure vegetable oil, a mixture of vegetable oils and petroleum based diesel fuel (petrodiesel), the esters of natural oils, and as mixtures of esters and petrodiesel among others. It became apparent early on that once the
May 2004 IEA Bioenergy – Liquid Biofuels Development of Biodiesel standards Page 31 philosophy for the development of the standard was agreed upon, a written description of ‘biodiesel’ was the next step.
The ASTM Biodiesel Task Force adopted the following description of biodiesel early on:
“Biodiesel is defined as the mono alkyl esters of long chain fatty acids derived from renewable lipid feedstocks, such as vegetable oils and animal fats, for use in compression ignition (diesel) engines.”
The first key point to this definition is that biodiesel is a mono alkyl ester. Conventionally, biodiesel is produced through a transesterification reaction of a natural oil triglyceride (animal fat or vegetable oil) with a short chain alcohol (typically methanol) in the presence of a catalyst (usually sodium or potassium hydroxide). The reaction occurs step wise, with one fatty acid chain being removed first (forming one mono alkyl ester and a diglyceride), the second fatty acid removed next (forming two mono alkyl esters and a monoglyceride), and lastly, reaction of the third fatty acid. The resulting products are three mono alkyl esters (biodiesel) and glycerine. Glycerine is removed as a valuable co-product.
The mono alkyl ester definition, therefore, eliminated pure vegetable oils as well as monoglycerides and diglycerides from consideration as biodiesel. During the 1970's and 1980's a fair amount of research was conducted with pure vegetable oils and partially esterified oils in their neat (or pure) form and with blends of petrodiesel. The use of these pure or partially esterified oils caused a variety of engine and injector problems and should not be confused with biodiesel being commercialized today.
The second key point is that biodiesel is produced from renewable lipid feedstocks. This eliminates any confusion over coal slurries or other materials referenced as 'biodiesel' in the past. The last key point is biodiesel's intended use in compression ignition (diesel) engines. Due to the newness of biodiesel, some still confuse biodiesel with ethanol or other substitutes for gasoline and ask how it will impact operation in their gasoline powered vehicle. Although the technical community is mostly aware of biodiesel's applications, this point must constantly be re-enforced in the commercial marketplace.
The ASTM Task Force identified the following as critical items in the determination of biodiesel quality:
1. Complete reaction to the mono alkyl esters 2. The removal of free glycerine 3. The removal of residual catalyst 4. The removal of reactant alcohol 5. The absence of free fatty acids
The standard was developed to address each of these quality assurance needs using the philosophy
3.3.4 Biodiesel standard
Several iterations of the standard have occurred within the ASTM Biodiesel Task Force with input from engine manufacturers, biodiesel production companies and researchers. In 1995, the National Biodiesel Board (NBB) adopted the first recognized biodiesel standard in the US as a trade association specification while the ASTM biodiesel standard was moving through the approval process. This formed the early basis for quality in the US, and was used by early suppliers and purchasers of biodiesel. The NBB also maintained a listing of biodiesel
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companies committed to meeting that standard (3). This first US biodiesel standard is described in Table 1.
While it is beyond the scope of this paper to provide the detailed rational for the values of each specification, the standard addresses the key biodiesel quality parameters in the following way: 1. Conversion of the fat or oil to mono alkyl esters is ensured through measurement of the total glycerine, which includes all mono-, di-, and triglycerides as well as free glycerine, 2. Removal of the glycerine is ensured through measurement of the free glycerine test. 3. Removal of the catalyst is ensured through the measurement of the ash content. 4. Removal of the alcohol is ensured through measurement of the flash point. 5. The absence of fatty acids is ensured through measurement of the acid number.
There are several other distinctions between petrodiesel and biodiesel that are evidenced in the biodiesel standard and the testing methods employed. Perhaps the most important is that the cetane number, ASTM D 613, must be used not the cetane index. The Calculated Cetane Index (CCI), ASTM D4737, is based on the historical data base for the distillation curve of petroleum diesel and is not applicable to biodiesel.
Biodiesel is defined as the mono alkyl esters of long chain fatty acids derived from renewable lipid feedstocks, such as vegetable oils or animal fats, for use in compression ignition (diesel) engines. This specification is for pure (100%) biodiesel*.
Table 5: National Biodiesel Board Biodiesel Specification for pure (100%) Biodiesel as of 3/4/96
Property ASTM Method Limits Units 1. Flash Point 93 100.0 min. degrees C 2. Water & Sediment 1796 0.050 max vol. % 3. Carbon Residue, 100% sample 4530** 0.050 max wt % 4. Sulfated Ash 874 0.020 max. wt % 5. Kinematic Viscosity, 40 C 445 1.9 - 6.0 mm2/sec 6. Sulfur 2622 0.05 max. wt % 7. Cetane 613 40 min. n/a 8. Cloud Point 2500 By Customer degree C 9. Copper Strip Corrosion 130 No 3 max n/a 10. Acid Number 664 0.80 max. mg KOH/g 11. Free Glycerine GC*** 0.020 max wt % 12. Total Glycerine GC*** 0.240 max wt %
* This specification is in the process of being evaluated by ASTM, A considerable amount of experience exists in the US with a 20% blend of biodiesel with 80% petroleum based diesel. Although biodiesel can be used in the pure form, use of blends of over 20% biodiesel should be evaluated on a case by case basis until further experience is available. ** Or equivalent ASTM testing method. *** Austrian (Christiana Plank) update of' the United Sales Department of Agriculture test method.
There are several distinctions between petrodiesel and biodiesel that were evidenced in this early biodiesel standard and the testing methods employed. Perhaps the most important is that the cetane number, ASTM D 613, must be used not the cetane index. The Calculated Cetane Index (CCI), ASTM D4737, is based on the historical data base for the distillation
May 2004 IEA Bioenergy – Liquid Biofuels Development of Biodiesel standards Page 33 curve of petroleum diesel and is not applicable to biodiesel. This is primarily due to the lack of a ‘distillation curve’ for biodiesel. Petrodiesel is comprised of hundreds of compounds boiling at differing temperatures (determined by the petroleum refining process and the crude oil raw material) biodiesel contains only a few compounds—primarily C16 to 18 carbon chain length alkyl esters (determined entirely by the feedstock) which all boil at approximately the same temperature. Biodiesel, therefore, exhibits more of a boiling point than a ‘distillation curve’.
In addition, the composition of naturally occurring oils and fats are very similar, as seen in Table 2 below, giving a very tight boiling range for biodiesel regardless of the feedstock. The composition of biodiesel is also the reason for its high flash point, which is an advantage in enclosed areas such as underground mines.
Table 6: Oil Types and Length of Fatty Acid Chains in US Fats and Oils* Number of Carbons In Fatty Acid Chain By Chain Length (percent)
Oil Type <14 16 18 >20 Corn 12 88 Tallow 5 32 64 Peanut 12 81 7 Used frying oil#* 4 19 76 1 Rapeseed 5 94 1 Pork 2 27 70 1 Soybean 13 87 *Source: Proctor and Gamble, #Source: Fats and Proteins Research Foundation
There are some additional important differences in the testing methods necessary for measurement of biodiesel. The carbon residue must be run on the 100% sample, not the 10% residue after distillation as done with petrodiesel. It is difficult to leave only 10% of the sample upon distillation since biodiesel all boils at about the same temperature. The ash content is changed from oxidative ash (ASTM D482) to sulfated ash (ASTM D874) in order to assure more accurate measurement of sodium or potassium which could be present as residual catalyst. There is no ‘specification’ for cloud point, since most biodiesel will be blended with petrodiesel, but the value should be reported to the customer.
3.3.5 Pure specification vs. blend specification
A significant amount of discussion within the industry has occurred regarding the concentration of biodiesel used in blends with petroleum diesel and the resulting impact on the specification. Biodiesel is completely miscible with both No. 1 and No. 2 petrodiesel fuel. It can be used as a 100% replacement for petrodiesel, or as a blending stock. At 1997 world market prices for crude petroleum oil and animal fats and vegetable oils, the cost of biodiesel was more than petroleum based diesel. Therefore, biodiesel markets developed where it could provide value added benefits (emissions, biodegradability, lubricity, etc.) or where it represented a cost competitive option to meet other legislative initiatives (alternative fuels, greenhouse gas reduction, economic development, etc.) for which petrodiesel was not an option.
Most of the experience with biodiesel in the US has been with 20% blends of biodiesel and 80% conventional petrodiesel. This appeared to be a good compromise between emissions reduction and cost, and also minimizes cold weather impacts. There are additional markets, however, which are using 100% biodiesel such as in marine applications where the
IEA Bioenergy – Liquid Biofuels May 2004 Page 34 Development of Biodiesel standards biodegradability of pure biodiesel and the reduction of black smoke (especially on sailing boats) are important.
As time has proven, when biodiesel is used as a blend with petrodiesel (blends are the most common usage in the US today) the biodiesel is usually produced by someone other than the seller of the finished blend. This created a need for a standard for pure biodiesel before blending. The standard developed by ASTM, therefore, was for the pure (or 100%) biodiesel. The original rationale being if biodiesel conforms with the pure biodiesel standard, and diesel fuel conforms to its standard, the two can be blended in any percent and there is no separate specification for the blended product. This is similar to the rational used for No. 1 and No. 2 diesel fuel in the US at the time. No. 1 and No. 2 diesel fuel each have a specifications but are commonly used in blends with no separate specification for the various blends. Since most experience in the US had been with a 20% blend of biodiesel with 80% petrodiesel, engine manufacturers requested a caveat be added to the specification that blends over 20% be evaluated on a case by case basis by the engine manufacturer until more data becomes available.
3.3.6 Provisional ASTM biodiesel standard
In the 1996/1997 timeframe, ASTM determined additional data would be necessary prior to approval of the full ASTM biodiesel standard. This included further field data confirming the specification values, precision and bias status on various analytical methods when used for biodiesel testing, and standardization through ASTM of the GC method for total and free glycerine. To secure this data would take some time, and there was an intense desire to get some sort of ASTM specification on the books that would serve to protect consumers and assist in standardizing the trading and sale of biodiesel in the US. A ‘Provisional’ ASTM Standard is a mechanism with which a standard can be published as a stand alone ASTM document prior to the development of all the items necessary for the full standard. It is reserved for situations where it is deemed that such special action is necessary and warranted. A provisional standard is allowed to be published by ASTM for two years, after which time approval of a full standard must be granted or the provisional standard re-issued.
Based upon the growth of the biodiesel industry, several upcoming EPA regulatory requirements, and a desire by both the biodiesel industry and the engine manufacturers to insure biodiesel being used is meeting the latest standard, ASTM Committee D.02 on Petroleum Products provided the approval to move forward with a provisional biodiesel standard at the December, 1996 meeting. The provisional ASTM Biodiesel Standard, ASTM PS 121, was formally approved by the ASTM membership in December of 1999. It included the entire GC test method, which was in the process of being approved by ASTM, as an appendix to the standard as this was quickest way to secure the provisional standard.
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Table 7: ASTM PS 121-99 Provisional Specification for Biodiesel Fuel (B100) Blend Stock for Distillate Fuels1 Detailed Requirements for Biodiesel (B100)A Property Test Method B Limits Units Flash point (closed cup) D 93 100.0 min °C Water and sediment D 2709 0.050 max % volume Kinematic viscosity, 40°C D 445 1.9-6.0 mm2/s Sulfated ash D 874 0.020 max % mass Sulfur C 2622 0.05 max % mass Copper strip corrosion D 130 No. 3 max Cetane number D 613 40 min Cloud point D 2500 Report °C Carbon residue D D 4530 0.050 max % mass Acid number D 664 0.80 max mg KOH/g Free glycerin F 0.020 max G % mass Total glycerin F 0.240 max G % mass
A To meet special operating conditions, modifications of individual limiting requirements may be agreed upon between purchaser, seller, and manufacturer. BThe test methods indicated are the approved referee methods. Other acceptable methods are indicated in 5.3. COther sulfur limits can apply in selected areas in the United States and in other countries. DCarbon residue shall be run on the 100 % sample. ESee Annex 1 for test method. A gas chromatographic technique is being converted to a standard test method. FThe test method is under ASTM consideration by Subcommittee D02.04.OL
The passage of ASTM PS 121 served to validate the standard adopted by the NBB and being used in the industry since 1995 and the use of these standards has served the industry well. Relatively early adoption of biodiesel standards, first by NBB and then by ASTM as a provisional standard, was instrumental in helping to engrain quality and the use of ASTM standards into the US biodiesel industry. Due to this, very few quality issues have surfaced thus far in the United States.
3.3.7 After ASTM PS 121
Subsequent to the passage of ASTM PS 121, the ASTM Biodiesel Task Force began immediately to secure the additional data needed for the full ASTM standard. Biodiesel volumes grew slowly during this period, and most biodiesel use continued to be in B20 blends. Most biodiesel at the time was being produced from soybean oil, the most common and least expensive vegetable oil in the United States, but the use of used frying oils (sometimes referred to as yellow grease) for biodiesel production began to grow during this period. The GC test method for total and free glycerine, ASTM D 6584, was approved during this time period and several precision and bias round robins were performed on various test methods. Also during this time period, the National Conference on Weights and Measures approved a listing of diesel properties that could be claimed as premium diesel fuel. In this list was a minimum cetane number of 47. The flash point round robin data indicated unacceptable variability as the level of methanol in the fuel increased and as the flash point value reached its specification limit of 100 C minimum, so the limit was place at 130 C minimum for the full standard ballot while improvements to the flash point method were investigated.
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Discussions continued on oxidation stability test methods, and a separate ASTM Biodiesel Stability Working Group was formed to investigate the best methods for biodiesel and biodiesel blends. These efforts were largely based on measuring the effects of fuel aging and degradation as they relate to actual engine and fuel system operation not on techniques that served only as indicators or surrogates for fuel system problems such as the iodine value or rancimat tests incorporated into European Standards. Recent evaluations of field results for B20 in the US (2,3) have shown no issues relating to fuel stability with B20 in the US market, even though most US based biodiesel would not meet the current European standards adopted for either iodine value or the rancimat. The full standard for biodiesel in the US progressed on the basis of continued work in the area of fuel stability, as well as the updating of stability information in the appendix similar to that contained in the ASTM diesel fuel specification, ASTM D 975. At this time, neither biodiesel nor diesel fuel have a stability requirement within their respective specifications largely because this issue has not surfaced as a major problem in the field with either diesel fuel or B20.
Several ballots of the full ASTM biodiesel standard occurred between 1999 and its final approval at the December 2001 ASTM meeting, and subsequent publishing by ASTM in March of 2002. Through the balloting process, several changes and additions were made to address negative ballots:
1. A phosphorous specification of 10 ppm maximum was added to address the potential negative affects of phosphorous on new diesel after-treatment systems. 2. A vacuum distillation specification of 360 C maximum was added to address the potential for contamination of biodiesel with higher boiling materials like used engine oil. 3. The sulfur method was changed to a UV method, ASTM D 5453, since oxygen interference with the x-ray method, D 2622, provided falsely high results when used to measure biodiesel sulfur content. 4. The cetane number specification was changed to 47 minimum, the value set for premium diesel fuel by the National Conference of Weights and Measures.
Subsequent to the passage of ASTM D 6751 in 2002, an additional change was approved in 2003 to account for the upcoming EPA regulation requiring 15 ppm maximum sulfur level on all on-road fuels beginning in 2006. Most of the oils and fats used to produce biodiesel have virtually no sulfur and there fore most biodiesel falls well below the 15 ppm maximum sulfur value. While rare, there have been some used cooking oil samples shown to have sulfur levels higher than 15 ppm, with values approaching 50 ppm. These biodiesel fuels are still legal for commerce in the US on-road market until 2006, and will continue to be legal in the off-road market after 2006. In addition, there is work on expanding the raw material base to other oils which are not commonly used in today’s market which could contain higher sulfur levels such as mustard oils. Therefore, the biodiesel standard was modified to include two grades of biodiesel with the only difference between the two being the maximum allowable sulfur level. The S15 grade D6751 biodiesel has a guaranteed sulfur level less than 15 ppm. The S 500 grade has a sulfur level guaranteed less than 500 ppm, while actual values fall well below 100 ppm. The latest ASTM biodiesel standard, published by ASTM in July of 1993, can be found in the table below:
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Table 8: ASTM D 6751-03 Standard Specification for Biodiesel Fuel (B100) Blend Stock for Distillate Fuels Detailed Requirements for Biodiesel (B100) Property Test Method Limits Units Flash point (closed cup) D 93 130.0 min °C Water and sediment D 2709 0.050 max % volume Kinematic viscosity, 40°C D 445 1.9-6.0 mm2/s Sulfated ash D 874 0.020 max % mass Sulfur (S15) D 5453 15 max ppm (S500) 500 max ppm Copper strip corrosion D 130 No. 3 max Cetane number D 613 47 min Cloud point D 2500 Report °C Carbon residue D 4530 0.050 max % mass Acid number D 664 0.80 max mg KOH/g Free glycerin D 6584 0.020 max % mass Total glycerin D 6584 0.240 max % mass Phosphorous D 4951 0.001 max % mass Distillation, AET, 90% D 1160 360 max °C
3.3.8 Future ASTM considerations
The current biodiesel standard, ASTM D 6751, has served the industry well and continues to be the centerpiece for biodiesel quality in the US. There have been requests from various ASTM members and the ASTM Biodiesel Task Force is currently considering the following additional work items in 2004:
1. Incorporation of up to 5% biodiesel into the existing diesel fuel standard, ASTM D 975. 2. Development of a stand alone specification for a finished B20 blend. 3. Update of D 6751 for oxidation stability, catalyst compounds (Na/K) and wash water compounds (Ca/Mg). 4. Development of a B100 specification specifically for B100 use.
3.3.9 US biodiesel quality programs
The National Biodiesel Board (whose members consist of farming groups, biodiesel and petrodiesel manufacturers and marketers, and equipment and analytical support interests) has taken a very proactive role in biodiesel quality. NBB continues to support the data and efforts needed to maintain and improve ASTM D 6751 and to encourage its use and adoption. The NBB has taken biodiesel fuel quality one step further, however, by sponsoring a voluntary fuel supplier certification program called BQ-9000. This innovative program combines both quality system management aspects as well as the ASTM specifications and is available to producers and marketers of biodiesel and biodiesel blends. It provides a kind of ‘Good Housekeeping Seal of Approval’ TM for biodiesel producers and marketers and will serve to increase the confidence of engine companies and users that biodiesel supplied by BQ-9000 Certified Marketers will meet ASTM specifications. The program was developed by an independent committee of the NBB called the National Biodiesel Accreditation Commission. The NBAC is currently chaired by Mr. Steve Howell of MARC-IV. The official BQ-9000 program was recently approved by the NBAC and is now available for use, with the
IEA Bioenergy – Liquid Biofuels May 2004 Page 38 Development of Biodiesel standards first company certifications expected in the summer of 2004. See the NBB web site at www.biodiesel.org for more details.
In addition to BQ-9000, the National Biodiesel Board and the US Department of Energy are sponsoring an annual fuel quality survey for both B100 and B20. The results from the first survey should become available in the summer of 2004.
3.3.10 Standard harmonization
The NBB has been working closely with the engine and OEM community on biodiesel standards and support for B20 blends in both existing and new diesel equipment. While the various standards for biodiesel around the world have been developed for different reasons and with differing markets and feedstocks, the engine and OEM companies working with NBB have requested efforts be undertaken to harmonize biodiesel standards around the world. Since most of these companies design and produce equipment that is used globally, having significantly different fuel standards in different countries provides an added burden when designing and building engines and vehicles. It would benefit the biodiesel industry around the world to work more closely and cooperatively with the global engine and OEM community. The situation with biodiesel standards, however, is not different than that of petroleum based gasoline or diesel fuel around the world as those are not harmonized either. The engine and OEM community have attempted to harmonize fuel standards for all fuels with their issuance of the World Wide Fuel Charter. As time goes on, cooperation and coordination of fuel standards around the world would benefit both the biodiesel industry and the engine and OEM industry and future efforts should be undertaken in this area as much as possible given regional and local constraints and conditions.
3.4 Biodiesel standardization in Australia
Provided by Daniel Sheedy, Australian Government Department of the Environment and Heritage [35], Environment Australia [79].
3.4.1 Introduction
Standards Australia (http://www.standards.org.au) is the equivalent to ASTM or CEN in Australia. However the standards made by this organization (as with ASTM and CEN) do not, generally, have legislative backing - the standards are generally voluntary for industry.
The Australian Government made the decision to develop and implement fuel quality standards via the Fuel Quality Standards Act 2000, therefore making mandatory standards for industry, with penalty clauses for non-compliance.
3.4.2 General aspects
The Department of the Environment and Heritage has initiatives in place to reduce the impact of road transport on environment quality, urban amenity and human health. A strategy for this is to improve the emissions performance of the Australian vehicle fleet, by implementing fuel quality standards.
The Fuel Quality Standards Act 2000 (the Act) provides a legislative framework for setting national fuel quality and fuel quality information standards for Australia. The objects of this Act are to:
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a) Regulate the quality of fuel supplied in Australia in order to: i. reduce the level of pollutants and emissions arising from the use of fuel that may cause environmental and health problems; and ii. facilitate the adoption of better engine technology and emission control technology; and iii. allow the more effective operation of engines; and b) Ensure that, where appropriate, information about fuel is provided when the fuel is supplied.
Where a State or Territory already has fuel quality standards in place, the Commonwealth standards operate concurrently. State or Territory standards apply where they regulate a fuel characteristic not covered by the Commonwealth standards.
The standards regulate the supply of fuel to consumers, reduce toxic vehicle emissions and ensure that, by using clean fuels, modern vehicles fitted with advanced emissions control technologies operate at peak performance. In order to operate at peak capacity and efficiency, new cars require fuels that meet higher standards. For example, advanced catalysts for petrol and diesel vehicles, and particulate traps for diesel vehicles, require low sulfur fuel to function properly.
The standardization process can be described as one set in a legislative framework involving extensive stakeholder (public, industry and government) consultation.
3.4.3 Standardization bodies and working groups
The Act established the Fuel Standards Consultative Committee (FSCC) as a formal consultation mechanism to ensure that the interests of State and Territory governments and other stakeholders are taken into account in the development of fuel standards.
The Act requires that the Committee include one representative of each State and Territory, and the Australian Government. It must also include at least one person representing fuel producers, a non-government body with an interest in the protection of the environment, and a person representing the interests of consumers. The Minister for the Environment and Heritage may also appoint additional members to the Committee. The Committee usually meets twice a year and also undertakes work in between these meetings.
The Department of the Environment and Heritage may also, from time to time, engage technical consultants and/or form technical working groups (with industry representation) to assess issues relating to the development and implementation of fuel quality standards. Results from this work are referred to the FSCC for review and recommendation prior to Ministerial approval or decision-making.
3.4.4 Mechanism for decision and approval
Under the Act, the Minister must have regard to the FSCC's recommendations about a range of matters. The Minister must consult the Committee before:
• Determining a fuel standard; • Granting an approval to vary a fuel standard for a specified period; • Changing the contents of the Register of Prohibited Fuel Additives; and • Preparing guidelines for more stringent fuel standards, which may apply in specified areas in Australia.
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Preparation of a Regulation Impact Statement (RIS) is a critical feature of the regulation making process. The RIS is a document prepared by the Department responsible for a regulatory proposal following consultation with affected parties, formalizing and evidencing some of the steps that must be taken in good policy formulation. It requires an assessment of the costs and benefits of each option, followed by a recommendation supporting the most effective and efficient option. It must be incorporated into the assessment process used by all areas of government responsible for reviewing and reforming regulations.
3.4.5 Initiatives and driving forces
A number of initiatives with respect to the improved management of transport emissions were announced by the Australian Government in May 1999 as part of A New Tax System for Australia.
These initiatives, known collectively as the Measures for a Better Environment, included timetables for Australian harmonization with international vehicle emissions standards (for both petrol and diesel engines) and the reduction of sulfur levels in diesel fuel, as well as foreshadowing the need for changes to petrol specifications. Setting national fuel quality standards (including that for biodiesel), to complement new vehicle emissions standards, formed part of these measures.
Biodiesel is a relatively new fuel alternative in Australia. Despite this, there is a large interest in biodiesel. Early stakeholder consultation revealed wide support for standardization, to ensure quality biodiesel was supplied to the market to protect consumer interests, ensure vehicle operability and emissions outcomes and improve consumer confidence in the new fuel.
The Department of the Environment and Heritage administers the Fuel Quality Standards Act 2000 and the Fuel Standard (Biodiesel) Determination 2003 (the biodiesel standard).
3.4.6 Current state
Fuel quality standards have been made under the Act for Petrol, diesel, biodiesel and LPG. Fuel quality information standards (e.g. labeling requirements) have been made for Ethanol.
The Fuel Standard (Biodiesel) Determination 2003 (the biodiesel standard) came into effect on 18 September 2003 [36]. A suite of 12 parameters came into effect on this date with a second set due in September 2004. A number of parameters require further technical assessment prior to introduction. These include cold filter plugging point, cetane number, total contamination and oxidation stability.
In the later part of the biodiesel standardization process, and after setting the standard, the Australian Government made several decisions regarding fuel excise and assistance to fuel producers. On 18 September 2003 biodiesel locally manufactured for use in diesel engines became subject to excise duty at the same rate as low sulfur diesel. This rate is currently 38.143 cents per liter. Biodiesel imported for use in diesel engines will also attract customs duty at the same rate from 18 September 2003.
The cleaner fuels grants scheme provides for the payment of a grant to licensed excise manufacturers (including holders of storage licenses) and to importers of eligible cleaner fuels. This scheme has been established to offset the excise and customs duty payable on alternative fuels.
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From 18 September 2003 to 30 June 2008 grants will be provided for the production and importation of eligible biodiesel. These grants will offset the excise and customs duty payable on biodiesel providing a net effective excise rate of zero. The grant will be progressively phased out from 1 July 2008 to 30 June 2012.
Biodiesel that meets the fuel quality standard is eligible for the offsetting grant. The table below shows how the grant will be reduced in 5 steps.
Table 9: Excise rates for biodiesel in Australia 1 July 1 July 1 July 1 July 1 July 2008 2009 2010 2011 2012 Effective rates of 3.8 7.6 11.4 15.3 19.1 excise for biodiesel (cents per liter)
The final rate of excise for biodiesel (19.1 cents per liter) represents a 50% discount when compared to diesel (38.143 cents per liter). The final rate was set having regard to a range of industry, regional and other factors. For more information on excise and grants please go to http://www.ato.gov.au/businesses/content.asp?doc=/content/38323.htm
The Government also announced a Biofuels Capital Grants Program to fund capital subsidies for projects that provide new or expanded biofuels capacity. The subsidy will be provided at a rate of 16 cents per liter to projects producing a minimum of 5 million liters of biofuels and grants will be limited to a maximum of $10 million per project.
Most of the information provided above is available on the Department of the Environment and Heritage website (http://www.deh.gov.au/atmosphere/transport/index.html). This includes links to discussion/technical papers and legislation. The introduction and background chapters of these papers include details on the standard setting process. For more information on the Biofuels Capital Grants Program please go to http://www.investaustralia.gov.au/index.cfm?id=6BE71852-9027-E533-1F5198AF8F762100.
3.5 Biodiesel standardization in Canada
Provided by Renè Pigeon (NRCan) [37], CGSB Website [38],
Natural Resources Canada (NRCan) is collaborating with other parties in drafting two fuel standards under the auspices of the Canadian General Standards Board (CGSB). The following standards are being considered:
• Automotive Low Sulphur Diesel Fuel Containing Low-Level Biodiesel Esters (B1.0-B5), • Automotive Low Sulphur Diesel Fuel Containing Mid-Level Biodiesel Esters (B6-B20).
They are similar to those being discussed in ASTM International, but differ in some respects: The two drafts specify ASTM D 6751 and EN 14214 for defining the "Biodiesel Ester" component and the B6-B20 draft recommends testing the biodiesel ester component against EN 14112.
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Whereas the European standard for diesel fuel EN 590 allows a content of fatty acid methyl ester in the range from 0% to 5%, the Canadian B1.0-B5 draft standard ranges from 0.95% to 5.5%. Any biodiesel esters that are mixed below 0.95% are already implicitly allowed in the existing petroleum diesel standard as a functional additive.
The B1.0-B5 proposal has been balloted in April 2004, while the B6-B20 draft might be considered in 2005.
As a result of a series of teleconferences which were held for consulting European experts who participated in the BIOSTAB project, NRCan is going to issue a contract to OLEOTEK Inc. (http://www.oleotek.org) for studying the applicability of the test method EN 14112 and its specification (6 h) stated in EN 14214, for inclusion in Canadian standards. Oleotek, an R&D centres for biodiesel, bio-heating fuels, bio lubricants and non-fuel oleo chemical products, offers fuel analysis, including the Rancimat determination.
The main stakeholders are: One biodiesel process licensor (BIOX Corp.), one biodiesel producer (Topia Energy Inc.), NRCan, one province that granted a tax exemption (Ontario), one of the refiners and the one provincial regulator (the government of Québec) which participate in CGSB committees.
In order to prepare a standard, the CGSB requires that a proponent acts as the "champion" which drafts the versions and incorporates the changes as agreed by the parties. BIOX Corporation, a process licensing firm www.bioxcorp.com, currently acts as the champion of the drafting process for biodiesel blend standards. It subcontracts the drafting work to a consultant, and it is financially supported, in part, by NRCan for carrying out this task. In addition, NRCan contributes technical data.
The Canadian General Standards Board (CGSB) is one of the largest standards development and conformity assessment organizations in Canada and has been in business since 1934. CGSB is a charter participant in the National Standards System (NSS) of Canada and a component of the Government of Canada, Department of Public Works and Government Services.
The Canadian General Standards Board provides administrative support for standards development and conformity assessment services, including programs for certification of products and services, registration of quality and environmental management systems, and related services. These services are provided in support of economic, regulatory, procurement, health, safety and environmental interests.
The Standards Council of Canada defines standards as "publications that establish accepted practices, technical requirements and terminologies for products and services." CGSB has published over 1,600 standards in Canada covering a wide range of products and services including petroleum, protective clothing, the transport of dangerous goods and organic agriculture. CGSB administers the standards-development process using balanced committees (producers, users, regulators, and general interest members) to arrive at voluntary consensus standards.
The Canadian General Standards Board (CGSB) is drafting fuel standards, which can be adopted, as such or after modification, by the provincial governments, which have the jurisdiction in Canada for regulating commercial fuels.
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Information about the "standardization process in general" can be obtained from: http://www.pwgsc.gc.ca/cgsb/prgsrv/stdsdev/stdsdev-e.html in the two official languages of the IEA and Canada (French and English). In addition, the CGSB and other standards writing bodies (e.g., CSA, UL) must also apply the criteria of the National Standards System, which is managed by the Standards Council of Canada: http://www.scc.ca/en/nss/index.shtml)
The CGSB notifies the public at http://www.pwgsc.gc.ca/cgsb/prgsrv/stdsdev/nsa-e.html whenever it undertakes a new work item, makes a draft available for public review, and issues a finished document. During the public review period, the draft can be obtained from the CGSB Sales Centre by phone at (819) 956-0425 or 1-800-665-2472 (Canada only), by fax at (819) 956-5644 or by e-mail at [email protected].
In the case of the B1.0-B5 standard, the draft is available for public review at: http://www.scc.ca/forum98/cgsb- ongc/dispatch.cgi/f.middledisti/showFile/100396/d20040326174957/No/003-520-E-N-CBD- 02%202004-03-26.pdf
The CGSB sells standards through http://www.techstreet.com/cgsbgate.html or from the abovementioned CGSB Sales Centre.
The following hyperlink provides the list of all the standards for Petroleum and Related Products published by the CGSB: http://www.techstreet.com/cgi- bin/browsePublisher?publisher_id=285034&subgroup_id=13684
3.6 Biodiesel standardization in Brazil
Provided by: L.P. Ramos, Brazil [39]
3.6.1 Introduction
The first attempt to produce biodiesel in Brazil was carried out in the mid 40’s, when both methyl and ethyl esters of cottonseed oil where demonstrated as alternative biofuels to replace petrodiesel in times of war [40], [41]. However, a National Program (OVEG) was launched only three decades later to evaluate a variety of vegetable oils and their ethyl esters for the substitution of diesel, particularly due to the oil crisis of the late 70’s [42]. In general, the results obtained in field tests with biodiesel were encouraging but the economics were rather unfavorable. As a result, the maintenance of the program could not be justified on the basis of political and/or environmental issues and its main activities were halted immediately after the international situation was improved, with oil prices coming back to reasonable market costs.
In the meantime, several countries developed a considerable effort towards the implementation of a national biodiesel program and many of these have been very successful, such as those carried out in Austria, Germany, France and Italy. Nowadays, Brazil is attempting to get back to its original objectives about biodiesel and the reasons that are now supporting this action are partly environmentally, partly economically. The overall economics of biodiesel is still very weak but discussions about sovereignty, sustainable development, public health, social justice, job availability and many other aspects of its externalities are on great political demand. Together with technological improvements that are about to be demonstrated in pre-industrial facilities, the future of biodiesel looks promising as a suitable way to support many of our social activities and transportation needs without compromising the environment as much as fossil fuels.
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Several arguments could be gathered together to support a biodiesel program in Brazil. These are the large availability of land for farming, the availability of a large variety of renewable lipid sources for biodiesel production, the need for reducing the amount of diesel imported from abroad, the state-owned refineries are near to their capacity limit, there is an increasing demand for energy (electricity) in remote areas, the air quality is decreasing in largely populated urban areas, there is a need for increasing job availability in the countryside, biodiesel is compatible with the current engine technology, the country has well established agro-industrial activities primarily based on soybeans and sugarcane and, for this latter reason, there is a clear choice for ethyl esters rather than methyl esters as a diesel fuel substitute. In addition, the new legislation for diesel quality, particularly in what sulfur content is concerned, clearly justify the search for an environmentally friendly additive that could improve fuel properties that are lost during the process of sulfur removal.
Table 10 shows a simple calculation of the main requirements for the implementation of B5 blends in the entire Brazilian fleet. In short, if the program is solely based on soybeans, nearly 9 million tons of oilseed would be required, from which 7.2 million tons of soybean meal would be produced, adding up to a total revenue of US$ 1.85 billion and to the creation of an impressive amount of 234 thousand jobs. For a country that is constantly fighting against its level of poverty and social injustice, biodiesel seems to be a more than reasonable option if oriented to local producers and small coops that could directly benefit from the growth of this new market for oil-bearing materials. Now, if that is so, soybeans are not likely to maintain the status of the ideal raw material for biodiesel production because both soybean oil and soybean meal are commodities closely controlled by the international market. Therefore, other (cheaper) raw materials are being searched for the production of biodiesel, keeping in mind that different solutions may be found in different regions of the country.
In conclusion, if one is asked about the driving forces that are orienting and/or supporting the Brazilian Biodiesel Program, one’s answer should include the following goals: provide a clear benefit for local (small) producers, promote a better income distribution and quality of living in remote areas, create new jobs in the countryside, make energy available throughout the country, reduce the environmental impact of energy production, open new market opportunities for agribusiness, reduce petrodiesel consumption nationwide and improve air quality in urban areas (among other externalities).
Table 10: Biodiesel requirement for a B5 blend with petrodiesel throughout the country. Diesel consumption Requirements for B5 Region Diesel, 103L Fraction, % Biodiesel, 103L Main crop Area, 103ha South 7200 20 360 Soybean 600 Southeast 15840 44 792 Soybean 1320 Northeast 5400 15 270 Castor 600 North 3240 9 162 Dendê 36 Center-West 4320 12 216 Soybean 360 Total 36000 100 1800 Total 2916
3.6.2 National Biodiesel Program
In Brazil, the National Biodiesel Program was initiated by the Ministry of Science and Technology in October 2002, but now it has been dealt with by a consortium of several Ministries, a working group established directly by the President. In general, the Federal Government itself should be indicated as the stakeholder through actions supported by national funding agencies such as CNPq (www.cnpq.br) and FINEP (www.finep.gov.br).
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Defining such a large biodiesel program is a difficult task that requires some very important technical decisions. Some of these include what is really defined as biodiesel, whether use will be based on blends or restricted to the neat fuel, which are the potential raw materials to be exploited nationwide, what is the industrial scale that has to be pursued (this includes the strategic location of industrial facilities), which market destinations are available for co- products, what is the actual demand of the end-users and, finally, which specifications are still on demand for technical improvements. Together with these, there are still a need for technological innovations that could alleviate several process bottlenecks such as the avoidance of soap formation during biodiesel production, the improvement of biodiesel purification by enhancing phase separation after washing (this is particularly important in ethanolysis) and the recovery of co-products such as glycerol in a suitable condition for upgrading [43], [44].
Biodiesel can be produced from a large variety of renewable lipid sources including vegetable oils and animal fats. In general, this could be considered a good advantage but care must be taken with regard to the viability and competitiveness of such materials, particularly in places where the availability is rich and diverse. This is certainly the case in Brazil, where biodiesel could be produced from a large variety of fatty materials such as soybeans, sunflower, colza and other Brassica sp., peanuts, corn, olives, cotton and sesame seeds, Jatropha curcas, Ricinus communis (castor oil), jojoba, linseed, used cooking oils, avocado, white tremoço, pequi, macaúba, buriti, dendê, palmiste and babaçu. Choosing the best feedstock for biodiesel production would depend on both agronomic and technological attributes. Agronomic attributes include the productivity per unit area, the oil content and composition of the feedstock, the nutritional value of the oil cake, the availability of reasonable agronomic data to establish large plantations, adequate plant cycle and reasonable territorial adaptation. On the other hand, technological attributes are also critical and will include the content in poly-unsaturated fatty acids (influence oxidation stability) and saturated fatty acids (influence cloud and pour points), the technology required for oil extraction, the presence of extraneous compounds in crude oil, the fuel properties of the biodiesel so derived and whether there are other valuable co-products in the oilseed that could help the economics of the process [44].
3.6.3 Biodiesel standardization
The first provisional specification for biodiesel in Brazil was released by the National Petroleum Agency (Agência Nacional do Petróleo, ANP) in September 15, 2003 after months of public consultation (see also chapter 4.1). ANP is known as the federal regulatory agency for petroleum derivatives. Since biodiesel is to be primarily used in blends with petrodiesel, the final specification must be approved and issued by the ANP technical staff. The current specification, named ANP 255 (available at http://www.anp.gov.br), was based on ASTM D 6751 and CEN EN 14214 to ensure good fuel properties for biodiesel products that are to be used in B20 blends or less. Likewise ASTM D 6751, the ANP 255 specification define biodiesel as a petrodiesel fuel substitute comprised of mono-alkyl esters of long chain fatty acids derived from vegetable oils or animal fats. Interestingly, no differentiation is made between biodiesel derived from methanol or ethanol, regardless of changes in physical and chemical properties that this structural modification may originate.
Ever since the first attempt to draft these specifications, there has been a tremendous effort to avoid the discrimination of any potential raw material that might be available for biodiesel production nationwide. This is because different regions have different social and economic interests and, in many cases, the weather and soil conditions in one region may not be appropriate for the cultivation of a given oil-bearing material. On the other hand, since the provisional ANP 255 specification restricts field tests to private fleets using B20 or less, it is
IEA Bioenergy – Liquid Biofuels May 2004 Page 46 Development of Biodiesel standards clear that biodiesel blends, regardless of their actual biodiesel content (B2 up to B20), shall never exceed some critical limits established by the engine technology used to date. For this reason, properties such as kinematic viscosity, cloud point and specific gravity are defined as equivalent to those found in the national specification for petrodiesel quality (ANP 310).
Most of the official methods listed and recommended by the ANP 255 are based on either ASTM or CEN/ISO standards and, in some cases, either one would be considered acceptable to indicate biodiesel quality. Only six parameters have a corresponding Brazilian standard procedure (NBR standards), which have been developed and/or proposed by the Brazilian Association of Technical Methods (ABNT, Associação Brasileira de Normas Técnicas). These include kinematic viscosity, copper corrosion, acid number, cloud point and specific gravity.
In general, the provisional Brazilian biodiesel standard (ANP 255) has most if not all parameters found in the ASTM D 6751, together with seven other parameters listed in the EN 14214. Out of the parameters similar to ASTM D 6751, only the total glycerol content is proposed to be different and equivalent to plus 50% of the maximum tolerance found in ASTM D 6751 for this parameter. It is not clear whether this decision was made on a solid technical basis, but it is probable that the greater flexibility of this parameter would be related to the general expectation that raw materials such as castor oil are less amenable to alcoholysis than other materials such as soybean or rapeseed oil.
One interesting observation about the provisional Brazilian specification is that the iodine number is required as to take note. This is another clear attempt to avoid ruling out most of the available feedstock for biodiesel production in Brazil. It is reasonable to assume that several vegetable oils that are likely to produce a good quality biodiesel would be completely out of specification in relation to this chemical property. This, together with the evidence that ANP 255 defines biodiesel as to be used in blends, encouraged the use of more flexible parameters to avoid situations such as that of the European standard, which is clearly restrictive to biodiesel made of rapeseed oil and, to a certain extent, sunflower oil.
One important consideration about the Brazilian specification for biodiesel is that many of the methods used to certify biodiesel quality are not necessarily adequate to analyze ethyl rather than methyl esters. For instance, there is some evidence indicating that the gas chromatography (GC) method used to determine total glycerol is not technically adequate to analyze ethyl esters because, under the conditions established in the method (such as temperature programming), there will be some peak overlapping that may interfere with the quantitative evaluation of unreacted glycerides. In fact, it is important to realize that both EN 14105 and ASTM D 6584 methods specifically apply to methyl esters. To have it adapted to ethyl esters, a new GC-related method would have to be developed including standards strictly related to ethyl esters. In other words, it is apparent to us that there is no specification yet available for analyzing total and/or free glycerol in esters samples other than methyl.
It is also worth mentioning that biodiesel specifications should be made as simple as possible. Therefore, procedures that are somewhat repetitive in providing similar conclusions should be avoided. One clear example is the requirement for measuring alcohol content by GC. EN 14110 for determination of alcohol is recommend by ANP as part of the specification, even though it only applies to methanol (rather than ethanol) content in biodiesel. Being ethanol-based, it is reasonable to assume that ethyl esters will always comply 100% with EN 14110 because ethyl esters would not contain methanol anyway. Therefore, the method may need to be adjusted for biodiesel types other than methyl esters. On the other hand, if biodiesel specifications are to be made simple, it may be possible to eliminate alcohol content from the methods list because a more general flash point specification would suffice as a general alcohol-limiting parameter.
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Other comparisons involving ethyl and methyl esters would include cetane number, cold flow (or low-temperature) properties and oxidation stability. Ethyl esters have cetane numbers slightly higher than methyl esters [52]. Therefore, it is apparently unnecessary to specify a limitation for cetane number lower than that already defined by ASTM D 613 and EN ISO 5165 for methyl esters. Whether this higher tolerance for cetane number is to be attributed in ANP 255 to the wide variety of lipid sources available in Brazil for biodiesel production is still a matter of debate because there is not enough experimental data to back up this technical assumption. In any case, by lowering the cetane number, ANP is indirectly suggesting that ethyl esters have worse fuel properties than methyl esters and this is definitely not true when esters derived from the same lipid source are directly compared.
Ethyl esters have also better low-temperature properties and are likely to have better oxidative stability because the Rancimat/OSI method uses material on a mass basis, not on a molar basis [53]. Higher viscosities are also expected for ethyl esters due to their inherently higher molar mass. Observations like these may strongly interfere with the validation of an ethyl ester sample under the current specifications found worldwide. Only that would already suggest the need for some important changes if a general biodiesel specification were to be proposed and accepted worldwide. Otherwise, biodiesel types other than methyl esters will require different specifications for good quality and process control. One of the main reasons why the specifications for biodiesel should be kept as simple as possible is the cost of validating a commercial sample throughout the several parameters described in the current legislation. Besides, in many situations such as those found in Brazil, biodiesel is not meant to be used as a neat fuel and dilution factors as high as 50, such as in the case of B2 mixtures, are reasonable arguments for a greater flexibility in the specifications.
3.6.4 Future perspectives
It is of public knowledge that the ANP 255 biodiesel standard, created in Brazil to support the preliminary activities of the National Biodiesel Program, were based on a compilation of both ASTM D 6751 and EN 14214. This was primarily done to provide a solid basis upon which the first activities of the program could be supported (including field trials with biodiesel blends up to B20). However, it soon became clear that, due to the greater variability of raw materials and working conditions found in Brazil, the local specification would have to be different from those developed in USA and Europe almost exclusively for soybean and rapeseed oil, respectively. Defining the best (or most appropriate) biodiesel standard in Brazil is a very complicated task because any exceedingly conservative specification could be very detrimental to the application of non-classical oily materials for biodiesel production.
At this moment, it is right to say that Brazilians have come a long way in understanding the need for changes in the biodiesel specifications available to date in order to accommodate other biodiesel alternatives such as ethyl esters. Definitions on this regard are on great demand to help defining the future of the National Biodiesel Program. However, these lively discussions about specifications must not overlook other important aspects of its sustainable development. These include (a) the search for both agronomical and technological information on potential raw materials available nationwide for biodiesel production, (b) the construction of a suitable demonstration plant in which the viability and competitiveness of ethyl esters could be demonstrated against the current knowledge on this field, (c) the development of technically monitored endurance tests with ethyl esters to demonstrate engine performance and durability, and (d) the definition of political and regulatory issues that are related to the use of biodiesel within the Brazilian energy matrix.
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3.7 Further Biodiesel specification activities
In Japan there are ongoing activities concerning biodiesel fuel utilization. Biodiesel today is used in municipal governments like in the city of Kyoto. However, at present there is no biodiesel specification or regulation existing, because biodiesel is not sold on the market. It is planned to use a 5 % blend of biodiesel in mineral fuel in the future. That fuel should meet the existing diesel oil specifications. Today an extensive testing program for the utilization of biodiesel is carried out in order to see the need for modification of the existing diesel specifications and to develop new biodiesel specifications.
South Korea today uses blends of 20 % biodiesel in mineral fuel. The Korea Ministry of Commerce, Industry and Energy (KMOCIE) decided to take the minor modified version of ASTM 121-99 as Korean biodiesel standards for the time being. However, it is planned to develop own specifications until the end of 2006. KMOCIE also considers establishing several research centers, which will do a series of tests to determine the quality of biodiesel as motor fuel in Korea.
In Argentina biodiesel is produced only in small scale pilot plants for private use. Nevertheless, the ministry of economics put forth the resolucion 129/01, a draft specification for biodiesel in 2001. Furthermore, IRAM – Argentina’s standardization institute elaborated a tentative standard for biodiesel produced out of methanol and being used as pure fuel in cars and lorries.
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4 BIODIESEL STANDARD PARAMETERS AND LIMITS
4.1 Comparison of the requirements
Comparing the parameters of the different biodiesel standards which appeared in Europe over time it can be seen that the number of parameters increased and the limits became stronger. It is reasoned by more and more knowledge and experiences in practice on the one hand but also by the development of sophisticated injection systems with strong requirements to the fuels on the other hand. Contrary discussions around the responsibility of vehicle manufacturer to minimize operation risks and the possibility to exploit new raw materials in order to reduce production costs by biodiesel producers always accompanied the development of standards. In some cases effects of parameters are overlapping: For instance, the content of methanol also is limited by the flash point. The iodine number, the content of poly-unsaturated fatty acids and the stability are linked directly.
In Europe most experiences were gained with rapeseed oil methyl ester. Although the new European standards define biodiesel as fatty acid methyl ester in general and don’t restrict the raw material the limits are based on the properties of rapeseed oil. In contradiction the US and also Brazil standards are more open for a broader basis of raw materials. The number of parameters in the US standard (14) is much lower in comparison with European standards (22) (see Table 14).
In the following tables requirements of former and also current valid biodiesel standards are reflected. The standards are sorted according to the date of publication. Table 11, Table 12 and Table 13 are more of historical interest because the standards of European countries were replaced by the common European standards EN 14213 and EN 14214. In US the ASTM D 6751-02 replaced the PS 121-99 standard of 1999. In Table 14 the parameters of standards are reflected which are currently valid.
Please consider the parameters and limits of the following tables only as informatively and without any guarantee. No cross check was done concerning the determination methods. For further and detailed information it is recommended to contact the appropriate standardization institutes and to use the original standards.
Abbreviations:
RME ...... Rapeseed oil methyl esters VOME...... Vegetable oil methyl esters FAME ...... Fatty acid methyl esters FAMAE...... Fatty acid mono alkyl esters DF...... (Fossil) Diesel fuel m.e...... methyl esters specify ...... is to specify doub.b...... double bonds I.B.P...... Initial boiling point CCR 100% ...... Conradson carbon residue from original sample CCR 10% ...... Conradson carbon residue determined from a 10% distillation residue
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Table 11: Biodiesel standards 1991 - 1995 Austria France France Germany Czech R. Austria Standard / ON Journal Journal DIN V CSN ON Unit Specification C1190 Officiel Officiel 51606 65 6507 C1190 Source [12] [87] [88] [21] [15] [13] 1 Feb. 20 Dec 1 Jan. Date 9 Aug 1994 June 1994 Nov 1994 1991 1993 1995 Application RME RME 3) RME 4) VOME RME RME - - 0.855 – Density 15°C g/cm³ 0.86-0.90 0.875-0.90 0.87-0.89 0.885 Kinematic 20°C mm²/s 6.5-9.0 - - - 6.5-9.0 6.5-8.0 Viscosity 40°C mm²/s - - - 3.5-5.0 - - I.B.P. °C ------Distillation 5% °C ------95% °C ------300°C % - - - - ≤ 5 - Distillation 360°C % - - - - ≥ 95 - 370°C % ------Flash point °C ≥ 55 - - ≥ 100 ≥ 56 ≥ 100 sum/inters/ CFPP °C ≤ -8 - - ≤ 0/-10/-20 ≤ -5/-15 ≤ 0/-15 winter Pour point sum/winter °C - - - - ≤ -8/-20 - Cloud point °C ------Total Sulfur % mass ≤ 0.02 - - ≤ 0.01 ≤ 0.02 ≤ 0.02 CCR 100% % mass ≤ 0.1 - - - − ≤ 0.05 10% % mass - - - ≤ 0.3 ≤ 0.3 - Sulfated ash % mass ≤ 0.02 - - - ≤ 0.02 ≤ 0.02 (Oxid) Ash % mass - - - ≤ 0.01 - - Water cont. mg/kg - ≤ 200 ≤ 200 ≤ 300 ≤ 1000 - Total contam. mg/kg - - ≤ 20 ≤ 20 - Water&sedim % vol. 1) - - - 1) Cu-Corros. 3h/50°C - - 1 1 - Cetane No. - ≥ 48 - ≥ 49 ≥ 48 ≥ 48 Acid value mgKOH/g ≤ 1 ≤ 1 ≤ 1 ≤ 0.5 ≤ 0.5 ≤ 0.8 Oxidation IP 306 g/cm³ - - - specify - - stability ISO12205 g/cm³ ------EN14112 h ------Thermal stab. ------Storage stab. ------Methanol % mass ≤ 0.3 ≤ 0.1 ≤ 0.1 ≤ 0.3 ≤ 0.30 ≤ 0.20 Saponif. No mgKOH/g - - - - Ester content % mass - ≥ 96.5 ≥ 96.5 - - - Monoglycerides % mass - ≤ 0.8 ≤ 0.8 ≤ 0.8 - - Diglycerides % mass - - - ≤ 0.1 - - Triglycerides % mass - - - ≤ 0.1 - - Free glycerol % mass ≤ 0.03 - - ≤ 0.02 ≤ 0.02 ≤ 0.02 Total glycerol % mass ≤ 0.25 ≤ 0.25 ≤ 0.25 ≤ 0.25 ≤ 0.24 ≤ 0.24 Iodine No. - - - ≤ 115 - - Linolenic m.e. C18:3 % m/m ------Polyunsaturated ≥4 doub.b. %m/m ------Phosphorus mg/kg - ≤ 10 ≤ 10 ≤ 10 - ≤ 20 Alkali met. Na + K mg/kg - ≤ 5 ≤ 5 - - - Alk. earth met. Ca + Mg mg/kg ------Net cal. value MJ/kg - - - - 37.1 2) - 1) ...... Clear, free of separated water 3) ...... ≤ 5% blends in fossil diesel fuel & solid substances at ambient temperatures 4) ...... ≤ 5% blends in domestic heating fuel 2) ...... Informatively
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Table 12: Biodiesel standards 1996 - 1997 Sweden Italy Austria Germ.y France France Standard / SS UNI DIN E Journal Journal Unit ON C1191 Specification 15 54 36 10635 51606 Officiel Officiel Source [29] [24] [14] [22] [19] [20] 27.Nov. 21. Apr. Sep. Date 1 July 1997 28 Aug.97 28 Aug.97 1996 1997 1997 Application VOME VOME FAME FAME VOME 3) VOME 4) Density 15°C g/cm³ 0.87 - 0.90 0.86 -0.90 0.85 - 0.89 0.875 - 0.90 0.87 - 0.90 0.87 - 0.90 Kinematic 20°C mm²/s ------Viscosity 40°C mm²/s 3.5-5.0 3.5-5.0 3.5-5.0 3.5-5.0 3.5-5.0 3.5-5.0 I.B.P. °C - ≥ 300 - - - - Distillation 5% °C ------95% °C - ≤ 360 - - - - 250°C % ------Distillation 350°C % ------370°C % - - - - ≥95/360° ≥95/390° Flash point °C ≥ 100 ≥ 100 ≥ 100 ≥ 110 ≥ 100 ≥ 100 sum/inters/ CFPP °C ≤ -5 - ≤ 0/-15 ≤ 0/-10/-20 - - winter Pour point sum/winter °C - ≤ 0/-15 - - ≤ -10 ≤ -0 Cloud point °C - - - - 5) 6) 5) 6) Total Sulfur % mass ≤ 0.001 ≤ 0.01 ≤ 0.02 ≤ 0.01 - - CCR 100% % mass - - ≤ 0.05 ≤ 0.05 - - 10% % mass - ≤0.5 - - ≤ 0.3 ≤ 0.8 Sulfated ash % mass - - ≤ 0.02 ≤ 0.03 - - (Oxid) Ash % mass ≤ 0.01 ≤ 0.01 - - - - Water cont. mg/kg ≤ 300 ≤ 700 - ≤ 300 ≤ 200 ≤ 200 Total contam. mg/kg ≤ 20 - - ≤ 20 - - Water&sed. % vol. 7) - 1) - - - Cu-Corros. 3h/50°C - - - 1 - - Cetane No. - ≥ 48 - ≥ 49 ≥ 49 ≥ 49 ≥ 49 Acid value mgKOH/g ≤ 0.6 ≤ 0.5 ≤ 0.8 ≤ 0.5 ≤ 0.5 ≤ 0.5 Oxidation IP 306 g/cm³ 8) - - specify - - stability ISO12205 g/cm³ ------EN14112 h ------Thermal stab ------Storage stab ------Methanol % mass ≤ 0.2 ≤ 0.2 ≤ 0.20 ≤ 0.3 ≤ 0.1 ≤ 0.1 Saponif. No mgKOH/g ≥ 170 - - - - Ester cont. % mass ≥ 98 ≥ 98 - - ≥ 96.5 ≥ 96.5 Monoglycer. % mass ≤ 0.8 ≤ 0.8 - ≤ 0.8 ≤ 0.8 ≤ 0.8 Diglycerides % mass ≤ 0.1 ≤ 0.2 - ≤ 0.4 ≤ 0.2 ≤ 0.2 Triglycerides % mass ≤ 0.1 ≤ 0.1 - ≤ 0.4 ≤ 0.2 ≤ 0.2 Free glycerol % mass ≤ 0.02 ≤ 0.05 ≤ 0.02 ≤ 0.02 ≤ 0.02 ≤ 0.05 Total glycer. % mass - - ≤ 0.24 ≤ 0.25 ≤ 0.25 ≤ 0.25 Iodine No. ≤ 125 - ≤ 120 ≤ 115 ≤ 115 ≤ 135 Linolen.m. e. C18:3 % m/m - - ≤ 15 Polyunsaturat. ≥4 doub.b. %m/m - - - Phosphorus mg/kg ≤ 109) ≤ 10 ≤ 20 ≤ 10 ≤ 10 ≤ 10 Alkaline met. Na + K mg/kg ≤ 10 10) - - ≤ 5 ≤ 5 ≤ 5 Alk. earth met. Ca + Mg mg/kg ------Net cal.value MJ/kg ------1) ...... clear, free of separated water 3) ...... ≤ 5% blends in fossil diesel fuel & solid substances at ambient temperatures 4) ...... ≤ 5% blends in domestic heating fuel 7) clear and without sediments 5) ...... clear & limpid at 15°C 8) ...... no method 6) ...... color ≤ 12 (ASTM D1544) 9) ...... mg/l 10) ...... Na < 0,001% and K < 0,001%
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Table 13: Biodiesel standards 1998 - 2001 Czech R. Czech R Czech R. USA Italy Italy Standard / CSN CSN CSN PS Unit UNI 10946 UNI 10947 Specification 65 6507 65 6509 65 6508 121-99 Source [16] [17] [18] [27] [25] [26] Date Sep 98 Aug 98 Sep 98 Sept 99 2001 2001 DF+ 5% DF+30% FAME FAME Application 100% RME FAMAE RME RME automotive heating Density 15°C g/cm³ 0.87 - 0.89 0.82 - 0.86 0.82 – 0.86 - 0.86 - 0.90 0.86 - 0.90 Kinematic 20°C mm²/s ------Viscosity 40°C mm²/s 3.5 - 5.0 2.0 - 4.5 2.0 – 4.5 1.9-6.0 3.5-5.0 3.5-5.0 I.B.P. °C ------Distillation 5% °C ------95% °C ------250°C % - < 65 < 65 - - - Distillation 350°C % - ≥ 85 ≥ 85 - - - 370°C % - ≥ 95 ≥ 95 - - - Flashpoint °C ≥110 > 55 > 55 ≥100 ≥ 120 ≥ 120 sum/inters/ CFPP °C ≤ -5 ≤ 0/-10/-20 ≤ 0/-10/-20 - - 14) winter Pour point sum/winter °C - - - - - 0 Cloud point °C - - - 11) - - Total Sulfur % mass ≤ 0.02 ≤ 0.05 ≤ 0.04 ≤ 0.05 ≤ 0.001 ≤ 0.001 CCR 100% % mass ≤ 0.05 - - ≤ 0.05 - - 10% % mass - ≤ 0.30 ≤ 0.30 - ≤ 0.3 ≤ 0.3 Sulfated ash % mass ≤ 0.02 - - ≤ 0.02 ≤ 0.02 ≤ 0.01 (Oxid) Ash % mass - ≤ 0.01 ≤ 0.01 - - - Water cont. mg/kg ≤500 ≤200 ≤350 - ≤ 500 ≤ 500 Total contam mg/kg ≤ 24 ≤ 24 ≤ 24 - ≤ 24 ≤ 24 Water&sed. % vol. - - - ≤ 0.05 - - Cu-Corros. 3h/50°C 1 1 1 ≤ No.3 class 1 class 1 Cetane No. - ≥ 48 2) ≥ 46 ≥ 46 ≥ 40 ≥ 51.0 ≥ 51.0 Acid value mgKOH/g ≤ 0.5 ≤ 0.1 ≤ 0.25 ≤ 0.8 ≤ 0.50 ≤ 0.50 15) Oxidation IP 306 g/cm³ ------stability ISO12205 g/cm³ - ≤ 25 - - - - EN14112 h - - - - ≥ 6 ≥ 6 Thermal stab - - - - 12) 13) Storage stab - - - - - 13) Methanol % mass - - - ≤ 0.02 - Saponif. No mgKOH/g 185-190 2) - - - - - Ester cont. % mass - 3.0 - 5.0 30 - 36 - ≥ 96.5 ≥ 96.5 Monoglycer. % mass - - - - ≤ 0.80 ≤ 0.80 Diglycerides % mass - - - - ≤ 0.20 ≤ 0.20 Triglycerides % mass - - - - ≤ 0.20 ≤ 0.20 Free glycerol % mass ≤ 0.02 - - ≤ 0.02 ≤ 0.02 ≤ 0.02 Total glycer. % mass ≤ 0.24 - - ≤ 0.24 ≤ 0.25 - Iodine No. - - - − ≤ 120 ≤ 120 Linolen.m. e. % m/m - ≤ 12 Polyunsaturated ≥4 doub.b. %m/m - ≤ 1 Phosphor. mg/kg ≤ 20 - - - ≤ 10.0 ≤ 10.0 Alkaline met. Na + K mg/kg ≤ 10 2) - - - ≤ 5 - Alk.earth met. Ca + Mg mg/kg ------Net cal.value MJ/kg 37.1 2) - 40.5 2) - - ≥ 35 2) ...... informatively 13) ...... not available 11) ...... report to costumer 14) ...... likewise UNI 6579 12) ...... under development 15) ...... organic acidity
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Table 14: Biodiesel standards in 2004 USA EU EU Australia Brasil EN EN ANP Standard / Specification Unit D6751-02 14213 14214 255 Source [28] [34] [33] [36] [39] Date 2002 July 2003 July 2003 Sep.03 Sep.03 FAME FAME FAMAE Application FAMAE FAME heating automotive automot Density 15°C kg/m³ - 860-900 860-900 860-890 like diesel Kinematic 20°C mm²/s - - - - Viscosity 40°C mm²/s 1.9-6.0 3.5-5.0 3.50-5.00 16) 3.5-5.0 like diesel I.B.P. °C - - - - - Distillation 5% °C - - - - - 95% °C ≤ 360 - - ≤ 360 / 90% ≤ 360 250°C % - - - - - Distillation 350°C % - - - - - 370°C % - - - - Flash point °C ≥ 130 ≥ 120 ≥ 120 ≥ 120 ≥ 100 CFPP °C - 25) 22) TBA21) - Pour point sum/winter °C - 0 26) - - - Cloud point °C report - - - like diesel ≤ 0.005 / Total Sulfur % mass ≤ 0.05 ≤ 0.0010 ≤ 0.0010 23) ≤ 0.001 0.001 CCR 100% % mass ≤ 0.05 - - ≤ 0.050 ≤ 0.05 10% % mass - ≤ 0.30 ≤ 0.30 17) or ≤ 0.30 Sulfated ash % mass ≤ 0.020 ≤ 0.02 ≤ 0.02 ≤ 0.020 ≤ 0.02 (Oxid) Ash % mass - - - - - Water cont. mg/kg - ≤ 500 ≤ 500 - - Total contamination mg/kg - ≤ 24 ≤ 24 18) ≤ 24 - Water&sediments % vol. ≤ 0.050 - - ≤ 0.050 ≤ 0.02 Cu-Corrosion 3h/50°C ≤ No. 3 class 1 class 1 ≤ No. 3 ≤ No. 1 Cetane No. - ≥ 47 ≥ 51 ≥ 51 ≥ 51 ≥ 45 Acid value mgKOH/g ≤ 0.80 ≤ 0.50 ≤ 0.50 ≤ 0.80 ≤ 0.8 Oxidation IP 306 g/cm³ - - - - - stability ISO12205 g/cm³ - - - - - EN14112 h - ≥ 4.0 ≥ 6.0 ≥ 6 ≥ 6 Thermal stability - - - - - Storage stability - - - - - Methanol content % mass - - ≤ 0.20 ≤ 0.20 ≤ 0.50 24) Saponification No mgKOH/g - - - - - Ester content % mass - ≥ 96.5 ≥ 96.5 ≥ 96.5 - Monoglycides % mass - ≤ 0.80 ≤ 0.80 - ≤ 1.0 Diglycerides % mass - ≤ 0.20 ≤ 0.20 - ≤ 0.25 Triglycerides % mass - ≤ 0.20 ≤ 0.20 - ≤ 0.25 Free glycerol % mass ≤ 0.020 ≤ 0.02 ≤ 0.020 ≤ 0.020 ≤ 0.02 Total glycerol % mass ≤ 0.240 - ≤ 0.25 ≤ 0.250 ≤ 0.38 Iodine No. - ≤ 130 ≤ 120 - take note Linolenic methyl ester % m/m - - ≤ 12.0 - - Polyunsaturated ≥4 doub.b. %m/m - 1 19) 1 19) - - Phosphorus content mg/kg ≤ 10 ≤ 10.0 ≤ 10.0 ≤ 10.0 ≤ 10 Alkali metals Na + K mg/kg - - ≤ 5.0 ≤ 5.0 ≤ 10 Alk.earth metals Ca + Mg mg/kg - - ≤ 5.0 ≤ 5.0 - Net calorific value MJ/kg - ≥ 35 - - - 16) ...... If CFPP is -20 °C or lower, the viscosity measured at -20 °C shall not exceed 48 mm2/s 17) ...... ASTM D 1160 shall be used to obtain the 10% distillation residue 18) ...... Pending development of a suitable method, EN 12662 shall be used 19) ...... Suitable test method to be developed 22) ...... like diesel fuel 21) ...... TBA… to be advised 23) ...... beginning with 1 Feb 2006 24) ...... Alcohol 25) ...... Only for FAME as heating fuel solely, same limit as for mineral oil according to national regulations 26) ...... Free of additives for cold flow improvement or cloud point depressing; only for blending purposes
IEA Bioenergy – Liquid Biofuels May 2004 Page 54 Biodiesel standard parameters and limits
4.2 Comparison of parameters and limits
4.2.1 Density
Table 15: Comparison of limits regarding density in international fuel quality standards Country/Region Norm Applicable to Date Density at 15°C [kg/m³] EU EN 14214 FAME July 2003 860-900 U.S.A. ASTM FAME February 2002 - D6751 Australia Draft FAME Draft (September 860-900 2003) EU EN 590 Fossil diesel May 2003 820-845
Density limits in all discussed biodiesel fuel standards are in the range of 860-900 kg/m³, with the exception of the American ASTM norm, including no regulation on this parameter. It is argued that the determination of density is superfluous for biodiesel samples complying with all other prescribed specifications, as these fuels will inevitably have densities in the desired range. Densities of biodiesel fuels are generally higher than those of petrodiesel samples, which have impacts on cetane number, heating value and fuel consumption, as the amount of fuel introduced into the combustion chamber is determined volumetrically. However, Tat and Van Gerpen (2000, [45]) showed that temperature-dependent changes in biodiesel densities are similar to those of fossil diesel. Rathbauer and Bachler (1995, [89] have determined the density alteration factor of 7 different vegetable oil methyl esters. In average the density varies with 0.000723 g/ml.K in a temperature range between 20 and 60°C. Values for FAME samples depend on their fatty acid composition as well as on their purity. On the one hand, density increases with decreasing chain length and increasing number of double bonds (Wörgetter et al., 1998, [46]), explaining high values for fuels rich in unsaturated compounds, such as sunflower oil methyl ester (885 kg/m³) or linseed oil methyl ester (891 kg/m³). On the other hand, density can be decreased by the presence of low- density contaminants, such as methanol. The standard analytical procedures for the determination of density in both fossil diesel and biodiesel fuels either involve the use of a standardized glass hydrometer (EN ISO 3675) or an oscillating U-tube (EN ISO 12185) at the prescribed temperature.
4.2.2 Kinematic viscosity
Table 16: Comparison of limits regarding kinematic viscosity in international fuel quality standards Country/Region Norm Applicable to Date Kin. viscosity at 40°C [mm²/s] EU EN 14214 FAME July 2003 3.5-5.0 U.S.A. ASTM FAME February 2002 1.9-6.0 D6751 Australia Draft FAME Draft (September 3.5-5.0 2003) EU EN 590 Fossil diesel May 2003 2.0-4.5
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Kinematic viscosity at 40°C is limited to 3.5 – 5 mm²/s in the European biodiesel standard and the other discussed norms, with the exception of the American specifications, allowing a broader range of values. The corresponding limit for fossil diesel fuel is considerably lower. Viscosity increases with higher contents of high molecular compounds like unreacted glycerides or polymers, which can be found in used frying oil. The standardized analytical procedure for both biodiesel and petrodiesel utilizes a calibrated glass capillary viscosimeter, measuring the time for a defined sample volume to flow through the device under gravity at the prescribed temperature (ISO 3104).
4.2.3 Flash point
Table 17: Comparison of limits regarding flash point in international fuel quality standards Country/Region Norm Applicable to Date Flash Point [°C] EU EN 14214 FAME July 2003 ≥ 120 U.S.A. ASTM FAME February 2002 ≥ 130 D6751 Australia Draft FAME Draft (September ≥ 120 2003) EU EN 590 Fossil diesel May 2003 ≥ 55
Flash point is a measure of flammability of fuels and thus an important safety criterion in transport and storage. EN 14214 and the Australian draft define a flash point minimum of ≥ 120°C for biodiesel fuels, in contrast to the American standard, which is stricter. In general flash points of petrodiesel samples are only about half the values of those for FAME, which constitutes an important safety asset for the biofuel. Especially for niche applications, such as underground mining, biodiesel fuels are to be preferred for both safety and health reasons. The flash points of pure biodiesel samples are considerably higher than the prescribed limits, so that values of about 170°C are reported for pure RME (Wörgetter et al., 1998 [46]). However, flash points rapidly decrease with increasing amounts of residual alcohol. As these two parameters are strictly correlated, it is argued that the regulation and determination of both may be redundant. The standard analytical procedure for the determination of the flash point in the European norm is the rapid equilibrium closed cup method.
4.2.4 Sulfur content
Table 18: Comparison of limits regarding sulfur content in international fuel quality standards Country/ Norm Applicable Date Sulfur content [mg/kg] Region to EU EN 14214 FAME July 2003 ≤ 10.0 U.S.A. ASTM D6751 FAME February 2002 ≤ 500 ≤ 15 Australia Draft FAME Draft (September ≤ 50 2003) ≤ 10 (effective Feb. 2006) EU EN 590 Fossil May 2003 ≤ 350 diesel ≤ 50 (effective Jan. 2005) or ≤ 10
Sulfur is limited to a maximum content of 10 ppm in the European norm. By 2006 this value will also be demanded in the Australian standard. A recent amendment to the
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American norm has added an additional limit of 15 ppm to define a sulfur free biodiesel. In Europe, fossil diesel fuel, for which now sulfur contents of up to 350 ppm are permissible, will have to be desulfurized to concentrations of 50 ppm and below by 2005. In addition to that, the new fossil diesel fuel standard considers the use of “sulfur-free” diesel fuels as well. Fuels with high sulfur contents have been associated with negative impacts on human health and on the environment, which is the reason for the current tightening of national limits. Vehicles operated on high-sulfur fuels produce more sulfur dioxide and particulate matter, and their emissions are ascribed a higher mutagenic potential. Moreover, fuels rich in sulfur may cause engine wear and reduce the efficiency and the life span of oxidation catalytic converters and various denitrification exhaust after-treatment systems. On the other hand, many ultra low-sulfur petrodiesel fuels have turned out to lack in lubricity, which can lead to injection pump failure. This phenomenon is due to the removal of nitrogen and oxygen compounds, normally responsible for lubrication, during the desulfurization process. As FAME has excellent lubricating qualities regardless of their sulfur contents, the addition of a small portion of biodiesel to sulfur-free fossil diesel fuel has been suggested as a remedy to this problem. Biodiesel fuels have traditionally been praised as virtually sulfur-free. This is still perfectly true for FAME produced from fresh vegetable oils, as they indeed contain only traces of sulfur, stemming from various minor components within the feedstock, such as glucosinolates and derived products in rapeseed oil (Daun and Hougen, 1976 [47]). For these fuels tremendous advantages over conventional petrodiesel samples have been proven in terms of sulfur dioxide emissions and particle-bound mutagenicity. The standardized analytical methods for both types of fuel either involve ultraviolet fluorescence spectrometry (EN ISO 20846) –applicable to sulfur concentrations of 3 to 500 ppm - or wavelength-dispersive X-ray fluorescence spectrometry (EN ISO 20884).
4.2.5 Carbon residue
Table 19: Comparison of limits regarding carbon residue in international fuel quality standards Country/Region Norm Applicable to Carbon residue Carbon residue on undistilled sample on 10% distillation [%m/m] residue [%m/m] EU EN 14214 FAME - ≤ 0.30 U.S.A. ASTM FAME ≤ 0.05 - D6751 Australia Draft FAME ≤ 0.05 ≤ 0.30 EU EN 590 Fossil diesel - ≤ 0.30
The standards for biodiesel and fossil diesel fuel consistently limit carbon residue (determined on the 10% distillation residue) to a maximum value of 0.30 % (m/m). The respective limit in the American norm is lower because here the determination is conducted on the original, undistilled sample. Carbon residue is defined as the amount of carbonaceous matter left after evaporation and pyrolysis of a fuel sample under specified conditions. Although this residue is not solely composed of carbon, the term “carbon residue” is found in all discussed standards because it has long been commonly used. The parameter serves as a measure for the tendency of a fuel sample to produce deposits on injector tips and inside the combustion chamber when used in an engine. It is considered one of the most important biodiesel quality criteria, as it is linked with many other limited parameters. So for FAME, carbon residue correlates with the respective amounts of glycerides, free fatty acids, soaps and remaining catalyst (Mittelbach, 1996 [48]). Moreover, the parameter is also influenced by
May 2004 IEA Bioenergy – Liquid Biofuels Biodiesel standard parameters and limits Page 57 high concentrations of polyunsaturated FAME and polymers (Mittelbach and Enzelsberger, 1999 [51]). According to EN 14214, carbon residue is determined from the 10% distillation residue of the respective sample (obtained according to ASTM D 1160). This additional step is required because modern fossil diesel fuels tend to have very low carbon residue values, which might even be below 0.1% (m/m) as the detection limit of the corresponding analytical procedure (EN ISO 10370). To enable comparison with fossil diesel, the strategy is also applied to biodiesel samples, although here analysis of the original sample would suffice and the recovery of a 10% distillation residue poses considerable problems due to the nearly identical boiling points of different FAME. A small portion of the distillation residue is placed into a glass vial, heated under defined conditions in a nitrogen stream, and the remaining carbonaceous residue within the vial is weighed. This “micro method” is a further development of the traditional, laborious “Conradson method” for the determination of carbon residue (ISO 6615). Nevertheless, the old-fashioned procedure is still widely used for biodiesel analysis, as it has been shown that it yields identical results, albeit with less precision than the standardized method (EN ISO 10370).
4.2.6 Cetane number
Table 20: Comparison of limits regarding cetane number in international fuel quality standards Country/Region Norm Applicable to Date Cetane number EU EN 14214 FAME July 2003 ≥ 51 U.S.A. ASTM FAME February 2002 ≥ 47 D6751 Australia Draft FAME Draft (September ≥ 51 2003) EU prEN 590 Fossil diesel Draft (May 2003) ≥ 51
All the described biodiesel quality standards and the European norm for fossil diesel fuel define a minimum value of ≥ 51 for cetane number (CN). The American norm, however, allows considerably lower values. High cetane numbers signify only short delays between fuel injection and ignition, and thus guarantee good cold start behaviour and a smooth run of the engine. Fuels with low cetane numbers tend to cause diesel knock and show increased gaseous and particulate exhaust emissions because of incomplete combustion.
In general biodiesel has slightly higher cetane numbers than fossil diesel. Systematic studies on the molecular properties of fatty acid esters revealed that 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 (Wörgetter et al., 1998 [46])
The recommended analytical procedure, applicable to both FAME and fossil diesel, is based on the comparison of the ignition performance of a fuel sample to the behaviour of blends of reference fuels with known cetane numbers in a standardized engine test (EN ISO 5165). Reference substances are hexadecane (= cetane) - a high-quality standard with a short ignition delay time, which has arbitrarily been assigned a cetane number of CN=100 – and 2,2,4,4,6,8,8, heptamethylnonane – a low-quality reference compound with a long ignition delay period and an assigned cetane number of CN=15 (Knothe and Dunn, 1998 [49]).
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4.2.7 Ash content
Table 21: Comparison of limits regarding ash content in international fuel quality standards Country/Region Norm Applicable to Sulphate ash Oxide ash [%m/m] [%m/m] EU EN 14214 FAME ≤ 0.02 - U.S.A. ASTM FAME ≤ 0.02 - D6751 Australia Draft FAME ≤ 0.02 - EU EN 590 Fossil diesel - ≤ 0.01
All the described biodiesel quality standards limit sulphate ash to a maximum content of 0.02 % (m/m). The corresponding value within the fossil diesel norm cannot directly be compared to these limits, as here the relevant contaminants are determined as oxides and not in the form of sulphates. 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 filter plugging (Mittelbach, 1996 [48]). The standardized analytical procedure for the determination of sulphate ash in biodiesel (ISO 3987) involves the addition of sulfuric acid to the sample prior to combustion to transfer metallic impurities into the corresponding sulphates. This strategy is preferred over the direct combustion – yielding oxide ash – because sodium and potassium sulphate produced from catalyst residues are less volatile than the corresponding oxides, so that material loss at higher temperatures can be minimized. For fossil diesel samples, however, the determination of oxide ash according to EN ISO 6245 is considered sufficient.
4.2.8 Water content
Table 22: Comparison of limits regarding water content in international fuel quality standards Country/Region Norm Applicable to Date Water content EU EN 14214 FAME July 2003 ≤ 500 mg/kg U.S.A. ASTM FAME February 2002 ≤ 0.05 % (vol/vol) D6751 water and sediments Australia Draft FAME Draft (September ≤ 500 mg/kg 2003) EU EN 590 Fossil diesel May 2003 ≤ 200 mg/kg
The described biodiesel quality standards limit water content to 500 ppm, with the American norm covering both the content of water and sediment with one limit of 0.05 % (vol/vol). The respective maximum concentration for fossil diesel fuel is less than half these values, but it is easily met due to the nonpolar nature of the fuel. For FAME the situation is different due to their higher polarity. Water is introduced into biodiesel during the production process (e.g. in the final washing step) and thus has to be reduced to values well below the limit by drying (Wörgetter et al., 1998 [46]). However, even very low water contents achieved directly after the production do not guarantee that biodiesel fuels will still meet the specifications during combustion. As FAME is hygroscopic, they can absorb water in a concentration of up to 1000 ppm during storage. Once the solubility limit is exceeded (at about 1500 ppm of water in fuels containing 0.2% of methanol), H2O separates inside the storage tank, collecting at the bottom (Mittelbach, 1996 [48]). Free water promotes biological growth, so that sludge and
May 2004 IEA Bioenergy – Liquid Biofuels Biodiesel standard parameters and limits Page 59 slime formation thus induced may cause blockage of fuel filters and fuel lines. Moreover, high water contents are also associated with hydrolysis reactions, partly converting FAME to free fatty acids, which are linked to filter blockages as well. Finally, also corrosion of chromium and zinc parts within the engine and injection system have been reported (Kossmehl and Heinrich, 1997 [50]). Lower water concentrations, which pose no difficulties in pure biodiesel fuels, may turn out problematic in blends with fossil diesel, as here phase separation is likely to occur. At the moment (financially) viable remedies to these problems are scarce. On the one hand, water can be drained from biodiesel storage tanks and precaution can be taken not to draw fuel directly from the bottom of the container. On the other hand, seals and valves of storage tanks should be checked to prevent humidity from entering the fuel. The analytical procedure for the determination of water in both biodiesel and fossil diesel fuel involves titration, using a Karl Fischer titration apparatus (EN ISO 12937). The basic principle of this procedure is a reaction between I2 and SO2, which only occurs in the presence of water.
4.2.9 Total contamination
Table 23: Comparison of limits regarding total contamination in international fuel quality standards Country/Region Norm Applicable to Date Total contamination [mg/kg] EU EN 14214 FAME July 2003 ≤ 24 U.S.A. ASTM FAME February 2002 - D6751 Australia Draft FAME Draft (September ≤ 24 2003) EU EN 590 Fossil diesel May 2003 ≤ 24
Total contamination is defined as the quota of insoluble material retained after filtration of a fuel sample under standardized conditions. It is limited to ≤ 24 ppm in the European standards for both biodiesel and fossil diesel fuel and in the Australian FAME draft. The American biodiesel norm does not contain the parameter, as it is argued that fuels meeting the specifications regarding ash content will show sufficiently low values for total contamination as well. Total contamination tends to be of minor relevance in fossil diesel fuels, as distillation steps during their production reduce the content of insolubles. For biodiesel fuels, however, the parameter has turned out to be an important quality criterion, as FAME with a high concentration of insoluble impurities tends to cause blockage of fuel filters and injection pumps. High concentrations of soaps and sediments are mainly associated with these phenomena (Mittelbach, 2000 [65]). According to EN 12662, total contamination in both biodiesel and fossil diesel fuels is determined by filtering the heated sample over a standardized membrane filter and weighing the collected residue. Because of poor reproducibility this method has to be further developed.
4.2.10 Copper strip corrosion
Table 24: Comparison of limits regarding copper strip corrosion in international fuel quality standards Country/Region Norm Applicable to Date Copper strip corrosion at 50°C (3h)
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[rating] EU EN 14214 FAME July 2003 1 U.S.A. ASTM FAME February 2002 3 D6751 Australia Draft FAME Draft (September 1 2003) EU EN 590 Fossil diesel May 2003 1
The tendency of a fuel sample to cause corrosion to copper, zinc and bronze parts of the engine and the storage tank is determined in a standardized test according to EN ISO 2160. During this test a polished copper strip is heated to 50°C within a fuel bath and left there for three hours. Afterwards the strip is washed and compared to standards, representing different degrees of corrosion. With the exception of the American standard, the other norms demand that corrosion must not exceed class 1. In biodiesel samples corrosion might be induced by some sulfur compounds and by acids, so that the parameter is correlated with acid number. In practice, however, FAME samples have turned out to be very unlikely to give ratings higher than class 1.
4.2.11 Ester content
Table 25: Comparison of limits regarding ester content in international biodiesel quality standards Country/Region Norm Applicable Date Ester content to [% m/m] EU EN 14214 FAME July 2003 ≥ 96.5 U.S.A. ASTM FAME February 2002 - D6751 Australia Draft FAME Draft (September ≥ 96.5 2003)
The common European standard (EN 14214) defines a minimum percentage of 96.5% (m/m) fatty acid methyl ester content for biodiesel fuels. This limit is also found in the Australian norm, but not in the national standard of the U.S.A, which does not include regulations on methyl ester content. The parameter is an important tool for proving the illegal admixture of other substances, such as fossil diesel. Low values for pure biodiesel samples may originate from inappropriate reaction conditions or from various minor components within the original fat or oil source. So the methyl ester content of used frying oil biodiesel tends to be low because triglyceride polymers typically contained in heated fats are partly converted into dimeric esters, which are not considered in the standard analytical procedure (Mittelbach and Enzelsberger, 1999 [51]). Also a high concentration of unsaponifiable matter (e.g. sterols), residual alcohol, partial glycerides and unseparated glycerol can lead to values below the limit. As most of these compounds are removed during distillation of the final product, distilled methyl ester samples generally display higher ester content than undistilled ones.
The proposed European reference method for the determination of methyl ester content (EN 14103) involves capillary gas chromatography on polyethylene glycol stationary phases (e.g. Carbowax 20M, DBwax, Cpwax), applying internal calibration with methyl heptadecanoate and detection via flame ionization. Under the prescribed injection parameters and temperature conditions, the methyl esters contained in the sample are
May 2004 IEA Bioenergy – Liquid Biofuels Biodiesel standard parameters and limits Page 61 separated according to ascending number of carbon atoms, with saturated compounds eluting before unsaturated compounds of the same chain length.
4.2.12 Free glycerol
Table 26: Comparison of limits regarding the content of free glycerol in international biodiesel quality standards Norm Applicable Date Content of free Country/Region to glycerol [% m/m] EU EN 14214 FAME July 2003 ≤ 0.02 U.S.A. ASTM FAME February 2002 ≤ 0.02 D6751 Australia Draft FAME Draft (September ≤ 0.02 2003)
A maximum content of 0.02 % (m/m) of free glycerol is consistently defined in all the standards discussed. The content of free glycerol in biodiesel solely depends on the production process and is therefore one major criterion of fuel quality. Values out of specification may stem from insufficient washing of the ester product, which makes glycerol separate upon storage, once methanol as the common solvent has evaporated. Alternatively, glycerol may also form due to hydrolysis of remaining mono, di- and triglycerides in stored fuel (Mittelbach et al., 1996 [48]). Free glycerol separates within the fuel tank, collecting at the bottom and attracting other polar compounds, such as water, monoglycerides and soaps, and causes damage to the injection system. Vicinal hydroxy groups contained in glycerol and monoglycerides are made responsible for causing corrosion of non-ferrous metals (especially copper and zinc) and chromium alloys due to complexing reactions (Kossmehl and Heinrich, 1997 [50]). Moreover, glycerol depositions in the fuel filter and increased aldehyde emissions have also been reported (Bailer et al., 1994 [56]).
4.2.13 Mono-, di- and triglycerides and total glycerol
Table 27: Comparison of limits regarding the contents of mono-, di- and triglycerides as well as total glycerol in international biodiesel quality standards Country/ Norm Mono- Diglycerides Triglycerides Total glycerol Region glycerides [%m/m] [%m/m] [%m/m] [%m/m] EU prEN 14214 ≤ 0.8 ≤ 0.2 ≤ 0.2 ≤ 0.25 U.S.A. ASTM - - - ≤ 0.24 D6751 Australia Draft (2003) - - - ≤ 0.25
The European standard limits the amounts of mono-, di- and triglycerides to ≤ 0.80%, ≤ 0.20% and ≤ 0.20% (m/m) respectively, and defines a maximum amount of 0.25% (m/m) for total glycerol (i.e. the sum of the concentrations of free glycerol and glycerol bound in the form of mono-, di- and triglycerides). The American and Australian norms do not provide explicit limits for the contents of partial glycerides. Similar to the concentration of free glycerol, also the amount of glycerides depends on the production process. Low concentrations of mono-, di- and triglycerides can only be achieved by selecting optimum
IEA Bioenergy – Liquid Biofuels May 2004 Page 62 Biodiesel standard parameters and limits reaction conditions and/or by distillation of the final ester product (Mittelbach, 1996 [48]). Fuels out of specifications with respect to the discussed parameters are prone to coking and may thus cause the formation of deposits on injection nozzles, pistons and valves (Mittelbach et al., 1983 [57]). Indirect hints at high glyceride contents in biodiesel samples are correspondingly increased values for viscosity (Wörgetter et al., 1998 [46]) and carbon residue (Mittelbach et al., 1992 [58]).
The standard method prescribed in EN 14105 is a further development of a procedure suggested by Plank and Lorbeer (1995) [59]. This gas chromatographic method is applicable to fatty acid methyl esters from rapeseed, sunflower and soybean oils, but it is not suitable for lauric oils due to superimpositions of peaks of long-chain FAME and short-chain monoglycerides. Detection limits are 0.001% (m/m) for free glycerol and 0.02% (m/m) for mono-, di- and triglycerides. Analysis is conducted on a non polar, high-temperature capillary column coated with a 100% dimethylpolysiloxane or a 95% dimethyl- 5% diphenyl- polysiloxane stationary phase (e.g. DB-5HT). On-column injection and flame ionization detection are required. In order to transfer glycerol as well as mono- and diglycerides into more volatile compounds, the free hydroxy groups of the sample are silylated with N-methyl- N-trimethylsilyltrifluoracetamide (MSTFA) in the presence of pyridine prior to the analysis. With 1,2,4 butanetriol (for the determination of free glycerol) and 1,2,3 tricaproylglycerol (= tricaprin; for the determination of glycerides) two internal standards are used in the calibration process as well as in the analyses. Calibration is conducted with glycerol, 1- monooleoylglycerol (monoolein), 1,3 dioleoylglycerol (diolein) and 1,2,3 trioleoylglycerol (triolein) as reference substances. Peak identification is accomplished by comparing retention times obtained from the calibration solutions and the sample. However, as the retention zones of methylesters and monoglycerides overlap to some extent, additional calibration with a commercial mixture of monopalmitin, monostearin and monoolein is required to identify the monoglyceride peaks.
4.2.14 Methanol
Table 28: Comparison of limits regarding methanol content in international biodiesel quality standards Country/Region Norm Applicable Date Methanol content to [% m/m] EU EN 14214 FAME July 2003 0.20 U.S.A. ASTM FAME February 2002 - D6751 Australia Draft FAME Draft (September 0.20 2003)
Within EN 14214 as well as the proposed national standard for Australia a maximum amount of 0.20% (m/m) methanol is prescribed, whereas the American norm does not contain a comparable limit. This is due to the fact that the US standard is valid for fatty acid alkyl esters, which could be either methyl or ethyl esters.
Residual methanol in the ester product is removed by distillation or by repeated aqueous washing steps. These treatments are vital for fuel quality, as high methanol contents pose safety risks in biodiesel transport and storage due to correspondingly low flash points. In general, the flashpoint already gives hints as to the residual alcohol content of a fuel sample, as values higher than 100°C guarantee that the maximum limit of 0.2% methanol is not exceeded (Mittelbach et al., 1996 [48]). However, gas chromatographic analysis enables a more exact determination of the content of residual methanol.
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The standard analytical procedure recommended in the proposed European norm involves capillary gas chromatography on polar capillary columns, using flame ionisation detection. It is applicable to samples containing 0.01 to 0.5% (m/m) of methanol. In order to separate the volatile alcohol from the non-volatile matrix, the samples are heated to 80°C in hermetically sealed vials prior to the analysis. After equilibrium has been reached, a defined volume of the gas phase is injected into the GC. According to the available analytical equipment, one of two procedures can be selected. If an automatic headspace system can be used, external calibration suffices. To this end, methanol-free FAME reference samples (obtained by distillation or repeated washing with distilled water) are mixed with defined amounts of methanol and analyzed under the same conditions as will later be used for the analyses to draw up a calibration function. Here methanol is the only compound in the chromatogram. However, if automatic headspace equipment is not available and therefore manual injection has to be conducted, internal calibration is recommended. In this case the calibration procedure is modified by adding a defined amount of 2-propanol to each standard solution to determine a calibration factor. This factor is used in the subsequent analyses, correlating peak areas and concentrations of methanol and 2-propanol as the two peaks in the chromatogram.
4.2.15 Iodine number, linolenic acid methyl ester and polyunsaturated FAME
Table 29: Comparison of limits regarding iodine number and the contents of linolenic acid methyl ester and polyunsaturated FAME (i.e. ≥ 4 double bonds ) in international biodiesel quality standards
Country Norm Iodine Content of Content of /Region number linolenic acid ME polyunsaturated FAME [g I2/100g] [% m/m] [% m/m] EU prEN 14214 ≤ 120 ≤ 12 ≤ 1 U.S.A. ASTM - - - D6751 Australia Draft (2003) - - -
Iodine number is a measure of total unsaturation within a mixture of fatty material, regardless of the relative shares of mono-, di-, tri- and polyunsaturated compounds. It is expressed in g iodine which react with 100g of the respective sample. Whereas the American norm does not contain regulations on this parameter, iodine number is limited to ≤ 120 (g I2/100g) in the European specification. Moreover, EN 14214 also regulates the maximum content of linolenic acid methyl ester and polyunsaturated FAME (i.e. compounds with four or more double bonds) to 12% and 1% (m/m) respectively. These limits are not undisputed among biodiesel experts world-wide. Engine manufacturers have long argued that fuels with a higher iodine number tend to polymerise and form deposits on injector nozzles, piston rings and piston ring grooves, when they are heated (Koßmehl and Heinrich, 1997 [50]). Moreover, unsaturated esters introduced into the engine oil are suspected of forming high-molecular compounds, which negatively affect the lubricating quality and can thus result in serious engine damage (Schäfer et al., 1997 [60]). However, the results of various engine tests indicate that polymerisation reactions appear to a significant extent only in fatty acid esters containing three or more double bonds (Wörgetter et al., 1998 [46], Prankl and Wörgetter, 1996 [81], Prankl et al., 1999 [80]). Three- or more-fold unsaturated esters, however, only constitute a minor share in the fatty acid pattern of various promising seed oils, which are excluded from serving as biodiesel feedstock according to some national standards due to their high iodine value (e.g. soybean oil with an iodine value of 125-140 g I2/100g). Therefore, many biodiesel experts have suggested limiting the content of linolenic acid methyl esters
IEA Bioenergy – Liquid Biofuels May 2004 Page 64 Biodiesel standard parameters and limits and polyunsaturated FAME rather than the total degree of unsaturation as it is expressed by iodine value (Mittelbach, 1996 [48]; Wörgetter et al., 1998 [46]; Knothe, 2002 [49]). Two procedures for the determination of iodine value are provided by EN 14214. On the one hand, a titrimetric method using Wijs reagent is suggested (EN 14 111). Alternatively, iodine number can also be calculated from the relative methyl ester contents as determined by capillary gas chromatography according to EN 14103. This method is admitted as a viable alternative to the titrimetric procedure in an annex to EN 14 214. 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. The content of linolenic acid methyl ester can easily be determined according to EN 14103 and is expressed in terms of mass per cent. However, the proposed method is not applicable to polyunsaturated (long-chain) FAME, so that an analytical procedure for this parameter is still to be developed.
4.2.16 Acid number
Table 30: Comparison of limits regarding neutralisation number in international biodiesel quality standards Country/Region Norm Applicable to Date Acid number [mg KOH/g] EU EN 14214 FAME July 2003 ≤ 0.5 U.S.A. ASTM FAME February 2002 ≤ 0.8 D6751 Australia Draft FAME Draft (September ≤ 0.8 2003)
Acid number or neutralisation number is a measure of mineral acids and free fatty acids contained in a fuel sample. It is expressed in mg KOH required to neutralize 1g of FAME. The respective limit in the European norm is ≤ 0.5 mg KOH/g sample, whereas the American standard and the Australian draft allow slightly higher values. Acid number of biodiesel depends on a variety of factors. On the one hand, it is influenced by the type of feedstock used for fuel production and on its respective degree of refinement. On the other hand, acidity can also be generated during the production process, for instance, by mineral acids introduced as catalysts or by free fatty acids resulting from acid work-up of soaps. Finally, the parameter also mirrors the degree of fuel ageing during storage, as it gradually increases due to hydrolytic cleavage of ester bonds. High fuel acidity has been discussed in the context of corrosion and the formation of deposits within the engine. However, it has been shown that free fatty acids as weak carboxylic acids pose far lower risks than strong mineral acids (Cvengros, 1998 [62]).
The standardized analytical procedure involves titration of the diluted sample with ethanolic potassium hydroxide solution, using phenolphthalein as an indicator for the detection of the titration endpoint (EN 14104). This method does not distinguish between acidity caused by mild carboxylic and strong mineral acids.
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4.2.17 Content of phosphorus
Table 31: Comparison of limits regarding phosphorus content in international biodiesel quality standards Country/Region Norm Applicable to Date Content of phosphorus [mg/kg] EU EN 14214 FAME July 2003 ≤ 10 U.S.A. ASTM FAME February 2002 ≤ 10 D6751 Australia Draft FAME Draft (September - 2003)
The European norm as well as the American standard limit the maximum content of phosphorus in biodiesel samples to 10 mg/kg. Phosphorus in FAME stems from phospholipids (animal and vegetable material) and inorganic salts (used frying oil) contained in the feedstock. In vegetable oils the type of oil recovery strongly influences this parameter. So cold-pressed plant oils usually contain less phosphorus than hot-pressed and extracted samples (Cvengros et al., 1999 [63]). As phospholipids may impede phase separation during the transesterification process due to their emulsifying properties, their content in biodiesel feedstock can be reduced by various forms of degumming before the reaction. The transesterification process itself has been identified as an efficient means of lowering phosphorus content as well, as reductions from 100 ppm in the original material to about 20 to 30 ppm in the ester product are feasible (Mittelbach, 1996 [48]). Residual phosphorus can also be removed by distillation of the final product, during which phospholipids as high- molecular weight compounds collect in the distillation residue. Fuels transgressing the limit of 10 ppm phosphorus are suspected of decreasing the efficiency of oxidation catalytic converters and of causing higher particulate matter emissions. The values for sulfated ash as another important fuel quality parameter are linked with the respective phosphorus content of biodiesel samples (Mittelbach, 1996 [48]).
The European analytical method, applicable to fuels with a phosphorus content of 2 to 20 mg/kg, applies inductively coupled argon plasma emission spectrometry at 213.618 and 178.287 nm. In the prescribed procedure the diluted sample is introduced into the ICP in aerosol form, and the phosphorus emissions of the test solution are compared to those of reference solutions at the same wavelengths (EN 14107).
4.2.18 Content of alkali and alkaline earth metals
Table 32: Comparison of limits regarding the contents of alkali and alkaline earth metals in international biodiesel quality standards
Country/Region Norm Date Group I metals Group II metals (Na + K) [mg/kg] (Mg + Ca) [mg/kg] EU EN 14214 July 2003 ≤ 5 ≤ 5 U.S.A. ASTM D6751 February 2002 - - Australia Draft Draft (September ≤ 5 ≤ 5 2003)
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The European standard limits the maximum concentrations of alkali and alkaline earth metals to 5 ppm each. These regulations are also found in the Australian norm but not in the American norm, where there is no limit on either parameter. The metal ions are introduced into biodiesel fuel during the production process. Whereas alkali metals stem from catalyst residues, alkaline-earth metals may originate from hard washing water. Sodium and potassium are associated with the formation of ash within the engine, calcium soaps are responsible for injection pump sticking (Mittelbach, 2000 [65]). The parameters are interrelated with several other fuel quality criteria, such as sulfated ash content and carbon residue (Mittelbach, 1996 [48]).
The standard analytical procedures for the direct determination of sodium and potassium (EN 14108 and EN14109) apply flame atomic-absorption spectrometry at a wavelength of 589 nm and 766.5 nm, respectively. The standard method for the determination of magnesium and calcium in biofuels is inductively coupled plasma optical emission spectrometry, with 279.553 and 422.673 nm as the spectral lines used for the analyses (EN 14538).
4.2.19 Oxidation stability
Table 33: Comparison of limits regarding the oxidation stability in international biodiesel quality standards Country/Region Norm Applicable to Date Induction period EU EN 14214 FAME July 2003 ≥ 6 h U.S.A. ASTM FAME February 2002 - D6751 Australia Draft FAME Draft (September ≥ 6 h 2003)
Due to their chemical composition, fatty acid methyl esters are more sensitive to oxidative degradation than fossil diesel fuel. This is especially true for fuels with a high content of twice and morefold unsaturated esters, as the methylene groups adjacent to double bonds have turned out to be particularly susceptible to radical attack as the first step of fuel oxidation (Dijkstra et al., 1995 [69]). The formed hydroperoxides may polymerise with other free radicals to form insoluble sediments and gums, which are associated with fuel filter plugging and deposits within the injection system and the combustion chamber (Mittelbach and Gangl, 2001 [70]). These changes are accompanied by an increase in viscosity observable in oxidized fatty acid methyl ester samples. On the other hand, further oxidation of primary oxidation products results in the formation of aldehydes, ketones and short-chain carboxylic acids, linked to increased corrosion of the injection system. Apart from the fatty acid composition of the feedstock, also the content of natural antioxidants, such as tocopherols and carotenes (Simkovsky, 1997 [71]), has been identified as a crucial factor for the oxidative stability of the respective sample. In general antioxidant concentrations are high for undistilled fuels prepared from fresh vegetable oils, whereas hardly any antioxidants are contained in distilled samples (as they have been removed during distillation) and in samples prepared from used frying oil (as they have largely been consumed during frying). The addition of synthetic antioxidants has been identified as a viable means of improving oxidation stability (Mittelbach and Schober, 2003 [72]), concentrating on tert-butyl hydrochinone (TBHQ), pyrogallol BHT and propylgallate. However, as Rancimat induction period has been found to decrease rapidly during storage, antioxidants might have to be added in comparatively high concentrations to ensure that fuels will still meet the specifications at the filling station (Mittelbach and Schober, 2003 [72]).
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Within an EU-funded project ‘Stability of biodiesel’ (BIOSTAB) [68], oxidation, thermal as well as storage stability of different kinds of biodiesel were excessively investigated (BIOSTAB, final report, 2003 [66]). The standard analytical method for the determination of biodiesel oxidation stability (EN 14112) is a method derived from food chemistry. In this so-called “Rancimat” procedure a fuel sample is aged at elevated temperature (110°C) by passing air through it at a constant rate. The effluent gases are collected in a measuring cell filled with distilled water, of which the conductivity is constantly recorded. When the sample brakes down a sharp increase of conductivity can be observed. The period of time up to this point is called induction period (IP) and is expressed in hours, whereby the temperature at which the measurements were conducted needs to be specified. Systematic tests showed that Rancimat induction period is well correlated to other biodiesel quality parameters, such as peroxide value, anisidine value, kinematic viscosity, ester content, acid value, and polymer content (Lacoste and Lagardere, 2003 [74]), so that fuels artificially oxidized to give IP values below the limit tend to be out of specification regarding the limited parameters among those listed above.
4.2.20 Cold temperature behavior
Table 34: Comparison of limits regarding cold-temperature behavior in international fuel quality standards Country/Region Norm Applicable to CP [°C] PP [°C] CFPP [°C] EU EN 14214 FAME -- - - 20 to + 5 (temperate climates) - 44 to - 20 (arctic climates) U.S.A. ASTM FAME Is to specify - - D6751 Australia Draft FAME - - To be announced EU EN 590 Fossil diesel - - - 20 to + 5 - (temperate - 34 to - 10 climates) (arctic - 44 to - 20 climates) (arctic climates)
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 fuel starvation and problems during engine start- up (Knothe and Dunn, 1998 [49]). For the assessment of cold-temperature properties of biodiesel and fossil diesel fuel various parameters have been suggested, including cloud point (CP), pour point (PP) and cold filter plugging point (CFPP). Cloud point denotes the temperature at which first visible crystals are formed within a fuel sample when it is cooled, whereas pour point stands for the lowest temperature to which the sample may be cooled while still retaining its fluidity. Cold filter plugging point (CFPP) describes the fuel filterability at low ambient temperatures. CFPP is a limited parameter in the European biodiesel and fossil diesel drafts as well as the Australian draft. For the European norms identical indicative limits apply to both biodiesel and fossil diesel fuels, which are to be specified by each single member state according to their specific climatic conditions.
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In general, biodiesel fuels fall behind fossil diesel regarding cold-flow properties. Melting points of neat FAME depend on chain length and degree of unsaturation, with long-chain saturated fatty acid methyl esters displaying particularly unfavourable cold-temperature behaviour. Thus neat biodiesel fuels derived from feedstock rich in these compounds (such as methyl esters of tallow) might even pose problems at room temperature, unless precautionary measures, such as heating fuel tanks, fuel lines and filters, are taken. Both the CFPP test protocol used in Europe (EN 116) and the LTFT (low temperature flow test) procedure preferred in the U.S.A. (ASTM D 4539) define a highest temperature at which a fuel portion fails to pass a standardized filtering device within a specified amount of time when cooled under standardized conditions.
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5 SUMMARY AND CONCLUSIONS
Standards are of high importance for the producers, suppliers and users of biodiesel. Authorities need approved standards for the evaluation of safety risks and environmental pollution. Standards are necessary for approvals of vehicles operated with biodiesel and are therefore a prerequisite for the market introduction and commercialization of biodiesel. If new fuels appear in the market engine and injection system manufacturer have to investigate the suitability. They also need standardized products with a homogenous quality.
Biodiesel can be used in existing distribution systems. Thus a broad market can be opened without dramatic investments and also without differences in the performance of the fuel. But on the other hand, biodiesel has to meet very strict demands coming from the existing systems, especially in view of long-term stability.
The development of biodiesel as alternative fuel for diesel engines always was accompanied by describing the quality requirements during a standardization process. In 1991 the worldwide first standard for rapeseed oil methyl ester could be published in Austria. Further standardization activities could be observed in those countries being interested in the new fuel. In the following years standards were published in Germany and the Czech Republic (1994), Sweden (1996), Italy and France (1997) and the U.S.A. (1999).
National standards of European countries were replaced by a common European standard for biodiesel as automotive diesel fuel (EN 14214) and as heating fuel (EN 14213). Automotive biodiesel is defined as fatty acid methyl ester (FAME) to be used either as pure fuel for diesel engines in a 100% concentration or as an extender for automotive fuel for diesel engines in accordance with the requirements of EN 590. The standards, which express more or less the experiences with rapeseed oil, contain approx. 22 different parameters in total.
In 2002 an update of the US standard for biodiesel was published, defining biodiesel as mono alkyl esters of long chain fatty acids derived from vegetable oils or animal fats. In comparison to the European standard the lower number of parameters (14 against 22 in Europe) is remarkably, which allows more flexibility in raw materials being used for the production.
Recent activities can be observed in Australia, Brazil and Canada. The new standards are based on the experiences gathered in Europe and U.S.A. so far. In Australia fuel quality standards for diesel fuel and biodiesel were developed within a legislative framework, the Fuel Quality Standards Act 2000. A draft was published in September 2003.
In Canada the Natural Resources Canada (NRCan) is collaborating with other parties to drafting two fuel standards under the auspices of the Canadian General Standards Board (CGSB). The following standards are considered: automotive low sulfur diesel fuel containing a low level biodiesel (B 1.0 – B5) and another one containing mid level biodiesel (B6 – B20).
The first provisional specification for biodiesel in Brazil was released by the National Petroleum Agency (Agência Nacional do Petróleo, ANP) in September 2003. In the ANP 255 no difference is made between biodiesel derived from methanol or ethanol. Furthermore, Brazil aims at considering many different vegetable oils as raw material basis in respect of the different agricultural conditions of the country.
IEA Bioenergy – Liquid Biofuels May 2004 Page 70 Summary and Conclusions
Further activities for developing biodiesel specifications such as in Japan, South Korea, Hong Kong or Argentina didn’t yet lead to a draft or final standard but also are based on published knowledge so far.
Standards always reflect the state of the art of the experiences so far. Thus, a standardization process is never completed. It can be regarded as a dynamic process, which has to be open for recent developments.
As biodiesel is a commercial product the quality requirements defined in standards always have to be a part of a quality management system. A control system with checkpoints at different levels (production, delivery system, storage) and actions in case of failing is necessary for ensuring a fuel quality at highest level. This is absolutely necessary because experiences have shown many problems in the field caused by quality failures, which appear during the whole life cycle of the fuel.
Although the conditions for biodiesel production and the raw materials are quite different in the countries all over the world, the requirements from the application of automotive fuels are very similar. Further standardization activities should aim at harmonizing biodiesel fuel quality requirements in order to develop “optimal” properties for a commercial product that can be used world-wide.
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