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MARINE ENVIRONMENT PROTECTION Original: ENGLISH PREVENTION OF AIR POLLUTION FROM SHIPSISO 8217:2010 revised specification of marine fuels
Submitted by the International Organization for Standardization (ISO)
Executive summary: This document provides the revised specification of marine fuels ISO 8217:2010, taking into account the issues raised by MEPC regarding fuel characteristics and parameters addressing air quality, ship safety, engine performance and crew health Strategic direction: High-level action: Planned output: Action to be taken: Related documents: MEPC 57/21; MEPC 59/4/3; MEPC 60/4/42 and MEPC 60/22
Background
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MEPC 57, in April 2008, agreed to request ISO to develop recommendations to be considered by the Committee concerning a fuel oil specification with recommendations on specific parameters related to air quality, ship safety, engine performance and crew health as well as specific values for each parameter. 2 MEPC 59, in July 2009, considered document MEPC 59/4/3 (ISO) responding to the request by MEPC 57 and providing the results of the review. ISO advised that it would undertake further examinations on marine fuel specifications in 2010, in which ISO would analyse the impact of bio-derived components contained in marine fuels that could lead to potential storage and handling problems. MEPC 59 agreed to invite ISO to provide further advice on marine fuel specifications as well as the outcome of the ISO 8217 review process. 3 MEPC 60, in March 2010, noted document MEPC 60/4/42 (ISO), providing the status for the revision of ISO 8217 "specification of marine fuels" and information provided by the ISO that the standard would be published in its final form by MEPC 61. MEPC 60 agreed to consider the matter in detail at this session and invited interested Members to submit further input (paragraph 4.5 of MEPC 60/22). I: MEPC 61 4-1.doc Published version of ISO 8217:2010
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The balloting for the FDIS (Final Draft International Standard) version of ISO 8217 has been completed in favour and ISO 8217:2010 was formally published on 15 June 2010.
The published standard is set out in annex to this document for consideration by the
Committee.
Action requested of the Committee
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The Committee is invited to consider the revised standard ISO 8217:2010 and take action as appropriate. I: MEPC 61 4-1.doc I: MEPC 61 4-1.doc ISO 8217:2010(E)
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Contents
ISO 2010 – All rights reserved ISO 8217:2010(E)
Foreword
ISO (the International Organization for Standardization) is a worldwide federation of national standards bodies (ISO member bodies). The work of preparing International Standards is normally carried out through ISO technical committees. Each member body interested in a subject for which a technical committee has been established has the right to be represented on that committee. International organizations, governmental and non-governmental, in liaison with ISO, also take part in the work. ISO collaborates closely with the International Electrotechnical Commission (IEC) on all matters of electrotechnical standardization. International Standards are drafted in accordance with the rules given in the ISO/IEC Directives, Part 2. The main task of technical committees is to prepare International Standards. Draft International Standards adopted by the technical committees are circulated to the member bodies for voting. Publication as an International Standard requires approval by at least 75 % of the member bodies casting a vote. Attention is drawn to the possibility that some of the elements of this document may be the subject of patent rights. ISO shall not be held responsible for identifying any or all such patent rights. 8217 was prepared by Technical Committee ISO/TC 28, Petroleum products and lubricants, Subcommittee SC 4, Classifications and specifications. This fourth edition cancels and replaces the third edition (ISO 8217:2005), which has been technically revised. ISO 2010 – All rights reserved ISO 8217:2010(E)
0.1 General
The specifications in this International Standard were prepared in co-operation with ship owners, ship operators, shipping associations, national standards bodies, classification societies, fuel testing services, engine designers, fuel suppliers and the petroleum industry to meet the requirements for fuels supplied on a world-wide basis for consumption on board ships. Crude oil supplies, refining methods, ships' machinery, environmental legislation and local conditions vary considerably. These factors have led historically to a large number of categories of residual fuels being available internationally, even though locally or nationally there can be relatively few categories available. 0.2 Classification
The categories of fuel in this International Standard have been classified in accordance with ISO 8216-1. 0.3 International
statutory
This International Standard takes into account the SOLAS Convention[1] in respect of the allowable minimum flash point of fuels. The Revised MARPOL Annex VI[2], which controls air pollution from ships, includes a requirement either that the fuel not exceed specified maximum sulfur content or that an approved equivalent alternative be used. During the lifetime of this International Standard, regional and/or national bodies can introduce their own local emission requirements, which can impact the al owable sulfur content, for example EU Sulfur Directive[3]. It is the users' responsibility to establish the requirement to comply with such statutory requirements and to specify the maximum sulfur content of the fuel to the supplier. Changes from ISO 8217:2005
This fourth edition of this International Standard reflects several important and significant changes. These include category rationalizations of both distil ate and residual fuels and substantial amendments to Clause 5. These changes reflect market demand, recognize regulatory developments and current industry experiences with the use of fuels. The limits contained in Tables 1 and 2 now reflect the test method reporting requirements. For example, viscosity limits are given to four significant figures. a) Changes to the distillate fuels (4 categories) include the following. ⎯ An additional grade, DMZ, has been added with a minimum viscosity of 3,000 mm2/s at 40 °C, but is otherwise identical in its characteristics to the DMA. ⎯ The previous DMC category has been modified and moved to Table 2 as RMA10. ⎯ Specifications for the following characteristics have been added to Table 1: hydrogen sulfide, acid number, oxidation stability and lubricity. ⎯ The minimum viscosity requirement for DMA has been raised to 2,000 mm2/s. ⎯ A minimum viscosity requirement of 2,000 mm2/s has been added for DMB. ⎯ The specifications for the "appearance" characteristic in Table 1 have been amended. ISO 2010 – All rights reserved ISO 8217:2010(E)
b) Changes to the residual fuels (6 categories) include the following. ⎯ RMA 10 has been added. ⎯ RMG and RMK have been expanded to include additional viscosity grades. ⎯ RMF and RMH categories have been removed. ⎯ To Table 2 have been added the Calculated Carbon Aromaticity Index (CCAI) and specifications for the following characteristics: hydrogen sulfide, acid number and sodium content. ⎯ Sulfur limits have not been tabulated, as these are controlled by statutory requirements. See 0.3 and ⎯ Potential Total Sediment (TSP) has been assigned as the reference test method. Accelerated Total Sediment (TSA) has been added as an alternative test method. ⎯ Ash limit values have been reduced for many of the categories. ⎯ Vanadium limit values have been reduced, with the exceptions of those for RMB 30 where the limit value is unchanged and for RMG 380 where the limit value has been slightly increased. ⎯ Aluminium-plus-silicon limit values have been reduced. ⎯ The criteria for assessing whether a fuel contains used lubricating oil have been amended. c) Changes to the informative annexes include the following. ⎯ Amendments have been made to a number of the annexes. ⎯ Annex C of the previous edition, dealing with viscosity conversions, has been deleted. ⎯ The equations dealing with specific energy in Annex E of this new edition have been revised and a gross specific energy equation for distillate fuel has been added. ⎯ Four new annexes have been added: ⎯ Annex A, dealing with bio-derived products; ⎯ Annex B, dealing with deleterious materials; ⎯ Annex C, dealing with sulfur content; ⎯ Annex D, dealing with hydrogen sulfide. ISO 2010 – All rights reserved INTERNATIONAL STANDARD
marine fuels
WARNING — The handling and use of products as specified in this International Standard can be
hazardous, if suitable precautions are not observed. This International Standard does not purport to
address all of the safety and health considerations that can be associated with its use. It is the
responsibility of the users of this International Standard to establish appropriate safety and health
practices and determine the applicability of regulatory limitations prior to use.
This International Standard specifies the requirements for petroleum fuels for use in marine diesel engines and boilers, prior to appropriate treatment before use. The specifications for fuels in this International Standard can also be applicable to fuels for stationary diesel engines of the same or similar make and type as those used for marine purposes. This International Standard specifies four categories of distillate fuel, one of which is for diesel engines for emergency purposes. It also specifies six categories of residual fuel. For the purpose of this International Standard, the term "petroleum" is used to include oil from tar sands and Appropriate guidance about fuel treatment systems for diesel engines is published by the International Council on Combustion Engines (CIMAC)[4]. Requirements for gas turbine fuels used in marine applications are specified in ISO 4261[5]. For the purposes of this International Standard, the terms "mass %" and "volume %" are used to represent the mass and volume fractions respectively. 2 Normative
references
The following referenced documents are indispensable for the application of this document. For dated references, only the edition cited applies. For undated references, the latest edition of the referenced document (including any amendments) applies. ISO 91-1:1992, Petroleum measurement tables — Part 1: Tables based on reference temperatures of 15 °C and 60 °F ISO 2719:2002, Determination of flash point — Pensky-Martens closed cup method ISO 3015:1992, Petroleum products — Determination of cloud point ISO 3016:1994, Petroleum products — Determination of pour point ISO 3104:1994, Petroleum products — Transparent and opaque liquids — Determination of kinematic viscosity and calculation of dynamic viscosity ISO 3675:1998, Crude petroleum and liquid petroleum products — Laboratory determination of density — Hydrometer method ISO 2010 – All rights reserved ISO 8217:2010(E)
ISO 3679:2004, Determination of flash point — Rapid equilibrium closed cup method ISO 3733:1999, Petroleum products and bituminous materials — Determination of water — Distillation method ISO 4259:2006, Petroleum products — Determination and application of precision data in relation to methods of test ISO 4264:2007, Petroleum products — Calculation of cetane index of middle-distillate fuels by the four-variable equation ISO 6245:2001, Petroleum products — Determination of ash ISO 8216-1:2010, Petroleum products — Fuels (class F) classification — Part 1: Categories of marine fuels ISO 8754:2003, Petroleum products — Determination of sulfur content — Energy-dispersive fluorescence spectrometry ISO 10307-1:2009, Petroleum products — Total sediment in residual fuel oils — Part 1: Determination by hot filtration ISO 10307-2:2009, Petroleum products — Total sediment in residual fuel oils — Part 2: Determination using standard procedures for ageing ISO 10370:1993, Petroleum products — Determination of carbon residue — Micro method ISO 10478:1994, Petroleum products — Determination of aluminium and silicon in fuel oils — Inductively coupled plasma emission and atomic absorption spectroscopy methods ISO 12156-1:2006, Diesel fuel — Assessment of lubricity using the high-frequency reciprocating rig (HFRR) — Part 1:Test method ISO 12185:1996, Crude petroleum and petroleum products — Determination of density — Oscillating U-tube method ISO 12205:1995, Petroleum products — Determination of the oxidation stability of middle-distillate fuels ISO 12937:2000, Petroleum products — Determination of water — Coulometric Karl Fischer titration method ISO 13739:2010, Petroleum products — Procedures for transfers of bunkers to vessels ISO 14596:2007, Petroleum products — Determination of sulfur content — Wavelength-dispersive X-ray fluorescence spectrometry ISO 14597:1999, Petroleum products — Determination of vanadium and nickel content — Wavelength-dispersive X-ray fluorescence spectrometry EN 14078:2009, Liquid petroleum products — Determination of fatty acid methyl ester (FAME) content in middle distillates — Infrared spectrometry method EN 14214, Automotive fuels — Fatty acid methyl esters (FAME) for diesel engines — Requirements and test methods IP 470:2005, Determination of aluminium, silicon, vanadium, nickel, iron, calcium, zinc and sodium in residual fuel oil by ashing, fusion and atomic absorption spectrometry IP 500:2003, Determination of the phosphorus content of residual fuels by ultra-violet spectrometry IP 501:2005, Determination of aluminium, silicon, vanadium, nickel, iron, sodium, calcium, zinc and phosphorus in residual fuel oil by ashing, fusion and inductively coupled plasma emission spectrometry ISO 2010 – All rights reserved ISO 8217:2010(E)
IP 570:2009, Determination of hydrogen sulfide in fuel oils — Rapid liquid phase extraction method ASTM D664-09, Standard Test Method for Acid Number of Petroleum Products by Potentiometric Titration ASTM D6751, Standard Specification for Biodiesel Fuel Blend Stock (B100) for Middle Distillate Fuels LEWIS, C.P.G; SCHENK, C.; STASSEN, W.J.M., Ignition quality of residual fuel oils, Conference paper in
Proceedings of the 22nd CIMAC International Congress on Combustion Engines, Volume 2, Copenhagen, DK,
May 18-21, 1998
3 Application
This International Standard specifies the required properties for fuels at the time and place of custody transfer. Samples for quality verification may be taken in any location agreed between the parties. 4 Sampling
The sampling of petroleum fuels for analysis shall be carried out in accordance with the procedures given in ISO 13739 or an equivalent national standard. Where specific sampling requirements are documented in the referenced test methods, these shall be adhered to. 5 General
The fuel shall conform to the characteristics and limits given in Table 1 or Table 2, as appropriate, when tested in accordance with the methods specified. The fuel shall be a homogeneous blend of hydrocarbons derived from petroleum refining. This shal not preclude the incorporation of additives intended to improve some aspects of the fuel's characteristics and performance. The fuel shall be free from inorganic acids and used lubricating oils. Fuels shall be free from any material that renders the fuel unacceptable for use in marine applications. The fuel shall be free from bio-derived materials other than 'de minimis' levels of FAME (FAME shall be in accordance with the requirements of EN 14214 or ASTM D6751). In the context of this International Standard, "de minimis" means an amount that does not render the fuel unacceptable for use in marine applications. The blending of FAME shall not be allowed. The fuel shal not contain any additive at the concentration used in the fuel, or any added substance or chemical waste that a) jeopardizes the safety of the ship or adversely affects the performance of the machinery; or b) is harmful to personnel; or c) contributes overall to additional air pollution. 1) This paper describes the CCAI calculation and is available from ISO 2010 – All rights reserved ISO 8217:2010(E)
6.1 Requirements for distillate and residual fuels
a) The hydrogen sulfide, H2S, concentration shall be as specified in Table 1 or Table 2. NOTE H2S is a highly toxic gas. Exposure to high vapour concentrations is hazardous and in extreme cases can be fatal. It is critical that ship owners, operators and other responsible parties continue to maintain appropriate safety practices designed to protect the crew and others who can be exposed to H2S; see Annex D. b) Acidity shall be as specified in Table 1 or Table 2. Acid number limits are included in this International Standard; see Annex H. 6.2 Requirements for distillate fuels
a) Oxidation stability shall be as specified in Table 1. The refinery processes used to manufacture distillate fuels can lead to products that can have limited oxidation stability. In addition, today's non-marine distillate fuels can contain a significant amount, for example in some areas currently 5 volume % to 7 volume %, of bio-derived products i.e., fatty acid methyl esters (FAMEs) that can impact on the oxidation stability of the fuel. Furthermore, the transportation of pure distillate fuel and distillate fuel containing bio-derived material (FAME), especially through multi-product pipeline installations, have shown that some FAME is transferred into the pure distillate fuel; see Annex A. b) The lubricity shall be as specified in Table 1. A lubricity requirement has been included in this International Standard and is applicable to clear and bright distillate fuels with a sulfur content below 500 mg/kg (0,050 mass %). The lubricity limit is based on the existing requirements for high-speed automotive and heavy-duty industrial diesel engines. 6.3 Requirements for residual fuels
a) Ignition characteristics, as determined by the Calculated Carbon Aromaticity Index (CCAI), shall be as specified in Table 2. NOTE 1 CCAI, an indication of ignition performance, has been added in Table 2 in order to avoid fuels with uncharacteristic density-viscosity relationships. For a determination of CCAI, see Annex F. For engines and/or applications where the ignition quality is known to be particularly critical, Annex F provides a basis for suppliers and purchasers of residual fuels to agree on tighter ignition quality characteristics. For RME 180 and RMK 380, when blending at or close to the maximum density, the CCAI limit can restrict the combination of density and viscosity. b) The sodium concentration shall be as specified in Table 2. A limit for sodium content has been included due to concerns regarding the influences of metals in fuels on ash deposition and high-temperature corrosion. Information on the subject is given in Annex I. 7.1 Density
When density is determined in accordance with ISO 3675, the hydrometer readings obtained at ambient temperature for distillate fuels, and at elevated temperatures of between 50 °C and 60 °C for fuels containing residual components, shall be converted to results at 15 °C using ISO 91-1:1992, Table 53B. When density is determined in accordance with ISO 12185, an appropriate correction for the glass expansion coefficient shall ISO 2010 – All rights reserved ISO 8217:2010(E)
be applied to readings obtained by a digital density analyser at any temperature other than 15 °C, before conversion and application of ISO 91-1:1992, Table 53B. The reference test method shall be ISO 3675. 7.2 Sulfur
The reference test method shall be ISO 8754. In the event of a dispute concerning sulfur content, all parties shall agree, prior to testing, upon the same sulfur certified reference material. 7.3 Flash
The flash point for fuels in Table 1 shall be determined in accordance with ISO 2719:2002, Procedure A. If the flash point result of DMX is less than 40 °C, it shall be determined in accordance with ISO 3679. The flash point of fuels in Table 2 shall be determined in accordance with ISO 2719:2002, Procedure B. 7.4 Total sediment by hot filtration
If the appearance of DMB is assessed as not clear and bright (see 7.6), the total sediment shall be determined by the test method ISO 10307-1, typically called total sediment existent. 7.5 Total sediment — Aged
Either of the standard procedures for ageing in ISO 10307-2 can be used; Accelerated Total Sediment (TSA) or Potential Total Sediment test (TSP). The reference test method shall be the Potential Total Sediment test. 7.6 Appearance
For distillate fuel, the appearance of a sample shall be assessed by visual inspection in good light, free from glare and shadow, at a temperature between 10 °C and 25 °C. ⎯ DMX, DMA or DMZ shall appear clear and bright. It has been reported that in some countries these grades of fuel are dyed (e.g., black) and not transparent. This affects the compliance with the requirement for clear and bright appearance and, in such circumstances, the water content shall not exceed 200 mg/kg, as determined by the Coulometric Karl Fischer titration method in accordance with ISO 12937. ⎯ If the appearance of DMB affords visual inspection and appears clear and bright, then testing for total sediment by hot filtration and for water is not required. 7.7 Vanadium
The reference test method shall be IP 501. 7.8 Sodium
The reference test method shall be IP 501. ISO 2010 – All rights reserved ISO 8217:2010(E)
7.9 Aluminium plus silicon
The reference test method shall be IP 501. 7.10 Used lubricating oil (ULO)
A fuel shall be free from ULO. In the context of this International Standard, a fuel shall be considered to contain ULO when combinations of calcium and zinc or calcium and phosphorus are above the specified levels; see Table 2. The reference test method shall be IP 501. 8 Precision and interpretation of test results
The test methods specified in Tables 1 and 2 al contain a statement of precision (repeatability and reproducibility). The determination of reproducibility for CCAI is contained in Annex F. ISO 4259:2006, which covers the use of precision data in the interpretation of test results, shall be used in cases of dispute. Information about precision and interpretation of test results is also given in Annex L. ISO 2010 – All rights reserved ISO 8217:2010(E)
6,000 6,000 11,00 2,000 3,000 2,000 890,0 890,0 900,0 0,010 0,010 0,010 stillate m
able 1 — Di
ISO 2010 – All rights reserved ISO 8217:2010(E)
ISO 2010 – All rights reserved ISO 8217:2010(E)
180 180 380 500 700 380 500
le 2 — Re
60,0 60,0 60,0 60,0 2,00 2,00 2,00 2,00 0,10 0,10 0,10 0,10 0,30 0,50 0,50 0,50 ISO 2010 – All rights reserved ISO 8217:2010(E)
180 180 380 500 700 380 500
ISO 2010 – All rights reserved ISO 8217:2010(E)
Bio-derived products and Fatty Acid Methyl Esters (FAMEs)
A.1 Bio-fuels and blends
Bio-derived fuels and blends of bio-derived fuels with petroleum products are included within the range of potential alternative energy sources being considered by some sections of marine industry since they are renewable and can result in reduced Green House Gases (GHGs) and SOx emissions. The bulk of bio-derived fuels currently available is the product of a transesterification process that removes the glyceride fraction to produce fatty acid methyl esters (FAMEs), commonly referred to as bio-diesel. Bio-diesels can also contain fatty acid ethyl esters, FAEEs, for which test methods and specifications are being developed. Bio-derived fuels can also be produced by other process methods; however, there is no general broad experience with regard to the application of any bio-derived fuels in marine systems and machinery. Hence, this International Standard does not address this issue but does outline some of the issues that have been encountered in other markets where bio-derived FAME fuels have been mandated. FAME is defined in EN 14214 and ASTM D6751. Notwithstanding that FAME has good ignition, lubricity properties and perceived environmental benefits, there are potentially specific complications with respect to storage and handling in a marine environment such as ⎯ a tendency to oxidation and long-term storage issues; ⎯ affinity to water and risk of microbial growth ; ⎯ degraded low-temperature flow properties; ⎯ FAME material deposition on exposed surfaces, including filter elements. Additionally, there is a variety of different sourced FAME products each with its own particular characteristics that have implications with respect to storage, handling, treatment, engine operations and emissions. In those instances where the use of fuels containing FAME is being contemplated, it should be ensured that the ship's storage, handling, treatment, service and machinery systems, together with any other machinery components (such as oily-water separator systems) are compatible with such a product. This International Standard specifically refers to petroleum-derived materials only, thereby excluding any bio-derived materials. However, the practice of blending FAME into automotive diesel and heating oils makes it almost inevitable, under current supply logistics, that some distillates supplied in the marine market can contain FAME. Even some residual fuels can contain FAME as a result of refinery processes or blending a distil ate cutterstock containing FAME. A.2 Precautionary approach
A.2.1 As there is no generalized experience with respect to storage, handling, treatment and service
performance (including overboard discharges) within the broad spectrum of the marine environment, adoption
of the precautionary principle to address any safety concerns in this area of using either blends of
FAME/petroleum products or 100 % FAME is considered necessary. Furthermore, there are the issues as to
the potential effects of FAME products on the range of marine engines and other equipment [i.e. oily-water
ISO 2010 – All rights reserved ISO 8217:2010(E)
separators (OWS) or overboard discharge monitors (ODM)] currently in service. Therefore, this International Standard limits the FAME content to a "de minimis" level. A.2.2 To date, determining a de minimis level is not straightforward given that
⎯ a wide range of types of FAME products from different sources is available in the market place; ⎯ varying levels of contamination can be present due to the use of common equipment or pipelines in refineries, fuel terminals or other supply facilities; ⎯ a wide range of different analytical techniques is used to detect these FAME products and associated by- products with no standardized approach; ⎯ in most cases, sufficient data are not yet available with respect to the effects of FAME products on marine A.2.3 For the purpose of this International Standard
⎯ in the case of distillate fuels (DMX, DMA, DMZ and DMB when clear and bright), it is recommended that "de minimis" be taken as not exceeding approximately 0,1 volume % when determined in accordance with EN 14078. ⎯ In the case of DMB when it is not clear and bright and all categories of residual fuels, "de minimis" cannot be expressed in numerical terms since no test method with formal precision statement is currently available. Thus, it should be treated as contamination from the supply chain system. Fuel producers and suppliers should ensure that adequate controls are in place so that the resultant fuel, as delivered, is compliant with the requirements of Clause 5 of this International Standard. ISO 2010 – All rights reserved ISO 8217:2010(E)
Deleterious materials
This International Standard precludes the incorporation of deleterious materials as stipulated in Clause 5. Such materials should not be present, mixed or blended in marine fuels. Determining the harmful level of a material or substance is not straightforward given that a) each fuel is a unique, complex blend of hydrocarbon species; b) a wide range of materials from different sources can enter the marine supply chain from the production, handling and transport systems; c) varying levels of contamination can be present in the fuel due to the use of common equipment or pipelines in refineries, fuel terminals or other supply facilities; d) various analytical techniques are used to detect these contaminants and specific chemical species with no standardized approach; e) in most cases, sufficient data are not available with respect to the effects of any one specific contaminant, or combinations thereof, on the variety of marine machinery systems in service, personnel or upon the environment. It is, therefore, not practical to require detailed chemical analysis for each delivery of fuels beyond the requirements listed in this International Standard. Instead, it is required that a refinery, fuel terminal or any other supply facility, including supply barges and truck deliveries, have in place adequate quality assurance and management of change procedures to ensure that the resultant fuel is compliant with the requirements of Clause 5 of this International Standard with regard to the exclusion of deleterious materials. ISO 2010 – All rights reserved ISO 8217:2010(E)
Sulfur content
The fourth edition of this International Standard has retained the third edition's limits for sulfur for distillate fuels, but does not include limits for residual fuels. Previously, such limits were included since the sulfur content acts to reduce the specific energy value and, given the appropriate post-combustion temperature conditions, can result in corrosion of susceptible components. Sulfur limits for distillate fuels in Table 1 were retained due to technical requirements to protect small, high-speed diesel engines. Statutory requirements, i.e. the Revised MARPOL Annex VI, either specify a maximum sulfur content of the fuel being used or al ow the adoption of technical solutions to ensure compliance with the emission regulations for sulfur oxides and particulate matter. Therefore, the sulfur content of both distillate and residual fuels is directly controlled by the statutory requirements. Consequently, the purchaser's responsibility is to define the maximum sulfur content of the fuels in accordance with the ship's engine design, emission control equipment and the prevailing statutory limitations in the areas in which the fuel will be used. ISO 2010 – All rights reserved ISO 8217:2010(E)
Hydrogen sulfide
H2S is a highly toxic gas and exposure to high vapour concentrations is hazardous, and in extreme cases can be fatal. At very low concentrations, the gas has the characteristic smell of rotten eggs. However, at higher concentrations, it causes a loss of smell, headaches and dizziness and at very high concentrations is immediately fatal. H2S can be formed during the refining process and can evolve from the fuels in storage tanks, in product barges and customer tanks. H2S can be present in both liquid and vapour phase and the degree and speed of partitioning between the liquid and vapour phase depend on several factors, e.g. the fuel chemistry, temperature, viscosity, level of agitation, storage time, heating applied, ambient conditions, tank shape, ullage and venting. Contact with H2S vapours can occur when personnel are exposed to fuel vapours, such as when dipping tanks, opening tank hatch covers, entering empty tanks, from vent/vent pipes when tanks are being filled and/or heated, in purifier rooms, breaking into fuel lines and during filter changing operations. The risks are highlighted in Material Safety Data Sheets (MSDSs) and the dangers presented to health and exposure guidelines are documented. A useful reference guidance is provided in Section 2.3.6 of ISGOTT[11]. There are many other sources of information regarding H2S but few are marine specific. The liquid-phase limit stated in this fourth edition of this International Standard is designed to provide an improved margin of safety over the previous edition. This limit alone does not constitute a safe level or eliminate the risk of very high levels of H2S vapour being evolved in enclosed spaces. Reference is made to footnote c in Table 1 and footnote d in Table 2 that specify the date for the implementation of the limit of H2S in liquid phase. The reasons for the implementation date not being in line with the publication of this International Standard are ⎯ to provide adequate time ⎯ for the development of a precision statement for distillate fuels in IP 570, the completion of which is anticipated before the implementation date, ⎯ for the world-wide dissemination and application of the new test method IP 570, ⎯ for the industry to engineer, procure and construct facility modifications, where required, in order to comply with the limit; ⎯ to avoid fuel supply disruption in the intervening period. The inclusion in this International Standard of an H2S in liquid phase limit of 2,00 mg/kg in the fuel directionally reduces the risk of H2S vapour exposure. However, it is critical that ship owners and operators continue to maintain appropriate safety processes and procedures designed to protect the crew and others (e.g. surveyors), who can be exposed to H2S vapour. ISO 2010 – All rights reserved ISO 8217:2010(E)
Specific energy
E.1 Specific energy is not controlled in the manufacture of fuel except in a secondary manner by the
specification of other properties.
E.2 For residual fuels, net specific energy, QRnp, and gross specific energy, QRgv, both expressed in
megajoules per kilogram, can be calculated with a degree of accuracy acceptable for normal purposes from Equations (E.1) and (E.2)[6], respectively: 46,704 − 8,802ρ15 ⋅ 10 + 3,167ρ15 ⋅10 )⋅ (E.1) wa ws ) + 0,094 2w s − 0,024 49w w 52,190 − 8,802ρ 0,01 ww wa ws ) + 0,094 2w ρ15 is the density at 15 °C, expressed in kilograms per cubic metre; ww is the water content, expressed as a mass percentage; is the ash content, expressed as a mass percentage; is the sulfur content, expressed as a mass percentage. For the purpose of rapid estimation, the net specific energy of residual fuel can be conveniently read from Figure E.1, which has been derived from Equation (E.1). However, the values obtained from the graph are only approximate. E.3 For distillate fuels, net specific energy, QDnp, and gross specific energy, QDgv, both expressed in
megajoules per kilogram, can be calculated with a degree of accuracy acceptable for normal purposes from Equations (E.3) and (E.4), respectively: 46,423 − 8,792ρ15 ⋅ 10 + 3,170ρ15 ⋅10 )⋅ (E.3) wa ws ) + 0,094 2w s − 0,024 49ww 51,916 − 8,792ρ 0,01 ww wa ws ) + 0,094 2w ρ15 is the density at 15 °C, expressed in kilograms per cubic metre; ww is the water content, expressed as a mass percentage; is the ash content, expressed as a mass percentage; is the sulfur content, expressed as a mass percentage. ISO 2010 – All rights reserved ISO 8217:2010(E)
Key
X sulfur concentration, expressed in percent mass fraction
Y density at 15 °C, expressed in kilograms per cubic metre
To correct for ash and water, subtract 0,01 QRnp(wa + ww) from the net specific energy, QRnp, read from this Figure E.1 — Net specific energy of residual fuel expressed in megajoules per kilogram
ISO 2010 – All rights reserved ISO 8217:2010(E)
Ignition characteristics of residual marine fuels
F.1 Application
The ignition and combustion characteristics of a residual fuel in a diesel engine is dependant on the particular type, design, operating and engine condition, load profile and the chemical properties of the fuel oil. The Calculated Carbon Aromaticity Index (CCAI) is determined from the density and viscosity of a residual fuel and, whilst it does not provide information related to the combustion characteristics of residual fuel, it does provide an indication of the ignition delay. CCAI has been included in order to avoid residual fuel oils with uncharacteristic density viscosity relationships, which can lead to an extended ignition delay. The CCAI value is calculated in accordance with Lewis, et al., using Equation (F.1): ⎣ (v 0,85) − 483 ⋅ lg is the temperature, expressed in degrees Celsius, at which the kinematic viscosity is determined; is the kinematic viscosity at temperature T, expressed in square millimetres per second; ρ15 is the density at 15 °C, expressed in kilograms per cubic metre; is the logarithm to base 10. In this International Standard, marine distillate categories DMX, DMA, DMZ and DMB (see Table 1) have a minimum specified cetane index; see ISO 4264. This provides a better approximation of ignition quality than the CCAI parameter, which was primarily developed for use with residual fuels of the type specified in Table 2. Work is continuing in a number of countries to identify alternative techniques to determine the overall combustion behaviour of residual fuels. In an attempt to address both ignition and combustion characteristics of a residual fuel, a standard test method has been established using a constant volume combustion chamber (CVCC); see IP 541. Whilst it has been recognized that fuels with similar densities and viscosities (i.e. similar CCAI's), can have significantly different ignition and combustion properties, work continues to relate the characteristics derived from IP 541[12] with both fuel quality and in-service experience. Most ships today are uni-fuel ships; hence, the engines with less tolerance towards ignition and combustion quality discrepancies should be taken into consideration when residual fuels are being ordered. The International Council on Combustion Engines, CIMAC, is developing guidelines regarding ignition and combustion quality recommendations for diesel engines. F.2 Use of the nomogram
For the purpose of a rapid estimation, the CCAI value of a residual fuel can be conveniently read from Figure F.1, which has been derived from Equation (F.1), by means of extending a straight line connecting the axes of viscosity, expressed in square millimetres per second, at 50 °C (see A in Figure F.1) and density, ISO 2010 – All rights reserved ISO 8217:2010(E)
expressed in kilograms per cubic metre, at 15 °C (see B in Figure F.1) to the CCAI axis (see C in Figure F.1). However, the values obtained from Figure F.1 are only approximate. Key
A kinematic viscosity at 50 °C, expressed in square millimetres per second
B density at 15°C, expressed in kilograms per cubic metre
C CCAI
Figure F.1 — Nomogram for deriving CCAI
ISO 2010 – All rights reserved ISO 8217:2010(E)
F.3 Calculation of CCAI precision
The reproducibility of the CCAI value of a particular residual fuel is dependant on the reproducibility, R, of the density and viscosity values from which that CCAI value has been calculated. The interaction of these CCAI factors is such that the highest positive CCAI reproducibility is achieved when the reproducibility for density is added to the density value and the reproducibility for viscosity is subtracted from the viscosity value. The curve of CCAI reproducibility plotted against viscosity is given in Figure F.2. The reproducibility of density is a constant (independent of the density value) and, therefore, the CCAI reproducibility varies only with the viscosity of the fuel. The application of the reproducibility is covered in Annex L. Key
X viscosity at 50 °C, expressed in square millimetres per second
Y CCAI
Figure F.2 — Plot of CCAI reproducibility against viscosity
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Flash point
The flash point value is not a physical constant but is dependent on the test method, the apparatus and the procedure used. In this International Standard, the test method described in ISO 2719 should used for both distil ate and residual fuels. Flash point is one of the valid indicators of the fire hazard posed by the fuel. For residual fuels, available information shows that flash point on its own is not a reliable indicator of the flammability conditions that can exist within the headspaces of storage tanks. This means that residual fuels can have the potential to produce a flammable atmosphere in the tank headspace, even when stored at a temperature below the measured flash point. Consequently, residual fuels should be considered as potentially hazardous and capable of producing light hydrocarbons that can result in tank headspace atmospheres being near, or within, the flammable range. Appropriate precautions are necessary, therefore, to ensure the safety of people and property. Further information is contained in ISO/TR 29662[8] and CEN/TR 15138:2006[9]. Additional advice on precautionary measures is given in The Flammability Hazards[10] and in International Safety Guide for Oil Tankers and Terminals[11]. ISO 2010 – All rights reserved ISO 8217:2010(E)
Fuels with high acid numbers arising from acidic compounds occasionally cause accelerated damage to marine diesel engines. Such damage is found primarily within the fuel injection equipment. Testing fuels for acid number, AN, (formerly known as total acid number or TAN) by ASTM D664-09 can give indications as to the likely presence of acidic compounds. Although al fuels have a naturally occurring, measurable acid number, these are generally (but not always) less than 0,5 mg KOH/g for distillate fuels and general y (but not always) less than 2,5 mg KOH/g for residual fuels. However, fuels manufactured from naphthenic crudes can have an acid number that, while greater than those stated in the tables, are acceptable for use. Confirmation that a fuel was manufactured from naphthenic crudes can be established by non-standard, specialized detailed analysis. In such circumstances, it is the responsibility of the supplier and the purchaser to agree on an acceptable acid number. Acid number levels significantly higher than those stated above can indicate significant amounts of acidic compounds and, possibly, other contaminants. However, acid numbers below the values stated above do not guarantee that the fuel is free from problems associated with the presence of acidic compounds. There is no currently recognized correlation between acid number test results and the corrosive activity of a fuel. A fuel in which a strong acid species is detected, even at a low level not detectable by the standard test method, SAN, as described in ASTM D664-09, is non-compliant with this International Standard, as there is a correlation between the presence of a strong acid and the corrosive activity of a fuel. ISO 2010 – All rights reserved ISO 8217:2010(E)
Sodium and vanadium
I.1 Introduction
All residual fuels contain some metallic species, either those that are naturally present such as vanadium, sodium, calcium and nickel, or those introduced primarily from external sources such as sodium, aluminium, silicon and iron. When a fuel is burned, some of these metals are converted into solid particles of oxides, sulfates, or more complex compounds, collectively known as ash. At certain temperatures, these solid ash particles become partly fluid and, in this state, can adhere to components in a combustion system, if the component surface temperatures are high enough. These adhering ash deposits can cause damage to components (piston crowns, exhaust valves, turbocharger blade surfaces in diesel engines and the waterwall, superheater and reheater tube surfaces of boilers), either by a process termed "hot corrosion" or by other mechanisms. The temperature at which the ash particles start to become fluid and to stick to surfaces, often referred to as the "stiction" temperature, is lowest for ashes that are rich in vanadium and/or sodium. It is for this reason that particular attention is paid to the amounts of these metals in fuels. I.2 Ash melting points
Melting points of ashes vary greatly depending on ash constituents. For example, sodium vanadyl vanadate, as an uncontaminated compound, has a melting temperature of 535 °C. However, this can be depressed further by solution of other metal oxides derived from corroding surfaces. For this reason, ash melting temperatures well below 400 °C are theoretically possible. A sodium/vanadium ratio of 1:3 is generally claimed to yield the lowest ash-melting temperature. This is applicable to a simple two-component (Na2SO4/ V2O5) ash complex. However ashes derived from the combustion of residual fuel oils are complex mixtures of compounds, which also incorporate compounds of calcium, nickel, silicon and aluminium, together with many other metals at various concentrations. All of these additional metals tend to influence ash-melting temperatures, in some cases exerting a beneficial effect by making the ash less prone to adhere to surfaces, while in other cases having the opposite effect. The 1:3 sodium/vanadium ratio assumes increasing importance as the vanadium content of the fuel oil rises, because the ash becomes increasingly vanadium-rich. While vanadium levels in some residual fuels can extend up to around 600 mg/kg, other metals do not usually reach such levels and, therefore, their influence on "stiction" temperatures is limited. Also, at high vanadium levels, the total ash burden is greater, thus exacerbating any problems that can arise due to ash deposition. It is not uncommon to find that some ship-owners stipulate the maximum sodium level to be one-third of the actual vanadium level. It is obvious from the above that such a generalized limit is not well founded scientifically and is unnecessarily restrictive, particularly at lower vanadium levels (less than 150 mg/kg). I.3 Vanadium
Vanadium is a natural component of fuel oil and is present as complex chemical molecules containing other elements. Such molecules are present in solution in the residual fuel oil. Thus, there are no practical methods by which vanadium can be removed from fuel oil on board ship. The only practical way to restrict vanadium is by limiting its content. What constitutes a realistic limit is dependent primarily on operational experience and the known sensitivity of the particular engine or boiler to ash-related problems. ISO 2010 – All rights reserved ISO 8217:2010(E)
I.4 Sodium
The usual source of sodium is seawater contamination. However, some sodium can be present in such a form that cannot be removed by on-board treatment. Typically, a 1 % mass fraction of seawater adds about 100 mg/kg to the sodium content of a fuel, while fuels that are essentially water-free normally have a sodium content between about 10 mg/kg and 50 mg/kg, rarely significantly higher. Unlike vanadium, sodium is not usually present in the fuel in an oil-soluble form. In most cases, high sodium levels are associated with seawater contamination; hence the amount of sodium removed is directly related to the amount of water that can be removed in settling tanks and by centrifugal treatment. Very occasionally, the sodium hydroxide used in the refining process can be the source of the contaminant. I.5 Engineering solutions to the problem
The engineering solution to the control of hot corrosion is primarily achieved by a combination of control of metal surface temperature and selection of al oys that have the optimum combination of physical properties and hot corrosion resistance. Modern engine design aims to prevent the ash from adhering to the critical components. Examples of this are more efficient cooling of valve seats and faces and the use of valve rotators to even out the thermal load on the valves. As a result of all the advances, modern engine designs are much more tolerant of vanadium and/or sodium than earlier designs. ISO 2010 – All rights reserved ISO 8217:2010(E)
Catalyst fines
The main source of potentially abrasive particles in bunker fuel is catalyst fines, which for many years have been controlled by the limitation of aluminium plus silicon, set at a level of 80 mg/kg. Engine builders have recommended that, after on-board treatment, the fuel entering the engine should contain less than 15 mg/kg. In this International Standard, the revised limits for aluminium plus silicon have been applied to the residual fuel grades in Table 2. These new specification limits reflect an overal operational cleaning efficiency lower than that previously determined on-board a ship. The aluminium plus silicon levels in Table 2 are intended to limit catalyst fines to a level that ensures a minimal risk of abrasive wear, given that adequate fuel pre-treatment is achieved, e.g. by maintaining the centrifugal purifier inlet temperature at a constant value, usually 98 °C, and that the fuel-cleaning system (tanks, centrifuges and filters) operate under optimum conditions. Consequently, in order to achieve the necessary reduction in catalytic fines, efficient fuel pre-treatment is of paramount importance; see Clause 1. ISO 2010 – All rights reserved ISO 8217:2010(E)
Used lubricating oils
Used lubricating oils (ULOs), which are predominantly spent motor vehicle crankcase oils, have been added to bunker fuels in some parts of the world for more than 25 years. The addition of ULO as a fuel blend component collected from inland sources with no or inadequate environmental regulations can provide a route for other waste materials to enter the residual fuel pool. Potentially, ULO is quite a variable material but, as noted above, it is comprised predominantly of used vehicle crankcase oils. Such oils contain significant amounts of detergent and anti-wear additives. Detergent additives are based mainly on calcium. Whilst the anti-wear additives are usually zinc-phosphorus compounds, some are zinc-free. Therefore, the principle used in setting limits for this International Standard is that the residual fuel is considered to contain ULO if either of the two groups of elements calcium and zinc or calcium and phosphorus are above the limits specified in Table 2. Limits for the selected elements of zinc, phosphorus and calcium have been set at levels that are as low as possible, taking into account both the background levels of these elements in residual fuel free from ULO and the reproducibility of the test methods. It is, therefore, not possible to set a zero upper limit on these "fingerprint" elements. On the basis of extensive statistical reports, the combination of these elements would not trigger the incorrect identification of ULO. The limits on zinc, phosphorus and calcium given in Table 2 serve as the basis for determining whether or not a fuel meets the specification, but do not imply that a fuel that is judged to contain ULO is necessarily unsuitable for use. ISO 2010 – All rights reserved ISO 8217:2010(E)
Precision and interpretation of test results
L.1 Introduction
Complaints relative to the quality of fuel can be categorized general y as either a problem that occurs on board or a dispute over the acceptability of the product prior to its use. Whichever the case, the fuel should be tested to ascertain its nature. When there is a dispute over whether a test result meets or exceeds a specification limit, reference is made to the processes contained in the relevant sections of ISO 4259. L.2 Use of ISO 4259
Table 1 and Table 2 of this International Standard specify maximum and/or minimum limits of the true value of a given property as measured by the specified test method. The true value, as defined by ISO 4259:2006, represents the average of an infinite number of single results obtained by an infinite number of laboratories. A fuel test, run a number of times at the same laboratory, by the same person, on the same sample, under the same conditions, might not necessarily yield exactly the same answer for each test run. These variations are quantified for each test method as repeatability, r. When two different laboratories test the same sample using the same method, the variation is called reproducibility, R. No test method can measure the true value with 100 % certainty. Each test method has a band of probability referred to as the test precision. This means that if the test is carried out exactly as defined in the test method by an operator in a laboratory that fully meets the requirements of an accreditation standard such as ISO 17025[13], the result falls within the precision band of the test method. The precision of standard test methods is determined using procedures defined within the ISO 4259. ISO 4259:2006, Clause 9, provides information to allow the supplier or the recipient of fuels to judge the quality of a product with regard to the specification when a single result is available. L.3 Recipient with a single test result
A recipient who has no other information on the true value of a characteristic other than a single test result can consider that the product fails the specification limit, with 95 % confidence, only if the test result is such that a) in the case of a maximum specification limit, the test result is greater than the specification limit plus 0,59 × R; b) In the case of a minimum specification limit, the test result is less than the specification limit minus 0,59 × R. The recipient has ordered a fuel to ISO-F-RMG 380 specification in which ⎯ the maximum specification limit is equal to 380 mm2/s at 50 °C; reproducibility, R, of the test method (ISO 3104) is equal to 0,074 × 380 mm2/s at 50 °C. Therefore, the recipient can consider that the product fails the specification, with 95 % confidence, if the single test result is greater than 396,59 mm2/s at 50 °C. ISO 2010 – All rights reserved ISO 8217:2010(E)
L.4 Supplier with a single test result
A supplier who has no other information on the true value of a characteristic other than a single test result can consider that the product meets the specification limit, with 95 % confidence, only if the test result is such that a) in the case of a maximum specification limit, the test result is less than or equal to the specification limit minus 0,59 × R; b) in the case of a minimum specification limit the test result is greater than or equal to the specification limit plus 0,59 × R. The use of the above equations is for the guidance of the supplier and should not be interpreted as an obligation. A reported value between the specification limit and the limit from L.4 a) or L.4 b) is not proof of non-compliance. The supplier has tested a fuel to ISO-F-RMG 380 specification in which ⎯ the maximum specification limit is equal to 380 mm2/s at 50 °C; reproducibility, R, of the test method (ISO 3104) is equal to 0,074 × 380 mm2/s at 50 °C. Therefore, the supplier can consider that the product meets the specification, with 95 % confidence, if the single test result is less than or equal to 363,41 mm2/s at 50 °C. L.5 Resolving disputes
ISO 4259:2006, Clause 10, gives the appropriate procedure if the supplier and recipient cannot reach agreement about the quality of the product. However, this procedure covers only the situation where each laboratory is analysing fuel samples that are subdivisions from one representative sample. ISO 2010 – All rights reserved ISO 8217:2010(E)
International Maritime Organization (IMO), International Convention for Safety of Life at Sea (SOLAS), 1974, Amendment 1, Chapter II- 2, Part B, Regulation 4, Section 2.1 VI, International Maritime Organization (IMO) Protocol of 1997, as amended by resolution MEPC.176(58) in 2008, to amend the International Convention for the Prevention of Pollution from Ships, 1973, as modified by the Protocol of 1978 related thereto Directive 2005/33/EC of 6 July 2005 amending 1999/32/EC as regards the sulfur content of marine fuels and amending Directive 93/12/EEC, Official Journal of the European Communities Recommendations concerning the design of heavy fuel treatment plants for diesel engines, Published by the International Council on Combustion Engines (CIMAC), number 25, November 2005 Petroleum products — Fuels (class F) — Specifications of gas turbine fuels for industrial and marine applications 18455:1999, Petroleum products — Calculation of specific energy of residual fuels from physical and compositional properties — Basic data Emissions from CI engines in non-road mobile machinery (NRMM) ISO/TR 29662:2009, Petroleum products and other liquids — Guidance for flash point testing Petroleum products and other liquids — Guide to flash point testing The Flammability Hazards associated with the Handling, Storage and Carriage of Residual Fuel Oil, Published by the Oil Companies International Marine Forum (OCIMF), December 1989 International Safety Guide for Oil Tankers and Terminals (ISGOTT), 5th edition, ISBN 978-1-85609-291-3 Determination of ignition and combustion characteristics of residual fuels — Constant volume combustion chamber method General requirements for the competence of testing and calibration laboratories ISO 2010 – All rights reserved ISO 8217:2010(E)
ICS 75.160.20
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TOXICOLOGICAL SCIENCES 67, 219 –231 (2002)Copyright © 2002 by the Society of Toxicology Gene Expression Analysis Reveals Chemical-Specific Profiles Hisham K. Hamadeh,* Pierre R. Bushel,* Supriya Jayadev,† Karla Martin,* Olimpia DiSorbo,† Stella Sieber,* Lee Bennett,* Raymond Tennant*,1 Raymond Stoll,† J. Carl Barrett,* Kerry Blanchard,† Richard S. Paules,* and Cynthia A. Afshari*,1
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HIV Services and QIPP Contents 1. Executive Summary What is ‘QIPP'? HIV Services – the current picture Outcomes – Developing measures that matter Treatment – Developing clinical and cost effective prescribing in the context of choice Care – Developing approaches to meet the needs of people living with HIV