Marine Fuel Specification and Test Methods DAY 1

Marine Fuel Specification and Test Methods DAY 1 09 th 10 th May 2012

Agenda Day 1 09.30 hrs Introduction. Fuel oil manufacture and refining. 10.00 hrs General fuel characteristics and marine engine operational and safety requirements 11:00 hrs Q&A session 11:30 hrs Coffee break 12:00 hrs ISO 8217 specifications 13:00 hrs Q&A session 13:30 hrs Lunch break 14:30 hrs Sampling requirements 15:30 hrs Q & A session 16.30 hrs Closing remarks

Presenters Michael Green Intertek-Lintec ShipCare Services Marine Services Technical Manager Bunker Fuel Testing Nigel Elliott ExxonMobil Research & Engineering Senior Fuels Technical Advisor Chair of EI TMS SCB-2 Calculation Methods Alister Jackson ExxonMobil Research & Engineering Technical Advisor Chair of EI TMS SCB-9 Volatility

ISO 8217 Marine Fuel Specifications Energy Institute Marine Fuels Workshop 9 May, 2012 Intertek-Lintec ShipCare Services Michael Green Marine Services Technical Manager Bunker Fuel Testing

Marine Fuel Specs and Test Methods Fuel Oil Refining and Products. General Characteristics. Operational Requirements. On board Treatment. Problem fuels.

Marine Fuel Oil 1948 John Lamb presents the paper The burning of boiler fuels in Marine Diesel Engines to the Institute of Marine Engineers. Proposing the use of residual fuels.

Crude Oil Distillation

The Cracking Process Thermal - heat large hydrocarbons at high temps (sometimes high pressures as well) until they break apart. Steam - high temperature steam (1500 degrees Fahrenheit / 816 degrees Celsius) is used to break ethane, butane and naptha into ethylene and benzene, which are used to manufacture chemicals. Visbreaking - residual from the distillation tower is heated (900 degrees Fahrenheit / 482 degrees Celsius), cooled with gas oil and rapidly burned (flashed) in a distillation tower. This process reduces the viscosity of heavy weight oils and produces tar. Coking - residual from the distillation tower is heated to temperatures above 900 degrees Fahrenheit / 482 degrees Celsius until it cracks into heavy oil, gasoline and naphtha. When the process is done, a heavy, almost pure carbon residue is left (coke); the coke is cleaned from the cokers and sold

Catalytic Cracking Catalytic Cracking- uses a catalyst to speed up the cracking reaction. Catalysts include zeolite, aluminum hydrosilicate, bauxite and silicaalumina. fluid catalytic cracking - a hot, fluid catalyst (1000 degrees Fahrenheit / 538 degrees Celsius) cracks heavy gas oil into diesel oils and gasoline. hydrocracking - similar to fluid catalytic cracking, but uses a different catalyst, lower temperatures, higher pressure, and hydrogen gas. It takes heavy oil and cracks it into gasoline and kerosene (jet fuel).

Why take samples? Record the product supplied. 1. Single most important piece of evidence regarding fuel quality. 2. Essential in the case of a quality dispute. Routine Analysis. 1. Damage Prevention. 2. Engine, Crew, Environment. Statutory Requirements. 1. MARPOL Annex VI. Commercial Implications.

Fuel Testing It is essential that the sample is representative. Recognised test methods. ISO ASTM IP Consider the fuel as a whole, rather than considering individual parameters in isolation. As far as Marine Residual / Distillate fuel are concerned analysis is conducted in accordance with ISO 8217:2005 / ISO 8217:2010.

Operational Concerns What can affect vessel operations? Not all ISO 8217 test parameters are directly linked to operational requirements. Key parameters: Density Viscosity Water Content Sulphur Content

Density ISO 12185/ASTM D4052 Absolute measure of mass per unit volume. Stated as kg/m 3 @ 15ºC in vacuum. Commercially & technically important: 1. Essential for Quantity Calculations 2. Setting Purifier, Indicates Specific Energy & Ignition Quality For main grades limit 991.0 kg/m 3. Above 991.0 kg/m 3 certain centrifuges are ineffective. ALCAP purifiers which can handle fuels up to 1,010.0 kg/m 3. A Densitometer is used which has an oscillating sample tube.

Kinematic viscosity ISO 3104 / ASTM D445 Automatic viscometer tends to be used. A sample of approx 50 ml is introduced. The time is measured for a fixed amount of sample to flow through a calibrated tube. The tube is immersed in a fixed temperature bath of 50 Deg C, (1996 ver was at 100 Deg C). The result is then the time taken against the calibrated flow time of the viscometer. Operational considerations relating to viscosity: Storage on board prior to use Injection temperature will depend on tested viscosity

Water content ISO 3733 / ASTM D95 Spec limit 0.5%. Usually found in fuels due to poor house keeping. Can be fresh, brackish or salt. Problems with sludge formation and corrosion of tanks and pipes. Can damage fuel pumps and injectors. Can cause combustion problems. Commercially ships are paying for fuel oil NOT water!

Sulphur % Sulphur 5 4 3 2 1 0 Marine Fuel Sulphur Limits 2008 2010 2012 2015 2020 Year SECA Global The Sulphur Specification limit has been removed from the Std for Residual Fuels in ISO 8217:2010. Buyers & Sellers must now agree Upper Limits based upon International, Regional and Port Regulations that apply when/where the fuel is consumed. For Distillates Sulphur limits vary according to grade: DMA/DMZ = 1.5% DMB = 2% DMX = 1.0%

Sulphur Technical Issues Cold Corrosion Alkaline Engine Oils Developed Lubricity Issues for Ultralow sulphur distillates May Require Different Cylinder Lub.Oils Environmental Issues SOX emissions Acid Rain SECA s control Sulphur Limits

Flash point ISO 2719 / ASTM D93 Legal Requirement. Property appears in SOLAS. SOLAS Chapter II-2, Regulation 15.1.1 no fuel with a flashpoint of less than 60 C shall be used. Strict go no go criteria.

Pour point ISO 3016 / ASTM D97 If a Fuel is stored at too cold a temperature, wax can drop out of the fuel. Pour Point is the: Temperature at which the wax solidifies and the fuel will no longer flow. Spec limit varies with grade/time of year. Solidified fuel oil can be a serious operational problems.

Carbon residue ISO 10370 / ASTM D4530 Spec limit varies with grade. Fuels with high carbon residues can cause combustion problems/deposits. High carbon residues can mean slow burning and reduced efficiency. Deposits can affect combustion chamber, exhaust system and turbochargers.

Ash content ISO 6245 / ASTM D482 If Excessive, Ash can give Fouling Deposits. Spec limit varies with grade Inorganic parts of fuel which are incombustible. Ash itself can cause problems but beware of the elements comprising the ash Eg Ca, Zn, P ULO presence

Vanadium & Sodium IP 501 Spec limit varies with grade. Vanadium and its oxides cause hot corrosion. Can adhere to exhaust valve and seats. Normally only melts above 800 C. Ratio of 1 part sodium to 3 parts Vanadium reduces melt point to 500 C. Combustion chamber temperature can be circa 500 C and hot corrosion can occur. Limits are V: 350ppm for an RMG 380 Na: 100ppm for an RMG 380

Aluminium & Silicon IP 501 ISO 10478 / ASTM D5184 Spec limit 80 mg/kg for fuel oil grades ISO 8217:2005. Spec limit 60 mg/kg for RMG & RMK fuel oil grades ISO 8217:2010. Indication that fuel is contaminated by catalytic fines. Catalytic fines are very hard and abrasive. Cause rapid wear to fuel pumps, injectors, cylinder liners and piston rings. Modern catalyst have a ratio of Al:Si of 1:2. Efficiently run centrifuges can reduce contaminant by up to 75%.

Other metals Vanadium, Zinc, Calcium, Phosphorus Same equipment as with Al+Si. Ca, Zn, P = Used lube oils Ca>30ppm & Zn>15ppm Ca>30ppm & P>15ppm Other metals : Iron Nickel Magnesium Lead

Operational Considerations What other characteristics need to be considered with regard to everyday vessel operations? Fuel Stability Acid Contamination / Corrosion Lubricity (Distillate Fuels) Fuel Combustion / Ignition Hydrogen Sulphide

Fuel Stability Within ISO 8217 fuel stability is covered by TSP. Instability can be caused by mixing / blending. Incompatibility of fuels. Introduction of cutter / blend stocks.

Fuel Stability - Total sediment potential (TSP) ISO 10307 / ASTM D4870 Fuel is stable if it does not break down giving heavy sediment. Spec limit 0.1% m/m. Measure of the cleanliness of the fuel. Stability precipitation of asphaltenes. Formation of sludge. Can cause blocking of filters, choking of purifiers and blocking of pipes leading to fuel starvation. Asphaltenes cause ignition delay and slow burning. Only applied for HFO samples; existent sediment is measured in distillates.

Fuel Stability Stability Issues: Excessive sludge formation. Filter blockage. Fouling / blocking of fuel tanks and transfer pipes. Poor Ignition / Combustion.

Stability Prevention / Treatment How do we prevent stability related issues? Avoid on board mixing of fuels. Very difficult to create fully homogenous blend. Even so called compatible fuels can become unstable when mixed. No Guarantee of compatibility. Compatibility testing is not 100% reliable approximate indication.

Stability Prevention / Treatment Treatment of Stability issues. Application of additive technology. Use of a stabiliser - dispersant additive. Stabiliser keeps the asphaltenes retained in solution. Dispersant re-emulsifies agglomerated material.

Acid Number ASTM D664 Total Acid Number. mg/g KOH <2.5mgKOH/g Weak Acid Number. Inherent in Crude Oil Strong Acid Number. Contamination High TAN can indicate potential sludge formation.

Acid Contamination Acid contamination is a very serious issue. Can result in very fast and extensive wear damage. Strong acid contamination is in direct breach of section 5 ISO 8217.

Lubricity ISO 12156-1, IP450 Testing only required on distillate fuels and only if the fuel has a Sulphur level below 500ppm. High Frequency Reciprocating Rig (HFRR). Specification: 520um Corrected Wear Scar Diameter (wsd 1,4). ULS MGO have greatly reduced lubricating value for fuel delivery systems exposing pumping systems to possible failure.

Lubricity and Sulphur Sulphur Content within the fuel offers lubrication True or False? False most common misconception regarding lubricity. Hydro processing to remove Sulphur removes minor species form the fuel. Minor species such as N Species, O Species and other Polyaromatics. These minor species provide the natural lubricating qualities of the fuel. Removal of Sulphur = Removal of Minor Species = Removal of Natural Lubricity.

Fuel Combustion Due to the nature of marine fuels combustion characteristics will vary significantly. Two fuels may have similar physical characteristics but they are unlikely to have the same combustion characteristics. Ignition and combustion quality of a fuel is key to ensure engine efficiency.

CCAI and CII CCAI Calcxulated Carbon Aromaticity Index. CII Calculated Ignition Index. Both provide an approximate indication of ignition quality of a fuel. Both are calculated values. Do not look at the physical combustion of the fuel.

CII Ignition Quality Used as an indication of ignition quality for residual fuels. As with CCAI it is calculated using tested Density, Kinematic Viscosity and temp at which viscosity determined. CII is designed such that the result is given in the same order as the Cetane Index for distillate fuels. CII of a residual fuel is measured between 15 and 60.

CCAI Ignition quality Calculated Carbon Aromaticity Index provides an estimate of the ignition delay of a fuel. Measure of ignition quality control via Density & Viscosity measurements. Fuels with similar Density & Viscosity may still have significantly different ignition properties. Specification: Index 850-870. A value is usually 800-880. The lower the valuethe better the ignition quality. Fuels higher than 880 are often problematic.

Hydrogen Sulphide IP570 (Annex D) Testing for H2S content allows assessment of a fuel s safety when stored and/or transported; also its potential to corrode pipelines, storage tanks and other ship components. Significant concentrations of H2S are known to accumulate in the headspaces of storage tanks and pose a potentially lethal hazard. Rapid Liquid Extraction Method. Becomes a mandatory test requirement as part of ISO 8217 on 1st July 2012. Specification Limit 2ppm. Health and Safety issue.

Summary ISO 8217 test spec covers a wide range of areas as far as test parameters are concerned. Some address operational issues Viscosity. Some address commercial issues Water. Some address health and safety Flash Point & H 2 S. A number of issues with certain tests can be dealt with on board treatment Viscosity and Water. Other issues cannot Sulphur Content. Testing of fuels to ISO 8217 is a vital tool for vessel owners and operators. THANK YOU.

ISO 8217 Marine Fuel Specifications Energy Institute Marine Fuels Workshop 9 May, 2012 Nigel Elliott Senior Fuels Technical Advisor ExxonMobil Research & Engineering

Timeline for Marine Fuel standards 1924 BS 209: Fuels for Heavy Oil Engines (predominantly sponsored by UK Admiralty) 1952 Voyage of the "Auricula", starts widespread modern use of residuals in marine diesels 1957 BS 2869: Oil Fuels Specifies marine distillates but not residuals Seen as a weak point 1978 BSI PTC/4 "Marine fuels" committee formed ISO TC28/SC4/WG6 proposed 1982 BS MA 100 first published 1986 ISO 8217 published (as BS MA 100: 1986) ISO 8216-1 published (as BS 6383 Part 1: 1986) 1996 ISO 8217 2 nd edition 2005 ISO 8217 3 rd edition 2010 ISO 8217 4 th edition

A History of Marine Fuel standards The UK, through British Standards, was essentially responsible for the development of what was later to become ISO 8217 through the publication of BS MA 100 Before this time, the marine grades of distillate were specified in BS 2869, 1957 as "Class B, while the marine residuals were unregulated, leaving the way open for a plethora of proprietary grades based on viscosity at 120 F (50 C), an inappropriate temperature which still haunts us to this day At a meeting of PTC/- in 1978 it was agreed that BS 2869 was not an appropriate forum for the marine grades, and BSI was requested to prepare a specifically marine standard and this was the remit to the new PTC/4 "Marine fuels" Committee This Committee recognised that marine fuels were international and that ideally an international specification should be the preferred route to standardisation PTC/4 approached ISO, who set up a working group of Sub-committee 4, Classification and Specifications, of TC 28, itself to study the draft of the UK proposal It was seen in the UK as a priority to develop a British Standard and, as international development can be slow to publish a British Standard promptly as an interim measure, with a commitment to implement the ISO standard when published Then, as now, the ISO process was not quick, and BS MA 100 "Petroleum fuels for marine engines and boilers" was published relatively expeditiously in 1982, but with a number of key omissions: SHF, Al+Si and Ignition quality In the event, ISO 8217 was not published until 1986 (along with its companion ISO 8216 Part 1, as SC4 also took its Classification role seriously ) at which stage BS MA 100 was withdrawn

How do ISO standards work? As a non-governmental organization, ISO has no legal authority to enforce the implementation of standards Hence no transition period between publication and implementation can be stipulated in ISO 8217 However the ISO 8217 marine standard adopts a legal attribute when included in the bunker quality clause of the purchase contract agreement Some countries have adopted ISO standards - mainly those concerned with health, safety or the environment - as part of their regulations, or these standards are referred to in their legislation as the technical basis

Membership of ISO TC28/SC4/WG6 A process of revision of an ISO standard is initiated by a three months balloting period of NWIP an ISO document listing changes proposed by the WG 6 members The experts are then nominated by member bodies and act in personal capacity, contributing their knowledge of the subject A broad range of marine industry s stakeholders is required with no need to balance nationalities Even if a member body is not participating in the WG, it has the right to ballot There is no balloting of the draft document at the WG stage. The draft is achieved by WG consensus

ISO 8216 & ISO 8217 Marine Fuel standards The specifications in ISO 8216 and ISO 8217 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 ISO takes into account: SOLAS (Safety Of Lives At Sea) Convention in respect of the allowable minimum flash point of fuels Revised MARPOL Annex VI, 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 Max sulphur contents have been included for distillate grades for those areas of the world that have not ratified MARPOL to protect end users During the lifetime of this International Standard, regional and/or national bodies can introduce their own local emission requirements, which can impact the allowable sulfur content, for example EU Sulfur in Liquid Fuels Directive 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

ISO 8216 & ISO 8217 2010 4 th Edition ISO 8216-1 Petroleum products Fuels (class F) classification Part 1: Categories of marine fuels FDIS ballot results 100% Approval ISO 8217 Petroleum products Fuels (class F) Specifications of marine fuels FDIS ballot results 90% Approval Both standards published on 15 June 2010

Changes from ISO8217 2005 The fourth edition of ISO8217 reflects several important and significant changes: Include category rationalizations of both distillate and residual fuels and substantial amendments to Clause 5 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: E.G. viscosity limits are given to four significant figures

Changes from ISO8217 2005 Distillate Fuels Changes to the distillate fuels (4 categories) include the following: An additional grade, DMZ, has been added with a minimum viscosity of 3,000 mm 2 /s at 40 C, but is otherwise identical in its characteristics to the DMA - Grade added to reflect engine and ship operator concerns about low viscosity when changing from residual fuel oil to distillate in port Problems with internal injector pump leakage, leading to loss of fuel injection pressure and delivery 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 Minimum viscosity requirement for DMA has been raised to 2,000 mm 2 /s 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

Changes from ISO8217 2005 Residual Fuels 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 Table 2 additions and changes: Calculated Carbon Aromaticity Index (CCAI), hydrogen sulfide, acid number and sodium content Sulfur limits have not been tabulated, as these are controlled by statutory requirements 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

Changes from ISO8217 2005 Informative annexes Changes to the informative annexes include the following: Annex C of the previous 2005 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 8217 Annex A Bio Derived Products Concern that bio derived products may have deleterious effects on marine fuel quality Combustion properties were not a concern as FAME has good ignition and lubricity characteristics Major concerns over fuel handling and storage with biodiesel blends: Degraded oxidation stability Affinity for water and microbiological growth Poor cold flow properties ISO 8217 takes a precautionary approach: Only deminimis levels of FAME recommended (1000ppm for FAME in distillate) Recognition that FAME is very surface active and can be picked up in distribution systems very easily FAME defined as meeting EN14214 or ASTM D6751 Raw vegetable and animal oils not allowed Since publication of the standard a number of companies have reported successful ship trials with biodiesel blends ISO TC28/SC4/WG6 working on the next revision of ISO8217 to include biodiesel blends with appropriate precautions

ISO 8217 Annex B Deleterious Materials 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: 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 and 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 the Standard 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

ISO 8217 Annex C Sulfur The fourth edition of ISO 8217 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 allow the adoption of technical solutions to ensure compliance with the emission regulations for sulfur oxides and particulate matter 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 Note with appropriate after-treatment (exhaust scrubbing) it is permisable to burn higher sulfur fuels

ISO 8217 Annex D Hydrogen Sulphide H 2 S is a highly toxic gas and exposure to high vapour concentrations is hazardous, and in extreme cases can be fatal H 2 S can be formed during the refining process and can evolve from the fuels in storage tanks, in product barges and customer tanks. H 2 S 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 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 H 2 S vapour being evolved in enclosed spaces Implementation of H 2 S specification delayed 2 years to July 2012 To provide adequate time for the development of a precision statement for distillate fuels in IP 570 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 H 2 S vapour.

Reasons for raising H2S issue The shipping industry has no reliable historical nor current data of the prevailing levels of H 2 S worldwide in marine fuels Similarly there is very limited data on the incidents regarding H 2 S in marine fuels The fact that the number of registered incidents is low is not a reason or justification for lack of action ISO WG6 included H 2 S, due to IMO s request and the shipping industry s need. The option and consequences of not controlling H 2 S were much worse and considered not acceptable

H2S measurement in vapour Result dependent on: fuel chemistry, temperature of product, volume of headspace, degree of agitation of product, configuration of tank venting arrangements and duration of storage Measurement on barge will therefore be different than on board the ship, the latter being beyond the control of supplier ASTM D5705 (Draeger tube) results-under controlled and equilibrium conditions, have poor precision (R=0.30x + 15), do not represent actual in service fuel handling situation, clause 5.3 no general correlation can be established between this field test and actual vapour phase concentrations of H 2 S in residual fuel oil storage or transports. For these reasons measurement in vapour is unsuitable for a specification limit in an ISO standard used as a sales specification

Why Hydrogen Sulfide in liquid? To measure the total potential H 2 S concentration of the fuel oil that could be released over a period of time from a bunker fuel at any suitable conditions, when the fuel is transferred, heated and agitated by the rolling action of the ship, rather than The measurement of variable equilibrium dynamics of the vapour phase capturing just one H 2 S concentration under specific set of conditions prevailing at the moment of measurement only.

Next steps for H2S To gather quality data on global H 2 S levels To gain industry experience with new test method and continue developing it accordingly To reduce/remove H 2 S from the supply chain To set out recommended handling practices and procedures to fully mitigate shipboard risk To generate dependable H 2 S liquid to vapour correlation To identify knowledge gaps we may still have To include an additional check point and sampling procedure for H 2 S after the fuel has been through the distribution system

What has ISO WG6 accomplished? Prepared detailed and practical marine fuel quality standard. Consensus between engine builders, suppliers and users. Standard praised by IMO MEPC delegations as a significant improvement on the last edition and a good outcome. For current needs revision of most fuel categories and characteristics, provision of new DMZ grade, inclusion of acid number and addressing the bio components issue For future needs introduction of oxidation stability and lubricity, revision of the ULO definition, further decisions on bio issue and study of contaminants Special industry issues introduction of ignition quality parameter inclusion of a limit for hydrogen sulfide (H 2 S)

Future development Ignition and combustion characteristics a better approach Incorporation of Bio-diesel into marine fuel generating technical data to pave the way for change Corrosion possibility of a new test method Contaminants new project to define a good fuel Acid number develop better precision data for this test Oxidation stability improvement on the test method H 2 S test method development and implementation of the limit

Final comments Delivering high quality market relevant standards is a critical undertaking that impacts trade and commerce Meeting these essential needs requires adaptability and alignment with the goals of industry and regulatory bodies. ISO 8217 demonstrated its capability to constantly evolve by keeping pace with the dynamic requirements of a rapidly shifting marine industry. The 4 th edition, reviewed in the light of latest industry s concerns, is a balanced and realistic standard that will serve the industry well over at least the next five years.

And Finally Thanks to Wanda Fabriek (Intertek) Retired ISO TC28/SC4/WG6 Chair Geoff Suckling (Total) BSI PTI/2 and Energy Institute

Sampling Requirements for Marine Fuels EI Workshop: Marine Fuels 9 th May 2012 Alister Jackson ExxonMobil Research & Engineering Chair EI SC-B-9

Marine Fuel Sampling Standards - Summary MARPOL Annex VI ISO 8217 MEPC 182(59) Drip Sample Intertanko Guide ISO 13739 Drip Sample D4057 / API Ch 8.1 D4177 Test Methods ISO 3170 / IP 475 ISO 3171 / IP 476 ISO 3170 / IP 475 Petroleum liquids Manual sampling ISO 3171 / IP 476 Petroleum liquids Automatic pipeline sampling API Manual of Petroleum Measurement Standards (MPMS) Chapter 8.1, Manual Sampling of Petroleum and Petroleum Products ASTM D4057 Practice for Manual Sampling of Petroleum and Petroleum Products ASTM D4177 Practice for Automatic Sampling of Petroleum and Petroleum Products MEPC 182(59) 2009 Guidelines for the sampling of fuel oil for determination of compliance with the revised MARPOL Annex VI INTERTANKO's "A Guide to Bunkering of Ships for the purposes of Annex VI to MARPOL"

ISO 8217 Sampling Requirements ISO 8217 specifies properties for marine fuels (residual & distillate) Applies at the time and place of custody transfer Samples for quality verification may be taken in any location agreed between parties ISO 8217 states that sampling shall be conducted in accordance with ISO 13739 or an equivalent national standard ISO 13739 Petroleum products - Procedures for transfer of bunkers to vessels specific sampling requirements in referenced test methods shall be adhered to No direct reference in ISO 8217 to ISO 3170 Petroleum Liquids Manual Sampling or ISO 3171 Petroleum Liquids Automatic Pipeline Sampling However indirect reference through test methods quoted in Tables 1 & 2 Primarily ISO methods in ISO 8217, but IP & ASTM methods are also quoted ISO / IP methods quote ISO 3170 ( IP 475) and ISO 3171 ( IP 476) ASTM methods quote D4057 (manual sampling) and D4177 (automatic sampling)

ISO 13739 Sampling Requirements Applies only to samples taken during bunker delivery to the vessel The objective is to obtain a single representative sample of the delivered bunker If a delivery is made from more than one bunker tanker, separate samples shall be drawn for each delivery A single sample shall be drawn continuously throughout the delivery using an automatic sampler or a continuous drip sampling device It is recommended that the commercial samples and the MARPOL sample be derived from this single sample For road tanker delivery, truck loading samples are common industry practice and may be designated as the representative samples for the delivery Detailed sampling procedure is given in Annex L See later slide

ISO 13739 Sampling Devices (Annex K) Due to accuracy of sampling devices, the preferential order is: Flow-proportional automatic sampler Time-proportional automatic sampler Manual valve-setting continuous-drip sampler Sampling container requirements: weather-tight capacity of at least 5 litres capable of being security sealed Sample bottles: suitable for air transportation & long-term storage bottle material shall not compromise the integrity of the sample

The Continuous Drip Sampling Process Photos provided by Lintec

ISO 13739 Sampling Procedure (Annex L) Ensure that the volume of the sample container is adequate to fill the number of sample bottles as agreed A continuous-drip sample should be collected throughout the entire duration of bunkering Sampling shall start simultaneously with commencement of the bunkering operation Sample shall be thoroughly shaken or stirred to promote homogeneity Pour the sample in small, equal portions into at least 4 sample bottles make 3 or 4 passes to fill each bottle in turn to obtain nominally identical samples minimum quantity in each sample bottle shall be 750 ml These sample bottles shall be distributed as follows: a) two for the vessel, one of which is a MARPOL sample; b) two retained by the bunker tanker (or terminal); c) one for the Bunker Surveyor, if engaged; d) one for fuel testing services, if required.

MARPOL Annex VI and MEPC 182(59) Regulation 18 of MARPOL Annex VI refers to fuel oil quality Appendix VI contains the Fuel Verification Procedure for MARPOL samples Detailed sampling requirements for Reg. 18 are found in Resolution MEPC 182(59) MEPC 182(59) requires that a representative sample of the fuel delivered to the ship should be obtained at the receiving ship s inlet bunker manifold & should be drawn continuously throughout delivery Representative Sample is defined as a product specimen having its physical and chemical characteristics identical to the average characteristics of the total volume being sampled the practical purpose of this sample is to enable authorities to verify sulphur content of the fuel The sample should be obtained by one of the following methods: 1. manual valve-setting continuous-drip sampler; or 2. time-proportional automatic sampler; or 3. flow-proportional automatic sampler.

MARPOL Annex VI and MEPC 182(59) cont. MEPC 182(59) requires that a sealed retained sample is taken immediately prior to filling the retained sample container, the primary sample quantity should be thoroughly agitated to ensure that it is homogeneous The retained sample should be of sufficient quantity to perform the tests required but should not be less than 400ml* the container should be filled to 90% ± 5% capacity *NOTE that INTERTANKO "Guide to Bunkering of Ships for the purposes of Annex VI to MARPOL recommends that sample volume is not less than 750ml. This is aligned with ISO 13739 which also requires a minimum volume of 750 ml. The retained sample should be stored in a sheltered location where it will not be subject to elevated temperatures, preferably at a cool / ambient temperature and where it will not be exposed to direct sunlight

ISO 8217 Test Methods Issues Raised Next slides highlight possible issues in more detail, but in summary: Many of the tests have conflicting sample heating requirements e.g. Acid Number and Viscosity - heat sample to 60 ± 5 C in original container e.g. Density heat sample until fluid but not so high as to cause loss of light-ends e.g. H 2 S - a sample that is not free flowing at ambient shall be gently warmed 40ºC Some tests have very specific sample container requirements e.g. Oxidation Stability - containers shall be epoxy lined (or similar) metal cans or borosilicate glass (if they are wrapped or boxed to exclude light). Do not use soft (soda) glass or plastic containers (due to the potential for leaching of plasticizers). Some tests have specific sample storage requirements e.g. Oxidation Stability - if a fuel cannot be tested within 1 day it should be blanketed with inert gas & stored at a temperature <10 C, but above its cloud point. ISO 13739 recommends that the Commercial Sample is derived from the same sample as the MARPOL sample (i.e. drip sample) The IP 570 H 2 S method states that samples should not be taken by continuous drip

ISO 8217 Test Method Requirements Parameter Fuel Oil / Distillate Test Method Sampling Standard Reference Additional Sampling Requirements Kinematic Viscosity (40 C distillate; 50 C fuel oil) Density Density Fuel Oils & Distillates Fuel Oils & Distillates Fuel Oils & Distillates ISO 3104 None Fuel Oil only: heat the sample in its original container in an oven at 60 C for 1h. Thoroughly stir the sample with a rod then shake vigorously for 1 min. ISO 3675 ISO 3170 ISO 3171 ISO 12185 ISO 3170 ISO 3171 The heating and/or mixing of petroleum products containing sediments and/or water may result in loss of light-ends. Waxy Distillates: warm sample to 3 C above cloud point. Fuel Oil: heat sample to test temperature prior to mixing. Test temperature shall be such that sample is sufficiently fluid, but not so high as to cause loss of light-ends, nor so low as to result in presence of wax in the test sample. Care should be taken to prevent loss of light-ends from the sample. Wherever possible samples should be drawn, transported & stored in the same container. Use of a fixedvolume receiver (whether it is pressurized or not) could result in light-end loss from the material being sampled, thereby affecting the density measurement. Distillates: mix by gentle shaking. Waxy Distillates: warm sample to 3 C above cloud point. Fuel Oil: heat sample until fluid.

ISO 8217 Test Method Requirements cont. Parameter Fuel Oil / Distillate Test Method Sampling Standard Reference Additional Sampling Requirements Cetane Index Distillates ISO 4264 Indirectly to ISO 3170 & ISO 3171 CCAI Fuel Oils Calculation n/a n/a Sample must be tested according to ISO 3405 Distillation - requires sampling in accordance with ISO 3170 / ISO 3171. ISO 3405: If the sample is not fluid at ambient temperature, maintain it at 9-21 C above its pour point. Shake sam ple vigorously prior to subsampling to ensure homogeneity. Sulfur Fuel Oils & Distillates ISO 8754 ISO 14596 ISO 3170 ISO 3171 Test portions from samples shall be drawn after thorough mixing & subdivision. Heat viscous samples to a temperature which renders the sample liquid & homogenize Flash Point Fuel Oils & Distillates ISO 2719 ISO 3170 ISO 3171 Place samples in tightly sealed containers, appropriate to the material being sampled. Ensure that sample container is filled to 85 95% of its capacity. Store samples in conditions that minimize vapour loss & pressure build-up. Avoid storing samples in excess of 30 C. Subsample at a temperature at least 28 C below expected flash point. I f an aliquot of the original sample is to be stored prior to testing, ensure that the container is filled to >50% of its capacity. Mix samples by gentle manual shaking prior to removal of the test portion, taking care to minimize loss of light-ends.

ISO 8217 Test Method Requirements cont. Parameter Fuel Oil / Distillate Test Method Sampling Standard Reference Additional Sampling Requirements Hydrogen Sulfide Fuel Oils & Distillates IP 570 IP 475 (ISO 3170) ISO 13739 Care shall be taken to ensure that integrity of material is maintained & possible loss of H2S is kept to a minimum. Where samples are drawn in a manner which does not minimise vapour loss (e.g. continuous drip sampling), dedicated samples for H2S determination shall be drawn Draw sample directly into a suitable clean H2S inert container, of a minimum vol. of 500 ml. Lower volume containers may be used, but precision could be affected. The closure aperture shall allow the drawing of a test portion with the pipette / syringe. To ensure sample integrity fill sample container to approx. 95 % full and replace cap immediately & securely. It is recommended that containers such as dark brown borosilicate bottles or epoxy lined containers fitted with impervious gas-tight closures are used. Equipment used to take samples through the roof of storage tanks, & closed system samplers such as those commonly used for ship compartments blanketed with inert gas may not allow samples to be drawn directly into the sample container. In these situations it is acceptable to transfer the sample from the sampling device into the sample container, however care should be taken to keep losses of H2S to a minimum during the transfer.

ISO 8217 Test Method Requirements cont. Parameter Fuel Oil / Distillate Test Method Sampling Standard Reference Additional Sampling Requirements Hydrogen Sulfide Cont. Take the samples to the laboratory as soon as is practicable after sampling. Test immediately if possible. If samples are not tested immediately, store in a cool place such as a refrigerator and analyse them within 3 days. H2S measurement shall be first test carried out on the sample as additional handling can lead to loss of H2S. To minimize loss of H2S, do not homogenize, avoid unnecessary shaking of the sample, do not transfer the sample to another container and avoid unnecessary openings of the container before taking a test portion. The sample needs to be flowing freely enough to allow it to be drawn into the pipette / syringe. A sample that is not free flowing at ambient shall be gently warmed in a water bath or oven set at a temperature 40ºC. Acid Number Fuel Oils & Distillates ASTM D664 D4057 D4177 Heat sample to 60 ± 5 C in original container & agitate until all of the sediment is homogeneously suspended. If original container is a can or glass and >75% full, transfer entire sample to a clear-glass bottle with a capacity at least 33% greater than the volume of sample. Transfer all traces of sediment from original container to the bottle by vigorous agitation. After complete suspension of all sediment, strain sample through a 100-mesh screen to remove large contaminating particles. NOTE - when samples visibly free of sediment this heating/straining procedure can be omitted

ISO 8217 Test Method Requirements cont. Parameter Fuel Oil / Distillate Test Method Sampling Standard Reference Additional Sampling Requirements Total Sediment by Hot Filtration Total Sediment Aged Distillates Fuel Oils ISO 10307-1 ISO 10307-2 ISO 3170 ISO 3171 [ISO 3170 & ISO 3171] Oxidation Stability Distillates ISO 12205 ISO 3170 ISO 3171 Mix the whole sample thoroughly using a high-speed mixer, if practicable, for 30 s. For fuels with a high wax content (high pour point) or of very high viscosity, heat the sample before stirring. The temperature shall be either 15 to 18 C above the pour point for low-viscosity fuels, or at a temperature sufficient to reduce the viscosity to between 150-250 cst for high-viscosity fuels. The temperature shall not exceed 80 C during this preparation stage. Refer to sampling requirements for ISO 10307-1 (which requires sampling in accordance with ISO 3170 / ISO 3171) Test portions from samples shall be drawn after thorough mixing & subdivision away from direct sunlight. Storage shall occur in the dark. Containers for samples shall be of metal lined with epoxy resin or similar material, previously rinsed twice with the material to be sampled, or borosilicate glass, if they are wrapped or boxed to exclude light. Do not use soft (soda) glass containers, or plastic containers (due to the potential for leaching of plasticizers). Analyse fuel samples as soon as possible after receipt. If a fuel cannot be tested within one day, it should be blanketed with an inert gas & stored at a temperature <10 C, but above its cloud point. Thoroughly mix samples before taking a laboratory sample.

ISO 8217 Test Method Requirements cont. Parameter Fuel Oil / Distillate Test Method Sampling Standard Reference Additional Sampling Requirements Carbon Residue micro method Fuel Oils & Distillates ISO 10370 None Thoroughly stir the sample to be tested, first warming if necessary to reduce its viscosity. Cloud Point Distillates ISO 3015 None None Pour Point Fuel Oils & Distillates ISO 3016 None None Water Fuel Oils ISO 3733 ISO 3170 ISO 3171 Liquid samples shall be mixed, after warming, if necessary, in the original container. If the analytical procedures to be applied have conflicting requirements, draw separate samples and apply the appropriate procedure to each sample. Take particular care in respect of the following: a) liquids containing volatile material, since loss by evaporation can occur; b) liquids containing water and/or sediment, since separation tends to occur in the sample container. Do not transfer samples of volatile liquids to other containers at the sampling location but transport them to the laboratory in the original sample container, cooled and inverted, if necessary. Great care is necessary if a sample contains both volatile components and free water.

ISO 8217 Test Method Requirements cont. Parameter Fuel Oil / Distillate Test Method Sampling Standard Reference Additional Sampling Requirements Ash Fuel Oils & Distillates ISO 6245 ISO 3170 ISO 3171 None Lubricity Distillates ISO 12156-1 Vanadium Sodium Aluminium + Silicon Used Lubricating Oils (Ca + Zn or Ca + P) Vanadium Sodium Aluminium + Silicon Used Lubricating Oils (Ca + Zn or Ca + P) None Fuel Oils IP 501 IP 475 IP 476 Fuel Oils IP 470 IP 475 IP 476 None Thoroughly mix samples in their containers immediately prior to withdrawal of the test portions. Place the sample container in the oven and maintain the sample at 50 60 C until all the sample is fluid and of uniform viscosity. Mix the sample for approximately 5 minutes. Failure to use this homogenization procedure will invalidate results. Thoroughly mix samples in their containers immediately prior to withdrawal of the test portions. Place the sample container in the oven and maintain the sample at 50 60 C until all the sample is fluid and of uniform viscosity. Mix the sample for approximately 5 minutes. Efficient mixing of the sample is essential to the accuracy and precision of this test method. Hand shaking alone will invalidate results.

ISO 8217 Test Method Requirements cont. Parameter Fuel Oil / Distillate Test Method Sampling Standard Reference Additional Sampling Requirements Vanadium Fuel Oils ISO 14597 ISO 3170 ISO 3171 Test portions from the samples shall be drawn after thorough mixing and subdivision. Heat viscous, opaque, semisolid or solid samples to a temperature which renders the sample liquid and homogenize using the homogenizer. Aluminium + Silicon Fuel Oils ISO 10478 None The sample shall be homogenized thoroughly before the test portion is taken. Place the sample container in an oven at a temperature between 50-60 C and maintain the sample at this temperature until all the sample has melted and reached a uniform viscosity. Homogenize the sample for approximately 5 minutes. Failure to use this homogenization procedure will invalidate results. Used Lubricating Oils Ca + Zn or Ca + P Fuel Oils IP 500 IP 475 IP 476 Thoroughly mix samples in their containers immediately prior to withdrawal of the test portions. Place the sample container in the oven and maintain the sample at 50 60 C until all the sample is fluid and of uniform viscosity. Mix the sample for approximately 5 minutes. Efficient mixing of the sample is essential to the accuracy and precision of this test method. Hand shaking alone will invalidate results.

OTHER REFERENCES CIMAC guide on ignition and combustion: http://www.cimac.com/cimac_cms/uploads/explorer/wor king%20groups/cimac_fuel_quality_guide_ignition_an d_combustion.pdf