AN INTRODUCTION TO FUEL ANALYSISAN INTRODUCTION TO FUEL ANALYSIS. Dedication anes ne ene ne ee ed eee This book is dedicated to the one person who never , my wife and icised the content. Nigel Draffin AN INTRODUCTION TO FUEL ANALYSIS by Nigel Draffin M.LMare.S.7, First Edition Published by Petrospot Limited England 2009AN INTRODUCTION TOLFUEL ANALYSIS Published in the United Kingdom by Potrospot Limited Pevrospot House, Somerville Court, Trinty Wy, ‘Adderbury, Oxfordshire OX17 3SN, Englend wns:petrospot.com “Tok +44 1295 a14a55 Fax: +44 1295 814486 © Nigel Drattn 2008, Fist published 2009, ish Library Catsloguing in Publication Dato ISBN 976-0.9548007-3-7 Al rights reserved. No part ofthis publication may be reproduced, stored system or transmitted in any form or by any mean hotograpic, recorded or otherwise, Permission ofthe publisher, Perospat Limited ‘This publication is designed to provide accurate and authoritative information in ‘competent professional person should be sought Petrospot books are avalable at special quently dscounts for use in corporat training progremmes or onboard ships Petrospot Limited Designed by Alison Jane Cutler, Petrospot Limited Printed in England by Advent Print Group Foreword No two fuels are exactly the same, even though they may appear to be identical. Fuel quality can change depending on the crude oll and feedstocks from which it is derived, on the type of processing it receives at the refinery and on the way its stored, blended and delivered to ships. Unti the early 1970s, and in some areas wel beyond that, shipowners never worried unduly about the quality of the fuel they were buying. Since then, once the quality of the fuel started to deteriorate as a result of ‘enhancements’ fo the refining process, bunker buyers have become all too aware of the operational, financial and legal dificuties associated with buying and using poor quality fuels. In the 1980s, in response to increasing concem over the steady deterioration of the quality of bunker fuels, the first dedicated specialist fuel testing services began to appear. Now, these services, with testing laboratories in all the main bunkering centres, play a vital role in determining whether a fue ble for burning in a diesel engine or whether it should be offioaded — or debunkered ~ to become subject to yet another bunker claim. Nowadays, for many owners, 2 laboratory for testing before the fuel ol is used onboard, and established and understood by buyers and suppliers alike, However, often the problems start when a testing laboratory has analysed the fuel and returned the results. What do those results mean? How should they be interpreted? What happens ifthe fu ightl outside the agreed specifications? What if other ~ ‘as yet unknown or unspecified ~ substances show up on the analysis? How can en ‘owner or charterer, or a supplier or trader find out what the lab results actually mean ‘and what to do about them? (On the basis that prevention is always better than cure, everyone involved in the supply or purchasing of bunker fuels should be aware of the many parameters that ‘are covered in marine fuel specifications and know what is reasonable to expect and possible to accept. Armed with this information, many routine problems can be avoided and costly mistakes can be averted, Nigel Draffin’s book, An Introduction to Fuel Analysis, brings home the importance of, fuels you are dealing with in a bright, simple and effective way. In this wealth of information that will enable everyone from the newcomer to the what they contain, how to test each key parameter and what the test results actually mean, and what happens when problem results appear. Although never a substitute for the huge amount of deta that can be ‘obtained from a professional analyst using a fully-equipped modem laboratory, this, book certainly provides a substantial amount of information that should be welcomed ‘and absorbed by anyone involved in any way with marine fuels. Is standard practice to send a bunker sample off to process is wellPO PNiieeticuenncalsannaclcs In An Introduction to Fuel Analysis, Nigel Draffin offers numerous detailed diagrams, tables, charts and photographs which will certainly help anyone who has any doubts about what can be found in marine fuels and, once found, what to do about it. In addition, some very useful appendices provide places to go for help, lists of abbreviations and a mult-lingual glossary of the words and terms most often found in fuel test analysis reports. I believe that An Introduction to Fuel Analysis is an important addition to the growing library of bunker-specific books now being published by Petrospot, and complements Nigel Dratfin’s previous best seller, An Introduction to Bunkering. Angus Ogilvie Technical Director Cockett Marine Oil Ltd June 2009 Preface After the effort of producing my only other book to date, A Introduction to Bunkering, in 2008, | was expecting to wait until after retirement before once again ‘picking up the pen’, However, | was then asked to consider writing another practical Book on bbunkering, this time focused on a single important area of the industry. e questions that | have been asked by colleagues and clients over the many years that | have been involved in this industry. The greatest number of ‘questions concerned fuel analysis and the results of that analysis. Many of those ‘asking the questions were from a commercial, general technical or operational background and wanted information, guidance and comment to help them deal with potential problems. My hope is that this book will bridge the gap between the general level of information on offer and that available from specialised sources. ‘An introduction to Fuel Anelysis is intended to provide a guide and reference for those ‘not specialists in the technical aspects of marine fuels, need to understand jology and the reporting used In fuel analysis as part of their work. This book is not intended as a definitive reference work on fuel analysis or fuel ing. Readers need to be aware that the professionals inthis field do not always: each other. The test methods are under constant review and changes are 0 the information contained inside is the best | could provide at time of pt Furthermore, the definiive references to the star and to the test methods mentioned in this book can only be found in the latest published editions of the standards concerned. Understanding fuel analysis need not be as complicated as it may seem, and if ‘book sheds some light on the processes involved and the reasons behind them, I fee! the effort will have been very wor Nigel Draftin June 2009PAU uicesueaon stot eCWN cies About the author pierre Nigel Draffin has been involved in sl bunker market for over 23 years, Atte ‘over 43 years and with the commercial ‘hell Tankers as an apprentice engineer in 1966, he progressed through the ranks, serving on ail classes of vessel including very large crude carriers (VLCCs) a ied natural gas (LNG) tankers. He came ashore in 1979 to join the newbuilding department of Shell Internationa! Marine, After two years of new construction in ireland, South Korea and the Netherlands, he transferred to Shell's Research & Development unit, specialising in ‘control systems, fuel combustion and safely systems, | 1986, Nigel moved to the commercial department as a bunker buyer and economics +1988, he was promoted to be Head of Operational Economics, responsible 18 fuel purchased for the Shell fleet, the operation ofthe risk management policy and the speed / performance of the owned fleet. In March 1996, he joined the staff of E.A.Gibson Shipbrokers Ltd in the bunker department, and became the manager. In 2006, this department merged with US-based broking house LOM Petroleum Services, where Nigel is currently Senior Broker and Technical Manager. Nigel is a founder member of the International Bunker Industry Association (BIA) and has served twice on its council of management, most recently as Honourary Treasurer. He currently serves as co-ordinator of the Education Working Group and Ig the author of BIA Basic Bunker Course. He is a member ofthe Institute of Marine Engineering Science and Technology and Past Master of the Worshipful Company of Fuellers. Nigel is @ bom communicator and dedicated teacher, whose knowledge of the subject mean that he is consistently voted one of the lecturers on the courses he teaches. His contributions to the well-estal Bunker Course over the past decade or {or his teaching abilities as for his undeniable social sk , An Introduction to Bunkering (published by Petro proved ‘capable of translating the most complex of issues i easily understood by readers everywhere, even those for whom Er ‘mother fongue. Llewellyn Bankes-Hughes: ‘Managing Director Potrospot Limited June 2008 style and vast ost effectiveAN INTRODUCTION TO FUEL ANALYSIS Acknowledgements ryone who has helped in the creation of An ly Wanda Fabriek, John |, Geoff Jones, have cast an eye over different parts of the text and suggested many additions and changes which hopefully make the book better, He also thanks Angus Ogilvie for writing the foreword and for his help and encouragement over many years working together on training courses. He has special thanks for all those who have allowed their photographs to appear ‘The author extends his thanks to Introduction to Fuel Analysis, part is his thanks to Llewellyn Bankes-Hughes and his team at through. In particule, more, seamlessly he thanks Alison Jane Cutler (née Parsons), who has, designed and produced the finished article,'AN INTRODUCTION TO FUEL ANALYSIS Contents Foreword v Preface vil About the author ix ‘Acknowledgements xi List of tables and figures xvi Chapter 1 - Fuel analysis Selecting an vein say. Legislation requirements on specifications... IMO raquo ent. Chapter 3 - ParametersPotaseium, Chapter 4 Other reported items Breaking the sea. Chapter 6 - Test methods 31 ee ee vane 32 33 a8] 38 38, 35 36 36 —— 36 “Tlal Sediment Acoolerated.. 37 é ‘38 “40 40 Iron (Fe), xiv European Union procedure for control on Sulphur. MARPOL procedure 5 Fuel Oil Verfeation Procedure for MARPOL Annex Vi Fuel Ol Samples son. 3 Chapter 8 - Problem results Vanadium: SOI Sodium / Vanadium Aluminium / Sion, Carbon residue... Ash Flesh point. Challenge Chapter 9 - Additional tests FT. sons. Turbiscan,List of Tables and Figures Figure 1. Ships offcer using hygrometer Chapter 10 - The future = Where to go for help Number (ECN) for given Figure 14. Drip samoler and cubitaner in U88 nnn nnn Photograph courtesy of Loye's Register Figure 15. Drip sampler and cubkalner Rating Numbers of Typical Spots... ‘Spot examples courtesy of Inertoc OCA ul xvilFAN INTROGUCTION'TO FUEL ANAL Figure 31. Aching 2 sample oe os A Photograph courtesy of DnVP Figure 62. Ash table. : os 40 Figure 83. ICP spectrom at ‘Photograph courtesy of Inpechom Inspectors B.V. Figure 34, Schem. a Figure 35. Determi 43 ‘Photograph courtesy of Inpachiem Insp Figure 36, aa Figure 37, a4 Figure 98. 4 Figure 30. 45 Figure 4. 45; Figure 41 46 Figure 42. 47 Figure 43. Manual Penskey-Martons closed cup tester in use. 47 ‘Phoiograph courtesy of Lintec Testing Services Ltd Figure 4. ar Figure 45. 48 Figure 46. : 50 Figuce 47. Sample voluma and time for resul tbe St True value chert = 53 ‘onfidence level able oo 58 jon viscosity / temperature table, 62 Figure 51. FTIR trace, wD Photograph courtesy of Lntec Testing Services Lid Figure 82, GC-MS and operator... : 7 ‘Photograph courtesy of Lintec Testing Services Ltd Figure 53. "Combustion pre n ‘Chart courtesy of Fusitec. Figure 54. Rate of hest release curve chart n ‘Chart courtesy of Fuetee Solutions AS Figure 55. Combustion pressure trace Chet nnnnnnsensnnn v2 Diagram courtesy of Fuelise Solutions AS Figure 86. Rate of heat release chart : 7 Diagram courtesy of Fuetee Solutions AS Figure 57. Table showing extract of parameters as defined in IP 641 test method m Courtesy of Fuetec Solutions AS Figure 58. Diagram showing the principle for constant volume combustion used in the FIA..74 Diagram courtesy of Fuetec Solutions AS Ploase note: The numerical data in all of the tables except for ISO 6217 in this book Is intended for guidance only and may be subject to minor errors of ‘rounding’ up or down and may be superseded by new methods or precision data as published from time to time, xvii Chapter 1 - Fuel analysis (Owners have always had concems about the quality of fuel for their ships but, before the 1980s, the only analysis made was by the use of on board test equipment. A small number of owners kitted out thelr vessels with sufficient equipment to measure viscosity, density and flash point but nothing else. It was only once the fuel quality started to deteriorate as a consequence of the advent of modern refinery techniques, that enginoers started to have concerns about the product that they were receiving. These concems led to the production of formal specifications, fuel standards and, In the 1980s, the creation of specialist fuel testing services. Selecting and verifying quality Fuel oils supplied to ships are ordered according to the requirements of the machinery ‘on the ship and the storage and treatment plant on the ship. Over the years, technology has changed, leading to more detalled and stringent limits on the quality of the fuel. ‘The days of ordering ‘Bunker C’ or ‘Any commercial grade fuel oll (ACGFO) are long gone. Figure 1. Ship's officer using hyerometer Shipowners and bunker buyers will generally stipulate grades in accordance with an international standard for fuel oil quality, possibly with additional requirements specific {o their company’s policy or to meet a particular need on an individual ship. In order 1AN INTROBUGTION TO FUEL ANALYSIS to verify that the quality received is in compliance with the ordered specification, a significant number of buyers arrange for the qu: a sample drawn a Sanderds They ispectorate and a number of to process a high volume of samples and have ‘services {o arrange the transport of samples, companies such as SGS, Saybolt and Intertek OCA, have the involved with referee ity to be assessed by analysing jost of this analysis Is performed be, at the least, the parameters cited in the international st for additional parameters if requested by their client ‘The reports sent by laboratories performing any specific tests or a referee analysis will only report on the tests they are instructed to undertake. Example of a typical analysis report Very Good Petroleum Services = Fuel Report dated: 31-May-09 Vessel + Optimist (9123456) Sample No 2714 Sample Type (HFO ) Bunker Port Houston Bunker Date 29-May-09 Sampling Point SHIP. MANIFOLD Sent From HOUSTON, Tx Date Sent 30-May-09 Arrived at Lab 30-May-09 Supplier Megalarge Loaded From Gopher 3 Quantity per C.Eng 720 Seal Data vaps 9420405 INTACT Related Samples Supplier 9420406 ship 9420407/9420408, Ship (DNVPS MARPOL) 9420409 MARPOL 7171483 continued. Arn Receipt Data EDN Density @ 15°C kg/m? Viscosity @ 50°C mnt/s sulphur Sn/n Volune @ 60F BBL Quantity Mr Tested Results Unite, Density @ 15°C kg/m? viscosity @ 50°C an?/s Water wy Micro Carbon Residue So/m Sulphur in/a Total Sediment Potential n/m Ash n/n Vanadium ng/kg Sodium ng/kg Aluninium ng/kg Silicon ng/kg Tron ng/kg Nickel mg / kG Gaictin g/kg otassiun ng/kg Pour Point °C Flach Point tc Calculated Values Net Specific Energy mg/kg 40.20 CAT (Ignition Quality) - 852 Aluniaium + siticon ngékg 19 20 Quantity (Weight) Mr 527.09 Quantity Difference ur 0.38 Note: LT means Less Than, GT means Greater Than. Quantity (Weight) is based on BON Volume, VGrS Density and a weight factor of 1.1 kg/m? (ASTM DL250-80 Table 56). Specification Comparison Results compared with IS0 8217:2005 specification RMG380. Based on this sample, the specification 1s met. operational Advice: Approxinate fuel temperatures: “injection: 140°C for 10 nni/s, 125°C for 15 mm/s = transfer: 40°C Regards, Bver B Nad, Houston, USA END OF REPORT FOR Optimist Figure 2. Exomple text ofa typical analyls report aTaceeMeneipolgul=) ANNRAIC Units In this book | have tried to use Systéme I ‘a metric system and accepted worldwide. Howe other counties, diferent units are used. Where appropriate, |! have included reference to those. Note uses cent ‘The SI naming convention uses lower case letters forall abbreviations except names of individuals and multipliers of 10° (M or Mega) or greater. The single exception is the Litre which can be I or L. Standard prefixes for the SI units of measure Name hhecto- megs: Multiples [Symbol p M Factor | 10% io 70" Name ‘cont ‘mlero- /Subalvisions | Symool e Factor | 10" Figure 2. Table of standard prefixes for Examples + CentiStokes (cSt), 100" of a Stoke. Stoke is the name ofa famous physicist. gramme (Mig). Joule was another famous physicist MegaJoules per ki Mitigrams per kilogramme (mo/kg). Other abbreviations + Parts per million based measurement + Percentage by mass (% mim), Percentage by volume (% vv). better to use mg/kg for anything except volume- Gree Chapter 2 - Fuel specifications id fuols have evolved over a period of about 100 years. The analysis of actual fuel oil sold by oil companies for use a {uel for intemal combustion engines, After the First Word ‘The specifications for In 1947, following extensive research by John Lamb, Shell started to burn fuel oil in ts motor ships. Other companies followed this lead, and by the late 1950s, most motor ships burned heavy fuel oll whilst at sea, progressively more important.AN INTRODUCTION To FUEL ANALYSIS vidual shipping companies started to produce their own fue! specifications ‘and action taken by Briish shipping companies encouraged the British Standards (BS) organisation fo develop a range of specifications for marine fuels. ‘This resulted in the first ‘proper’ specification for fuel oll, BSMA-100 of 1982. This ‘values for a number of parameters and contained 15 different grades of sted as M1, whilst normal heavy fuel oll (today's 380 centiStoke mat was listed as M7. ‘This publication was followed in 1987 by a standard produced by the International n for Standardization (ISO), called ISO 8217. The engine builders’ forum, Congr national des Machines & Combustion (CIMAC), which had worked closely with BS in the late 1970s and early 1980s, released its own specification for fuel as delivered to ships in 1990, By that time, the British Standard MA100 had been reissued as a document identical to ISO 8217, Both ISO and CIMAC have working ‘groups revising and relssuing thelr specifications fror Some engine builders (and consequently ship builders and owners) specity ial fuel specifications ium and high speed engines. These lustrial Standard (JIS) specifications and, always to the relevant ISO or CIMAC grades, the differences are insi ‘The reason that they are used Is normally just to cover the initial guarantee period of operation. The specifications in question often do not comply with maritime legal requirements, especially with regard to flash point. Some inthe 19% Current standards 180 8217 ‘The current ISO standard for marine fuols is 1S 6217 (E) 2005. It was published in November 2005 and is likely to remain current until 2010 or later. It has grades for four types of distillate (DMX, DMA, DMB and DMC) and 10 marine fuel oils (from RMA 30 to RMK 700). DM stands for Distilate Marine whilst RM stands for Residual Marine. The numbers in the fuel oil grades are the viscosity at 60°C. The standard has eight toxt sections with clauses describing features of the fuel. ISO 8217 Clause 8 is especially important as it states that the fuel must be a homogenous blend of hydrocarbons derived from 3 there may be no inorganic acids ‘and no used lubricat precludes the inclusion of any added substance or chemical waste which jeopardises the safety of the ship or adversely attects the 1e machinery, which Is harmful o personnel or contributes overall 0 the harmful adulterants found in fue! 20 years, without the nee 1S0 8217 also contains informative annexes covering other issues which the ISO working group felt needed clarification. Some of these are likely tobe included in the standard in subsequent revisions. Always remember that the standards contain much more than just the tables of parameters with minimum or maximum values. There are a number of pages of Clauses which are an integral part of the standard as well as the ‘informative’ annexes ‘which are not part of the standard. The topics covered by the annexes are: (ash points below is tered outside the engine room ‘DMo_| Blended diesel RMA [Light fuel of blend [RAE [Residual fue for some medium speed enginas and some older slow speed engines Most commen grado of ful for modem medium speed and almost al slow speed engines RARK__| High viscosity, igh doneiy fuel used by modern container sips Figure 6. Summary table o principal gredes ‘The number following the grade letters is the viscosity maximum for the fuel at 60°C. I ports, and in some ports the most Be aware that not all grades are avaliable at common grades are not avai ‘cimac 2003 ‘The CIMAC ‘Recommendations regarding fuel quality for diesel engines’ isa technicel paper re-issued from time have the status of an international standard within the industry. CIMAC 2003 is almost prefix DM or RM. The CIMAC and ISO working groups work closely together and in ‘many cases working group delegates are members of both. The CIMAC organisation has the advantage of having a simpler structure and @ more direct focus on the ‘machinery and the fuel ly han ISO and, over the years, the CIMAC specification has been revised at least one or two years earlier than the ISO 8217 standard. ASTM “The American Society for the Test {or fuel ols and standards for test methods for many years. The specifica thay obo noauntred are ASTM D908 gras 119 6 and ‘ASTM 978 grades 2 and ts Japanese Industrial Standard (JIS) standards are similar to ASTM standards with te fuels‘AN INTRODUCTION TO FUEL ANALYSIS : = ETE ET TTFeR ETP a SO. Peete ETE PRE E| § omezwnte finn Jtme Fo foun ous owe i 5 iB ki WHT! i | 5 alsgeeels| # on iso aereer | at eaae : He Fes) ig) 3] F Dens e150 - [aso [smo fomo [Soe eh gsig3 3| & i 3] 2 tet eostoo? dp Ge) gf ; ieee fiw feo [ESE He ean 4 8 a eye Ye Js fisoarie OnE PERSIE Heel Fuel = in |? (PP eee HOPE apa" [ie femal 2k kes i te le : é HOE Gy Tle ileal? [File sem ee ea ee Ie eae eos a 2 segre fete] eels sw + [200 35 3 35 [eeag] 8 ]3) | s [eigl=|"> [2g] 8 [egg cma | hig? u ihe g ane naar The ae T5026 : E 5 coor oe Pes ub aa f ee] | fe leg Seeerteeninaee |x imine. lox foo |- |. [sore tie ug See ee come (ees |e an feo [eos ige abe ike ie erele ciesee esl eee ah evn) [nex [007001 [oot [0s so eaas Hid Pr Hi a] ~ Je] 8] 8 /Ple 5 appearance : Gear ana bight |" 7 Sea TA and eile ag Shaere ye egiee age ke utcednort eset |xonm|nx |- | _[asor favo [500-4 is g i i id a ier Reng [max [— | fof so ens ges 8 i} 2 a3 EF ned ee) [Pet er s70 be s zi ia (c0078) 3 i 7 i as Bb alee] es leeise® (eel & eg nirimetsston —|rotg |mae | |e fas orate ag a | E q : i a Taare ATTY ee, Za Pa z he mag |x. |. ferttoets | es0t orp azo aa é Phosphorus max. - ‘or oeled sq | [fe REE FF ic IRE Elid Aa [ex oR [8 2 ae Ra pd cog Ui ltl apn cn oc a i # 8 ig] 8/8 leisy [Pig 2 eg Soon ne ene een e en be i |_| *{ "| sername nnnaren " moe A Ralearintl 13% pape Bocce relrt conga eae eB z Le ala atatstaa alain tte ai ena a 5 if Ss [33]s/2a/e gigigiglgs |giges| £ Spolinora. S200 andere a i eee (Eslea QeS|SIS\slee (SIRS i 1 tos iu ant errr we sre te arr ig i j Pee jeasleales ig) 52 0 lal snl be considera tab fee cf uted uioatng ols (ULOs) on or mere oho ments zn, 2 |g ag |gea Psigy ala g Preciosa atime oot paced bs Aes anens nlc! tare xs ui : 24 lee | Sis| 8) 2 8) ) s Frew a tel shat bo dori cotan ULE B EogF less | spl § 5 S|) 4 Figur 7. Beret em 150 8217 () 2005 cleo fe! g ® 9UK standard is Defence Standard 94-1 Buyer's specifications Many buyers and many sellers have their own specifications, especially where they have requirements more strict than those of ISO or CIMAC, 2 requirement for ‘acdltional parameters or a need to meet thelr own national legislation. They may use analysis to ensure that their agreed specifications have been met. Legislation requirements on specifications \dards, such as the Singapore Standard Code of Practice for Bunkering, CP60, and its replacement, the new Singapore Standard SS 600:2008, ‘enforced from July 2009, IMO requirements hur content and density) and the requirement for a sample of each delivery for use by port state control in determining 1ce with the regulations. It also detalis the test methods to be used and the (which are discussed in Chapter 6). con Safety of Li Fuels used and the test procedures for veriica SOLAS is the IMO’ ‘minimum flash pe 3 found in fuel analysis reports. Density The heaviness of the ol, measured in kilograms per cubic metre (kg/m). Density typically is between 960 and 991 for normal fuel ols and between 830 and 880 for gasol at 15°C. Its sometimes measured inKlograms per litre (kl), which gives us ‘ypical values of 0.960 to 0.991 or 0.830 and 0.880 al 15°C. In general lighter than water. The density of fesh waters 889.1 ka he term specific gravity used Used. The density also affects the specific energy of the fuel. There is a specific irement to identify the density of fuel supplied detailed in VARPOL Annex VI osity Viscosity represents the runniness ofthe oil. itis a way of defining the resistance of flow. There are two measures of viscosity, the Dynamic viscosity measured centiStokes as a preferred unit, it should be more correctly indicated as mm‘. In the past, fue! oil viscosities were measured using the Redwood Saybolt Universal ‘and Saybolt Furol viscosity scales. The names refer to different designs of viscomet but both measured the number of seconds taken for the sample to flow through ‘an orifice, The original standard fuel grades, from the 1970s, 00 seconds Redwood Number 1 and 3,500 seconds Redwood Number 1 (equivalent to the 180 St and 380 cSt fuel oil of today),‘spaces. Fuels produced from io and, hence produce many factors affect the increased depos thermal oracking processes show a higher carbon/hydrogen more carbon residue. It should be remembere ‘combustion process in a diesel engine: fuel 19. Some engines are more engine t by carbon depos temperature and carbon content. Careful control of nozzle temperature reduce this effect. eed engines are much more of the 1970s, Medium spee 16 to burn the fuel, can be quite sens rant of elevated carbon residue levels, es faster ive to elevated carbon residue levels, Sediment of Insoluble substances in a fue! fal but can also include asp fed or in suspension in the fu 1 fuel system. The sedi diesel oll or fuel le mixture today are blends of two or more products, e sediment tests is formed from organic ~ metallic. and debris such as sand, rust and ‘of the engine. The ash content also 1 3Flash point ‘The flash point of a flammable liquid is the lowest temperature at which it can form an ‘gnitable mixture in related to, but not the same as, the release of flammable vapour fom a fue, The lower the flash point the greater the potent hazard of legal minimum for flash point is 60" the minimum flash point of fuel suf Cloud point ‘The cloud point of a liquid is the temperature at which dissolved solids in the gasci cloudy appearance. temperature below whi filters and injectors in engines Cold filter plugging point let gives an estimate forthe lowest temperature tiesel engine fuel systems, This is a more re operation limts than the cloud point and pour pein. ate fuels, only of relevance with dis Cetane Index The Cetane Index is only of relevance 92. It calculated based on the Cetane Number higher the Cetane Number or Cetane Index required to allow complete combustion of the fuel, The Cetane Index will not reflect the influence of cetane improvers added to the fuel. This may become significant with bio-ciesets, Acid Number ‘Acid Number (AN) in the amount of alkali needed to neutr in the fuel. The higher the number, the greater the amount of acidic mater 14 of the degree to which they can be ionised in wat (for exemple, sulphuric acid or hydrochioric a 180 8217 standards. Organic acids are weak acids, some of which can be harmt, even in small quantiles. The Total Acid Number (TAN) is an old name for Acid Number (AN) and is @ measure of the total amount of acidic material inthe fue. ‘The Strong Acid Number (SAN) is @ measure of the presence of inorganic acids. Asphaitenes ‘Asphaltenes are particular molecules in crude oll and in fue oll witha high molecular ‘weight and, because they are not soluble in certain solvents in crude oll and fuel ol, they remain as separate ‘solids’ in suspension in the fuel. They are found especially in fue! produced by modern refineries. They cause problems if they come out of suspension and form a sludge. Hydrogen Sulphide Hydrogen Sulphid present in crude the stored fuel refinery process. Vanadium | found in crude oil from certain geographical areas (especially resent inthe resultant fuel and in addition to its contribution th any sodium present, form compounds which depress the the exhaust. Vanadium is am ‘western Venezuel to the ash level, it can, melting point of the ash Sodium Sodium is a metal found in crude il, Its presence can be the result of the use of sodium hydroxide to remove hydrogen sulphide in the present as 2 sait in salt water. It can be pros present as a contaminant from transportation level, ican, with any vanadium present, form compounds point ofthe ash in the exhaust, Water in the refinery, storage a ‘also contribute to some of the other salts found 15 transportation. Ifitis sea waterFittest uch alae wn aeiel in the fuel (especially sodium and magnesium). The water content also affects the specific energy ofthe fuel. Sulphur Sulphur is found in all crude olls and is not removed from residuat fuel oll during refining. It can be removed from distillate fuels after refining. The quantity of sulphur affects the exhaust emissions and affects acid deposition within the cylinders of engine. The sulphur content also affects the specific energy of the fuel. also affects the specific energy of the fuel. There is a specific requirement to identify the sulphur content of fuel supplied detailed in MARPOL Annex VI. Aluminium ‘Aluminium is one element used as a catalyst talyic conversion plant in a refinery and Is always present ‘compounds wich contain be proportion of aluminium to silicon varies from one pr on Iron ‘Any iron found in fuel oll comes from iron particles from pipelines and valves and from Italso comes from rust. Iron from engine wear the wear of moving metal component ricating oll added to the fuel. ccan be found in any waste automotive Nickel Nickel is an element that comes from the crude oll. Its tested in order to provide @ jnature’ for an oil sample. Sulphur, vanadium and nickel content cannot be reduced by treatment, so two samples claiming to be of the same oil, if they are the same oll, will have very similar levels of sulphur, vanadium and nickel. Calcium Calaium can be present in crude oil but also forms part of the ‘signature’ for the presence of lubricating oi Magnesium Magnesium is from salts in sea water. The presence of magnesium (oye) Dens max [600 908 “| Dens imax [800 900. cq Dens imax [920 520.9 Dens [ax [960 980.8 is o place the sample into a steel tube and Densi max 978 975.9 xr than the diameter of the tube, to fall through the Commie imax [980 $809 sample under the influence of gravity. The time it takes for the bal to pass two poin's ay ina 9948 —| along the length of the tube is measured. [Density [kgire [max___[1010_| 1000-4 lia stated atthe temper Figure 24. Dena table tument (50°C for residual 3s and 40°C for distilates). Specific gravity (SG) There are @ number of difere gravity of fuel ols made as the rato of density of #boratories are fuly automated fh both being measured at 60°F. The result has no MuSt Pe use °F. rument and those favoured by the 180 3104 test method Units, being stated as SG a aePUN iuea el tured gst TASES) Spice amount of warn te sorte, ami 1@ result can also be influenced by the presence of solids, so the sample is mm/s but in the bunker industry It is routinely The reporting temperature is 50°C for residual fuel and 40° C for Spec [85% confidence In [98% confidence out Paranal it {spec t=<(supplier)_|of spec I> (buyer) scosiy @ 40°C a6 34 viscosity @ 40°C har [14a viscosity @ 40°C 28 578 viscosity @ 40°C 74 628 Viscosity @ 40°C 05; viscosity @ 40°C 134 [Viscosity @ 50°C 28.7 31.3 viscosity @ 50°C 765 a3 Viscosity @ 50°C [mils |max [100 [1722 1878 [viscosity @ 50°C |mmiis [max [300 [3654 396.8 Viscosity @ 50°C |mm's [mex [700 [608.4 7308 Figure 24. Viscosty table a Copper strip corrosion of the strip after the test is compared against a standard, The result is quoted as a number from ta to 4c. Distillation range This is not part of the ISO 8217 standard. The test method is ASTM D86 or ASTM. . tis @ routine requirement for many naval vessels. The sample Is heated sively higher temperatures and the amount of product recovered in the ‘condenseris recorded. There are two ways to reportthe results; either the temperatures are reported for the percentage of product distiled (for example, 5%, 10%, 50% and 90%), or the distillation percentage is reported for certain fixed temperatures (for ‘example, 300°C, 340°C and 370°C). Hydrogen Sulphide (H,S) Hydrogen Sulphide is not part of the ISO 8217 standard. The laboratory test used is IP 309 for H,S in liquid. It uses spectrophotometty. The test is complex and time consuming. There is an alternative, ASTM D 5076, which measures the H,S in the vapour produced when nitrogen is bubbled through the sample by passing the vapour through ‘Draeger uwich changes colour wher is designed. The level of ‘sample of the vapour through Draegé ‘The level of H,S in the headspace of a tank cannot be predicted from the level of H,S in the liquid as itis influenced by too many dynamic fa is not practical to contfol product quality by specifying headspace vapour lev 10d under development for measuring H,S ‘method should be in use from 2008 but does not yet have an provisional method should be published in 2009, “Tne unit for hydrogen sulphide is ppm. Water (H,) ‘The test method in the ISO 8217 standard is ISO 3733. The water is measured by boiling the sample luene, condensing the vapour produced and measuring the volume of water collected from the condenser. ‘The unit for water is % viv. 35PAN INTRODUCTION TO FUEL ANALYSIS Pe i rameter [Units “Tin max [epee mit poe f=<(supplier) |of spec f> (buyer) | feu [max —Jo3_o2 [oa [water——[9¢ wv [max [oslo os Figure 25. Water (H,0) table Carbon residue / Carbon residue 10% The test method i tho 180 8217 standard is ISO 10970, There are two version of this, one for residual fuel, DMB and DMC, and one for DMA. The gasoil testis car ‘out on the residue from distillation of the gascil (after 90% has been evaporated off). Earlier test methods were Conradson Carbon Residue (CCR) and Ramsbottom Carbon Residue (RCR) but the current standard test is often referred to as Micro Carbon Residue (MCR). In this test the sample is heated up to 500°C in an inert atmosphere (nitrogen) so that it will not catch fire, then cooled and the residue is weighed. ‘The unit for carbon residue is % mim, The test subjects the sample to a beam of radiation and compares the radiati emitted to the radiation from a standard. The different methods relate to different techniques of analysing the emitted radiation. Note that the results are dependant on the correct calibration of the equipment. “The unit for sulphur is % mim, _ Parametor|Unite —[inmax [spec tint Be canieenos ot én is of spec I> (buyer) [Sulphur —[mgikg [max oT [oat - Sulphur —_[matka [max iatenee Ti08 | suptur [mot [max [18 1.58 | [Sulphur —[mgikg [max 2.0 _ 24 - Suphur —|rgig” [max [35.30 her : [SuphuImotg [mex 48429 — a2 : Figure 27. Sulphur (S) table Total Sediment Existent / Total Sediment Potential / Total Sediment Accelerated The test method in the ISO 8217 standard is ISO 10307, This test series was developed from the Shell Hot Filtration Test and occasionally referred to as SHFT. ‘The sample is heated and drawn through two paper fers by a vacuum. The sample ‘must have completely passed through the fiter apparatus within 25 minutes for the result to be valid. The result is obtained by the difference in weight of the two filters after the test Toe Jilin [p00 [85% confidence n [85% confidence oat] Parameter [UKs linux spect =<(eupplr) | of epect> (buyer Carbon ese [mim max Jos —Joza_ Jose - ‘Garbonescuo | % min-max 23 fermamua Carbon residue _|% mim [max a a [Carbon residue |% mlm | max 18 15 [atbon restive | rn [max he [arbonresdue | vin [max 7 7 7 argon residue [% mim_[max [is ae Carbon reve | mn_[max i [_— [Carbon resdve 705 [3 min-max oze 035 Figure 26. Carbon residue table Asphaltenes This is not part of the ISO 8217 standard, The test method normally used is ASTM 13279 or IP 139, where the sample Is dispersed in n-heptane (a solvent) and then filtered. The ingolubles are washed, dried and weighed giving the percentage of asphaltenes present. The unit for asphattenes is % m/m Sulphur (8) ‘There are two test methods in the standard ISO 8754 (xray uorescence ~ energy dispersion) and ISO 14596 (x-ray fluorescence — wavelength dispersion). In case of a dispute, the standard rofers to ISO 8754 as the reference method, aaPO TMusehileuen eda, Wia ce called Total Sediment Existent (TSE). It may also be carried out after feat 100% for 24 hours fo ego tho cample, The resus the Tots ASTHTRAGT Tp ‘Adsorption Sot (TSP). A second option i o add cotane fo the sample and heat -—Baetsroundl SE to 100°C for one hour, which gives approximately the same ‘ageing’ effect in a much shorter ime, This is the Total Sediment Accelerated test (TSA). The TSP and TSA results are usually quite close, but note thatthe standard refers tothe TSP tes. |, ‘The diference between the TSE and TSP (or TSA) results can give an inciation of tho stability ofthe product | Test methods are : +180 10207-1 for TSE 2 | + 180 10307-2 procedure A for TSP e a + 180 10307-2 procedure B for TSA ‘The unit for TSE, TSA and TSP is % mim ES 5% eontidonce out ~ Parametor [Units [Min max [Spee nit are certincs oy Tal 1 3 Sediment [nvm |mex jor oos 0.19 Extent " 7 a Sediment |%6 mim | max + |oas 018 Pate | _ - Figure 28. Teal sediment able 4 Compatibility This Is not part of the ISO 8217 standard. The test method used is ASTM D4740, A drop of the sample is dripped onto a fiter paper and allowed to dry at a specified temperature. The drop will spread and form a spot. A stable blend should leave @ larger spot of uniform colour. A spot of unstable fuel will have a large light-coloured ‘spot, with a smaller darker spot within the large spot. The rest e quoted as ‘a number from 1 to 5, where 1 indicates a uniform spot and 5 indicates a separate distinct dark spot in the centre, There are no units for the spot test, just a number, from 1 to 5, Figure 20. Exampies of Rating Numbers of Typical Spots aR 39‘ANINTROBUGTION 10 FUEUANALYSIS Ash ‘The test method in the ISO 8217 standard is ISO 6245, The sample is burne « crucible and then the residue transferred and heated in a furnace at a sp temperature until only unburnable residue remains. The result is determined by weighing the ash Figure 31. Ashing a sample ‘The specialist fuel analysis laboratories only use the above method when the ash is in dispute. They normally use a modified method which allows them to take the ash after testing and use that for the determination of metals as mentioned below. The results from the modified method are usuelly slightly higher than the standard test method. The units for ash are % m/m, cal T 35% confidence in [85% confidence out Parameter]Unts _|¥inmax_[Spectimit [SS contanes [9S confers sh [enn Imax oot oor __|o.o2 sh} % mim max 0.05 [0.08 (0.08 - Ash |% dn —|max Jo. 00 at [sem [max [0.15 To. 016 Figure 32, Ash tablo Tests for metals Specific test methods for determination of the presence of vanadium use the same equipment as the test for sulphur but with a different procedure. The method in icon uses either an Inductively Coupled Plasma n Spectrometer (|CPE) or an Atomic Absorption Spectrometer (AAS) with a specific test method, ISO 10478, Sometimes these two are abbreviated as ICP and AA, 40 ‘The testing laboratories making tests of metals for routine analysis generally use a diferent method for these and other metals. Ths is IP 501, which uses the Inductively Coupled Plasma Spectrometer (ICPE) method, or IP 470, which uses the Atomic Absorption Spectrometer (AAS) method, The reason for using one of these tests Is that Just one procedure will produce the results for ail of the metals below in one test ‘They will only need to run the ISO standard test method if there is @ dispute. The most common method is the IP 501 test, In the test method, the ash (from the ash test) is treated with a flux to produce a liquid which can be injected into the measuring ‘equipment. The equipment uses a very high temperature (more than 6000°C) form of a plasma to reduce the metals in the liquid to atoms which will emi can be detected by a spectrometer. Each metal gives off light at different wavelengths {and by measuring the amount of ight emitted at each wavelength, the equipment can identify not only each metal but also its concentration. The diagram below shows a simplified layout of the ICPE equipment. awajsks go ue yo snewaung “pe eunfiy g a|2 gy) 3 si 3 g 2 \t e s 3 | 3 z ia | . g 3 2 ei FL IQ T By UpT yee lis @ g eee ee 3 i fei ik? earls 3 Fouoniboss oppey = a Niue Figure 25. Determination of motals By Atomie Absorption Chromatography 2M. cutesy of np ICP Spectrometer ‘The plasma ‘flame’ is argon gas which is heated to nearly 7000°C by radio frequency induction The plasma is held at the top of three concentric tubes. The outer tube carries the coolant gas (nitrogen), the middle tube argon for the ‘flame’ and with the sample supplied as a liquid, converted to an aerosol in a nebuliser and passed in the cartier {gas (also argon) up the inner tube into the flame. Here the metals give off thelr own characteristic wavelengths of light. These pass through Into the polychromator, where each separate light wavelength is sent to a detector which determines the amount of of that wavelength emitted ‘The computer interprets the result into individual metals and thelr concentrations. is a high technology version of the workshop spark test, where engineers would test a metal by holding it against a grinding wheel to observe the colour of the sparks siven off Each device has its own particular strengths and weaknesses but provided the methods are followed, the calibration of the equipment is correct and the method Used has published data for the repeatability and reproducibility of the results, they Provide a generally reliable way to identify the metals in the sample tested, o 43PAIN 2) Louie] anon gute /e16 Alto Aluminium plus Silicon (Al + Si) ‘The test methods in the !SO 8217 standard are ISO 10478, IP 601 and IP 470. In case of dispute, the standard refers fo ISO 10478 as the reference method ‘The units are mg/kg. 35% confidence in [98% confidence out Parametar|Units [tin max | Spec imi | 9 ores | OF ance Iter) ‘Asuminium Micon” [mora max | 80 64 96 Figure 36. Aluminum plus Silcon (Al + S) table Vanadium (V) ‘The test methods in the ISO 8217 standard are ISO 14597, IP 501 and IP 470. In case of dispute, the standard refers to ISO 14597 as the reference method. The units are mgikg. [95% confidence in| 95% confidence out Parameter| Units |inmax | Spec timit of spec if> buyer. Vanadium |mgikg [max | 100 Vanadium | mgikg—|max [150 Vanadium [make [max [200 Vanadium | mg/kg max 300 Vanadium | mgfkg max | 360 [Vanadium [mg/kg | max 500, [vanadium [mag [max 600 Figure 37. Vanadium (V) table Sodium (Na) Sodium is not part of the ISO 8217 standard. The test methods used are IP 501 or 1P 470. ‘The units are mg/kg. Iron (Fe) Iron is not part of the ISO 8217 standard, The test methods used are IP 501 or IP 470. The units are mglkg. Nickel (Ni) Nickel is not part of the ISO 8217 standard. The test methods used are IP 50% 470, 44 sees The units are moi. Calcium (Ca) ‘The test methods in the ISO 8217 standard are IP 501 and IP 470. The units are mg/kg. vramater [unt [winmax Tapoc nn [98% confidence in [85% confidence out Parameter [Unis _ [Minas [Spee limit |specit=e(supplon)|of spec > buyer) (caicuin [mai [max 130 {7 EA Figure 0. Coleum (Ca) bio Zine (2n) ‘The test methods in the ISO 8217 standard are IP 501 and IP 470. The units are mg/kg. saan | re inmax |Spoc timit [95% confidence in [95% confidence out erates [ta | ‘Spee limit | spec if =<(supplier) | of spec i> (buyer) zine Tigig [max |78 13 7 Figure 39. Zinc (2n) table Phosphorus (P) The test methods in tho ISO 8217 standard are IP 601 and IP 609. The units are mg/kg. SER confidence out Parameter [Units [Min max |poe tim . i Spec mit of spec if > (buyer) Phosphor [maka ~tmex 118 8 Figure 40. Phosphorus (P) table Magnesium (Mg) Magnesium is not part of the scope of the test method so no precision data is availabe, ‘The units are mg/kg. Lead (Pb) This is not part of the ISO 8217 standard but the test methods used are IP 50’ 470. 45ee This metal is not part of the scope of the test method so no precision data is available, ‘The units are mglkg, Potassium (K) Potassium is not part ofthe ISO 8217 standard but the test methods used are IP 601 or IP 470, This metal is not part of the scope of the test method so no precision data Is available The units are mglkg. Pour point The tost method inthe standard is [SO 3016. The tet involves heating the sample ina cyindcal container to 46°C, then allowing th ol to coo, ting the container to the horizontal every 3°C and observing the movement of the oi, When the ol does, not move within a certain time, the pour point as been reached (the result being 3°C higher tran the point at which the sample no longer lows The units are °C. [arametor [unis [win mex [Spec unt [88% confidence in [85% confidence out Pourpomnt [SC [max [6 7 _ Pour point [°C max fo ~ a —_ [ourpon [Cmax Js l2 rn Pour point [°C —_|max 124 — 28 our point [SC max [30 [2s The Figure 41, Pour point obo Flash point 180.2719, The test uses the Penskey-Martens test apparatus and this equipment is specifically ions for storage of fuel on ships. The test method in the standard Closed Cup (PMc) flash poi referred to in the IMO’s SOLAS regu The sample is placed in a temperature bath and its temperature slowly increased ited. At each 1°C change, a naked flame is introduced through an ‘opening in the top ofthe container. The flash point is registered when a flame is seen 10 spread across the top of the sample. There are more modern test methods under investigation but the legal status of the PMce means that this test has to be used. ‘The units are °C. Se tise 98% confidence in_ | 95% confidence out | spec if=<(supplier) | of spec if> (buyer) at [ss ttin mex [Spec Paramter| Unite ssh point |°6 nin 8 Fiash pont [min [0 Cloud point ‘The test method in the standard is ISO 3015. It involves cooling the sample until wax rystals are observed to form a ‘cloud’ in the sample. This test is only relevant for grade DMX. The units are °C, [95% confidence in] 85% confide 0 out | Spec limit | spec if =<(suppler) | of spec it > buyer) 1 [parameter Units ‘Min max ‘Cloud pont °C mex |-46 ara Figure 44. Cloud point tabio 46 47AN INTRODUCTION TO FUEL ANALYSIS. Cetane Index The test method in the standard is ISO 4264. It requi and the temperature for three specific points on the range). ‘There are no units, the density of the product tion curve (see dist unis [ai moe [pesmi [9S contne in, [95% conrdene it [min [ase at unit min 40, 42 _ 38 unit min 45, 47 a 43. Fire 45 Cote dentate Acid Number of the full standard. The test method in the informative annex of the ‘The units are mg KOH /g (KOH Is the symbol for Potassium Hydroxide). Microbiological contamination ‘This Is not part of the ISO 8217 standard. The normal test method would be ASTM (06974 but the test most often used is a proprietary test, ‘Easicul’, which uses prepared {est strips which are immersed in the sample. After expost strip Is compared ‘number of ‘colony-forming units’ (CFU) Below 10*'s, or 10° is moderate infection and above 10” is severe contamination. Organic contaminants ‘These are only covered in the standard if they are in breach of Clause 5.1. They will usually be picked up in a Fourier Transform Infra Red (FTIR) spectrometry screening and then Identified by Gas Chromatography-Mass Spectroscopy (GC-MS). Both of the above are covered in Chapter 9. Equivalent tests h test method is to be used for each parameter. stipulates which te be used in case of a ISO test methods except for a very few for which these cases, the test methods stipulated are IP Energy Institute) test methods. {isthte of Petroleum, now rena There are many other test methods in regular use worldwide. Some aro ASTM test methods. Others, usually new methods awaiting formal acceptance and ratification, issued by commercial companies. Many of today's standard test methods were the laboratories of the ‘companies. ‘accepted for inclusion in the catalogue of i ries around the world to ensure 's independent ofthe operator and This is done by the laboratories participati the laboratory performing the ‘round robin’ programmes, where they test identical samples and the res | _slastcaly assessed, This contibutes to the production and revision ofthe ‘pre data, their time analysing many products, not just marine fuel, and may routinely use, for ‘example, an ASTM test method rather than an ISO test method. That does not mean that the results not to be trusted or may be different if the method in the standard is used For the lay person itis confusing to be confronted with an argumenton sulphur analysis 104204. Ths Is especialy 50 when he has to be done using ISO 8754. In pr standard stipulates ISO 8754, then thats what must be used incase of dispute, Why do the laboratories use different methods? Some methods are more expensive than others, some methods are faster than others, and some methods can be automated whilst others cannot. There are many factor laboratories which specialise in marine fuel testing will normally use the ISO test methods throughout, as stipulated in ISO 8217. Test method date identifier ft unchanged, then the number is. rated by appending the new sst method ISO 8754:1992 has ‘method isthe same but the test precision 19 composition of modern fuels. lent tests but needs to be treated with he test equipment is identical, small differences in procedure will sive a potential difference in the results. unchanged. But the new reproduc! date to the test method. For exampl been supersededby ISO 8754:2008. Th data was r 48‘Sample volume and time for result YO ie aera Pari se [ask Rober 1288, — | Tho folowing table gives the approximate volume of sample needed and the typical [aiuninim Ez as | time taken forthe routine test methods used by the specialist fuel analysis services. 2. Paramoir Soriple volume mi] Tine taken] Remarka [nspaones Ack Number Sr 25h, Ao pteniomatic rr eae tin Ast anele [Carbon residue tga a The odio a ! a ae determine metals es | TReatones Toa Bs Cid | [eam sh sala = aa Caton rete Ido WORT s675 or 12185 | Catan inde Auto dit ara [cba on Cota itr uoging point [Ae 7 7 Compatiity Fash pont Soci Cooper ord rgon Suphice a Donsiy io Bou [nesioneprewre roeraro Setaton ren [ional [lead Pe Fash pat [Magnes _ Hycrogen SuBhide Headspace Baper tect ingen enpeatee Catulalon Nickel sehecate ia fehsamoe Phosthons soto ste i [te [Ash sarpe Passi 2 as [Magnes ash sample Per oot Mroboloical coraninaon [20m Bite —|sia — kl ah 50% 0 70 t seme ach some afea or 14806 [6 8 f ou a eal Tol SeanariAosisaied 1 - - ha iol Sone xr ea ate empl : “ial Sediment Potrtal aaa cho Calaaion [Venedium tag | EDXRF [Viscosity | Visual ppearance = ~ | en [water rz —_— [ne 1 ash samo — Figue ‘entity of ‘equivalent’ tests table 50mi O.2he | Autovis vel appearance Water Soccer| atv | Bon BS Ze ash sample 50 =f Figure 47. Sample volume and tine for result tableANINTROBUCTION TO FUEL ANALYSIS Chapter 7 - Interpretation of results i a ne ISO 4259 probebilty 12 average score wil reflect hs true ability. Our problem is that our champion lab technician) normally only fires one arrow. True value Ifwe ask our laboratory technician to test a sample to determine the viscosity at 50°C, he wl perform he tes rl rode an ano, If we ask him to repeat the test on 10st probably get a slightly different answer. The more tests Me doos tha Senet average othe fouls il bo the te val. The satis concerned here is haw easy Is it to repeat the test and got the true value. This is the repeatability. Itwe get the test done by a different laboratory and a different technician using exactly the same sample and the same test method, we will probably get a different result ‘The more laboratories we try, the closer the average will be to the ‘tue value’. This time, the statistic is how easy it Is to reproduce the test and get the true value, This is the reproducibi Reproducibility allows us to link the result we have from a single test with a degree of confidence that that result isthe true value iespective of where the testis done. This is where we have to think about statistics. out 2% 24% 01 00 04 02 03 of do 20 to op to 2 30 Figure 48. ‘Tve volue chart ‘The distribution of test results around the true value follows a well known statistical pattern, Statisticians talk about confidence that a single result is correct on the basis 57 53‘AN INTROBUCTION TO FUEL ANALYSIS. tue value. Effectively that le, a 95% chance that itis For analysis, we work with two standard deviations or 95% confidence. For every test method, the controling institutions (ISO, IP, ASTM) publish factors for repeatability and reproducibi ‘Our concem is with reprodi be applied, 95% confidence level ‘The objective is to find the true value of the parameter which is bei would be the average of an infinite number of tests on the same samol statistics we can find a point at which we have 95% certainty that the specifi limit has been exceeded. Each published test method has associated precision data identifying the repeatati (7) and the reproduci there will be separ precision deta mey be diferent fr diferent ranges of values for each parameter plus the reproducibility, : umber or a formula including the limit value. It depends on the test parameter and method. i 95% confidence buyer's formula example For a 380 cSt fuel Viscosity reproducibility = R which is 0.074 * the limit value. ‘The 95% confidence of failure is 380 + (380°R*0.59) = 396.59 cSt. 95% confidence seller’s formula example Fora 380 cSt fuel viscosity reproducibility = R which is 0.074 * the ‘The 95% confidence of fallure is 360 - (3B0°R'0. If the result is more than 363.41 ¢St, he cannot have confidence that le the specification, Note that for a seller, with & maximum 0.59. Allofthe above is described in Annex F of the ISO 8217 specication. For some reason, many suppliers are happy to refer buyers to the buyers formula for the 95% confidence limi but seldom acknowledge the seller's formula, equivalent 95% confidence upper and it Value, he must subtract the reprodu: Included for g iin [95% confidence out of spec it> (buyer) (Calcium malkg ‘Carbon residue % mim (Carbon residue 3 rim (Gatane index uit Getane inciex unit [min 8 |max [18 [174 gin® |max [890__| 689.4, ikgim® [max [900 | 860.1, kgim® [max [920 | 919.1, gi [max [960 | 960.1, ikgim® [max [975 [974.1 55PMRinccemence mei tlaueunineis Flash point ee Tmin [a Flash point = [min [60 Phosphorus max [15 ur point eo [max [8 fo 6 max |24 30 max [2.0 Viscosity @ 40°C | mms [min Viscosty @ 40°C | mms | max Viscosity @ 40°C ___[mmils [max Viscosiy @ 40°C |mmrls [max Viscosity @ 4° [mais [max Viscosty @ 50°C | mmels [max Viscosity @ 50°C _|mmile max Viscosity @ 50°___|mms_|max Viscosity @ 50°C mms [max Viscosity @ 60°C [mnie [max Water 6 viv [mae Water viv mex Zine malig | mex Figure 49. 95% confidence level table ‘The convenor of t produced a note ‘concems sulph 1 application of ISO.4259 which | quote here. Her note applied to any parameter in the standard. 1up which deals with ISO 8217, Wanda Fabriek, has “Ig the supplier and buyer cannot reach an agreement about the sulphur content of a fuel, Clause 10 of 150 4255, entitled ‘Acceptance and rejection rules in case of dispute’, gives the appropriate procedures to be followed. The Procedures only cover the situation where each laboratory is analysing fuel samples that are Subdivisions from one representative sample. In addition to provision of the supplier's safety margin calculations, clause 9.1 of 180 4259 states that ‘a reported vaiue between the specification value and the calculated limit is not proof of non- compliance’. such cases would nead to be further investigated by additional testing of the original representative sample. In this scenario, Lab One and Lab Tvo would produce fone result each, marked here as Lixl and L2x1. Both results are accepted when their difference is less than or equal to test method reproducibility Lil ~ L2x] < or = to &. The average of these two results shall be considered as the estimated value of the sulphur content. However, when Lixl ~ 12x > R, both results are suspect and each laboratory will need to obtain at least three other results. ‘The procedure and calculation for the resolution of a dispute based on further testing is fully described in 10 4259.” It is important to understand that a single result inside the ‘grey’ area of the 95% confidence boundaries does not indicate that the fuel IS on specification, only that it should not be rejected out of hand, European Union procedure for control on Sulphur ‘The European Union (EU) stipulates in Directive 32 of 1999 and Directive 33 of 2005 thet the determination of the sulphur content shall be assessed in accordance with test methods and that in case of dispute the procedures of ISO 4258 must be followed. MARPOL procedure ‘The verification of sulphur results is important for vessels areas which are subject to sulphur restrictions by law. The legislators working with MARPOL rules Were unwiling to foliow ISO 4259 and have produced a specific protocol in any case \where port state control requites verification ofthe level of sulphur in fuel MARPOL verification. This is my own précis of the agreed protocol (the protocol is ‘uite long), 56 57AN INTROBUCTION T6 FUEL ANALYSIS 1g@ of the two tests is less than the it, then the other two portions ar OK, otherwise the fuel is non-compliant ‘The actual procedure is as follows. Fuol Oil Verification Procedure for MARPOL Annex VI Fuel Oil Samplos ‘The following procedure should be used to determine whether the fuel oil delivered to and used on board ships is compliant with the sulphur limits required by regulation 14 of MARPOL Annex VI. 1 General Requirenente 1.1 The representative fuel oi1 sample, which is required by paragraph 8(a) of regulation 18 (the “MARPOL sample’) shall be used to verify the sulphur content of the fuel ofl supplied to a ship. 1,2 an Adninistration, through its competent authority, should manage the veritication procedure. 1.3 The laboratories responsible for the verification procedure set forth in this appendix should be fully accredited for the purpose of conducting the test method (s) . 2 Verification Procedure Stage One 2.1 The MARPOL sample should be delivered by the competent authority to the laboratory. 2.2 The laboratory should: +1 record the details of the seal number and the Sample label on the test record; 2 confirm that the condition of the seal on the MARPOL Sample has not been broken; and 3 reject any MARPOL sample where the seal has been broken. 2.3 Tf the seal of the MARPOL sample has not been broken, the laboratory should proceed with the veritication procedure and should -l ensure that the MARPOL sample is thoroughly Homogenised? +2 draw two sub-samples from the MARPOL sample; and .3 reseal the MARPOL sample and record the new reseal details on the test record, 2.4 The two sub-samples should be tested in succession, in accordance with the specified test method referred to in Appendix V. For the purposes of this verification procedure, the results of the test analysis should be referred to as ‘A’ and "B’, 58 (ested and the average of al fours assessed, | :1 If the results of ‘a’ and ‘B/ are within the Fepeatability (r) of the test method, the results should be considered valid, .2 Tf the results of ‘Ar and \B’ are not within the Eepeatability (r) of the test method, both reaules should be rejected and to new sub-aamples should be taken by the laboratory and analysed. The sample bottle should be resealed in accordance with paragraph 2.3.3 above after the new sub-samples nave been taken, 2.5 If the test results of ‘A’ and ‘BY are valid, an average of these two results should be calculated, thus giving the result referred to as ‘x’. :1 If the result of ‘x’ is equal to or falls below the Standards required by Annex VI, the fuel oil should be deened to mest the requirenents. .2 If the result of ‘x’ is greater than the standards Eequired by Annex VI, Verification Pracedure Stage Two should be conducted; however, if the result of *x' i3 greater than the specification limit by 0.59R (where R is the reproducibility of the test method), the fuel od should be considered non-compliant and’no further testing is necessary. 3 Verification Procedure Stage Two 3.1 If Stage Two of the verification procedure is necessary in accordance with paragraph 2.5.2 above, the competent authority should send the NARPOL sample to a second accredited laboratory. 3.2 Upon receiving the MARPOL sample, the laboratory Should: <1 record the details of the reseal number in accordance with 2.3.3 and the sample label on the test record; +2 draw two sub-samples from the MARPOL sample; and +3 reseal the MARPOL sample and record the new reseal details on the test record. 3.3 The two sub-samples should he tested in succession, in accordance with the test method specified in Appendix V. For the purposes of this verification procedure, the results of the test analysis should be referred to as °C’ and “0, <1 Tf the results of 'c’ and ‘D’ are within the Fepeatability (r) of the test method, the results should be considered valid. 2 If the results of ‘Cc’ and ‘D' are not within the Tepeatability (r) of the test method, both results should be rejected and two new sub-samples should be taken by the laboratory and analysed. The sanple bottle should be resealed in accordance with paragraph 3.1.3 after the new sub-samples have been taken. 59AN INTROBUGTION'TOFUEUANALYsig are valid, and ‘b! are within the Feproducibility (n} of the test method thet te akeratory should average the results, which is referred to as‘! -1 If the result of ‘Y" is equal to or falls below the Standards required by Annex VI, the fuel oll should be deemed to meet the requirements. 2 Tf the result of *Y is greater than the standards Required by Annex VI, thea the fuel oll fails to meet the standards required by Annex VI. 3.5 TE the result of ‘AY, ‘BY, ‘Cr, and ‘DY are not within the reproducibility (R) Of the test method, then the Adninistration may discard all of the test results and, in its discretion, repeat the entire testing process: 3,6 The results obtained from the veritieation procedure ate final. a chiens ue Chapter 8 - Problem results \No introductory book can hope to present answers to all ofthe problems that can be identified as a result of fuel analysis. This chapter is Intended to give some general guidance on a number of the more common problems and comments on the technical aspects of some parameter results. Density ‘The main limitat handle the prod Conventional centrifugal separators, also known as purifier, ra with residual fuel is the abilly of the onboard treatment plant to ‘separates into solids, water and ‘clean oll. is filed with water, and itis the presence of fo in density between the fuel and the water. Once the fuel density ig kg/m’, the design limit ofthe centrifuge water seal is reached, and the seal is likely to break down. Practical experience shows that, with careful operation, the seal can be maintained up to 982 kg/m but this is not guaranteed. ‘Some centrifuge designs do not use a water seal and are intended to work effectively on fuel densities up to 1010 kg/m. These centrifuges still collect the solids and separated water atthe periphery of the bow, but Instead of having a continuous ‘water outlet, the tow! Is opened to discharge the solids and water when an electronic sensor detects water in the clean ol outlet Injection viscosity Most engine builders recommend that residual fuel should be injected at a viscosity between 10 and 15 mm/s (cSt). If the fue! injection viscosi t ‘greater than 15 cSt, then there isa chance that the fuel spray cylinder, causing damage as the oil bums. Ship builders will ensure that the fuel handling plant is able to heat the fuel toa temperature high enough to ensure that the fuel grade specifid can be lower end of the engine builder's range. This should be achievable with one heater in reasonable working order. All vessels will have at least two fuel oll heaters. 60 61| i) AN INTRODUCTION TO FUEL ANALYSIS. The table below indicates the viscosities and temperatures which can arise if the wrong grade of fuel supplied. Delvaadvieoaly ets 57° me Bo eas De ‘2e00st 138°C ones 0 420 cSt 146°C am 480 cSt 149°C ~ ers las or ery or we 680 6St 155°C } += Notional 180 estlimits. = Notional 380 cs it Figure 60. Injection viscosity temperature table ‘is only a guide, as the actual relationship between viscosity and temperature itferent for each oil and the constants can only be ascertained by testing the fuel different temperatures, It does provide a good reference, however, and should discourage rejection of a fuel on grounds of viscosity alone. Water Water in fuel can be present as free wate settling and centrifuge) or as an erulsi content of at least show that a combination of effective storage, water content of up t0 5%. ‘Water can contribute to the overioading of injection pumps, gassing and foaming of the oil, and raised combustion temperatures, Water, especially salt water, can increase the quantities of sludge formed and will, of, course, affect the energy content of the fuel Water is the one contaminant that can find its way onboard the receiving ship. This needs to be consi taken from a ship's tank samples. The principal is the heating ooils in fuel tanks. The main sources of salt water onboard ship are leaking tank hatches, leaks in sounding pipes on deck, and sounding pipes and vent pipes that pass through ballast tanks. settling, and purification can deal with a (o fuel on ships from sources when looking at an an: 62 Vanadium On its own, this metal has no significant impact on the performance ofthe fuel. High Jevels of vanadium will contribute to the overall ash burden and hence will cause an increase in the bulld up of fouling in the exhaust side of the engine. On its own, it should not give undue cause for concern. Sodium been contaminated by water, the result of sodium analysis will ter the water is fresh, brackish or sea water. If the cause is sea water contamination, the level of sodium should be significantly reduced by settling and the correct use of the centrifugal separator. This reduction will be much less if the water is in the {form of an emulsion is salt water contamination, then in addition to elevated sodium levels there will also be an elevated level of magnesium. Whi salt in sea water vary considerably, as a rule of thumb, 1% sea wal about 100 mgrkg of sodium and between 10 and 20 mgikg of magnesium. Salt water ‘contamination wil also tend to increase the quantities of sludge. Sodium / Vanadium ‘Many buyers are concerned about the presence of significant amounts of sodium and. vanadium In residual fuel. is common to see buyers specifying sodium content to be ‘at most one third dium, The presence of sodium and vanadi ting point of the ash in the ‘exhaust gas to be depressed. This can lead to deposits forming on hot parts of the ‘exhaust system. The deposits can lead to corrosion of the components as well as causing fouling of the system, This is not part ofthe standard but there is an informative annex in ISO 8217 on this subject. The International Bunker Industry Association (IBIA) has published a booklet on the problem. ‘The problem is less likely to affect slow speed engines with relatively low exhaust temperatures than medium speed engines with exhaust temperatures over 500°C, It is also unlikely to be significant i the levels of vanadium are below 100 mg/kg, a8 is the case with most fuels. Aluminium / Silicon ‘These two elements ~ always considered together (as per the ISO 8217 standard) Used as an Indication of the gu of catalyst fines present inthe fuel. The limit in based on experience and research in the late 1970s which identified that 30 mg/kg was workable limit for aluminium (Appendix 63ROicoecn sel een 8 of the old BSMA-100 standard). Because of the variation of the ratio of aluminium icon in many proprietary catalysts, the CiMIAC recommendations and eventually 30 8217 standard came up with a combined limit of 80 mg/kg for aluminium plug icon. This was ‘inferred’ from the 30 mg/kg aluminium limit. The effect of elevated levels of catalyst is important when the fuel reaches the finely-machined fuel injection ‘equipment at the engine. The level permed in the ISO standard would destroy the {uel pumps and injectors if it had not been reduced. If the purifiers are operating as designed, at the correct temperature, then using a fuel with 80 mg/kg aluminium end slicon combined as bunkered will not cause a problem if the content at the engine ts less than 15 mg/kg, At that level, the engine builders are happy. However, there are two areas of risk associated with the content level of aluminium and silicon. One is that the purifiers are not operating effectively; the other is that the quantity is within specification limits but the particle size is too large. The first is Outside of the control of the supplier, and often of the buyer. The second is notin the standard and is not measured. ‘There is plenty of anecdotal evidence of vessels using fuels with combined levels ‘of more than 150 mg/kg of aluminium and silicon without encountering problems (albeit with great care taken with the overall fuel treatment). Some operators have fuel treatment analysis records covering samples taken at each stage of the process, demonstrating an overall reduction from 150 mg/kg down to 12 mgikg at the engine, | have personal experience of this. Other operators have seen significant damage done to engine fuel injection equipment with aluminium and silicon levels below 80 mg/kg combined. In the latter cases, the cause was probably linked to heavy weather disturbing sediment laden with aluminium and silicon in the tanks on board. The disturbance caused by heavy weather can significantly increase the amount of, aluminium and silicon passing out of the storage tanks and raise it substantially above the amounts present in the fuel as supplied. Bunker buyers should also be aware that the reproducibility of the test is not Particularly good and should note the limits of the 95% confidence level as detailed in Chapter 7. Carbon residue The level of carbon residue in residual fuels can have serious implications, espe for older engine designs and for medium speed engines. The impact on engine ‘operation of elevated carbon levels is seen by increased deposits in the piston ring ‘grooves which can cause the rings to stick in the grooves. This will allow exhaust {gas to ‘blow by’ the rings, increasing wear, the risk of ring breakage and the risk of scavenge fires. Most modem slow speed engines can deal with carbon levels of up to 24% BUT as their buying specification will normally have a limit of 18%, itis not something that the shipowners like to do. If there is no alternative, the risks can be Feduced by running the engine at reduced power. Medium speed engines are much less tolerant of high carbon levels as the amount of time available for combustion in those is much reduced. Ash High ash levels willbe directly atributable to high levels of metals inthe fuel. Ifthe ash content is high, then observation of the indi hazards are described in this chapter in the sections on sodium / vanadium and aluminium | si Flash point Flash points a chellenge. The limit is statutory, absolute and the test method defined. The test method reproducibility is poor (see Chapter 7 for the 95% confidence limits). ‘The legal and commercial implications of a fuel which does not comply with the flesh point limit are considerable. Ifthe fuel has a flash point of below 60°C and the vessel does not have an exemption from the flag state, then that vessel is no longer complying with the conditions of class. If the vessel is out of class, then the Protection ‘and Indemnity (P&!) cover may be breached and, more seriously, the vessel owner may no longer have the protection of ity on the cargo under Hague or Hague-Visby rules. If a breach is discussed permission to use the fuel other problems mal the society will often grant In such as case, all of the Pour point High pour point indicates @ waxy fuel and that the fuel will need to be Kept at a ‘temperature of at least 10°C above the pour point to avoid the wax content settling out ofthe fuel. Vessel bunker storage tank heating is usually capable of maintaining a temperature of between 40°C to 50°C, but this would need to be checked. It is possible fo use an additive (a pour point depressant) to adjust the pour point, but this |s more commonly used with disilate fuels than with residual fuels, Sulphur Until 2006, nobody cared about the sulphur content of fuel oil, but now ithas become the biggest source of quality disputes. Because of the legislative requirement, there is ‘uch more attention being placed on interpretation of results as discussed in Chapter 7. The test reproducbily for sulphur is not perfect, and the results are very dependant ofthe calibration routines of the testing laboratory. The technical impact is negligible. Selection of the correct grade of cylinder lubricating oil is the only real issue, and even that is not critical in the short term. Running on the wrong lubricating oil grade ~ for example with a Total Base Number (TEN) of 70 instead of 40 TBN — for one month will nt have a serious long-term impact on the engine. TBN is a measure ofthe ability of a cylinder lubricating ol to neutralise the effect of acid formed in the cylinder as & consequence of the sulphur content ofthe fuel. ot 65Total Sediment Potential (TSP) A high reading for TSP is often interpreted as in fairy common to see emotive comments such as ‘this fuel is chemically falling apart’. A high reading on TSP may just moan that a fuel is very ‘drt. tis much more important, {0 compare the result for Total Sediment Existent (TSE) and the result for TSP. Ifthe ris much higher after ageing then it was before demonstrating that being held at an elevated temperature for a period of time changes the nature of the subject fuel Cetane Index This can be a problem with some medium speed and high speed engines. The cetane The faster the engine runs, the more here is no easy way to correct ths, Used Lubricating Oil ‘The presence of used lubricating oil level of calcium, phosphorous and zinc. Ifall three parameters exceed th ‘standard then this is evidence that the fuel contains used lubricating ol Studies by Alfa Laval and BP, published in 1999, demonstrated that the addition of 5% of lubricating cil to fuel oll could have a significant reduction in the separating cfficiency of the centrifugal separators or purifiers. The tests showed a reduction in separating efficiency of up to 4% in removing catalyst fines, up to 20% in removing iron and over 30% in removing salt water, ‘The limit in the standard represents a lubricating oll content of about 0.5% and, at this level, the impact on separator efficiency is very small bunker fuel is controlled by monitoring the imits in the Microbiological contamination (One problem area with test results showing high levels of contamination is the amount of time elapsed between the taking of the sample and the taking of the test, If there: is some level of contamination in the product and the sample has been left in a warm cation and undisturbed for a period of time in between sampling and testing, then the contamination level will increase at a considerable speed, When a bunker buyer's analysis (or a shipowner’s analysis) disagrees with the supplier's statement of quality, then it is usual to seek independent confirmation of the q Referee analysis ‘The majority of sales contracts include a clause to cover the referral of a sample for analysis to an independer erfication of quality. This is often called a referee or confirmatory analysis. Its usually provided for both parties to agree on the Pine eile choice of independent laboratory and in some clauses it allows for an independent referee from the Energy Ins ta laboratory ifthe two principals cannot agree. itis usual to exclude from the choice any laboratory which acted elther for the buyer or the in the initial notice or rejection of claim. There are occasions where very specific tests are needed and the only laboratory able to Undertake these tests is one that would have been routinely excluded. In such cases. « compromise is usually the best solution. The sample in question must be the sample defined conditions as the ‘representative’ sample, and this vi 1 time of delivery, ‘The supplier will provide the receiving ship with atleast one sample and will et least one sample for himself from that sampling operation. All of these samples will be Identified by labels signed by both parties and recording the details ofthe delivery, The referee analysis can take place using any one of these samples, but ONLY these samples, as any other samples taken (by the receiving vessel for example) recognised as having any relevance under the seller's sales terms and con the sellers sales terms and 8 one taken by the supplier Witness When a referee analysis is to take place, both present ‘to witness the breaking of the seals’ original analysis professionals who drafted early versions of the clauses in use for the witness to take any part in the analysis, the conduct of that analysis being left to the professionals at the laboratory in question. it has recently Deen noted that some buyers have appointed a professional to act as their witness and there has been an ‘ssue with how much that individual should contribute. It is quite common for one or other party to deciine the opportunity to witness but to request the laboratory to document the seal breaking and to submit photographic records of the sample botle, label and seal Challenge Ifa buyer wishes to challenge the results of tt demonstrate that the supplier's sample was not ‘ropresentative’. This is extremely difficult to do, especialy if no note of protest as to the method, location or conduct of the original sampling operation was lodged at the time of the sampling operation, The only recent successful challenges over a supplier's sample of which | am aware are those where @ manifest fraud was proven, This was coneeming organic acid Contamination incidents in Singapore in 2002. referee analysis he will have to 66 a7‘AN INTRODUCTION TO FUEL ANALYSIS aR Chapter 9 - Additional tests SS There can be contaminants in marine fuel which are not readily identified. Many are ‘obscure and if you do not know what they are you do not know what test to use. One solution, fist applied in the marine fuel Industry in the 1990s, was to use @ technique called infrared Spectroscopy together with a mathematical technique called a Fast Fourier Transformation. This provides a graphical signature of the fuel FTIR Fourier Transform Infra Red spectrometry invalves subjecting a sample to infra red light and examining the resulting light transmitted. The sample will absorb parts of the spectrum depending on the composition of the sample and, by analysing what is not ~absorbed, the composition of the sample can be represented. The method was slow 8s the frequency of each part of the spectrum produced had to be measured, ane ea 1@ using computer power (The Fourier Id be constructed froma single measurement thother Transformation) the whole spectrum coul ‘un, This produced a ‘signature’ of the sample and this could be compared known signatures for normal samples, It became possible to identity peculi ‘should not be there’. ryMIS erties aise urbe all fuels as a GC-MS technique which permits the vidual compounds in @ fuel sample. Gas Chromatography ules after whi ‘Tho equipment ely expensive and the test requires skilled and experienced staff to produce the results. In almost all cases of unusual contami GC-MS analysis that has identi only used when initial sc ‘The majority of problem contaminants identified in recent years have been organic ‘compounds which have caused specific wear or performance problems in diesel engines. Fuel Ignition Analyser / Fuel Combustion Analyser FIA-100/8 and FIA-100 FCA, Test mothod IP 541 This equipment is a constant pressure fuel combustion analyser which assesses the ts of a combustion chamber which is 10 those found in a modern diesel engine pressurised and heated to conditions si eS under partial load conditions. The process parameters are: charge air temperature ‘approximately 500°C, charge pressure 45 bar, fuel injection pressure 400 bar. 100 h is no longer in commercial use) produces a together with other data on combustion (FIA-100 FIA) and test method IP S41 produces gether with other data on combustion The alder instrumer Cetane Number (Ct ‘The more modem instrument fan Estimated Cetane Number (ECN) properties. ‘good fuel?JAN INTRODUCTION TO FUEL ANALYSIS Figure 55. Comtustion pressure wace chart m courtesy of Func Solutons AS Figure 56, Rate of heat release chart Diagn coun of 72 ‘The other data is as follows: lay: The time from start of injection to the point ‘where the chamber pressure is three bar above start pressure in ms used for calculating ECN start of combustion of the main component + can be different from ID, depending on composition light verses heavy ‘components EC - End of Combustion (Combustion Period): + long combustion period: heavy molecular weight ~ dificult to burn + smoke, ‘ash, particulates. Jong afterburning increased thermal load en cylinder liner + PMR - Position of maxROHR (maximum rate of heat release) + timing for maximum rate of energy release important for efficient conversion to mechanical energy > reduce excessive toad on piston rings + maxROHR - Maximum ROHR value: The maximum rate of rise of pressure in barims + rate of combustion — rate of pressure increase low value: inefficient burning + high value: high rate of pressure increase > may occur for 2-stage combustion, Ve proved of value with medium and slow speed engines and the use of rameters from IP 641 are being considered for inclusion in a future revision of the (0 8217 specification for bunker fuel. {tis claimed that the combination of these results can give a measure of the potential ignition and combustion properties of bunker fuel which can be used as a guieline for evaluating a specific uel for use on a specific engine. ‘The specialised fuel analysis services have consi perience withthe use of these techniques end wil advise thelr clients if they feel the use of these techniques is necessary. Noe that many commercial laboratories do not have the equipment or experience to Use these methods at ths time, 7”AN INTRODUCTION To FUELANALYSIS Parameter | Description Unit 0 Ignition dotay ms Ignition properties [MCD Main combustion delay me | CN [Estimated Cotane Number 7 EMC End of main combustion ms. EC | End-of combustion im | [mor Main combustion period ms Combustion properties ~ ABP. Aer burning period me [maxROHR_ | Maximum rate of heat release MPaims PUR Position of maximum rate of heat alaase | me Eneray NEC Net heat of combustion td Figure 87. Table showing extract of paramete as defined in IP 541 test mothod Turbiscan The test method is ASTM D7061. ‘This isa test used by some spec stabilly reserve of a residual fuel, ‘The sample is diluted with toluene and heptane which forces the asphaltenes to settle, even in a stable fuel. The turbiscan then measures the rate at which these asphaltenes settle by means of light scattering, referred to as the separability number (SN). An SN of ess than five indicates a stable fuel. An SN of between five and 10 is with minimum stabilty reserve, whereas an SN of more than 10 has no stabil t one of the services using this rent refers to the Reserve Stability Number (RSN), which would appear to be Ito the SN, There is published work which questions the consistency of the correlation between SN and the actual stability reserve ofthe fuel determined by laboratory dilution and ‘observation (CIMAC paper 198 of 2007). fuel analysis services which claims to show the Onboard tests ‘Some shipowners have equipped their vessels with a selection of onboard testing equipment. If used correctly, onboard test kits can provide ings and/or ‘confirmation of some of the characteristics of the fuel on board. In addition, there are a number of simple confirmatory tests which can be employed onboard without special equipment when, for example, a vessel needs to check if an analysis result .d0es in fect represent the fuel on board when a problem is indicated. ples of fuel already on board must be as representative as the vessel to take anything other than a spot sample. A. valve on the bunker tank is not good enough. The sample from a sample can drawn from mid height in the tank or from, 1@ pump is running. Do not take a sample from ssurised side of the fuel system as any water in the sample will lash off. Proprietary tests Viscosity There are a number of onboard test kits that will permit a quick assessment of the viscosity of a sample fuel. Most of those in use today employ the falling ball’ method, The sample is placed in @ container which heats the sample to an appropriate temperatureis reached, the instrumentit tipped through lowing the falling ball to pass through the oil sample. The time 's detected by sensors. The equipment is designed to give a result in viscosity at 50° Cin about 10 minutes. 75EMSs louteni xe ae ele Density Test kits for density usually have a packaged controlled heating system and permit the use of a hydrometer on the heated sample. The instrument will then calet the viscosity at 15°C. There is at least one portable cigital density meter which gives very good results from a hand-held instrument which uses a vibrating glass ‘U' tube sensor. Water content ‘Most kits for testing water content consist of a pressure tight coll which contains the sample and a chemical reagent. They rely on a chemical reaction and measure the ‘change in pressure in the call, giving a read out. They work in the range from 0.2% to 2.5% water. Compatibility interpreting the results, but the more sophisticated kits can provide good, consistent results ‘Sulphur ‘There is now at least one proprietary test system for use on board ships which claims. to give reasonable results for sulphur content. This uses the well-proven technique ay fluorescence, bi laboratory. For the moment, however, the accuracy of the results remains subject to ‘some debate. Aluminium and Silicon ‘There is now at least one pre system for use on board ships which claims togive reasonable results plus silicon content, butas yet, the accuracy of the results, especially the resolution, remains subject to some debate. The technique (ray fluorescence) may be subject to interference from other elements in the fuel hich could affect the resutts. Details of some suppliers of proprietary on board testing equipment are listed in Appendix |. There are many companies active in this field, with new products becoming available all the time, so | am not able to identify them all in this book. Remember that results from proprietary tests will not be accepted as definitive evidence that a fuel does not meet a particular standard. Emergency tests Emergency tests are ones which I have used to good effect when I needed to check ‘@ parameter of a fuel on a ship which had no on board test equipment. Viscosity Drip test: Obtain a sample of the fuel in question and a sample of previous fuel where the viscosity is known to be in specification. Place both samples in a location which will allow them to warm up to about 40°C. Fi , flat, polished surface — a porthole glass is good for this. Then lay the polished surface down flat and, using @ brass rod, place a drip of each sample, side by side about 2 cm apart, neat to the codge of the glass. Lift that edge of the flat surface up so that the surface Is at about 45 degrees to horizontal. ‘Then watch the of the surface, left by the two drips until the longest trail is near the other edge y the surface down flat is significantly different. By signifcantly difer than 15% shorter than the other. Water Crackle test: Obtain a sample of the fuel and place iti disposable aluminium food tray or clean disposable alu ot be more than 6 mm deep. Apply a flame to the underside of the container. if there is a significant amount of water present, the sample will crackle and spit. Sludge {fa vessel is experiencing a build up of sludge in to understand if that sludge Is asphaltenic or waxy ‘Take a clean, emply food tin. Half fil it with a sample of the sludge and stand the tin in very hot water. Ifthe sludge melts, itis waxy sludge. If it does not melt, itis asphattenie sludge. in metal tray (a clean ium pie dish works well) FS oF purifiers, itis important 76 77PUM oll enforce sor aie) Chapter 10 - The future ‘The ISO 8217 working group is consulting within the industry and working on {and information to be included in the next issue of the standard. The ‘membership of the group covers spot shipping companies and other intoreste and the concems of the interational community related to safe vessel operation and the need to reduce environmental pollution caused by the use of fuels, ‘At the IBIA Annual Convention in Cape Town in November 2008, Wanda Fabriek, the convenor of the working group (ISO technical committee 28, sub committee 44, working group 6) which is responsible for the standard, Identified the following reasons for early review of the standard. ‘+ IMO MEPC 58 — ratification of Revised Annex VI + Quality problems ~ related to acid numbers, presence of bio-wastes, of chemicals, causing corrosion, sticking of fuel pumps, damaged injectors, black out to start the engines with even + Blending practices - Sulphur reduction creating side effects like: elevated calalytic fines, presence of polymers and chemical waste affecting stability, ignition, combustion properties. ‘The current work programme ‘additional parameters, char and accepted test methods. ‘changes to the standard unless there is solid scientific evidence showing a direct link between a part property and its impact on the performance of the fuel in servic bbe acceptance of the test method and of the precision of the results (repeatability and reproducibil ‘Work is ongoing with regard to hydrogen sulphide te IP 41 ECN to dit potassium, asphaltenes, of extemal contaminants. {In addition, the group Is considering the impact of bio-derived components. probable that some of these wi Inthe next issue of the standard ‘but many items will need longer to establish the evidence needed to justfy inclusion. 78 79| Appendix I - Where to go for help i anc Websites Information and help For specific help the ol majors are a good source of information from thelr websites ‘and from thelr specific customer support departments. For example: + Shell Marine Products: http:/mww-shell.com/homelcontent/marine-er + Chevron: hitp:/imww.fammile.comifammifuel_home.asp «BP: htipsAww.bp.com/homepage.do?categoryld=64008contentld=59059 + Total: hitp:/www.marinefuels.total.comi. ‘There are a number of others: 11 Bunker Industry Association (IBIA) has members active 'spects of the Industry. IBIA can provide help and direct you to members who are specialists in many different fields: htp:/wawibia.net ing Science and Technology (IMarEST) is 2 jon: http imweimarest.orgitheimarest/default +The Institute of Mar ‘good source of technical asp + TheAmerican Bureau of Shipping (ABS) has good site onregulatory matters at: http:siwvew eagle. orgy + DetNorskeVeritashas.agooddownloaden MARPOLAnnexV, SECAsandECAS: http:wonw.cnv.cormbinaries/Marpol_Annex_V|_tom4-126462 pdt «The North of England P & | Club has 2 good page to follow industry news on regulation: hitp:/wwwr.nepia.com/news/industrynews, links. php. Technical Issues There are some useful manufacturers websites dealing with technical issues. + Lars Josefsson site on boilers: httpsswww.steamesteem.com! + The Diesel Duck site on diesel engines: _hitp:/iwwn.dieselduck.nel! machine/01%20prime%20moversidl je/diesel_engine,01.him + Warsash Maritime Academy site on marine diesels: http:/www.marinediesels co.uk! + Kittiwake Developments Ltd specialises in fuel sampling and testing equipment: http: www kitiwake.com! 81‘AN INTRODUCTION TO FUEL ANALYSIS. + Maersk Fluid Technology is developing novel onboard test equipment: hitp:i/ \wunzmaerskiuid,com/mxcms.aspx + Anton-Paar'is amaker of specialist portable digital density measuring equipment: http:siwww.anton-paar.com/GBlenv60/3, Fuel specifications Information on fuel specifications can be obtained from the following sources: + International Organization for Standardization (ISO) at http:/hwww.iso.org or contact your own national standards organisation + CIMAC can be contacted at hitphwwwcimac.org + JIS can be found at hitp:/hvwwjsa.org. Fuel sampling Information on fuel sampling and analysis can be found at 2 number of websites. A selection Is included here: + DnVPS: _htip:/www.dnv.comfindustryimaritime/servicessolutionsitueltesting! Index.asp + Lloyd's Register’s FOBAS: _hitp:/iwww!r.org/lndustries/Marine/Services! Consultancy/FOBAS.htm + Lintee Testing Services: http:/iwwlintec-group.com! + Viswa Lab: hitp:liwvwviswalab.com + Maritee: http:lwww.mar Survey and analysis Information on survey and analysis services from a variety international surveying ‘companies can be found here: + Intertek Ol Chemicals and Agri: http:/imwwintertek-cb.com/ + Saybolt: htipyivww.saybolt.convindex.him + $GS:_http:/www.sas.comvinspection_and_testing_services?catld=567 1&lobId= 55538type=service, Test methods Information on individual test methods including the published repeatability and reproducibilty data is only available from the organisation that publishes and oversees the test method. + International Organization for Standardization (ISO): hitp:Ihwwwiso.org + Energy Institute: http:/wormenergyinst.org.uk + American Society for the Testing of Materials (ASTM): hitp:/www.asim.org, com. a. For details on the history of the oil industry and th shipping: Appendix | Where to go for help Publications For more detailed technical information I can recommend: Bunkers: An Analysis of the Practical, Technical and Legal Issues. Thiré ceition. ISBN 0-9548097-0-X. Chris Fisher and Jonathan Lux. Published in 2004 by Petrospot Limited, Oxfordshire, An Introduction to Bunkering. First edition. 1SBI Dratfin, with a Foreword by Capt. M. Segar, Di Maritime and Port Authority of Singapore, Also avai Abastecimiento del Combustible Marino, First 20. Both published in 2008 by Petrospot hitpii:swww.petrospot.com, troduction of bunker fuel for 1 Dani rhe Epic Quest for Oil, Money and Power. ISBN 0-671-75705-, Published in 1992 by Touchstone, New York, USA. For details on all aspects of the petroleum industry: The Petroleum Handbook. 6th Edition, ISBN 0-444-42118-4. Staff of Royal Dutch / Shell companies, Elsevier, Amsterdam, 1983,Appendix II - Abbreviations eviton | What stands for at manne = semin | Propoton of substance by make Skviv | Propoon of substance by vlume — [Ak] Romic absorption Speconcopy locnigve ks Noni tvoten Speier | svececoyteenive ag American glo (US gallon) ta volume - a oa . aa | cn ae American Petleum insite re ed bbl Borel ‘American unit of volume BON | Bunker davery rote 7 7 BoR Bunker delivery receipt - JASWA100 [Bish landard for mare fuels |Nwidorcal.o 808217 aT [enter Troma ey cle ose é Carbon _ ca aku [cai | Galeuated Carbon romaty Idx ‘COR | Conradson Carbon Resicue - corre — ~ cru Wieobiogealconarton [cr |Cetane indox _ 7 ncaa ans a | oN otane Number — [ore | nose nine Rome — est Jeanttokes ro Degrees Celsius _ EC End of combustion —_ ECA | Emisson Conti area New name for SEGA EON [Estimated Cetane Number Fe ron BSMit couemonusilaenane ae FIA | Fuel ignition Analyser ' fot ros sada ; ere ee eee a = [fants atest cous [Seay PMS |spososony mane "| Jnastieiseee fm - Ho [War | [sw [Reser Sibi ear Say otg ioc) ial see a TAT | meant i Trenepon Assoloion | : — em _[Iematonl Bunker industry Ce oe J ior Inductively coupled plasma Spectroscopy technique t SECA ‘Sulphur Emission Control Area ‘Now called ECA ie _[btcha ~ | (so feseaons foot ina] intanetienal Waste Orparicaion | [suet Sediment by Hot Fitraton tat 7 iP Instlute of Petroleum Now called Energy institute si Sica ma aie a S| Spar remcnea eats Wet cccsemand| servations cy ioral nia opera | Febe—Jeapheoaas oe sou [Ratatat cao aera eT KOH [Potassium Hydroxide Units for TAN and SAN. a Saybolt seconds Furl Measure of viscosity on fr a Sealine fees ray a Eo | rx fea Sotnetoeaey — [oi cma Soe ise nn crs WT wee te aceon : | [ise fender et bani coonors ta] hen feat ce Veal aaa ips va a) | fn " Muikg ‘Mega Joule per kilogramme ‘Specific energy i aa oe fluorescence ‘Sulphur test, Maersk onboard test ae aren DS | i ay em a i ero Tiina oa | Ne Seon — | Ni Nickel { |g a | a “ ' eat PMos Penskey Martens Closed Cup Flash point testing eniasesal acres BGco [English French [Spanish [Portugese [German Russian rcesnumber | ies 75! 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Fe ge 5 |* a i ge: cae a3 eo Fei gre BE i Pog i sas B EB &@ 5 BF gees Selexrakheke® 208 Oo oka PI ggreg Pega p ER gag: BaaRe evasteiseeg tite Scania foge SEES 5 fy e)e8 2 52 gbetss bog a: a 8s 2 gig e 2 g 2 38 a gif g a3 2 BE 3 8 z z- * 2 e Kbd 2 882 28 le ees) ata BoB Ob RM nele routes tainCal fiter plugging point... 14 accuracy 24 2 FE on oor ts. reece Gas Cromatoraphy Mess SPECS2PHTO seas ison “ test, oe 38 ‘microbiological contamination test, 48 GC-MS Confematerysnaiyss sunun-68 Emergenoy eat SS explanation mL Emulsion Sra u Lead ‘Conradson carbon residue. 36 baie oe escription AT Contractual sample ae ‘combusti 73, Hydrogen Sulphide ‘e teat, 45 nergy Inst. 4 esapton.. ‘commercial sample. 23 somes 6 desoript eoanme Equivalent et. “8 tet 2M Estee 21 destin 24 noone “e Estimated ote number 1 Macros test. 35, fos a description 17 CPé0. von 7 23. iB vee ea Ignition delay Stone 45 Singapore Bunkering Procedure 10 tnylene. = description, ore ‘Main combusion delay. 73 Cubitainer F usration. wT aaRPOL procedure sample container... 28 Independent referee ae sr FB independent exper. oe tig a naval gas 10 Injection temperatures ‘ol ioosours a Fl jescription 20 Defence standard 94-4 eee nD escrpt summary. er UK naval standard 10 FN rte Pe Matera Safety Data Sheets ety omen 70 Intemational Wartime Orcarizt chston nace cat definition | 11 FuRTO0 FCA eeeeioemencel ey ‘sample transport. 27 on boat test. ee 7 1a! Organization for Standordzatojaximum ROHR va. 73 Fash poi oo Problem results 61 Poin 4g Metals : Si eee 4 test 40 eae tJ ipton 16 Microbiological contamination i . 4 2t ‘ : eee 44 Geserpion| 2 gq FoweTanstorm ina Red.. 0 a - o Fra water “ a a 180 4259 53 et “ =, saepann 8 Mero carbon residue 7 Sees maar 36 60 iause Kone 7 ‘Fue! combusti h 70, ue combustion anaysr Draeger tubes ee Has. 36 93OuinhastelleuTel tel ty beta NATO fuel standard... Nickel description tot. ° (On Board 2818. Organic contaminants description test. P Penshy-Martens SOLAS flash point method Phosphorus doserption a Position of maxROHR... Potassium esciption. 108t roan Pour point sception problem results test _ Pour point depressant dV wave em parts per milion Precision test method, Precision data assessment. 189 IM 180 4258 oan Procodures Port delivery procedure Proprietary tests (on board tos. Propylene. R Ramsbottom carbon residue. Referee analysis, challenge WAR E88 non Repeatability canon Representative samples Roproductilt.. Reserve stably nunber stabil test... RMA RME. SAMPLE en eccuracy, breaking the seal ‘composite Cn flow proportional. numberof semples.. ‘sampling location. $70 nsenmnnaninnninsinnnnen2h — Systime Internationa. snc samp vol... eet saybott a Fro SSF) svat TBN, Universal (SUS). 11 Fela Base Number ns 6S ‘sediment “Test method date dent 49 e101 nnn $2 time taken for test. st Separabity number Total Acid Number... son 78 Total Sediment Accelerated ar scription 37 ‘studge emergency test Se) rection renthe ee eaten SN {28h 7 separabilly AUMBEF on 78 TRis799. 2 Sot on ssnseansmannneelS Trangporaon description sample transportation... vB problem results ‘True Value 53 tes — ‘Turbiscan ‘Sodium / Vanadium stability test. erect 78 problem results Specific energy a 91088 ee ee a Used Lubricating OF Specie gravity. 86 88600 ‘Singopore bunker standard ‘Standard density... Strong Acid Number 8 ‘Sulphur desertion ‘on board test. problm results. aPRIN Cicnennel ite kes {08to 33 Visual appearance 9 20 i w test Water | 082809 = 18 | erergena tes. 7 | ‘on board test. oT | problem results... 62 test 198 i Woter seat [ Purtinsn oft 12 Zine 680 nnn ee : 48 ‘96