Marine Fuel Specification

and Test Methods

DAY 1

09th 10th May 2012

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

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

ISO 8217 Marine Fuel

Specifications
Energy Institute Marine Fuels Workshop
9 May, 2012

Intertek-Lintec ShipCare Services

Michael Green Marine Services
Technical Manager Bunker Fuel Testing

Marine Fuel Specs and Test Methods

Fuel Oil Refining and Products.

General Characteristics.
Operational Requirements.
On board Treatment.
Problem fuels.

Marine Fuel Oil

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

Crude Oil Distillation

The Cracking Process

Thermal - heat large hydrocarbons at high

temps (sometimes high pressures as well)
until they break apart.

Steam - high temperature steam (1500

degrees Fahrenheit / 816 degrees Celsius)
is used to break ethane, butane and naptha
into ethylene and benzene, which are used
to manufacture chemicals.

Visbreaking - residual from the distillation

tower is heated (900 degrees Fahrenheit /
482 degrees Celsius), cooled with gas oil
and rapidly burned (flashed) in a distillation
tower. This process reduces the viscosity of
heavy weight oils and produces tar.

Coking - residual from the distillation tower

is heated to temperatures above 900
degrees Fahrenheit / 482 degrees Celsius
until it cracks into heavy oil, gasoline and
naphtha. When the process is done, a
heavy, almost pure carbon residue is left
(coke); the coke is cleaned from the cokers
and sold

Catalytic Cracking

Catalytic Cracking- uses a catalyst to

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

Why take samples ?

Record the product supplied.

1.
2.

Routine Analysis.
1.
2.

Damage Prevention.
Engine, Crew, Environment.

Statutory Requirements.
1.

Single most important piece of

evidence regarding fuel quality.
Essential in the case of a quality
dispute.

MARPOL Annex VI.

Commercial Implications.

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

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

Density ISO 12185/ASTM D4052

Absolute measure of mass per unit

volume.
Stated as kg/m3 @ 15C in vacuum.
Commercially & technically important:
1. Essential for Quantity
Calculations
2. Setting Purifier, Indicates
Specific Energy & Ignition
Quality
For main grades limit 991.0 kg/m3.
Above 991.0 kg/m3 certain centrifuges
are ineffective.
ALCAP purifiers which can handle
fuels up to 1,010.0 kg/m3.
A Densitometer is used which has an
oscillating sample tube.

Kinematic viscosity ISO 3104 / ASTM D445

Automatic viscometer tends to be

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

Water content ISO 3733 / ASTM D95

Spec limit 0.5%.

Usually found in fuels due to
poor house keeping.
Can be fresh, brackish or salt.
Problems with sludge
formation and corrosion of
tanks and pipes.
Can damage fuel pumps and
injectors.
Can cause combustion
problems.
Commercially ships are
paying for fuel oil NOT water!

Sulphur

Marine Fuel Sulphur Limits

5

% S u lp h u r

4
3
2
1
0
2008

2010

2012
Year
SECA Global

2015

2020

The Sulphur Specification limit has

been removed from the Std for
Residual Fuels in ISO 8217:2010.
Buyers & Sellers must now agree
Upper Limits based upon
International, Regional and Port
Regulations that apply
when/where the fuel is consumed.
For Distillates Sulphur limits vary
according to grade:
DMA/DMZ = 1.5%
DMB = 2%
DMX = 1.0%

Sulphur

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

Flash point ISO 2719 / ASTM D93

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

Pour point ISO 3016 / ASTM D97

If a Fuel is stored at too cold a

temperature, wax can drop out of the fuel.
Pour Point is the:
Temperature at which the wax solidifies
and the fuel will no longer flow.
Spec limit varies with grade/time of year.
Solidified fuel oil can be a serious
operational problems.

Carbon residue ISO 10370 / ASTM D4530

Spec limit varies with grade.

Fuels with high carbon
residues can cause
combustion problems/deposits.
High carbon residues can
mean slow burning and
reduced efficiency.
Deposits can affect
combustion chamber, exhaust
system and turbochargers.

Ash content ISO 6245 / ASTM D482

If Excessive, Ash can give

Fouling Deposits.
Spec limit varies with grade
Inorganic parts of fuel which
are incombustible.
Ash itself can cause problems
but beware of the elements
comprising the ash
Eg Ca, Zn, P ULO
presence

Vanadium & Sodium IP 501

Spec limit varies with grade.

Vanadium and its oxides cause hot corrosion.
Can adhere to exhaust valve and seats.
Normally only melts above 800C.
Ratio of 1 part sodium to 3 parts Vanadium reduces melt point to 500C.
Combustion chamber temperature can be circa 500C and hot corrosion can occur.
Limits are

V: 350ppm for an RMG 380

Na: 100ppm for an RMG 380

Aluminium & Silicon IP 501

ISO 10478 / ASTM D5184

Spec limit 80 mg/kg for fuel oil

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

Other metals Vanadium, Zinc, Calcium, Phosphorus

Same equipment as
with Al+Si.
Ca, Zn, P = Used lube
oils
Ca>30ppm &
Zn>15ppm
Ca>30ppm & P>15ppm

Other metals :

Iron
Nickel
Magnesium
Lead

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

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

Fuel Stability - Total sediment potential (TSP)

ISO 10307 / ASTM D4870

Fuel is stable if it does not break

down giving heavy sediment.
Spec limit 0.1% m/m.
Measure of the cleanliness of the
fuel.
Stability precipitation of
asphaltenes.
Formation of sludge.
Can cause blocking of filters,
choking of purifiers and blocking
of pipes leading to fuel starvation.
Asphaltenes cause ignition delay
and slow burning.
Only applied for HFO samples;
existent sediment is measured in
distillates.

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

Stability Prevention / Treatment

How do we prevent stability related issues?

Avoid on board mixing of fuels.
Very difficult to create fully homogenous blend.
Even so called compatible fuels can become
unstable when mixed.
No Guarantee of compatibility.
Compatibility testing is not 100% reliable
approximate indication.

Stability Prevention / Treatment

Treatment of Stability issues.

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

Acid Number ASTM D664

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

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

Lubricity ISO 12156-1, IP450

Testing only required on

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

Lubricity and Sulphur

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

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

CCAI and CII

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

CII Ignition Quality

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

CCAI Ignition quality

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

Hydrogen Sulphide IP570 (Annex D)

Testing for H2S content allows

assessment of a fuels safety when
stored and/or transported; also its
potential to corrode pipelines, storage
tanks and other ship components.

Significant concentrations of H2S are

known to accumulate in the
headspaces of storage tanks and pose
a potentially lethal hazard.

Rapid Liquid Extraction Method.

Becomes a mandatory test

requirement as part of ISO 8217 on
1st July 2012.

Specification Limit 2ppm.

Health and Safety issue.

Summary
ISO 8217 test spec covers a wide range of areas as far as
test parameters are concerned.
Some address operational issues Viscosity.
Some address commercial issues Water.
Some address health and safety Flash Point & H2S.
A number of issues with certain tests can be dealt with on
board treatment Viscosity and Water.
Other issues cannot Sulphur Content.
Testing of fuels to ISO 8217 is a vital tool for vessel owners
and operators.
THANK YOU.

ISO 8217 Marine Fuel Specifications

Energy Institute Marine Fuels Workshop
9 May, 2012

Nigel Elliott
Senior Fuels Technical Advisor
ExxonMobil Research & Engineering

Timeline for Marine Fuel standards

1924 BS 209: Fuels for Heavy Oil Engines (predominantly sponsored

by UK Admiralty)
1952 Voyage of the "Auricula", starts widespread modern use of
residuals in marine diesels
1957 BS 2869: Oil Fuels Specifies marine distillates but not residuals
Seen as a weak point

1978 BSI PTC/4 "Marine fuels" committee formed

ISO TC28/SC4/WG6 proposed

1982 BS MA 100 first published

1986 ISO 8217 published (as BS MA 100: 1986)

ISO 8216-1 published (as BS 6383 Part 1: 1986)

1996 ISO 8217 2nd edition

2005 ISO 8217 3rd edition
2010 ISO 8217 4th edition

A History of Marine Fuel standards

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

SHF, Al+Si and Ignition quality

In the event, ISO 8217 was not published until 1986 (along with its companion ISO 8216 Part 1, as
SC4 also took its Classification role seriously ) at which stage BS MA 100 was withdrawn

How do ISO standards work?

As a non-governmental organization, ISO has no legal

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

Membership of ISO TC28/SC4/WG6

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

ISO 8216 & ISO 8217 Marine Fuel standards

The specifications in ISO 8216 and ISO 8217 were prepared in co-operation with:

Crude oil supplies, refining methods, ships' machinery, environmental legislation

and local conditions vary considerably:

These factors have led historically to a large number of categories of residual fuels being
available internationally, even though locally or nationally there can be relatively few categories
available

ISO takes into account:

ship owners, ship operators, shipping associations, national standards bodies, classification
societies, fuel testing services, engine designers, fuel suppliers and the petroleum industry to
meet the requirements for fuels supplied on a world-wide basis for consumption on board ships.

SOLAS (Safety Of Lives At Sea) Convention in respect of the allowable minimum flash point of
fuels
Revised MARPOL Annex VI, which controls air pollution from ships, includes a requirement
either that the fuel not exceed specified maximum sulfur content or that an approved equivalent
alternative be used
Max sulphur contents have been included for distillate grades for those areas of the world that
have not ratified MARPOL to protect end users

During the lifetime of this International Standard, regional and/or national bodies
can introduce their own local emission requirements, which can impact the
allowable sulfur content, for example EU Sulfur in Liquid Fuels Directive

It is the users responsibility to establish the requirement to comply with such statutory
requirements and to specify the maximum sulfur content of the fuel to the supplier

ISO 8216 & ISO 8217 2010 4th Edition

ISO 8216-1 Petroleum products Fuels (class F)
classification Part 1: Categories of marine fuels
9 FDIS ballot results 100% Approval
ISO 8217 Petroleum products Fuels (class F)
Specifications of marine fuels
9 FDIS ballot results 90% Approval

Both standards published on 15 June 2010

Changes from ISO8217 2005

The fourth edition of ISO8217 reflects several important and

significant changes:
Include category rationalizations of both distillate and residual fuels and
substantial amendments to Clause 5

Changes reflect market demand, recognize regulatory developments

and current industry experiences with the use of fuels
The limits contained in Tables 1 and 2 now reflect the test method
reporting requirements:
E.G. viscosity limits are given to four significant figures

Changes from ISO8217 2005 Distillate Fuels

Changes to the distillate fuels (4 categories) include the following:

An additional grade, DMZ, has been added with a minimum viscosity of
3,000 mm2/s at 40 C, but is otherwise identical in its characteristics to
the DMA
- Grade added to reflect engine and ship operator concerns about low
viscosity when changing from residual fuel oil to distillate in port
Problems with internal injector pump leakage, leading to loss of fuel injection
pressure and delivery

The previous DMC category has been modified and moved to Table 2 as
RMA10
Specifications for the following characteristics have been added to Table 1:

Hydrogen sulfide, acid number, oxidation stability and lubricity

Minimum viscosity requirement for DMA has been raised to 2,000 mm2/s
minimum viscosity requirement of 2,000 mm2/s has been added for DMB
The specifications for the appearance characteristic in Table 1 have been
amended

Changes from ISO8217 2005 Residual Fuels

Changes to the residual fuels (6 categories) include the following:

RMA 10 has been added
RMG and RMK have been expanded to include additional viscosity grades
RMF and RMH categories have been removed

Table 2 additions and changes:

Calculated Carbon Aromaticity Index (CCAI), hydrogen sulfide, acid number and
sodium content
Sulfur limits have not been tabulated, as these are controlled by statutory requirements
Potential Total Sediment (TSP) has been assigned as the reference test method
Accelerated Total Sediment (TSA) has been added as an alternative test method
Ash limit values have been reduced for many of the categories.
Vanadium limit values have been reduced, with the exceptions of those for RMB 30
where the limit value is unchanged and for RMG 380 where the limit value has been
slightly increased
Aluminium-plus-silicon limit values have been reduced
The criteria for assessing whether a fuel contains used lubricating oil have been
amended

Changes from ISO8217 2005 Informative

annexes

Changes to the informative annexes include the following:

Annex C of the previous 2005 edition, dealing with viscosity conversions, has
been deleted
The equations dealing with specific energy in Annex E of this new edition have
been revised and a gross specific energy equation for distillate fuel has been
added

Four new annexes have been added:

Annex A, dealing with bio-derived products

Annex B, dealing with deleterious materials
Annex C, dealing with sulfur content
Annex D, dealing with hydrogen sulfide

ISO 8217 Annex A Bio Derived Products

Concern that bio derived products may have deleterious effects on
marine fuel quality
Combustion properties were not a concern as FAME has good
ignition and lubricity characteristics
Major concerns over fuel handling and storage with biodiesel
blends:
Degraded oxidation stability
Affinity for water and microbiological growth
Poor cold flow properties

ISO 8217 takes a precautionary approach:

Only deminimis levels of FAME recommended (1000ppm for FAME in distillate)

Recognition that FAME is very surface active and can be picked up in distribution systems
very easily

FAME defined as meeting EN14214 or ASTM D6751

Raw vegetable and animal oils not allowed

Since publication of the standard a number of companies have

reported successful ship trials with biodiesel blends
ISO TC28/SC4/WG6 working on the next revision of ISO8217 to
include biodiesel blends with appropriate precautions

ISO 8217 Annex B Deleterious Materials

Precludes the incorporation of deleterious materials as stipulated in Clause 5

Such materials should not be present, mixed or blended in marine fuels
Determining the harmful level of a material or substance is not straightforward:
a)
b)
c)
d)

Each fuel is a unique, complex blend of hydrocarbon species

A wide range of materials from different sources can enter the marine supply chain from the
production, handling and transport systems
Varying levels of contamination can be present in the fuel due to the use of common equipment
or pipelines in refineries, fuel terminals or other supply facilities
Various analytical techniques are used to detect these contaminants and specific chemical
species with no standardized approach and in most cases, sufficient data are not available with
respect to the effects of any one specific contaminant, or combinations thereof, on the variety of
marine machinery systems in service, personnel or upon the environment

It is, therefore, not practical to require detailed chemical analysis for each
delivery of fuels beyond the requirements listed in the Standard

It is required that a refinery, fuel terminal or any other supply facility, including supply barges
and truck deliveries, have in place adequate quality assurance and management of change
procedures to ensure that the resultant fuel is compliant with the requirements of clause 5

ISO 8217 Annex C Sulfur

The fourth edition of ISO 8217 retained the third edition's limits for sulfur for distillate
fuels, but does not include limits for residual fuels
Previously, such limits were included since the sulfur content acts to reduce the specific
energy value and, given the appropriate post-combustion temperature conditions, can
result in corrosion of susceptible components
Sulfur limits for distillate fuels in Table 1 were retained due to technical requirements to
protect small, high-speed diesel engines
Statutory requirements, i.e. the Revised MARPOL Annex VI, either specify a maximum
sulfur content of the fuel being used or allow the adoption of technical solutions to
ensure compliance with the emission regulations for sulfur oxides and particulate matter
Sulfur content of both distillate and residual fuels is directly controlled by the statutory
requirements
Consequently, the purchaser's responsibility is to define the maximum sulfur content of
the fuels in accordance with the ship's engine design, emission control equipment and
the prevailing statutory limitations in the areas in which the fuel will be used
Note with appropriate after-treatment (exhaust scrubbing) it is permisable to burn higher
sulfur fuels

ISO 8217 Annex D Hydrogen Sulphide

H2S is a highly toxic gas and exposure to high vapour concentrations is hazardous, and in
extreme cases can be fatal
H2S can be formed during the refining process and can evolve from the fuels in storage
tanks, in product barges and customer tanks.
H2S can be present in both liquid and vapour phase and the degree and speed of partitioning
between the liquid and vapour phase depend on several factors:

The liquid-phase limit stated in this fourth edition of this International Standard is designed to
provide an improved margin of safety over the previous edition

This limit alone does not constitute a safe level or eliminate the risk of very high levels of H2S vapour being evolved in
enclosed spaces

Implementation of H2S specification delayed 2 years to July 2012

e.g. the fuel chemistry, temperature, viscosity, level of agitation, storage time, heating applied, ambient conditions, tank
shape, ullage and venting

To provide adequate time for the development of a precision statement for distillate fuels in IP 570
For the world-wide dissemination and application of the new test method IP 570
For the industry to engineer, procure and construct facility modifications, where required, in order to comply with the limit
To avoid fuel supply disruption in the intervening period.

The inclusion in this International Standard of an H2S in liquid phase limit of 2,00 mg/kg in
the fuel directionally reduces the risk of H2S vapour exposure

However, it is critical that ship owners and operators continue to maintain appropriate safety processes and

procedures designed to protect the crew and others (e.g. surveyors), who can be exposed to H2S vapour.

Reasons for raising H2S issue

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

H2S measurement in vapour

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

Why Hydrogen Sulfide in liquid?

To measure the total potential H2S concentration of the fuel
oil that could be released over a period of time from a
bunker fuel at any suitable conditions, when the fuel is
transferred, heated and agitated by the rolling action of the
ship,
rather than
The measurement of variable equilibrium dynamics of the
vapour phase capturing just one H2S concentration under
specific set of conditions prevailing at the moment of
measurement only.

Next steps for H2S

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

What has ISO WG6 accomplished?

Prepared detailed and practical marine fuel quality standard.
Consensus between engine builders, suppliers and users.
Standard praised by IMO MEPC delegations as a significant
improvement on the last edition and a good outcome.

For current needs

revision of most fuel categories and characteristics, provision
of new DMZ grade, inclusion of acid number and addressing
the bio components issue

For future needs

introduction of oxidation stability and lubricity, revision of the
ULO definition, further decisions on bio issue and study of
contaminants

Special industry issues

introduction of ignition quality parameter
inclusion of a limit for hydrogen sulfide (H2S)

Future development
9 Ignition and combustion characteristics a better
approach
9 Incorporation of Bio-diesel into marine fuel generating
technical data to pave the way for change
9 Corrosion possibility of a new test method
9 Contaminants new project to define a good fuel
9 Acid number develop better precision data for this test
9 Oxidation stability improvement on the test method
9 H2S test method development and implementation of the
limit

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

And Finally Thanks to

Wanda Fabriek (Intertek) Retired ISO TC28/SC4/WG6 Chair

Geoff Suckling (Total) BSI PTI/2 and Energy Institute

Sampling Requirements for

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

Marine Fuel Sampling Standards - Summary

MARPOL Annex VI

ISO 13739

Drip
Sample

MEPC
182(59)

ISO 8217

Drip
Sample

Intertanko
Guide

Test Methods
D4057 /
API Ch 8.1

ISO 3170 /
IP 475

D4177

ISO 3171 /
IP 476

ISO 3170 / IP 475 Petroleum liquids Manual sampling

ISO 3171 / IP 476 Petroleum liquids Automatic pipeline sampling
API Manual of Petroleum Measurement Standards (MPMS) Chapter 8.1, Manual Sampling of Petroleum and Petroleum Products
ASTM D4057 Practice for Manual Sampling of Petroleum and Petroleum Products
ASTM D4177 Practice for Automatic Sampling of Petroleum and Petroleum Products
MEPC 182(59) 2009 Guidelines for the sampling of fuel oil for determination of compliance with the revised MARPOL Annex VI
INTERTANKO's "A Guide to Bunkering of Ships for the purposes of Annex VI to MARPOL"

ISO 8217 Sampling Requirements

ISO 8217 specifies properties for marine fuels (residual & distillate)
Applies at the time and place of custody transfer
Samples for quality verification may be taken in any location agreed between parties

ISO 8217 states that sampling shall be conducted in accordance with

ISO 13739 or an equivalent national standard
ISO 13739 Petroleum products - Procedures for transfer of bunkers to vessels
specific sampling requirements in referenced test methods shall be adhered to

No direct reference in ISO 8217 to ISO 3170 Petroleum Liquids

Manual Sampling or ISO 3171 Petroleum Liquids Automatic
Pipeline Sampling

However indirect reference through test methods quoted in Tables 1 & 2

Primarily ISO methods in ISO 8217, but IP & ASTM methods are also quoted
ISO / IP methods quote ISO 3170 ( IP 475) and ISO 3171 ( IP 476)
ASTM methods quote D4057 (manual sampling) and D4177 (automatic sampling)

ISO 13739 Sampling Requirements

Applies only to samples taken during bunker delivery to the vessel
The objective is to obtain a single representative sample of the
delivered bunker

If a delivery is made from more than one bunker tanker, separate samples shall be
drawn for each delivery

A single sample shall be drawn continuously throughout the delivery

using an automatic sampler or a continuous drip sampling device
It is recommended that the commercial samples and the MARPOL sample be
derived from this single sample
For road tanker delivery, truck loading samples are common industry practice and
may be designated as the representative samples for the delivery

Detailed sampling procedure is given in Annex L

See later slide

ISO 13739 Sampling Devices (Annex K)

Due to accuracy of sampling devices, the preferential order is:
Flow-proportional automatic sampler
Time-proportional automatic sampler
Manual valve-setting continuous-drip sampler

Sampling container requirements:

weather-tight
capacity of at least 5 litres
capable of being security sealed

Sample bottles:
suitable for air transportation & long-term storage
bottle material shall not compromise the integrity of the sample

The Continuous Drip Sampling Process

Photos provided by Lintec

ISO 13739 Sampling Procedure (Annex L)

Ensure that the volume of the sample container is adequate to fill the
number of sample bottles as agreed
A continuous-drip sample should be collected throughout the entire
duration of bunkering
Sampling shall start simultaneously with commencement of the bunkering operation

Sample shall be thoroughly shaken or stirred to promote homogeneity

Pour the sample in small, equal portions into at least 4 sample bottles
make 3 or 4 passes to fill each bottle in turn to obtain nominally identical samples
minimum quantity in each sample bottle shall be 750 ml

These sample bottles shall be distributed as follows:

a)
b)
c)
d)

two for the vessel, one of which is a MARPOL sample;

two retained by the bunker tanker (or terminal);
one for the Bunker Surveyor, if engaged;
one for fuel testing services, if required.

MARPOL Annex VI and MEPC 182(59)

Regulation 18 of MARPOL Annex VI refers to fuel oil quality
Appendix VI contains the Fuel Verification Procedure for MARPOL samples
Detailed sampling requirements for Reg. 18 are found in Resolution MEPC 182(59)

MEPC 182(59) requires that a representative sample of the fuel

delivered to the ship should be obtained at the receiving ships inlet
bunker manifold & should be drawn continuously throughout delivery
Representative Sample is defined as a product specimen having its physical and
chemical characteristics identical to the average characteristics of the total volume
being sampled
the practical purpose of this sample is to enable authorities to verify sulphur content
of the fuel

The sample should be obtained by one of the following methods:

1. manual valve-setting continuous-drip sampler; or
2. time-proportional automatic sampler; or
3. flow-proportional automatic sampler.

MARPOL Annex VI and MEPC 182(59) cont.

MEPC 182(59) requires that a sealed retained sample is taken
immediately prior to filling the retained sample container, the primary sample
quantity should be thoroughly agitated to ensure that it is homogeneous

The retained sample should be of sufficient quantity to perform the

tests required but should not be less than 400ml*
the container should be filled to 90% 5% capacity
*NOTE that INTERTANKO "Guide to Bunkering of Ships for the purposes of Annex VI to MARPOL
recommends that sample volume is not less than 750ml. This is aligned with ISO 13739 which
also requires a minimum volume of 750 ml.

The retained sample should be stored in a sheltered location where it

will not be subject to elevated temperatures, preferably at a cool /
ambient temperature and where it will not be exposed to direct sunlight

ISO 8217 Test Methods Issues Raised

Next slides highlight possible issues in more detail, but in summary:
Many of the tests have conflicting sample heating requirements
e.g. Acid Number and Viscosity - heat sample to 60 5C in original container
e.g. Density heat sample until fluid but not so high as to cause loss of light-ends
e.g. H2S - a sample that is not free flowing at ambient shall be gently warmed 40C

Some tests have very specific sample container requirements

e.g. Oxidation Stability - containers shall be epoxy lined (or similar) metal cans or
borosilicate glass (if they are wrapped or boxed to exclude light). Do not use soft
(soda) glass or plastic containers (due to the potential for leaching of plasticizers).

Some tests have specific sample storage requirements

e.g. Oxidation Stability - if a fuel cannot be tested within 1 day it should be
blanketed with inert gas & stored at a temperature <10 C, but above its cloud point.

ISO 13739 recommends that the Commercial Sample is derived from

the same sample as the MARPOL sample (i.e. drip sample)
The IP 570 H2S method states that samples should not be taken by continuous drip

ISO 8217 Test Method Requirements

Parameter

Fuel Oil /
Distillate

Test
Method

Sampling
Standard
Reference

Additional Sampling Requirements

Kinematic Viscosity
(40C distillate;
50C fuel oil)

Fuel Oils &

Distillates

ISO 3104

None

Fuel Oil only: heat the sample in its original container in

an oven at 60C for 1h. Thoroughly stir the sample with a
rod then shake vigorously for 1 min.

Density

Fuel Oils &

Distillates

ISO 3675

ISO 3170
ISO 3171

The heating and/or mixing of petroleum products containing

sediments and/or water may result in loss of light-ends.
Waxy Distillates: warm sample to 3C above cloud point.
Fuel Oil: heat sample to test temperature prior to mixing.
Test temperature shall be such that sample is sufficiently
fluid, but not so high as to cause loss of light-ends, nor so
low as to result in presence of wax in the test sample.

Density

Fuel Oils &

Distillates

ISO 12185

ISO 3170
ISO 3171

Care should be taken to prevent loss of light-ends from the

sample. Wherever possible samples should be drawn,
transported & stored in the same container. Use of a fixedvolume receiver (whether it is pressurized or not) could
result in light-end loss from the material being sampled,
thereby affecting the density measurement.
Distillates: mix by gentle shaking.
Waxy Distillates: warm sample to 3C above cloud point.
Fuel Oil: heat sample until fluid.

ISO 8217 Test Method Requirements cont.

Parameter

Fuel Oil /
Distillate

Test
Method

Sampling
Standard
Reference

Additional Sampling Requirements

Cetane Index

Distillates

ISO 4264

Indirectly to
ISO 3170 &
ISO 3171

Sample must be tested according to ISO 3405 Distillation requires sampling in accordance with ISO 3170 / ISO 3171.
ISO 3405: If the sample is not fluid at ambient temperature,
maintain it at 9 - 21C above its pour point. Shake sam ple
vigorously prior to subsampling to ensure homogeneity.

CCAI

Fuel Oils

Calculation

n/a

n/a

Sulfur

Fuel Oils &

Distillates

ISO 8754
ISO 14596

ISO 3170
ISO 3171

Test portions from samples shall be drawn after thorough

mixing & subdivision. Heat viscous samples to a
temperature which renders the sample liquid & homogenize

Flash Point

Fuel Oils &

Distillates

ISO 2719

ISO 3170
ISO 3171

Place samples in tightly sealed containers, appropriate to

the material being sampled. Ensure that sample container
is filled to 85 95% of its capacity. Store samples in
conditions that minimize vapour loss & pressure build-up.
Avoid storing samples in excess of 30C. Subsample at a
temperature at least 28C below expected flash point. I f an
aliquot of the original sample is to be stored prior to testing,
ensure that the container is filled to >50% of its capacity.
Mix samples by gentle manual shaking prior to removal of
the test portion, taking care to minimize loss of light-ends.

ISO 8217 Test Method Requirements cont.

Parameter

Hydrogen Sulfide

Fuel Oil /
Distillate

Fuel Oils &

Distillates

Test
Method

IP 570

Sampling
Standard
Reference
IP 475 (ISO
3170)
ISO 13739

Additional Sampling Requirements

Care shall be taken to ensure that integrity of material is

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

ISO 8217 Test Method Requirements cont.

Parameter

Fuel Oil /
Distillate

Test
Method

Sampling
Standard
Reference

Hydrogen Sulfide
Cont.

Acid Number

Additional Sampling Requirements

Take the samples to the laboratory as soon as is

practicable after sampling. Test immediately if possible. If
samples are not tested immediately, store in a cool place
such as a refrigerator and analyse them within 3 days.
H2S measurement shall be first test carried out on the
sample as additional handling can lead to loss of H2S.
To minimize loss of H2S, do not homogenize, avoid
unnecessary shaking of the sample, do not transfer the
sample to another container and avoid unnecessary
openings of the container before taking a test portion.
The sample needs to be flowing freely enough to allow it
to be drawn into the pipette / syringe. A sample that is
not free flowing at ambient shall be gently warmed in a
water bath or oven set at a temperature 40C.
Fuel Oils &
Distillates

ASTM
D664

D4057
D4177

Heat sample to 60 5C in original container & agitate until

all of the sediment is homogeneously suspended. If original
container is a can or glass and >75% full, transfer entire
sample to a clear-glass bottle with a capacity at least 33%
greater than the volume of sample. Transfer all traces of
sediment from original container to the bottle by vigorous
agitation. After complete suspension of all sediment, strain
sample through a 100-mesh screen to remove large
contaminating particles. NOTE - when samples visibly free
of sediment this heating/straining procedure can be omitted

ISO 8217 Test Method Requirements cont.

Parameter

Fuel Oil /
Distillate

Test
Method

Sampling
Standard
Reference

Additional Sampling Requirements

Total Sediment by
Hot Filtration

Distillates

ISO
10307-1

ISO 3170
ISO 3171

Mix the whole sample thoroughly using a high-speed mixer,

if practicable, for 30 s. For fuels with a high wax content
(high pour point) or of very high viscosity, heat the sample
before stirring. The temperature shall be either 15 to 18C
above the pour point for low-viscosity fuels, or at a
temperature sufficient to reduce the viscosity to between
150 - 250 cSt for high-viscosity fuels. The temperature shall
not exceed 80C during this preparation stage.

Total Sediment
Aged

Fuel Oils

ISO
10307-2

[ISO 3170 &

ISO 3171]

Refer to sampling requirements for ISO 10307-1 (which

requires sampling in accordance with ISO 3170 / ISO 3171)

Oxidation Stability

Distillates

ISO 12205

ISO 3170
ISO 3171

Test portions from samples shall be drawn after thorough

mixing & subdivision away from direct sunlight. Storage
shall occur in the dark. Containers for samples shall be of
metal lined with epoxy resin or similar material, previously
rinsed twice with the material to be sampled, or borosilicate
glass, if they are wrapped or boxed to exclude light. Do not
use soft (soda) glass containers, or plastic containers (due
to the potential for leaching of plasticizers). Analyse fuel
samples as soon as possible after receipt. If a fuel cannot
be tested within one day, it should be blanketed with an
inert gas & stored at a temperature <10 C, but above its
cloud point. Thoroughly mix samples before taking a
laboratory sample.

ISO 8217 Test Method Requirements cont.

Parameter

Fuel Oil /
Distillate

Test
Method

Sampling
Standard
Reference

Additional Sampling Requirements

Carbon Residue
micro method

Fuel Oils &

Distillates

ISO 10370

None

Thoroughly stir the sample to be tested, first warming if

necessary to reduce its viscosity.

Cloud Point

Distillates

ISO 3015

None

None

Pour Point

Fuel Oils &

Distillates

ISO 3016

None

None

Water

Fuel Oils

ISO 3733

ISO 3170
ISO 3171

Liquid samples shall be mixed, after warming, if necessary,

in the original container.
If the analytical procedures to be applied have conflicting
requirements, draw separate samples and apply the
appropriate procedure to each sample.
Take particular care in respect of the following:
a) liquids containing volatile material, since loss by
evaporation can occur;
b) liquids containing water and/or sediment, since
separation tends to occur in the sample container.
Do not transfer samples of volatile liquids to other
containers at the sampling location but transport them to
the laboratory in the original sample container, cooled and
inverted, if necessary. Great care is necessary if a sample
contains both volatile components and free water.

ISO 8217 Test Method Requirements cont.

Parameter

Fuel Oil /
Distillate

Test
Method

Sampling
Standard
Reference

Additional Sampling Requirements

Ash

Fuel Oils &

Distillates

ISO 6245

ISO 3170
ISO 3171

None

Lubricity

Distillates

ISO
12156-1

None

None

Vanadium
Sodium
Aluminium + Silicon
Used Lubricating
Oils (Ca + Zn or
Ca + P)

Fuel Oils

IP 501

IP 475
IP 476

Thoroughly mix samples in their containers immediately

prior to withdrawal of the test portions. Place the sample
container in the oven and maintain the sample at 50 60
C until all the sample is fluid and of uniform viscosity. Mix
the sample for approximately 5 minutes. Failure to use this
homogenization procedure will invalidate results.

Vanadium
Sodium
Aluminium + Silicon
Used Lubricating
Oils (Ca + Zn or
Ca + P)

Fuel Oils

IP 470

IP 475
IP 476

Thoroughly mix samples in their containers immediately

prior to withdrawal of the test portions. Place the sample
container in the oven and maintain the sample at 50 60
C until all the sample is fluid and of uniform viscosity. Mix
the sample for approximately 5 minutes. Efficient mixing of
the sample is essential to the accuracy and precision of this
test method. Hand shaking alone will invalidate results.

ISO 8217 Test Method Requirements cont.

Parameter

Fuel Oil /
Distillate

Test
Method

Sampling
Standard
Reference

Additional Sampling Requirements

Vanadium

Fuel Oils

ISO 14597

ISO 3170
ISO 3171

Test portions from the samples shall be drawn after

thorough mixing and subdivision. Heat viscous, opaque,
semisolid or solid samples to a temperature which renders
the sample liquid and homogenize using the homogenizer.

Aluminium + Silicon

Fuel Oils

ISO 10478

None

The sample shall be homogenized thoroughly before the

test portion is taken. Place the sample container in an oven
at a temperature between 50 - 60 C and maintain the
sample at this temperature until all the sample has melted
and reached a uniform viscosity. Homogenize the sample
for approximately 5 minutes. Failure to use this
homogenization procedure will invalidate results.

Used Lubricating
Oils
Ca + Zn or
Ca + P

Fuel Oils

IP 500

IP 475
IP 476

Thoroughly mix samples in their containers immediately

prior to withdrawal of the test portions. Place the sample
container in the oven and maintain the sample at 50 60
C until all the sample is fluid and of uniform viscosity. Mix
the sample for approximately 5 minutes. Efficient mixing of
the sample is essential to the accuracy and precision of this
test method. Hand shaking alone will invalidate results.

OTHER REFERENCES

CIMAC guide on ignition and combustion:

http://www.cimac.com/cimac_cms/uploads/explorer/Wor
king%20groups/CIMAC_Fuel_Quality_Guide_Ignition_an
d_Combustion.pdf