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MARINE FUELS
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IBIA is thankful to Chris Leigh-Jones, and the Technical Working Group,
for producing this interesting report
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LLOYD’S REGISTER
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Section One
Introduction
Fuel Additives
Section Two
Introduction
Lubricants
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SECTION ONE
The Effect of Vanadium in Marine Fuels
1. Introduction
Vanadium is a naturally occurring element in marine fuel oil and also
one, that when combined with Sodium, can cause engine damage.
The following notes have been written by IBIA to offer an initial point of
reference with regard to vanadium levels. Information has been
gathered from publications and verbal reports and represents a
synopsis of the information available.
Aluminium
Iron
Nickel
Calcium
Silicon
Sodium
Vanadium
Before injection into the diesel engine the fuel is treated onboard which
results in a reduction in the ash level when compared to that delivered
over the ships rail.
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Maximum vanadium levers defined in the marine world are specified in
ISO 8217 as:
Figure 1
Ash Content in Marine Fuel Oil
Figure 2
Water Content in Marine Fuels
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Figure 2 shows the distribution of water content, measured in fuel
samples, from many sources, over an extended period. As a general
rule, 1% water is associated with 100 mg/kg sodium. Unlike vanadium,
sodium associated with water contamination, can usually be effectively
removed by a well operated centrifuge system.
From time to time high vanadium fuel is found in other areas and this is
attributable to the use of variable crude sources by different refineries.
The crude stocks with the highest levels of vanadium are those from
Venezuela and Mexico. The level of sodium usually found in residual
fuels is less than 50 mg/kg, and it has been estimated that some 95%
are less than 100mg/kg. (See Figure 2 where sodium is often
associated with sea water contamination.)
The form in which the sodium is present determines the extent of the
possible reduction in the ship’s fuel treatment plant. Sodium
contamination, in the absence of water, is probably the most difficult
form of this contamination to remove.
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3. What is wrong with Vanadium?
3.1 The Quick Explanation
The sodium in the fuel reacts with the water vapour formed during
combustion to generate sodium hydroxide. This in turn combines with the
sulphur dioxide present in the exhaust gas forming Sodium Sulphate
(Na2SO4). This condenses below about 890oC and will adhere to
surfaces already coated with V2O5. The resultant deposits block gas
passages and corrode metal surfaces.
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In addition to this, the melting points of these salts are further affected by the
ratio of vanadium to sodium in which the salts are present. An example of this
is given in Figure 4.
Figure 4
Effect of Ratio on Melting Point
For example, a complex, where the vanadium is in the ratio of 3:1 to the
sodium, has a melting point of about 300-400oC (depending on whose graph
you look at). The melting point of the various complexes is only part of the
story and the propensity of the solid particles to adhere to metal surfaces may
be increased at temperatures far below melting point. This is illustrated in
Figure 5.
Figure 5
V / Na Eutectic Diagram
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5. What might it do to the Engine?
Figure 6 shows a large hole in the seat of an exhaust valve. This is the result
of a phenomenon which involves three distinct phases.
1. Erosion: the wearing away of the metal by hot exhaust gases possibly
initiated by the impacting of ash and carbon on the valve.
3. Gas phase oxidation: the effect of oxygen in the hot exhaust on metal
engine surfaces.
Figure 6
The extent of hot corrosion and fouling is generally kept at an acceptable level
by the design and operation of diesel engines. The principal means by which
corrosion is minimised is by control of temperature. It is essential to ensure
that exhaust valve temperatures are maintained at temperatures below the
levels at which liquid sodium and vanadium complexes are formed. This is
the reason why the temperature of exhaust valve seats and faces is usually
limited to below 4500C. In recent years, engine designers have incorporated
materials into exhaust valve and seats which are resistant to the corrosive
components of the fuel oil ash. Some engine builders use a Stellite facing
whilst others use nimonic steels in valve manufacture. Also, an increasing
number of designs include exhaust valve rotators which are said to extend the
life. This is achieved of the valve by smoothing the radial temperature
distribution around the valve and preventing repeated impact damage at a
single point on the valve face.
Some older designs of diesel engines do not have the benefit of modern
materials and have high operating temperatures. As a result of this they are
prone to hot corrosion problems and in general the fuel specifications for such
engines have a low limiting value for vanadium. As discussed above it is the
combination of vanadium and sodium that may lead to problems in the post
combustion phase.
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It is for this reason that the ISO 8217 (1987) standard provides fuel grades
with lower vanadium (and MCR) limits than the original BS MA 100 (1982)
levels (e.g. 600 became 300 or 600, 500 became 500 or 200 mg/kg). This
was partly the result of a revised CIMAC recommendation issued during the
interim period between the creation of the two standards. The lower limits
reflected the view of the diesel engine industry (CIMAC) that some older
engine designs were susceptible to hot corrosion. These engines would
typically be those originally designed for operation on distillate fuels.
6. Fuel Additives
In order to reduce these corrosion problems an additive which has the effect
of an ash modifier may, under certain circumstances, be beneficial. The
actual type of ash formed, and its properties depend upon the operating
conditions, and are also influenced by the sulphur gases present and carbon.
Hence, the ash modifier should have the ability to increase the melting point
temperature and makes the ash more friable. By increasing the melting point
temperature, the temperature may reach a point when the ash is not in a
molten form and will not be corrosive. In being more friable the ash is likely to
stick to metal surfaces and affect heat transfer.
Vanadium is a significant ash forming constituent of fuel oil and reportedly the
one that arouses most interest from ship owners.
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the ships fuel settling and centrifuge systems will remove the great majority of
water contamination (>90% removal efficiency). Care should be taken to
correctly centrifuge fuel where there is a risk of high water and vanadium
levels.
Modern generation engines designed from the outset for operation on residual
fuels will not be susceptible to high temperature corrosion provided they are
well maintained and operated within their design envelope. Such engines will
typically have sophisticated alloy valve seats and valve rotators.
High vanadium and sodium fuels will increase the tendency for deposit
formation in the exhaust passages. Ash deposits can cause fouling in
addition to corrosion problems. Fouling in the exhaust ducts and turbocharger
passages can be controlled by means of regular water washing. Pre and post
combustion additives can assist in maintaining cleanliness in the exhaust
passages.
In the present generation of diesel engines high levels of vanadium in the fuel
should not present any operational problems if regular water washing of the
turbocharger is carried out.
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SECTION TWO
Low Sulphur Fuels in Marine Diesel Engines
Introduction
From time to time comments are circulated around the bunker and marine
industry about problems associated with engine operation on fuels with a low
sulphur content. The notes below have been written by IBIA to offer an initial
point of reference with regard to this perceived problem. Information has
been gathered from publications and verbal reports and represents synopses
of the total information available.
Sulphur levels, as defined in the marine world, are specified in ISO 8217 as:
It should be noted that these levels represent maximum limits and in its
present form ISO 8217 does not attempt to specify a minimum level for
sulphur content.
The sulphur level in marine distillate fuels (defined by DMA and DMB) varies
on a worldwide basis. In the case of DMA, which may be described as gas
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oil, this is manufactured primarily for the inland market, and may have a very
low sulphur content to meet local regulations. For example 0.05% sulphur is
commonly used in automotive engines. It is known that at very low sulphur
levels a distillate fuel has reduced lubricity properties and this is overcome by
the use of suitable additives.
Figure 1
Sulphur Content in Marine Fuel Deliveries
Residual fuels used in land based applications can have much lower sulphur
content than the maximum levels specified in ISO 8217. This is due to the
overriding influence of air pollution control legislation. Normally such fuel
commands a higher price than marine fuel oil, which by ISO 8217 may contain
up to 5% wt sulphur fuel designated for the land market to enter the marine
bunker network.
Sulphur will burn and release useful energy so this extent it is a least more
useful than water contamination. However the amount of energy released is
less than would be obtained from typical fuel hydrocarbons in so far as each
percentage of fuel sulphur represents an energy loss of about 0.3 MJ/kg.
Figure 2 shows the relationship between energy content and sulphur levels for
a range of differing fuel densities.
Sulphur will attack the surface of fuel injection components forming very thin
layers of metallic sulfides. This appears to be a distinct disadvantage but is in
reality exactly the opposite. These layers will easily shear and help to prevent
micro-welding and scuffing of the machined surfaces as they rub against each
other during normal engine operation. In effect what is happening is the
sulphur in a fuel acts as a natural EP (Extreme Pressure) additive in much the
same way as those artificially added to high performance lubricants. Fuel
injection components are subject to quite extreme forces during operation and
their designs often rely on some natural lubricity in the fuel passing through
the pumps. Take this away and damage often ensues.
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Figure 3 shows an injector needle from a fuel injector used on a large 2 stroke
marine diesel engine. The needle shows polished marks on the guide and
was the result of 24 hours operation on very low sulphur gas oil.
Figure 3
Damaged Injector Needle
To counter this effect it is common to find that artificial lubricity additives are
added to low sulphur distillate fuels, typically those fuels destined for use in
the road transport industry. These engines often use rotary type fuel injection
pumps which are very sensitive to fuel lubricity properties. It is worth noting at
this point that use of these additives is not a legal requirement and that ISO
8217 merely provides for a maximum sulphur content. Hence, the scenario
that a very low sulphur fuel, with no lubricity additives, can satisfy the
requirements of ISO 8217 but still is unfit for its intended purpose. Beware!
Fuel sulphur content (%) Below 0.25 0.25 – 1.0 1.0 – 3.0 Over 3.5
BN cylinder oil (mgKOH/g) About 10 10 – 20 70 More than 70
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3b. Theories on Engine Wear Reported when Using Low
Sulphur Fuels
Engine Manufacturers have different theories for the high wear that can
sometimes occur when low sulphur fuels are used. One opinion is that
this wear is basically associated with poor “running in”. According to
this theory a certain degree of continuous controlled wear between the
piston rings and cylinder is necessary to maintain a good seal between
the rubbing surfaces by preventing the surfaces from becoming
polished. Polished metal surfaces lose their ability to retain a reservoir
of oil within the surface topography. With little or no oil retention there
is an increased likelihood of micro-seizure leading to scuffing and high
wear rates.
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Figure 4
Plot of the surface of a cylinder liner
High wear rates with low sulphur fuel have been attributed to
deposits on the crown lands of the piston. This is the area
between the top piston groove and the top of the piston crown.
This area can contact the cylinder liner as the piston tilts during
load reversal between compression and firing strokes. This can
occur especially on trunk piston type engines where there is no
cross head guide, and the piston skirt provides vertical
alignment as shown in Figure 5.
Figure 5
Diesel Engine Piston
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This technical update is provided in good faith by IBIA
for the information of IBIA Members only
and no responsibility can be taken by IBIA
for the information and recommendations contained herein.
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