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Marine Chemistry
Marine Chemistry
Structure of atom.
An atom consists of three fundamental particles namely electron, protons and neutrons.
Atom has nucleus and shells around it.
Electrons are present outside the nucleus and are negatively charged.
Protons are positively charged and are present inside the nucleus.
Neutrons are neutral and are present inside the nucleus.
Electrons
Protons
Neutrons
symbol
charge
Mass,g
electron
e-
-1
9.109 x10-28
proton
+1
1.673 x 10-24
neutron
1.675 x 10-24
Element:
All the atoms in a block of gold are of same kind. Similarly, all atoms in a block of lead
are of the same kind (but different from those in a block of gold).
Gold block
lead crystals
1
Symbol:
Generally while writing the symbol of an element, the atomic number is written above
the symbol (superscript). Eg: H1, C6, Al13, Si14and Cl17.
It is not necessary that atomic number should be written above the symbol, it can be
written below (sub script) as well. Eg 80Hg (mercury), 11Na, 12Mg (magnesium) and 29Cu
(copper).
Symbol
Name of an element
Symbol
Hydrogen
Sodium
Na
Zinc
Zn
Calcium
Ca
Boron
Potassium
Carbon
Aluminium
Al
Nitrogen
Copper
Cu
Oxygen
Sulphur
Magnesium
Mg
Chlorine
Cl
Vanadium
Silicon
Si
Fe
Nickel
Ni
Gold
Au
Arsenic
As
Titanium
Ti
Tin
Sn
Elements are broadly divided by physical and chemical character into metals and nonmetals. A few elements display characteristics of metallic and non-metallic elements and
are referred to as semi-metals or metalloids.
Atomic number:
ATOMIC NUNBER = NUMBER OF PROTONS IN ATOM
When two or more then two atoms combine together they form a compound. The forces
that hold atoms together in compounds are called chemical bonds.
Molecule:
One way that atoms can form bonds is by sharing electrons. The bonds are called
covalent bond, and the resulting collection of atoms is called molecule.
The examples of molecules that contain covalent bonds are hydrogen (H2), water (H2O).
Oxygen (O2).
The chemical composition of a pure substance can be represented using the element
symbols, and where necessary, subscripted numbers.
Note that the formula of a particular pure substance does NOT change just because
it becomes part of a mixture. If it retains its own chemical identity in a mixture, i.e. it
does not change chemically, then it must have the same formula.
Compound
NaCl
KI
CaS
Li3N
MgO
CsBr
K+ICa2+S2_
Li+, N3Mg2+, O2Cs+, Br-
Potassium Iodide
Calcium sulfide
lithium Nitride
Magnesium Oxide
Cesium bromide
Mixture : A MIXTURE is a material made up of at least two substances which may be elements
or compounds. They are usually easily separated by physical means e.g. filtration, distillation,
chromatography etc
Eg., Sea water, mixed drinks, metal alloys, sugar water, the atmosphere, milk, hand cream,
smoke, whipped cream.
Chemical Reaction: It is a process that leads to the transformation of one set of chemical
substances to another. Classically, chemical reactions include changes that strictly involve the
motion of electrons in the forming and breaking of chemical bonds between atoms, and can often
be described by a chemical equation.
NaCl(aq) + AgNO3(aq) NaNO3(aq) + AgCl(s)
reactants
products
Steel
aluminum alloys
Titanium alloys
Copper alloys
Zinc
is rather corrosion-resistant material both in air and in water. Rolled zinc is
used in inboard planking of ship rooms. Also, thick plates of rolled zinc are
used in manufacture of protectors. Zinc coating becomes common use in
5
CHAPTER-2
Atom: An atom is a neutral species, in which number of electrons is equal to number of protons
Ion: An ion is an atom or group of atoms that has a net positive or negative charge. negative ion
is called anion and positive ion is called cation.
The best known ionic compound is Common table salt, or sodium chloride, which forms
when neutral chlorine and sodium react.
The oppositely charged sodium and chloride ions attract each other and ionic bonds are formed.
Hydroxyl ion: Hydroxide is a diatomic anion with chemical formula OH. It consists of
an oxygen and a hydrogen atom held together by a covalent bond, and carrying a
negative electric charge. It is an important but usually minor constituent of water.
It functions as a base. The hydroxide ion form salts, some of which dissociate in aqueous
solution, liberating solvated hydroxide ions. Sodium hydroxide is a multi-million-ton per
6
Hydrogen ion: The positively charged ion of hydrogen, H+, formed by removal of the electron
from atomic hydrogen and found in all aqueous solutions of acids.
[H+]
pH - The Power of Hydrogen
functions
used to make mineral stain removers,
toilet bowl cleaners, metal cleaners
and rust removers.
Phosphoric
Nitirc
Citric
Base
Ammonium hydroxide
Salts
Sodium lauryl sulfate, sodium
EDTA
Ammonium ethoxysulfate
CHAPTER -3
CORROSION
Metals and its applications:
Metals are often extracted from the Earth by means of mining, resulting in ores that are relatively
rich sources of the requisite elements.
Metals are widely used because of their various properties and functions:
Property
Function
heat sinks
thermal conductivity
overheating.
Types of metals:
a. Base metal
b. Noble metal
Base metal refers to a metal that oxidizes or corrodes easily. It is common and
inexpensive metal. Examples include iron, nickel, lead and zinc
Noble metal: These metals those are resistant to corrosion or oxidation. They tend to be
precious metals. Examples include tantalum, gold, platinum, silver and rhodium.
Galvanic chart:
(anode)
10
(cathode)
Alloy composition
Water chemistry
pH (7.8 to 8.3)
biofouling
pollution and contamination
galvanic interaction
oxygen content
heat transfer rate
i. temperature
j. Environmental zone
k. Sea water composition and its salinity
l. Velocity of sea water
m. The time of wetness
n. Wind
Types of Corrosion
Stress Fatigue of Metals
When two different metals are connected in the presence of an electrolyte, corrosion occurs.
Galvanic corrosion can damage or destroy underwater metal parts of boats, dock hardware
and other equipment.
11
When two different metals are touching each other or are electrically connected by a
conductor, and are immersed in an electrolyte (an electrically conductive fluid, like salt
water) an electro-chemical reaction can occur. One of the metals (the least noble metal,
called the anode) will corrode faster than it normally would, and the other (the most noble
metal, or the cathode) will dissolve more slowly.
The seawater Galvanic Sequence lists metals in order, based on their voltage potential and
tendency to corrode. More active metals, the faster-dissolving anodes, are at the top of the
series. Passive metals, the cathodes, are located at the bottom.
Your boat might have a collection of submerged, electrically-connected metal parts immersed
in salt water surrounding the boat, in bilge water or the water in the engine cooling system.
The stainless prop shaft, for example, because it is more active (less noble) than the bronze
propeller, will begin to dissolve, leaving the prop intact.
Cathodic protection.
The salt bridge is necessary to complete the circuit and maintain charge neutrality.
Zn+2
Anode
cathode and
SO4-2
anode
Cathode
12
Oxidation occurs
Reduction occurs
Eectrons produced
It is a peculiar form of disintegration that attacks grey cast iron {Fe+C(2.5-4%)+Si (1-3%)}.
Cast iron is an alloy made of iron and carbon, the carbon being in the form of graphite.
When cast iron with such a composition is subjected to graphitization, the iron dissolves
out and leaves only the graphite. This action leaves cast-iron pipes mechanically
weakened, reducing the strength and plasticity.
However, after graphitization corrosion occurs, the graphite pipe may last for many years
because of its lubricity which increases its durability if it is not subjected to any mechanical
forces or sudden pressures.
It has very good damping capacity and hence used as the base machine tool mountings
It can be arrested by using Chromium and Manganese which increase stability of carbides.
13
Graphite
flakes
Fretting Corrosion
Lubrication with oils or greases, to reduce friction and exclude oxygen from the interface.
Increase in the hardness of one or both materials in contact. Certain material
combinations show better friction behaviour than others. Surface hardening treatments can be
beneficial.
Use of seals to absorb vibrations and exclude oxygen and/or moisture.
14
Reductions of the friction loads in certain cases, or on the contrary, increase of the
friction loads to attenuate vibrations.
Modification of the amplitude of the relative movement between the two contacting
surfaces.
Pitting corrosion
Pitting corrosion is particularly dangerous. The attack is in the form of highly localized holes
that can penetrate inwards extremely rapidly, while the rest of the surface remains intact.
A component can be perforated in a few days with no appreciable loss in weight on the
structure as a whole.
The stainless steels are particularly sensitive to pitting corrosion, but other metals, such as
passive iron, chromium, cobalt, aluminium, copper and their alloys are also prone to this form
of damage. Molybdenum is added to stainless steel which can prevent pitting corrosion
Cathodic protection.
15
Fatigue Corrosion
Corrosion-fatigue is due to the applied stresses which are no longer static, but cyclic
(periodically fluctuating or alternating loads).
The cracks are generally trans-granular in nature, with little tendency for branching.
However, a few small secondary cracks may appear in the vicinity of the main crack.
High strength alloys like steel, aluminium, titanium tend to be most highly prone.
Surface shear stress is measured of force applied by fluid flow to the corrosion product film with
sea water density, kinematic viscosity with temperature and salinity.
Under high flow condition corrosion may take the form of impingement (hollow) or cavitation.
The effect of sea water velocity on a metals corrosion rate varies with the particular alloy.
Alloy
Flow rate
Corrosion
Pitting
Ni, Cr, Mo
Pitting
Fe, Co
Pitting
Cu, Fe
Low corrosion
321 Titanium (Ti) and 347 Niobium (Nb) has no affect on sea water velocity
Boiler water:
Boiler is an apparatus which converts water to steam at high pressure and temperature. At such
high temperature and pressure, if we use salty or dirty water, the water will damage the boiler
metal and other parts.
Salts present in sea water are following:
Salt
1) Sodium Chloride
Salt in ppm
25000ppm
2) Magnesium chloride
3000ppm
scale
3) Magnesium Sulphate
4) Calcium Sulphate
5) Calcium Bicarbonate
2000ppm
1200ppm
200ppm
Corrosion in boilers:
When iron is in contact with water containing hydrogen ions, electrochemical corrosion (similar
to battery action) may start and metal may start corroding. You can see this phenomenon by
keeping an iron nail in test tube full of water. After some days you will find that the nail has
started corroding.
To stop electrochemical corrosion, boiler water should be alkaline with no dissolved oxygen in
the feed water. Presence of dissolved oxygen causes corrosion in boiler. In prevention of scale
the BFW (Boiler feed water) must be softened or de-mineralized water.
In order to be non-corrosive to the carbon-steel or low-alloy steel components from which
boilers are usually constructed, the water must be thoroughly de-aerated by using de-aeration
heating tanks, while the last traces of dissolved oxygen are removed by chemical agents
("oxygen scavengers").
Oxygen scavengers include both volatile products (e.g., hydrazine, or carbohydrazine,
hydroquinone, diethylhydroxyethanol, methylethylketoxime, etc.)
N2H4 + O2 = 2 H2O + N2
Non-volatile salts (normally: sodium sulphite, Na2SO3, or a derivative of Cobaltous chloride).
The latter salts often contain catalysing compounds to increase of rate of reaction with dissolved
oxygen.
18
One more method used to reduce the amount of oxygen in boiler feed water is to maintain as
high a temperature as possible. This is because increasing the water temperature can drive off the
oxygen in gaseous form. It is therefore essential to ensure good feed tank design, and that as
much condensate as possible is returned to the system. The use of condensate is preferable for
heating the feed tank rather than a steam sparge (spray) or external heat source, because it is a
recycled heat source and so helps to conserve energy and reduce operating costs.
Types of Corrosion in Boilers:
Caustic Gouging or Caustic embrittlement:
Sodium carbonate is used in softening of water by lime soda process, due to this some
sodium carbonate maybe left behind in the water. As the concentration of sodium carbonate
increases, it undergoes hydrolysis to form sodium hydroxide which dissolves the iron of the
boiler. As water evaporates in the boiler, the concentration of sodium carbonate increases in
the boiler. Thus formed NaOH again attacks iron in stressed region and dissolve it. This
causes embrittlement of boiler parts like rivets, bends and joints, which are under load owing
to stress concentration.
This can be prevented by using sodium phosphate instead of sodium carbonate as softening
reagents. Addition of sodium phosphate produces an insoluble precipitate with magnesium
hydroxide and magnesium and calcium silicates which can be removed through filters.
19
Adding tannin or lignin to boiler water blocks the hair-line cracks and prevents infiltration of
NaOH into these areas. Adding Na2SO4 to boiler water also blocks hair-line cracks.
Scaling
As water is heated and converted into steam, contaminants brought into a boiler with makeup
water are left behind. The boiler functions as a distillation unit, taking pure water out as steam,
and leaving behind concentrated minerals and other contaminants in the boiler. Scale forms as a
result of the precipitation of normally soluble solids that become insoluble as temperature
increases. Some examples of boiler scale are calcium carbonate, calcium sulphate, and calcium
silicate.
Mechanical straining: It is break down of surface of the metal, which causes groove
It is due to:
Grooves are occurred through mechanical straining which results in pitting corrosion.
20
Carryover
in steam demand.
It is aggravated by impurities in boiler water.
Foaming is the carryover of fine suspended particles in the boiler water which causes a stable
froth on the surface of the boiler water, which is then carried out with the steam.
These suspended particles collect in the surface film surrounding the steam bubbles and make
it tougher and the steam bubble resists breaking and builds foam.
The finer the suspended particles the greater the collection in the bubbles.
Over a period of time, deposits due to foaming can completely plug a steam or condensate
line.
Prevention of corrosion in boiler and feed system by maintaining the boiler water in an
alkaline condition, free from dissolved gases.
Control of sludge formation and prevention of carry over with the steam.
Prevention of entry into boiler of any foreign matter such as oil, waste, mill scale, iron
oxide, copper particles, sand, weld spatter etc.
21
Purpose
Chemical
To prevent scale
Na3PO4
NaOH or Na2CO3
To condition sludge
Sodium aluminate,
Polyelectrloytes, tannins, starch
Na2SO3 or N2H4
Na2SO4 or NaNO3
Anti foams
Cathodic protection
Two methods are used to apply the cathodic protection to a metal structure.
a. ICCP method
For example, steel when submerged in sea water generally has a normal potential of -500mV to
-600mV w.r.t.( with respect to) an Ag/AgCl reference electrode. At this potential steel corrodes.
But if by impressing a current onto the surface the potential of the steel can be moved to -750mV
or more negative w.r.t an Ag/AgCl reference electrode corrosion stops and the steel is protected.
[ top]
23
Carefully designed ICCP Systems can compensate for a fair amount of coating damage
and help extend dry-docking intervals.
There are typically no anode removals required during the dry-docks unlike in the case of
Sacrificial Anode system and hence, maintenance costs are reduced.
The instrumentation on the ICCP control panels enables the protection levels to be
continuously monitored.
The ICCP anodes are generally flush mounted on the hull or even if surface mounted are
very few in number thereby reducing structural loading as compared to sacrificial anode
and providing significantly less hydrostatic and hydrodynamic resistance, thereby
reducing fuel consumption of the ship.
brushes on a silver race ensure maximum contact with the least resistance to allow for
optimal drainage of the current.
In summary, corrosion can thus be seen to be an electro-chemical phenomenon. Its
prevention by cathodic protection is also an electro-chemical process. The principle of
cathodic protection is to create a potential gradient opposing the flow of electrons from
the surface to be protected.
The silver brushes are held onto the shaft via brush holders, which ensure a constant
contact between the brushes and the slip ring. An optional monitoring unit can be
provided to monitor the shaft to hull potential and change the brushes when they are
worn.
This method is used for the protection of pipelines and the hulls of ships in sea water. In
this method, an electric current is applied to the metal surface by use of DC electrical
circuit. The negative and positive terminal of the current source is connected to the metal
requiring protection and an auxiliary anode respectively. The flow of electric current
charges the structure with electrons and changes the electrode potential in the negative
direction. This process continues till it reaches the immunity region. The current flows
from anode to cathode. Thus it protects the metal surface from corrosion.
25
Sacrificial anode cathodic protection: This is especially used for ships, offshore oil and
gas production platform etc. Sacrificial Anodes are highly active metals (Zn, Mg, Al
alloys) that are used to prevent a less active material surface from corroding. Sacrificial
Anodes are created from a metal alloy with a more negative electrochemical potential
than the other metal it will be used to protect. The sacrificial anode will be consumed in
place of the metal it is protecting, which is why it is referred to as a "sacrificial" anode.
Surface protection
There are many ways in which we can minimize, and sometimes even prevent the occurrence of
corrosion. Protective surface layer can prevent oxygen and water from reaching the metal
surface.
Concept
Industrial Process
Protective Coatings
1.
Organic
Paint
2.
Metallic
Electro plating
Galvanizing
Metallic spray
3.
Non Metallic
Anodizing
26
Paint: It is a liquid product applied on objects usually in a relative thin layer of 1 micron, which
creates a film that has tendency to tighten into a thin continuous layer. On drying this film
becomes solid hard or tough layer to protect the surface from corroding.
Components of paints:
Binding agent
Pigments
Solvents(volatile)
Cohesive substance
Dissolve and dilute the binding agent
Prevent sagging
Protection of underlying material from heat
Counteract film forming
27
Electroplating: Electroplating is the process of plating one metal onto another, to prevent
corrosion of a metal. There are also specific types of electroplating such as copper plating, silver
plating, and chromium plating. Electroplating allows to use inexpensive metals such as steel or
zinc for the majority of the product and then apply different metals on the outside to account for
appearance, protection, and other properties desired for the product.
The overall process of electroplating uses an electrolytic cell, which consists of putting a
negative charge on the metal and dipping it into a solution that contains metal salt (electrolytes)
which contain positively charged metal ions. Then, due to the negative and positive charges, the
two metals are attracted to each other.
28
When exposed to the atmosphere, the pure zinc (Zn) reacts with oxygen (O2) to form zinc
oxide (ZnO), which further reacts with carbon dioxide (CO2) to form zinc carbonate
(ZnCO3), a usually dull grey, fairly strong material that stops further corrosion in many
circumstances, protecting the steel below from the elements.
Galvanized steel is widely used in applications where rust resistance is needed, and can be
identified by the crystallization patterning on the surface (often called a spangle).
Galvanized steel can be welded; however, one must exercise caution around the resulting
zinc fumes. Galvanized steel is suitable for high-temperature applications of up to 392F
(200C). The use of galvanized steel at temperatures above this will result in peeling of the
zinc at the intermetallic layer.
Metallic sprays: It is directly sprayed onto metal surfaces to stop and prevent rust.
No primer needed; direct to metal
Long-lasting rust protection; prevents future rust formation
Superior fade resistance
Anodizing: It is an electrolytic process used to increase thickness of oxide layer on the surface
of metals parts to increase corrosion resistance and provides better adhesion for paints and glues.
Eg., Chromium(Cr) in stainless steel form chromium oxide ( Cr2O3)on the surface of steel to
prevent corrosion; Aluminium (Al), which corrodes rapidly, becomes noncorrosive due to
aluminium oxide (Al2O3) film on its surface.
29
CHAPTER -4
Classification of crude petroleum
30
31
Refineries convert the crude oil feedstock into commercial products by means of suitable
distillation and chemical reactions, resulting in the production of a variety of valuable fuels and
32
Paraffinic hydrocarbons (CnH(2n+2)) are lower in specific gravity than aromatic hydrocarbons
of the same boiling point, while naphthenic and olefinic compounds are intermediate in density.
Their resistance to chemical change or oxidation is very good. These hydrocarbons are clean
burning, and thus are desirable in distillates such as gas oil or diesel oil.
Aromatic hydrocarbons (CnH(2n-6)) possess a much higher specific gravity than the other three
classes. Aromatics are very stable under heat and are chemically active to a moderate degree. The
aromatic compounds contain a higher proportion of carbon than the other hydrocarbon types.
Due to this characteristic, they have a tendency to smoke, which somewhat limits their use in
diesel engines.
Naphthenic hydrocarbons (CnH2n-ring type) are extremely stable, cyclo-ring compounds and
in many cases have more stability than the paraffins. These hydrocarbons are more commonly
33
Atmospheric Distillation
Fractions of atmospheric distillation is characterized by:
a. Generally low density and viscosity
34
This is the oldest and most common refining process and consists of boiling
crude oil at atmospheric pressure in a fractionating tower up to temperatures
not exceeding 371 degrees Centigrade. Beyond this temperature, heavy
hydrocarbons begin to crack and materials form which are not desired at this
Vacuum Distillation
Vacuum distillation fraction is characterized by:
a. High density and viscosity
b. A residual oil will yield additional heavy distillates with a much higher
concentration of the impurities originally present in the crude oil.
c. Operated below atmospheric pressure
The high viscosity feed stock is broken down to a residuum which is considerably
lower in viscosity than the original feed stock. While this product can be utilized
as a heavy marine fuel with little or no blending back with a lighter distillate, it
has increased specific gravity, and less desirable characteristics, such as high
Conradson carbon and high asphaltenes. It is usually less stable
and less compatible with other residuals than the original feed stock. These
characteristics can present problems for marine diesel power plant and fuel
treatment system operation.
36
37
In this process, the feed stock, straight-run residual, is heated to high pressure and
temperature in the reaction chamber. The heavy, large, long chain oil molecules of
the residual fuel are cracked or broken, producing both short chain and additional
longchain molecules.
These cracked products are then vaporized in the flash chamber and flow to the
fractionating tower where they are condensed at different levels to the products.
Thermal cracking increases the yield of high quality distillate fuels from crude oil,
and reduces the yield of residual fuel. Like vis-breaking, this process also yields
residual fuels with a high specific gravity and a high sulfur, vanadium, Conradson
38
Catalytic cracking:
Characteristics of fractions from catalytic cracking
a. Very high density and high viscosity
b. High contents of aromatics
c. A danger for the presence of catalytic particle and fines in the residual oil.
d. It is operated at low temperatures (665 to 760 C) and pressures in the presence of a
catalyst.
39
40
Alkylation Process:
The alkylation process in petroleum refining combines low-molecular-weight olefins (primarily a
mixture of propylene and butylenes) with isobutane in the presence of a catalyst, either sulfuric
acid or hydrofluoric acid. The product is called alkylate and is composed of a mixture of highoctane, branched-chain paraffinic hydrocarbons. Alkylate is a premium blending stock because it
has exceptional antiknock properties and is clean burning. The octane number of the alkylate
depends mainly upon the kind of olefins used and upon operating conditions.
41
CHAPTER -5
A hazardous material is a material which is capable of producing harmful physical or health
effects.
Harmful physical effects include fire, sudden release of pressure, explosion, and other violent
reactions.
Harmful health effects include acute conditions and chronic conditions.
Acute conditions develop soon after over-exposure to hazardous materials and include burns,
rashes, respiratory distress, convulsion, and possibly even death.
Chronic conditions develop after long term exposure to hazardous materials and include cancers,
nervous system disorders, and damage to other organ systems.
42
Many Federal, State, and Local agencies regulate hazardous materials in order to protect human
health and the environment.
LABELS AND DOCUMENT FOR TRANSPORT OF DANGEROUS CHEMICALS
CLASS 1
DIVISION 1.1
DIVISION 1.2
DIVISION 1.3
DIVISION 1.4
DIVISION 1.5
DIVISION 1.6
EXPLOSIVE
MASS EXPLOSIVE HAZARD
PROJECTION HAZARD
MASS FIRE HAZARD
MINOR EXPLOSION HAZARD
VERY INSENSITIVE EXPLOSIVES
EXTREMELY INSENSITIVE EXPLOSIVES
Background: orange
(* Place for class or division number as appropriate) and (*** Place for compatibility group)
Class 2: Gases
Division 2.1 (Flammable Gas) is a gas which will readily ignite at a concentration of
13 % of less in air and has a flammable range of at least 12% regardless of the lower
flammability limit. Example: Flammable gases: Hydrogen, Propane, Silane.
Division 2.2 (Non-Flammable Gas) Example: Non-Flammable gases: Nitrogen,
Carbon dioxide, etc.
Division 2.3 (Poisonous Gas) is a gas which is known to be so toxic to humans as to
pose a hazard to health during transportation or for which actual testing has shown
that the lethal concentration which kills 50% of the test animals (LC50) is less than or
43
equal to 5000 ml/m3 (0.5% by volume in air). example: Poisonous gases: Hydrogen
sulfide, Hydrogen cyanide, Arsine.
Flammable solids are solids which readily ignite under appropriate conditions, which
may include exposure to air or water, friction, or an ignition source.
Division 4.1 (Flammable Solid) includes certain explosives which have been wetted
with water or alcohol and are not sensitive to explosion, but can ignite and burn; and
chemicals which are specifically assigned to Division 4.1 by the DOT.
Division 4.2 (Spontaneously Combustible Material) means a pyrophoric material
or a self-heating material. Lithium alkyls are an example of a pyrophoric material (a
chemical which spontaneously ignites when exposed to air)
44
Division 4.3 (Dangerous when wet material) means a material that, by contact with
water, is liable to become spontaneously flammable or to give off flammable or toxic
gas example: Sodium, Potassium, and Lithium hydride.
Degree of Danger
Great
II
Medium
III
Minor
46
Class 8: Corrosive
A CORROSIVE material (Class 8) means a liquid or solid that causes full thickness
destruction of human skin at the site of contact within a specified period of time; or a
liquid that exhibits a corrosion rate on steel or aluminum surface.
Hazardous materials must be stored based on their compatibility, Store materials of the same
hazard together i.e. flammables with flammables and oxidizers with oxidizers. Incompatible
materials must not be stored such that they may come in contact with each other.
If incompatible materials are allowed to mix dangerous conditions will result. Combining these
materials may result in the following:
heat or pressure;
fire or explosion;
47
violent reaction;
OXYGEN
48
49
CHAPTER -6
In the late 1960s, marine diesel engines were the primary means of ship propulsion. Through the
late 1970s, marine engine heavy fuel oil grades remained identified solely by their maximum
viscosity. This worked well with heavy fuel originating from atmospheric refineries.
Fuel-related operational problems arose with the generalized upgrading of refinery operations in
the second half of the 1970s from straight run to complex refining. 1982 saw the publication of
marine fuel specification requirements by the British Standard Organization (BS MA 100), and
by CIMAC (Conseil International de Machines Combustion).
An international ISO standard has existed since 1987: ISO 8217. The stated purpose of ISO 8217
is to define the requirements for petroleum fuels for use in marine diesel engines and boilers, for
the guidance of interested parties such as marine equipment designers, suppliers and purchasers
of marine fuels. These specifications are regularly revised to accommodate changes in marine
diesel engine technology, crude oil refining processes and environmental developments.
50
51
(note: Sulphur level is 0.0050 m/m % max., and subject to decrease to 0.0010 m/m % max. in
2009. Again, the alkalinity (BN) and dispersancy of the lubricant may have to be adjusted
accordingly)
Distillate Marine diesel Oil (MDO/DMB): Distillate marine diesel typically has a lower cetane
index than marine gasoil, and has a higher density. With the production slate of a catalytic
cracking refinery, distillate marine diesel can therefore contain a higher percentage of LGO than
marine gasoil.
(note: marine diesel has a sulphur content between approx. 0.3 and 2.0 m/m %. Due to recent
EU legislation (Directive 2005/33/EC amending Directive 1999/32/EC), the sale of marine
diesel oil with a sulphur content above 1.5 m/m % within the EU is prohibited as of August 11,
2006.)
Blended marine diesel (MDO/DMC): With atmospheric refining, blended marine diesel
(MDO) can contain up to 10% IFO with either marine gasoil (MGO or distillate marine diesel
(MD). With complex refining, MDO no longer corresponds to a specific composition and
extreme care must be used when blending this grade to prevent stability and/or combustion
problems.
Heavy Fuel oil (HCO): Heavy fuel oil (typical viscosity at 50C: 130 mm2/s) contains
approximately 60% aromatics, and is a high-density fraction: the density at 15C is above 1 kg/l
(typically 1.02). It is the bottom fraction of the FCC unit. The catalytic process of this unit is
based on an aluminum silicate. Some mechanical deterioration of the catalyst occurs in the FCC
process, and the resulting cat fines are removed from the HCO in the refinery. This removal,
however, is not 100% efficient and a certain amount (ppm level) of cat fines remains in the HCO.
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53
Pour point: For pumping and handling purposes, it is often necessary to know the minimum
temperature at which a particular fuel oil loses its fluid characteristics.
Crude oils tend to have higher pour points and can require more attention to storage and heating.
Also, straight-run residuals tend to have higher pour points than the corresponding cracked
residuals would possess.
The behavior of an oil at low temperature depends upon the type of crude from which it is
refined, the method of refining and the presence, if any, of additives Paraffinic base stocks
contain waxy components which remain in solution at warmer temperatures. When the
temperature is decreased, these waxy components begin to crystallize. They become fully
crystallized at a temperature slightly below the pour point. At this temperature, the undisturbed
oil generally will not flow under the influence of gravity.
Crystallization of the waxy components does not mean that the oil as a whole is solidified flow
simply is prevented by the crystalline wax structure. This structure can be ruptured by agitation
and the oil will proceed to flow, even though its temperature remains somewhat below the pour
point.
An oil that is predominantly naphthenic, on the other hand, reacts in a somewhat different
manner. Even with a comparatively low wax content, a naphthenic oil as a whole thickens more
than a paraffinic oil of comparable viscosity when it is cooled. For this reason, at its pour point
the entire body of oil is congealed. Agitation has little effect upon fluidity, unless it raises the
temperature.
The pour point of a fuel takes on importance from the handling and storage aspects. If a fuel has
a high pour point (that is to say, it ceases to flow at a relatively high temperature), then sufficient
tank heating is required to maintain fuel temperature at least l2-28 degrees Centigrade above its
pour point for satisfactory pumping. Additional facilities may be required to purge fuel lines,
especially those exposed to temperatures lower than the pour point of all fuel once the pumping
operation is completed.
Ideally, the pour point limit should not exceed 40 degrees Centigrade. However, 27 degrees is
becoming a more practical, working pour point with todays fuels. Care must be taken not to
55
allow the fuel to reach its pour point while in storage, because a high pour point may indicate the
presence of paraffin crystals which, once formed, will prevent pumping even at 6-12 degrees
Centigrade above the pour point.
Viscosity: It is a measure of the resistance of fluid to shear or flow and is measured in
centistokes (cSt) with a quoted reference temperature (normally 500C).
Viscosity is used principally to give information about the handling treatment and atomization of
the fuel.
The viscosity of a fuel decreases with increasing temperature. Viscosity is needed to determine
the required preheat for obtaining the correct viscosity at the high pressure pumps. Typical
viscosities here should be in the range 10-15cSt in relationship viscosity/temperature.
Caution must be exercised when heating prior to injection to temperatures above
135 degrees
Centigrade because cracking may occur, gases may be given off, and water may
vaporize forming
steam pockets in the fuel line. Insufficiently heated fuel, on the other hand, can
result in poor
atomization and delayed burning, which may lead to higher thermal loading,
scuffing problems,
possible piston and piston ring failure, and to an increase in fuel consumption.
Excess viscosity:
Inadequate viscosity:
Viscosity outside manufacturers specifications at the injectors will lead to poor combustion,
deposit formation and energy loss. The viscosity of the fuel must be such that the required
injection viscosity can be reached by the ships.
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Density: Density of the fuel is needed for quality and quantity calculations and also the value is
needed to select the optimum size of the gravity ring for purification. Density is an absolute
relationship between mass and volume at a stated temperature and normally expressed in kg/m3
(kg/litre) at 15C. The density gives an indication of the ignition quality of the fuel within a
certain product class. This is particularly the case for the low-viscosity IFOs. The product density
is important for the onboard purification of the fuel.
The higher the density determines the effective separation of water, sludge and solid
impurities, because density of fuel oil changes more rapidly with temperature
High density indicates heavily cracked, highly stable hydrocarbons, aromatic fuel with
poor combustion qualities, which can cause abnormal liner wear.
High density in fuel oil leads to poor ignition and combustion. It also further increases in
carbonaceous deposits and debris
Density is important factor for bunker capacities, heating arrangements, injectors and
purifiers.
The maximum specific gravity of 0.991( at150C) can be handled satisfactorily.
Water content:
Water is the one of the contaminant in marine fuel oils and does not yield energy. From the
production source the water contents normally are very low.
Water contamination occurs in transportation system or onboard the ship itself, either as salt
water or fresh water.
Free water should effectively be removed by centrifugal separation, provided the density of the
fuel does not exceed 0.991 at 150C. Special centrifuges able to separate fuels with densities
above 0.991 are available.
Water content in the fuel should not exceed 1.0%. A high water content causes an extra load on
the preheat system. If after purification, the water content remains too high, water vapor lock can
occur and pumps can cut out. If water-contaminated fuel reaches the injectors, combustion can
be erratic. Water in fuel that remains standing in lines for a longer period can cause corrosion.
One of the problems with cracked fuels is their tendency to form very stable emulsions which are
difficult to break in the centrifuge, causing the emulsions to follow through to the day tank and
causing filter blockage of the fine filters. So it is very important to avoid contact between water
and heavy oils by using bunkers tanks to carry ballast water.
57
If emulsion occurs they can be broken by adding a low concentration of 0.05% of an emulsion
breaker to the fuel.
Ash Content: The ash content describes the quantity of non-inflammable material like inorganic
metallic content (vanadium, nickel, iron, sodium, potassium or calcium) other non
combustibles in the fuel oil.
The actual value depends upon:
The ash present in the heavy oil.
The refinery process employed
Contaminations due to sand, dirt, rust scale.
The ash constituents from crude oils are concentrated in residual fuels during the distillation
process, the major being vanadium and nickel in an oil soluble form from f few ppm to
hundred ppm. The fuel oil standards specify maximum ash content by 0.2% by
weight for heavy fuels. There is no economic process to remove these particles
from crude oil residue.
The catalytic fines (Al and Si) at high contents cause problems in cylinder wears
so these should not be exceed 30ppm
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be avoided and in case limited to on-line blending to avoid prolonged storage time of such
blends.
Chemical composition:
Sulphur: The sulphur content of a marine fuel depends on the crude oil origin and the refining
process. When a fuel burns, sulphur is converted into sulphur oxides. These oxides reach the
lubricating oil via the blow-by gas. These oxides are corrosive to engine piston liners and must
be neutralized by the cylinder lubricant.
Sulphur can bring negative effects on diesel engines:
Sulphur cannot be removed from the fuel by pre-treatment and so marine engine lubricants
are developed to cope with this acidity (high BN). If the correct lubricant is used, the sulphur
content of a marine fuel is technically not important but may have environmental
implications. The fuel oil standard specify the sulphur content of any fuel oil used onboard
ships not to exceed 4.5 % by weight.
Sodium: Sodium is an element that is found in the combined form of common salt,
NaCl. The sodium found in fuel can come from several sources. This contamination
is a direct result of storing and handling procedures from the time the fuel leaves
the refinery until it is delivered to bunkers. To some extent, even salt air
condensation in fuel tanks contributes to the overall sodium content.
Sodium in fuel is usually water soluble and can, therefore, be removed with the
centrifugal separator.
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Vanadium:
Vanadium salts come in the residual oils after refining. Vanadium itself is
responsible for forming slag on exhaust valves and seats on 4-cycle engines, and
piston crowns on both 2- and 4-cycle engines, causing localized hot spots leading
eventually to burning away of exhaust valves, seats and piston crowns. When
combined with sodium, this occurs at lower temperatures and reduces exhaust
valve life. As the vanadium content (ppm) increases, so does the relative corrosion
rate.
It cannot be removed by pre-treatment, it can be neutralized during combustion by
the use of chemical inhibitors (such as magnesium or silicon).
Aluminium silicates: Alumina/silica catalyst is carried-over, when this powdered
catalyst is added to the charge stock of a fluidic catalytic cracking (F.C.C.) unit. Due
to erosion and fracture, or not permitted time to settle-out in heated storage some
of the catalyst is not recovered but is carried over with the bottoms from the F.C.C.
unit. The catalyst particles cause accelerated wear in injection pumps and injectors,
piston rings, piston grooves and liners.
Cyclone separators are used to remove the traces of catalyst particles.
Recommended standard for aluminium is 30ppm.
Carbon residue: Conradson Carbon residue(CCR):
It is determined by a laboratory test performed under specified reduced air supply.
It gives an indication of the amount of hydrocarbons in the fuel which have difficult
combustion characteristics leading to engine fouling and abrasive wear. Poor engine
performance caused by slow burning, high boiling point constituents results in
higher thermal loading and changes in the rate of heat release in the cylinder.
Calculated carbon aromaticity index (CCAI): CCAI is an indicator of the ignition
delay of an IFO. CCAI is calculated from the density and the viscosity of the fuel oil.
Although it is not an official specification, it has found its way into many users
60
bunker fuel specification requirements. Some manufacturers specify CCAI limits for
their engines, depending on engine type and application.
CCAI value
Ignition quality
790-830
Excellent
830-850
Good
850-870
satisfactory
870-950
Poor to unstable
Cetane number/ Cetane index: It is only applicable for gasoil and distillate fuels. It is a
measure for the ignition quality of the fuel in a diesel engine. The higher the rpm of
the engine, the higher the required cetane index. The cetane index is an
approximate calculated value of the cetane number, based on the density and the
distillation of the fuel. The cetane index is not applicable when cetane-improving
additives have been used.
The lower the cetane number of a fuel, the greater the ignition delay, and the
longer the period of time between fuel injection and the beginning of the rapid
pressure rise associated with fuel ignition and combustion.
Calorific value: Heat of combustion, specific energy or calorific value, is a
measure of the energy
content of the fuel. It decreases as density, sulphur, water and ash content
increase.
The energy that is stored in fuels is expressed by the calorific value. When burning
mineral oils not only CO2 is produced but also water vapour. The net calorific value
only specifies the energy that can be used without the condensation heat of this
water vapour. It is therefore applicable for diesel engines.
Net specific energy can be calculated with a degree of accuracy from the equation:
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Type of oil
(MDO)/ (MGO)
(IFO)/ (HFO)
kJ/kg.
Flash point: Flash point is the temperature at which the vapors of a fuel ignite
(under specified test conditions), when a test flame is applied. The flash point for all
fuels to be used in bulk onboard vessels is set at PM, CC, 60C minimum. DMX, a
special low cloud point gasoil, may only be stored onboard in drums because of its
< 60C flash point. (PM=particulate matter, CC=closed cup).
Flash point is important from a handling and storage consideration, but is of little
value in determining
combustion characteristics of a fuel. Maintain 10 degrees Centigrade below flash
point in all storage,
settling or service tanks.
The accepted, safe, minimum flash point for fuel oils established by most regulatory
bodies is 60
degrees Centigrade. The primary purpose of reporting flash point is for safety during
storage, heating
and handling of liquid marine fuels. A high viscosity fuel with high specific gravity
and a low flash
point would be difficult to handle, because preheating above its flash point might be
required for
pumping and storage.
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63
Fuel oils can produce dangerous vapours which may be both flammable and poisonous.
Fuel oil which is heated to facilitate efficient bunker transfer and then further heated prior
to consumption in ships engine can reach temperatures approaching 150 0C. Therefore,
Therefore bunkering should be considered a high risk operation, where mistakes can result in
pollution, high financial penalties or even imprisonment.
Responsibility:
The Master, in consultation with the Chief Engineer, shall ensure that the bunker fuel(s) when
taken are in accordance with the fuel specification relating to the particular ship's engines and
auxiliary machinery and as described in the vessels charter party. In particular the bunker receipt
should be examined prior to delivery to ensure that the viscosity and density stated are suitable
for the vessels heating and fuel treatment equipment.
Bunker plan
The bunker plan is a systematic, accurate and representative of the bunkering system onboard.
The plan should show the distribution of the bunkers and be posted by the bunkering station
during bunkering, and must be fully understood and signed by the officers involved in the
operation. Communication
Before commencing bunkers, an effective and reliable means of communication is to be
established and agreed between both parties. The ship is to ensure that an agreed stop command
and slow down command has been established with the bunker provider. The most common
means of communication during bunker operations is by VHF (very high frequency) radio.
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65
The illustration below is a typical emergency communication guide for use when bunkering. It is
good practice for the ship to issue the bunker supplier with this before commencing bunkers.
Before bunkering commences it is highly recommended to inspect the bunker hose for any signs
of damage. Shown below is a section of bunker hose that was found to be damaged before
bunkering commenced. The damaged section was cut out and the hose was satisfactorily pressure
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tested. This caused a delay in the bunkering time, but things could have been much worse had the
split not been identified.
It is strongly recommended that the main fuel bunker tanks are segregated to avoid the mixing of
newly bunkered fuel with fuel remaining on board. Before bunkering, pumps spill back valves to
other tanks are to be in closed. Open the discharge valve from the tank from which discharge is
done and ensure all other tanks discharge valves in closed to avoid mixing of oils.
Mixing of oils can lead to increased stability and compatibility problems, increased ignition and
combustion problems. The bunker storage tanks must be fitted with heating coils sufficient to
maintain the fuel at a temperature necessary to achieve efficient pumping.
To avoid fuel solidifying in transfer pipes, when no fuel is transferred, heat-tracing must be used.
The transfer pumps should be of the positive displacement type, e.g. screw- pumps. This type of
pump will minimise emulsification with any water present.
Tank capacities
Tank capacities should be monitored during bunkering by the use of soundings or ullages.
Sometimes it is easier to use ullages if the bunker tank is large, as this saves time by not having
to clean a large section of the sounding tape after each dip. Ullages should always be taken using
the ullage pipe and reference to the ullage tables for tank contents used.
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Bunkering checklist:
1. state of adjacent waters reviewed and deemed acceptable
2. ship properly secured (unless STS ship to ship)
3. check suppliers specification for the product corresponds to what was ordered
4. agree quantity to be supplied and in what units (m, tonnes, barrels etc)
5. agree maximum pumping rate and line pressure at start, at maximum flow and at
the end
6. ensure that the bunker barge checklist is understood and completed
7. ensure that the bunker plan is understood and posted at the bunker station
8. emergency stop for bunker barge transfer pump at the ships bunker station has been
tested if supplied
9. ensure the MARPOL drip sampler is clean and fitted
10. check correct bunker valves are open
11. cross-check correct bunker valve set-up
12. fuel oil daily service tanks at maximum safe working level, and filling valves closed
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72
73
Determination of the sample point position and the type of sampling equipment to be used
should be agreed prior to the start of bunkering, and this should form part of bunkering
procedures.
The sample should be taken at the ships manifold. It is recommended that shipowners also take
their own commercial samples at the ships receiving manifold which is also the custody transfer
point.
The ship owner has three principal sampling options:
Taking sample by continuous drip at the receiving vessels manifold has long been recognized as
being the most representative sample of the fuel oil supplied. An automatic or manual continuous
drip sampling method is therefore recommended.
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Drip sampling at the appropriate manifold on board should start at the very beginning of
bunker loading to the ship and complete at stoppage of loading thus representing an average
sample of the fuel loaded. Individual samples taken by the above method are to be collected
for each barge delivery
The introduction of the smallest quantity of foreign matter into oil samples will severely
affect the accuracy of the analysis and the following recommendations should be observed:
All sampling equipment should be cleaned before use. The use of aluminium or rusty steel
containers is to be avoided
Collections and handling of samples should be carried out with clean hands by one
designated person
Bunker lines should be drained as soon as possible after each grade is loaded to avoid
consequences of fuels remaining in the line which could lead to future mixing or affect purity
of samples. In addition high pour point / viscosity fuel may block unheated loading lines.
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A minimum of 5 liters of sample over the Bunkering period should be collected for each
grade and regulated manually by the drip sample needle valve. These manifold drip sample
connections should be installed as near as possible to the ship / shore bunker connections
onboard enabling samples to be drawn irrespective of which side the vessel bunkers. The type
of drip sample connection is illustrated in the VPS Instruction Manual. To ensure samples are
identical in quality, the collecting container should be thoroughly mixed prior to official
sample bottles being filled and sealed.
The sample bottles and packaging will meet the requirements of the International Air
Transport Association (IATA) regulations for carriage of marine fuel samples and classed as
"not restricted" flash point above 60.5 c on the label supplied. Sample bottles should be filled
to a maximum of 90 % capacity to allow for volumetric variations
Three sample bottles should be filled for each loading, sealed witnessed by supplier and
Chief Engineer, and labelled accordingly for distribution as follows:
1.
2.
3.
4.
1 sample will be retained for 90 days then may be disposed of unless advised by
the office for reasons such as handling problems, engine damage, pumping purification
problems, or pending investigations.
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Fuel oil loaded onto a ship frequently requires extensive shipboard treatment before it can be
consumed in the main or auxillary engines, ranging from simple filtration to centrifuging and
purification. The condition of fuel oil arriving onboard determines what shipboard treatment is
required, only confirmed after analysis of a representative sample.
The basic shipboard treatment methods include
Heating
Settling and draining
Centrifuging
Filtering
Pre-injection heating
The treatment is primarily determined by the fuel oil condition on loading, it also depends on
treatment equipment onboard and the expertise of the ships marine engineers.
Fuel oil is initially loaded into a ships storage tanks, be they double bottom tanks or others,
where it remains until required for consumption.
Heating may be required, depending upon the pour point and viscosity of the fuel. Bunker
storage tanks must be fitted with heating coils sufficient to maintain the fuel at a temperature
Settling and draining: The fuel oil is then transferred via transfer pumps to ships settling
tanks.
They provide a settling function for suspended water and solids, a heating function, a
de-aeration function, and a thermal stabilizing function.
Ships settling tanks are designed to accept fuel oils with a 60C minimum flash-point. The
two settling tank concept is the most common arrangement fitted.
Thermal insulation of the settling tanks is recommended to avoid heat losses and help to
keep the temperature in the engine room at a tolerable level.
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During normal operation sediment, including cat fines, will collect at the bottom of the
tank. Therefore provision for regular tank-cleaning and total drainage is necessary.
Centrifugal Separators: It is the first major stage of fuel treatment. In order to have effective
operation of separators one must know the fuel oil properties like:
Viscosity
Specific Gravity
Compatibility of fuel oil
Water content
Ash content
Bottom Sediments
Water and sediment levels in the fuel can be effectively controlled in well maintained and
correctly operated purifiers. On the flip side, poorly maintained and operated purifiers will fail to
improve fuel oils to an acceptable quality and result in undue wear or damage to the engine.
The separator heaters and associated control circuits supply heavy fuel oils at the required
temperature i.e., 980C for reliable, efficient separator operation. All installed heavy fuel oil
separators should be online and operated continuously. The only acceptable reason
for not operating a unit is during manual cleaning or overhaul. Single separator flow
rate (for series operation) or combined separator flow rate (for parallel operation)
should not exceed the existing engine fuel consumption rate by more than ten
percent (10%). Each time a new settling tank is pumped, a specific gravity check of
the settling tank should
be made and the separator gravity disc checked and changed if necessary. Each
separator should have all parts necessary to operate as a purifier and as a clarifier.
Its efficient operation is critical to the safety and reliability of the main and auxiliary
propulsion equipment.
Centrifuges use centripetal forces, they operate between 6000-9000 rpm and the
centripetal forces generated enable fast and efficient separation of fuel oil and
liquids (water) if set up as purifier or the fuel oil and solids of set up as clarifiers.
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Purifier manufacturers have performed various tests on particle size and purifier throughput to
determine the effects this has on particle removal. Below is a table showing some interesting
results.
This table illustrates that the best particle removal is when the purifier is operating at 25%
throughput. This of course assumes that the correct gravity disc has been fitted. It should be
noted that most modern purifiers operate without a gravity disc and are known as high density
purifiers. These machines operate as a clarifier but also use water monitoring and control devices
to ensure that no water passes through.
Some basic situations which can cause separators to operate below maximum
efficiency, or not work
at all, are:
Incorrect
Unstable
Incorrect
Unstable
Incorrect
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Filters: The separator system, preferably operating in series, can provide a sizeable initial
reduction in the solids, but not always enough to prevent an increase in engine wear rates. The
remainder of the small solids, as well as a small percentage of large particles, can be effectively
stopped by a five (5) micron (nominal), replaceable element, filters. In addition to solids, trace
quantities of free water carried over from the separators also are removed by these filters.
Service tanks:
Service tanks, or day tanks, have a very important function they provide a final settling function
for water and solids, a heating function and a thermal stabilising function. The settling function is
primarily a backup in the event of a failure of the separators that can damage engine fuel
injection equipment and the engine if this is carried out.
Two service tanks are normally provided. While one service tank is supplying fuel oil to the
system, the other is receiving fuel oil conditioned through the separator and filtration systems.
The tanks normally have high and low suction lines with downturned diffusers. The cleanest fuel
oil is available from the upper (high) suction. The service tanks should have bottom drain
connections for water and sludge stripping. The water and sludge from this bottom drain should
be removed at regular intervals.
Mixing Tank
The mixing tank is usually a narrow, cylindrical insulated tank into which clean, heavy fuel oil
flows from the fuel oil service tank. It also functions as a return tank for recirculated fuel oil
from the engine injection pump return rail. A primary function of the tank is to stabilize service
fuel oil temperature by mixing hotter return oil with cooler service tank fuel oil. The mixing tank
is fitted with a bottom drain. Steam heating coils maintain stable temperature during start-up.
Fuel Oil Service Heaters and Viscometer
Two fuel oil service, steam heated heat exchangers with a capability of heating heavy fuel oil to
150 degrees Centigrade should be installed. The final fuel oil outlet temperature is controlled by
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the viscometer. The viscometer continuously provides a viscosity readout and control signal to
the steam control valve regulating the steam flow to the heat exchanger.
In this system, the viscosity to the diesel engine injectors is held constant even though the fuel
oil temperature might vary slightly. When heating heavy fuel oils to almost 150 degrees
centigrade the
use of properly sized, steam heat exchangers will provide the necessary heat without thermally
stressing the fuel oil with hot spots which produce coked heaters and cracked fuel.
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Recommended Procedures for the Onboard Treatment of Problem Fuels: Very Poor Quality or
Highly Contaminated Fuel Oils:
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Contact with hot product may cause skin burns, including to the underlying skin. Owing to its
high viscosity, this product does not normally constitute an ingestion hazard. Ingestion will only
occur in grossly abnormal circumstances. If ingested can lead to irritation of the mouth,
irritation of the throat, irritation of the digestive tract, vomiting. Aspiration into the lungs may
occur directly or following ingestion. This can cause chemical pneumonitis which may be fatal.
Prolonged exposure to vapour/mist concentrations above the recommended occupational
exposure standard may cause headache, dizziness, nausea, asphyxiation, unconsciousness and
even death.
Protection of first aiders: Wear self-contained breathing apparatus if presence of hydrogen
sulphide is suspected.
First Aid
Inhalation: Remove to fresh air. If breathing but unconscious, place in the recovery position. If
breathing has stopped, apply artificial respiration. If heartbeat absent give external cardiac
compression. Monitor breathing and pulse. OBTAIN MEDICAL ATTENTION
IMMEDIATELY.
Skin: If high pressure injection injuries occur, obtain medical attention immediately. In the case
of burns, wash skin thoroughly with water using soap if available. Do not use kerosene, gasoline
or solvents. Contaminated clothing must be removed as soon as possible. It must be laundered
before reuse. If persistent irritation occurs, obtain medical attention.
Eye: Flush eye with water. If persistent irritation occurs or if there is any suspicion of damage
from hot product, obtain medical attention immediately.
Ingestion: DO NOT DELAY. Do not induce vomiting. Protect the airway if vomiting begins.
Give nothing by mouth. If breathing but unconscious, place in the recovery position. If breathing
has stopped, apply artificial respiration. OBTAIN MEDICAL ATTENTION IMMEDIATELY.
Advice to physicians: Treat symptomatically. High-pressure injection injuries require early
surgical intervention and possible steroid therapy to minimise tissue damage and loss of nerve
function. X-ray examination is required to assess the extent of the injury. Local anaesthetics or
hot soaks should not be used with such injuries since they can contribute to local swelling,
vasospasm and ischaemia. Prompt surgical decompression, debridement and evacuation of
foreign bodies should be carried out under general anaesthetic. Because injected material may be
deposited at some distance from the point of injection, wide exploration is essential. Prolonged
86
within the tank must be monitored using an oxygen meter and/or explosimeter. In addition,
appropriate electrochemical sensors or colorimetric tubes must be used to check for the presence
of hydrogen sulphide.
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when brought into contact with a flame. The fire point is the higher temperature at which the oil
vapor will continue to burn when ignited.
The future of mineral-based lubricating oil is limited, because the natural supplies of petroleum
are both finite and non-renewable. Experts estimate the total recoverable light to medium
petroleum reserves at 1.6 trillion barrels, of which a third has been used. Thus, synthetic-based
oils will probably be increasingly important as natural reserves dwindle.
Synthetic lubricants are organic fluids having specialized and effective properties that are
required in cases where petroleum derived lubricants are inadequate. These are stable
over a wide range to heat and oxidation. They are exceptionally resistant to ionizing
radiation.
Synthetic lube oil
Application
Poly glycols
Phosphate esters
Fire resistance
Chloro- fluorocarbons
Silicate esters
Lubricant: It is a material that has characteristic crystalline habit which cause it to shear
into thin, flat plates, which readily slide over one another to produce an antifriction or
lubricating effect. Eg., mica, graphite, molybdenum disulphide, talc, boron nitride.
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ADDITIVES
These are chemical compounds which are dissolved in the oil to improve the quality for
various suitable applications.
Depending on the application, chemicals called additives may be mixed with the refined
oil to give it desired physical properties.
Common additives include metals such as lead or metal sulphide, which enhance lube
oil's ability to prevent galling and scoring when metal surfaces come in contact under
extremely high pressures.
High-molecular weight polymer are another common additive: they improve viscosity,
counteracting the tendency of oils to thin at high temperatures.
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too viscous, it will require a large amount of energy to move (as in honey); if it is too thin, the
surfaces will rub and friction will increase.
The Viscosity Index highlights how a lubricant's viscosity changes with variations in
temperature. Many lubricant applications require the lubricant to perform across a wide range of
conditions: for example, in an engine.
Automotive lubricants must reduce friction between engine components when it is started from
cold (relative to engine operating temperatures) as well as when it is running (up to
200 C/392 F). The best oils (with the highest VI) will not vary much in viscosity over such a
temperature range and therefore will perform well throughout.
The VI scale was set up by the Society of Automotive Engineers (SAE). The temperatures
chosen arbitrarily for reference are 100 and 210 F (37.8 and 98.9 C).
The original scale only stretched between VI=0 (worst oil, naphthalene) and VI=100 (best
oil, paraffin) but since the conception of the scale better oils have also been produced, leading to
VIs greater than 100.
VI improving additives and higher quality base oils are widely used nowadays which increase
the VIs attainable beyond the value of 100. The Viscosity Index of synthetic oils ranges from 80
to over 400.
vi=(L-U)/(L-H)100 this is the formula used to find the viscosity index.
Where:
Alkalinity additives
Total base number (TBN) is a measure of a lubricant's reserve alkalinity. It is measured
in milligrams of potassium hydroxide per gram (mg KOH/g)
TBN determines how effective the control of acids formed will be during the combustion
process. The higher the TBN, the more effective it is in suspending wear-causing
contaminants and reducing the corrosive effects of acids over an extended period of time.
The associated measurement ASTM D2896 and ASTM D4739-06 generally range from
6-80mg KOH/g in modern lubricants, 7-10mg for general automotive use and 10-15 for
Diesel operations.
Marine grade lubricants generally will run from 15-50mgKOH/g, but can be as high as 70
or 80mg KOH/g as is the case of Exxons MobileGuard 570(It is a superior quality, extra
high performance, marine diesel engine cylinder oil) or respectively Castrols Cyltech
80AW(it is specifically developed for todays and future slow speed engines, it is
eminently suitable for the cylinder lubrication of all types of crosshead engines operating
on todays typical high sulphur residual fuel)this high level is designed to allow a longer
operating period between changes, under harsh operating conditions. When the TBN is
measured at 2mg KOH/g or less the lubricant is considered inadequate for engine
protection, and is at risk for allowing corrosion to take place. Higher sulfur fuel will
decrease the TBN faster due to the increased formation of sulfuric acid.
Calcium sulphocates are added to oil to stop corrosion by the presence of acid during
combustion.
Detergent additives
These additives have greater ability to neutralize combustion acids and oxidation acids.
Common detergents are salts of calcium, magnesium or barium, sulphonic acids, phenols,
salicylic acids.
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These detergents prevent the build-up of carbon deposits.(piston rings, piston skirts etc)
Dispersant additives
It holds the solids in the oil and prevents the build-up sludge.
Helps to keep engine clean.
Anti-Oxidant additives:
It prevents absorb of oxygen from air
Prevents the raise of viscosity of oil
Neutralizing of metallic catalyst like Cu and Fe.
Eg., Nitrosomines
Pour point depressants additives:
Use to control wax crystal growth at low temperature and allow lubricant flow. They co-
Grease
"A solid to semi fluid product of dispersion of a thickening agent in liquid lubricant.
The components of grease are oil, thickener and additives. The base oil and additives are the
major components in grease formulations, and exert considerable influence on the behavior of
the grease. The thickener is often referred to as a sponge that holds the lubricant (base oil +
additives).
Base Oil
Most greases produced today use mineral oil as their fluid components. These mineral oil-based
greases typically provide satisfactory performance in most industrial applications. In temperature
extremes (low or high), a grease that utilizes a synthetic base oil will provide better stability.
Thickener
The thickener is a material that, in combination with the selected lubricant, will produce the solid
to semifluid structure. The primary type of thickener used in current grease is metallic soap.
These soaps include lithium, aluminum, clay, polyurea, sodium and calcium. Lately, complex
thickener-type greases are gaining popularity. They are being selected because of their high
dropping points and excellent load-carrying abilities.
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Complex greases are made by combining the conventional metallic soap with a complexing
agent. The most widely used complex grease is lithium based. These are made with a
combination of conventional lithium soap and a low- molecular-weight organic acid as the
complexing agent.
Nonsoap thickeners are also gaining popularity in special applications such as high-temperature
environments. Bentonite and silica aerogel are two examples of thickeners that do not melt at
high temperatures. There is a misconception, however, that even though the thickener may be
able to withstand the high temperatures, the base oil will oxidize quickly at elevated
temperatures, thus requiring a frequent relube interval.
Additives
Additives can play several roles in lubricating grease. These primarily include enhancing the
existing desirable properties, suppressing the existing undesirable properties, and imparting new
properties. The most common additives are oxidation and rust inhibitors, extreme pressure,
antiwear, and friction-reducing agents.
In addition to these additives, boundary lubricants such as molybdenum disulfide (moly) or
graphite may be suspended in the grease to reduce friction and wear without adverse chemical
reactions to the metal surfaces during heavy loading and slow speeds.
Function
The function of grease is to remain in contact with and lubricate moving surfaces without leaking
out under the force of gravity, centrifugal action or being squeezed out under pressure. Its major
practical requirement is that it retains its properties under shear forces at all temperatures it
experiences during use.
Applications Suitable for Grease
Grease and oil are not interchangeable. Grease is used when it is not practical or convenient to
use oil. The lubricant choice for a specific application is determined by matching the machinery
design and operating conditions with desired lubricant characteristics. Grease is generally used
for:
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Characteristics
As with oil, grease displays its own set of characteristics that must be considered when being
chosen for an application. The characteristics commonly found on product data sheets include
the following:
may be used.
Oxidation stability. This is the ability of grease to resist a chemical union with oxygen.
The reaction of grease with oxygen produces insoluble gum, sludges and lacquer-like
deposits that cause sluggish operation, increased wear and reduction of clearances.
Prolonged exposure to high temperatures accelerates oxidation in greases.
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High-temperature effects. High temperatures harm greases more than they harm oils.
Grease, by its nature, cannot dissipate heat by convection like circulating oil.
Consequently, without the ability to transfer away heat, excessive temperatures result in
accelerated oxidation or even carbonization where grease hardens or forms a crust.
Effective grease lubrication depends on the grease's consistency. High temperatures
induce softening and bleeding, causing grease to flow away from needed areas. The
mineral oil in grease can flash, burn or evaporate at temperatures greater than 177C
(350F).
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