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CHAPTER-1

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

Properties of subatomic particles


Particle

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:

An ELEMENT is a pure substance made up of only one type of atom

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
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Symbol:

It is the shortest representation of Greek, Latin or English name of an element. Symbol


can be one or two English letters.

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).

Examples of some common elements:


Name of an element

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

Iron (latin name ferrum)

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

Hydrogen atom has one proton so the atomic number of hydrogen is 1

He(helium) has two protons so its atomic number is equal to 2

Li (lithium) has 3 protons so its atomic number is equal to 3

C (carbon) has 6 protons so the atomic number is equal to 6.

U (uranium) has 92 protons so the atomic number is equal to 92.

Mass Number: Mass Number = Number of protons + Number of neutrons


For example Carbon 12C6 its atomic number is 6 (which is always less than mass number) mass
number is 12. We can find out no of electrons, protons and neutrons in it.

Mass number = number of proton + number of neutrons


12 = 6 (atomic number is 6) + neutrons

Number of Neutrons are = 12 6 = 6


Number of electrons are = 6

Compounds , ions and molecules:

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).

COMPOUND is a chemical combination of two or more different elements.

The chemical composition of a pure substance can be represented using the element
symbols, and where necessary, subscripted numbers.

A formula represents the relative numbers of atoms of each element in a substance.

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

Ion present Name


Na+, ClSodium Chloride

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

Oxide: A protective film that develops on the surface of a metal.

Eg., Rust is an oxide of iron.


Alloy: An alloy is a metal (parent metal) combined with other substances resulting in superior
properties such as; strength, hardness, durability, ductility, tensile strength and toughness. The
parent metal is the majority of the alloy.
Eg., Stainless steel: iron ore, chromium, silicon, nickel, carbon, nitrogen, and manganese.
Brass is an alloy of copper and zinc
Bronze: Alloy of Cu and Sn
Monel: Ni(67%) Cu and Fe
Materials used to construct ships:

The diversity of materials used in shipbuilding is conditioned by diversity of requirements to


operating characteristics of mechanisms and structural components of the vessel. All these
materials are classified as follows:

Hull metallic and non-metallic materials for shipbuilding


Materials for ship and general machine-building
Materials for fabrication of nuclear and heat engines.
Material
Functions

Steel

strength, flexibility, high manufacturability, weldability, cost, reparability

aluminum alloys

increased corrosion resistance , used as cast in manufacture of various critical


parts particularly, pistons and casings for internal combustion engines

Titanium alloys

became common use in marine facilities. Distinctive characteristic of their


usage is wide spectrum of operational environment with long service life

Copper alloys

are very common. It is conditioned by their high corrosion resistance, adequate


strength under various loads, high antifriction properties, heat and electro
conductivity as well as resistance to fouling

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
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corrosion prevention for metal surfaces of ship systems.

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
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annum commodity chemical. A hydroxide group attached to a strongly electropositive center


may itself dissociate, liberating a hydrogen cation (H+), making the parent compound an acid.

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

ACIDS, BASES AND SALTS


Acids, bases and salts contain ions of the element hydrogen. It is the presence of the hydrogen
ions in solutions that allows us to measure the pH of a solution. The quantity of hydrogen or
hydroxyl ions in a solution determines whether the solution is acid or alkaline.
Substance
Acids
Hydrochloric

functions
used to make mineral stain removers,
toilet bowl cleaners, metal cleaners
and rust removers.

Phosphoric
Nitirc
Citric

Base

degreasers, oven cleaners and drain


openers

Sodium hydroxide, potassium


Hydroxide, sodium metasilicate,
Trisodium phosphate and
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Ammonium hydroxide
Salts
Sodium lauryl sulfate, sodium
EDTA

carpet shampoos, hand soaps and


carwash detergents to provide more
efficient cleaning.

Ammonium ethoxysulfate

pH is defined as the negative logarithm of the H+ concentration.


pH = - log [H+]
The pure water contained a hydrogen ion concentration of 1 x 10-7 moles.
The acidic water (hydrochloric acid) contained a hydrogen ion concentration of 1 x 100 moles and
alkaline water (sodium hydroxide) contained a hydrogen ion concentration of 1 x 1014 moles.
The pH of a neutral solution is 7. Thus the range of acid pH values extends from 0 to 7, and that
of alkaline values from 7 to 14.
pH is a critical measurement. Life depends upon it. For instance, human blood is basic with a pH
between 7.3 and 7.5. If the pH of blood drops below 7.3, acidosis occurs. If the blood pH rises
above 7.5, alkalosis occurs. Death will occur if blood pH goes below 7.0 or above 7.8. Our
human existence depends upon a balanced and buffered blood pH.
SEVERAL METHODS FOR MEASURING pH
1. Litmus paper 2. liquid acid-base indicators. 3. pH meter. The amount of alkali or acid in
a solution, they use a process called, titration. Titration measures the amount of alkali
and/or acid in a solution.

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

high structural strength high

carry large loads or resisting impact


damage.

resistance to shear, torque and


deformation
good conductors

making them valuable in electrical


appliances and for carrying an electric
current over a distance with little energy
lost.

strength and resilience

frequent use in --- high rise building and


bridge construction, vehicles, many
appliances, tools, pipes, non-illuminated
signs and railroad tracks.
to protect sensitive equipment from

heat sinks

thermal conductivity

overheating.

useful for containers to heat materials


over a flame

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)

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(cathode)

Factors that affect the corrosion process:


a.
b.
c.
d.
e.
f.
g.
h.

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

Fundamental process of corrosion


Corrosion by sea water, is an electrochemical process, and all metals and alloys when in contact
with sea water have a specific electrical potential (or corrosion potential) at the pH.
Sea-water is, unfortunately, an excellent electrolyte and gets everywhere on a boat.
Galvanic corrosion:

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.
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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.

Means of reducing or preventing pitting corrosion:

Reduce the aggressivity of the acidic medium,

Cathodic protection.

The salt bridge is necessary to complete the circuit and maintain charge neutrality.
Zn+2

Anode

cathode and

SO4-2

anode

Cathode

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Oxidation occurs

Reduction occurs

Eectrons produced

Electrons are consumed

Anions migrate toward

Cations migrate toward

Has negative sign

Has positive sign

Graphitization of cast iron or graphitic softening:

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.

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Graphite
flakes
Fretting Corrosion

Fretting-corrosion is a combined damage mechanism involving corrosion at points where


two moving metal surfaces make rubbing contact.
It occurs essentially when the interface is subjected to vibrations and to compressive
loads. The amplitude of the relative movement is very small, typically of the order of a
few microns.
When the frictional movement in a corrosive medium is continuous, the resulting process
is termed tribocorrosion.

Friction-wear at an axle-cylinder contact point

Means of preventing 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.

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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.

Pitting corrosion is most aggressive in acidic solutions containing chloride, bromide or


hypochlorite ions. The presence of sulfides and H2S increases pitting corrosion, and
systematically impairs the resistance criteria for this type of attack. The presence of an
oxidizing cation (Fe+3, Cu+2, etc.) enables the formation of pits even in the absence of oxygen.

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

Very often, in non-passivatable metals, a "tubercular" surface morphology is observed,


beneath which pits develop.
Means of reducing or preventing pitting corrosion : Choose the material most appropriate
for the service conditions, avoid stagnant zones and deposits

Reduce the aggressivity of the acidic medium,

Cathodic protection.

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Tubercle on surface of copper tube

Pit on stainless steel tank

Fatigue Corrosion

Corrosion-fatigue is due to the applied stresses which are no longer static, but cyclic
(periodically fluctuating or alternating loads).

It rupture the protective passive film and corrosion is accelerated

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.

Methods to reduce fatigue corrosion

Corrosion-fatigue damage can be prevented or reduced by decreasing the tensile stresses,


either by the use of stress-relief annealing, by modifying component design, or by applying
mechanical surface treatments such as peening(working on metal surface to improve its
properties), to introduce surface compressive stresses.

Improvement of the surface condition by polishing is generally beneficial.

Corrosion inhibitors are highly effective.

Relation of Sea water velocity with increased rate of corrosion:


Fluid velocity can significantly affect metal corrosion rates in sea water
Fluid flow can increase corrosion rates by
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Removing protective films


By increasing the diffusion or migration of deleterious species like HCO3-, Cl-, SO4-2, CO32
( break passivity and leads to pitting and stress corrosion as they has high penetrating
power through metal surfaces)

An increase in fluid flow can decrease corrosion rates by

Eliminating aggressive ion concentration


Enhancing Passivation
Inhibition by transporting the protective species to the fluid or metal interface.

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

304, 316 stainless steel (low


grade carbon steel)

Low flow conditions

Pitting

Ni, Cr, Mo

Low flow conditions

Pitting

Fe, Co

High flow condition

Pitting

Cu, Fe

Low flow conditions

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

Effect in feed water


Priming and foaming
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2) Magnesium chloride

3000ppm

scale

3) Magnesium Sulphate
4) Calcium Sulphate
5) Calcium Bicarbonate

2000ppm
1200ppm
200ppm

scale -effect heat transfer


Hard tenacious scale effect heat transfer
Scale

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.

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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:

Caustic embrittlement is the phenomenon in which the material of


a boiler becomes brittle due to the accumulation of caustic substances.

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.
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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:

Mal operations of the boiler

Raising steam too rapidly from cold

Missing or poorly connected internal feed pipes

Fluctuating feed temperature and steaming conditions.

Due to differential aeration of a portion of a metal

Grooves are occurred through mechanical straining which results in pitting corrosion.
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Carryover

Carryover is caused by either priming or foaming.


Priming is the carryover of varying amounts of droplets of water in the steam (water/mist)
which lowers the energy efficiency of the steam and leads to the deposit of salt crystals on the

super heaters and in the turbines.


Priming results in sudden violent eruption of boiler water, which is carried along with steam

out of the boiler, usually caused by mechanical conditions.


Priming caused due to improper construction of boiler, excessive ratings or sudden fluctuation

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.

Boiler water treatment:


Following are the preventive measures used in boiler water treatment.
Prevention of scale formation in boiler and feed system by using distilled water or
precipitating all scale forming salts into non adherent sludge.

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.

Measures taken to prevent corrosion

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Purpose

Chemical

To prevent scale

Na3PO4

To prevent Alkalinity and


minimize corrosion

NaOH or Na2CO3

To condition sludge

Sodium aluminate,
Polyelectrloytes, tannins, starch

To removes traces of oxygen

Na2SO3 or N2H4

To reduce risk of caustic


cracking

Na2SO4 or NaNO3

To reduce risk of carryover foam

Anti foams

To protect feed and condensate


systems from corrosion

Filming amines or neutralizing


amines

Cathodic protection
Two methods are used to apply the cathodic protection to a metal structure.
a. ICCP method

b. Sacrificial anode protection

Impressed Current Cathodic Protection(ICCP):


It is mostly used on ships with the length exceeding 40m and fast ships like patrol vessels and
hydro foil boats
Impressed Current Cathodic Protection System works on the principle that current flowing on to
any metal shifts its normal potential in the negative direction and if correct amounts of current
can be impressed on the surface to be protected, the potential of the surface can be shifted
sufficiently to a level where the surface will not corrode.
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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]

FUNCTIONING OF AN IMPRESSED CURRENT CATHODIC PROTECTION SYSTEM


ICCP Systems work by taking the ships power, converting it using as a transformer rectifier unit
into direct current and impressing this on to the hull through inert anodes strategically positioned
on the hull.
The current will flow from the inert anodes through the sea water and back to the hull. This is
ensured by a sufficiently large dielectric coating applied on the hull around the anode.
ICCP Systems are generally self-regulating using a feedback control system. This is done by
positioning suitable Reference Electrodes at various points on the structure to measure the
potential of the structure at those points. By comparing the measured potential with the desired
non-corroding structure potential, the control unit of the ICCP System determines whether the
current feed to the hull through the anodes should be increased, decreased or maintained. The
objective is to ensure that the potential of the structure as measured by the Reference Electrodes
is as close to the desired protection potential as possible.

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ADVANTAGES OF AN ICCP SYSTEM

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.

For complete protection of ships, it is imperative to electrically ground the ships


propeller to the hull. The propeller shaft being a rotating item needs to be properly
grounded to the hull to minimise stern area corrosion and current induced damage to the
propeller shaft bearings and gearboxes.
This is achieved, whether the main hull is protected by a sacrificial or impressed current
system, by using a Propeller Shaft Grounding System.
Cuprobans shaft grounding systems consist of a set of silver graphite brushes sliding
over a copper slip ring layered in with a silver race mounted on the shaft. The silver
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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.

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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
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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

Coherence of the paint


Connecting the pigment
Adhering paint to the base

Pigments

It gives colour to the paint

Solvents(volatile)

Cohesive substance
Dissolve and dilute the binding agent

Additives and fillers

Prevent sagging
Protection of underlying material from heat
Counteract film forming

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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

Galvanization (or galvanisation):

It is the process of applying a protective zinc coating to steel or iron, in order to


prevent rusting. The most common method in current use is hot-dip galvanization, in which
steel parts are submerged in a bath of molten zinc at a temperature of around 460 C.

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

lubricants, as well as feed stocks for other downstream processes

Crude Oil Sources


Petroleum products, in general, whether diesel oil, lubricating oil, light fuel oil or heavy fuel oil,
are essentially composed of two major elements, carbon and hydrogen. The combination of these
two elements is called a hydrocarbon. Its ultimate source is crude oil as found in its natural states
in various geological formations throughout the world.
Crude oil consists of a very broad spectrum of hydrocarbons ranging from very light, volatile
gases to heavy residues.
The hydrocarbons mostly found in marine fuel oils fall into four (4) main classes paraffinic,
aromatic, naphthenic and olefinic.
These basic compound types are further categorized below.

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

found in heavy marine fuel oils rather than distillate oils.


Olefinic hydrocarbons (CnH2n-straight chain) are more chemically active than the other three
classes of hydrocarbons. Olefins are subject to oxidation or polymerization, forming gums.
Olefins are not present in large amounts in straight-run distillates, but are found in large
quantities in cracked marine fuel oils.
Crude Oil Distillation
REFINING PROCESS
Introduction
The first step in the refining process is the separation of crude oil into various fractions or
straight-run cuts by distillation in atmospheric towers.

Atmospheric Distillation
Fractions of atmospheric distillation is characterized by:
a. Generally low density and viscosity
34

b. Mainly paraffin type


c. operated at pressures slightly above atmospheric and at temperatures ranging from
350 0C to 3710C

Atmospheric or Straight-Run Method of Crude Oil Distillation

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

point in the process.


As the various constituents of the crude oil vaporize at different rates, the
lighter, more volatile gases rise high in the tower before condensing and
being collected. The heavier, less volatile gases condense and are collected
lower in the fractionating tower.

Straight-run residual fuels obtained from atmospheric distillation were


the primary heavy fuels used in marine diesels in the 1950s, 60s and early
70s.
35

They provided clean combustion, ease of fuel, handling and treatment,

storage stability and compatibility.


Specific gravities were usually below 0.980, the separation of water and
sediment was well within the capability of installed shipboard fuel oil
purification systems.

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

This process is essentially a modified version of the straight-run method of


distillation.
Vacuum distillers produce residual oils that are feed stocks for other refinery
processes. They are not generally available in the marine fuel marketplace due
to their very high viscosity. The vacuum distillation bottoms can be further
refined by the use of a secondary process such as viscosity
breaking. In this procedure, the feed stock, vacuum bottoms, is heated to a
higher temperature and
pressure for cracking.

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

Vacuum distillation and vis breaking process

37

Thermal cracking or vis-breaking


Characteristics of fractions from thermal cracking:
a. Medium to high density and viscosity
b. Fairly high content of atmosphere
c. Operated at high pressures (700KPa) and temperatures (750-900 0C) without a
catalyst.

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

carbon/asphaltenes content together with poorer stability and compatibility.


The impact of this process is to produce a cracked residual fuel which is more
difficult to burn, and has a lower calorific value (on weight basis), and a higher
sludge and impurities content, all of which can result in increased engine downtime,
maintenance, and repair costs.

38

Thermal cracking process

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

Catalytic cracking, including fluidic catalytic cracking, (F.C.C.), are processes


in which a chemical catalyst is used to increase the yield of the thermal
cracking process. The presence of a powdered catalyst added to the feed
stock stream allows the breakdown of long chain molecules into lighter,short

chain hydrocarbon molecules at lower pressures and temperatures.


In addition, the fine, powdered catalyst used with the charge stock can carry

over into the resultant cracked residuum.


This powdered catalyst, sometimes referred to as catalyst fines or cat
cracker catalyst, is very hard and extremely abrasive. It is not unlike fine
sand, and can rapidly increase the wear of injection pumps, fuel valves,
injectors, piston rings, piston ring grooves, liners, stuffing box seals, and
turbocharger blading.
Whenever a straight-run residual oil has been processed through an F.C.C.
unit to produce a cracked residuum, there is a very high probability that some
of these abrasive catalyst particles, comprised of aluminum oxide and/or
silicon dioxide, will be carried over and find their way into even the lightest
blends of intermediate marine fuels derived from the contaminated cracked
residuum.

Catalytic cracking process

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)

eg,. RDX, TNT, Black powder, Lead azide etc

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.

Class 3 Flammable Liquids

Flammable Liquid: Liquid chemical which will readily ignite, if subjected to a


flame, or other ignition source. Example: Gasoline, Hexane, Toluene.

Class 4: Flammable Solids

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.

Class 5: Oxidizer & Organic Peroxide


Division 5.1 (OXIDIZER) is a substance that yields oxygen readily to stimulate the
combustion of other materials.
Division 5.2 (ORGANIC PEROXIDE) means any organic compound containing
oxygen (O) in the bivalent -O-O- structure and which may be considered a derivative
of hydrogen peroxide, where one or more of the hydrogen atoms have been replaced
by organic radicals.

Class 6: Toxic & Infectious Substances


Toxic 6: Toxic material that poses an oral or dermal hazard.
Inhalation Hazard: Toxic material that poses an inhalation hazard.
Division 6.1 Toxic Substances includes toxic substances, poisons, and irritating
materials. Toxic substance is a poisonous material, other than a gas, that is known to
be so toxic to humans as to cause death, injury or harm to human health if swallowed,
inhaled or brought into contact with skin.
45

Division 6.2 Infectious Substance It means a material known or reasonably expected


to contain a pathogen. A pathogen is a micro-organism that can cause disease in
humans or animals.

The shipper is responsible for determining the appropriate packing group.


Packing Group

Degree of Danger

Great

II

Medium

III

Minor

Class 7: Radioactive Materials


Radioactive materials contain charged particles (ions) may cause damage to
molecules, cells or tissue. Atoms that emit ionizing radiation are said to be
radioactive; radioactivity is the process whereby atomic changes, known as decay or
disintegration, occur through the emission of ionizing radiation.

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.

Class 9: Misc. Dangerous Goods


A material which presents a hazard during transportation but which does not meet the
definition of any other hazard class.

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;

toxic dusts, mist, vapors, or gases;

flammable vapors or gases.

Incompatible materials which Do Not Contact like:


ALKALI METALS
such as calcium, potassium, and
sodium
with: water, carbon dioxide,
carbon tetrachloride, and other
chlorinated hydrocarbons.

OXYGEN

with: oils greases, hydrogen, flammable liquids, solids, or


gases

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.

SPECIFICATIONS OF FUEL OIL

52

53

Properties of Fuel oil


54

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:

Suction of the fuel worsen


Impurities are hard to separate
Incomplete combustion occurs

Inadequate viscosity:

Fuel consumption increases


Break down of engine due to decrease in lubricating action

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.

56

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

These are expected to be removed by separation, settling, and filtration.


Stability and Compatibility: It describes fuel oils ability to remain unchanged conditions or
keep the heavy hydrocarbon in suspension in the fuel oil or resistance of an oil to break
down. Fuel oils with poor stability will deposit sludge of asphaltic or carbonaceous matter in
the function of time or temperature.
The stability of high viscosity fuel oil and blends of such oils with other oils with the same
high viscosity will normally not cause any problems provided both oils are stable. If
however, a high viscosity oil is blended back with distillate to a thinner IF-grade, asphaltene
precipitation might occur. The reason being that distillate being used as a diluent has not the
necessary solvent power to keep the asphaltene precipitation causing sludge formation. This
sludge will tend to blockage of the preheat systems and in more critical cases cause a full
stop of the fuel flow to the engine. Blends of heavy fuel with distillate onboard should thus

58

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:

Reduction in the fuel oils by calorific value


A danger for low temperature corrosion
A danger that it may act as a catalyser for fouling and high temperature corrosion

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.

59

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

Calculated Ignition Index Value- CII:

It is used for evaluating fuel oil ignition quality.


The CII values form ranging 65-15.
A high CII value indicate good ignition quality where as low value indicates a poor
ignition quality

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:
61

Type of oil
(MDO)/ (MGO)
(IFO)/ (HFO)

Net calorific value


42,700 kJ/kg
39,000 - 41,000

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.

62

Bunkering and Taking fuel samples


It is important to realize that many of the substances which are regularly handled by crew
onboard ship-including fuel oils- are potentially hazardous. Thus before focusing on ship board
bunkering procedures, it is important to consider the importance of handling fuel oils with care
Material safety data sheets published by the bunkers suppliers and producers should be passed to
the master or chief engineer by the bunker supplier before the transfer of any fuel oil begins, and
ships crew should be familiarise themselves with their contents.
Ship board personnel are usually well aware of the risks involved in handling fuel oils and the
injuries that may result.

63

General risk in handling the fuel oils:

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,

system components can reach dangerously high temperatures.


Vapours given off by heated fuel oil may cause asphyxiation and disorientation.
Fuel oil which comes into direct contact with the skin may cause skin disorders.
Some fuel oil vapours may contain hydrogen sulphide, which is very dangerously and
highly poisonous.

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.

64

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

66

tested. This caused a delay in the bunkering time, but things could have been much worse had the
split not been identified.

Shipboard Oil Pollution Emergency Plan (SOPEP) equipment:


At the bunker manifold and wherever necessary, as per the ships SOPEP plan, the SOPEP
equipment should be kept in a state of immediate readiness, to avoid the risk of an oil spill and
pollution during the bunkering operation.
The SOPEP locker should have a minimum of these items:
1. absorbent rolls
2. absorbent pads
3. absorbent granules
4. absorbent materials
5. brooms
6. shovels
7. mops
8. scoops
9. empty receptacles (200 litres capacity)
10. portable air driven pumps
11. oil boom for small spill containment
12. oil spill dispersants
These items must be stowed in an easily accessible locker, clearly marked, and must be brought
on deck ready for immediate use, prior to all bunkering operations.
Bunker tanks
67

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.

68

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
69

13. warning signs in position, for instance No Smoking


14. material safety data sheet for HFO is available
15. SOPEP plan is available
16. spill clean-up material readily available
17. ensure all save-all and drip tray plugs are screwed in position
18. provisions made to drain off any accumulations of sea or rain water on deck
during bunkering
19. plug all deck scuppers and ensure they are oil and watertight
20. foam fire extinguisher placed at bunker station
21. purifiers and transfer pumps off
22. check that the sounding and ullage pipe caps are screwed down, unless dipping a tank
23. check that the air vents and flame arrestors for the bunker tanks are intact and free from
blockages
24. re-confirm remaining space in bunker tanks to be filled
25. check bunker tank high level alarms if fitted
26. ensure that the designated overflow tank and overflow sight glasses/alarms are
prepared and monitored
27. agree stop and start signals between ship and barge or road tanker
28. bravo flag flying and red light showing at night
29. agree emergency shutdown procedure
30. ensure all fire precautions are observed
31. all hot work permits should have been suspended for the duration of bunkering
32. check hose and couplings are secure and in good order
33. fuel connection and hose secured to vessel
34. check barge or road tanker flowmeter tamper seal and check soundings on barge
or road tanker
35. carry out a spot analysis or compatibility test if ship has the test kit
36. check on shipboard flowmeter
37. ensure ship and barge moorings will be tended during bunkering
38. bunker manifold valve open
39. unused manifold connections isolated and blanked off
70

40. all ship communications confirmed as operational


41. all ship to shore or barge communications agreed and operational
42. officer on watch/master informed
43. signal pumping to commence
When commencing the bunkers, ensure that the pumping rate is very slow to enable the
system to be checked for leaks and that the fuel is being received in the desired location.
Once this has been verified, the pumping rate can be increased to the safest maximum rate,
ensuring that the bunker line maximum pressure is monitored and not exceeded.
During bunkering procedures:
Fuels from different deliveries should be segregated as far as is practicable
1. witness taking and sealing of a minimum of three representative product samples
2. check the bunker line pressure regularly to ensure it is not too high
3. check and record the temperature of the fuel as it is pumped on board
4. monitor fuel connections for leaks and fuel flow
5. monitor the sight glass in the engine room to ensure no overflow is taking place
6. changeover tanks whenever necessary. (Always open the other tank before isolating
the full one)
7. check the rate at which bunkers are received
8. check the tightness and slackness of mooring ropes
9. check trim and list of the bunker barge and the ship
10. continuous monitoring and look-outs for the ships position and mooring arrangements
when at anchor
When the chief engineer is satisfied that the quantity received is correct then the bunker
delivery receipt can be signed either by that officer or by the master.
The post-bunker checklist is as follows:
1. bunker valve closed
2. disconnect hose (drain and/or blow through before disconnecting)
3. check barge or road tanker meter readings
71

4. check ships meter reading and soundings for quantity verification


5. sign Bunker Delivery Receipt BDR
The Bunker Delivery Receipt:
Name and IMO number of receiving ship.
Port.
Date of commencement of delivery.
Name, address and telephone number of marine fuel oil supplier.
Product name(s).
Quantity (metric tons).
Density at 15 deg. C (kg/m3).
Sulphur content (%).
A declaration signed and certified by the fuel oil suppliers representative that the fuel oil
supplied is in conformity with regulation 14.1 or 14.4 and regulation 18.3 of MARPOL Annex
VI.
6. retain BDR with product sample
7. return SOPEP to bridge
8. clean-up equipment stowed back in the correct place
9. bravo flag/red light stowed and switched off
10. remove and pack away warning and safety signs
11. foam fire extinguisher placed back in correct location
12. complete Oil Record Book and confirm bunkering is complete
13. master informed of completion

72

73

Sampling and analysis


The process of sampling and analysis fuel oil is one of the most important aspects of bunkering.
Certainly it provides the most important piece of single evidence in any bunker quality disputes.
The main objective of sampling is to obtain truly representative samples
SAMPLING METHODS:
Before any bunkering begin, the supplier or its representative barge master and the ships
personnel must agree several important points relating to the sample process, including

Location of the sample point


Sampling method
Volume of the samples to be taken
Number of the samples to be taken
Sample sealing arrangements
Authorized signatories
Custody of bunker samples.

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:

Install a manual spot sampling device


Install a manual in-line continuous drip sampler
Install an automatic continuous drip sampler which can be either set up to give a flow
proportional sample or time-proportional sample.

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.
74

Bunker Fuel Sampling Procedures

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

Cloths used during operation should be clean and lint free

Adequate precautions to prevent dirt, rain water, salt or contamination of samples by


other extraneous material is essential

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.

75

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.

1 sample to remain on board

2.

1 sample to forward via the Agent to be dispatched to VPS on an urgent priority


basis. Address, customs declaration and sample labels should be completed prior to
dispatch. (Full details are provided in the VPS instruction manual)

3.

1 sample given to the fuel supplier

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.

76

THE FUEL OIL SYSTEM

77

Pre-Treatment of Fuel Oils on Shipboard System

78

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

necessary to achieve efficient pumping.


To avoid fuel solidifying in transfer pipes, when no fuel is transferred, heat-tracing must be
used.

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.

79

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.

80

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

fuel handling before the centrifuge


flow
flow, (usually too high a flow)
temperature
temperature

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Incorrect positioning of the water/oil interface, thereby inhibiting the correct


flow of oil through all discs, (usually caused by incorrect gravity data and/or

choice of an incorrect gravity disc)


Overfilling of sludge space caused by extended intervals between desludging,
or incompatible
heavy fuel oils with higher than normal sludge deposits

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

82

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.

83

Recommended Procedures for the Onboard Treatment of Problem Fuels: Very Poor Quality or
Highly Contaminated Fuel Oils:

84

Health Aspects of Contact with Fuel oils


Marine Fuel Oil: Fuel for use in marine diesel engines and boilers.
Residual Fuel oil - The liquid product from various refinery streams, usually residues. The
position is complex and varies with the source of the crude oil.
Dangerous components/constituents:
Contains cracked components in which polycyclic aromatic compounds, mainly 3-ring but some
4- to 6-ring species, are present. Contains sulphur, oxygen and nitrogen compounds and organometallic compounds. Hydrogen sulphide may be present both in the liquid and vapour.
HAZARDS IDENTIFICATION
Human health hazards: May cause cancer, carcinogenic. Prolonged/repeated contact may cause
defatting of the skin which can lead to dermatitis. Under conditions of poor personal hygiene,
excessive exposure may lead to irritation, oil acne and folliculitis and development of warty
growths which may subsequently become malignant. Prolonged exposure to vapour
concentrations may affect the central nervous system.
Hydrogen sulphide may accumulate in the head space of containers. Hydrogen sulphide is very
toxic by inhalation and is an asphyxiant.
Safety hazards: Not classified as flammable, but will burn. Therefore it should be treated as a
potentially flammable liquid. Flammable vapours may be present even at temperatures below
the flash point.
FIRST AID MEASURES
Symptoms and effects: Exposure to hydrogen sulphide at concentrations above the recommended
occupational exposure standard may cause headache, dizziness, irritation of the eyes, upper
respiratory tract, mouth and digestive tract, convulsions, respiratory paralysis, unconsciousness
and even death. Unconsciousness as a result of exposure to hydrogen sulphide may occur
extremely rapidly and without other symptoms.

85

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

exposure to high concentrations of hydrogen sulphide may lead to a delayed chemical


pneumonitis (pulmonary oedema). In cases of excessive inhalation, observe in hospital for 48
hours for signs of pulmonary oedema. Diagnosis of ingestion of this product is by the
characteristic odour on the victim's breath and from the history of events. In cases of ingestion,
consider gastric lavage. Gastric lavage must only be undertaken after cuffed endotracheal
intubation in view of the risk of aspiration. In cases of chemical pneumonitis, antibiotic and
corticosteroid therapy should be considered.
ACCIDENTAL RELEASE MEASURES
Personal precautions: Remove all possible sources of ignition in the surrounding area and
evacuate all personnel. Ventilate contaminated area thoroughly. Do not breathe: vapour, mists.
Avoid contact with: skin, eyes and clothing. Take off immediately all contaminated clothing.
Wear: impervious overalls, PVC or nitrile rubber gloves, safety shoes or boots - chemical
resistant, monogoggles.
Environmental precautions: Prevent from entering into drains, ditches or rivers. Use
appropriate containment to avoid environmental contamination.
Clean-up methods - small spillage: Absorb or contain liquid with sand, earth or spill control
material. Shovel up and place in a labelled sealable container for subsequent safe disposal. Do
not disperse using water.
Clean-up methods - large spillage: Transfer to a labelled, sealable container for product
recovery or safe disposal. Otherwise treat as for small spillage.
Other information: Local authorities should be advised if significant spillages cannot be
contained. Observe all relevant local and international regulations.
In international waters, any spillage should be reported to the nearest coastal state by the quickest
means possible and additional guidance sought immediately from the vessels owner or charterer.
Product transfer: Electrostatic charges may be generated during pumping. Ensure electrical
continuity by bonding all equipment. Wait 10 minutes after tank filling before opening hatches or
manholes.
Tank cleaning:Cleaning, inspection and maintenance of storage tanks is a specialist operation
which requires the implementation of strict procedures and precautions. These include issuing of
work permits, gas-freeing of tanks, using a manned harness and lifelines and wearing airsupplied breathing apparatus. Prior to entry and whilst cleaning is underway, the atmosphere
87

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.

Lubricating oil (lube-oil):


Lubricating oil (lube-oil): It is selected fraction of refined mineral oil used for lubrication of
moving surfaces, usually metallic and ranging from small precision machinery to the heaviest
equipment.
Lubricating oils usually have small amount of additives to impart special properties such as
viscosity index and detergency. It does not contain solid or fibrous materials.
Although there are many types of lube oils to choose from, mineral oils are the most commonly
used because the supply of crude oil has rendered them inexpensive.
Another advantage of mineral-based lube oils is that they can be produced in a wide range of
viscosities for diverse applications. They range from low-viscosity oils, which consist of
hydrogen-carbon chains with molecular weights of around 200 atomic mass units (amu), to
highly viscous lubricants with molecular weights as high as 1000 amu.
Mineral-based oils with different viscosities can even be blended together to improve their
performance in a given application. The application and operating temperature range are key
factors in determining the proper viscosity for an oil. For example, if the oil is too viscous, it
offers too much resistance to the metal parts moving against each other. On the other hand, if it
not viscous enough, it will be squeezed out from between the mating surfaces and will not be
able to lubricate them sufficiently.
The specific gravity of an oil depends on the refining method and the types of additives present,
such as lead, which gives the lube oil the ability to resist extreme mating surface pressure and
cold temperatures. The lube oil's color indicates the uniformity of a particular grade or brand.
The oil's flash and fire points vary with the crude oil's origin. The flash point is the temperature
to which an oil has to be heated until sufficient flammable vapor is driven off so that it will flash

88

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

Good hydraulic and brake fluid

Phosphate esters

Fire resistance

Dibasic acid ester

Aircraft and turbine engines

Chloro- fluorocarbons

Good for aerospace

Silicone oils and greases

Electric motors and antifriction bearings

Silicate esters

Heat transfer agent and hydraulic fluids

Neopentyl polyol esters

Used for turbine engines

Poly phenyl ethers

Excellent for their heat and oxidant resistance


but poor in performance at low temperatures

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.

89

Mineral oils: It is a bi-product in distillation of petroleum to produce gasoline. It is


transparent colourless oil composed of mainly alkanes, it has low efficiency value.

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.

Different types of additives:


Viscosity Improvement Additives:The viscosity of a lubricant is closely related to its ability to reduce friction. Generally, the least
viscous lubricant which still forces the two moving surfaces apart is desired. If the lubricant is

90

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:

U = Kinematic Viscosity at 100F of the oil whose viscosity is to


be calculated
L = Kinematic Viscosity at 100F of an oil with a zero viscosity
index which has the same viscosity at 210F as the oil whose
viscosity index is being calculated
H = Kinematic Viscosity at 100F of an oil with viscosity index of
100 which has the same viscosity at 210F as the oil whose
viscosity index is being calculated
All U, L, and H have units of Saybolt Universal Seconds.
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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-

crystallize with wax crystal modify wax crystal structure.


Small wax particles do not interlock permitting flow.
Anti-foam additives
It allows a rapid collapse of foam bubbles due to decrease in surface tension of oil, air
interfaces
Eg: Polysilicones are effective antifoam agents. () reduce the
ability to whip in air.
Rust inhibitor additives
Prevents rust by forming a protective barrier to water from metal surface.

Adhere firmly to metal surfaced forming a coherent film. Eg.Organic phosphorous


compounds with esters or amines.

Nitrosomines are employed as antioxidants and corrosion inhibitors because they


neutralize acids and form protective films on metal surfaces.

Extreme pressure additives


It prevents gear tooth wear by reacting with metal when high flash temperature occurs
due to metal to metal contact.
The fat oil starts to form resins.
It resists high surface pressure.
Produce lubricating film of metallic salt.
Oiliness
Addition of fatty materials increases lubricity without increasing viscosity.
It improves performance and longevity.
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Flush away dirt and wear particles to carry to machine filters.


It seal bearing to prevent entry of contaminants
It dissipates heat.

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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1. Machinery that runs intermittently or is in storage for an extended period of time.


Because grease remains in place, a lubricating film can instantly form.
2. Machinery that is not easily accessible for frequent lubrication. High-quality greases can
lubricate isolated or relatively inaccessible components for extended periods of time
without frequent replenishing. These greases are also used in sealed-for-life applications
such as some electrical motors and gearboxes.
3. Machinery operating under extreme conditions such as high temperatures and pressures,
shock loads or slow speed under heavy load.
4. Worn components. Grease maintains thicker films in clearances enlarged by wear and can
extend the life of worn parts that were previously lubricated by oil.

Functional Properties of Grease


1. Grease functions as a sealant to minimize leakage and to keep out contaminants. Because
of its consistency, grease acts as a sealant to prevent lubricant leakage and also to prevent
entrance of corrosive contaminants and foreign materials. It also acts to keep deteriorated
seals effective.
2. Grease is easier to contain than oil. Oil lubrication can require an expensive system of
circulating equipment and complex retention devices. In comparison, grease, by virtue of
its rigidity, is easily confined with simplified, less costly retention devices.
3. Grease holds solid lubricants in suspension. Finely ground solid lubricants, such as
molybdenum disulfide (moly) and graphite, are mixed with grease in high-temperature
service or in extreme high-pressure applications. Grease holds solids in suspension while
solids will settle out of oils.

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4. Fluid level does not have to be controlled and monitored.

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:

Pumpability. Pumpability is the ability of a grease to be pumped or pushed through a


system. More practically, pumpability is the ease with which a pressurized grease can

flow through lines, nozzles and fittings of grease-dispensing systems.


Water resistance. This is the ability of a grease to withstand the effects of water with no
change in its ability to lubricate. A soap/water lather may suspend the oil in the grease,
forming an emulsion that can wash away or, to a lesser extent, reduce lubricity by

diluting and changing grease consistency and texture.


Consistency. Grease consistency depends on the type and amount of thickener used and
the viscosity of its base oil. A grease's consistency is its resistance to deformation by an
applied force. The measure of consistency is called penetration. Penetration depends on

whether the consistency has been altered by handling or working.


Dropping point. Dropping point is an indicator of the heat resistance of grease. As
grease temperature increases, penetration increases until the grease liquefies and the
desired consistency is lost. The dropping point is the temperature at which a grease
becomes fluid enough to drip. The dropping point indicates the upper temperature limit
at which a grease retains its structure, not the maximum temperature at which a grease

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).

Low-temperature effects. If the temperature of a grease is lowered enough, it will become


so viscous that it can be classified as a hard grease. Pumpability suffers and machinery
operation may become impossible due to torque limitations and power requirements. As a
guideline, the base oil's pour point is considered the low-temperature limit of a grease.

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