Petroleum Technology

Atmadeep Dutta(18BCM0135)
DIGITAL ASSIGNMENT 1
1. What are the different types of exploration practices followed
globally? How it varies depending on the reservoir properties

Ans. Deciding where to drill may be as much of an art as it is a

science. The primary search for hydrocarbons frequently begins
with observation of surface terrain. Location of faults at the
surface are very important because they indicated where
potential structural traps may lie beneath the surface in reservoir
rocks. The observation of anticlines, another type of structural
trap, also indicate potential traps at depth. Naturally existing
crude oil seeps blacken the ground and spread rainbow films on
streams. Such direct evidence is useful, but most such places
have long ago been identified and explored. So, the modern
exploration geologist (a person who explores for petroleum)
must rely on other techniques.
There are three (3) primary methodologies used to find
hydrocarbons in the subsurface: Geophysical, Remote Sensing,
and Wildcatting.
GEOPHYSICAL SURVEYS
Geophysical techniques used for petroleum exploration utilize
equipment to measure such things as: electrical currents,
gravitational and magnetic anomalies, heat flow, geochemical
relationships, and density variations from deep within the
earth. Each technique records a different set of characteristics
which can be used to locate hydrocarbons beneath the surface
of the earth.
Seismic surveys use vibration (induced by an explosive charge
or sound generating equipment) to provide a picture of
subterranean rock formations at depth, often as deep as
30,000 feet below ground level (BGL). This is accomplished by
generating sound waves downward into the earth's crust which
reflect off various boundaries between different rock strata. On
land, the sound waves are generated by small explosive charges
embedded in the ground or by vibrator trucks, sometimes
referred to as thumpers which shake the ground with
hydraulically driven metal pads. The human ear can barely
hear the thump, but the frequency generated penetrates the
earth's crust. The echoes are detected by electronic devices
called geophones which receive the reflected sound waves and
the data are recorded on magnetic tape which is printed to
produce a two-dimensional graphic illustrating the subsurface
geology.
Offshore surveys are conducted in a slightly different
manner. Boats tow cables containing hydrophones in the
water, which is similar to geophones on land. Sound waves use
to be created by dynamite, but this method killed a variety of
sea life. The most acceptable method today is to generate
sound waves using pulses of compressed air which creates
large bubbles that burst beneath the water surface creating
sound. The sound waves travel down to the sea floor,
penetrate the rocks beneath, and return to the surface where
they are intercepted by the hydrophones. Processing and
illustration is the same as the dry land method.
In this type of survey, sound waves are sent into the earth
where they are reflected by the different layers of rock. The
time taken for them to return to the surface is measured as a
function of time. This measurement reveals how deep the
reflecting layers are; the greater the time interval, the deeper
the rock layer. Moreover, this technique also can determine
what type of rock is present because different rocks transmit
sound waves differently.
The most sophisticated seismic surveys are three-dimensional
(3-D). The recorded data is processed by computer and the
results are a detailed, 3-D picture of the formations and
structures below the surface. The process is expensive, on the
order of $30,000 per mile (Satterwhite, pers comm). But drilling
a well can cost multiple millions of dollars, so time and money
spent on accurate seismic surveys can be a good investment
since it helps locate prospects and minimize dry holes. In
general, seismic surveys can be carried out without disturbing
people or damaging the environment, whether they are being
conducted on land or water. It is a primary tool used by
exploration geologists to locate [hydrocarbon] prospects.
There are a number of other geophysical techniques such as
magnetometers and gravimeters, and geochemical prospecting,
a relatively new technique. A magnetometer is a device that is
pulled behind an airplane on a long cable that detects
variations in the earth's magnetic field. Sedimentary rocks
generally have low magnetic properties compared to other rock
types. A gravimeter measures minute differences in the pull of
gravity at the earth's surface. Mapping these differences
reveals large masses of dense subsurface rock which allows
geologists to have a better idea of the structures below ground.
Geochemical prospecting uses sensitive instruments to detect
minute quantities of gases that seep upward from petroleum
deposits. This is a relatively new technique, but is one that is
gaining wider acceptance.
REMOTE SENSING
Remote Sensing (RS) is the use of aerial photographs to locate
and map surface features. Increasing use of satellite imagery is
being made because it shows large areas on the surface of the
earth. Even though the photographs are taken form several
hundred miles up in space, they are able to show features only
a few feet in size. And satellite imagery not only indicates what
the human eye can see, but they can also reveal subtle
variations in soil moisture, mineral and vegetation distribution,
and soil type, all of which are import pieces to the exploration
puzzle.
Once an area is selected and the satellite imagery obtained, the
exploration geologist utilizes mapping techniques to produce a
geologic map (a map that indicates geological structures by
using conventional symbols) for the area. The series of lines
and arrows indicate the type of structure that exists at the
surface. For example, , taken in November 1972 by a NASA
satellite orbiting over 500 miles out in space, shows the surface
topography very clearly for an area in Southeastern Oklahoma
known as the Ouachita Mountains. These mountains are
comprised of folded and faulted Paleozoic strata which are
buried beneath younger sediments toward the south. These
mountains are made of a combination of structures called
anticlines, synclines, and faults, all of which form various types
of hydrocarbon traps.
Another type of RS technique uses imagery that was created
from a radar looking at the ground called Side Looking Airborne
Radar (SLAR). Some of this imagery is flown with an aircraft
while some of it is onboard satellites or the US Space Shuttle. It
produces an image much like a photograph that also shows
earth structure at the surface. This figure is an area in South
America that has never been explored. Until this SLAR image
was made, there were no accurate maps of the region because
the area is usually covered by clouds. But now, there are new
opportunities based on this image.
These types of maps allow geologists to determine where
hydrocarbons might be located. Remember in Chapter 4, we
discussed various types of structural traps. Anticlines are ideal
structural traps while synclines do not tend to trap
 hydrocarbons. Thus both Figures and above show anticlines
that will aid in the development of new prospects.
WILDCAT
A wildcat well is one that is drilled in a new area where no
other wells exist and generally with scant information. It is
drilled in an effort to locate undiscovered accumulation of
hydrocarbons. About 1 in 10 wildcat wells strike oil or gas, but
only one in perhaps 50 locate economically significant
amounts. Many wildcat wells are drilled on a hunch, intuition,
or a small amount of geology. Many times they are based on
photography and experience in a particular area. Wildcat wells
are generally drilled at a smaller diameter than normal because
this saves money (the average onshore well at present costs
about 10 MM dollars to drill).
One of the earliest exploration tools was referred to
as Creekology, discussed earlier. But recent technological
advances have lead to computer-enhanced capabilities using
laptops that has had a major affect on the petroleum industry.
New seismic techniques, for example, have created more
mobile, less expensive, and easier to operate exploration tools
that has created a wealth of information designed specifically
for hydrocarbon exploration. Field equipment is smaller,
lighter, more accurate and reliable and provides far greater
detailed data.
But the basic tool needed for the search for hydrocarbons still
remains a knowledge of the Earth and earth processes of
formation, lithology, and structure. But even with all of this,
wildcat wells are still drilled, but their success rate is
substantially lower than a well spudded in (to begin a new well)
using all of the geological tools available.

2. a) List out five major refineries present in India. Explain about

their basic process flow diagram for refining.
b) What are different types of unit operations and processes
used for removing the water, sulphur, nitrogen, heavy metals
and other impurities present in the crude before distillation
c) Discuss in detail about the advantages and limitations with
different pre-processing methods. Give proper justification for
your choice.

Ans.
a. ) The 5 major refineries are

Reliance Industries
i Jamnagar Refinery Limited

Nayara Energy
ii Nayara Energy Refinery Limited

Bharat Petroleum
iii Kochi Refinery Corporation Limited

Mangalore Refinery and Oil and Natural Gas

iv Corporation
Petrochemicals Limited

v Paradip Refinery Indian oil corp. Ltd.

Diagram for Reliance Industries limited

Flow process for Nayara Energy Limited
Flow process for Bharat Petroleum Corporation Limited

Flow process for oil and natural gas composition

Flow process for Indian Oil corporation Ltd.

b) Pre-treatments
Here, the various pre-treatment processes that ensure
significant reduction or complete removal of impurities in
heavy oils before they are taken to the refining process units
are discussed. These pre-treatments mitigate downstream
consequences which include corrosion and fouling of
equipment, catalyst poisoning, more elaborate water
treatment process, and higher energy cost. It is also worthy of
note that prior to pre-treatment, the delivery system, handling
and storage of the feed (heavy oil), goes a long way to affect
the pre-treatment system requirements, efficiency, and cost [1]
Demulsifying
Crude oil emulsion is formed as dispersed water phase in an oil
medium. The water globules are protected by an oil layer which
prevents their coalescence. This protective oil layer increases in
mechanical strength with time (aging) due to long storage, thus
stabilizing the emulsion. Agitation during transportation in
 pipes has a yet more stabilizing effect on emulsions due to high
shear, which leads to smaller sizes of water droplets. Smaller
droplets are relatively more stable than larger ones; hence, it is
more challenging to demulsify the crude oil emulsion at the
refinery than at the production site . Chemical demulsifiers or
emulsion breakers are used to break the crude oil emulsion
into oil and water phases. They destroy the interfacial film and
enhance the coalescence of the water droplets. Some chemical
demulsifiers include amines, polyhydric alcohols, acids, and
polymers.
The quality of a demulsifier is determined by the rate of oil
separation from water, amount of water left in the crude oil
after separation, and quality of separated water for disposal. It
is desirable to have a fast separation rate, a low amount of
residual water in the crude oil, and a low percentage of oil in
the separated waste water. Both the water phase and its
dissolved salt contents need to be removed because they lead
to corrosion in the refinery equipment. Dehydration in
thermochemical steel tanks at temperatures as low as 50–55°C
is effective for demulsifying heavy oil emulsions as well as
stage-wise electrode-assisted desalting units. Other
demulsification techniques, such as biological, membrane,
electrical, and microwave irradiation, have also been employed
in the oil industry. Low-temperature demulsifiers in delivery
and storage facilities are used to improve feedstock quality and
optimize desalter operations . Some factors that need to be
addressed in order to enhance demulsification and oil-water
separation are discussed here.
1. Agitation: This should be minimized during transportation,
pumping, and storage and avoided wherever possible to reduce
the mechanical strength of the interfacial film between the
water and the oil phases. Mechanical chokes and flow
obstructions can be employed to reduce agitation, though a
 necessary degree of agitation is required to achieve an
adequate mixing of the demulsifiers into the bulk of the oil-
water emulsion.
2. Heat: When heat is applied to an oil-water emulsion, the
viscosity of the oil is increased to enhance its flow, water
expands and breaks the interfacial film, there is a higher rate of
droplet collision leading to faster coalescence, and density
difference between the oil and the water is increased. All these
result in an increased rate of phase separation. There is,
however, an optimum amount of heat requirement beyond
which it can become disadvantageous and lead to loss of low-
boiling hydrocarbons.
3. Time: The retention time, during which the emulsion is held at
the treating temperature, affects the separation efficiency.
Longer retention time results in greater separation efficiency.
Conventional crudes are treated for about 10–30 minutes,
while heavy oils would require a much longer retention time
[12].
4. Solids: The presence of solids, whether oil-wet or water-wet,
has a further stabilizing effect on emulsions and so needs to be
removed, especially fine particles [17, 18].
Deasphalting
Heavy oils contain significant amounts of asphaltenes which, if
not removed, will decrease the efficiency of the refining
process and reduce product quality. Asphaltenes comprise a
dark brown to black solid with no definite melting point but
foams and swells when heated leaving a carbonaceous residue.
Their molecular weight can span from 1000 to 100,000 [19].
Some common solids such as asphaltenes and waxes may be
removed with the water after being water-wetted or dispersing
them into the oil.
They contain hydrocarbons and heteroelements, namely
oxygen, nitrogen, and sulfur. In asphaltenes, hydrogen-to-
carbon ratio varies over a very narrow range of between 0.5
and 1.15%. Larger variations are seen in their heteroelement
contents: oxygen varies from 0.3 to 4.9%, sulfur varies from 0.3
to 10.3%, and nitrogen varies from 0.6 to 3.3% .
The heteroatoms (sulfur, oxygen, and nitrogen) in asphaltenes
cause other problems such as corrosion, catalyst deactivation,
and environmental pollution. Solvent deasphalting processes
have been used to significantly remove asphaltenes from heavy
oils at mild temperature conditions. In this process, an alkane
(the solvent) is injected into the heavy oil feedstock to disrupt
the dispersion of the oil components and, hence, cause the
polar constituents to precipitate. Alkane solvents, most
common of which is propane or a mixture of propane and
butane, are used to obtain a good yield of deasphalted oil.
Practically, any conventional deasphalting process and
equipment can be used. For example, the residual oil
supercritical extraction (ROSE) process, which is currently used
for residue fraction as feed, may be easily adapted and
modified to accommodate the whole crude feedstocks. Some
of the adaptations to address will include increasing the
solvent/oil ratio, increasing the temperature, and the mixing
effect, which may involve the use of pumps, mixing valves, or
medium speed centrifuges. The deasphalted whole crude, after
separation, may contain some of the solvents but has much less
asphaltenes and metal content. The deasphalted crude stream
is passed through a flash vaporization step to recover the
solvent for reuse before it goes for refining.
The Solvahl process is a solvent deasphalting process suitable
for application to heavy oils, extra-heavy oils, tar sands, and
bitumen. It removes the asphaltene constituents, gives very
high yields of deasphalted oil, and reduces metal content in the
viscous feedstock. Various solvents used in this process include
liquid propane, butane, pentane, hexane, and heptane
depending on downstream process objectives and feedstock
properties.
Solvent recovery for reuse is a crucial part of the deasphalting
unit because the solvent is expensive and its ratio to the oil
feed is high. Solvent recovery from the deasphalted oil is
carried out at a high temperature of about 200°C. Carbon
dioxide can be employed to effectively separate the solvent
from the deasphalted oil at a much lower temperature of about
40°C. This is achievable due to the increase in the interaction
between the CO2 and the solvent.
Some classes of asphaltenes, which are insoluble in paraffin
solvents, are removed using aromatic solvents. The drawback,
however, is the high solvent-to-oil ratio required to remove
most of the asphaltenes and the consequent high cost of
solvent recovery. Asphaltene removal achieves sulfur content
reduction, API gravity increase, viscosity reduction, and
improvement in other oil properties. Some conventional
deasphalting processes are done at the crude production site to
upgrade heavy oil and bitumen but may also be carried out as a
pre-treatment in the refinery. Deasphalting is achieved under
high-temperature condition, which simultaneously achieves
cracking and upgrading of the heavy oil. Subsurface
deasphalting may be done for heavy oils using solvents but will
not be addressed here.
Demetallization
Most crudes, especially heavy oils, contain various metals in
different concentrations ranging from 1000 to a few million
ppm depending on the origin of the crude. These metals are
mainly sodium (Na), potassium (K), lithium (Li), calcium (Ca),
strontium (Sr), iron (Fe), cupper (Cu), silver (Ag), manganese
(Mn), tin (Sn), lead (Pb), cobalt (Co), titanium (Ti), gold (Au),
chromium (Cr), vanadium (V), and nickel (Ni). These metals are
present either as inorganic salts or as organometallic
 compounds such as porphyrins. They are accumulated in resins
and asphaltenes and need to be removed to their barest
minimum if not completely before refining because they lead to
catalyst deactivation and corrosion in equipment and
contribute to “acid rain.” The water-soluble salts, such as
sodium chloride and magnesium chloride, produce hydrochloric
acid which is very corrosive. Calcium and magnesium combine
with carboxylic acid to form soaps which act as emulsifiers and
so are undesirable. Most of these metals combine with
naphthenic acids to form complex organometallic compounds,
while others are present as oil-soluble metalloporphyrins.
These metallic complexes contain asphaltenic aggregates which
have low reactivity; thus, most conventional metal removal
methods require severe conditions. The water-soluble salts are
significantly removed during the desalting step before refining.
The most abundant of trace metals in crude oils are nickel and
vanadium which cause catalyst poisoning. It is, therefore, easier
and preferable to demetallize heavy crudes before refining. The
existing methods of demetallization can be broadly classified
into three, namely:
1. thermal and chemical methods, where the nature of the
organic matrix is modified;
2. solvent and adsorption methods, where the metal-containing
compounds are separated from the oil; and
3. unconventional methods, where electric fields, magnetic fields,
or radiation is employed.
Currently, demetallization is most commonly achieved during
hydrotreating, deasphalting, and hydrocracking. However, the
efficiencies of these processes are greatly hampered by the
presence of the metals that poison the catalysts. It has been
reported that for greater effectiveness in metal removal, the
usual hydrotreating catalysts should be dosed with very small
amounts of active metals belonging to the sixth and seventh
subgroups of the periodic table. The chemical reaction, by
which metals (especially the more common nickel and
vanadium) are removed, is given in Eq. (1). By a sequence of
two mechanisms, the porphyrins are first dehydrogenated to
form precursor species which thereafter undergo ring-cleavage
reactions leading to metal deposition on the catalyst surface.
(MP)+H2⇌(MPH2)⟶M+PH2
E1
where MP is the metalloporphyrin, MPH2 is the intermediate
hydrogenated metalloporphyrin, M is the deposited metal, and
PH2 is the resulting hydrocarbon.
Using chemical methods, metalloporphyrins react with an acid
as given in Eq. (2):
MP+HX⇌MX+PH
E2
where MP is the metalloporphyrin, HX is the acid, MX is the
metal-acid complex, and PH is the resulting hydrocarbon [28].
It is, therefore, very necessary, especially for heavy metals, that
a pre-treatment step be employed to first reduce or remove
these harmful metals. There are newer technologies for metal
removal, such as solvent extraction, by which up to 51%
vanadium and over 65% nickel can be removed using
cyclohexane and other organic solvents. Other methods include
oxidation, electrochemical process, immiscible ionic liquid
extraction, and adsorption. Some natural and synthetic zeolites
have been successfully employed to selectively remove nickel
and vanadium. A special challenge encountered in the removal
of calcium due to the presence of calcium naphthenate (CaNA)
that is formed from calcium cation and the anion of naphthenic
acids has been reported. An aqueous solution, containing a
calcium-removal agent, was successfully employed to
completely remove calcium from heavy crude oil.
Denitrogenation
Nitrogen is one of the major heteroatoms but is also present in
crudes as nitrogen-containing compounds which need to be
removed from crude oil to avoid downstream problems.
Common nitrogen-containing compounds are mainly in form of
complex structures such as porphyrins and quinolines as well as
simple ones such as pyridine (C5H5N) and pyrrole (C4H5N),
which are prone to free radical addition reactions to form gums
and amines. These react with acid catalysts and cause
deactivation. Nitrogen content in most conventional oils is
<0.3 wt%, but in heavy crudes, it can be as high as 1 wt% and
can exceed that in some high nitrogenous crudes. They are
more thermally stable than sulfur compounds and so require
higher heat to be removed. Though organonitrogen
compounds occur at such low levels, they are undesirable
because they cause catalyst poisoning in the refining process
and generate a pollutant (NOx) upon combustion.
Hydrotreating units serve for effective denitrogenation and are
the benchmark against which other methods are measured. Of
the common heteroatoms, nitrogen is relatively more difficult
to remove. Hydrodenitrogenation removes nitrogen by forming
other compounds such as ammonia, which are then separated
from the oil. This method of nitrogen removal leaves the
hydrocarbon part of the nitrogenous compound in the oil. A
typical dehydrogenation reaction removes nitrogen in the form
of ammonia as shown in Eq. (3). The common catalysts are
cobalt, nickel, and molybdenum disulfide but are combined in
appropriate ratios for the particular feedstock.
R3N+3H2⟶3RH+NH3
E3
Other methods, however, are also applicable: these remove the
nitrogen-containing compounds completely from the oil
thereby reducing the hydrocarbon content of the oil itself. One
such method is liquid-liquid solvent extraction that exploits the
difference in solubility parameters and employs polar solvents,
acidic solvents, ionic liquids, and deep eutectic solvents. Some
others are liquid-solid solvent extraction, physical adsorption
and chemisorption between the solid adsorbent and the
nitrogen-containing compound. Adsorption beds can be packed
with activated carbon, silica gel, resins, polymers, and zeolites.
Nitrogen limit is not directly given in fuel specification but is
indirectly specified as gum content, storage stability, and
thermal stability.
Deoxygenation
Oxygen is present as one of the heteroatoms and in other
forms in oxygen-containing compounds that are natural
contaminants in crude oil. A wide variety of oxygen-compounds
have been identified in literature. More than 20 such
compounds (containing both oxygen and nitrogen) in amounts
significant enough to be regarded as above trace amounts have
been reported. Some of these compounds, being weakly acidic,
are responsible for petroleum acidity and include carboxylic
acids, cresylic acid, phenols, and naphthenic acids. Oxygen
content in crude oils can vary from 0.05 to 1.5 wt%. Generally,
heavy oils contain larger amounts of oxygen than light oils.
Naphthenic acids can be extracted using dilute caustic
solutions; other oxygen-containing compounds, which are non-
acidic, include esters, ketones, and amides but are quite
negligible. These compounds along with sulfur are
simultaneously removed during hydrotreating and other
processes. Much of the unwanted oxygen is actually in the
produced water, which is removed in the desalter. There is no
special process to selectively remove oxygen alone from crude
oil.
Desulfurization
Sulfur is a major drawback in the pricing of oil products because
it contributes most significantly to equipment fouling and
environmental pollution. Sulfur-containing compounds in crude
oils vary in nature and concentration with boiling range; with
the heaviest fraction, it containing the highest amount of
sulfur. Compounds that contain aliphatic sulfur (sulfides and
thiols) have been found easier to remove than compounds
containing aromatic sulfur (thiophenic compounds), which are
present in higher proportions in heavy crude oils. High
percentage removal of sulfur (above 70%) can be achieved
using combined oxidants (KMn04-H2O2) in a formic acid
catalyzed reaction system.
Conventional high-pressure hydrodesulfurization process is
being replaced by more effective oxidative desulfurization
(ODS) at mild conditions without hydrogen pressure but with
various catalysts. ODS is sometimes assisted and further
enhanced with ultrasound technology and the use of ionic
liquids. This has become necessary due to the shift in global oil
supply from light to heavy oil, which usually has higher sulfur
content. Microwave irradiation can also be used as a pre-
treatment for heavy crude oil where the sulfur content is not
relatively high though fragmentation and recombination
reactions may not be avoidable. Currently, however, most
desulfurization processes are carried out during refining and
not as a pre-treatment (except for crudes with very high sulfur
content), and if as a pre-treatment, then it serves also to
upgrade the feedstock.
Desalting
The desalting process derives its name from the fact that
soluble salts in the crude oil enter the aqueous phase and are
easily removed by phase separation in the desalter. The wash
water to oil ratio is 3–4 for light oils of API > 30o and 7–10 for
light oils of API < 30o; a pH of 6 is ideal for the wash water and
may be adjusted using caustic soda or acid. For the case of
heavy oils, however, with API < 20o but >10o, much higher
water volume ratios will be required.
The desalting unit is where virtually all the aforementioned pre-
treatments take place to some extent apart from the
deasphalting step. For heavy and extra-heavy crude oils,
however, there may be need to include one or more of the
above specific pre-treatment steps to be carried out before the
general desalting process. This may be warranted if the heavy
oil has a peculiar need for such a step; otherwise, a two or
three stage desalting unit may very-well serve all the purposes
needed to achieve about 90% removal of contaminants from
the heavy crude. This is because heavy crudes have higher
proportions and wider ranges of contaminants such that a one-
stage desalting process alone will not be adequate to pre-treat
them for efficient refining . In a typical single-step desalting
unit as shown in Figure 1, the crude oil is pumped from storage
through a heater, and fresh water, dosed with demulsifying
agents, is added to the oil stream, which goes through a mixing
valve for proper mixing. The stream then enters the gravity
settling tank, where the water phase settles by gravity at the
bottom of the tank, while the oil phase remains above it.
c)

Ionic Liquid will be the best pre treatment choice as the number of
limitations in that case is vey low. Apart from the solvent cost being
high everything else is perfect.

3.) Crude oil has been transported from Chennai port to refineries
in north Chennai. Due to ageing, underground pipeline
carrying the oil has bursted. This accident was happened in a
densely populated urban location. More than a week, the
leakage was not noticed by the people. Oil seeped fastly
through the sandy soil and entered into the nearby bore wells.
Then the incident was identified and reported by the
residents. The fate and transport of spilled oil from the spilled
 location to a receptor involves the resolution of the
equilibrium partitioning between two phases and its transport
across interfaces in the environment. The partitioning and of
transport governs the timescale of oil dynamics in the
environment and plays a critical role in the exposure of
receptors.
a) What are the commonly used oil-spill clean-up strategy for air,
soil and water clean up?
b) Considering the densely populated urban location with
different social and environmental issues, Suggest an clean-up
and remediation strategy for all the three phases. Give proper
justification for your selection and also identify limitation
associated with your choice.

Ans)
3 a) 1. Using Oil Booms
The use of oil booms is a very simple and popular method of
controlling oil spills. Equipment called containment booms acts
like a fence to prevent the oil from further spreading or floating
away. Booms float on the water surface and have three parts –
• A ‘freeboard’ is the part that rises above the water surface,
containing the oil and preventing it from splashing over the top
• A ‘skirt’ is placed below the surface and keeps the oil from
being squeezed under the booms and escaping
• A kind of cable or chain that connects the parts to strengthen
and stabilize the boom.
Connected sections of the boom are placed around the area of
the oil spill until it is totally surrounded and contained.
Additional Information:
 → This method is Effective only when the oil is in one spot.
→ It works when the spill is accessible within a few hours of
taking place, otherwise, the area of the spill becomes too large
to manage
→ It cannot be successfully employed under rough sea waves,
high wind velocities or fluctuating tides.
2. Using Skimmers
Once the oil has been confined by using oil booms, skimmers or
oil scoops can be deployed onto boats to remove the
contaminants from the water surface. Skimmers are machines
specially designed to suck up the oil from the water surface like
a vacuum cleaner. They are used to physically separate the oil
from the water so that it can be collected and processed for re-
use.
Additional Information:
• Skimmers can be used to effectively recover most of the spilt
oil, so it is economically viable.
• The presence of debris poses a major roadblock to this
technique, as skimmers can get clogged easily.
3. Using Sorbents
Sorbents are materials that soak up liquids by either absorption
(pulling in through pores) or adsorption (forming a layer on the
surface). Both these properties make the process of clean-up
much easier. Materials commonly used as oil sorbents are hay,
peat moss, straw or vermiculite.
Additional Information:
• The oil can be recovered, and this prevents wastage and further
pollution.
• After the absorption, the sorbent materials must be effectively
retrieved. This is a difficult task and may prove to be worse if
ignored.
• Sorbents after absorption become heavier (3 to 15 times their
weight), and as a result, may sink, making them difficult to
retrieve and also pose a risk to aquatic life in the sea bottom.
• They are most effective in small spills or to manage the leftover
traces of a larger spill.
4. Burning In-situ
In this method, the oil floating on the surface is ignited to burn
it off. This in-situ burning of oil can effectively remove up to
98% of an oil spill, which is more than most of the other
methods.
According to Obi et al, (2008), “The minimum concentration
(thickness) of the slick on the water surface for any measurable
effectiveness of in-situ burning is 3mm. This is because it would
be very difficult (and even nearly impossible) to ignite a layer
which is not thick enough.
Additional Information:
• The toxic fumes released from the burning can cause significant
damage to the environment as well as marine life.
• The procedure works on spills that are relatively fresh before
the oil spreads to a larger area and decreases in thickness.
5. Using Dispersants
When the spilled oil cannot be contained by using booms, the
only option left is to accelerate the disintegration of oil.
Dispersal agents, such as Corexit 9500, are chemicals that are
sprayed upon the spill with the help of aircraft and boats, which
aid the natural breakdown of oil components.
 They allow the oil to chemically bond with water by increasing
the surface area of each molecule. This ensures that the slick
does not travel over the surface of the water, and is easier to
degrade by microbes.
Additional Information:
• It can effectively be used for spills over large areas.
• Use of dispersants can create tarballs. As the oil combines with
water, it also gets mixed with sand and debris present in the
water. This results in the formation of large tar balls floating on
the surface of the water, which often find their way to the
shores.
• The toxicity of dispersants can affect marine organisms,
especially the non-mobile ones such as corals and seagrass.
6. Hot Water and High-Pressure Washing
This procedure is mainly used in situations where the oil is
inaccessible to methods of mechanical removal such as using
booms and skimmers. It is used to dislodge the trapped and
weathered oil from locations which are generally inaccessible
to machinery.
Water heaters are used to heat up water to around 170°C,
which is then sprayed by hand with high-pressure wands or
nozzles. The oil is thus flushed to the water surface, which can
be collected with skimmers or sorbents.
Additional Information:
• The released oil must be immediately and adequately
recovered to prevent any further contamination.
• Organisms falling in the direct spray zone have a high chance of
being adversely affected by the hot water.
7. Using Manual Labour
 As the name suggests, the method requires hand-held tools and
manual labour to clean up the contaminants. It involves the use
of manual means like hands, rakes, shovels etc. to clean the
surface oil and oily debris and place them in special containers
to be removed from the shoreline.
Sometimes, mechanized equipment may be employed for
providing any additional help and reach out to any inaccessible
areas.
Additional Information:
• This method is applicable only for cleaning up the slick in
shorelines.
• The process is more economically viable, as unskilled workers
with minimal training can be employed for the process
• Apart from being labour intensive, this process is also time-
consuming.
• The use of heavy machinery can inflict damage upon shorelines,
so they should be avoided as much as possible.
8. Bioremediation
Bioremediation refers to the use of specific microorganisms to
remove any toxic or harmful substances. There are various
classes of bacteria, fungi, archaea and algae that degrade
petroleum products by metabolizing and breaking them into
simpler and non-toxic molecules (mostly fatty acids and carbon
dioxide). Sometimes, reagents and fertilizers may be added to
the area. These phosphorus-based and nitrogen-based
fertilizers provide adequate nutrients to the microbes so that
they are able to grow and multiply quickly.
 This process is generally not used when the spill has happened
in the deep seas and is gradually put into action once the oil
starts to approach the shoreline.
Additional Information:
• It is a time taking procedure and may even take years, so
quicker solutions like using booms and skimmers or sorbents
may be used if any urgent action is required.
• The fertilizers have an equally high chance of aiding the growth
of unwanted algae, which consume much of the available
oxygen and cut off sunlight from going to the deeper water
levels. This can negatively impact marine life, and prove to be
counter-productive.
9. Chemical Stabilisation of oil by Elastomizers
Right after an oil spill, the immediate concern is to prevent the
oil from spreading and contaminating the adjacent areas. While
mechanical methods like using oil booms effectively contain the
oil, they have certain limitations to their use.
Quite recently, experts have been using compounds like
‘Elastol’, which is basically poly iso-butylene (PIB) in a white
powdered form, to confine oil spills. The compound gelatinizes
or solidifies the oil on the water surface and thus keeps it from
spreading or escaping. The gelatin is easy to retrieve, and this
makes the process highly efficient.
Additional Information:
• It is a quick action method, with typical reaction times of 15-40
minutes.
• While PIB is non-toxic and commonly found in foodstuffs, the
gelatin may pose a risk of entangling or suffocating the aquatic
animals.
 10. Natural Recovery
The simplest method of dealing with the oil spill cleanup
operation is to make use of the vagaries of nature like the sun,
the wind, the weather, tides, or naturally occurring microbes. It
is used in certain cases when the shoreline is too remote or
inaccessible, or the environmental impact of cleaning up a spill
could potentially far outweigh the benefits.
Due to the constancy of these elements, the oil generally
evaporates or is broken down into simpler components.
Additional Information:
• It is one of the most cost-effective methods.
• It is a highly time consuming and unreliable process and thus
needs constant and close monitoring. It should not be confused
with ‘sitting down and doing nothing’.
A pivotal factor in cleaning up an oil spill is the location where it
has happened. Most of the oil spills take place far out in the
sea, so they are generally left to naturally decompose in the
environment. As they get closer to the shores, we gradually
begin to treat them.
The treatments follow a general rule: (All distances measured
from the shoreline)
• 200 nautical miles and beyond – No treatment is used, unless
the case is very severe.
• Between 20 and 200 nautical miles, booms and skimmers may
be used.
• Between 20 and 10 nautical miles, dispersants are used.
• For areas very close to the shoreline, biological agents are used.
These are only general rules and can be altered based on the
type of oil that has been spilt and the prevailing weather
conditions. No two oil spill cases are the same, so each one is
evaluated individually based on its own merit.

3 b) CHEMICAL DISPERSANTS
Chemical oil dispersants are proprietary mixtures of surfactants
and solvents that are applied directly to an oil spill in order to
reduce the natural attractive forces within the oil. The use of
chemical oil dispersants offshore can be effective in preventing
heavy oiling of sensitive coastal environments, such as beaches
and wetlands, and in mitigating risks associated with marine
and terrestrial wildlife coming into direct contact with a surface
oil slick. Some researchers (Lehr et al., 2010) have estimated
that the use of dispersants helped to keep 500,000 barrels of
the DWH oil away from the highly productive and sensitive
coastal areas, but there is no feasible way to verify this
estimate.
When an oil slick is sprayed with dispersant and exposed to
mixing energy, typically from wave action, some of the oil is
broken up into small droplets, which may then become
entrained in the water column (Li et al., 2008, 2009a,b; Lunel,
1995). Because the chemically dispersed oil droplets may be
small enough to be neutrally buoyant, diffusion and advection
transport processes are expected to dilute the plume over a
large volume to concentrations below toxicity threshold
limits—a key objective for the use of dispersants. Furthermore,
as microbial degradation of oil spilled at sea primarily occurs at
the oil-water interface, oil biodegradation rates should be
enhanced, provided that the dissolved oil concentration is not
so large as to be toxic to the microbes. At the large scale, the
overall biodegradation rate is increased when dispersants are
used effectively (Venosa and Holder, 2007; Venosa and Zhu,
2003). In addition, small droplets enhance dissolution of soluble
and semivolatile compounds into surrounding waters, resulting
in fewer airborne volatiles, which enhances safety for cleanup
workers. However, one consequence of dispersant use is that
oil concentrations may increase in the water column and
potentially increase exposure for pelagic species.