Report on Internship on Waste Management in Petroleum Refinery.

A
Internship
Report
On
“Waste Management in Petroleum Refinery”
Submitted by
OM A ZAVARE (10303320181152713001)
DEPARTMENT OF PETROCHEMICAL ENGINEERING
DR. BABASAHEB AMBEDKAR TECHNOLOGICAL
UNIVERSITY, LONERE
2020-2021

ii
CERTIFICATE
This is to certify that the internship report entitled “Waste Management in Petroleum
Refinery” is a bonafide work carried out by Om A Zavare (10303320181152713001), of
Third Year Bachelor of Technology in Petrochemical Engineering of Dr. Babasaheb
Ambedkar Technological University, Lonere in academic year 2020-2021.
Examiners:
1.
2.
Place: Lonere
Date:
Dr. S. S. Metkar
(Head of Department)
Dr. BABASAHEB AMBEDKAR TECHNOLOGICAL UNIVERSITY
Lonere 402103, Tal. - Mangaon, Dist. - Raigad, (M.S.)
DEPARTMENT OF PETROCHEMICAL ENGINEERING

iii
ABSTRACT
Petroleum industry is one of the fastest growing industries, and it significantly contributes
to economic growth in developing countries like India. The waste from a petroleum industry
consists a wide variety of pollutants like petroleum hydrocarbons, mercaptans, sludge, oil and
grease, phenol, ammonia, sulfide, and other organic compounds. All these compounds are
present as very complex form in discharged water of petroleum industry, which are harmful
for environment directly or indirectly. Some of the techniques used to treat oily
waste/wastewater are bioremediation, incineration, Oil sludge separation using cyclone,
Vapor Recovery, Electrokinetic method, Deep Well Injection, Re-refining Used/Waste
Oil etc. In this report, we aim to discuss past and present scenario of using various treatment
technologies for treatment of petroleum industry waste/wastewater. The treatment of
petroleum industry waste involves physical, chemical, and biological processes.
Crude oil is a kind of water/oil emulsion. The oil phase consists of organic molecules with
different molecular weights. Re-refining is the used oil processing aiming at recovering a
valuable resource of mineral base oil, being as good as or better than the virgin base stock,
and from which any petroleum-based lubricant can be produced. The 1 billion gal of used oil
generated in the U.S. each year are managed in three primary ways: re-refined into base oil
for reuse, distilled into marine diesel oil fuel, and marketed as untreated fuel oil. Management
of used oil has local, regional and global impacts. Because of the globally distributed nature
of fuel markets, used oil as fuel has localized and regional impacts in many areas.

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ACKNOWLEDGEMENT
I would like to express my gratitude to my guide for his excellent encouragement and
constant guidance throughout the internship. I am thankful to the Head of Department, Dr. S.
S. Metkar for giving opportunity for internship.
I am thankful for their suggestions and invaluable support in executing my internship
successfully. And finally, heartfelt gratitude to all my friends and well-wishers who have
helped me directly or indirectly.
OM A ZAVARE
(10303320181152713001)

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CONTENTS
TITLE .....................................................................................................................................................i
CERTIFICATE.....................................................................................................................................ii
ABSTRACT..........................................................................................................................................iii
ACKNOWLEDGEMENT...................................................................................................................iv
CONTENTS...........................................................................................................................................v
LIST OF FIGURES............................................................................................................................vii
LIST OF TABLES.............................................................................................................................viii
SESSION I.............................................................................................................................................1
BIOREMEDIATION OF PETROLEUM INDUSTRY EFFLUENTS FOR SUSTAINABLE
WASTE MANAGEMENT...................................................................................................................1
1.1 Petroleum Industry Effluents (PIE) ................................................................................1
1.2 Composition of Petroleum Industry Effluent.................................................................1
1.3 Treatment of Petroleum Industry Effluent.....................................................................2
1.4 Importance of Pretreatment ............................................................................................3
1.5 Physical Treatment ...........................................................................................................3
1.6 Chemical Treatment .........................................................................................................4
1.7 Biological Treatment.........................................................................................................4
SESSION II ...........................................................................................................................................6
PETROLEUM SLUDGE TREATMENT AND DISPOSAL............................................................6
2.1 Petroleum Sludge...............................................................................................................6
2.2 Composition of Oily Sludge..............................................................................................6
2.3 Classification of Refinery Sludge.....................................................................................7
2.4 Conventional Sludge treatment methods........................................................................8
2.5 Alternat Methods ............................................................................................................11
SESSION III........................................................................................................................................15
REFINERY CONSTRUCTION WASTE MANAGEMENT..........................................................15
3.1 Activities Involved in Refinery Construction................................................................15
3.2 Waste Classification ........................................................................................................15
3.3 Waste Management.........................................................................................................16
3.4 Waste collection & Segregation......................................................................................17
3.5 Temporary Waste Storage..............................................................................................18
3.6 Transportation.................................................................................................................19
3.7 Recovery and Disposal of Waste ....................................................................................19
SESSION IV ........................................................................................................................................22
WASTE MANAGEMENT & MINIMIZATION.............................................................................22
4.1 Refinery Operation..........................................................................................................22
4.2 Waste Management Hierarchy ......................................................................................22
4.3 Waste Management Plan................................................................................................24

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4.4 Strategies to Improve......................................................................................................24
4.5 Waste Minimization ........................................................................................................26
4.6 Drilling Operations..........................................................................................................27
4.7 Production and Workover Operations..........................................................................27
4.8 Natural Gas Treating and Processing Operations........................................................29
4.9 Pipeline Transport Operations.......................................................................................31
SESSION V..........................................................................................................................................32
APPLICATION OF JET MIXER IN SLUDGE MITIGATION DURING CRUDE OIL
STORAGE...........................................................................................................................................32
5.1 Sludge Formation during Storage of crude oil .............................................................32
5.2 Impact of sludge on storage capacity.............................................................................32
5.3 Jet mixers .........................................................................................................................33
5.4 Sludge Mitigation by Jet Mixers ....................................................................................33
5.5 Jet Mixer Operation........................................................................................................34
5.6 Factors Influencing the Suspension characteristics of a Jet Mixer.............................35
5.7 Advantage of Jet Mixer...................................................................................................36
SESSION VI ........................................................................................................................................37
USED OIL & WASTE OIL MANAGEMENT ................................................................................37
6.1 Lubricants / Lubricating Oil ..........................................................................................37
6.2 Used Oil............................................................................................................................37
6.3 Re-refining of Used Oils..................................................................................................38
6.4 Commercial Re-refining Plants......................................................................................39
6.5 Waste Oils ........................................................................................................................40
CONCLUSION ...................................................................................................................................43
REFERENCES....................................................................................................................................44

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LIST OF FIGURES
Figure 1.1: Sequence for Treating PRE’s ...............................................................................................3
Figure 2.1: Petroleum Sludge .................................................................................................................6
Figure 2.2: Solvent Extraction Method (Flow Diagram)........................................................................8
Figure 2.3: Ultra-High Temperature Gasification...................................................................................9
Figure 2.4: Oil sludge Separation using Cyclone Separator ...................................................................9
Figure 2.5: Microwave Heating Method...............................................................................................11
Figure 2.6: Schematic diagram of centrifugation method.....................................................................12
Figure 2.7: Circuit - Electrokinetic method ..........................................................................................13
Figure 2.8: Froth Flotation Method.......................................................................................................14
Figure 3.1: Recycle Reduce Reuse Recovery .......................................................................................16
Figure 3.2: Incinerator ..........................................................................................................................19
Figure 3.3: Deep Well Injection............................................................................................................20
Figure 4.1: Refinery Operations............................................................................................................22
Figure 4.2: Waste Management Hierarchy ...........................................................................................23
Figure 4.3: Strategies to Improve..........................................................................................................25
Figure 4.4: Vapor Recovery..................................................................................................................28
Figure 4.5: Pipeline Transport ..............................................................................................................31
Figure 5.1: Oil residue in Storage Tank................................................................................................32
Figure 5.2: Jet Mixers ...........................................................................................................................33
Figure 5.3: Jet Mixer Operation............................................................................................................34
Figure 5.4: Jet Mixer Nozzle ................................................................................................................35

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LIST OF TABLES
Table 5.1: Re-refining / Recycling Plants in India................................................................................41

A Report on “Waste Management in Petroleum Refinery”
1
Dept. of Petrochemical Engg. Dr. BATU. Lonere
SESSION I
BIOREMEDIATION OF PETROLEUM INDUSTRY EFFLUENTS FOR
SUSTAINABLE WASTE MANAGEMENT
1.1 Petroleum Industry Effluents (PIE)
Industrial effluents result from various types of industrial processes and disposal practices,
and may contain pollutants at levels that could affect the quality of receiving waters, as well
as the aquatic ecosystem. The emission of industrial pollutants in liquid effluents has to
comply with stringent regulatory requirements and guidelines, in which chemicals listed
should not exceed a given concentration. On the other hand, a chemical company may release
a large number of different chemicals, which are not considered by regulatory requirements
and in many cases are unknown. These compounds may be the final products, precursors, or
intermediates of the process, or impurities and by-products.
One of the distinguishing characteristics of effluents of industrial origin, as compared to
municipal wastewaters, is that often they may contain a mixture of different and very toxic
substances. Approved analytical methods exist for compliance monitoring of conventional
pollutants in industrial effluents; however, because of the complexity of the sample matrix,
several analytical methods are required to determine polar and nonpolar organic compounds
and new emerging pollutants that may impact water quality.
As a consequence, modifications in instrumentation, sampling, and sample preparation
techniques have become essential to comply with the regulatory water standards, as well as to
achieve a faster speed of analysis.
Petroleum industry is one of the fastest growing industries, and it significantly contributes to
economic growth in developing countries like India. Petroleum refinery effluents are major
source of aquatic environmental pollution.
Processing of crude oil requires large amount of water (volume of effluents generated is 0.4
to 1.6 times the crude oil processed). The compositions of the refinery wastewater can vary
depending upon the operational units for different products at specific time and locations. The
wastewater can be from cooling systems, distillation, hydro treating, and desalting.
1.2 Composition of Petroleum Industry Effluent
The sources of petrochemical wastewater are diverse and can originate from oilfield
production, crude oil refinery plants, the olefin process plants, refrigeration, energy units, and
other sporadic wastewaters. The wastewater from a petroleum industry consists a wide

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variety of pollutants like petroleum hydrocarbons (aliphatic and aromatic), mercaptans, oil
and grease, phenol, ammonia, sulfide, and other organic compounds. Different concentrations
of ammonia, sulfide, phenols, Benzo, and other hydrocarbons are normally present in such
wastewater. The pollutants include both intermediates and final products/byproducts.
Petroleum refinery wastewater is generated in oil refinery processes that produce more than
2500 refined products. The common pollutants of petroleum refinery and oil processing
industries are
• Aliphatic
• Aromatic
• Olefinic hydrocarbons
• Phenols
• Thiophenols
• Mercaptans
• Alkanolamines
• H2S and its salts
• Ammoniacal compounds
• Chlorides
• Cyanide etc.
All these compounds are present as very complex form in discharged water of petroleum
industry, which are harmful for environment directly or indirectly. Direct discharge of this
will affect plants and aquatic life of surface and ground water sources. Hence, Petroleum
industry effluents need to be well managed before they can be discharged to any receiving
waters.
Due to its organic origination, complex nature, and toxic effects, wastewater treatment prior
to discharge is obligatory. The complexity of the wastewater and stringent discharge limit
push the development of wastewater treatment by combinations of different methods.
1.3 Treatment of Petroleum Industry Effluent
Some of the techniques used to treat oily waste/wastewater are membrane technology,
photocatalytic degradation, advanced oxidation process, electrochemical catalysis, etc.
But, main aim of treatment is to achieve complete degradation or mineralization of harmful
components by various methods.

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Stringent regulations have motivated researchers to design advanced treatment facilities to
give high treatment efficiency, low maintenance, footprint, and operational costs. The
treatment of petroleum industry wastewater involves physical, chemical, and biological
processes.
1.4 Importance of Pretreatment
As the PIEs are complex and complicated ones with wide variety of pollutants, they should
be pre-treated using physical and chemical processes in order to make it suitable for
bioremediation.
Optimizing pre-treatment process using physicochemical processes is also important for
getting suitable pre-treatment wastewater for efficient biological secondary treatment.
A primary treatment includes the elimination of free oil and gross solids; elimination of
dispersed oil and solids by flocculation, flotation, sedimentation, filtration, micro electrolysis,
etc.; increasing the biodegradability of wastewater, etc.
1.5 Physical Treatment
• Adsorption by active carbon, copolymers, zeolite, etc. - removing hydrocarbons in the
PIE.
• Evaporation - remove oil residuals in saline wastewater.
• Dissolved air flotation (DAF) – remove oil/fat as well as suspended solids.
• Microfiltration (MF) and ultrafiltration (UF).
Figure 1.1: Sequence for Treating PRE’s

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1.6 Chemical Treatment
Enhancing hydrolysis by adding chemicals for removing the long-chain organics, toxic
material, or suspended solids can increase the Biochemical Oxygen Demand (BOD) ratio of
the wastewater. Three chemical treatment processes are listed here.
• Micro-aeration breaks down high hydrocarbon content components from
wastewater, which leads to easily biodegradable organic generation. At a dissolved
oxygen (DO) concentration from 0.2 to 0.3 mg/L, the hydrolysis of wastewater
organics is enhanced. Benzene ring organics’, such as benzene, toluene, ethylbenzene,
and xylenes, treatability in the biological stage can be improved.
• Coagulation-flocculation for specific petrochemical wastewater treatment, such as
purified terephthalic acid (PTA) production wastewater; the wastewater contains
aromatic compounds such as p-toluic acid, benzoic acid, 4-carboxybenzaldehyde,
phthalic acid (PA), and terephthalic acid (TA), etc. Ferric chloride is found to be the
most effective coagulant with COD removal efficiency at 75.5% at wastewater COD
of 2776 mg/L and dose of pH 5.6. Adding cationic polyacrylamide improves the
sludge filtration. Certain streams that combine coagulation and flocculation as
pretreatment followed by MF and UF achieved significant suspended solid removal.
• Ozonation for wastewater that contains phenol, benzoic acid, amino benzoic acid,
and petrochemical industry wastewater containing acrylonitrile butadiene styrene
(ABS) at 30 min and 100–200 mg O3/h showed an increased BOD/COD ratio.
• Other Treatment - Micro electrolysis of petrochemical wastewater has been tested
with positive effects on the COD removal as well as increasing the BOD-to-COD
ratio levels
1.7 Biological Treatment
Biological treatment incorporates actions of different microbes to eliminate organics and
stabilize hazardous pollutants in petrochemical wastewater. Stringent environmental
standards and recycling of water for reuse have shifted focus to biological treatments because
of its cost and pollutant removal efficiency. Biological wastewater treatments that have been
well developed for organic and inorganic wastewater treatment are thus a potential method
for petrochemical wastewater management.
Acrylonitrile and cyclohexane are not degraded easily and when degraded, it is co-
metabolism (Co-metabolism is defined as the metabolism of an organic compound in the
presence of a growth substrate that is used as the primary carbon and energy source).

5
Absence of nitrogen and phosphorus sources required by bacterial metabolism and affect the
biodegradability of pollutants.
Choosing of appropriate bio treatment plant is as important as setting up the main production
plant. Biological anaerobic, anoxic, and aerobic digestion (or a combination of each other)
have been implemented to treat petrochemical wastewater.
Complex structures of aromatic, polycyclic, and heterocyclic ringed chemicals are known to
be restraint to biological degradation.
However, recent research activities have produced notable removal percentages of pollutants
from petrochemical wastewater. Anaerobic digestion (AD), aerobic digestion, or an
integration of both methods is commonly applied in biological processes to treat
petrochemical wastewater.

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SESSION II
PETROLEUM SLUDGE TREATMENT AND DISPOSAL
2.1 Petroleum Sludge
Crude oil is an important energy source as well as feed stock of oil refineries. India is the
fifth largest Petroleum energy consumer in the world. India’s petroleum product consumption
has grown by 4-5% over the past 10 years and the oil demand in India is expected to rise to
368 MMTPA by 2025. Petroleum refineries are responsible for the generation of large
quantities of sludge, which is a major source of environmental pollution.
Petroleum sludge is a complex mixture containing different quantities of waste oil, waste
water, sand, and mineral matter. The sludge quantity generated from petroleum refining
processes depends on several factors such as crude oil properties (e.g., density and viscosity),
refinery processing scheme, oil storage method, and most importantly, the refining capacity.
In refineries hydrocarbon sludge is usually generated by
• Cleaning up of crude oil storage tanks.
• Maintenance of associated facilities and pre-export processing like
Tank farms, desalter failure, oil draining from tanks and operation units, pipeline ruptures and
processing of oil.
2.2 Composition of Oily Sludge
Composition of Oily Sludge is very complex. Stable system of suspension emulsion. It
comprises of oil-in-water, water-in-oil emulsion and suspended solids. Contains toxic
substances like aromatic hydrocarbons, polyaromatic hydrocarbons and high total
hydrocarbon content. Bear negative charge. Because of high viscosity, oily sludge is difficult
to be dehydrated.
Figure 2.1: Petroleum Sludge

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Composition of Sludge:
• Water - 55.13%
• Sediments - 9.246%
• Asphaltenes - 1.9173%
• Wax - 10.514%
• Light hydrocarbons - 23.19%
• Vanadium - 204 ppm,
• Fe - 0.6%
• Nickel - 506 ppm.
The Ministry of Environment and Forests, Government of India has categorized refinery oily
sludge as the hazardous waste causes environmental and public health issue in India, like
other developed and developing countries. Thus, increased attention has been turned to look
into potential technology for sludge treatment. In India, oil refineries generate approximately
20,000 tons of oily sludge per annum. It has been accumulating at an alarming rate.
Impact:
• The contamination of superficial and ground water.
• The contamination of the surrounding air.
• The risk of fires, explosions, poisoning of the food chain and destruction of green
areas.
• Many of the constituents of oil sludge are carcinogenic and immuno-toxicant.
• Uncontrolled handling of these sludges often leads to environmental pollution and
also affects the aesthetic quality.
These sludges cannot be disposed of as landfill. The sludges containing recoverable oil less
than 40% are considered as low oil content sludges. The refinery sludges contain oil content
more than 40% and several methods are used to separate the oil, water and solids. These
sludges have to be treated and made harmless before disposal.
2.3 Classification of Refinery Sludge
These sludges cannot be disposed of as landfill. The sludges containing recoverable oil less
than 40% are considered as low oil content sludges. The refinery sludges contain oil content
more than 40% and several methods are used to separate the oil, water and solids. These
sludges have to be treated and made harmless before disposal.

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2.4 Conventional Sludge treatment methods
Manual Cleaning:
• The low-cost method.
• The cleaning is done by entering in the tank.
• The sludge is moved out of the tank manually or to pumps present in the tanks.
Incineration:
• Typically, oil sludge can’t be incinerated because it contains too much oil and
water, making it almost impossible to incinerate.
• CO and dioxin are produced, during incineration, so that more and more
incinerators are being shut down and restrictions on incineration have been
multiplying.
Solvent Extraction Method: Various solvents are used in this method. This method requires
mixing and agitation apparatus. Sludge has waxy and non-waxy (asphaltenes) organic
components along with salt, oxides and other inorganic materials. These may be dissolved by
selecting appropriate solvent.
Solvent is allowed to flow into the extractor where non-reactive contact is made with the feed
slurry. Organics contained in the sludge are dissolved into the solvent. The extractor contents
flow to a decanter where gravity phase separation takes place. The product, containing the
water and treated solids is collected from the bottom of the decanter/separator. The solvent-
organic mixture collected from the top of separator is sent to solvent recovery still for oil and
solvent recovery.
Figure 2.2: Solvent Extraction Method (Flow Diagram)

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Ultra-high temperature gasification: Thermal oxidation of sludge is carried out. The sludge
is heated to a very high temperature (1000o
C) using plasma arc without oxygen.
The sludge is converted to pyro gas by this method and this can be used as fuel.
Oil sludge separation using cyclone: The cyclonic separation is a method of removing the
residue and recovery of oil from the oily sludge
Chemical Treatment:
• Oily sludge is diluted by heating water
• Certain chemical reagents are added for extraction of oil from solid-phase.
• Widely used for high oil content
Figure 2.3: Ultra-High Temperature Gasification
Figure 2.4: Oil sludge Separation using Cyclone Separator

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Bioremediation: Uses living organisms (bacteria, fungi, some algae, and plants) to reduce or
eliminate toxic pollutants. Uses living organisms (bacteria, fungi, some algae, and plants) to
reduce or eliminate toxic pollutants. These organisms may be either naturally occurring or
may be cultivated in the laboratory. Oilzapper, Oilivorous – S,Oilivorous - A, KT – Oil
zapper, and so on. They either eat up the contaminants (organic compounds) or assimilate
within them all harmful compounds (heavy metals) from the surrounding; thereby, rendering
the region contaminant free.
Bioremediation can be enhanced with the use of fertilizers, compost, bulking agents and
some chemicals including oil dispersant. Bioremediation of waste oil in soil (land farming) or
also land spreading had been carried out in different parts of the world.
Limitations:
Traditional methods for waste disposal and treatment don’t really work on oil sludge
• Takes long time.
• Expensive
• Energy intensive
• Low efficiency requires the secondary treatment processes to recover the valuables.
• These treatment processes might again generate secondary wastes that must also be
disposed or treated further for safe or eco-friendly disposal.
• Solvent extraction methods have limits on VOC (volatile organic compounds).
• Emissions and concerns for worker safety and regulations.
• Even bioremediation for disposal of sludge was found slow.
• The oil sludge can’t be filtered because the solids content is too high, and attempts at
filtering will just clog the filtration systems.
• The oil sludge can’t be pumped to a waste water treatment facility because of the high
oil and solid content, and the waste has too high COD/BOD.

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2.5 Alternat Methods
Microwave heating method: In conventional thermal heating, heat is transferred to the
material through convection, conduction, and radiation of heat from the surfaces of the
material. In heat transfer, energy is transferred due to thermal gradients.
But Microwave energy is reached directly to the materials through molecular interaction with
the electromagnetic field. Microwave heating is the transfer of electromagnetic energy to
thermal energy and is energy conversion, rather than heat transfer
Advantages:
• Rapid
• Uniform heating
Centrifugation method: In this method, components are separated on the basis of their
densities such as solids, oil and pasty mixtures in oily sludge by generating centrifugal force.
Uses a special high speed rotation equipment by reducing viscosity of oily sludge by adding
organic solvents, demulsifying agents & tensioactive chemicals and the injection of steam
and direct heating.
A small amount of a coagulant, CaCl2 (0.01-0.5 M) can improve the water-oil separation
process by centrifugation, with a high oil separation efficiency of 92-96%.
Procedure:
• Oily sludge is mixed with demulsifying agent or other chemical conditioners
• The mixture is then treated by hot steam in a pre-treatment tank in order to reduce the
viscosity.
• This less viscous petroleum is mixed with water for high-speed centrifugation.
Figure 2.5: Microwave Heating Method

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• The separated oil containing water and solids is sent to a gravimetric separator for
further separation to obtain the recovered oil.
• The separated water from the separator is sent to wastewater treatment.
• The sediments from centrifugation and separator are collected as solid residue for
further treatment.
• Centrifugation is a relatively clean and mature technology for oily sludge treatment,
and its oil separation from sludge is effective.
Disadvantages:
• Centrifugation equipment does not occupy large space.
• High energy consumption is required to produce high centrifugal force to separate oil
from petroleum sludge.
• High equipment investment is responsible for the limited use of centrifugation
method.
• The addition of demulsifying agents and tensioactive chemicals for pre-treatment
increases the processing cost.
• Centrifugation process creates high noise.
Electrokinetic method: In this method, an electrode pair is used on two sides of a porous
medium and a low direct current is passed through the medium causing the electro-osmosis of
liquid phase, migration of ions and electrophoresis of charged particles in a colloidal system
to the respective electrode. The separation of water, oil, and solids from oily sludge can be
carried out by electrokinetic method.
Figure 2.6: Schematic diagram of centrifugation method

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Colloidal aggregates in oil sludge can be broken due to electric field and this leads to the
movement of colloidal particles and solid particles of oily sludge towards the anode as a
result of electrophoresis. Water and oil move towards the cathode as a result of electro-
osmosis. The electro-coagulation of the separated solid phase occurs near the anode, this
increases the concentration of solid phase and the sediments.
The separated liquid phase (water and oil, without colloidal particles and fine solids) can
form an unstable secondary oil-in-water emulsion, which could be gradually electro-
coalesced near the cathode through charging and agglomeration of droplets; thus, forming
two separated phases of water and oil.
Ultrasonic Irradiation: Ultrasonic waves generate compressions and rarefactions in the
medium through, which they are passed. The rarefaction cycle exerts a negative pressure by
pulling molecules from each other. Microbubbles are produced in the medium and these will
be grown due to negative pressure.
These microbubbles grow to unstable dimension and collapse violently generating shock
waves, which results in high pressure and temperature immediately. This increases the
temperature of the emulsion system and decreases its viscosity, increases the mass transfer of
liquid phase, and thus leads to destabilization of W/O emulsion.
Smaller droplets in emulsion move faster than the larger ones under the influence of
ultrasonic irradiation. This can increase their collision frequency to form aggregates and
coalescence of droplets, which then promotes the separation of water/ oil phases.
Figure 2.7: Circuit - Electrokinetic method

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Froth flotation method: Water is mixed with oily sludge to form oily sludge slurry. Air is
passed through the sludge slurry, which form air bubbles in the water sludge mixture. These
air bubbles approach oil droplets in the slurry mixture.
The water film between oil and air bubble becomes very thin and then it is ruptured causing
spreading of oil in the air bubbles. The oil droplets with air bubbles can quickly rise to the top
of water-oil mixture, and the accumulated oil can be skimmed off and collected for further
purification.
Figure 2.8: Froth Flotation Method

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SESSION III
REFINERY CONSTRUCTION WASTE MANAGEMENT
3.1 Activities Involved in Refinery Construction
Site Cleaning and Area Segregation consist of removal of vegetative matter like plants, all
leaves, hedge clippings, twigs, tree trimmings, grass clippings etc. Removal of top soil or
surface soil, usually the top 5–10 inches (13–25 cm) of soil.
Mechanical Works like tank formation, erection of pipes, erection of structures, erection of
pumps, erection of equipment’s. Tanks formation is required to hold the waste water. Tanks
ranging the capacity from 10 KL to 5000 KL are constructed.
Substation installation, Panel board installation, Street light pole installation, testing work
comes under electrical works. Substation is used to distribute the power through the motor
of the treatment plant. Street Light Pole installation is necessary as the plants operate 24
hours a day, 7 days a week.
Instruments like Coriolis (Mass) Flowmeters, pH/ORP measurement, Pressure Gauges,
Water Purification Equipment, Diaphragm Operated Valves, etc. are attached to tanks and
pipes.
A Coriolis mass flow meter measures mass through inertia. Liquid or a dense gas flows
through a tube which is vibrated by a small actuator. This acceleration produces a measurable
twisting force on the tube proportional to the mass. ORP (Oxidation Reduction Potential) is
a popular water quality parameter that is normally measured as the voltage between a
platinum measuring electrode and a reference electrode. Diaphragm valves (or membrane
valves) consists of a valve body with two or more ports, an elastomeric diaphragm, and a
"weir or saddle" or seat upon which the diaphragm closes the valve. The valve body may be
constructed from plastic, metal, wood or other materials depending on the intended use.
Before a plant or facility is handed over for normal operation, it should be inspected,
checked, cleaned, flushed, verified and tested. This process is called Commissioning and
involves both the contractor and operator of a facility. Energizing and testing, Water flushing,
Chemical filling, Air blowing, circulating chemicals are some non-operating work included
in Commissioning.
3.2 Waste Classification
Waste is a product or substance which is no longer suited for its intended use. Whereas in
natural ecosystems waste is used as food or a reactant, waste materials resulting from human

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activities are often highly resilient and take a long time to decompose.
Waste is classified in 2 types; Hazardous Waste and Non-Hazardous Waste.
Hazardous waste is waste that has been identified as potentially causing harm to the
environment and human health and therefore needs special, separate treatment and handling.
Chemical and physical characteristics determine the exact collection and recycling process.
Flammability, corrosiveness, toxicity, ecotoxicity and explosiveness are the main
characteristics of hazardous waste. Liquid, gaseous and powder waste need special treatment
by default to avoid the dispersal of the waste. Generally, separate collection and handling are
established to avoid contact with non-hazardous waste. Chemical treatment, incineration or
high-temperature treatment, safe storage, recovery and recycling are possible modes of
treatment for hazardous waste.
Non-hazardous/solid waste is all waste which has not been classified as hazardous: paper,
plastics, glass, metal and beverage cans, organic waste etc. While not hazardous, solid waste
can have serious environmental and health impact if left uncollected and untreated. While a
significant proportion of solid waste could theoretically be reused or recycled, collection by
type of waste (selective waste collection) – a prerequisite for reuse and recycling – is one of
the biggest waste management challenges.
3.3 Waste Management
Recycling and reusing used motor oil are preferable to disposal and can provide great
environmental benefits. Recycled used motor oil can be re-refined into new oil, processed
into fuel oils, and used as raw materials for the petroleum industry.
Figure 3.1: Recycle Reduce Reuse Recovery

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Used oils such as engine lubrication oil, hydraulic fluids, and gear oils used in cars, bikes, or
lawnmowers can pollute the environment if they are not recycled or disposed of properly.
Used oil must be managed properly by local waste management authorities or automotive
repair shops to prevent contaminating the environment. Used oil filters pose similar waste
concerns. If properly drained, they can be safely recycled or disposed.
Some of the many reasons to reuse and recycle used oil include:
• Recycling used oil keeps it from polluting soil and water.
• Motor oil does not wear out—it just gets dirty—so recycling it saves a valuable
resource.
• Less energy is required to produce a gallon of re-refined base stock than a base stock
from crude oil.
• One gallon of used motor oil provides the same 2.5 quarts of lubricating oil as 42
gallons of crude oil.
Used oil can be re-refined into lubricants, processed into fuel oils, and used as raw materials
for the refining and petrochemical industries. Additionally, used oil filters contain reusable
scrap metal, which steel producers can reuse as scrap feed.
So, how is used oil recycled? Note that the most preferred option, re-refined oil—must meet
the same stringent refining, compounding, and performance standards as virgin oil for use in
automotive, heavy-duty diesel, and other internal combustion engines, and hydraulic fluids
and gear oils. Extensive laboratory testing and field studies conclude that re-refined oil is
equivalent to virgin oil—it passes all prescribed tests and, in some situations, even
outperforms virgin oil.
The same consumers and businesses that use regular oil also can use re-refined oil, since re-
refining simply re-processes used oil into new, high-quality lubricating oil. Any vehicle
maintenance facilities, automobile owners, and other machinery maintenance operations that
use oil also can use re-refined oil. In some cases, fleet maintenance facilities that use large
volumes of oil arrange to reuse the same oil that they send to be re-refined—a true closed
recycling loop.
3.4 Waste collection & Segregation
The type and quantities of waste likely to generated during every operation. Gathering of all
waste including the preliminary sorting and preliminary storage of waste before disposal.
Waste generated by refineries fall into four categories of materials: oily materials, spent
chemicals, spent catalysts, and other residuals.

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Oily materials are the primary source of waste for most refineries and are generated when oil
coalesces on solids, such as dirt particles. Oily residues are collected at several points within
the refinery: oil/water separators: dissolved air flotation units which are part of the
wastewater treatment process; heat exchanger cleanings, and tank bottoms cleanings.
The quantity of oily materials generated from one refinery to the next is highly variable. In a
sampling of six refineries that varied in complexity from highly complex to simple ranged
from 0.004 kg (1/100 lb.) of residue per barrel of crude processed to almost 0.4 kg (1 lb.) of
residue per barrel of crude processed (a difference of two orders of magnitude).
A method of preventing solids from entering the sewer system is to redesign storm catch
basins to allow runoff but filter solids out. The amount of oil entering the sewer systems can
be minimized by using a holding tank to separate oil and water drawn from storage tanks.
Segregation of waste based on the type (Hazardous & Non-Hazardous). Segregating
stormwater water runoff from the process wastewater prevents the mixing of dirt-containing
water with process waters containing oil and emulsifiers, one method of segregating waters is
to install above ground lines to prevent the commingling of process water with stormwater.
Stormwater can be recycled for various uses within the refinery, such as fire water, with
minimal pretreatment in the wastewater treatment system.
3.5 Temporary Waste Storage
The main objective of temporary storing of hazardous wastes is to collect them in a licensed
facility and to store them safely for a temporary period before they are moved to a recycling
plant and/or final disposal facilities.
Hazardous waste management facilities receive hazardous wastes for treatment, storage or
disposal. These facilities are often referred to as treatment, storage and disposal facilities, or
TSDFs.
Within the scope of our license obtained from Environment and Urban Planning Ministry, our
facility with all the safety precautions applied provides intermediate storage service for
hazardous wastes of all our industrialists
As per EPA guidelines temporary storage should be
• Specific types of skips with lid.
• Fire protection should be available nearby.
• If Hazardous trained employees should be available to handle.
• Need classification based on the state of waste materials.
• Hazardous waste must be removed to disposal within 60 days.

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3.6 Transportation
Hazardous waste transporters are individuals or entities that move hazardous waste from one
site to another by highway, rail, water, or air. Hazardous waste transporters play an integral
role in the hazardous waste management system by delivering hazardous waste from its point
of generation to ultimate destination.
This includes transporting hazardous waste from a generator's site to a facility that can
recycle, treat, store or dispose of the waste. It can also include transporting treated hazardous
waste to a site for further treatment or disposal.
• Transportation should be done by authorized waste contractor (KEPA approved)
• Handling person/ driver should have permit for transfer waste and he must undergo
adequate training.
• Manifest should be with the handler/driver.
• Waste should be transported to approved dumping/ treatment plant.
3.7 Recovery and Disposal of Waste
The final disposition of waste after attempts to reuse, recycle and recovery
Incineration is the process by which waste sludge from the petroleum industry undergoes
complete combustion in the presence of abundant air and auxiliary fuel. Two major
incinerator types used are rotary kiln and fluidized bed. Combustion temperatures in rotary
kiln incinerators range between 980–1200°C, with a residence time of 30 min, while
combustion temperatures in the fluidized bed range between 730–760°C, with a residence
time measured in days.
Fluidized bed is best in treatment of sludge with low-quality because of it has high mixing
efficiency, fuel flexibility, low pollutant emissions and high combustion efficiency.
Figure 3.2: Incinerator

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The treatment method whereby petroleum wastes are turned into piles meant for degradation
through indigenous or extraneous micro-organisms is known as Bio pile. This treatment
technology can replace land treatment which requires large areas of land. This technology is
called composting when organic materials are added to improve its efficiency. Bio
pile/composting treatment is environmentally friendly and requires less land space
compared to landing farming; however, large area of land is still needed and is also consume
more time.
Biodegradation of petroleum hydrocarbons is a complex process that depends on the nature
and on the amount of the hydrocarbons present. Petroleum hydrocarbons can be divided into
four classes: the saturates, the aromatics, the asphaltenes (phenols, fatty acids, ketones, esters,
and porphyrins), and the resins (pyridines, carbazoles, sulfoxides, and amides). One of the
important factors that limit biodegradation of oil pollutants in the environment is their limited
availability to microorganisms. Petroleum hydrocarbon compounds bind to soil
components, and they are difficult to be removed or degraded.
Deep well injection is a liquid waste disposal technology. This alternative use injection
wells to place treated or untreated liquid waste into geologic formations that have no
potential to allow migration of contaminants into potential potable water aquifers. Deep well
injection is a disposal method that can be used for many different types of wastes, so the EPA
has developed a classification system to differentiate between types of wells. The division of
injection wells also helps to regulate the different types of wells to standards that best fit the
given situation.
Figure 3.3: Deep Well Injection

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The different classes of wells and their purpose is listed below:
• CLASS I - Wells used to dispose of industrial and municipal waste.
• CLASS II - Wells used to dispose of oil and gas related wastes.
• CLASS III - Wells used for extraction of minerals.
• CLASS IV - Shallow wells for disposal of hazardous wastes, or radioactive injection
wells.
• CLASS V - Wells used to dispose of non-hazardous fluids either into or above the
underground drinking water source.
• CLASS VI - Wells used for geologic sequestration.
Deep well injection has been an inexpensive, effective method for waste disposal for a very
long time now. Growing community concern and proven failures resulted in deep well
injection being considered not as safe as initially thought.
Land farming treatment is a biological, chemical, and physical degradation of oily
sludge contaminants by mixing it with soil. Land treatment is more preferable to other
disposal methods because of its low cost, low energy consumption, has potential to
accommodate large volumes of sludge, and require simple operating procedure. However, it
is time consuming and requires a very large area of land; it may not be effective in cold
regions.
A study on land farming reported that land farming treatment of oily sludge can remove 80%
of PHCs within 11 months of treatment in a semi-arid climate, the removal of half of the
oily sludge occurred within the first three months.
70–90% of PHCs degradation can be achieved within 2 months when land farming
treatment was applied to oily sludge; it was observed that most of the degradation occurs
within the first 3 weeks of treatment.
Oily sludge land treatment for 12 months under arid condition was investigated, it was
observed that tilling (addition of water and nutrients) were the main parameters responsible
for the highest PHCs removal in land treatment of oily sludge with a removal rate of 76%.

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SESSION IV
WASTE MANAGEMENT & MINIMIZATION
4.1 Refinery Operation
Petroleum refining processes are the chemical engineering processes and other facilities used
in petroleum refineries to transform crude oil into useful products such as liquefied petroleum
gas, gasoline or petrol, kerosene, jet fuel, diesel oil and fuel oils.
Refineries are very large industrial complexes that involve many different processing units
and auxiliary facilities such as utility units and storage tanks. Each refinery has its own
unique arrangement and combination of refining processes largely determined by the refinery
location, desired products and economic considerations.
Each segment of industry generates different types of wastes. Variation of processes used in
each area. Therefore, different waste minimization technologies available. The oil comes
down, it kills the mangroves, which then kills the root system. And the root is holding
together this island, and without that root system holding together, the sediment it just erodes
away.
4.2 Waste Management Hierarchy
The waste management hierarchy is a concept that promotes waste avoidance ahead of
recycling and disposal. The shortened version of the hierarchy, ‘reduce reuse recycle’ is
frequently used in community education campaigns, and has become a well-recognized
slogan for waste reduction and resource recovery. Avoid & Reduce, Reuse, Recycle, Recover
Figure 4.1: Refinery Operations

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are most preferable in the Waste Management Hierarchy while treat and disposal are least
preferable.
Source reduction involves efforts to reduce hazardous waste and other materials by
modifying industrial production. Source reduction methods involve changes in manufacturing
technology, raw material inputs, and product formulation. At times, the term "pollution
prevention" may refer to source reduction. Source reduction is typically measured by
efficiencies and cutbacks in waste. Toxics use reduction is a more controversial approach to
source reduction that targets and measures reductions in the upstream use of toxic materials.
Recycling and reusing used motor oil are preferable to disposal and can provide great
environmental benefits. Recycled used motor oil can be re-refined into new oil, processed
into fuel oils, and used as raw materials for the petroleum industry. The process for
recycling waste oil includes water extraction, filtering, de-asphalting, and distillation.
The oil can then be reused for use in motorized equipment, turned into hydraulic oil,
or used to make plastics. Another way to use waste oil efficiently is as heating fuel. Used oil
can be re-refined into lubricants, processed into fuel oils, and used as raw materials for
the refining and petrochemical industries. Choosing products, packages and other materials
that can be used several times.
Petroleum treating processes stabilize and upgrade petroleum products by separating them
from less desirable products and by removing objectionable elements. Undesirable elements
such as sulfur, nitrogen, and oxygen are removed by hydrodesulfurization, hydrotreating,
chemical sweetening, and acid gas removal.
Disposal is the elimination of the Oil. Last resort and only after confirming that the waste
cannot be reused, recycled or recovered.
Figure 4.2: Waste Management Hierarchy

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4.3 Waste Management Plan
The primary goal of pre-incident waste management planning is to prepare a community to
effectively manage waste, debris and materials generated by a homeland security incident,
including reducing the potential amount of waste generated at the outset. The Waste
Management Plan points as per API (American Petroleum Institute), EPA (United States
Environmental Protection Agency) are as follows:
• Company Management Approval - Company’s Guiding Principles and Objectives,
and Environmental Policy.
• Area Definition – Specific area which includes ecological description and types of
business operation.
• Regulatory Analysis - Federal, state, and local laws and regulations.
• Waste Identification - Identify the type, amount, and frequency of generation of each
waste generated within the plan’s area.
• Waste Classification - Classify each waste stream with respect to its regulatory status
like hazardous or nonhazardous and exempt or nonexempt.
• LIST AND EVALUATE WASTE MANAGEMENT AND DISPOSAL OPTIONS
- Consider regulatory restrictions, engineering limitations, economics, and intangible
benefits.
• Waste Minimization - To reduce the volume generated, reduce the toxicity, recycle,
reclaim, or reuse.
• Preferred Waste Management Practices - Implement waste minimization options
identified (whenever feasible).
• Prepare and Implement Waste Management Plan - Compile all the preferred
waste management and minimization practices.
• REVIEW AND UPDATE WASTE MANAGEMENT PLAN - Periodically review
the plan and evaluate new or modified waste management and minimization practices
4.4 Strategies to Improve
Technology Strategy is improving day by day in Petroleum Industries. The digital
transformation in upstream oil and gas is growing rapidly. Industries are embracing
technology to reshape their operating landscape and reap the benefits of improved
productivity, higher efficiency, and increased cost savings. The oil and gas industry are not
a stranger to this and is progressing towards digital maturity.

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Advance Sensing technologies have been widely adopted in the oil and gas industry in order
to monitor various processes in petroleum production, from exploration, Enhanced Oil
Recovery (EOR), well drilling, well completion, pigging, fracking, and refining, to
decommissioning. Different modalities, including temperature, pressure, vibration, and
strain/stress, are required to sense and monitor continuously in order to guarantee integrity of
oil and gas production, storage and transport infrastructure onshore and offshore. Thus, the
safety and reliability of oil production can be assured.
Various advanced sensing techniques have been developed to satisfy the sensing
requirements under high-pressure-high-temperature (HPHT) environments in oil and gas
applications in recent decades. Recent advances in computer technology, including artificial
intelligence, machine learning, augmented reality, Internet of Things (IoT), big data, cloud
computing, blockchain technology and so on, together with advanced sensing techniques will
definitely facilitate better monitoring, security and management of oil and gas industry with
higher productivity and reduced cost and causalities.
Materials management includes all those activities necessary to ensure that materials flow
from source to production sites to the final customer in the form of a finished product. It is a
complete process that includes planning material requirements, releasing purchase
orders, providing transportation to sites, material storage and shipping to operational
Figure 4.3: Strategies to Improve

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sites, when required. Materials management for large oil and gas companies includes not just
material supply for day-to-day operational activities at production facilities but also the
construction of large capital projects. Perhaps the fundamental purpose of materials
management is to ensure that the right materials, of the right quality, in the right quantities,
are available at the right time and all of it at the optimum cost. A very challenging task, but it
is vital for Oil & Gas operations.
Quality Management is necessary in Oil and Gas Industry. The Oil and gas industry is one
of the critical industries that need to follow heavy regulations and scrutiny. Even a single
failure could mean disaster for the environment in addition to the harms and impacts on the
other connected sectors of the industry. The industry needs a quality management system
with an emphasis on compliance that can provide them comprehensive insights into processes
and product quality to identify the scope of improvements going forward.
4.5 Waste Minimization
Waste minimization is a set of processes and practices intended to reduce the amount of
waste produced. By reducing or eliminating the generation of harmful and persistent
wastes, waste minimization supports efforts to promote a more sustainable society.
Waste minimization techniques focus on preventing waste from ever being created,
otherwise known as source reduction, and recycling. These techniques can be practiced at
several stages in most waste generating processes, but require careful planning, creative
problem solving, changes in attitude, sometimes capital investment, a d genuine commitment.
Waste minimization is important because it helps protect the environment and it makes
good business sense. In fact, businesses can simultaneously manage both business and
environmental objectives by focusing on waste minimization.
Waste minimization at source reduction are as follows:
• To reduce or eliminate the generation of pollutants and wastes.
• To reduce the volume and or toxicity of waste that is generated.
• Changes in products (substitution and composition).
• Source control (process changes, equipment modification, increased automation, and
material handling changes).
• Product substitution, inventory control, reduction of water use, good housekeeping,
equipment maintenance or replacement, in process recycling, and careful selection of
third-party contractors.

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4.6 Drilling Operations
Petroleum is among the world’s most important natural resources. The production of
petroleum involves the generation of drilling waste which forms a major source of
pollution in oil producing environment. Almost every process in the finding and production
of petroleum generates many types of wastes which impacts the environment negatively such
as the generation and disposal of cuttings and excess drilling fluids. These materials are
discharged overboard in offshore operations or buried when drilling in land-based locations.
As an effort to manage and reduce the impact of drilling waste on the environment there have
been a number of techniques.
Technologies such as directional drilling, slim-hole drilling, coil-tubing drilling and
pneumatic drilling are few of the drilling practices that generates less amount of drilling
waste. In this we discuss the environmentally responsible actions that require an
understanding of the types of wastes and how they are generated and also a number of
drilling waste managing technologies of minimizing and eliminating the effect of drilling
waste on environment.
All activities related to Oil & Gas Exploration, Production, Storage and Transportation
involve waste generation associated to potential risk to environment. Waste types are related
to Exploration and Producing (E&P) activities. These activities are: Drilling operations,
Production operations, Completion operations, Work-over operations, Gas plant operations.
Pre-planning of Drilling Operation can reduce waste at source itself by many methods.
Drilling fluid system can be installed to prevent waste water at source. Better Pit design can
help in preventing waste. Reduction in use of water during drilling is important.
Product Substitution of Drill fluids, drilling fluid additives and Pipe dope may help in
reducing waste. Modified and Well-maintained equipment’s are necessary.
Reusing and Recycling of Drilling Fluids and Waste drilling fluid which can be used for
other projects too. Find another source of water can help in boosting the drilling process.
4.7 Production and Workover Operations
The term workover is used to refer to any kind of oil well intervention involving invasive
techniques, such as wireline, coiled tubing or snubbing. More specifically, a workover refers
to the expensive process of pulling and replacing completion or production hardware in
order to extend the life of the well.

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The process of performing major maintenance or remedial treatments on an oil or gas well. In
many cases, workover implies the removal and replacement of the production tubing string
after the well has been killed and a workover rig has been placed on location.
Workovers rank among the most complex, difficult and expensive types of well work.
They are only performed if the completion of a well is terminally unsuitable for the job at
hand. The production tubing may have become damaged due to operational factors like
corrosion to the point where well integrity is threatened. Downhole components such as
tubing, retrievable downhole safety valves, or electrical submersible pumps may have
malfunctioned, needing replacement. Equipment Modification like Basic sediment & waste
(BS&W) must be installed.
Basic sediment and water (BS&W) are both a technical specification of certain impurities
in crude oil and the method for measuring it. When extracted from an oil reservoir, the crude
oil will contain some amount of water and suspended solids from the reservoir formation.
BS&W is an emulsion of oil, water and sediment. Most crude oil purchasers specify the
maximum BS&W content that they will accept, usually only a small fraction of 1 percent,
although BS&W up to 3 percent is common for transport. Vapor Recovery technique is also
used.
As oil is held in these stock tanks, residual natural gas and other vapors can flash off and
collect above the liquid level. Vapor recovery is the process to collect, compress and prepare
this gas to be used or sold and send the liquid condensates back to the liquids in the tank.
This modification can be used to reuse oil from its vapor.
Figure 4.4: Vapor Recovery

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Naturally occurring radioactive material (NORM) is a waste product of oil production, and
its presence in pipelines, plants, and machinery may restrict operability and cause potential
radiological health hazards.
Radioactive materials, sealed sources and radiation generators are used extensively by the oil
and gas industry, and various solid and liquid wastes containing naturally occurring
radioactive material (NORM) are produced. The presence of these radioactive materials and
radiation generators results in the need to control occupational and public exposures to
ionizing radiation.
Various radioactive wastes are produced in the oil and gas industry including the following:
• Discrete sealed sources, e.g., spent and disused sealed sources
• Unsealed sources, e.g., tracers.
• Contaminated items.
• Wastes arising from decontamination activities, e.g., scales and sludges.
These wastes are generated predominantly in solid and liquid forms and may contain
radionuclides of artificial or natural origin with a wide range of half-lives. Some equipment
modification like Chemical coating, ion plating, scale formation reduction, etc. are able to
reduce NORM at the source.
4.8 Natural Gas Treating and Processing Operations
Natural-gas processing is a range of industrial processes designed to purify raw natural
gas by removing impurities, contaminants and higher molecular mass hydrocarbons to
produce what is known as pipeline quality dry natural gas.
Natural-gas processing begins at the well head. The composition of the raw natural gas
extracted from producing wells depends on the type, depth, and location of the underground
deposit and the geology of the area. Oil and natural gas are often found together in the
same reservoir. The natural gas produced from oil wells is generally classified as
associated-dissolved gas meaning that the gas had been associated with or dissolved in crude
oil. Natural gas production not associated with crude oil is classified as “non-associated.”
To meet pipeline specifications, operators are often required to dehydrate their produced
natural gas that is saturated with water vapor. Water vapor in natural gas pipelines can
result in the formation of hydrates that can obstruct or plug the pipe. Also, water vapor in
a pipeline can cause corrosion due to the presence of carbon dioxide (CO2) or hydrogen
sulfide (H2S) in the natural gas.

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In the petroleum refining industry, caustic solutions (NaOH) are regularly used to remove
H2S and organic sulfur compounds from hydrocarbon streams. The hydrocarbon processing
industry has historically used caustic solutions to extract or treat acidic impurities in liquid
hydrocarbon streams. A number of caustic processes, both regenerative and
nonregenerative, can be used to remove sulfur compounds from hydrocarbon liquids. The
simplest process is the use of a nonregenerative solid potassium hydroxide (KOH) bed,
which is effective for removal of H2S but not for other sulfur compounds. One of the
common processes for treating hydrocarbon liquids is the use of regenerative caustic wash
with sodium hydroxide (NaOH).
Installing Flash Tank Separators (FTS) on glycol dehydrators further reduces methane,
Volatile Organic Compound (VOC), and Hazardous Air Pollutants (HAP) emissions and
saves even more money. Recovered gas can be recycled to the compressor suction and/or
used as a fuel for the Tri-ethylene Glycol (TEG) reboiler and compressor engine. Economic
analyses show flash tank separators installed on dehydration unit’s payback costs in 4 to 11
months. This also reduce VOC released in the air after production.
High-bleed pneumatic devices are automated control devices powered by pressurized
natural gas that continuously modulate a process condition. The process measurement
signal gas flows to the valve controller continuously and vents (bleeds) to the atmosphere.
The upstream oil and gas industry utilizes pneumatic devices to take measurements and
control processes typically by sending a signal to a valve to adjust its position.
A cooling system is used to reject heat from a process or plant. There are many types of
cooling systems available that are used in the oil and gas industry. To best optimize the
efficiency of a cooling system, a “systems approach” should be used to identify potential
savings and performance enhancement. This approach looks at the entire cooling system,
including the pumps, motors, fans, nozzles, fill, drift losses, evaporative losses, blow down,
makeup rate, chemicals, flow rates, temperatures, pressure drop, as well as operating and
maintenance practices.
By focusing on the whole system as opposed to just individual components, the system can
be configured to avoid inefficiencies and energy losses. Cooling systems do not operate under
one condition all the time and system loads vary according to cyclical demands,
environmental conditions, and changes in process requirements.
Equipment Modification like Flash Tank Separators (FTS), High-bleed pneumatic devices
and Cooling Systems are very useful and beneficial for the industry.

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4.9 Pipeline Transport Operations
Oil pipelines are made from steel or plastic tubes which are usually buried. The oil is moved
through the pipelines by pump stations along the pipeline. Natural gas (and similar gaseous
fuels) is pressurized into liquids known as Natural Gas Liquids (NGLs). Natural gas
pipelines are constructed of carbon steel.
Pipelines transport a variety of products such as sewage and water. However, the most
common products transported are for energy purposes, which include natural gas,
biofuels, and liquid petroleum. Pipelines exist throughout the country, and they vary by the
goods transported, the size of the pipes, and the material used to make pipes.
While some pipelines are built above ground, the majority of pipelines in the U.S. are
buried underground. Because oil and gas pipelines are well concealed from the public,
most individuals are unaware of the existence of the vast network of pipelines.
Figure 4.5: Pipeline Transport

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SESSION V
APPLICATION OF JET MIXER IN SLUDGE MITIGATION DURING
CRUDE OIL STORAGE
5.1 Sludge Formation during Storage of crude oil
Composition of crude oil:
• Hydrocarbons of various molecular weight
• Alkanes
• Naphthene’s
• Aromatics Hydrocarbons
• Asphaltic
• Nitrogen
• Sulfur
• Oxygen
Oil residue in Storage Tank: Due to the change in physicochemical conditions during the
production, transportation, storage, and refining, heavier molecules can precipitate from
crude oil.
The heavy ends that separate from the crude oil and are deposited on the bottoms of storage
vessels are known as “sludge.” It is a combination of hydrocarbons, sediment, paraffin and
water.
5.2 Impact of sludge on storage capacity
Viscous sludge formed at the bottom of storage tanks can cause many problems including
reduction of storage capacity of tank, oil contamination, corrosion, repair costs,
environmental pollution, etc.
Figure 5.1: Oil residue in Storage Tank

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Sludge Mitigation: The reduction of sludge viscosity can be achieved by reduction of its
interfacial tension. Non-ionic surfactants (like bitumen emulsifier), and solvents (such as
mixed xylene, AW-400, and AW- 402), injection of additives, applying pressure, and mixing
operations had a positive effect on reduction of emulsion viscosity. Agitation is commonly
used to combat the formation of sludge in static volumes of crude oil.
5.3 Jet mixers
A Tank Jet Mixer is a mass momentum exchange device that uses pressurized liquid energy
to entrain, mix and pump a secondary fluid. It can normally be employed on any application
in which the process liquid is capable of being handled by a centrifugal pump. Over the past
15 years, jet mixing has developed as an alternative to conventional prop mixers to combat
the build-up of sludge. The jet mixing system is more effective than other mixing methods
because they are very expensive for large storage tanks and underground tanks.
In jet mixing a part of liquid from the tank is circulated into the tank at high velocities with
the help of pump through JET nozzle. The high velocity imparted into the bulk liquid creates
a negative pressure in the mixing chamber and entrains some of the surrounding fluid in to
the jet, which leads to circulation inside the tank. There are no moving parts inside the tank.
5.4 Sludge Mitigation by Jet Mixers
Jet mixers are intended to be run for a short duration on an infrequent basis. Duration is
dependent on the amount of sludge to be dissolved in the tank, and the frequency is
dependent on both the rate of sludge formation and limitations on basic sediment and water
(BS&W) levels allowed in the tank contents (more frequent mixes for lower changes in
BS&W). A typical jet mix sludge management program would involve jet mixing for a week
once every year or two.
Figure 5.2: Jet Mixers

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The downsides of jet mixing are the clutter from pump, pipe and hoses on the tank lot when
the mixer is active and the system needs to be monitored during operation. Considering the
short, infrequent nature of active use and the overall effectiveness of the system, these
shortcomings should not be seen as significant by the user. These are highly useful for the
small spills with the highest efficiency.
5.5 Jet Mixer Operation
The jet mixer uses oil from the tank and re-circulates it through the mixer via the re-
circulation pump. Therefore, there are no chemicals or water or steam required or any other
intermediary plant and equipment. The technique is purely based on creating a ‘jet flux’, a
powerful shearing effect, breaking up sludge which has compacted at the base of the tank
using the oil already in the tank.
This enables soluble petroleum hydrocarbons to be released back into the overhead oil in the
tank. In some cases, as much as 90% of sludge is a recoverable, saleable product.
Figure 5.3: Jet Mixer Operation

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5.6 Factors Influencing the Suspension characteristics of a Jet Mixer
Effect of Nozzle size on Suspension characteristics: From the figure it can be seen that the
critical velocity increases with increase in nozzle diameter for all the three nozzle positions
employed.
Among the three nozzles used 10mm nozzle shows shortest critical velocity for suspension
compared to 15 mm and 22 mm nozzles. This implies, for a particular liquid flow rate the jet
velocity imparted into the bulk liquid through 10 mm nozzle is more than that of 15 mm and
22 mm nozzles.
This high velocity creates required turbulence to lift the solid particles at the tank bottom.
Once the solids are lifted from base of the tank, they can be entrained into the mean flow of
the liquid. When 15 mm and 22 mm nozzles were used the nozzle, velocity required to
achieve same level of suspension is more than that of 10 mm nozzle.
Effect of Sludge Density on Suspension Characteristics: The critical velocity was found to
be increased when density of the particle increased, this implies that higher density particle
has high settling velocity which requires higher critical velocity to suspend the entire solid
particles. Thus, critical velocity for suspension is directly proportional to particle density.
Effect of Heavy molecules Concentration on Suspension characteristics: The critical
velocity was found to be increasing when solid loading increases, this is due to an increase in
the solid loading results in higher dissipation of energy at the solid liquid interface. This
causes a reduction in the liquid circulation velocity in the vessel. Thus, a higher nozzle
velocity is required to suspend the solid particle.
Effect of settling velocity of Heavy molecules on Suspension characteristics: The critical
velocity for suspension is increases with increase in particle settling velocity irrespective of
solid loading and nature of solids. Also, critical velocity was found to be increased when
solid loading was increased.
Figure 5.4: Jet Mixer Nozzle

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5.7 Advantage of Jet Mixer
• High efficiency
• High operational safety
• Long life time
• No turning parts so little wear and tear
• Simple construction
• Available in any material used in the equipment
• Resistant to fouling
• Low Installation Cost
• Low power Consumption
• Low Maintenance Cost
• Superior Process Performance
• Eliminates vortexing and unwanted product air entrainment
• Eliminates problems with stratification and dead mixing areas throughout the vessel
• Reduces blend times by as much as 80%
• Easily suspends and re-suspends high-settling-rate solids
• Significantly improves heat transfer rates
• Easily maintains complete tank motion of non-Newtonian fluids

37
SESSION VI
USED OIL & WASTE OIL MANAGEMENT
6.1 Lubricants / Lubricating Oil
Lubricants are obtained either from crude oils (mineral based) or is synthetic based. These
form a protective film between metal surfaces in contact. Act as a coolant for internal engine
/ machinery parts.
These are required to
• Be stable at elevated temperature
• Have sufficiently low pour point to work satisfactorily at lowest operating
temperature
• Have sufficiently high flash point
• Have sufficient viscosity at various operating conditions (In engine etc.) to reduce
friction, minimize wear & tear and not impose additional viscous drag.
Lubricating oil is a low volume, high-cost products. Lubricating oils constitute about 1.0 %
of the crude processed.
6.2 Used Oil
Used motor oil is a valuable resource. Oil doesn't wear out; it just gets dirty. The used oil you
take to a collection site can be recycled into new products, burned for heat or
the production of asphalt, or used in power plants to generate electricity.
Used oil is generated from a broad variety of sources within the transportation, construction,
and industrial sectors and consists of lubricating oils (motor and transmission oils) and
industrial oils (hydraulic and cutting oils). Used oils are collected from decentralized stocks
and ultimately aggregated at permitted treatment, storage and disposal facilities (TSDF).
Some examples of types of products that after use, can be labelled as used oil are: hydraulic
oil, transmission oil, brake fluids, motor oil, crankcase oil, gear box oil, synthetic oil, and
grades 1, 2, 3 and 4 fuel oil.
Contaminants generally present in used oil are:
• Sediments
• Water
• Fuel Components
• Heavy Metals (As, Cd, Cr, Ni, Cu, Zn, Pb etc.)

38
• Halogenated Solvents
• Polyaromatic Hydrocarbons (PAH)
• Polychlorinated Biphenyls (PCBs)
Typical Composition of Used Oils:
• Water - 5 to 9 Wt. %
• Light ends - 2 to 4 Wt. %
• Gas Oil - 4 to 7 Wt. %
• Base Oil - 75 to 64 Wt. %
• Residue - 13 to 17 Wt. %
Under HW Rules:
• Used Oils have been categorized as hazardous wastes as per Schedule –1
• The used oils must confirm to specifications given in Schedule-V (Part A) for
undergoing re-refining &
• Unsuitable for re-refining, if schedule-V specifications are not met.
Why Reuse and Recycle used oil?
Motor oil does not wear out-it just gets dirty-so recycling it saves a valuable resource.
Recycling used oil prevents it from polluting soil and water. Less energy is required to
produce a gallon of re-refined base stock than a base stock from crude oil. A preferred option
as the oil is used number of times.
Other Benefits:
• Reduces pollution threat
• Reduces dependence on imported oil
• Re-refining is energy efficient
• Provides direct and indirect employment
6.3 Re-refining of Used Oils
Re-refining means applying a process to the used oils so as to produce high quality lube base
stock for further manufacture of lubricants. For resource conservation this is practiced all
over the world. Re-refining technologies are required to be environmentally sound as per the
HW Rules. Environmentally sound management means wastes are managed in a manner
which shall protect health and environment against the adverse effects which may result from
such waste. Vacuum distillation / thin film distillation-based processes have been widely
adopted in the country being environment friendly. Residue generated during pre-treatment,

39
distillation residues and spent clays need to be disposed as per the HW Rules. Major Re-
refining Technologies in use in the world are
• Vacuum Distillation Based Technology
• Extraction Based Re-Refining Technology
• Ultra-filtration Technology
• Hydrogenation Based Technology- HyLube Process
Indian Re-refining Industry: Re-refining in India is generally in small sector. Large
number of units are operating at a same time. Most of the units are based on vacuum
distillation / clay treatment technology with some working on thin film concept. Residue are
disposed as per HW Rules. Air, water & soil pollution abatement measures are generally
poor.
Disposal of Residue & Spent clay: Residue left after re-refining of used oil needs to be
incinerated or is allowed to be burnt in cement kilns as per HW Rules. Two chamber
incinerators are to be used, temperature in second chamber must be above 1250o
C, no furans
/dioxin generation (cement kiln temp exceeds 1250o
C). The spent clay is allowed to be
disposed of two brick kiln units.
Re-refining Technologies in use in the world: In most of the developed countries, more
than 50% of used oil is supplied for re-refining. Developing countries also have good
collection rates, since people understand that the used oil has an economic value. But, the
share of re-refining is less than 20% due to lax enforcement of regulations, which means most
of the used oil collected is disposed of as fuel.
These are some of the technologies use to re-refining
• Vacuum Distillation based Revac process, STP-Sotulub, Probex, Tiqson
• Thin film distillation based KTI Relub, CEP, Safety kleen & Mohawk, Balmer Lawrie
process
• Solvent (Propane) Extraction based Viscolube IFP, IFP- Snam Progetti, Interline
• Hydrotreating based UOP HyLube
6.4 Commercial Re-refining Plants
Re-Refined Oil is recycled oil that goes through more processes, removing both soluble and
insoluble impurities. Typical Re-refining plant capacities globally range from 16,000 to
100,000 Tonnes/ Annum for larger plants. The Re-refining plant capacities in India are much
smaller.

40
Factors affecting Re-refining Economics:
• Used oil cost / Crude oil prices
• Availability
• Transportation cost
• Re-refining process used
• Regulatory compliance to dispose residues
• Scale of operation
There are some challenges faced for Commercial Re-refining Plants for Re-refining used
oil/waste oil. Location of waste must be located far from public reach. If not, it may harm
their health. The daily fluctuations in the price of crude oil makes the re-refining cost go high.
Numerous technical challenges occur while recycling of used oil.
6.5 Waste Oils
Waste oil is defined as any petroleum-based or synthetic oil that, through contamination, has
become unsuitable for its original purpose due to the presence of impurities or loss of original
properties. Waste oil is a more generic term for oil that has been contaminated with
substances that may or may not be hazardous. Any oil contaminated with hazardous waste
may itself be a hazardous waste, and if so, must be managed subject to hazardous waste
management standards. Both used oil and waste oil require proper recycling or disposal to
avoid creating an environmental problem.
Waste Oils are Hazardous as per Schedule -1 (Sr. no-3) of Hazardous Waste (HW) rules,
these include:
• Crude oil spills, emulsions
• Tank bottom sludge(s)
• Slope oils generated in refineries, installations or ships
As per HW Rules, these can be used as fuels if meeting Schedule-V (part B) specifications as
such or after processing.
The process of refining waste oil to produce lubrication oils or fuel oils is technologically
possible and currently is being practiced in many areas. Difficulties in removing impurities of
lead, dirt, metals, oxidation products, and water, along with environmental standards and
product specifications, have hampered the widespread practice of recycling in the past.
However, the improvement of recycling technology, coupled with economic incentives, may
result in a resurgence of recycling petroleum products in the near future.

41
Specifications of fuel, derived from waste oils:
• Sediment - 0.25% (Maximum)
• Heavy Metals - Pb - 100 PPM, As - 5 PPM, Cd+Cr+Ni - 500 PPM
• Polyaromatic hydrocarbons (PAH) - 6% (Maximum)
• Total Halogens - 4000 PPM, Max
• Polychlorinated Biphenyles (PCBs) - < 2 PPM
• Sulphur - 4.5 wt %
• Water content 1 wt % (Maximum)
Re-refining / Recycling Plants in India:
Sr.no Technology Location Used oil Waste oil
1
EST as per MW
hazardous rules
Tanu Petrochem,
Medak, AP
14,000 KLA 18,000 KLA
2 ----
Supreme Lub,
Hyd, AP
9,600 KLA 12,000 KLA
3 ---- Spear Petro, Goa ---- 11,000 KLA
4 ----
Daman Ganga,
Valsad Gujarat
480 KLA 13,000 KLA
5 ----
Mangalam Lub,
Ranchi
16,650 KLA 7,400 KLA
6 ----
Southern Ref,
Thiruvanthpuram
13,500 KLA 6,000 KLA
7
EST as per MW
hazardous rules
Anna
Petrochem,
Sirohi (Raj)
---- 30,000 KLA
8 ----
Bharat oil,
Ghaziabad (UP)
10,000 KLA ----
9 ----
Paswara
Chemicals,
Merrut (UP)
36,000 KLA 31,500 KLA
10 ----
Sai Om, Thane
Maharashtra
---- 15,000 KLA
11 ----
RHJ Petrochem,
Thane (Maharashtra.)
6,000 KLA 18,000 KLA
Table 5.1: Re-refining / Recycling Plants in India

42
Registration of Re-refining/Recycling unit:
• State Pollution Control Boards (SPCB) grant registration to anyone who desires to put
up/operate such units
• The bulk used or waste oil generators like railways, state transport corporations,
Industrial units etc dispose their hazardous wastes to such registered units for re-
refining/ recycling
• The operations in these registered units are as per the guidelines provided by SPCBs
• Residue disposal from such units is also as per the guidelines (environment sound
disposal to TSDFs)

43
CONCLUSION
The total petroleum hydrocarbon (TPH) in oily sludge is normally reduced more than 80%
during bioremediation. Suspension characteristics show that the critical velocity required for
solid suspension increases with increase in solid loading, particle diameter and particle
density. Used oil / Waste oil recycling is very important for resource conservation as well as
for environment protection. Waste oil and its impurities pose potential threats to the
environment, whether the waste oil is indiscriminately dumped on land or into water courses
or burned. Plant performance monitoring need to be adopted at the earliest in a very effective
way. Environment friendly aspects of the re-refining process need to be made better and
better.

44
REFERENCES
1. “Pre-treatment of super viscous oil wastewater and its application in refinery”
Chen, C., Yan, G., Guo, S., Yang, Y., 2008. Pet. Sci. 5, 269–274.
2. “Treatment of wastewater from petroleum industry: current practices and
perspectives” Varjani, S., Joshi, R., Srivastava, V.K. et al. Environ Sci Pollut Res 27,
27172–27180 (2020). DOI: 10.1007/s11356-019-04725-x
3. “Petroleum sludge treatment and disposal: A review”. October 1, 2018.
Environmental Engineering Research 2019; 24(2): 191-201. DOI: 10.4491/eer.2018.134
4. "Solid Waste Management." 2005. United Nations Environment Programme. Chapter
III: Waste Quantities and Characteristics, 31-38. unep.or.jp Archived 2009-10-22 at
the Wayback Machine
5. "Wastewater Characterization". Development Document for Final Effluent
Limitations Guidelines and Standards for the Iron and Steel Manufacturing Point Source
Category (Report). EPA. 2002. pp. 7–1ff. EPA 821-R-02-004.
6. “Environmental management in oil and gas exploration and production – An
overview of issues and management approaches”, J.P. Visser, and Jacqueline Aloes de
Lardered, (1997), E&P Forum United Kingdom/UNEP Industry and Environment,
France.
7. “Waste minimization practices in the petroleum refining industry”, Linda M.
Curran, (1992)), Journal of Hazardous Materials, 29 (1992) 189-197
8. “Process Design Aspects of Jet Mixers”. Patwardhan, A.W. and Thatte, A.R. (2004),
Can. J. Chem. Eng., 82: 198-205. DOI: 10.1002/cjce.5450820126
9. “Environmental Assessment of Used Oil Management Methods”, Bob Boughton and
Arpad Horvath, Environmental Science & Technology 2004 38 (2), 353-358, DOI:
10.1021/es034236p
10. “Encyclopedia of Lubricants and Lubrication”. Kajdas C. (2014) Re-refining
Technologies. In: Mang T. (eds) Springer, Berlin, Heidelberg. DOI: 10.1007/978-3-642-
22647-2_311

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