PETROLEUM INDUSTRIES
PETROLEUM INDUSTRIES
• Petroleum is a dark colored oily liquid with a characteristic
odor . It is a mixture of hydrocarbons formed by decomposition
of plant and animal remains buried inside the earth.
• Petroleum is extracted by drilling holes in the earth’s crust and
sinking pipes until the drill penetrates the oil bearing sands
sometimes the oil rushes out through due to the pressure exerted by
natural gas inside. If the pressure of the gas diminishes, the oil is
obtained by plumping. The crude oil thus obtained is then taken to
refineries.
• Petroleum is separated into its constituents by the process of
fractional Crude oil consist of a mixture of various gases, liquid,
solids, semisolids of hydrocarbons, water, salt, earth particles
and many useful organic compounds.
Role of Oil and Gas
Global Energy Mix Bangladesh Scenario
Total Gas Production in 2007-08 = 601 BCF [1647 MMCFD]
O SL
CNG
1% 3%
4%
Domestic
12%
Power
39%
Oil & Gas are VITAL for both Global & Industry
15%
Bangladesh Scenario O - Others
SL - System Loss
Fertilizer
13% Captive
13%
Reserves & Production
Global Reserves
NG
Oil
6534 TCF
Production
81,820 BOPD 108.2 TCFD
Reserves & Production (Contd.)
• Bangladesh Scenario
• Total number of Gas fields = 23
• Number of Producing Gas fields = 18
• Proven+Probable (2P) reserve = 12.2 TCF
(December 2008)
• Production in 2008-09 = 0.64 TCF
• Extraction of Oil & Gas is a major activity around the world, and will
continue for decades to come
• The environmental consequences must be reckoned with
Activities in the Petroleum
• Upstream Industry
– Exploration
• Land & Aerial surveys, Satellite Images
• Gravitational, Magnetic & Seismic Surveys
• Exploration Drilling (“Wildcat”)
• Formation Evaluation
– Development
• Drilling Appraisal/production wells
• Production Facilities
• Gathering Systems
– Production
• Downstream
– Transportation
– Refining
– Marketing
Occurrence of Oil & Gas
• On land
• Offshore
• Continental Shelves
• Deep sea
• Deserts
• Wetlands
• Forests
• Mountainous areas
• Arctic Region
Technological & Environmental challenges change with location type
Environmental Impact
Atmospheric impacts
• flaring, venting and purging gases
• combustion processes such as diesel engines and gas turbines
• fugitive gases from loading operations and losses from process
equipment
• airborne particulates from soil disturbance during construction and
from vehicle traffic
• The principal emission gases include
– carbon dioxide, carbon monoxide, methane, volatile organic carbons
and nitrogen oxides
Environmental Impact (Contd.)
Aquatic impacts
• produced water
• drilling fluids, cuttings and well treatment chemicals
• process, wash and drainage water
• sewerage, sanitary and domestic wastes
• spills and leakage
Potential impact on aquatic life, irrigation, drinking water, etc
Environmental Impact (Contd.)
Terrestrial impacts
• physical disturbance as a result of construction
• contamination resulting from spillage and leakage
• solid waste disposal
• indirect impact arising from opening access and social change
Potential impact on forests, vegetation, agriculture, human and
animal life
Exploration
• Noise/Vibration
– Dynamite
– Vibration Truck
– Air Gun
– Marine Vessels
• Disturbance to
human/wildlife/marine life
• Low Impact/Transient
Drilling (wildcats, appraisal, development)
• Drilling Fluid (Mud)
– Water/Oil/Synthetic based
• Recycle, treatment, disposal
by injection
• Drill Cuttings
– Land farming, burial, bio-
remediation, injection
• Site preparing
• Roads
• Camps-waste generation
• Long lasting Impact
Production
• Produced water
– Salinity
– Chemicals
– Produced water containing
dissolved and emulsified
crude oil constituents, natural
salts, organic chemicals and
trace metals
– Oil content (Oil spills)
• Treatment
• Re-injection
• Camp waste
• Leakage/spillage
• Flare: Products of combustion
due to flaring (low pressure,
high pressure or technical
flare)
Transportation
Oil tanker
Pipeline under
construction
LNG tanker
• land affected by construction
• leakage/spillage
• accidents – pipeline explosion, oil
spill from tankers, etc.
Waste Steam of Concern
• Drilling Fluid
• Drill Cuttings
• Workover and completion waste
• Produced Water
• Bottom Waste
• Dehydration and Sweetening Waste
• Camp Waste
• Radioactive Material
3R Principle for waste management:
Reduce, Re-use, Recycle
Potential Emergencies
Oil rig on fire Oil spill from a tanker
• Spillage of fuel, oil, gas, chemicals and hazardous materials
• Oil or gas well blowout
• Explosions and Fires (facility and surrounds)
• Natural disasters such as flood, earthquake, lightning
• War and sabotage
Potential Emergencies (Spill)
• The spill may include crude oil, or refined products such as gasoline,
diesel fuel, etc.
• Spills take months or even years to clean up.
• Oil is also released into the environment from natural geologic seeps
on the sea floor
• Cleanup methods:
– Bioremediation: use of microorganisms to break down or remove oil
– Controlled burning: can reduce the amount of oil in water, but it can
cause air pollution.
– Dispersants: act as detergents, clustering around oil globules and
allowing them to be carried away in the water.
– Dredging: for oils dispersed with detergents
– Skimming: Requires calm waters
• Exxon Valdez accident, occurred in Alaska, on March 24, 1989. The
vessel spilled about 40 million litres of crude oil into the sea, and the
oil eventually covered 28,000,000 sq. km of ocean.
Potential Emergencies (Contd.)
• Explosion and Fire: The Piper Alpha oil production platform
operated by Occidental Petroleum in the North Sea. An explosion
and resulting fire destroyed it on July 6, 1988, killing 167 persons.
Total insured loss was about US$ 3.4 billion.
• Indonesia Mud Volcano: It is in East Java, Indonesia that has been
discharging mud since May 2006. Approximately 2,500 m³ of mud is
expelled per day. It is expected that the flow will continue for the
next 30 years. As of November 2008, the mud flow is contained by
levees, but further breakouts are possible. It is not conclusively
decided whether it started due to drilling activity or by a local
earthquake
Waste Water Treatment
Waste water storage tanks and systems in Refinery
Waste Water
• Cooling water blow down
• Storm water
• Process effluents
• Leakage, drainage and unforeseen discharges from
process equipment. All the major processes produce
waste waters (hydrocarbons, hydrogen sulfide,
ammonia, organic sulfur compounds, organic acids, and
phenol).
• Combination of treatment methods to remove oil and
other contaminants before [Link] wise
treatment inside battery limit (ISBL)and combined
treatment outside battery limit(OSBL)
Waste Water Treatment
Typical wastewater treatment steps include:
grease traps, skimmers, dissolved air floatation or oil water separators for
separation of oils and floatable solids;
filtration for separation of filterable solids;
flow and load equalization;
sedimentation for suspended solids reduction using clarifiers;
biological aerobic treatment, for reduction of soluble organic matter (BOD);
chemical or biological nutrient removal for reduction in nitrogen and phosphorus;
chlorination of effluent when disinfection is required;
dewatering and disposal of residuals in designated hazardous waste landfills
Waste Water Treatment
Additional engineering controls may be required for water water treatment
(i) containment and treatment of volatile organics stripped from various unit
operations in the wastewater treatment system,
(ii) advanced metals removal using membrane filtration or other physical/
chemical treatment technologies,
(iii) removal of recalcitrant organics and non biodegradable COD using activated
carbon or advanced chemical oxidation,
(iv) reduction in effluent toxicity using appropriate technology (such as reverse
osmosis, ion exchange, activated carbon, etc.), and
(v) containment and neutralization of nuisance odors.
Biological Waste Water Treatment
Some refineries have lagoons or final polishing ponds
Aerobic bacteria convert wastes into CO2, NH3, and phosphates, which, in turn, are
used by the algae as food. Anaerobic bacteria convert substances in wastewater to
gases, such as H2S, NH3, and CH3OH. Many of these by products are then used as
food by both aerobic bacteria and algae in the layers above.
Air pollution
• Emissions of VOC’s/ organic HAP’s from
process vents, storage vessels, transfer
tanks, equipment and fittings (fugitive
emissions)
• Combustiondevices(Incinerators/flares/hea
ters), recovery/recapture devices
(adsorption, condensation etc) and
specific techniques for transfer racks
Petroleum Refinery
Air pollution in refinery
Sulphur oxides
Hydrocarbons
Particulates
Malodorous emissions
Carbon monoxide
Nitrogen oxides
Pollution Sources
Fugitive emission/spillage from storage area
Individual process and operation
Leakage and the use of fuel for production of the refinery’s own heat and power
Crude oil composition ranges
Carbon: 85-90%
Hydrogen: 10-14%
Sulphur: 0.1-7%
Oxygen: 0.06-0.4%
Nitrogen: 0.01-0.9% and trace metals: Vanadium, Nickel etc
Refinery process
Entire refinery operation can be broken down into four (4) major Steps:
Separation
Conversion
Treatment and
Blending
1. Separation
Crude oil distillation: primary separation of crude oil is accomplished by
simple distillation in which the pre heated crude is passed to fractionation
towers for separation, according to boiling range, into ‘straight-run’ fractions
such as refinery gas, gasoline, kerosine, diesel oils and residual oils.
Heavy or residual fractions of the crude oil which do not vaporize at this stage
may be further fractionated by distillation in the presence of steam and
under vacuum. Main uses of vacuum units are to make feedstock for
catalytic crackers, to produce lubricating oil and to make residues for
bitumen manufacture.
2. Conversions
Cracking: large molecules are broken down into smaller molecules under the
influences of heat, pressure and catalyst.
Catalytic cracking: Feed is normally gas oil or vacuum distillate range and
yields a mixture of gaseous hydrocarbons and liquid products of boiling
range through gasoline to gas oil, which are separated by distillation.
Hydrocracking: Uses a hydrogen atmosphere and different catalysts to
yield more paraffinic/saturated hydrocarbon product from a similar feedstock
used for catalytic cracking.
Thermal cracking: Treats gasoline feedstock to produce ethylene and
similar products and also treats heavy residue feedstock, the trace heavy
metals that can poison the catalyst. Products are: Gaseous hydrocarbons,
gasoline, gas oils, residual fuel oil and coke.
Catalytic Reforming: Methods of upgrading feedstock in the gasoline range,
by rearranging component molecules in the presence of catalysts. In this
process large quantities of hydrogen is produced, which is used in
desulphurization process of feedstock.
Polymerization, alkylation, isomerization: Polymerization and alkylation are
the process whereby gasoline is produced by combining the olefinc
gaseous hydrocarbons produced in cracking process.
Isomerization, molecular rearranging process, coverts low grade gasoline to
high grade gasoline blending components.
3. Treatment
To improve product quality , it is necessary to remove minor concentrations of
constituents which may be of crude oil origin or produced during processing.
Removal of Sulphur is one of the most important treatment process in a refinery
and is effected by hydrogen treatment in the presence of a catalyst. H2S is
produced and sulphur is subsequently recovered as elemental sulphur.
Important Treatment:
Acid treatment: removal of aromatic compounds from lubricant fractions using
sulphuric acids.
Solvent extraction: removal of asphaltenes from residues with liquid propane
Sweetening: conversion of sulphur compounds to less obnoxious materials
4. Blending
Refinery produces few separate products and wide market demand is met by
blending these ‘base stocks’ to give the required products.
Refinery Emission and Control
Sulphur dioxide
Some naturally occurring sulphur compounds in crude oils are malodorous. These
compounds should be converted to non-odorous compounds and removed from
oil to overcome odour problem and corrosion problem in subsequent uses.
In light fraction gasoline, some malodorous sulphur compounds are found.
But in heavior fraction, gas-oil, malodorous compounds of sulphur are absent. Other
forms of sulphur compounds are present there. These compounds should be
removed to minimize emission during subsequent uses.
Sulphur bearing compounds are removed from processing oil stream not only to
mitigate environmental pollution but also to upgrade gasoline anti-knock property
and to reduce corrosion in refinery process plant and inside the internal
combustion engines.
Odorous forms of ‘S’: Hydrogen sulfide and mercaptans
Non-odorous forms of ‘S’: Thiophenes, polysulphides etc
Treatment of process streams
Refinery streams having boiling point < 250oC
Oil and air are brought into contact with copper chloride catalyst deposited on
fuller’s earth. Odours mercaptans is converted to non-odorous disulfides.
Here, S compounds are not removed, but converted to non-odorous
compounds. The whole mixture is separated under gravity and the catalyst
is recycled.
Jet fuel is treated in this way.
Merox sweetening process: Used for low hydrogen sulphide content oil.
Mercaptans form a complex with the catalyst. The complex is decomposed
to disulphide in presence of oxygen (air) and an alkaline environment
(NaOH). Disulphide compounds formed pass from the bed in the oil
streams.
Feedstocks with high hydrogen sulphide contents are usually scrubbed with
aqueous NaOH solution before Merox treatment.
Sometimes hydrogen sulphide and more volatile mercapans are removed from
gasoline or kerosene by washing with NaOH solution with ‘solutizer’ that
increases solubility of mercaptans. NaOH solution can be regenerated by
steam stripping/by air oxidation.
Refinery streams having boiling point > 250oC
Catalytic desulphurization is widely used for all distillates up to temperature 550oC
Overhead products (like gasoline) desulphurization: Hydrotreating
Bottom products (like gas oil) desulphurization: Hydrofining
Hydrofining process: Gas oil feed stock is passed with hydrogen (from catalytic
reformer) over a pelleted alumina catalyst containing cobalt and molybdenum
oxide at temperature of 300-450oC and 40-70 bar. Sulphur in the feedstock is
converted into hydrogen sulphide.
Sulphur recovery: Hydrogen sulphide production from hydrofining process (Gas
oil) is much higher than that produced in hydrotreating process for gasoline.
A typical hydrofining process of capacity 1300 tons/day can produce as much as
11.7 tons of hydrogen sulphide if the sulphur content of gas oil is to be removed
from 1 to 0.1 wt%.
It is common practice to recover ‘S’ in elemental form rather than burning of
hydrogen sulphide in the kiln to produce ‘SO2’ and pass it through long chimney
to atmosphere
Sulphur Recovery
1st stage: Sour gas stream is scrubbed with aqueous amine solution
(monoethanolamine, diethanolamine) at 35-50oC to absorb hydrogen
sulphide. The sorbent, rich in hydrogen sulphide is then regenerated by
steam stripping and returned to absorber.
2nd stage: Stripped hydrogen sulphide at a concentration of 90 vol% is
converted to sulphur in a CLAUS REACTOR. Here, the hydrogen sulphide
is first burnt in a limited supply of air to convert 1/3 of the hydrogen sulphide
into SO2. This mixture is then treated catalytically (bauxite) at 210oC to
produce elemental sulphur.
H2S+SO2 = 3S + 2H2O
SO2 during production of heat and power
A 5 MT Crude oil processing/yr can require about 2 MT of low grade heavy fuel
oil annually.
This refinery is expected to produce about 15 tons SO2 per day from burning of
2MT of heavy fuel oil annually.
Desulphurization of the flue gases can be done with wet scrubber using
various methods.
Other sources of SO2
SO2 is produced during the regeneration of catalysts used in catalytic cracking
and catalytic desulphurization processes.
Particulates
Gases from heaters and boilers are also the sources of PM emission to a lesser extent
Catalyst regeneration is the main source of PM emission in refinery. Coke and sulphur
deposit on Catalyst surface during catalytic processes with time. catalyst activity is
restored through the regeneration periodically. Catalyst contaminants are burnt off to
satisfactory degree. During catalytic process in fluidized bed, catalyst attrition occurs
resulting particulate matters.
Refinery catalytic process:
Circulating: Catalysts are continuously circulated between reactor and regenerator
due to rapid build up of deposits.
Fluid catalytic cracking (catalysts are moved suspended in gas stream)
Moving bed catalytic cracking (air lift/mechanical lift)
Fluid cracking Unit: 4000 tons feedstock/day; catalyst circulating rate: 1000 tons/hr
Catalyst regenerator: air at 660oC and 1.7 bar; gaseous emission: 4200m 3/min
The emission stream from continuous regeneration system is passed through
CYCLONES which limits catalyst dust losses to 45-450 kg/hr.
If an ELECTROSTATIC PRECIPITATOR is used after CYCLONES, it can removes
particulates upto 99.9%. In this combination catalyst dust loss is reduced to 23 kg/hr.
Emission gases are cooled to 260oC before entering the E. Precipitator. Ammonia is
injected to emission stream to enhance the conductivity.
Fixed bed type: Deactivation of catalyst occurs much more slowly. Catalyst bed
is regenerated batch wise usually at an interval of 3 months.
Desulphurization (hydrofining): 2000 tons/day gas oil capacity; 13 tons
catalyst; regeneration takes time up to 24 hrs; stream of air and steam
at 370oC and atmospheric pressure
Catalytic reforming: 1300 tons/day capacity; 25 tons catalyst;
regeneration by stream of air-inert gas at 400oC and atmospheric
pressure.
Emission stream from desulphurization and reforming unit is sent to the
furnace and combustion gases are routed to scrubber before dispersing
through long chimney
Hydrocarbons
Storage:
Crude storage tanks
Intermediate storage tanks and
Final product storage tank
A typical refinery with capacity 5 million tons/yr will require:
3 million tons of storage capacity for crude at any one time
4 million tons of storage capacity for intermediate and finished products
Filling loss: Losses during filling occur by displacement of air containing
hydrocarbon vapor
Breathing loss: On standing, changes in temperature and pressure affect the
liquid and vapor volume within a tank, and air containing
hydrocarbon can be displaced
Factors that affect losses:
Temperature, pressure, vapor pressure, rates of throughput, color of the
tank, type and condition of the tank
Storage of gas oil range product
Products of gas oil range and above, have low vapor pressure, that is why filling
loss, breathing loss are minimal
These products are stored in a cylindrical storage with fixed conical roof.
Storage of light liquid product
Liquids with high vapor pressure (crude oil, gasoline) losses are minimized by
eliminating the vapor space above the liquid by employing roofs which float on the
liquid surface. The roof rises and falls during filling and emptying the storage.
About 340 tons of gasoline may loss annually from a 10,000 tons fixed roof tank
during normal service.
90-95% of this loss can be recovered with a floating roof tank
Losses through loading facilities
Tanks can be filled through overhead hatches or a bottom connection
Overhead loading is of two types: SPLASH and SUBMERGED FILLING
Emission from bottom and top loading can be controlled by isolating the tank from
atmosphere, collecting all the vapors and piping them toward recovery unit (vapor
mix. Is compressed to condense out hydrocarbon).
Emergency safety measures for Waste gas disposal
Scheduled shut-down and process upset caused by compressor, pump, power
failure may occur which overload the recovery system.
To safeguard personnel, process and reduce atmospheric emission waste gas
disposal system is designed which comprises with a manifolded pressure
relieving, blow down system and a blow down recovery system and a system of
flare for combustion of excess gases.
Flare with height 80 m above the ground at down wind location of the refinery.
Quenching steam sometimes used with emission stream to convert some
hydrocarbons into oxygenated compounds for better combustion. Strainer is
placed inline toward the flare.
Other sources of hydrocarbon
Catalyst regeneration (routed to boiler)
Pumps, valves, compressors, flanges (frequent checking and maintenance)
Vacuum jet (uncondensed hydrocarbon routed to boiler)
Air blowing of asphalt (air contaminated with sulphur compounds and hydrocarbon
and nitrogen compounds routed to scrubber and incinerator)
Sour condensate and spent caustic solution:
Steam is used as diluents in catalytic and thermal cracking to reduce
hydrocarbon partial pressure for less coke formation. This water under
condensation of steam is contaminated with hydrogen sulphide, ammonia
and phenols.
Stripping pretreatment is performed. Stripping is done by steam or flue gas.
Sour water can be acidified to fix the ammonia (ammonium chloride) before
stripping hydrogen sulphide. Non condensable is incinerated or led to
sulphur recovery
Sulphidic sour condensate is oxidized with air at elevated temperature and
pressure to produce thiosulphates and sulphates solution. Then any
mercaptans is stripped and incinerated.
Oxidation with air is satisfactory of treating spent caustic soda solution used for
removal of H2S and Mercaptans from product stream.
Phenol rich spent caustic solution is first neutralized with CO2 of the flue gas
and then stripped with flue gas. Phenol and cyanides are partially stripped
and incinerated.
CO
Main source is catalyst regenerator system. Coke is burned off the catalyst in a
limited supply of air to control the operating temperature. This generates
huge CO. This CO is routed to WASTE HEAT BOILER where it is converted
to CO2 at 1000oC.
NOx
When any fuel is burnt, NOx is formed. Fuel NOx and thermal NOx.
