4. WHAT IS PETROLEUM?
Petroleum: A general term for all naturally occurring hydrocarbons (hydrogen + carbon)
Solid Hydrocarbons: Asphalt
Liquid Hydrocarbons: Crude oil
Gas Hydrocarbons: Natural Gas: methane, butane, propane, etc.
5. CONTINUED…
The dark colored viscous, oily mixture of hydrocarbons found in the
impervious rock deep below the earth’s crust from which the various
petrochemicals are obtained directly or indirectly is called
Petroleum. The gas in the atmosphere of petroleum is called natural
gas.
6. ORIGIN OF PETROLEUM
Petroleum is formed by decay and decomposition of biological
material from both plants and animals by radioactive
elements or bacteria.
7. FORMATION…
Roy Nurmi , described the process as follows: "Plankton and algae, proteins
and the life that's floating in the sea, as it dies, falls to the bottom, and these
organisms are going to be the source of our oil and gas. When they're buried
with the accumulating sediment and reach an adequate temperature,
something above 50 to 70 °C they start to cook. This transformation, this
change, changes them into the liquid hydrocarbons that move and migrate,
will become our oil and gas reservoir.
9. DETECTION…..
Visual means detection of oil on earth surface by naked eye
Geophysical include measurement by density, elasticity, magnetic &
electrical properties of rocks in the crust of earth
Geological include measurement of age & nature of rocks inside the earths
crust
Drilling method is the final test when petroleum deposits have been proved
by either earlier methods.
10. DETECTION…..
• Oil seeps, natural gas seeps, pockmarks.
• Highly sophisticated technology to detect and determine the extent
of these deposits using exploration geophysics.
• Seismic surveys which work on the principle of the time it takes for
reflected sound waves to travel through matter (rock) of varying
densities and using the process of depth conversion to create a
profile of the substructure.
11. DRILLING
Petroleum always occur with natural gas
Wet Well:
Contains both oil & gas.
oil producers producing predominantly liquid hydrocarbons, but
mostly with some associated gas
Dry Well:
Contains only gas.
12. WELLS….
• Wildcat wells are those drilled outside of and not in the vicinity of known oil or gas fields.
• Exploration wells are drilled purely for exploratory (information gathering) purposes in a new
area.
• Appraisal wells are used to assess characteristics (such as flow rate) of a proven hydrocarbon
accumulation.
• Production wells are drilled primarily for producing oil or gas, once the producing structure and
characteristics are determined.
• Abandoned well are wells permanently plugged in the drilling phase for technical reasons.
13. PRODUCTION OF PETROLEUM
After drilling Oil and Gas initially flow up under pressure.
When pressure decreases it is sucked up by pump.
Another method is also used by injecting compressed gas or high
pressure water through the pipe bored by the side of oil delivery pipe.
16. PHYSICAL PROCESS
A process in which only physical changes takes place.
There are following physical process takes place in this industry.
• Distillation.
• Solvent extraction.
• Propane Deasphalting.
• Solvent Dewaxing.
• Blending.
20. ATMOSPHERIC DISTILLATION UNIT
It is also called crude oil distillation unit. It is basically the intial unit of all processes in
crude material is separated into different fractions but here the atmospheric pressure is kept
furthur high because the oil present is boiled at elevated temperature at higher pressure and
more fractions are obtained. there are at least five material that are extracted from the crude
oil I.e
• Naphtha .
• Kerosene
• Light gas oil.
• Heavy gas oil.
• Atmospheric gas residue.
In some industries these are also referred as LPG,Petroleum products, Jet fuel e.t.c
21.
22. UNITS USED IN DISTILLATION COLUMN
• Desalter.
• Furnace.
• Pumps around units.
• Heat exchanger units.
• Side strippers.
23. FEED DESALTER
• There are two methods I.e chemical and electrostatic method.
• As crude oil is in its raw form so it contain salts and other material so its
necessary to remove all the unnecessary things that damage the whole
process.In this portion water, caustic soda and acid are mixed with the crude
oil and the mixture is further passed through electrostatic precipitator cum
gravity settlers.The electrostatic field enables the agglomeration of water
droplets and helps faster gravity settling.
• The initial temperature required in this process is about 350 F So first crude
oil is heated by different streams and pumps around it.
24. CONT'D
• The crude oil is heated to reduce viscosity and surface tension for easier
mixing and separation of water.
• In both methods chemical may be added. Ammonia may be added in some
cases for corrosion resistance.Caustic soda maybe added to adjust the ph of
water.
25. FURNACE
• In this process the crude is heated to 398 C and there are also the portions of
fuel and fuel gas because there are recycled from the refinery process to
increase the temperature (economic) and sent to distillation column.
26. PUMPS AROUND UNITS
• Pumps are important part of distillation column.
• They sent liquids from one place to another.
• They are used to maintain good reflux conditions.
• Usually there are two or three pumps used in this process.
27. HEAT EXCHANGER UNIT
• Two heat exchangers are used in this unit , one before the desalter and one
after desalter.
• They are used to recover energy (steam) to provide the process more energy
efficient.
• They increased the temperature I.e 200 to 300 C from the temprature 20 to
30 C.
• If these are used in this process then there is more pollution and process
become more expensive.
28. SIDE STRIPPERS
• In general there are two parts of distillation column the above part is called
rectifying unit and the bottom part called stripper.
• In stripper section materials are separated from the other things.
• e.g
• Sour water stripper in which steam is used to remove H2s and NH3 for sour
waters.
• Side-cut strippers on crude oil in which steam in which steam is used to
remove the lightest components from the side cut products such as kerosene ,
jet fuel or diesel oil.
29.
30. VACUUM DISTILLATION COLUMN
• In this process the pressure is maintained bellow the atmospheric pressure
because bellow this pressure atmospheric residue doesnot allow decomposition
and therefore produces LVGO(light vacuum gas oil),HVGO(heavy vacuum
gas oil) and vacuum residue.
• They are supported by side strippers to obtain the desired product .
• They are subjected to cracking which yields the high octane number products.
31. PROPANE DE ASPHALTING:
• In this process asphalt is removed by using propane.
• Liquid propane is a good solvent (butane and pentane are also commonly
used).
• Vacuum residue is fed to a countercurrent de asphalting tower. Alkanes
dissolve in propane whereas asphaltenic materials (aromatic compounds),
‘coke-precursors’ do not.
• Asphalt is sent for thermal processing.
32.
33. SOLVENT EXTRACTION AND DEWAXING:
• Since distillation (fractionation) separates petroleum products into groups
only by their boiling-point ranges, impurities may remain. These include
organic compounds containing sulfur, nitrogen, and oxygen; inorganic salts
and dissolved metals; and soluble salts that were present in the crude
feedstock.
• In addition, kerosene and distillates may have trace amounts of aromatics and
naphthenes, and lubricating oil base-stocks may contain wax.
• Solvent refining processes including solvent extraction and solvent dewaxing
usually remove these undesirables at intermediate refining stages or just
before sending the product to storage.
34. SOLVENT EXTRACTION:
• The purpose of solvent extraction is to prevent corrosion, protect catalyst in
subsequent processes, and improve finished products by removing unsaturated,
aromatic hydrocarbons from lubricant and grease stocks.
• The solvent extraction process separates aromatics, naphthenes, and impurities
from the product stream by dissolving or precipitation. The feedstock is first
dried and then treated using a continuous countercurrent solvent treatment
operation.
• In one type of process, the feedstock is washed with a liquid in which the
substances to be removed are more soluble than in the desired resultant
product. In another process, selected solvents are added to cause impurities to
precipitate out of the product.
• Electric precipitation may be used for separation of inorganic compounds.
• The solvent is regenerated for reused in the process.
• The most widely used extraction solvents are phenol, furfural, and cresylic
acid.
35.
36. SOLVENT DE WAXING:
• Solvent de waxing is used to remove wax from either distillate or residual base stock at any
stage in the refining process.
• There are several processes in use for solvent de waxing, but all have the same general
steps, which are::
• mixing the feedstock with a solvent;
• precipitating the wax from the mixture by chilling; and
• recovering the solvent from the wax and de waxed oil for recycling by distillation and
steam stripping.
• Usually two solvents are used: toluene, which dissolves the oil and maintains fluidity at low
temperatures, and methyl ethyl ketone (MEK), which dissolves little wax at low
temperatures and acts as a wax precipitating agent.
• Other solvents sometimes used include benzene, methyl isobutyl ketone, propane,
petroleum naphtha, ethylene dichloride, methylene chloride, and sulfur dioxide
37.
38. BLENDING:
• Blending is the physical mixture of a number of different liquid hydrocarbons to
produce a finished product with certain desired characteristics.
• Products can be blended in-line through a manifold system, or batch blended in tanks
and vessels.
• In-line blending of gasoline, distillates, jet fuel, and kerosene is accomplished by
injecting proportionate amounts of each component into the main stream where
turbulence promotes thorough mixing.
• Additives including octane enhancers, anti-oxidants, anti-knock agents, gum and rust
inhibitors, detergents, etc. are added during and/or after blending to provide specific
properties not inherent in hydrocarbons.
41. OCTANE NUMBER
THE QUALITY OF FUEL IS CHECKED BY OCTANE NUMBER. IT DETERMINES
THE PETROL ANTI KNOCK QUALITY OR RESISTANCE TO PRE IGNITION.
IT IS THE NO. OF N-HEPTANE IN ISO-OCTANE.
CALCULATED BY RON+MON/2
RON IS USED IN NORMAL CONDITION AND LOW SPEED AROUND
600RPM WHILE
MON IS USED IN SEVER CONDITION AND HIGH SPEED AROUND 900RPM
THUS RON IS ALWAYS HIGHER THAN MON
42. HOW OCTANE IS TESTED
THE MOST ACCURATE WAY OF TESTING THE ACTUAL OCTANE VALUE IS
TO USE A COMBUSTION FUEL RESEARCH (CFR) ENGINE (ALSO KNOWN
AS A KNOCK ENGINE) THE CFR ENGINE MEASURES OCTANE BY
COMBUSTING THE FUEL AND PHYSICALLY MEASURING THE KNOCK THAT
OCCURS. THIS IS THE METHOD USED FOR TESTING AT FUEL REFINERIES.
43. CATALYTIC CRACKING
• MAIN INCENTIVE FOR CATALYTIC CRACKING IS THE NEED TO
INCREASE GASOLINE PRODUCTION.
• FEEDSTOCK ARE TYPICALLY VACUUM GAS OIL.
• CRACKING IS CATALYZED BY SOLID ACIDS WHICH PROMOTE
THE RUPTURE OF C-C BONDS. THE CRUCIAL INTERMEDIATES
ARE CARBOCATION (+VE CHARGED HC IONS) FORMED BY THE
ACTION OF THE ACID SITES ON THE CATALYST.
• BESIDES C-C CLEAVAGE MANY OTHER REACTIONS OCCUR:
- ISOMERIZATION
- PROTONATION AND DEPROTONATION
- ALKYLATION
- POLYMERIZATION
- CYCLIZATION AND CONDENSATION
44. CATALYTIC CRACKING
• CATALYTIC CRACKING COMPRISES A COMPLEX NETWORK OF
REACTIONS, BOTH INTRA-MOLECULAR AND INTER-
MOLECULAR.
• THE FORMATION OF COKE IS AN ESSENTIAL FEATURE OF THE
CRACKING PROCESS AND THIS COKE DEACTIVATES THE
CATALYST.
• CATALYTIC CRACKING WAS THE FIRST LARGE-SCALE
APPLICATION OF FLUIDIZED BEDS WHICH EXPLAINS THE
NAME FLUID CATALYTIC CRACKING (FCC).
• NOWADAYS ENTRAINED-FLOW REACTORS ARE USED INSTEAD
OF FLUIDIZED BEDS BUT THE NAME FCC IS STILL RETAINED.
45. REACTIONS IN CATALYTIC CRACKING
ISOMERIZATION
Reforming
Alkylation
Dealkylation
Disproportion
46. FLUID CATALYTIC CRACKING
Spent catalyst is regenerated to get rid of coke that collects on the catalyst during the process.
Spent catalyst flows through the catalyst stripper to the regenerator, where most of the coke deposits
burn off at the bottom where preheated air and spent catalyst are mixed.
Fresh catalyst is added and worn-out catalyst removed to optimize the cracking process.
48. REACTOR PERFORMANCE
FEED OIL ENTERS THE RISER NEAR THE BASE
CONTACTS THE INCOMING REGENERATED CATALYST
CRACKING REACTION OCCURS IN VAPORS PHASE
EXPANDED VOLUME OF VAPORS LIFT THE CATALYST AND
VAPORIZED OIL TO RISES
FAST REACTION, FEW SECONDS CONTACT TIME
49. RISER
DIMENSIONS
DIAMETER 1.2 METER
HEIGHT 36.6 METER
PLUG FLOW WITH MINIMUM BACK MIXING
STEAM IS USED TO ATOMIZED THE FEED
OUTLET VAPOUR VELOCITY 18 M/S
HYDROCARBON RESIDENCE TIME 2 SECOND
50. CYCLONES
LOCATED AT THE END OF RISER TO SEPARATE THE BULK OF
CATALYST FROM VAPOUR
USE DEFLECTOR TO TURN CATALYST DIRECTION DOWNWARD
TWO STAGE CYCLONES
TO SEPARATE THE REMAINING OF CATALYST
• RETURNS THE CATALYST TO THE STRIPPER
THE PRODUCT VAPORS EXIT THE CYCLONES AND FLOW THE
MAIN FRACTIONATOR COLUMN
52. STRIPPING SECTION
THE SPENT CATALYST FALLS INTO THE STRIPPER
VALUABLE HYDROCARBONS ARE ABSORBED WITHIN THE
CATALYST BED
STRIPPING STREAM CIRCULATING THE CATALYST, IS USED TO
STRIP THE HYDROCARBON FROM THE CATALYST
THE CATALYST LEVEL PROVIDE THE PRESSURE HEAD WHICH
ALLOWS THE CATALYST TO FOLLOW INTO REGENERATOR
53. REGENERATOR
TWO FUNCTIONS
• RESTORES CATALYST ACTIVITY
• SUPPLIES HEAT TO CRACK FEED
AIR IS A SOURCE OF OXYGEN FOR COMBUSTION OF COKE
THE AIR BLOWER WITH AIR VELOCITY 1M/S TO MAINTAIN THE
CATALYST BED IN FLUIDIZED STATE
55. HYDROTREATING
• CATALYTIC HYDROTREATING IS A HYDROGENATION PROCESS USED
TO REMOVE ABOUT 90% OF CONTAMINANTS SUCH AS NITROGEN,
SULFUR, OXYGEN, AND METALS FROM LIQUID PETROLEUM
FRACTIONS.
• IF THESE CONTAMINANTS ARE NOT REMOVED FROM THE
PETROLEUM FRACTIONS THEY CAN HAVE DETRIMENTAL EFFECTS ON
EQUIPMENT, CATALYSTS, AND THE QUALITY OF THE FINISHED
PRODUCT.
• TYPICALLY, HYDROTREATING IS DONE PRIOR TO PROCESSES SUCH AS
CATALYTIC REFORMING SO THAT THE CATALYST IS NOT
CONTAMINATED BY UNTREATED FEEDSTOCK. HYDROTREATING IS
ALSO USED PRIOR TO CATALYTIC CRACKING TO REDUCE SULFUR AND
IMPROVE PRODUCT YIELDS, AND TO UPGRADE MIDDLE-DISTILLATE
PETROLEUM FRACTIONS INTO FINISHED KEROSENE, DIESEL FUEL,
AND HEATING FUEL OILS.
• IN ADDITION, HYDROTREATING CONVERTS OLEFINS AND
AROMATICS TO SATURATED COMPOUNDS.
56. CATALYTIC HYDRODESULFURIZATION PROCESS
• HYDROTREATING FOR SULFUR REMOVAL IS CALLED
HYDRODESULFURIZATION.
• IN A TYPICAL CATALYTIC HYDRODESULFURIZATION UNIT, THE
FEEDSTOCK IS DEAERATED AND MIXED WITH HYDROGEN,
PREHEATED IN A FIRED HEATER (315°-425° C) AND THEN
CHARGED UNDER PRESSURE (UP TO 70 BAR) THROUGH A
TRICKLE-BED CATALYTIC REACTOR.
• IN THE REACTOR, THE SULFUR AND NITROGEN COMPOUNDS IN
THE FEEDSTOCK ARE CONVERTED INTO H2S AND NH3.
• THE REACTION PRODUCTS LEAVE THE REACTOR AND AFTER
COOLING TO A LOW TEMPERATURE ENTER A LIQUID/GAS
SEPARATOR. THE HYDROGEN-RICH GAS FROM THE HIGH-
PRESSURE SEPARATION IS RECYCLED TO COMBINE WITH THE
FEEDSTOCK, AND THE LOW-PRESSURE GAS STREAM RICH IN H2S IS
SENT TO A GAS TREATING UNIT WHERE H2S IS REMOVED.
57. CATALYTIC HYDRODESULFURIZATION PROCESS
THE CLEAN GAS IS THEN SUITABLE AS FUEL FOR THE REFINERY
FURNACES. THE LIQUID STREAM IS THE PRODUCT FROM
HYDROTREATING AND IS NORMALLY SENT TO A STRIPPING
COLUMN FOR REMOVAL OF H2S AND OTHER UNDESIRABLE
COMPONENTS.
IN CASES WHERE STEAM IS USED FOR STRIPPING, THE PRODUCT
IS SENT TO A VACUUM DRIER FOR REMOVAL OF WATER.
HYDRODESULFURIZED PRODUCTS ARE BLENDED OR USED AS
CATALYTIC REFORMING FEEDSTOCK.
59. HYDROCRACKING
• HYDROCRACKING IS A TWO-STAGE PROCESS COMBINING
CATALYTIC CRACKING AND HYDROGENATION, WHEREIN HEAVIER
FEEDSTOCK IS CRACKED IN THE PRESENCE OF HYDROGEN TO
PRODUCE MORE DESIRABLE PRODUCTS.
• THE PROCESS EMPLOYS HIGH PRESSURE, HIGH TEMPERATURE, A
CATALYST, AND HYDROGEN. HYDROCRACKING IS USED FOR
FEEDSTOCK THAT ARE DIFFICULT TO PROCESS BY EITHER CATALYTIC
CRACKING OR REFORMING, SINCE THESE FEEDSTOCK ARE
CHARACTERIZED USUALLY BY A HIGH POLYCYCLIC AROMATIC
CONTENT AND/OR HIGH CONCENTRATIONS OF THE TWO
PRINCIPAL CATALYST POISONS, SULFUR AND NITROGEN
COMPOUNDS.
• THE PROCESS LARGELY DEPENDS ON THE NATURE OF THE
FEEDSTOCK AND THE RELATIVE RATES OF THE TWO COMPETING
REACTIONS, HYDROGENATION AND CRACKING. HEAVY AROMATIC
FEEDSTOCK IS CONVERTED INTO LIGHTER PRODUCTS UNDER A
WIDE RANGE OF VERY HIGH PRESSURES (70-140 BAR) AND FAIRLY
HIGH TEMPERATURES (400°-800°C), IN THE PRESENCE OF
HYDROGEN AND SPECIAL CATALYSTS.
60. HYDROCRACKING
WHEN THE FEEDSTOCK HAS A HIGH PARAFFINIC CONTENT, THE
PRIMARY FUNCTION OF HYDROGEN IS TO PREVENT THE
FORMATION OF POLYCYCLIC AROMATIC COMPOUNDS.
ANOTHER IMPORTANT ROLE OF HYDROGEN IN THE
HYDROCRACKING PROCESS IS TO REDUCE TAR FORMATION AND
PREVENT BUILDUP OF COKE ON THE CATALYST.
HYDROGENATION ALSO SERVES TO CONVERT SULFUR AND
NITROGEN COMPOUNDS PRESENT IN THE FEEDSTOCK TO
HYDROGEN SULFIDE AND AMMONIA.
HYDROCRACKING PRODUCES RELATIVELY LARGE AMOUNTS OF
ISOBUTANE FOR ALKYLATION FEEDSTOCK AND ALSO PERFORMS
ISOMERIZATION FOR POUR-POINT CONTROL AND SMOKE-POINT
CONTROL, BOTH OF WHICH ARE IMPORTANT IN HIGH-QUALITY
JET FUEL.
61. HYDROCRACKING PROCESS
Preheated feedstock is mixed with recycled hydrogen and sent to the first-
stage reactor, where catalysts convert sulfur and nitrogen compounds to
H2S and NH3. Limited hydrocracking also occurs.
After the hydrocarbon leaves the first stage, it is cooled and liquefied and
run through a separator. The hydrogen is recycled to the feedstock.
The liquid is charged to a fractionator.
The fractionator bottoms are again mixed with a hydrogen stream and
charged to the second stage. Since this material has already been subjected
to some hydrogenation, cracking, and reforming in the first stage, the
operations of the second stage are more severe (higher temperatures and
pressures). Again, the second stage product is separated from the hydrogen
and charged to the fractionator.
63. THERMAL PROCESSES
When a hydrocarbon is heated to a sufficiently high temperature thermal
cracking occurs. This is sometimes referred to as pyrolysis. When steam is
used it is called steam cracking. We will examine two thermal processes
used in refineries.
• Visbreaking
• Delayed coking
64. VISBREAKING
A VISBREAKER IS A PROCESSING UNIT IN AN OIL REFINERY WHOSE PURPOSE IS TO REDUCE THE
QUANTITY OF RESIDUAL OIL PRODUCED IN THE DISTILLATION OF CRUDE OIL AND TO INCREASE
THE YIELD OF MORE VALUABLE MIDDLE DISTILLATES (HEATING OIL AND DIESEL) BY THE
REFINERY
A VISBREAKER THERMALLY LARGE HYDROCARBONS MOLECULES IN THE OIL BY HEATING IN A
FURNACE TO REDUCE ITS VISCOSITY AND TO PRODUCE SMALL QUANTITIES OF LIGHT
HYDROCARBONS (LPG AND GASOLINE).THE PROCESS NAME OF "VISBREAKER" REFERS TO THE
FACT THAT THE PROCESS REDUCES (I.E., BREAKS) THE VISCOSITY OF THE RESIDUAL OIL.
65. Continue…
• Residuum from the atmospheric distillation tower is heated (425-510ºC)
at atmospheric pressure and mildly cracked in a heater.
• It is then quenched with cool gas oil to control over-cracking, and
flashed in a distillation tower.
• Visbreaking is used to reduce the pour point of waxy residues and reduce
the viscosity of residues used for blending with lighter fuel oils. Middle
distillates may also be produced, depending on product demand.
• The thermally cracked residue tar, which accumulates in the bottom of
the fractionation tower.
66. VISBREAKING
• Alternatively, vacuum residue can be cracked. The severity of the visbreaking
depends upon temperature and reaction time (1-8 min).
• Usually < 10 wt% of gasoline and lighter products are produced.
67. DELAYED COKING
• Coking is a severe method of thermal cracking used to upgrade heavy
residuals into lighter products or distillates.
• Coking produces straight-run gasoline (Coker naphtha) and various
middle-distillate fractions used as catalytic cracking feedstock.
• The process completely reduces hydrogen so that the residue is a form
of carbon called "coke."
• Three typical types of coke are obtained (sponge coke, honeycomb
coke, and needle coke) depending upon the reaction mechanism, time,
temperature, and the crude feedstock.
• In delayed coking the heated charge (typically residuum from
atmospheric distillation towers) is transferred to large coke drums
which provide the long residence time needed to allow the cracking
reactions to proceed to completion.
68. SPONGE COKE DERIVED FROM A PETROLEUM FEEDSTOCK THAT SHOWS ABUNDANT PORE STRUCTURE. NOTE THE FLOW
TEXTURE IN THE COKE CELL WALLS.
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69. TYPICAL NEEDLE COKE DERIVED FROM A PETROLEUM FEEDSTOCK. THE PARALLEL LAYERS AND LINEAR FRACTURES ARE
DISTINCTIVE AND PROVIDE SLIP PLANES TO RELIEVE STRESS IN THE COKE .
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70. USES
• UPGRADE LOWER GRADE PRODUCT
• INCREASE VALUE ADDED PRODUCT
• MAXIMIZE THE PRODUCTION OF THE PRODUCTS IN MORE DEMAND
• MINIMIZE THE PRODUCTION OF LOWER VALUE PRODUCTS