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Refinery Processes
History of Petroleum Refining
History of Petroleum Refineries
• Available in small quantities through natural
seepage
• Drilling of petroleum from first oil well was in
Pennsylvania, US in 1859.
• The availability of crude oil in abundant
quantities led to the development large scale
Simple Distillation units.
• Primary product was Kerosene, used for
lighting lamps.
History of Petroleum Refineries
• The lowest boiling fraction obtained was
straight naptha, primarily used as a solvent
• Higher boiling fractions were used as Fuel oils,
and lubricants
• Development of the IC engine, and
subsequently automobile, in the end of 19th
Century increased the demand of light
petroleum gasoline, and led to advancements
in petroleum refining.
History of Petroleum Refineries
• Major landmarks in the development of
petroleum refineries have been:
– Automobile industry
– Increased demand for transportation fuels during
WW
– Increased demand for jet fuels during 1950’s-60’s
– Realisation of adverse impacts on Environment in
th 1990’s
Raw Material: Crude oil
• Hydrocarbons made of carbon and H2 atoms
• Simplest is having one carbon, and four
Hydrogen atoms, called Methane.
• Molecules join each other and form long
hydrocarbon chains.
• Carbon atom has four valence electrons,
which can combine with hydrogen in different
ways to form Alkanes, Alkenes, Alkynes, and
naphthenes.
Raw Material: Crude oil
• Saturated chain molecule: Paraffins
– General formula CnH2n
– Also known as paraffins
– Saturated hydrocarbons as all the four valences of
Carbon atoms are taken up by hydrogen atoms.
– Chemically most stable
– Arrangement of chains of paraffins can be
straight(normal) or branched chains(iso)
– Naturally occurring paraffins are straight chain,
and refinery processes produced branched
Raw Material: Crude oil
• Saturated Cyclo-Comounds
– More than four carbon atoms, with a ringed
structure
– Saturated cyclo compounds are called Naphthenes
– Naphthenic crude oils have low potential for
manufacture of lube oil, but higher conversion to
gasoline fractions.
Raw Material: Crude oil
• Unsaturated ringed Comounds
– All available valencies of carbon arent bonded with
hydrogen
– Double or triple carbon-carbon bond may be formed
– Arrangement of carbon atoms is either as chained
structure (Olefins) or rings (Aromatics)
– Chemically unstable and reactive, good combustion
properties
– Small volumes found in crude oil, but produced as a
result of petroleum refining processes
– Simplest Aromatic compound is benzene (C6H6)
Raw Material: Crude oil
• Crude oil composition:
– Complex mixure of very long chain hydrocarbon
molecules
– Broad characterization of crude oil is based on the
most prevailent form of HC ie, Praffins,
Naphthenes or Aromatics
– Small quantities of compounds of sulfur, Nitrogen,
and Oxygen are also present
– Minute traces of heavy metals like Ni, V, Na,Ar etc
decide the quality of refined products
AGENDA
• Feed Stock to products
• Refinery Processes
• Integration of Process Units
0
100
200
300
400
IncreasingBoilingPoint(degC)
CRUDE OIL
REFINING
Main Products
Crude Oil to Products
LPG
PETROL
KERO
HSD
FO
Main process - simple distillation
C3-C4
C9-C16
C14-C24
>C22
C5-C10
500
Lt Distillate
Middle
Distillate
Heavy ends
Key Refined Products
Key Qualities
Octane, Sulfur,
Vapour Pressure,Benzene
Vapour Pressure
C2 & C5 content
Sulfur, Cetane, Pour point
Distillation,Flash point
Viscosity, Pour point,
Metals, Cal value
Main Applications
Domestic & Industrial
heating,Transport
Transport
Aviation, heating,
lighting
Transport, Power
Industries, Power
Sea transport
LPG
PETROL
KERO/ATF
HSD
FO/LSHS
Freezing point,
Smoke point, Flash
NAPHTHA
DENSITY / API GRAVITY
Density is used for:
₋ Weight to volume or vice versa calculations
₋ Checking the consistency of crude supply
₋ Control of refinery operations
₋ Used in various correlations
₋ Also gives a rough indication of type of crude oil
API GRAVITY=
SP.GR.@ 60/60°F
Examples:
Water = 10 API
Kerosene = 45 API
Motor Gasoline = 58 API
Natural Gasoline = 75 API
Crude oils are categorized based on gravity
Light grades : Above 33 degree API
Medium grades: 23-33 degree API
Heavy grades: up to 22 degree API
141.5
- 131.5
Crude Oil
Quality indicators
API gravity
Above 50 : Condensate
33 to 50 : Light
24 to 33 : Intermediate
Below 24 : Heavy
Sulphur
Below 0.5% : Low
0.5 %- 1.5% : Medium
Above 1.5% : High
Different crude – different yields
Lt Distillate
Middle
Distillate
Heavy ends
0.17 0.18 1.9 2.7
O API 40 33.6 34.2 31.0
% Sulfur
 COMPOSTION OF CRUDE OIL:
– LARGE NO. OF DIFFERENT HYDROCARBONS
– IMPURITIES SUCH AS ‘S’, N, O2 METALS, ETC.
– BOTTOM SEDIMENTS & WATER (BS & W)
– SALTS, SUCH AS NACL, MGCL2, ETC.
 TYPES OF HYDROCARBONS:
– PARAFFINS
– NAPHTENES
– AROMATICS
– OLEFINS
CRUDE OIL COMPOSITION
TYPES OF HYDROCARBON
• PARAFFINS :
- Open chain saturated compounds of C & H
having general formula CnH2n+2.
– Have great chemical stability.
– Two types
• n - Paraffins
• Iso - Paraffins.
– N-Paraffins have low Octane No. & high ignition
properties.
– Iso-Paraffins have high Octane No.
TYPES OF HYDROCARBON (Contd…)
• NAPHTHENES :
– Saturated Cyclic hydrocarbons.
– High chemical stability.
– General Formula CnH2n.
• OLEFINS :
– Unsaturated open chain hydrocarbons.
– Highly reactive.
– Generally formed during cracking / conversion processes.
TYPES OF HYDROCARBON (Contd…)
• AROMATICS :
– Unsaturated Cyclic hydrocarbons having general formula
CnHn.
– Chemically reactive.
– Aromatics in Gasoline increases Octane number.
– Undesirable in Kerosene because of their tendency to
give smoky flame.
• SULPHUR:
– Major impurity and present in elemental form.
– Sulfides / oxides of sulfur (H2S, Mercaptans, SO2 etc)
generated in refinery processes.
– Present as H2S / Mercaptans in LPG, as Sulfur / Mercaptans in
Gasoline, Kerosene, ATF and as sulfur in HSD & Residues.
– Sweetening Processes (caustic washing, Mercaptan Oxidation)
are used to remove these impurities from products.
IMPURITIES IN CRUDE OIL
• NITROGEN :
– Present in elemental form and also as oxides of Nitrogen.
– Forms Acids and causes corrosion.
– Removal is necessary to get on-grade products and
secondary units feedstocks.
• OXYGEN :
– Present in elemental form and also as compounds of
Oxygen.
– Forms Naphthenic Acids and causes stress corrosion.
IMPURITIES IN CRUDE OIL (Contd..)
• METALS :
– Main metals in Crude oil are - Lead, Nickel, Vanadium & Copper.
– Present in very small quantity (ppm level), in Crude and gets distributed
in various products.
– Poison to catalysts even in very small amount.
• SALTS :
– Are formed during Refining process.
– Main salts - NaCL, MgCL2, KCL.
– Acids formed from these salts attacks plant equipments and corrosion
sets In.
IMPURITIES IN CRUDE OIL (Contd..)
• SEDIMENTS & WATER:
– Sediment: Fine particles of sand clay, volcanic ash,drilling mud, rust, iron
sulphide, metals and scale.
– Damaging Effects Plugging Abrasion and residual product contamination.
– Water causes irregular behaviour in distillation.
Reid Vapour Pressure (RVP) and Light End Analysis
RVP indicates relative Percentage of gaseous and
lighter hydrocarbons in crude oil.
POUR POINT
• Indicates relative amount of wax present in crude oil
• Is the temperature below which pumping and
transportation problems may be encountered
• Along with viscosity, is used in pumping and design
calculations:
WAX CONTENT
Normal paraffins above CI6 are solid at somewhat ambient
temperatures. These hydrocarbons
• Affect the flow behaviour of crude
• Affect the product quality of gas oil, VGO and asphalt
• Lube manufacture is also dependent on wax content of
the crude.
COMPARISON OF IND. & ME CRUDES QUALITY
PROPERTIES UNIT BH KUWAIT ARAB
MIX
IRN
LT.
IRN
HY.
API Gravity @ 150
C --- 38.3 31.2 30.3 34.0 31.1
Pour Point 0
C +30 -17 -15 -12 -6
Wax Content % wt
14.7 4.5 5.6 5.7 4.4
Asphaltenes % wt
0.05 1.3 2.7 0.9 2.0
Total Sulfur % wt
0.2 2.54 2.65 1.4 1.65
Primary Yields
Light Distillates % wt
24 14 16 17 16
Middle Distillates % wt
46 36 36 43 36
Residue % wt
30 50 48 40 48
YIELD PATTERN OF VARIOUS CRUDES (% WT)
STREAMS BH KUWAIT DUBAI
GAS 0.2 0.3 0.1
LPG 1.1 1.2 2.5
NAPHTHA 23.0 16.0 12.9
KEROSENE 20.5 16.5 15.3
HSD 25.0 18.0 27.2
RCO 30.0 48.0 42.0
LVGO + HVGO 74.0 58.0 52.0
VACUUM DIESEL 3.0 1.0 2.0
VACUUM RESIDUE 23.0 41.0 46.0
REFINERY CONFIGURATION
• Catalytic Cracking, Hydro Cracking, Coking, Reformer, etc are referred to as
secondary processing units
• Nelson Complexity Index
• Captures the proportion of the secondary conversion unit capacities
relative to the primary distillation or topping capacity
• Typically varies from ~ 2 for Hydro skimming refineries to ~ 5 for
Cracking refineries and > 9 for Coking refineries
• Refineries with high Nelson Complexity Index have
• Flexibility to process wide range of cheap crudes
• Capable of achieving higher distillate yields & hence higher value
addition
Yields are dependent on
Refinery configuration
Relative
capital cost
(per MMT) 1.0 2.1 3.6 4.3 >9
LPG
Naphtha
Petrol
Kerosene
Diesel
Heavy ends
Fuel & loss
Typical Refinery economics
26.4
53.4
13.9
117.0 120.0
70.0
30.9
64.1
9.7
0.0
20.0
40.0
60.0
80.0
100.0
120.0
140.0
Light distillate Middle distillate Heavy ends
Yield Wt. Avg Price Realization
Yield - %wt on crude,
Price - % of crude price
Avg product price – 104.6 %
Crude
%
Improving yield of value added products
is the mantra of any Refinery
REFINERY CONFIGURATION - TOPPING
Separates the crude into petroleum products by Atmospheric Distillation. Topping
Refinery produces naphtha but no gasoline
LPG
Naphtha
Jet / Kerosene
Diesel / Gas oil
Fuel Oil
(Atmospheric
Residue)
CRUDE
OIL
CDU
CrudeDistillationUnit
0
100
200
300
400
HYDRO SKIMMING REFINERY
Refinery equipped with Atmospheric Distillation, Naphtha reforming and necessary treating
processes. More complex than topping refinery and produces gasoline
LPG
Naphtha
Jet / Kerosene
Low-sulphur
Diesel / Gas oil
Fuel Oil
(Atmospheric Residue)
C R U
Catalytic Reformer
Mogas
LPG
Mogas
Gas Oil
Desulphuriser
CDU
CrudeDistillationUnit
0
100
200
300
400
CRUDE
OIL
CRACKING REFINERY
Also has Vacuum Distillation and Catalytic Cracking. Adds complexity to the hydro skimming
refinery & converts fuel oil to light and middle distillates
LPG
Naphtha
Jet / Kerosene
Low-sulphur
Diesel / Gasoil
Fuel Oil Component
(Vacuum Residue)
CDU
CrudeDistillationUnit
CRUDE
OIL
C R U
Catalytic Reformer
Mogas
LPG
Mogas
Gas oil
Desulphuriser
VDU
VacuumDistillation
Vacuum Distillate
(Vacuum Gasoil,
Waxy Distillate)
FCCU
CatalyticCracker
LPG
Mogas
COKING REFINERY
Converts the vacuum residue into high value products using Delayed Coker. Adds further
complexity to the cracking refinery by high conversion of fuel oil into distillates and petroleum
coke (used as power fuel)
LPG
Naphtha
Jet / Kerosene
Low-sulphur
Diesel / Gasoil
Coke
CDU
CrudeDistillationUnit
CRUDE
OIL
C R U
Catalytic Reformer
Mogas
LPG
Mogas
Gasoil
Desulphuriser
VDU
VacuumDistillation
Vacuum Distillate
(Vacuum Gasoil,
Waxy Distillate)
HCCU
Hydrocracker
Mogas
VLS
Diesel
Jet
Hydrogen
Coker
LPGLPG
HYDROCRACKING + RDS REFINERY
LPG
Naphtha
Jet / Kerosene
Low-sulphur
Diesel / Gasoil
Low Sulfur Fuel Oil
CDU
CrudeDistillationUnit
CRUDE
OIL
C R U
Catalytic Reformer
Mogas
LPG
Mogas
Gasoil
Desulphuriser
VDU
VacuumDistillation
Vacuum Distillate
(Vacuum Gasoil,
Waxy Distillate)
HCCU
Hydrocracker
LPG
Mogas
VLS
Diesel
Jet
Hydrogen
0
100
200
300
400
AR/VRDS
Adds further complexity to the hydro cracker cracking refinery by high conversion of
fuel oil into distillates. Also has Residue Desulfuriser. Produces low sulphur fuels
REFINERY CONFIGURATION
Refinery Processes
• Crude Distillation
• Catalytic Naphtha Reforming
• Fluidized Catalytic Cracking
• Hydro Processing (DHDS, HCU/LOBS, NHT)
• Residue Upgradation (BBU, VRDS, Coking)
• MISC – Aromatics, Treatment, MTBE, Merox
Atmospheric Distillation
• First Step in the refining of crude oil
• Crude oil is fractionated into sharp cuts in an atmospheric
distillation column
• These cuts are generally Unstabilized Naphtha, HN, Kero/ATF,
Light gas oil, Heavy gas oil
• Bottoms of the crude column is known as reduced crude oil
• A single or multiple columns could be used for fractionation
• Crude is first preheated in preheat exchangers / heaters and
then pumped to Crude column
Atmospheric Distillation
• Crude column operates at normally 2-3 Kg/Cm2g
pressure
• Yield of various products depends on type of crude
oil
• Products obtained from crude column are known as
straight run products / components
• Energy intensive process
• Maximum distillates recovered in CDU till cracking
temperatures at operating pressure
Crude Distillation Unit
Distillation
column
Gas
Naphtha
upto 170 C
Kerosine
upto 270 C
Diesel
upto 360 C
RCO/Atmospheric Residue
>360 C
CRUDE
LPG
Heater
370 C
360 C
2.2 ata
110 C
2.0 ata Lt Distillate
Middle
Distillate
Heavy ends
Typical Product Pattern
Product TBP Cuts, 0C Yield wt%, LS
(Mumbai High)
Yields, %wt
HS (AMX)
Fuel Gas C1-C2 0.3 0.04
LPG C3-C4 1.5 1.36
Stabilized
Naphtha
C5-90 16.5 11.58
Heavy Naphtha 90-140 3.3 3.42
Kero/ATF 140-280 23.3 16.67
LGO 150-360 16.1 16.35
HGO 220-415 6.0 8.81
RCO 360+ 33.0 41.77
Vacuum Distillation
• To recover distillates from RCO, vacuum distillation is
utilized
• By reducing the operating pressure further distillates
are recovered at lower than cracking temperatures
• Vacuum unit generally prepare feedstock for FCC and
Hydrocracking Units
• Main distillates from vacuum units are called Vacuum
Gas Oil (VGO)
• Vacuum column bottom is known as short residue
VDU Process
VDU
10-20
mmHg abs
400-405
Deg C
Atmospheric
Residue
Off gas
Vacuum Diesel
LVGO
HVGO
Slops
Vacuum
Residue
Heavy vacuum
gas oil
Typical Product Pattern
Product TBP Cuts, 0C Yield wt%, LS
(Mumbai High)
Yields, %wt
HS (AMX)
Off Gas C1-C2 0.4 0.5
Vacuum Diesel 200-360 11.5 7.8
Vacuum Gas Oil 320-580 78.1 48.1
Slops 500-650 0.0 6.0
Short Residue 580+ 10.0 37.6
Catalytic Naphtha Reforming
• Cat Reforming produces high octane
reformate (gasoline) or aromatics raw material
for further downstream processing
• By products are H2 and LPG
• Accomplished in H2 atmosphere at elevated
temperature & pressure in presence of a PT-
Rh catalyst
CRU Process
CRU
505-535 Deg C
22-23 kg/cm2g
Hydrotreated
Naphtha
H2 rich gas
Fuel Gas
LPG
Reformate
Typical Yield
Parameter MS Mode Aromatic Mode
Naphtha Feed Heavier Lighter
H2 rich gases 6.5 10.1
Fuel gas 1.2 1.6
LPG 1.9 4.1
Reformate 90.3 84.3
Reformate RON 92 95
FCC
• Purpose of FCC unit is to convert the low value
vacuum gas oils to high value products such as
LPG and Gasoline
• VGO is catalytically cracked to lighter
molecules
• Most profitable unit in the refinery
FCC
• FCC “heart” of a modern Refinery
– Nearly every major fuels refinery has an FCCU
• One of the most important & sophisticated
contributions to petroleum refining technology
• Capacity usually 25% to 35% of the crude distillation
capacity
• Contributes the highest volume to the gasoline pool
(35-40%)
FCC Process
FCC
Vacuum
Gas Oil
Fuel gas
Cracked LPG
Gasoline
Light Cycle Oil
Heavy Cycle Oil
Slurry Recycle
Clarified Oil
Fluid Catalytic Cracking unit
Regenerator
Stripper
Riser
Air
Vapors to fractionator
Flue gases to Co-boiler
VGO
Steam
P-1.7-2.1 bar
T-700 C
P-2.0 bar T-495 to 515 C
Reaction
C30  C-C-C + C-C-C-C-C + C-C-C-C
+ C8 +C 10
Catalyst
T-685 C
Typical Product Pattern
Product TBP Cuts, 0C Yield wt%, LS
(Mumbai High)
Yields, %wt
HS (Kuwait)
Fuel Gas C1-C2 1.85 2.52
LPG C3-C4 20.0 15.19
Gasoline C5-180 41.6 41.61
Light Cycle Oil 180-360 16.22 18.36
Heavy Cycle Oil 220-415 12.46 14.46
Clarified Oil 415+ 3.7 3.55
Coke 4.17 4.31
Hydroprocessing
• Hydrotreating
– Removal of hetero atoms & saturation of carbon-carbon
bonds
• Nitrogen, oxygen & metals removed
• Olefinic & aromatic bonds saturated
– Reduce average molecular weight & produce higher yields
of fuel products
• Hydrodesulfurization
– Remove sulfur compounds
– Minimum conversion of feed to lighter products
– 10% to 20% conversion
• Hydrocracking
– Severe type of hydrotreating
• Cracking of carbon-carbon bonds
• Drastic reduction of molecular weight
– 50%+ conversion
Purpose of Hydrotreating
• Desirable for feeds with small concentrations of aromatics &
contaminants
• Remove contaminants & break aromatic bonds
– Sulfur removed as hydrogen sulfide
– Metals deposited on catalysts
• Breaks aromatic bonds
– Lowers average molecular weight
– Produces higher yields of fuel products
• Minimum cracking
• Products suitable for further processing: reforming, catalytic
cracking, hydrocracking
Types
• Naphtha hydrotreating
– For preparing feedstock to Catalytic Reformer
– 230-330 Deg C, 22 kg/cm2g
• Distillate Hydrotreating
– For clean fuels (Diesel)
– 310-390 C, 40 kg/cm2g
• Vacuum Gas Oil Hydrotreating
– For better FCC feedstock
• Residue Hydrotreating
– Pretreatment of Coker/VRDS feedstock
What Does a Hydrocracker Do?
• Removes Metals (HDM) 100%
• Removes Olefins 100%
• Removes Sulfur (HDS) 100%
• Removes Nitrogen (HDN) 100%
• Saturates Aromatics (HDA) 50-95%
• Convert Feed to Products 40-100%
• H2 Consumption 1000-2500 SCF/Bbl
• Operating Pressure 70-210 Kg/Cm2
• Operating Temperature 315-430°C
Hydrocracker Process
HCU
170-180
Kg/cm2g
380-390 C
350-360 C
Vacuum
Gas Oil
Fuel gas
LPG
Light Naphtha
Heavy Naphtha
Kerosene / ATF
Unconverted Oil
HSD
Residue Upgradation Process
RUP
Atmospheric
/ Vacuum
Residue
Fuel gas
Cracked LPG
Naphtha
LCGO
HCGO
Coke
/ Unconverted Oil
PRODUCT TREATMENT- OBJECTIVES
 Primary separation only physical separation; products need
treatment to meet desired specifications.
 To make petroleum products suitable for use with respect to
performance, corrosively, suitability of storage, odor etc.
 Treatment of products to render them marketable – e.g.
Hydro-treating of HSD, Merox sweetening of LPG and
Gasoline.
 Recovery of environmentally hazardous materials through
processing e.g. Sulfur Recovery Unit.
 Treatment of intermediate product cuts (e.g. Naphtha, VGO,
VR, etc.) before secondary processing (like reforming,
cracking) helps to protect catalyst, improve yields.
Major contaminants of Petroleum
distillates and their effects
Contaminants Effects
Hydrogen Sulfide Acidity, corrosion, obnoxious combustion products,
reduced octane no., foul odour
Mereaptans Corrosion, obnoxious combustion products, reduced
octane no., gum deposits, engine deposits, foul odour
Naphthenic Acid Acidity and corrosion
Phenol compounds Engine deposits
Total Sulfur Corrosion, obnoxious combustion products, reduced
octane no.
Nitrogen bases Foul odour, colour formation, possible engine deposits
Traces of Metals Gum formation, Engine deposits
PRODUCT TREATMENT
• Intermediate & Raw Product Streams from CDU/VDU and
Secondary Processing Units like FCC / VBU / DCU are
treated to remove impurities to maintain desired Product
Specifications.
LPG - Caustic Wash / Merox
Naphtha – Hydrodesulfurization (NHDS) / Hydrotreater (NHDT)
ATF/ Kerosene – Kero Merox (KMU) / Kero Hydrotreater (KHDT)
HSD – Hydrodesulfurization (DHDS) / Hydrotreater (DHDT)
VGO – Hydrotreater (VGO-HDT)
AR – Hydrodesulfurization (ARDS)
VR – Hydrodesulfurization (VRDS)
FCC Gasoline – Hydrodesulfurization
Coker Naphtha & Gas Oil – Hydrotreater
Vis-breaker Naphtha & Gas Oil – Hydrotreater
PRODUCT TREATMENT (Contd.)
• Fuel Oil produced from VR, Asphalt produced in SDA & Petroleum Coke from
Coker Unit can be utilized for Power Generation.
• Petroleum Coke can also be calcined to produce calcined petroleum coke (CPC).
Sulphur is a By-product produced in Product Treatment Units
De-asphalted Oil (DAO) from SDA - is processed in
- Solvent Extraction Unit and
- De-waxing Unit,
for the removal of aromatics & wax respectively, and Hydrotreated in
- Hydro-finishing Unit,
for the manufacture of Finished Lube Oil Base Stocks (LOBS).
PRODUCT BLENDING
• OBJECTIVE –
To produce marketable finished product of required quality / specifications and
suitable for a particular application / end use.
• NEED FOR PRODUCT BLENDING –
- Availability of multiple streams of same finished product from
primary / secondary processing units.
- Streams of same finished product needs to be stored
together to reduce product tanks requirements.
- Finished product optimization with respect to quality
giveaway.
- Certain intermediate product stream (ex. VR, LDO) doesnot
meet finished product specifications.
PRODUCT BLENDING
• TYPES OF BLENDING
1. On-line blending – For products like LPG,
Naphtha, MS, ATF, Kerosene, Diesel, etc.
2. Tank to tank blending – For products like
Furnace oil, LDO, Lube oil base stocks.
* Sometimes ATF and MS are also blended
using tank to tank blending.
LOBS PRODUCTS:
1. NEUTRAL OILS
2. TURBINE OILS
3. INDUSTRIAL OILS
4. AXLE OILS
5. TRANSFORMER OIL
6. BRIGHT STOCK
BY-PRODUCT
1. SULPHUR
SPECIAL PRODUCTS
1. FG HEXANE
2. MTO
3. INDUSTRIAL
SOLVENTS
4. BENZENE
5. TOLUENE
6. MIX XYLENES
7. MTBE
8. LABFS
9. CBFS
10. CALCINED COKE
REFINERY PRODUCTS
CRITERIAS FOR PRODUCT SPECIFICATIONS
1) End Use and Applications
2) Safety in Handling & Storage
3) Environmental Protection
4) Equipment Corrosion
5) Flow Properties
PRODUCT PROPERTIES
• FLASH POINT : Lowest temperature at which vapors from the oil
ignite instantaneously.
• POUR POINT : Lowest temperature at which no oil flows.
• FREEZING POINT : Constant temperature at which oil solidifies.
• VISCOSITY : A measure of resistance to flow of oil.
• RECOVERY(%) : Percent of oil Distilled at 370 deg. C.
• OCTANE NO. : Determines the anti-knock property of Gasoline.
Higher the octane, better the anti-knock property.
• VISCOSITY INDEX : Determines temperature stability of lube oil with
respect to viscosity.
PRODUCT SPECIFICATIONS
 Important specifications for main Refinery Products
Refinery Product Specification
L.P.G. Vapor. Pressure, H2S.
Gasoline Octane No., Boiling Range, Sulfur, Aromatic / Olefins content
Naphtha Boiling Range, Sulfur
Kerosene Smoke point, Flash Pt. Sulfur content
Jet Fuel Freezing point, Flash point,
Boiling point
Diesel Oil Cetane no., Carbon Residue
Pour point, Flash Point.
Lubricating Oil Viscosity, Viscosity Index,
TEST - DISTILLATION
- Significance varies from Product to Product.
- For Crude oil, ASTM Distillation gives idea about the quantum of various
fractions.
- TBP Distillation reveals characteristics useful for the design of the
Refinery.
- 10% vol. of Distillation for MS is the indication of ease of Engine start.
- Too high FBP will cause crank case oil dilution.
PRODUCT QUALITY TESTS &
THEIR SIGNIFICANCE
PRODUCT QUALITY TESTS &
THEIR SIGNIFICANCE
TEST - VAPOUR PRESSURE
- Pressure exerted by vapors when it is in equilibrium with the liquid.
- Vapor pressure of volatile, non-viscous products is determined by
Reid Method.
Significance
- Test is important with respect to safety in transport, vapor lock in the gasoline engines,
types and design of storage tanks employed.
- High vapor pressure entails loss of product during storage and transportation.
PRODUCT QUALITY TESTS &
THEIR SIGNIFICANCE
TEST - OCTANE NUMBER
- Test for rating the antiknock of motor fuels
- O.N. is defined as the % volume of ISO-octane in a Mixture of ISO-octane and
n-Heptane that gives the same knocking as the fuel.
- Octane requirements of gasoline engines depend on their compression ratio.
Significance
- O.N. signifies the ignition quality of gasoline in automobile engines.
- For optimum delivery of power to the engine, fuel-air mixture injected into the engine
should ignite at the right time.
- Due to heat of compression, the temp. in the cylinder goes high and there could be
mistimed ignition. A high octane gasoline is better for ignition. Mistimed ignition
produce knocking in the engine.
- Knocking in an engine may result in loss of energy and may cause severe damage
-Minimum required octane ensures trouble free operation.
• The different hydrocarbon in gasoline :
 Straight chains paraffin
 ISO –paraffin
 Naphthenes
 Aromatics
₋ For the same Carbon No; straight chain paraffin have lowest octane No.
₋ Branched chain paraffin (isomers), Naphthenes have higher octane No.
₋ Olefins also have high O.N. but they cause gum deposits in the fuel tank
and are not desirable.
₋ Aromatic have high O.N. but their content is being restricted due to their
carcinogenic nature.
PRODUCT QUALITY TESTS &
THEIR SIGNIFICANCE
TEST - FLASH POINT
- Lowest temp. at which application of test flame causes vapor above the sample
to ignite.
- Flash point below 500C - Abel apparatus
- Flash point above 500C - Pensky / Martenes.
Significance
- Low flash products are potential to fire hazards.
PRODUCT QUALITY TESTS &
THEIR SIGNIFICANCE
TEST - CETANE NUMBER
- Determined in a single cylinder CFR engine.
- Compares ignition delay characteristics of fuel with reference blend of known
cetane number.
- Reference fuel used are normal Cetane (100 c.n.) and alpha-methyl-
naphthalene (0 c.n.).
Significance
- Indication of ignition quality of fuel
- High Cetane number facilitate easy starting of compression ignition engines
and lessen engine roughness.
PRODUCT QUALITY TESTS &
THEIR SIGNIFICANCE
TEST - SMOKE POINT
- Maximum flame height in mm at which fuel will burn without
smoking when determined in a smoke point apparatus under
specified conditions.
Significance
- Important test for kerosene evaluating their ability to burn
without producing smoke.
- Higher the smoke point, better it is for domestic use.
- Serves as a guide to assess the aromatic content of kerosene.
PRODUCT QUALITY TESTS &
THEIR SIGNIFICANCE
TEST - FREEZING POINT
- Temperature at which crystals of hydrocarbons formed on cooling,
disappear.
Significance
- Detection of separated solids in aviation engine fuels at
temperatures likely to be encountered during flight.
PRODUCT QUALITY TESTS &
THEIR SIGNIFICANCE
TEST - POUR POINT
- Lowest temperature at which oil is observed to flow when cooled
and examined under prescribed conditions.
Significance
- Serves as a guide to its pump-ability.
- Indicates waxy nature of the oil.
Gasoline Specification
Characteristics Bharat
Stage II
Euro III
Equivalent
Euro IV
Equivalent
Sulfur, % mass, total, max. 0.05 150 (mg/Kg) 50 (mg/Kg)
RVP, kPa, max. 35 – 60 60 60
Benzene,% vol., max. 3 1 1
Aromatics, %vol., max. - 42 35
Olefins %, vol., max. - 21 21
Distillation :
@ rec. up to 700C,% vol.
@ rec. up to 1000C,% vol.
@ rec. up to 1800C,% vol.
Final BP, 00 C, max.
Residue, % vol., max.
10 – 45
40 – 70
90
215
2
10 – 45
40 – 70
75, min.
210
2
10 – 45
40 – 70
75, min.
210
2
RON, min. 88 91 91
MON, min. - 81 81
Diesel Specifications
Characteristics Bharat Stage II Euro III
Equivalent
Euro IV
Equivalent
Sulfur, % mass, total,
max.
0.05 350 (mg/kg) 50 (mg/kg)
Cetane No., min. 48
45 (for Assam
crude)
51
48 (for Assam
Crude)
51
48 (for Assam
Crude)
Poly-cyclic Aromatics HC
(PAH), % mass, max.
- 11 11
Distillation :
95% vol. Recovery @ 0 C,
max.
85 min. @
3500C & 95 min.
@ 3700 C
3600 C 3600 C
Light distillate
LPG / C3
Naphtha
MS
Benzene
Toluene
Hexane
SBP
CDU-1
CDU-2 FPU
HVU CCU
FCCU
Crude unit Secondary unit
PRODUCTS
Vacuum unit
Atm residue
BH +LS crude
Simple Refinery Process Flow
Chart
CDU-3 VDU HCUImp HS crude
Middle distillate
MTO
Kerosene
ATF
HSD
LOBS
LDO
Heavy ends
Furnace oil
LSHS
Bitumen
Sulfur
Train-1
Train-2
Train-3
BH +LS crude
HGU1
HGU2
Naphtha
DHDS
Atm residue
VGO
VGO
BBU
NHDS
CCR
Naphtha
ARU
LPG C3-C4/MTBE
ATU / SRU
Acid gas
LOBS
BLENDING
VGO
2.0 mmta
4.0 mmta
6.0 mmta
GO
GASOLINE
SPLITTER
Blending streams – 110
To make 32 different grade products
Crude & product tanks – >100
CRU

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Refinery process

  • 3. History of Petroleum Refineries • Available in small quantities through natural seepage • Drilling of petroleum from first oil well was in Pennsylvania, US in 1859. • The availability of crude oil in abundant quantities led to the development large scale Simple Distillation units. • Primary product was Kerosene, used for lighting lamps.
  • 4. History of Petroleum Refineries • The lowest boiling fraction obtained was straight naptha, primarily used as a solvent • Higher boiling fractions were used as Fuel oils, and lubricants • Development of the IC engine, and subsequently automobile, in the end of 19th Century increased the demand of light petroleum gasoline, and led to advancements in petroleum refining.
  • 5. History of Petroleum Refineries • Major landmarks in the development of petroleum refineries have been: – Automobile industry – Increased demand for transportation fuels during WW – Increased demand for jet fuels during 1950’s-60’s – Realisation of adverse impacts on Environment in th 1990’s
  • 6. Raw Material: Crude oil • Hydrocarbons made of carbon and H2 atoms • Simplest is having one carbon, and four Hydrogen atoms, called Methane. • Molecules join each other and form long hydrocarbon chains. • Carbon atom has four valence electrons, which can combine with hydrogen in different ways to form Alkanes, Alkenes, Alkynes, and naphthenes.
  • 7. Raw Material: Crude oil • Saturated chain molecule: Paraffins – General formula CnH2n – Also known as paraffins – Saturated hydrocarbons as all the four valences of Carbon atoms are taken up by hydrogen atoms. – Chemically most stable – Arrangement of chains of paraffins can be straight(normal) or branched chains(iso) – Naturally occurring paraffins are straight chain, and refinery processes produced branched
  • 8. Raw Material: Crude oil • Saturated Cyclo-Comounds – More than four carbon atoms, with a ringed structure – Saturated cyclo compounds are called Naphthenes – Naphthenic crude oils have low potential for manufacture of lube oil, but higher conversion to gasoline fractions.
  • 9. Raw Material: Crude oil • Unsaturated ringed Comounds – All available valencies of carbon arent bonded with hydrogen – Double or triple carbon-carbon bond may be formed – Arrangement of carbon atoms is either as chained structure (Olefins) or rings (Aromatics) – Chemically unstable and reactive, good combustion properties – Small volumes found in crude oil, but produced as a result of petroleum refining processes – Simplest Aromatic compound is benzene (C6H6)
  • 10. Raw Material: Crude oil • Crude oil composition: – Complex mixure of very long chain hydrocarbon molecules – Broad characterization of crude oil is based on the most prevailent form of HC ie, Praffins, Naphthenes or Aromatics – Small quantities of compounds of sulfur, Nitrogen, and Oxygen are also present – Minute traces of heavy metals like Ni, V, Na,Ar etc decide the quality of refined products
  • 11. AGENDA • Feed Stock to products • Refinery Processes • Integration of Process Units
  • 12. 0 100 200 300 400 IncreasingBoilingPoint(degC) CRUDE OIL REFINING Main Products Crude Oil to Products LPG PETROL KERO HSD FO Main process - simple distillation C3-C4 C9-C16 C14-C24 >C22 C5-C10 500 Lt Distillate Middle Distillate Heavy ends
  • 13. Key Refined Products Key Qualities Octane, Sulfur, Vapour Pressure,Benzene Vapour Pressure C2 & C5 content Sulfur, Cetane, Pour point Distillation,Flash point Viscosity, Pour point, Metals, Cal value Main Applications Domestic & Industrial heating,Transport Transport Aviation, heating, lighting Transport, Power Industries, Power Sea transport LPG PETROL KERO/ATF HSD FO/LSHS Freezing point, Smoke point, Flash NAPHTHA
  • 14. DENSITY / API GRAVITY Density is used for: ₋ Weight to volume or vice versa calculations ₋ Checking the consistency of crude supply ₋ Control of refinery operations ₋ Used in various correlations ₋ Also gives a rough indication of type of crude oil API GRAVITY= SP.GR.@ 60/60°F Examples: Water = 10 API Kerosene = 45 API Motor Gasoline = 58 API Natural Gasoline = 75 API Crude oils are categorized based on gravity Light grades : Above 33 degree API Medium grades: 23-33 degree API Heavy grades: up to 22 degree API 141.5 - 131.5
  • 15. Crude Oil Quality indicators API gravity Above 50 : Condensate 33 to 50 : Light 24 to 33 : Intermediate Below 24 : Heavy Sulphur Below 0.5% : Low 0.5 %- 1.5% : Medium Above 1.5% : High
  • 16. Different crude – different yields Lt Distillate Middle Distillate Heavy ends 0.17 0.18 1.9 2.7 O API 40 33.6 34.2 31.0 % Sulfur
  • 17.  COMPOSTION OF CRUDE OIL: – LARGE NO. OF DIFFERENT HYDROCARBONS – IMPURITIES SUCH AS ‘S’, N, O2 METALS, ETC. – BOTTOM SEDIMENTS & WATER (BS & W) – SALTS, SUCH AS NACL, MGCL2, ETC.  TYPES OF HYDROCARBONS: – PARAFFINS – NAPHTENES – AROMATICS – OLEFINS CRUDE OIL COMPOSITION
  • 18. TYPES OF HYDROCARBON • PARAFFINS : - Open chain saturated compounds of C & H having general formula CnH2n+2. – Have great chemical stability. – Two types • n - Paraffins • Iso - Paraffins. – N-Paraffins have low Octane No. & high ignition properties. – Iso-Paraffins have high Octane No.
  • 19. TYPES OF HYDROCARBON (Contd…) • NAPHTHENES : – Saturated Cyclic hydrocarbons. – High chemical stability. – General Formula CnH2n. • OLEFINS : – Unsaturated open chain hydrocarbons. – Highly reactive. – Generally formed during cracking / conversion processes.
  • 20. TYPES OF HYDROCARBON (Contd…) • AROMATICS : – Unsaturated Cyclic hydrocarbons having general formula CnHn. – Chemically reactive. – Aromatics in Gasoline increases Octane number. – Undesirable in Kerosene because of their tendency to give smoky flame.
  • 21. • SULPHUR: – Major impurity and present in elemental form. – Sulfides / oxides of sulfur (H2S, Mercaptans, SO2 etc) generated in refinery processes. – Present as H2S / Mercaptans in LPG, as Sulfur / Mercaptans in Gasoline, Kerosene, ATF and as sulfur in HSD & Residues. – Sweetening Processes (caustic washing, Mercaptan Oxidation) are used to remove these impurities from products. IMPURITIES IN CRUDE OIL
  • 22. • NITROGEN : – Present in elemental form and also as oxides of Nitrogen. – Forms Acids and causes corrosion. – Removal is necessary to get on-grade products and secondary units feedstocks. • OXYGEN : – Present in elemental form and also as compounds of Oxygen. – Forms Naphthenic Acids and causes stress corrosion. IMPURITIES IN CRUDE OIL (Contd..)
  • 23. • METALS : – Main metals in Crude oil are - Lead, Nickel, Vanadium & Copper. – Present in very small quantity (ppm level), in Crude and gets distributed in various products. – Poison to catalysts even in very small amount. • SALTS : – Are formed during Refining process. – Main salts - NaCL, MgCL2, KCL. – Acids formed from these salts attacks plant equipments and corrosion sets In. IMPURITIES IN CRUDE OIL (Contd..) • SEDIMENTS & WATER: – Sediment: Fine particles of sand clay, volcanic ash,drilling mud, rust, iron sulphide, metals and scale. – Damaging Effects Plugging Abrasion and residual product contamination. – Water causes irregular behaviour in distillation.
  • 24. Reid Vapour Pressure (RVP) and Light End Analysis RVP indicates relative Percentage of gaseous and lighter hydrocarbons in crude oil.
  • 25. POUR POINT • Indicates relative amount of wax present in crude oil • Is the temperature below which pumping and transportation problems may be encountered • Along with viscosity, is used in pumping and design calculations: WAX CONTENT Normal paraffins above CI6 are solid at somewhat ambient temperatures. These hydrocarbons • Affect the flow behaviour of crude • Affect the product quality of gas oil, VGO and asphalt • Lube manufacture is also dependent on wax content of the crude.
  • 26. COMPARISON OF IND. & ME CRUDES QUALITY PROPERTIES UNIT BH KUWAIT ARAB MIX IRN LT. IRN HY. API Gravity @ 150 C --- 38.3 31.2 30.3 34.0 31.1 Pour Point 0 C +30 -17 -15 -12 -6 Wax Content % wt 14.7 4.5 5.6 5.7 4.4 Asphaltenes % wt 0.05 1.3 2.7 0.9 2.0 Total Sulfur % wt 0.2 2.54 2.65 1.4 1.65 Primary Yields Light Distillates % wt 24 14 16 17 16 Middle Distillates % wt 46 36 36 43 36 Residue % wt 30 50 48 40 48
  • 27. YIELD PATTERN OF VARIOUS CRUDES (% WT) STREAMS BH KUWAIT DUBAI GAS 0.2 0.3 0.1 LPG 1.1 1.2 2.5 NAPHTHA 23.0 16.0 12.9 KEROSENE 20.5 16.5 15.3 HSD 25.0 18.0 27.2 RCO 30.0 48.0 42.0 LVGO + HVGO 74.0 58.0 52.0 VACUUM DIESEL 3.0 1.0 2.0 VACUUM RESIDUE 23.0 41.0 46.0
  • 28. REFINERY CONFIGURATION • Catalytic Cracking, Hydro Cracking, Coking, Reformer, etc are referred to as secondary processing units • Nelson Complexity Index • Captures the proportion of the secondary conversion unit capacities relative to the primary distillation or topping capacity • Typically varies from ~ 2 for Hydro skimming refineries to ~ 5 for Cracking refineries and > 9 for Coking refineries • Refineries with high Nelson Complexity Index have • Flexibility to process wide range of cheap crudes • Capable of achieving higher distillate yields & hence higher value addition
  • 29. Yields are dependent on Refinery configuration Relative capital cost (per MMT) 1.0 2.1 3.6 4.3 >9 LPG Naphtha Petrol Kerosene Diesel Heavy ends Fuel & loss
  • 30. Typical Refinery economics 26.4 53.4 13.9 117.0 120.0 70.0 30.9 64.1 9.7 0.0 20.0 40.0 60.0 80.0 100.0 120.0 140.0 Light distillate Middle distillate Heavy ends Yield Wt. Avg Price Realization Yield - %wt on crude, Price - % of crude price Avg product price – 104.6 % Crude % Improving yield of value added products is the mantra of any Refinery
  • 31. REFINERY CONFIGURATION - TOPPING Separates the crude into petroleum products by Atmospheric Distillation. Topping Refinery produces naphtha but no gasoline LPG Naphtha Jet / Kerosene Diesel / Gas oil Fuel Oil (Atmospheric Residue) CRUDE OIL CDU CrudeDistillationUnit 0 100 200 300 400
  • 32. HYDRO SKIMMING REFINERY Refinery equipped with Atmospheric Distillation, Naphtha reforming and necessary treating processes. More complex than topping refinery and produces gasoline LPG Naphtha Jet / Kerosene Low-sulphur Diesel / Gas oil Fuel Oil (Atmospheric Residue) C R U Catalytic Reformer Mogas LPG Mogas Gas Oil Desulphuriser CDU CrudeDistillationUnit 0 100 200 300 400 CRUDE OIL
  • 33. CRACKING REFINERY Also has Vacuum Distillation and Catalytic Cracking. Adds complexity to the hydro skimming refinery & converts fuel oil to light and middle distillates LPG Naphtha Jet / Kerosene Low-sulphur Diesel / Gasoil Fuel Oil Component (Vacuum Residue) CDU CrudeDistillationUnit CRUDE OIL C R U Catalytic Reformer Mogas LPG Mogas Gas oil Desulphuriser VDU VacuumDistillation Vacuum Distillate (Vacuum Gasoil, Waxy Distillate) FCCU CatalyticCracker LPG Mogas
  • 34. COKING REFINERY Converts the vacuum residue into high value products using Delayed Coker. Adds further complexity to the cracking refinery by high conversion of fuel oil into distillates and petroleum coke (used as power fuel) LPG Naphtha Jet / Kerosene Low-sulphur Diesel / Gasoil Coke CDU CrudeDistillationUnit CRUDE OIL C R U Catalytic Reformer Mogas LPG Mogas Gasoil Desulphuriser VDU VacuumDistillation Vacuum Distillate (Vacuum Gasoil, Waxy Distillate) HCCU Hydrocracker Mogas VLS Diesel Jet Hydrogen Coker LPGLPG
  • 35. HYDROCRACKING + RDS REFINERY LPG Naphtha Jet / Kerosene Low-sulphur Diesel / Gasoil Low Sulfur Fuel Oil CDU CrudeDistillationUnit CRUDE OIL C R U Catalytic Reformer Mogas LPG Mogas Gasoil Desulphuriser VDU VacuumDistillation Vacuum Distillate (Vacuum Gasoil, Waxy Distillate) HCCU Hydrocracker LPG Mogas VLS Diesel Jet Hydrogen 0 100 200 300 400 AR/VRDS Adds further complexity to the hydro cracker cracking refinery by high conversion of fuel oil into distillates. Also has Residue Desulfuriser. Produces low sulphur fuels
  • 37. Refinery Processes • Crude Distillation • Catalytic Naphtha Reforming • Fluidized Catalytic Cracking • Hydro Processing (DHDS, HCU/LOBS, NHT) • Residue Upgradation (BBU, VRDS, Coking) • MISC – Aromatics, Treatment, MTBE, Merox
  • 38. Atmospheric Distillation • First Step in the refining of crude oil • Crude oil is fractionated into sharp cuts in an atmospheric distillation column • These cuts are generally Unstabilized Naphtha, HN, Kero/ATF, Light gas oil, Heavy gas oil • Bottoms of the crude column is known as reduced crude oil • A single or multiple columns could be used for fractionation • Crude is first preheated in preheat exchangers / heaters and then pumped to Crude column
  • 39. Atmospheric Distillation • Crude column operates at normally 2-3 Kg/Cm2g pressure • Yield of various products depends on type of crude oil • Products obtained from crude column are known as straight run products / components • Energy intensive process • Maximum distillates recovered in CDU till cracking temperatures at operating pressure
  • 40. Crude Distillation Unit Distillation column Gas Naphtha upto 170 C Kerosine upto 270 C Diesel upto 360 C RCO/Atmospheric Residue >360 C CRUDE LPG Heater 370 C 360 C 2.2 ata 110 C 2.0 ata Lt Distillate Middle Distillate Heavy ends
  • 41. Typical Product Pattern Product TBP Cuts, 0C Yield wt%, LS (Mumbai High) Yields, %wt HS (AMX) Fuel Gas C1-C2 0.3 0.04 LPG C3-C4 1.5 1.36 Stabilized Naphtha C5-90 16.5 11.58 Heavy Naphtha 90-140 3.3 3.42 Kero/ATF 140-280 23.3 16.67 LGO 150-360 16.1 16.35 HGO 220-415 6.0 8.81 RCO 360+ 33.0 41.77
  • 42. Vacuum Distillation • To recover distillates from RCO, vacuum distillation is utilized • By reducing the operating pressure further distillates are recovered at lower than cracking temperatures • Vacuum unit generally prepare feedstock for FCC and Hydrocracking Units • Main distillates from vacuum units are called Vacuum Gas Oil (VGO) • Vacuum column bottom is known as short residue
  • 43. VDU Process VDU 10-20 mmHg abs 400-405 Deg C Atmospheric Residue Off gas Vacuum Diesel LVGO HVGO Slops Vacuum Residue Heavy vacuum gas oil
  • 44. Typical Product Pattern Product TBP Cuts, 0C Yield wt%, LS (Mumbai High) Yields, %wt HS (AMX) Off Gas C1-C2 0.4 0.5 Vacuum Diesel 200-360 11.5 7.8 Vacuum Gas Oil 320-580 78.1 48.1 Slops 500-650 0.0 6.0 Short Residue 580+ 10.0 37.6
  • 45. Catalytic Naphtha Reforming • Cat Reforming produces high octane reformate (gasoline) or aromatics raw material for further downstream processing • By products are H2 and LPG • Accomplished in H2 atmosphere at elevated temperature & pressure in presence of a PT- Rh catalyst
  • 46. CRU Process CRU 505-535 Deg C 22-23 kg/cm2g Hydrotreated Naphtha H2 rich gas Fuel Gas LPG Reformate
  • 47. Typical Yield Parameter MS Mode Aromatic Mode Naphtha Feed Heavier Lighter H2 rich gases 6.5 10.1 Fuel gas 1.2 1.6 LPG 1.9 4.1 Reformate 90.3 84.3 Reformate RON 92 95
  • 48. FCC • Purpose of FCC unit is to convert the low value vacuum gas oils to high value products such as LPG and Gasoline • VGO is catalytically cracked to lighter molecules • Most profitable unit in the refinery
  • 49. FCC • FCC “heart” of a modern Refinery – Nearly every major fuels refinery has an FCCU • One of the most important & sophisticated contributions to petroleum refining technology • Capacity usually 25% to 35% of the crude distillation capacity • Contributes the highest volume to the gasoline pool (35-40%)
  • 50. FCC Process FCC Vacuum Gas Oil Fuel gas Cracked LPG Gasoline Light Cycle Oil Heavy Cycle Oil Slurry Recycle Clarified Oil
  • 51. Fluid Catalytic Cracking unit Regenerator Stripper Riser Air Vapors to fractionator Flue gases to Co-boiler VGO Steam P-1.7-2.1 bar T-700 C P-2.0 bar T-495 to 515 C Reaction C30  C-C-C + C-C-C-C-C + C-C-C-C + C8 +C 10 Catalyst T-685 C
  • 52. Typical Product Pattern Product TBP Cuts, 0C Yield wt%, LS (Mumbai High) Yields, %wt HS (Kuwait) Fuel Gas C1-C2 1.85 2.52 LPG C3-C4 20.0 15.19 Gasoline C5-180 41.6 41.61 Light Cycle Oil 180-360 16.22 18.36 Heavy Cycle Oil 220-415 12.46 14.46 Clarified Oil 415+ 3.7 3.55 Coke 4.17 4.31
  • 53. Hydroprocessing • Hydrotreating – Removal of hetero atoms & saturation of carbon-carbon bonds • Nitrogen, oxygen & metals removed • Olefinic & aromatic bonds saturated – Reduce average molecular weight & produce higher yields of fuel products • Hydrodesulfurization – Remove sulfur compounds – Minimum conversion of feed to lighter products – 10% to 20% conversion • Hydrocracking – Severe type of hydrotreating • Cracking of carbon-carbon bonds • Drastic reduction of molecular weight – 50%+ conversion
  • 54. Purpose of Hydrotreating • Desirable for feeds with small concentrations of aromatics & contaminants • Remove contaminants & break aromatic bonds – Sulfur removed as hydrogen sulfide – Metals deposited on catalysts • Breaks aromatic bonds – Lowers average molecular weight – Produces higher yields of fuel products • Minimum cracking • Products suitable for further processing: reforming, catalytic cracking, hydrocracking
  • 55. Types • Naphtha hydrotreating – For preparing feedstock to Catalytic Reformer – 230-330 Deg C, 22 kg/cm2g • Distillate Hydrotreating – For clean fuels (Diesel) – 310-390 C, 40 kg/cm2g • Vacuum Gas Oil Hydrotreating – For better FCC feedstock • Residue Hydrotreating – Pretreatment of Coker/VRDS feedstock
  • 56. What Does a Hydrocracker Do? • Removes Metals (HDM) 100% • Removes Olefins 100% • Removes Sulfur (HDS) 100% • Removes Nitrogen (HDN) 100% • Saturates Aromatics (HDA) 50-95% • Convert Feed to Products 40-100% • H2 Consumption 1000-2500 SCF/Bbl • Operating Pressure 70-210 Kg/Cm2 • Operating Temperature 315-430°C
  • 57. Hydrocracker Process HCU 170-180 Kg/cm2g 380-390 C 350-360 C Vacuum Gas Oil Fuel gas LPG Light Naphtha Heavy Naphtha Kerosene / ATF Unconverted Oil HSD
  • 58. Residue Upgradation Process RUP Atmospheric / Vacuum Residue Fuel gas Cracked LPG Naphtha LCGO HCGO Coke / Unconverted Oil
  • 59. PRODUCT TREATMENT- OBJECTIVES  Primary separation only physical separation; products need treatment to meet desired specifications.  To make petroleum products suitable for use with respect to performance, corrosively, suitability of storage, odor etc.  Treatment of products to render them marketable – e.g. Hydro-treating of HSD, Merox sweetening of LPG and Gasoline.  Recovery of environmentally hazardous materials through processing e.g. Sulfur Recovery Unit.  Treatment of intermediate product cuts (e.g. Naphtha, VGO, VR, etc.) before secondary processing (like reforming, cracking) helps to protect catalyst, improve yields.
  • 60. Major contaminants of Petroleum distillates and their effects Contaminants Effects Hydrogen Sulfide Acidity, corrosion, obnoxious combustion products, reduced octane no., foul odour Mereaptans Corrosion, obnoxious combustion products, reduced octane no., gum deposits, engine deposits, foul odour Naphthenic Acid Acidity and corrosion Phenol compounds Engine deposits Total Sulfur Corrosion, obnoxious combustion products, reduced octane no. Nitrogen bases Foul odour, colour formation, possible engine deposits Traces of Metals Gum formation, Engine deposits
  • 61. PRODUCT TREATMENT • Intermediate & Raw Product Streams from CDU/VDU and Secondary Processing Units like FCC / VBU / DCU are treated to remove impurities to maintain desired Product Specifications. LPG - Caustic Wash / Merox Naphtha – Hydrodesulfurization (NHDS) / Hydrotreater (NHDT) ATF/ Kerosene – Kero Merox (KMU) / Kero Hydrotreater (KHDT) HSD – Hydrodesulfurization (DHDS) / Hydrotreater (DHDT) VGO – Hydrotreater (VGO-HDT) AR – Hydrodesulfurization (ARDS) VR – Hydrodesulfurization (VRDS) FCC Gasoline – Hydrodesulfurization Coker Naphtha & Gas Oil – Hydrotreater Vis-breaker Naphtha & Gas Oil – Hydrotreater
  • 62. PRODUCT TREATMENT (Contd.) • Fuel Oil produced from VR, Asphalt produced in SDA & Petroleum Coke from Coker Unit can be utilized for Power Generation. • Petroleum Coke can also be calcined to produce calcined petroleum coke (CPC). Sulphur is a By-product produced in Product Treatment Units De-asphalted Oil (DAO) from SDA - is processed in - Solvent Extraction Unit and - De-waxing Unit, for the removal of aromatics & wax respectively, and Hydrotreated in - Hydro-finishing Unit, for the manufacture of Finished Lube Oil Base Stocks (LOBS).
  • 63. PRODUCT BLENDING • OBJECTIVE – To produce marketable finished product of required quality / specifications and suitable for a particular application / end use. • NEED FOR PRODUCT BLENDING – - Availability of multiple streams of same finished product from primary / secondary processing units. - Streams of same finished product needs to be stored together to reduce product tanks requirements. - Finished product optimization with respect to quality giveaway. - Certain intermediate product stream (ex. VR, LDO) doesnot meet finished product specifications.
  • 64. PRODUCT BLENDING • TYPES OF BLENDING 1. On-line blending – For products like LPG, Naphtha, MS, ATF, Kerosene, Diesel, etc. 2. Tank to tank blending – For products like Furnace oil, LDO, Lube oil base stocks. * Sometimes ATF and MS are also blended using tank to tank blending.
  • 65. LOBS PRODUCTS: 1. NEUTRAL OILS 2. TURBINE OILS 3. INDUSTRIAL OILS 4. AXLE OILS 5. TRANSFORMER OIL 6. BRIGHT STOCK BY-PRODUCT 1. SULPHUR SPECIAL PRODUCTS 1. FG HEXANE 2. MTO 3. INDUSTRIAL SOLVENTS 4. BENZENE 5. TOLUENE 6. MIX XYLENES 7. MTBE 8. LABFS 9. CBFS 10. CALCINED COKE REFINERY PRODUCTS
  • 66.
  • 67. CRITERIAS FOR PRODUCT SPECIFICATIONS 1) End Use and Applications 2) Safety in Handling & Storage 3) Environmental Protection 4) Equipment Corrosion 5) Flow Properties
  • 68. PRODUCT PROPERTIES • FLASH POINT : Lowest temperature at which vapors from the oil ignite instantaneously. • POUR POINT : Lowest temperature at which no oil flows. • FREEZING POINT : Constant temperature at which oil solidifies. • VISCOSITY : A measure of resistance to flow of oil. • RECOVERY(%) : Percent of oil Distilled at 370 deg. C. • OCTANE NO. : Determines the anti-knock property of Gasoline. Higher the octane, better the anti-knock property. • VISCOSITY INDEX : Determines temperature stability of lube oil with respect to viscosity.
  • 69. PRODUCT SPECIFICATIONS  Important specifications for main Refinery Products Refinery Product Specification L.P.G. Vapor. Pressure, H2S. Gasoline Octane No., Boiling Range, Sulfur, Aromatic / Olefins content Naphtha Boiling Range, Sulfur Kerosene Smoke point, Flash Pt. Sulfur content Jet Fuel Freezing point, Flash point, Boiling point Diesel Oil Cetane no., Carbon Residue Pour point, Flash Point. Lubricating Oil Viscosity, Viscosity Index,
  • 70. TEST - DISTILLATION - Significance varies from Product to Product. - For Crude oil, ASTM Distillation gives idea about the quantum of various fractions. - TBP Distillation reveals characteristics useful for the design of the Refinery. - 10% vol. of Distillation for MS is the indication of ease of Engine start. - Too high FBP will cause crank case oil dilution. PRODUCT QUALITY TESTS & THEIR SIGNIFICANCE
  • 71. PRODUCT QUALITY TESTS & THEIR SIGNIFICANCE TEST - VAPOUR PRESSURE - Pressure exerted by vapors when it is in equilibrium with the liquid. - Vapor pressure of volatile, non-viscous products is determined by Reid Method. Significance - Test is important with respect to safety in transport, vapor lock in the gasoline engines, types and design of storage tanks employed. - High vapor pressure entails loss of product during storage and transportation.
  • 72. PRODUCT QUALITY TESTS & THEIR SIGNIFICANCE TEST - OCTANE NUMBER - Test for rating the antiknock of motor fuels - O.N. is defined as the % volume of ISO-octane in a Mixture of ISO-octane and n-Heptane that gives the same knocking as the fuel. - Octane requirements of gasoline engines depend on their compression ratio. Significance - O.N. signifies the ignition quality of gasoline in automobile engines.
  • 73. - For optimum delivery of power to the engine, fuel-air mixture injected into the engine should ignite at the right time. - Due to heat of compression, the temp. in the cylinder goes high and there could be mistimed ignition. A high octane gasoline is better for ignition. Mistimed ignition produce knocking in the engine. - Knocking in an engine may result in loss of energy and may cause severe damage -Minimum required octane ensures trouble free operation.
  • 74. • The different hydrocarbon in gasoline :  Straight chains paraffin  ISO –paraffin  Naphthenes  Aromatics ₋ For the same Carbon No; straight chain paraffin have lowest octane No. ₋ Branched chain paraffin (isomers), Naphthenes have higher octane No. ₋ Olefins also have high O.N. but they cause gum deposits in the fuel tank and are not desirable. ₋ Aromatic have high O.N. but their content is being restricted due to their carcinogenic nature.
  • 75. PRODUCT QUALITY TESTS & THEIR SIGNIFICANCE TEST - FLASH POINT - Lowest temp. at which application of test flame causes vapor above the sample to ignite. - Flash point below 500C - Abel apparatus - Flash point above 500C - Pensky / Martenes. Significance - Low flash products are potential to fire hazards.
  • 76. PRODUCT QUALITY TESTS & THEIR SIGNIFICANCE TEST - CETANE NUMBER - Determined in a single cylinder CFR engine. - Compares ignition delay characteristics of fuel with reference blend of known cetane number. - Reference fuel used are normal Cetane (100 c.n.) and alpha-methyl- naphthalene (0 c.n.). Significance - Indication of ignition quality of fuel - High Cetane number facilitate easy starting of compression ignition engines and lessen engine roughness.
  • 77. PRODUCT QUALITY TESTS & THEIR SIGNIFICANCE TEST - SMOKE POINT - Maximum flame height in mm at which fuel will burn without smoking when determined in a smoke point apparatus under specified conditions. Significance - Important test for kerosene evaluating their ability to burn without producing smoke. - Higher the smoke point, better it is for domestic use. - Serves as a guide to assess the aromatic content of kerosene.
  • 78. PRODUCT QUALITY TESTS & THEIR SIGNIFICANCE TEST - FREEZING POINT - Temperature at which crystals of hydrocarbons formed on cooling, disappear. Significance - Detection of separated solids in aviation engine fuels at temperatures likely to be encountered during flight.
  • 79. PRODUCT QUALITY TESTS & THEIR SIGNIFICANCE TEST - POUR POINT - Lowest temperature at which oil is observed to flow when cooled and examined under prescribed conditions. Significance - Serves as a guide to its pump-ability. - Indicates waxy nature of the oil.
  • 80. Gasoline Specification Characteristics Bharat Stage II Euro III Equivalent Euro IV Equivalent Sulfur, % mass, total, max. 0.05 150 (mg/Kg) 50 (mg/Kg) RVP, kPa, max. 35 – 60 60 60 Benzene,% vol., max. 3 1 1 Aromatics, %vol., max. - 42 35 Olefins %, vol., max. - 21 21 Distillation : @ rec. up to 700C,% vol. @ rec. up to 1000C,% vol. @ rec. up to 1800C,% vol. Final BP, 00 C, max. Residue, % vol., max. 10 – 45 40 – 70 90 215 2 10 – 45 40 – 70 75, min. 210 2 10 – 45 40 – 70 75, min. 210 2 RON, min. 88 91 91 MON, min. - 81 81
  • 81. Diesel Specifications Characteristics Bharat Stage II Euro III Equivalent Euro IV Equivalent Sulfur, % mass, total, max. 0.05 350 (mg/kg) 50 (mg/kg) Cetane No., min. 48 45 (for Assam crude) 51 48 (for Assam Crude) 51 48 (for Assam Crude) Poly-cyclic Aromatics HC (PAH), % mass, max. - 11 11 Distillation : 95% vol. Recovery @ 0 C, max. 85 min. @ 3500C & 95 min. @ 3700 C 3600 C 3600 C
  • 82. Light distillate LPG / C3 Naphtha MS Benzene Toluene Hexane SBP CDU-1 CDU-2 FPU HVU CCU FCCU Crude unit Secondary unit PRODUCTS Vacuum unit Atm residue BH +LS crude Simple Refinery Process Flow Chart CDU-3 VDU HCUImp HS crude Middle distillate MTO Kerosene ATF HSD LOBS LDO Heavy ends Furnace oil LSHS Bitumen Sulfur Train-1 Train-2 Train-3 BH +LS crude HGU1 HGU2 Naphtha DHDS Atm residue VGO VGO BBU NHDS CCR Naphtha ARU LPG C3-C4/MTBE ATU / SRU Acid gas LOBS BLENDING VGO 2.0 mmta 4.0 mmta 6.0 mmta GO GASOLINE SPLITTER Blending streams – 110 To make 32 different grade products Crude & product tanks – >100 CRU