Petroleum Origin & Manufacture

May 2010
Crude Oil Origin
Crude Oil Origin
Crude Oil in Underground Pockets
First Recorded Lubrication

Earliest lubricants were undoubtedly animal fats and probably the first
recording of use of a lubricant was found in the Egyptian tomb of Ra-Em-Ka
of about 1880 B.C. that show a man pouring a liquid on the runners of a
sledge used to transport a stone monument
Early Chinese Drilling Rig
Finding Oil
Drilling for Crude Oil
Drilling for Crude Oil
Offshore Drilling Platform
 crude oil
 crude oils are classified historically composition & classification
according to their composition
 paraffinic, naphthenic, mixed base,
asphaltic
 lower density - waxy through high
density, low wax but asphaltic
 naphthenic does not mean they
necessarily contain mainly naphthenes
but are asphaltic with small amounts of
wax.
 selected paraffinic and naphthenic
sources are used for making base oils
by conventional processing
 sweet crudes have a low sulphur
content - since sulphur must be
removed to meet fuel specifications
these crudes are more expensive to
process than sour crudes.
Petroleum Constituents

 Petroleum consists basically of hydrogen and carbon atoms

commonly known as hydrocarbons
 Hydrogen & carbon atoms can combine in an infinite number of
ways to form chains that also vary in length
 Divided into 3 groups
Typical Hydrocarbon Configuration

Saturated straight chain – Paraffin's / Aliphatics

Methane n-Hexane
Cyclo-paraffin / Napthenic

Saturated carbon atoms in a ring structure, low octane, high wax,

Cyclohexane
Aromatic
Unsaturated hydrocarbon chain containing one or more benzene rings
Their presence causes a smoky flame in lamps and the knock in diesel
engines

Benzene Ring
Petroleum Production
VI POUR
N - PARAFFINS VERY HIGH HIGH

IS0 - PARAFFINS HIGH LOW

NAPHTHENES MODERATE LOW

(CYCLO PARAFFINS)

AROMATICS LOW LOW

BASE OILS ALSO CONTAIN SULPHUR,OXYGEN AND METAL COMPOUNDS

e.g

PARAFFINIC BASE OILS CONTAIN 45-60% PARAFFINIC COMPOUNDS

AROMATIC BASE OILS CONTAIN 20-25% AROMATIC COMPOUNDS
NAPHTHENIC BASE OILS CONTAIN 65-75% NAPHTHENIC COMPOUNDS

Base oil components

base oil chemistry - Note that this is a great simplification - real base oils contain
many thousands of different compounds.

normal Paraffins

iso Paraffins

Naphthenes sulphur, nitrogen

and oxygen
Aromatics compounds

note that most naphthenes and aromatics also

have alkyl groups attached - the pure aromatic is
called the “parent” compound
Some Boiling Points
Hydrocarbon Configuration Boiling Pt °C
Methane CH4 -161
Ethane C2H6 -87
Propane C3H8 -48
N-Butane C4H10 0
N-Pentane C5H12 36
N-Hexane C6H14 68
Benzene C6H6 80
N-Heptane C7H16 98
N-Octane C8H18 126
ISO-Octane C8H18 99
N-Hexadecane (Cetane) C16H34 280
Manufacturing process
 Refining is a complex process (physical and chemical) consisting of three
basic phases necessary to extract lubricating base oils from the crude oil
 Separate
 Fractional distillation (physical process, separation)
 The crude oil is fractionated in various base oil cuts

 Purify
 Undesired compounds removed (propane deasphalting, Furfural extraction, MEK dewaxing)

 Convert
 converted into more desirable material (Hydrotreating, hydrofinishing & hydrocracking)

 Process design and conditions depend mainly on three factors

 Feedstock composition (crude oil provenance)
 Desired properties of finished base oil product or respectively the application of
the lubricant
 Refining and world economics
Fractional distillation
 By fractional distillation crude oil is cut into various
fractions defined by their boiling range
 Since hydrocarbons start cracking at temperatures
beyond 350°C, the distillation process is divided into
two steps.
 Distillation Tower - Operation
 The crude oil is heated in a furnace
 Most components enter the distillation tower as a vapour

 A temperature gradient is maintained in the tower

 Trays are inserted at various levels to collect the liquids that condense at those
levels
 ‘Bubble caps’ in each tray force the vapour through a liquid bath maintained at a
particular temperature
 Thus fractions of different boiling points condense on different layers in the
distillation tower
 Light hydrocarbons are carried over the top of the column as vapour and
condensed to liquid by cooling (raw gasoline)
 crude oil
atmospheric distillation - the first step
CRUDE Distillation Unit (CDU)
Boiling range

Propane/Butane (-10 - 25 C)
O

Gasoline (Petrol) (25 - 70 C)

O

Naphtha (Chemical feed) (70 - 140 C)

O

Kerosene (Aviation fuel) (140 - 250 C)

O

Diesel (Gas oil) (250 - 350 C)

O

Crude Oil

VDU Atmospheric Residue used for LUBRICANTS (> 350º C)

Steam
Atmospheric Distillation Tower

TO VACUUM DISTILATION TOWER

Why Vacuum Distillation ?

 A heavy, black residue is drawn from the bottom of the

atmospheric distillation tower
 This is often called the ‘bottoms’
 This residue will decompose at high temperatures (>350°C)

 Under a vacuum these heavy components will vapourise

(boil) at a considerably lower temperature
 Enables separation of heavier oils into fractions without changing the
molecular structure – (i.e. Without ‘cracking’ the oil)
 Remember - the boiling point of water decreases with altitude
 Pressure cooker works on the reverse principle
vacuum distillation
separation of lube fractions by boiling point

 second stage is distillation in a

vacuum to produce several
vacuum distillates and a Light Spindle Oil
vacuum residue
 distillates are used to make Heavy Spindle Oil
solvent neutral base grades or
Light Lube Oil
distillate grades
 residue is used to make bright Heavy Lube Oil
stocks or used for bitumen or
fuel Atmospheric
Residue
 the distillation conditions Brightstock
dictate the final viscosity grade
Steam
and volatility properties of the Vacuum
finished base oil Deasphaltor
Vacuum
residue

Asphalt/Bitumen
Purification

 Mineral base oils after atmospheric and vacuum

distillation still contain some undesirables
 Waxes (high molecular paraffins) precipitate even at moderate low
temperatures
 Aromatics are carcinogenic and could form sludge
 Unsaturated hydrocarbons have poor oxidation stability and could
form sludge / varnish
 Nitrogen compounds catalyse oxidation
Purification

 However when removing undesirables care has to be

taken to keep other desired components
 Sulphur compounds are natural anti-oxidants
 High molecular paraffins show little change of fluidity with temperature
 Hence every refinery step is a balance between reducing
undesirable and maintaining desirable compounds, thus
achieving the highest possible yield at the lowest possible
raw material and process costs
Furfural Extraction

WAXY RAFFINATE
EACH OF THE PARTICULAR
BASE OIL "CUTS" IS MIXED WITH
A SPECIAL SOLVENT

THE SOLVENT IS REMOVED, TAKING SPECIAL

MOST OF THE AROMATICS WITH IT SOLVENT
MIX
IMPROVES - VISCOSITY INDEX
- COLOUR
- OXIDATION STABILITY
- LOWERS THE
CARCINOGENICITY BASE OIL FEEDSTOCK
PROCESS OILS ARE PRODUCED AS A FROM VACUUM TOWER
BY-PRODUCT, AND USED IN RUBBER
TYRE MANUFACTURE SOLVENT EXTRACT
waxy distillate - note the wax suspended in the oil and the dark colour. The distillate still
contains aromatics that must be removed by solvent extraction or hydrogenation (catalytic
dewaxing)
Solvent (MEK) Dewaxing

OIL AND SOLVENT ARE MIXED AND COOLED

TO A SET TEMPERATURE

LARGE PARAFFINIC MOLECULES PRECIPITATE AS DEWAXING

WAX, WHICH IS FILTERED OFF SOLVENT

EFFECT - REDUCES POUR POINT

- REDUCES VISCOSITY INDEX (VI)

BY-PRODUCT IS WAX BASE OIL FEEDSTOCK

- USED FOR CANDLE INDUSTRY SOLVENT EXTRACTION
- TO FORM SYNTHETIC BASESTOCKS
(SLACK WAX ISOMERATES) WAX

FOR MANY BASE STOCKS DEWAXING IS THE FINAL PROCESS

MEK Dewaxing - schematic
 conventional
dewaxing - chilling to
precipitate the wax
 the raffinate mixed with a solvent to
reduce viscosity & chilled to below
the temperature at which the finished
base oil must remain fluid
 more wax removed the lower the
viscosity index
 dewaxed as little as possible
 pour point reduced by additives that
modify the wax
 solvents must be low viscosity at the
dewaxing temperature
 easily removed by flash distillation
 chemically stable
 have the right solvent properties to
allow the wax to crystallise.
 a solvent dewaxing unit - note the ice
forming around the pipes carrying the
chilled solvent.

hard wax - wax taken from the dewaxer still

has some oil and is called slack wax. Further
processing in the dewaxer - called de-oiling,
produces a hard wax suitable for candles
Hydrofinishing

Hydrogen is reacted with the base oil in the

presence

of a catalyst under high temperature and pressure

Sulphur and nitrogen components are removed DEWAXING
SOLVENT

Unsarurated
- hydrocarbons are converted into
saturated -hydrocarbons

After hydrofinishing base oils show

•Lighter colour
•Less unsaturated components BASE OIL FEEDSTOCK
SOLVENT EXTRACTION
•Reduced acidity
•Slightly higher wax contents NAPTHA
•Reduced Nitrogen, Sulphur and Oxygen components
Grade pattern - each manufacturer will choose a particular way of taking the
distillation “cuts” to give the desired viscosity of base oils he needs. There are
several different grade patterns - one of the common ones is shown here.

Distillate “cut” A spindle oil

Distillate “cut” B 150 solvent neutral

after solvent
extraction,
Distillate “cut” C 300 solvent neutral
dewaxing &
finishing give

Distillate “cut” D 600 solvent neutral

Vacuum residue bright stock

Engen Refinery Process
ATMOSPHERIC DISTILLATION
TOWER

FUELS & SOLVENTS

VACUUM DISTILLATION EXTRACTION DEWAXING HYDROFINISHING

STILL TOWER UNIT TOWER

CRUDE *
*

RESIDUE *
ENGEN
BASE
DEASPHALTER
OIL
RESIDUE SOLVENT WAX NAPTHA
EXTRACT

ASPHALT / BITUMEN
Base Lubricating Oil Refinery
base oil quality factors - here are some of the key points to check.

Pour Point
Refined for Health & Safety
low PCAs When does it
freeze? - low Pour Good flow
point at low temperatures

Small difference in viscosity

at different temperatures BA IL
= High VISCOSITY INDEX
Viscometrics Appearance
Compatibility
Clarity - base oils must
be clear & bright - free
from wax particles, free
water etc.. Volatility
Strict Quality Checks in Transport

Safety Oxidation Stability

Low Flammability = High Flash point
Refinery Process - Summary

Separation
 By distillation into the different fractions
 Does not alter the molecular structure

Conversion
 Catalytic cracking, visbreaking, alkylation
 Alters the molecular structure of hydrocarbons
 To increase yield and align production with demand

Purification
 Removal of impurities (sulphur, aromatics...)
 Removal of undesirable components (wax...)
Petroleum Production

CRUDE OIL

PETROLEUM SYNTHETIC
BASESTOCK BASESTOCK

PRODUCT

ADDITIVES

 Composition of top quality lubricant

Blending Lubricating Oils

Lubricating oil = base oil(s) + additives

 Base oils with suitable properties are combined to achieve the

required oil viscosity
 Additives to suit the application requirements are added to the base
oil

 The oil will then undergo thorough testing

The End