Prof. K. V.

Rao
Programme Director
Petroleum Courses
JNTUK
B. Tech. Petrochemical Engineering

Petroleum Refinery Engineering


University College of Engineering (A) Kakinada
Dept. of Petroleum Engineering & Petrochemical Engineering
Petroleum Distillation Products
Fraction Size Range BP Range (
o
C) Uses
Gas C1 - C4 0 - 30 Gas Fuels
Gasoline C4 - C12 30 - 200
Motor Fuels

Kerosene C12 - C16 180 - 300
Jet fuel, diesel
oil
Gas oil C16 - C18 >300
Diesel fuel,
cracking stock
Lubricating
Stock
C18-C20 >350
Lubricating oil,
cracking stock
Paraffin wax C20-C40
Low-melting
solids
Candles, wax
paper
Asphalt > C40
Gummy
residues
asphalt,
roofing tar
Lube Oils
REDUCED CRUDE OIL
TO LUBE REFINERY
FUEL REFINERY PROCESS
CRUDE OIL
LAN
SKO
HAN
LGO
HGO
LPG
N
M
P

E
X
T
R
A
C
T
I
O
N

P
R
O
P
A
N
E

D

E
A
S
P
H
A
L
-
T
I
N
G

BITUMEN
150 SS
500 SS
1300 SS
75 SS/ SPINDLE
RPO
(AROMATIC
EXTRACTS)
D
E
W
A
X
I
N
G

U
N
I
T

BRIGHT STOCK
WAX
150 BS
1300 N
500 N
150 N
75 SM
R
C
O
LUBE REFINING
BASE OIL TERMINOLOGY
LUBES ARE HIGH VALUE PRODUCTS WITH BROAD VARIETY OF
USES

Automotive: Engine oils, Automatic Transmission Fluids
(ATF)

Industrial: Turbine oils, Hydraulic oils, Industrial Gear oils,
Compressor oils,

Refrigeration oils, Machine oils, Electrical oils, Drilling
Fluids etc

Medicinal: Food Grade oils, White oils,..

REFINERIES PRODUCE BASE OILS OR BASE STOCKS
Finished Products are Blends of Base stock with(out)
Additives

BASE OIL TERMINOLOGY

BASE STOCKS ARE CALLED BY VARIOUS NAMES:
Neutrals (100N, 150N, 600N,...) Bright Stocks
Grades (SAE 5, 10, 30, ..; ISO 22, 32,...)

MOST COMMON LUBE NAME IS NEUTRAL
Number is the Viscosity @ 40 or 100
o
C

BRIGHT STOCK IS HEAVY LUBE PRODUCED FROM
RESIDUE
Name Refers to Appearance and Typical Viscosity is
2,500 SSU @ 100
o
F

GRADE NAMES MAY REFER TO VISCOSITY OR TO
TRADEMARKS
BASESTOCK PROPERTIES AND DEFINITIONS
BASE STOCK COMPOSITION DETERMINES PERFORMANCE
OF FINISHED PRODUCTS

Viscosity Index or VI
Higher VI improves Volatility, Fuel Economy, and
Operating Range

Saturate Content
Higher Saturates improves Oxidation Stability and
Soot Handling

Wax Content
Lower Wax Improves Operating Range
Lower Wax improves Low Temperature
Performance
Pour Point
Cloud Point



BASESTOCK PROPERTIES AND DEFINITIONS
Base oil groups

Group I Saturates <90% and/or sulfur >0.03%, and Society
of Automotive Engineers (SAE) viscosity index (VI) of 80 to
120
Manufactured by solvent extraction, solvent or catalytic
dewaxing, and hydro-finishing processes. Common Group I
base oil are 150SN (solvent neutral), 500SN, and 150BS
(brightstock)

Group II Saturates over 90% and sulfur under 0.03%, and
SAE viscosity index of 80 to 120
Manufactured by hydrocracking and solvent or catalytic
dewaxing processes. Group II base oil has superior anti-
oxidation properties since virtually all hydrocarbon
molecules are saturated. It has water-white color.
BASESTOCK PROPERTIES AND DEFINITIONS
Group III Saturates > 90%, sulfur <0.03%, and SAE
viscosity index over 120
Manufactured by special processes such as
isohydromerization. Can be manufactured from base oil or
slax wax from dewaxing process.

Group IV Polylphaolefins(PAO)

Group V All others not included above such as
naphthenics, PAG, esters.

In North America, Groups III, IV and V are now described as
synthetic lubricants, with group III frequently described as
synthesised hydrocarbons, or SHCs. In Europe, only Groups IV
and V may be classed as synthetics.

BASESTOCK PROPERTIES AND DEFINITIONS
The lubricant industry commonly extends this group
terminology to include:

Group I+ with a Viscosity Index of 103108
Group II+ with a Viscosity Index of 113119
Group III+ with a Viscosity Index of at least 140

Can also be classified into three categories depending on the
prevailing compositions:

Paraffinic
Naphthenic
Aromatic

KEY LUBE OIL PROPERTIES
VISCOSITY (MEASURE OF FLUIDITY)
Range from ~ 4 to 20 cSt @ 100oC for Neutrals up to 32 cSt
for Bright Stock
Brookfield Measures Low Temperature Fluidity on Finished
Oils @ -40
o
C


VISCOSITY INDEX (INVERSE MEASURE OF CHANGE OF
VISCOSITY WITH TEMPERATURE)
Ranges from ~85 to ~105 for most Base stocks, Higher for
Speciality Grades
(ex: Exxsyn ~140, PAO ~150, XHVI~140+, Ultra S ~ 125)


POUR POINT (TEMPERATURE AT WHICH FLUID BECOMES
NEARLY SOLID)
Typically from -9 to -24
o
C
Cloud Point is Temperature at Which Wax Crystals Appear


KEY LUBE OIL PROPERTIES

VOLATILITY (MEASURE OF OIL LOSS DUE TO
EVAPORATION)
Noack Volatility Measures Actual Evaporation
(Typically 20-35 wt%)
GCD Volatility Measures Front End of Boiling Curve (e.g
10% @375
o
C)

COLOR (APPEARANCE) AND STABILITY (MEASURE OF
COLOR CHANGE IN LIGHT)

CONRADSON Carbon (MEASURE OF CARBON RESIDUE
LEFT ON IGNITION)

SATURATES, AROMATICS and ASPHALTENE CONTENTS

INDIAN LUBE REFINING CAPACITY
TMTPA
HPCL, Mumbai - 330
IOC,Haldia - 200
CPCL, Chennai - 240
BPC, Mumbai - 180
TOTAL - 950
LUBE MANUFACTURING
Lube
Refinery
Blending
Plants


Function
Base Oils
Viscosity Index
Pour Point
Flash Point
Lubricants
Improved
Improved
No change
Oxidation Stability
Additives
Key Properties
C
U
S
T
O
M
E
R
S
Special Properties
GENERAL CATEGORIES
AUTOMOTIVE
LUBRICANTS
INDUSTRIAL
LUBRICANTS
GREASES SPECIALTIES
ENGINE OILS
TRANSMISSION
OILS

TURBINE OILS
HYDRAULIC OILS
COMPRESSOR
OILS
REFRIGERATION
OILS
SPINDLE OILS
CYLINDER OILS
GEAR OILS
TEXTILE OILS etc

WHEEL BEARING
CHASSIS
INDUSTRIAL

CUTTING FLUIDS
METAL ROLLING
OILS
RUBBER
PROCESS OILS
RUST
PREVENTIVES
HEAT TRANFER
FLUIDS
METAL DRAWING
COMPOUNDS
QUENCHING OILS
etc

FUNCTIONS OF ENGINE OILS
o PERMIT EASIER STARTING
o LUBRICATE AND PREVENT WEAR
o REDUCE FRICTION
o PROTECT AGAINST RUST AND CORROSION
o KEEP ENGINE INTERIORS CLEAN
o COOL ENGINE PARTS
o SEAL COMBUSTION PRODUCTS
o BE NON-FOAMING
o AID FUEL ECONOMY


TECHNICAL SPECIFICATIONS
PARAMETERS ASTM 60N 100N 150N 500N 600N 150BS
Specific Gravity,
15/4C D1298 0.8773
0.852
0
0.866
6
0.881
1
0.881
7 0.8940
Colour, Say bolt D1500 L0.5 L0.5 L1.0 L2.0 L1.5 L2.0
Kinetic
Viscosity @40,cSt
D445
7.498 20.31 30.14 95.79 115 480.6
@100,cS
t
2.036 4.166 5.189 10.97 12.43 31.32
Viscosity Index D2270 66 107 101 99 97 98
Flash Point,
C(COC) D92 156 208 212 242 253 310
Pour Point, C D97 -20.0 -15.0 -12.5 -12.5 -12.5 -12.5
TECHNICAL SPECIFICATIONS
PARAMETERS ASTM 60N 100N 150N 500N 600N 150BS
Sulphur Content, wt
ppm D5453 <10 <10 <100 <100 <100 <100
Carbon
Residue(CCR), wt% D189 <0.01 0.01 0.04 0.01 0.01 0.01
Copper Corrosion,
100C/3hr D130 1a 1a 1a 1a 1a 1a
TAN, mgKOH/g D974 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01
Ring
Analysis, wt%CA 8.4 2.2 1.8 7.2 6.4 7.3
wt%CN D3238 42.5 29.4 32.1 26.0 26.5 21.7
wt%CP 49.1 68.4 66.1 66.8 67.1 71.0
Aniline Point, C D611 77.8 107.0 107.1 116.3 116.9 129.7
GREASES

BASE OIL + THICKENER + ADDITIVES

MINERAL SOAP ANTI-OXIDANT


COMPOSITION
WHY USE A GREASE?
A GREASE OFFERS UNIQUE CHARACTERISTICS WHICH
MAKES IT PARTICULARLY USEFUL IN MACHINE ELEMENTS

STAY WHERE IT IS PUT
ALLOWS UNATTENDED SERVICE FOR LONG PERIODS
(SEALED FOR LIFE)
REQUIRES LESS FREQUENT APPLICATION FOR AREAS
OF POOR ACCESSIBILITY
SEALS OUT CONTAMINANTS
OPERATE OVER A WIDE TEMPERATURE RANGE
SOLID ADDITIVES CAN BE USED WITHOUT CONCERN
OF SETTLING OUT
LOW LEAKAGE MEANS THEY ARE EFFECTIVE IN WARM
EQUIPMENT

NLGI CLASSIFICATION OF GREASES
NATIONAL LUBRICRATING GREASE INSTITUTE

NLGI NO. ASTM PENETRATION
@ 25O
o
C*
1 310-340
2 265-295
3 220-250
4 175-205
5 130-260
6 85-115

* After working 60 strokes.

Petroleum Wax
General features of wax
Solid at ambient temperature
Thermoplastic in nature
Combustible
Liquid at 100 to 200F
Insoluble in water

3 general categories of petroleum wax
Paraffin waxes : from the light lubricating oil
distillates, contain straight-chain HC with an average
chain length of 20 to 30 carbon atoms.
Microcrystalline waxes (micro wax): from a
combination of heavy lube distillates and residual oils.
have poorly defined crystalline structure, darker
color, and higher viscosity and MP. Vary much more
widely than paraffin waxes with regard to physical
characteristics.
Petrolatums from heavy residual oils and are
separated by a dilution and filtering (or centrifuging)
process. Petrolatums are microcrystalline in nature
and semi-solid at room temperature.
Other terms used to refer to petroleum wax:
refering to the amount of oil contained in the product.
Slack wax containing anywhere from 3 to 50% oil
content.
Scale wax containing 1 to 3% oil content.
Fully refined paraffin (FRP) wax having less than
0.5% oil content. THe wax that has had nearly all
of the oil refined out of it.
26 IHPT 2008 Petro.
Wax Properties
Property Test Method Description Typical Values
Melt Point
ASTM D87 Provides information on temperature at
which most of a given wax changes from
a solid to a liquid. Widely used for
paraffin waxes.
100-160
O
F (43-71
O
F) for
paraffin waxes from a solid to a
liquid.
Congealing
Point
ASTM D938 Measures when a wax ceases to flow. Varies widely
Drop Melt Point
ASTM D127 Generally used on waxes that dont show
a melting plateau e.g. petrolatums and
microcrystalline waxes.
140-200
O
F (60-93
O
C) for
microcrystalline waxes
Needle
Penetration
ASTM D1321 Measures the hardness of wax. Usually
determined at 77
O
F (25
O
C) or 100
O
F.
Higher values indicate softer wax.
9-20 (0.1dmm) for paraffin @ 77
O
F (25
O
C)
Oil Content
ASTM D721 The amount of oil in wax. Indicates
degree of refining
Fully Refined <0.5%, Semi-
refined 0.5-1.0%, Scale 1.0-3.0%
http://www.igiwax.com/resource/Test_Methods
Oil content in wax (ASTM-D721)
Oil content or solvent extractables in wax can affect
key properties such as strength, hardness, melting
point, etc.
ASTM-D721
HEAVY FUEL OILS
HEAVY FUEL OILS

Heavy fuel oil consists primarily of the residue from
distillation or cracking units in the refinery.

Historically, fuel oils were based on long residues from the
atmospheric distillation column and were known as straight
run fuels.

However, the increasing demand for transportation fuels
such as gasoline, kerosene and diesel has led to an increased
value for the atmospheric residue as a feedstock for vacuum
distillation and for cracking processes.
As a consequence, most heavy fuel oils are currently based
on short residues and residues from thermal and catalytic
cracking operations.

These fuels differ in character from straight run fuels in that
the density and mean molecular weight are higher, as is the
carbon/hydrogen ratio.

The density of some heavy fuel oils can be above 1,000
kg/m
3
, which has environmental implications in the event of
a spillage into fresh water.

In refineries with catalytic cracking units, catalytically cracked
cycle oils are common fuel oil diluents.

As a result, the composition of residual fuel oils can vary
widely and will depend on the refinery configuration, the
crude oils being processed and the overall refinery demand.
Residual fuel oils are complex mixtures of high molecular
weight compounds having a typical boiling range from 350 to
650C.

They consist of aromatic, aliphatic and naphthenic
hydrocarbons, typically having carbon numbers from C
20
to
C
50
, together with asphaltenes and smaller amounts of
heterocyclic compounds containing sulphur, nitrogen and
oxygen.

They have chemical characteristics similar to asphalt and
hence, are considered to be stabilised suspensions of
asphaltenes in an oily medium.

Asphaltenes are highly polar aromatic compounds of very high
molecular weight (2000-5000) and in the blending of heavy
fuel oils, it is necessary to ensure that these compounds
remain in suspension over the normal range of storage
temperatures.
Heavy fuel oils also contain organo-metallic compounds
from their presence in the original crude oils. The most
important of these trace metals is vanadium.

Some crude sources, for example, from the Caribbean area
and Mexico are particularly high in vanadium and this is
reflected in high vanadium contents in heavy fuel oils
produced from these crudes.

Vanadium is of major significance for fuels burned in both
diesel engines and boilers because when combined with
sodium (perhaps from seawater contamination) and other
metallic compounds in critical proportions it can form high
melting point ashes which are corrosive to engine exhaust
valves, valve seats and super heater elements.
Other elements that occur in heavy fuel oils include nickel,
iron, potassium, sodium, aluminium and silicon.

Aluminium and silicon are mainly derived from refinery
catalyst fines.

Significant concentrations of hydrogen sulphide (H
2
S) are
known to accumulate in the headspaces of storage tanks that
contain heavy fuel oils.

Heating of such tanks may cause decomposition of some of
the sulphur-containing compounds, which release H
2
S.

In addition to the hazard from H
2
S, there is also evidence that
accumulations of vapours of light hydrocarbons are also to be
found in the headspaces of heavy fuel oil tanks.
Appreciable concentrations of polycyclic aromatic compounds
(PAC) can be present in heavy fuel oils depending on the
nature and amount of the low viscosity diluent used and
whether the residue component is cracked or un-cracked.

If the residue components are from the atmospheric or
vacuum distillation columns, the concentration of three to
seven ring aromatic hydrocarbons is likely to be in the order of
6 to 8%; if heavy catalytically cracked or steam-cracked
components are used, the level may approach 20% .

One of the diluent fractions commonly used is catalytically
cracked cycle oil, which has been reported to contain 58%
three to five ring aromatic hydrocarbons .
HEAVY FUEL OIL BLENDING COMPONENTS.

Heavy fuel oils can be blended from a wide range of refinery
components, the most important of which are:

Long residue: the residue from the atmospheric distillation of
crude oil. As mentioned earlier, historically this was a major
fuel oil blending component, but it is now mainly used as a
feedstock for the vacuum distillation unit or for a thermal or
catalytic cracking unit.

Short residue: the residue from the vacuum distillation of
crude oil.
Thermal cracker or visbreaker residue: the residue
from thermal cracking processes designed to increase
the yield of distillate components from atmospheric
and vacuum residues.

Cat cracker slurry oil (clarified oil): a heavy fraction
from a catalytic cracking operation, a process for the
conversion of heavy hydrocarbon fractions into high
quality gasoline components.

Thermally cracked or visbreaker gas oil: a middle
distillate fraction from thermal cracker or visbreaker
units.
Cat cracker cycle oil: a middle distillate fraction from the
catalytic cracking unit.

Kerosine: a lighter middle distillate fraction from the
atmospheric column.

Gas oil: a heavier middle distillate fraction from the
atmospheric column.

Vacuum gas oil: a heavy gas oil fraction from the vacuum
column.
TYPICAL PROPERTIES

Marketing specifications have been established by a
number of authorities to ensure the satisfactory
operation of industrial and marine equipment utilising
heavy fuel oils.

Such specifications include ASTM D-396 (ASTM 1992), BS
2869 for inland fuels (BSI 1988), ISO 8217 for marine
fuels (ISO 1996) and CIMAC requirements for residual
fuels for diesel engines (CIMAC 1990).

Typical properties for heavy fuel oils can vary widely
within the specification limits:

normally they would be expected to fall within the ranges
listed in Table 1.
Table 1: Range of physico-chemical properties for heavy fuel oils