Properties and applications of

major petroleum products

Products Light
Fuel Gas
Ends

LPG

Distillation
Naphtha
Kerosene
Diesel /
Gas Oil
Residue /
Bottoms
Gasoline
mixture of volatile,
flammable liquid
hydrocarbons used
as fuel for internal-
combustion engines

USA and Canada:

gas
Great Britain: petrol
Europe: benzine
Gasoline
Intake

Compression

Power

Exhaust

Products of carbon
water nitrogen
Combustion dioxide
Composition
Paraffins Olefins
Aromatics
Isoparaffins Naphthenes

BP below
4 – 12 C
200C
Requirements of Good Gasoline
evaporates easily chemically stable
and burns (does not form
completely when gums or other
the spark plug fires deposit precursors)

no particulate
contaminants or
entrained water
Properties
Octane Rating
• percent of isooctane in the
isooctane/n-heptane blend that
knocks at the same compression ratio
as the gasoline or component being
evaluated
• standard: Isooctane •100
n-heptane •0
Octane Rating
• Knock – caused by unwanted chemical reactions in the
combustion chamber
Change in Knocking
• Chemical Factors
Tendency
Change in Chemical Increase Decrease
Structure
1. Longer paraffin chains ✓
2. Isomerizing normal ✓
paraffins
3. Aromatizing normal ✓
paraffins
4. Alkylating aromatics ✓
5. Saturating aromatic ✓
rings Overview of Petroleum Refining Processes
Octane Rating
Research Octane Number (RON)

• simulates driving under mild, cruising conditions

Motor Octane Number (MON)

• run under more severe conditions and simulates

operations under load or accelerating

Display Octane Number (Anti-Knock Index)

RON + MON
AKI =
2
Octane Rating
• Example: How much alkylate would have to be
added to meet a minimum octane specification
of 87 [(R+M)/2]. The octane number of the
alkylate is 96.5. Component
Volum (R+M)/
e, MBD 2
Straight Run
4 63
Naphtha
Reformate 6 89
Hydrocrackate 1 74
Cat-cracked
8 85
Gasoline
Overview of Petroleum Refining Processes
Normal Butane 3.131 92.5
Octane Rating
• Compression Ratio

V1
CR =
V2

Knocking: self-ignition without

the aid of the spark plug
Octane Rating
• Tetraethyl Lead (TEL) as Gasoline Additive
– used as anti-knock agent, without affecting other performance
characteristics including vapor pressure
– 3 grams per gallon can increase the octane number by as much as 5
RON
– toxic, causes memory loss, blindness, mental retardation and death
Octane Rating
• Petrochemical Blending Components

RVP, psi RON MON (R+M)/2

Methanol 40 135 105 120
Ethanol 11 132 106 119
TBA 6 106 89 98
MTBE 9 118 101 110
ETBE 4 118 102 110
TAME 1.5 111 98 105
Properties
Volatility
• Reid Vapor Pressure
– measure of the surface pressure it takes to keep a
liquid from vaporizing (measured at 38C)

Too Low Too High

Difficulty in starting
Vapor lock
engine
• Vapor Lock
– too much of the fuel evaporates and either starves
the engine of fuel or provides too much fuel to the
engine
Volatility
• Example: RVP Specification = 10 psi
Volum
Component RVP
e, MBD
Straight Run
4 1 by
Naphtha weighted
Reformate 6 2.8 averaging
Hydrocrackate 1 2.5
Cat-cracked
8 4.4
Gasoline
Normal Butane 52
Volatility
• Why use normal butane instead of
isobutane?
Normal Butane Isobutane
RVP 52 71
Occurrence More abundant Less abundant
Other Use/s Alkylation
Price Less expensive More expensive
Properties
Cleanliness
• Chemical Cleanliness
– does not contain nor react under conditions of
storage and use to form unwanted by-
products such as gums, sludge and deposits
• Physical Cleanliness
– no undissolved solids or large amounts of free
water
Properties
Other Requirements
• No mercaptan Sulfur
!
• Should not promote corrosion in pipelines, service
! station tanks or vehicle metals

• Clear and bright in appearance and should not

! pick up water either as a haze or as an emulsion
• should not contain more than trace amounts of
carbonyls (dissolve elastomeric seals and
! diaphragms)
• should not contain phosphorus which can
! damage catalytic converters
Gasoline Additives
• Petrochemical Blending Components
Methanol, CH3OH or MeOH M-85:
85% gasoline
15% methanol
CH 4 + H 2O → CO + 3H 2 500F to 800F
4,000 to 5,000 psi
CO + 2H 2 → CH3OH

corrosive has an undergroun when

affinity for d water burned in
and water, pollution ICE, emits
toxic handling formaldehy
would be
de
difficult
Gasoline Additives
• Petrochemical Blending Components

Tertiary Butyl Alcohol, TBA

by- may be worked in abandon

prepared by
product reacting sympathy ed with
from butane with with the
water or
making isobutylene methanol demise of
propylene and propylene as M-85
oxide cosolvent
Gasoline Additives
• Petrochemical Blending Components
Methyl Tertiary Butyl Ether,
MTBE
– expensive but more user-friendly successor to methanol
– does not phase separate, unlike methanol
– gives an octane boost at 109 DON and has RVP of 8

soluble in leaches
water in
aquifers
Gasoline Additives
• Petrochemical Blending Components

Ethyl Tertiary Butyl Ether, ETBE

– gives an octane boost at 109 DON and has RVP of 4

soluble leaches expensiv

in aquifers e
in
water
Gasoline Additives
• Petrochemical Blending Components
Biofuels
Ethanol, C2H5OH or EtOH Act:
E-10
– comes from the natural fermentation of vegetables
– gives an octane boost at 114 RON but has an RVP of 19
– gasoline blend: 90% gasoline, 10% ethanol
– may be produced from ethylene and water in the
presence of a phosphoric acid catalyst

soluble in leaches in
water aquifers
Gasoline Additives
• Petrochemical Blending Components

TAME, THxME, THpME, THxEE, THpEE

– from removal processes of C5, C6 and C7 olefins

– have high octane numbers, low RVPs, no sulfur
– production cost and regulations
TAME: THxME: THpME:
Tertiary amyl Tertiary hexyl Tertiary heptyl
methyl ether methyl ether ethyl ether

THxEE: THpEE:
Tertiary hexyl Tertiary heptyl
ethyl ether ethyl ether
Environmental Considerations

NOx + VOCs → ozone + particulates → smog

Environmental Considerations
• minimum oxygen content of gasoline to assure more complete
burning of the hydrocarbons to carbon dioxide and water, also
to reduce the amount of unburned hydrocarbons in the exhaust
• use of oxygenates – ethanol, MTBE, etc.
Environmental Considerations

Toxic Nitrogen
Compounds Oxides

Volatile
Sulfur
Organic
Oxides
Compounds
Trends in Specifications
• Pre 1994 Lower Reid
Phase out of
Vapor
lead
Pressure

• 1995-2000
Reformulated Aromatics
gasoline Zero lead content: 25%
(Phase I) vol max

Reid Vapor
Benzene: 1% Oxygen: 2%
Pressure: 8.1
vol max wt minimum
psi max
Trends in Specifications
• Post 2000

Reformulated Aromatics
Sulfur: 30 ppm Benzene: 0.8%
gasoline content:
max vol max
(Phase II) 22%vol max

Reid Vapor
Oxygen: > 2%
Olefins: 4% vol Pressure: 7.0
wt
psi max
Impact on Operations
• Meet all the specifications – AKI, RVP, pollutability –
without leftover components
• Vary the operating conditions of some of the process units
• Divert streams in and out of units

CONSTRAINTS

Linear
Programming
Impact on Operations
Additional Considerations
• The process unit yields fed into the model are only estimates
• The inevitable unscheduled shutdown of equipment interrupts
orderly flow
• The crude composition vary over the period
• The product demands and prices vary
Properties and applications of
major petroleum products
Products
Light Ends Fuel Gas

LPG

Distillation
Naphtha
Kerosene

Diesel / Gas Oil

Residue /
Bottoms
 Kerosene

flammable pale
also called paraffin
yellow or colorless
oil
oily liquid

boils in the range of

140 – 280C;
heavier than
naphtha but lighter
than diesel oil
Uses
for burning in
lamps and
domestic
heaters or
furnaces

as a fuel or fuel
component for
jet engines

as a solvent for
greases and
insecticides
Components
Paraffinic • Elemental Composition of
Hydrocarbons
a Typical Domestic
Naphthenic Heating Oil
Hydrocarbons

Aromatic Element Concentration

Hydrocarbons
Carbon 86.5 %m
Sulfur Hydrogen 13.3 %m
compounds Sulfur < 0.2 %m
Nitrogen and Nitrogen 50 – 400 ppm
Oxygen
compounds Oxygen Traces
Specifications
Flash Point
❑ temperature at which the fuels start to
give off enough vapors to form a
combustible mixture
❑ indication of the maximum temperature at
which it can be stored and handled
without serious fire hazard
❑ should not be below the ambient
temperature
Specifications
Flash Point
❑ Laboratory Test:
❑ Open Cup Method (Abel’s method)
❑ Closed Cup Method (Pensky-Mertinus
Method)
Specifications
Smoke Point
❑ determined as the height of the flame produced
by the oil in the wick of a stove or a lamp
without forming any smoke.
❑ the greater the smoke point, the better the
burning quality
Specifications
Pour Point
❑ lowest temperature at which a fuel oil can be
stored and is still capable to flow under very
weak forces

Cloud Point
❑ temperature at which heating oil begins to
become turbid at a defined cooling rate
because of the formation of small wax
crystals
Specifications
Char Point
❑ the coke and ash left on the wick after
complete burning of the oil

Bloom Formation

❑ the darkness produced by the flame of

the oil while burning in a standard glass
Specifications
Sulfur Content
❑ usually limited by national legislations
❑ produces oxides (when burned) that
contaminate surroundings
❑ promotes corrosion
❑ corrosion test used: copper strip corrosion
method
Additional Requirements for Jet Fuel
remain fluid at
burn cleanly low
temperatures

free from
free from wax
suspended
particles
water particles
Types of Jet Fuel
Type Description
Jet-A Narrow cut kerosene product
Standard commercial and general jet fuel in the US
Contains no additives, except anti-icing chemicals
Jet-A1 Identical to Jet A, except freezing point
Used outside the US, especially for long-haul flights
Contains static dissipater additive
Jet-B Wide cut kerosene with lighter gasoline type naphtha
Used widely in Canada
Contains static dissipater additive
Has a very low flash point
JP-4 Military designation for fuel like Jet-B
Contains full additive package
Jet Fuel Additives
• Oxidation Inhibitors
• Metal Deactivators
• Corrosion Inhibitors and Lubricity Improvers
• Static Dissipater
• Anti-Icing
• Biocides
• Thermal Stability