AT 2305 – Automotive Fuels & Lubricants

Unit I

Introduction to Automotive Fuels:

Automobile: Suitable Engine Classification

IC Engines (A type of Heat Engine)

Heat Engine: Heat Energy Mechanical Energy

Fuel Chemical Energy

Types of Fuels

1. Solid fuels – coal, biomass etc.

2. Liquid fuels – petrol, diesel, methanol, ethanol, biodiesel etc
3. Gaseous fuels – LPG, CNG, methane etc.

1. Liquid and gaseous fuels are widely being used in IC engines.

2. Solid fuel can also be used in IC engines after suitable modifications like
gasification, slurry production.

Chemical reactions are fast enough to release heat energy but the method
of preparing the mixture and its introduction into the engine depends mainly
upon the nature of the fuel. Hence the automotive fuels should have certain
physical, chemical and combustion properties.

1. High energy density – mass basis or volume basis

2. Good combustion qualities
3. High thermal stability
4. Low deposit forming tendencies
5. Compatibility with the engine hardware
6. Good fire safety
7. Low toxicity
8. Low pollution
9. Easy transferability and onboard vehicle storage

The natural petroleum oil is the largest single source of almost all internal
combustion engine fuels.
Boiling range of petrol: 30 to 200 0C
Boiling range of diesel: 200 to 375 0C
 Other IC engine fuels are hydrocarbon mixtures, coal, oil shale and
fermentation products such as ethyl alcohol, methanol etc. Mixture of Carbon
monoxide and hydrogen if catalytically converted can form good automotive
engine fuel. But these processes are very costly and technical know-how is not
available.

Structure of Petroleum

Usually the fuels used in IC engines are complex mixtures of

hydrocarbons made by refining process. In addition, it may contain small
quantities of other compounds such as nitrogen, oxygen and sulphur. In some
petroleum, metallic compounds such as derivatives of vanadium, nickel, iron
and arsenic etc may also found.

Physical properties of the individual compound vary according to the

carbon and hydrogen atoms in the molecule. The physical differences even in the
group influence the way in which the fuel evaporates and hence the formation of
combustible mixture. The chemical differences between the hydrocarbon types,
which depend on the chemical composition and hence on the crude source and
the nature of refining process, affect mainly the combustion processes and hence
the proportions of fuel and air required.
Refining Process

The crude oil, as it comes out from the oil wells, contains impurities such
as water, solids and gases consisting mainly of ethane and methane. By simple
atmospheric pressure distillation, utilizing the fact that the boiling points of
various hydrocarbons increase with an increase in molecular weight, the crude
oil I separated into gasoline, kerosene, fuel oil or reduced crude oil.
First of all the lightest fractions such butane, propane, ethane etc., which
were either standing above the liquid in earth or dissolved in the crude, are
obtained at low temperature and form natural gas. Then comes gasoline,
naphtha kerosene, and fuel and gas oils, in order of increasing molecular weight.
After distillation residue of paraffin wax or asphalt depending on the base of the
crude is left.
The gasoline demand is much more than that of other petroleum
products. This led to the development of refinery processes to convert unwanted
streams of crude into salable products and to upgrade quality of these streams.
i.e. to crack the larger molecules into smaller molecules having low boiling point
as in the gasoline range, and in processes to polymerize or alkylate small
molecules into larger molecules into larger molecules, both having boiling points
as in the gasoline range.
The main refinery processes of petroleum are as follows:
 Fig. Petroleum refining process

A) Thermal cracking
If large hydrocarbon molecules are heated to a high temperature
and pressure they decompose into smaller, lower boiling point molecules.
This process of thermal decomposition is called cracking. The more stable
molecules form cracked gasoline and the reactive ones polymerize,
forming cracked oil and petroleum coke. Gasoline is the primary final
product from the cracking plant.
Products of refining process

The important products of refining process are as follows.

Natural Gas:
Natural gas is found dissolved in petroleum or in huge amounts under
earth surface in oil and gas bearing areas. Natural gas is made up mainly of the
paraffinic compound methane, as small amount of propane, ethane, butane and
other light hydrocarbons plus some nitrogen and oxygen.

Liquified Petroleum Gas, LPG:

Propane and butane and some other light hydrocarbons after separation
from natural gas, if stored under pressure, from liquid and this is called Liquified
Petroleum Gas (LPG). LPG is supplied in containers under pressure.

Gasoline:
Gasoline is the lightest liquid petroleum fraction. All material boiling up
to 200 0 C is generally considered as gasoline. This is mixture of a number of
hydrocarbons (more than 40). The composition depends upon the crude oil and
refining process. Gasoline lies in specific gravity range 0.70 to 0.78. This covers
most of the fuels used for spark-ignition engines.

Kerosene:
The kerosene is a fraction heavier than gasoline. Its boiling range is 150 to
300 C and the specific gravity range is 0.78 to 0.85. Kerosenes are used in
0

aviation gas turbines, as jet fuel and in lamps and stoves.

Distillate:
The distillate is slightly heavier than kerosene. These are used as tractor
fuels and domestic fuels.

Diesel Oils:
Diesel oils are fuels which lie between kerosene and lubricating oils. These
cover a wide range of specific gravity and boiling point. Boiling range is 200 to
370 0 C. These form the fuels for compression ignition engines.

Fuel Oils:
Fuel oils are similar to diesel fuel in specific gravity and distillation range
but their composition varies in a range wider than those of diesel fuels. These are
used as industrial fuels.

Lubricating Oils:
Lubricating oils are made up of heavy distillate of petroleum and residual
oil. These are used for lubricating purposes.

Tar and Asphalt:

Tar and asphalt are solid or semi-solid undistilled products of petroleum.

Petroleum Coke:
Petroleum coke is used as solid industrial fuel.
Lubricating Oil Base Stocks

Base oil, also called base stock, is the name given to the main liquid
component (or components) of a lubricant. Base oils may be mineral oil based
(mineral refers to the fact it was extracted from rocks in the form of crude oil),
vegetable, or synthetic in origin. Synthetics may be petroleum-based or chemical-
based. The base stock provides the basic lubricating requirements of a lubricant
i.e. the "oiliness". In most modern lubricants, a base oil mixture alone is
insufficient to deliver the technical performance characteristics required.
Therefore, the base oils are mixed with a variety of different additives, each
chosen to impart additional performance benefits to the finished oil.

There are two types of conventional mineral base oil – naphthenic and
paraffinic – depending on the composition of the crude oil from which they are
produced. All oils are composed of various ratios of these types of oil.

Fig. Base Oil Chemical Composition

Paraffinic base oils have higher viscosity index (generally >95) and a high pour
point. They are produced from feed stocks rich in paraffins, and are used for
lubricants for which VI and oxidation stability are important. Paraffinic base oils
are not very good at dissolving additives and they do not emulsify easily.
Because of their structure - long chains - they have high film strength and
excellent lubricating properties. That is why paraffinics are used as the base fluid
in engine oils, hydraulics and industrial lubes.

Naphthenic base oils have low viscosity index (VI) (generally 0-40) and a low
pour point. They are produced from feed stocks rich in naphthenes and low in
wax content. They are used mainly for lubricants in which color and color
stability are important, and VI and oxidation stability are of secondary
importance. Naphthenic oils also have a greater propensity to solublize
additives. Their structure does not lend them to the film strength and lubricating
properties of the paraffinics but they are still good. They are therefore used
extensively in the formulation of oil-based metalworking fluids.

Each of these types of oil has several grades, according to its viscosity. The
American Petroleum Institute has developed a classification system for base oils
in order to facilitate engine oil interchange guidelines.

The five groups are:

Group I: base stocks contain less than 90 percent saturates and/or greater than
0.03 percent sulfur and have viscosity index greater than or equal to 80 and less
than 120.
Group II: base stocks contain greater than or equal to 90 percent saturates and
less than or equal to 0.03 percent sulfur and have viscosity index greater than or
equal to 80 and less than 120.
Group III: base stocks contain greater than or equal to 90 percent saturates and
less than or equal to 0.03 percent sulfur and have viscosity index greater than or
equal to 120.
Group IV: base stocks are polyalphaolefins (PAO).
Group V: base stocks include all other base stocks not included in groups I, II, III
or IV. Naphthenic oils are considered Group V.

Fig. API Base Oil Classification System

Group II base oils are differentiated from Group I base oils because they
contain significantly lower levels of impurities. They also look different. Group II
and Group III oils made using modern hydroisomerization technology are so
pure that they have almost no color at all. From a performance standpoint,
improved purity means that the base oil and the additives in the finished
product can last much longer. Some refiners sell intermediate grades labeled as
Group 1+ or Group II +.

Historically, PAOs have had superior lubricating performance

characteristics such as VI, pour point, volatility, and oxidation stability that could
not be achieved with conventional mineral oils. Now, in modern base oil
manufacturing, VI, pour point, volatility, and oxidation stability can be
independently controlled. Modern Group III oils today can be designed and
manufactured so that their performance closely matches PAOs in most
commercially significant finished lube applications. From a processing
standpoint, modern Group III base oils are manufactured by essentially the same
processing route as modern Group II base oils. Higher VI Is achieved by
increasing the temperature or time in the hydro cracker.

Base Oil Properties

Certain properties are very important in determining the usefulness and

application for a particular base oil:

Viscosity - The viscosity of an oil is a measure of its resistance to flow, and

depends on the temperature at which the measurement is made. It has high
values at low temperatures, and low values at high temperatures. A viscosity
measurement has no value unless it is associated with a temperature. In the past,
viscosity was expressed in Engler (Europe), Redwood (UK) and Saybolt (USA).
Nowadays, centistoke (kinematic viscosity) and centipoise (dynamic viscosity)
are commonly used units.

Viscosity index - As viscosity depends on temperature, a measure of its

sensitivity to temperature is expressed by its viscosity index (VI) value. VI is
determined by comparing the change of viscosity with temperature to two
reference oils – one of which changes very little with temperature and is given a
VI = 100, and another which changes a lot and is given a VI = 0.

Oxidation stability - Most oils, when exposed to air over time, react with
oxygen. The Turbine Oil Stability Test (TOST) and the resulting TOST life are
measures of the oxidation stability, i.e. how much it degrades in the presence of
air. Oils used to blend lubricants must have high oxidation stability; otherwise,
they become discolored during storage. When base oils with poor oxidation
stability are used in engines, the high temperature causes them to form corrosive
acids and insoluble sludge. This can hamper the engine's performance by
forming a hard layer in the grooves of the piston rings.

Aniline Point - Aniline point is defined as the minimum temperature at which

equal volumes of anhydrous aniline and oil mix together. Its main use is
determining the quality of fuels. Since aniline is an aromatic compound, it freely
mixes with other aromatics so a low aniline point indicates low diesel index
(because of high percentage of aromatics). High aniline point indicates that the
fuel is highly paraffinic and hence has a high diesel index and very good ignition
quality. In case of aromatics the aniline point is low and the ignition quality is
poor.
In the metalworking industry, the aniline point is useful in determining the
solvency power of your base oil. The lower the aniline point, the better the base
oil will be at solublizing and holding onto additives and emulsifiers.

Pour point and cloud point - The cloud point of an oil is the temperature at
which the first trace of wax starts to separate out, causing it to become turbid or
cloudy. If the temperature is reduced further, more wax will crystallize out until
a point is reached when the oil and wax crystallize together as a whole, and will
not flow when poured. The temperature at which this just happens is the pour
point of the oil. Oils used for lubricants must have a low pour point so that in
areas where the temperature is very low, they remain as fluids. A low cloud
point ensures that they remain clear and bright in such areas.

Flash point - The flash point of oil is the temperature at which its vapor ignites
when exposed to a flame. A minimum flash point is normally specified for safety
reasons.

What is a lubricant?

A lubricant is made from base oil and additives. The quality of a lubricant,
therefore, depends on the quality of the base oil and additives used in the
formulation. Additives, although used in relatively small quantities, play a very
important role in the performance and composition of the lubricants. Many types
of additives are used including:

1. Pour-point depressants to decrease the pour point of the oil.

2. VI improvers to increase the viscosity index, i.e. to reduce the viscosity at low
temperatures
3. Anti-wear additives to decrease the engine/unit wear
4. Anti-oxidants to extend lubricant life by reducing degradation by oxygen from
the air
5. Corrosion inhibitors and detergents to prevent the corrosion of various metals

6. Ash less dispersants to keep particles or deposits in suspension

7. Extreme-pressure load-carrying additives for gear oils
8. Various other additives such as anti-foams and friction modifiers
Why are additives used in lubricating oil?

Additives are used in lubricating oil to change, alter, or enhance its

properties. Base oil as such cannot be used in most of the present-day lubricating
applications. Their properties - like resistance to heat, oxygen, wear etc - have to
be increased. This improvement is done with the use of these additives. To
increase the resistance to oxidation, we add antioxidants; to increase resistance to
wear, we add anti-wear additives, etc.

Lubricating Oil Refining Process

Lubricant base oil processes

Vacuum distillation unit

The first step in the processing of lubricating oils is separation in the

distillation units of the individual fractions according to viscosity and boiling
range specifications. The heavier lube oil raw stocks are included in the vacuum
fractionating tower bottoms with asphaltenes, resins and other undesirable
materials. The raw lube oil fractions from most crude oils contain components
which have undesirable characteristics for finished lubricating oils. These must
be removed or reconstituted by processes such as extraction, crystallization,
hydro cracking and hydrogenation. Vacuum distillation separates raw lube oil
into two or three streams with increasing viscosity. The heavier stream is derived
by removing asphalt from the residue in a de-asphalting unit. The lighter feed
stocks are sent directly to a solvent extraction. This first stage determines the
final base oil viscosity grades. The further process sequence is usually in the
order of deasphalting, solvent extraction, dewaxing and finishing.

De-asphalting

Propane is usually used as the solvent in de-asphalting but it may also be

used with ethane or butane in order to obtain the desired solvent properties.
Propane has unusual solvent properties in temperatures from 40°C (104°F) to
60°C (140°F). Paraffins are very soluble in propane but the solubility decreases
with an increase in temperature until at the critical temperature of propane
(96.8°C/206.2°F) all hydrocarbons become insoluble. In the range of 40°C (104°F)
to 96.8°C (206°F) the higher molecular weight asphaltenes and resins are largely
insoluble in propane. Separation by distillation is generally by molecular weight
of the components and solvent extraction by type of molecule structure.

Solvent extraction

There are three solvents used for the extraction of aromatics from lube oil
feedstock’s and the solvent recovery portions of the systems are different for
each. The solvents are furfural, phenol and N-methyl-2- pyrrolidione (NMP). The
purpose of solvent extraction is to improve the viscosity index (VI), oxidation
resistance, and colour of the lube oil base stock and to reduce the carbon- and
sludge-forming tendencies of the lubricants by separating the aromatic portion
from the naphthenic and paraffinic portion of the feed stock.

Furfural extraction

The process flow through the furfural extraction unit is similar to that of
the propane de-asphalting unit except for the solvent recovery section which is
more complex. The oil feedstock is introduced into a continuous countercurrent
extractor at a temperature which is a function of the viscosity of the feed; the
greater the viscosity the higher temperature is used.

Phenol extraction

The process flow for the phenol extraction unit is somewhat similar to that of the
furfural extraction unit but differs markedly in the solvent recovery section
because phenol is easier to recover than furfural.

NMP extraction

NMP extraction uses N-methyl-2- pyrrolidione as the solvent to remove the

condensed ring aromatics and polar components from the lubricating oil
distillate bright stocks. This process was developed as a replacement for phenol
extraction because of the safety, health, and environmental problems associated
with the use of phenol.

De-waxing

All lube oil stocks, except those from a relatively few highly naphthenic crude
oils, must be de-waxed or they will not flow properly at ambient temperatures.
Dewaxing is one of the most important and most difficult processes in
lubricating oil manufacture.

Hydro finishing

Hydro treating of de-waxed lube oil stocks is needed to remove chemically active
compounds that affect the color and color stability of lube oils.