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Chemical Engineering-2013
RE-REFINING OF USED LUBRICATING OIL
Chemical Engineering-2013
RE-REFINING OF USED LUBRICATING OIL
ABSTRACT
Used oil – as its name implies – is any petroleum -based or synthetic oil that has been used.
During normal use, impurities such as dirt, metal scrapings, water or chemicals can get mixed
in with the oil or be generated in it due to thermal degradation or oxidation. Therefore, the oil
quality gradually decreases to a level that the used oil should be replaced by a new one.
Disposing the used oil off in nature creates an intense dangerous pollution. But by proper
recovery and refinement of it, a lot of valuable product can be obtained. This article studies
one of the best methods of used oil re-refining and compares its product specifications with
those of a virgin base oil.
The re-refiner's job is to remove all the contaminants and restore the oil to its original
condition. The important point to note is that the technology used by Dominion Oil
is virtually identical to that used to refine crude petroleum, the difference being that the level
of contamination in used oil is much lower that that in crude oil. Used oil is uplifted from
centralized collection points at places such as service stations, workshops, recycling depots
and factory sites. The oil is burned at temperatures of approximately 1400oC, ensuring
complete combustion. At this temperature dioxins are not formed as they may be at lower
temperatures. This method has been endorsed by the Department of the Environment as the
preferred alternative to re-refining.
Chemical Engineering-2013
RE-REFINING OF USED LUBRICATING OIL
ACKNOWLEDGMENTS
We are also thankful to Prof. Dr. Bhatkhande sir, Head of Chemical Engineering
Department for his valuable support.
Chemical Engineering-2013
RE-REFINING OF USED LUBRICATING OIL
NOVEMBER-2013
CERTIFICATE
It is certified that the project work entitled
Submitted by
is the original work carried out by them under the supervision of Prof. A. K. Vaddi and is
approved for the partial fulfilment of the requirement of University of Pune, Pune for the
award of the Degree of Bachelor of Engineering (Chemical)
This Project Work has not been earlier submitted to any other Institute or University for the
award of any degree or diploma.
Chemical Engineering-2013
RE-REFINING OF USED LUBRICATING OIL
TABLE OF CONTENTS
ABSTRACT
ACKNOWLEDGEMENT
CERTIFICATE
Chapter 1 INTRODUCTION
Importance
Oil chemistry
Properties
Theory
Dehydration
Vacuum distillation
Lube oil Distillation and Condensation
Chapter 9 CONCLUSION
REFERENCES
Chemical Engineering-2013
RE-REFINING OF USED LUBRICATING OIL
INTRODUCTION
Lubricating oil is an important resource. One of the more valuable lubricating oils is the
motor oil used in passenger cars, vans, and trucks. Every year, privately owned
automobiles and light trucks in the U.S. generate over 300 million gallons of used
crankcase oil.
In addition to the environmental problems, improper used oil disposal is simply a waste
of a valuable resource. Every gallon of used motor oil not recovered results in the need to
drill for more oil and in some cases it results in increases in oil import. Today, however, most
of the crude petroleum produced throughout the world contains very little of the special
hydrocarbon chains necessary for motor oil. As a result, refining crude petroleum to
produce virgin lube oil is an elaborate, complex, and expensive process that requires
nearly three times as much energy as rerefining used oil.
Lube base oil is one of the most valuable components in a barrel of crude oil. While many
components of crude oil such as gasoline, jet and diesel fuels are „lost‟ after combustion, lube
base oil can be recovered and „regenerated‟ to the quality equal to or better than its original
virgin form.
The re-refiner's job is to remove all the aforementioned contaminants and restore the oil to its
original condition. The important point to note is that the technology used by Dominion Oil
is virtually identical to that used to refine crude petroleum, the difference being that the level
of contamination in used oil is much lower that that in crude oil.
Chemical Engineering-2013
RE-REFINING OF USED LUBRICATING OIL
OIL CHEMISTRY
Petroleum products are essentially composed of hydrocarbons, i.e. compounds containing
exclusively carbon and hydrogen. The simplest hydrocarbon molecule is methane, CH4.
This basic molecule is the main constituent of natural gas. It can be extended with the
addition of more carbon and hydrogen atoms, usually forming into longer chains. Four
carbon atoms in a chain forms butane, one of the main constituents of LPG. The atoms may
also form side chains off the main chain, or form into ring structures such as the benzene
ring. Lubricating oils are just extensions of these basic hydrocarbon structures, containing
from 20 to 70 carbon atoms per molecule, often in an extremely complex arrangement of
straight chains, side chains and five and six membered ring structures
The lubricating oil molecules can be divided into three broad groupings:
Paraffinic: Predominantly straight chains, tend to be waxy, have a high pour point and
good viscosity/temperature stability.
Naphthenic: Straight chains with a high proportion of five and to a lesser extent six
membered ring structures. Tend to have a low pour point. For this reason
they are used as refrigeration oils. They are highly carcinogenic and are little
used in engine oil. Dominion Oil treats used refrigerator oils separately from
the main plant. As refrigerator oils do not come in contact with products of
combustion they are much cleaner than engine oils.
Chemical Engineering-2013
RE-REFINING OF USED LUBRICATING OIL
LUBE OIL
Motor oil or engine oil is an oil used for lubrication of various internal combustion engines.
The main function is to lubricate moving parts; it also cleans, inhibits corrosion, improves
sealing, and cools the engine by carrying heat away from moving parts.
Motor oils are derived from petroleum-based and non-petroleum-synthesized chemical
compounds. Motor oils today are mainly blended by using base oils composed
of hydrocarbons, polyalphaolefins (PAO), and polyinternal olefins] (PIO), thus organic
compounds consisting entirely of carbon and hydrogen. The base oils of some high-
performance motor oils however contain up to 20% by weight of esters
Motor oil is a lubricant used in internal combustion engines. These include motor or road
vehicles such as cars and motorcycles, heavier vehicles such as buses and commercial
vehicles, non-road vehicles such as go-karts, snowmobiles, boats (fixed engine installations
and outboards), lawn mowers, large agricultural and construction equipment, locomotives
and aircraft and static engines such as electrical generators. In engines, there are parts which
move against each other causing friction which wastes otherwise useful power by converting
the energy to heat. Contact between moving surfaces also wears away those parts, which
could lead to lower efficiency and degradation of the engine. This increases fuel
consumption, decreases power output and can lead to engine failure.
Lubricating oil creates a separating film between surfaces of adjacent moving parts to
minimize direct contact between them, decreasing heat caused by friction and reducing wear,
thus protecting the engine. In use, motor oil transfers heat through convection as it flows
through the engine by means of air flow over the surface of the oil pan, an oil cooler and
through the build up of oil gases evacuated by the Positive Crankcase Ventilation (PCV)
system.
In petrol (gasoline) engines, the top piston ring can expose the motor oil to temperatures of
160 °C (320 °F). In diesel engines the top ring can expose the oil to temperatures over 315 °C
(600 °F). Motor oils with higher viscosity indices thin less at these higher temperatures.
Coating metal parts with oil also keeps them from being exposed to oxygen,
inhibiting oxidation elevated operating temperatures preventing rust or corrosion. Corrosion
inhibitors may also be added to the motor oil. Many motor oils also
have detergents and dispersants added to help keep the engine clean and minimize oil
sludge build-up. The oil is able to trap soot from combustion in itself, rather than leaving it
deposited on the internal surfaces. It is a combination of this, and some singeing that turns
used oil black after some running.
Rubbing of metal engine parts inevitably produces some microscopic metallic particles from
the wearing of the surfaces. Such particles could circulate in the oil and grind against moving
parts, causing wear. Because particles accumulate in the oil, it is typically circulated through
an oil filter to remove harmful particles. An oil pump, a vane or gear pump powered by the
engine, pumps the oil throughout the engine, including the oil filter. Oil filters can be a full
flow or bypass type.
Chemical Engineering-2013
RE-REFINING OF USED LUBRICATING OIL
Most motor oils are made from a heavier, thicker petroleum hydrocarbon base stock derived
from crude oil, with additives to improve certain properties. The bulk of a typical motor oil
consists of hydrocarbons with between 18 and 34 carbon atoms per molecule. One of the
most important properties of motor oil in maintaining a lubricating film between moving
parts is its viscosity. The viscosity of a liquid can be thought of as its "thickness" or a
measure of its resistance to flow. The viscosity must be high enough to maintain a lubricating
film, but low enough that the oil can flow around the engine parts under all conditions. The
viscosity index is a measure of how much the oil's viscosity changes as temperature changes.
A higher viscosity index indicates the viscosity changes less with temperature than a lower
viscosity index.
Motor oil must be able to flow adequately at the lowest temperature it is expected to
experience in order to minimize metal to metal contact between moving parts upon starting
up the engine. The pour point defined first this property of motor oil, as defined by ASTM
D97 as "... an index of the lowest temperature of its utility ..." for a given application, but the
"cold cranking simulator" and "Mini-Rotary Viscometer" are today the properties required
in motor oil specs and define the SAE classifications.
Chemical Engineering-2013
RE-REFINING OF USED LUBRICATING OIL
Used lube oil is defined as the petroleum derived or synthetic oil which remains after
applications in lubrications, cutting purposes, etc After a certain period of useful life, the
lubricating oil loses its properties and cannot be used as such in machinery. Build up of
temperature degrade the lubricating oil, thus leading to reduction in properties such as :
Viscosity, Specific gravity, etc Dirt and metal parts worn out from the surfaces are also
deposited into the lubricating oils. With increased time of uses, the lubricating loses its
lubricating properties as a result of over reduction of desired properties and thus must be
replaced with fresh one.
A lubricating oil becomes unfit for further use for two main reasons: accumulation of
contaminants in the oil and chemical changes in the oil. The main contaminants are listed
below.
Combustion products
Water: Fuel burns to CO2 and H2O. For every litre of fuel burnt, a litre of water is created.
This normally passes out through the exhaust when the engine is hot, but when cold it can run
down and collect in the oil. This leads to sludge formation and rust.
Soot and carbon :These make the oil go black. They form as the result of incomplete
combustion, especially during warm-up with a rich mixture.
Lead :Tetraethyl lead, which used to be used as an anti-knock agent in petrol, passes into the
oil. A typical used engine oil may have contained up to 2% lead, but today any lead comes
from bearing wear and is likely to be in the 2 - 12 ppm range.
Fuel: Unburnt gasoline or diesel can pass into the lubricant, again especially during start-up.
Abrasives
Road dust: This passes into the engine through the air-cleaner. Composed of small particles
of silicates. Wear metals. Iron, copper and aluminium released due to normal engine wear.
Chemical products
Oxidation products: Some of the oil molecules, at elevated temperatures, will oxidise to
form complex and corrosive organic acids.
Chemical Engineering-2013
RE-REFINING OF USED LUBRICATING OIL
Chemical Engineering-2013
RE-REFINING OF USED LUBRICATING OIL
The re-refiner's job is to remove all the aforementioned contaminants and restore the oil to its
original condition. The important point to note is that the technology used by Dominion Oil
is virtually identical to that used to refine crude petroleum, the difference being that the level
of contamination in used oil is much lower that that in crude oil. Used oil is uplifted from
centralised collection points at places such as service stations, workshops, recycling depots
and factory sites. The collector is contracted to the Used Oil Monitoring Group, whose
members include BP, Dominion Oil Refining, Caltex, Castrol, Shell, Milburn Cement and the
Department of the Environment. Milburn Cement administer the Group, whilst the
Department of the Environment represent the Government. Milburn Cement also combust
any used oil that cannot be recycled, using it as an alternative to coal. The oil is burned at
temperatures of approximately 1400oC, ensuring complete combustion. At this temperature
dioxins are not formed as they may be at lower temperatures. This method has been endorsed
by the Department of the Environment as the preferred alternative to re-refining.
Step 1 - Dehydration
The oil is stored to allow water and solids to separate out from the oil, then the oil is heated
to 120oC in a closed vessel to boil off any emulsified water and some of the fuel diluents.
1. Light fuel and diesel: Dominion Oil produces enough diesel from the used oil
feedstock to run all the burners and boilers, giving total self-sufficiency in fuel.
2. Lubricating oi: The bulk of the feedstock will distill off in the plant to produce a
lubricating oil fraction.
3. Residue: The non-distillable part of the feedstock. This contains all the carbon, wear
metals, degraded additives and most of the lead and oxidation products. This residue
is successfully used as bitumen extender for roading.
Chemical Engineering-2013
RE-REFINING OF USED LUBRICATING OIL
PROCESS DISCRIPTION
STEP-1: DEHYDRATION
The oil is stored to allow water and solids to separate out from the oil, then the oil is heated
to 120oC in a closed vessel to boil off any emulsified water and some of the fuel diluents.
The point at which an oil contains the maximum amount of dissolved water is termed the
saturation point. The saturation point is dependent on the oil‟s temperature, age and additive
composition. The higher the temperature, the higher the saturation point and hence more
water held in solution, in the dissolved phase. This is the same as being able to dissolve more
sugar in hot water, than in cold water. Similarly, the older the oil, the higher the level of
water that can be dissolved. This is due to polar by-products of oxidation in the oil, which act
as “hooks” holding on to the water molecules and keeping them in solution. Likewise, highly
additized oils, like crankcase oils, have a higher saturation point than lightly additized oils
like turbine oils, because the additives - many of which are polar - also hold the water in
solution.
Water can also affect the additive package through water washing and hydrolysis, leading to
acids and additive depletion. Water encourages rust and corrosion and will cause increased
wear as a result of aeration, changes in viscosity resulting in film strength failure, hydrogen
blistering and embrittlement, and vaporous cavitation. Finally, water is a generator of other
contaminants in the oil such as waxes, suspensions, carbon and oxide insolubles and even
micro-organisms.
Chemical Engineering-2013
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The dehydrated oil is then fed continuously into a vacuum distillation plant for fractionation
in exactly the same fashion as crude petroleum. The fractions obtained are as follows:
1. Light fuel and diesel: Dominion Oil produces enough diesel from the used oil
feedstock to run all the burners and boilers, giving total self-sufficiency in fuel.
2. Lubricating oil: The bulk of the feedstock will distill off in the plant to produce a
lubricating oil fraction.
3. Residue: The non-distillable part of the feedstock. This contains all the carbon, wear
metals, degraded additives and most of the lead and oxidation products. This residue is
successfully used as bitumen extender for roading.
The lubricating oil fractions are then passed through an extraction tower in the presence of
Nmethylpyrolidone (NMP). The NMP is an aromatic selective solvent which, in addition to
removing some colour and odour, is able to extract all unwanted aromatic contaminants
present in the paraffinic lubricating oil fraction, subsequent to fractional distillation. This is
important as polycyclic aromatics are very carcinogenic. This process is commonly used in
virgin oil refineries, but Dominion Oil Refining is the only manufacturer of re-refined oil to
use it.
Chemical Engineering-2013
RE-REFINING OF USED LUBRICATING OIL
Environmental Issues
Oil in any form is potentially harmful to the environment. Post-studies of oil spills indicate
that it takes up to twenty years for an aquatic environment to return to a healthy condition.
Once oil has been used by industry or the DIY, it has even more potential for environmental
damage. In aquatic communities oil residue tends to settle on the bottom, coating the
substrate and whatever organisms live there. When poured on the ground, oil can rapidly
migrate through the soil. In both instances, bacteria, plants, invertebrates, and vertebrates
experience physiological stress. Oil film on water can reduce the penetration of light into the
water and, consequently, reduce the rate of photosynthesis. When photosynthesis is reduced,
oxygen production is also reduced. The oil film may also inhibit the movement of oxygen
from the air through the surface of the water. The reduction of dissolved oxygen in the water
stresses animals living in the water. Oil can clog respiratory (breathing) mechanisms and
even be incorporated into the tissues of these organisms. These substances in the tissues of
the organisms make them unfit for human consumption and, therefore, contribute to
economic loss. If the contaminants are not incorporated into a human food source, they may
be passed along the food chain, thereby contributing to environmental degradation.
Some of the substances found in both virgin crude and refined oil can affect the nervous
systems of living things. This reduces their ability to find food or reproduce.
Some of the oil components (on the light end) evaporate into the air and/or dissolve into the
water. Many of these light end compounds are known carcinogens and/or mutagens.
Microscopically, oil compounds impinge on algae, bacteria, and plankton, the basis of the
aquatic food chain. Larger organisms such as mammals and birds are the most dramatic
victims of oil pollution because of their visibility and emotional appeal to humans. Feathers
and fur become coated with oil and lose their ability to control body temperature. Death
results from exposure or ingestion of the oil compounds via grooming.
In ground, oil can rapidly percolate through the soil particles and create similar problems for
soil microbes and macroscopic invertebrates. Eventually this oil may make its way into
thewater table or into a water body such as a lake.
Used oil is a valuable resource. One definition for pollution is a resource out of place, and
used oil certainly fits that description. The potential impact on our environment depends on
how we manage this resource to make sure it is not out of place. To summarize, pollution can
be defined as a resource in the wrong place or one that has not been completely used.
Improper disposal of used oil is a source of significant pollution. The potential impact on our
water and environment is serious. Of all petroleum related pollution in the U.S. including oil
spills in coastal waterways, 62% is estimated to be runoff of used lubricating oil, much of
which eventually works its way to the ocean environment.
The energy saved by collecting and recycling used motor oil can help reduce our dependence
on foreign oil imports. Although current crude oil prices have dropped in recent years,
valuable energy reserves can be conserved by the use of fuel oil made from reclaimed motor
oil. One gallon of used oil can be re-refined into 2-1/2 quarts of quality lubricating oil. In
contrast, 42 gallons of crude oil must be refined to produce the same 2-1/2 quart volume
(though many other products are derived from the 42 gallons of crude). In fact, recycling
used oil could reduce petroleum imports by 25.5 million barrels of oil per year, saving 1.3
million barrels of oil per day or half the annual production of the Alaskan pipeline.
Chemical Engineering-2013
RE-REFINING OF USED LUBRICATING OIL
Chemical Engineering-2013
RE-REFINING OF USED LUBRICATING OIL
CALCULATIONS
COMPARISON OF PROPERTIES
Material balance
FEEDSTOCK ML
PRODUCTS
TOTAL 200
Chemical Engineering-2013
RE-REFINING OF USED LUBRICATING OIL
CONCLUSION
1) Used oil is pollutant and by re-refining, the pollution is reduced. Hence it should get a
status of eco-friendly technology and get grants and incentives from the ministry of
enviourment.
2) The quality of thoroughly re-refined oil is comparable with nascent base oil. Hence it
should be evaluation awarded import-substitute status.
3) While making fresh lubricating oils blending with 5-10% of re-refined base oils
should be done for viscosity correction.
4) All such blended oils should be stamped with green lable to make the public aware
about the concept of re-refining.
5) The eco-conscious customer would buy the product with green labels.
Chemical Engineering-2013
RE-REFINING OF USED LUBRICATING OIL
REFERENCES
1) "Used Oil. A Renewable Resource and an Environmental Pollutant" by David
Layzell,
2) L.M. Magnabosco and W.A. Rondeau, "Improved Process forthe Production of Base
Stock Oils from Used Oil.
,
3) Frankl, P., Fullana, P., Baitz, M., 2005, Europe Life Cycle Considerations on
Waste Oils and Implications.
5)Hunter, B. Scott. “Disposing of Used Motor Oil: A Slippery Issue.” Delaware Valley
Energy Report, Volume 8, Number 1, Winter 1991/92.
Chemical Engineering-2013