TREAMENT OF LUBES

• The efficiency and life of machine increases by applying

lubrication as a thin film of oil between sliding surfaces.

• Lubrication disposes the heat developed in frictional movements.

• A lube oil must maintain fluidity and viscosity at the operating

conditions like temp. , load, shocks etc.

• The nature of the lube oil depends upon:

1. The source of oil (Base of crude)

2. Blending with other oils or additives.

 Lubes Compositions
• A raw lube oil (350oC) consist of the following compounds:
1. Paraffins - high viscosity index
2. Naphthenes
3. Aromatics (Poly, Condensed , Branched chains) - low
viscosity index
4. Waxes
5. Asphalts and resins
6. Inorganic constituents

• Paraffins in higher ranges are more branched and invariably

increase the pour point of oil thereby increasing fluidity, viscosity.
•Wax has very high pour point but undesirable although having
very high viscosity index.
 lubes Treatment Processes

• The following are the established process for improvement in

quality of lubes:
1. Sulfuric acid treatment
2. Clay treatment
3. Solvent refining
4. Hydro treatment
 Sulfuric acid treatment (SAT)

• SAT is used for stocks containing more inorganic.

• This treatment has disappeared because of inherent losses of
materials, no much improvement in viscosity index, sludge
disposal and tedious procedure.
 SAT - METHODOLOGY
1. Acid treatment is done with 93% if sulfuric acid at 60o C.
2. 2 Kg’s to 50 Kg’s of acid are required per barrel of stock treated.
3. Cylindrical lead lined tanks with conical bottoms are used.
4. Air is used for agitation.
5. Required temp. is attained by using steam coils placed in agitator.
6. Sludge from reactor is removed and oil is subjected with water for
washing till the pH is in neutral region.
7. Caustic neutralization is used for naphthenic stocks.
8. Naphthenic acids form sulfonates which decrease the formation of
sludge.
9. Color improves as asphaltenes, resins and unsaturated compounds get
depleted in treating process.
10. SAT is used for specialty oils like transformer oils, medicinal and
white oils ( not worried about materials losses)
11. Acid treatment is followed by clay treatment to avoid any
emulsification difficulties during caustic or water wash.
 Clay Treatment (CT)
• CT is one of the oldest methods.
• Mineral clays and synthetic adsorbents are used.
• Asphalts and resins are adsorbed on these clays.
• These clays adsorb asphalts( color contributors),sulfur compounds
& metallic bodies.
• Material loss is very much because of wetting the whole quantity
of clay and retention of some in pores.
• The materials adsorbed is governed by Freundlich equation, used
for decolorizing operations.

Where, X= units of impurities adsorbed, M = quantity of

adsorbent, C = concentration of impurities. , a & n = constants.
 CT - METHODOLOGY

• CT is conducted in two ways:

1. Contact filtration
2. Percolation filtration

• After treatment the clays are regenerated by

burning(controlled oxidations) carbon deposits. Residues
upto 6% are left out even at temp(500-600oC) of
regenerations.
• OIL to adsorbent ratio is critical in CT.
 Continuous Contact Filtrations

1) Heat exchanger
2) Mixer
3) Heater
4) Contact tower
5) Filters
6) Stripper(flash tower)
• In CCF finely divided clay (-100 mesh ) is thoroughly mixed with
stock and allowed to stay in a tower to complete the
reaction(adsorption).
• Resultant slurry is filtered in filters.
• Addition of diluents or elevation in temperature are carried out to
resist the choking of the lines and filtration equipment because of
heavy oils which are viscous and tends to settle.
• Addition of sulfuric acid is desirable to keep the activity of the
clay.
 Percolation Technique
• Percolation is simple and single step.
• The oil is allowed to flow through a bed of clay.
• Treatment of viscous oils is also possible by diluting with naphtha's and
then percolating.
• The nature of the adsorbent get spoiled because of fluctuations in
temperature arising from oxidation of carbonaceous materials on clay.
Which is overcome using Thermofor kilns(TK).
• TK are used for activating these spent clays.
• In to, the spent clays are heated by means of molten salts under
circulation in tubes at 500 to 600oC which does not comes in contact
with fire directly.
• As the spent catalyst moves from top of kiln via. Baffles it comes in
contact with hot tubes which ensures the burning of coke particles
without fusing surface pores.
 Solvent Treatment (CT)

• Solvent treatment is an multifunctional

designs.
• Viscosity index improvement, deasphalting &
dewaxing etc. are some major applications of
ST.
 Viscosity index improvement
• Furfural, phenol, mixtures of cresols and propane are
widely used for solvent extraction which increase the
viscosity to max. levels.
• General characteristics of solvent for good extraction
are as follows:
1. high electro negativity of the hetero atom.
2. High dipole moment.
3. Presence of atoms of O,N,S with activity to form hydrogen
bonds.
4. Increase selectivity.
5. Free rotatability of the molecules
6. Accumulation of selectively acting groups.
 Selection of solvent

• Solvent selection is based upon the following

criterion.
1. Solubility
2. Adoptability to various feeds
3. Ease of recovery
4. High density
5. Less corrosiveness and good stability in presence of
moisture
6. Low viscosity, less cost, less toxicity
7. Low interfacial tension
8. Low freezing point and less latent heat.
 Phenol and Furfural as solvents
• Furfural extraction may require a higher temperature of
extraction and more number of stages.
• Yield of raffinate is more with phenol.
• Phenol treated lubes have better oxidation stability.
• VI. Improving may be same in both cases.
• Phenol is more adoptable to different stocks and is unavoidable
when naphthenic acids are more.
• The selectivity of phenol increases with water ( upto 10%).
• Furfural is unstable, hence requires nitrogen seals during storage
and recovery.
• Losses can be negligible with phenol.
• Residual solvent in treated stocks is not harmful; provided the
solvent is phenol.
 Phenol Extraction(PE) of lubes
• Plate or packed bed extractors are used for PE.
• PE can’t be carried out < 50oC, as it has high melting point(40oC).
• Addition of Water upto 10% is approved.(forming anhydrous phenol)
• Operating Temp: 60 to 100oC.
• Solvent to feed ratio of 1.5 to 2.5 for processing paraffinic and naphthenic
stocks.
• An increase of viscosity index (V.I) by 25 to 50 units is confirmed.
• Phenol treated oils possess good oxidation stability with less sludge forming
and carbon depositing tendencies.
• No of stages for PE- Max 4 or 3.
• Barauni Refiner and Bharat Refiner (Bombay) are practicing this process
 PE - METHODOLOGY

80-100OC

1) Exchangers
2) Absorbers
3) Extraction unit
4) Separator
5) Fractionators
6) Stripper
7) Separation unit
 Furfural Extraction
• Furfural extraction uses rotating disc contactor.
• Haldia, Cochin, Madras refineries, Mathura refineries are
using FE.
• Operating Temp. 75 to 125oC.
• No of stages are more compared to PE., for the same V.I.
• FE is applied to extract:
a) Lubes
b) Gas oils
c) Catalytic cycle oils special application like butadiene
extraction.
d) Removal of low cetane index components from diesels.
FE - METHODOLOGY
 Duo-Sol (Selecto)

• In Duo-sol two solvents are simultaneously

employed.
• Solvents used in this process are propane and
selecto or cresylic acids.
• Propane - extensively dissolves paraffinic groups,
While other solvents are good for naphthenic
groups.
• The extractor has horizontal with separate mixing
and settling zones.
• This different zones cause a perfect counter
current extraction.
Duo-Sol (Selecto)- Methodology
WAX AND PURIFICATION
• All heavy fractions of crude oils contains some amount of waxy materials, referred

as paraffin wax (Paraffin + other components).

• n-paraffins are largely present along with little naphthenes.

• All waxy materials consists of 20 to 30 or more C-atoms.

• Due to high molecular weight paraffins ( more branched chains), contributes to

different structural appearances ranging from crystalline to colloidal form to wax.

• Wax (Paraffin wax) undergoes stripping and bleaching operation to give a shiny

white look.

• Different form of paraffin wax:

– Micro crystalline

– Plate forms (Crystalline form)

– Needle forms
Important properties of wax
a) Specific gravity
b) Melting point
c) Viscosity
d) Colour
e) Penetration index
• Melting point (MP) of commercial waxes is 50oC

• Compounds having less then 50oC MP are called Cerols.

• Microcrystalline (MC) waxes are produced from tank bottoms or
form residuum's.
• Needle crystals are pure form of wax and are obtained by urea
adduction (Only n-paraffins).
Characteristic of waxes
• Specific gravity of waxes increases with increase in MP.
• Refractive index and MP are true characteristic properties used to distinguish
between MC and other forms.
• Paraffinic waxed lies near to the straight line when plotted with MP and
refractive index of waxes, away are MC.
• Viscosity of MC is high owing to high MP.
• MC has higher molecular weight of the order 580-700 where as mal or needle
crystals have 325-500.
• MC has affinity for oils, usually 40 to 70% oils is contained in waxes and are
know as Petrolatums.
• Commercial waxes are classified on the basis of penetration index and MP,
higher the PI higher the MP, and vice versa.
Dewaxing
• Dewaxing operation are classified into two types, one with the use of solvents
and other without solvents.
• Wax removal , based on the natural principle of decreasing solubility of wax in
oil at lower temperatures is commercially know as chilling and pressing.
Chilling and pressing
• This process is time consuming.
• The whole mass of was is kept in homogeneous phase by initially warming oil a
few degrees above it pour point.
• This mixture is cooled in agitators fitted with coils for circulating cold water or
refrigerant as per requirement.
• Cooling must be uniform and not more than 3oC per hour for good growth of
crystals.
• When heavy oils or residuums are chilled, the wax in it does not crystallize
easily due to its colloidal nature in that case diluents is added.
• Crystallisation of was is a slow process and is carried out for long time until the
final temperature of the mixture falls 10 to 15oC below the required pour point
of dewaxed oil.
Separation of wax
• Wax can be separated by using convenient filter or centrifuge.
• A filter press which can be operated upto 100 atmospheres pressure is
employed to force out the oil from the cake, still 50% oil is retained in cakes
which necessitates the use of centrifuge which decreases to 20% oil in cakes.
• Microcrystallines are not efficiently removed using the above said operation
which lead to contamination making the wax impure and is called as crude wax
or slack wax which is sent to sweating operations.
Sweating
• Sweating consists of gradual rise and maintenance of temperature, in large
shallow sweat pans.
• The sweat pans are shallow and have perforated plates at the bottom and are
covered with convenient size of screens if required.
• Diameters of sweat pans goes up to 3 meters and depth to half a meter.
• These pans are equipped with heating coils through which tepid water flows.
• Oil droplets released from the voids and interstices of wax collect in drips into
the trays kept beneath the pans.
Dewaxing and Sweating
Operations
 Dewaxing with solvents
• Commercial process for solvent Dewaxing
a) Barisol process (Ethylene dichloride and benzol solvents)
b) Ketone dewaxing ( Methyl ethyl ketone, methyl propyl ketone etc.)
c) Propane Dewaxing.

Barisol process
• Solvent mixture, constituting equal volumes of ethylene dichloride and benzol
is used for dewaxing.
• Wax being insoluble in this mixture precipitates out and floats permitting easy
filtration by a rotary continuous vacuum filter or aided by centrifuge.
• Chilling temperature are governed by pour point desired.
• Recovery of solvents from oil and cake is done by fractionation of these phases
separately.
• Barisol is flexible in treating different feed stocks ranging from long residuums
to waxy distillates.
Ketone Dewaxing
• This process is called MEK dewaxing which employs methyl ethyl ketone as a
solvent.
• Lower molecular weight ketones with low viscosity are preferred as they
contribute towards high filter rates and effective dewaxing.
• Ketones enhance the crystalisability of wax without dissolving oil.
• The precipitation of wax at low temperatures is directed by addition of suitable
hydrocarbon as the ketone shows lyophobic tendency.
MEK Dewaxing
 Propane Self Refrigeration Process
• Propane is available in abundance in all refineries.
• It has duel function of precipitation of wax and rejection of asphalt.
• It overcame the chilling difficulties offered by feed stocks by self evaporation
resulting in rapid rate of chilling, Recovery of solvent with ease and high purity.
Propane Dewaxing
 Dewaxing by Catalysts
• These are solid catalysts of Zeolite type.
• It’s a chemical process whereby wax is selectively cracked and hydrogenated
to yield HVT oils by addition of noble metals simultaneous structural changes.
• The structure of the zeolite is more porous and can selectively handle paraffins
but not ring structures. It decreases the pour point to greater extent.
• Catalyst can be altered by loading noble metals which can isomerizes the
structure.
• The pressure is usually maintained around 40 to 50 atm and the reactor is kept
at 400-500oC as there is hydrogen present in the reactor.
 Propane Deasphalting (PD)
• All the lube oils of naphthenic base requires PD.
• Propane acts as a solvent which exhibits unique capacity in separation
of asphalts and resins even from highly viscous stocks like residuums.
• Contacting of residuums and propane under a pressure of 15atm and at
a temp. of 30 to 70oC take place in the operation.
• Higher temp. increase the tendency of asphalt materials to separate out.
• Relatively large volumes of propane about eight to ten times the stock
are required. Thorough mixing and settling shall separate the asphalts.
• Propane rich phase contains all the oil, while asphalts are rejected by
propane and they collect as a heavy phase.
• The two phase are separately processed for solvent recovery.