Module 2_Lecture 4:

Product Treatment process

Department of Chemical Engineering, National Institute of Technology, Calicut

 Lubes Processing Flow Scheme

Department of Chemical Engineering, National Institute of Technology, Calicut

 Hydrofining

• Hydrofining, or hydrotreating, of lubes raffinate is done to remove sulphur and

nitrogen, and to improve the colour stability.

• The process and operating conditions are similar to those of a typical

hydrotreating unit.

• The hydrofined raffinate is fed downstream for further processing (paraffin

dewaxing).

Department of Chemical Engineering, National Institute of Technology, Calicut

 Dewaxing

• Wax- paraffin wax - all heavy fraction of crude oil contains at least some amount of
waxy materials.
• It can not be distilled as it boils in the range of lubricating oils.
• It contains mainly large MW n-paraffins and around 20 -25 carbon atoms
• Boiling point 32-100°C
• Forms: microcrystalline form, plate, and needle form
• Important property of wax:
• Pour point; penetration index
• Higher melting point higher penetration index
• Lower wax content: lower the pour point
• Dewaxing is done to lower the pour point.

Department of Chemical Engineering, National Institute of Technology, Calicut

 Dewaxing
• The hydrofined raffinate is dewaxed in order to achieve the required flow properties
(pour point).
• Typically, refrigeration is used to crystallise the paraffinic wax and solvent is added
to dilute the raffinate oil and permit separation of the wax by filtration.
• Chilled solvent is added to the raffinate and the long chain paraffins come out of
solution in the crystalliser. The cold slurry is then fed to rotary vacuum filters for
removal of the crystalline wax.
• Solvent is recovered from the filtrate and the wax by heating and flashing followed
by steam stripping.
• The dewaxed oil is now base stock ready for mixing with additives to produce a
range of lubricating oils.

Department of Chemical Engineering, National Institute of Technology, Calicut

 Dewaxing methods

1. Chilling and Pressing (without solvent) – Old Dewaxing method.

2. Solvent Dewaxing
3. Other Method: Urea Dewaxing

Department of Chemical Engineering, National Institute of Technology, Calicut

 Chilling and Pressing

• Dewaxing method is simple process but time consuming. Based on the

principle of decreases solubility of wax in cold settling process.
• Dilutant such as naphtha added to speed settling.
• Paraffins wax cannot be separated by settling, then certifying and
Filtration can be used.
• Cold pressing : T= -17 °C (O° F)
• For microcrystalline wax, cold pressing cannot be used because these
wax either pass through filter on may clog it.
• Lighter change-Pressing.
Heavier change-Settling.

Department of Chemical Engineering, National Institute of Technology, Calicut

 Solvent Dewaxing

• Solvent dewaxing - by utilizing a proper solvent which can remove wax from the
lube oil cut.
• This process involves : crystallization, filtration, and solvent recovery.
• In the crystallization step, solvent is added with the feedstock and the diluted
feed is chilled at a temperature where wax components are solidified.
• The solid wax is filtered to remove it from oil.
• The solvent in the oil is recovered by solvent recovery step using flash distillation
and stripping.
• The solvent is then recycled. The major solvent dewaxing process used in the
refinery is ketone dewaxing process.

Department of Chemical Engineering, National Institute of Technology, Calicut

 Solvent Dewaxing

The criteria for a good commercial dewaxing solvent are as following

• Sufficiently low boiling point to facilitate separation from the wax and dewaxed oil

• Low sensible and latent heat for economy in chilling and recovery.

• Completely Miscible with the oil at the temperature of filtration and incapable to

dissolve wax.

• Non corrosive to equipment and non toxic to avoid health hazards.

Department of Chemical Engineering, National Institute of Technology, Calicut

 Dewaxing methods

• Solvent Dewaxing
• Barisol process (Ethlyene chloride and benzol solvent)
• Ketone dewaxing (Methyl ethyl ketone)
• Propane dewaxing

• Aromatic components – benzene or Toluene maintains good oil solubility and

Dewaxing temperature.
• Ketone (MEK) – used to maintain wax solubility. It causes the wax to solidify in a
easy of filterable form without dissolve oil.
• Solvent concentration: Maximum solvent concentration required in order to
obtain highest filtration rate.

Department of Chemical Engineering, National Institute of Technology, Calicut

 Solvent Dewaxing

Department of Chemical Engineering, National Institute of Technology, Calicut

 MEK Dewaxing

• In India, most of dewaxing units, at present producing lube oil are based on MEK
dewaxing process while rest of the units are following either propane dewaxing
process or catalytic dewaxing process

• MEK dewaxing process is suitable for dewaxing the entire range of lube oil fraction
for the removal of waxy paraffinic hydrocarbon from the raffinate obtained from
solvent extraction unit.

• The dual solvent system, Methyl ethyl ketone (MEK) and toluene is used in the
proportion of 2:3. Each component of the solvent has a specific function. The
ketonic part (MEK) facilitates wax to crystallise while toluene increases capacity of
the solvent for dissolving oil.

Department of Chemical Engineering, National Institute of Technology, Calicut

 MEK Dewaxing

Department of Chemical Engineering, National Institute of Technology, Calicut

 MEK Dewaxing

Department of Chemical Engineering, National Institute of Technology, Calicut

 MEK Dewaxing

Chilling section:
• Waxy oil feed is mixed with solvent and heated to a temperature 35-45°C for
complete dissolution of the wax.

• The solvent and oil mixture is then chilled in stages to crystallize the wax.

• Chilling is accomplished in scraped surface double-pipe heat exchanger first by

exchange with cold product and then with a refrigerant at 1.5 °C per minute.

• The final temperature after chilling is maintained around -20°C.

Department of Chemical Engineering, National Institute of Technology, Calicut

 MEK Dewaxing
Filtration section
• The chilled mixture is then filtered continuously on rotary vacuum, filter to separate
crystallised wax from the oil solvent solution.
• Wax separated on the filter is in the form of thin cake, washed with chilled solvent
to displace retained oil.
• The filter cake is transferred by screw conveyors to wax boots for slack wax
recovery.
• Filters require periodic washing with hot solvent to remove materials that plug the
cloth.
Solvent recovery section
• The dewaxed oil/solvent mixture is heated and sent to four flash towers in series,
the last one is used as steam stripper.
• The evaporated solvent is condensed and recycled.

Department of Chemical Engineering, National Institute of Technology, Calicut

 MEK Dewaxing

Department of Chemical Engineering, National Institute of Technology, Calicut

 MEK Dewaxing- Limitations
• Solvent composition:
• The solvent composition is needed to be adjusted to contain optimum MEK concentration
so that highest filtration rate as well as lower dewaxing temperature differential can be
obtained for saving the refrigeration cost.
• Size and shape of the crystal :
• Feed composition; Boiling range of feed; rate of cooling; rate of agitation; Viscosity of
crystallising medium. Dependence of solvent / oil dilution on feed viscosity for a given
solvent viscosity ( High viscous feed requires higher dilution ratio than lighter feed stocks)
• Rate of chilling :
• The crystal formation and subsequent filtration rate are influenced by the rate of cooling, A
slow chilling rate produces large crystals which are easier to filter.
• Filtration operation
• The important operating variables of rotary filters are Drum speed, Pressure differential for
filtration and wash and Cake thickness.
• Operation cost
• Solvent cost and refrigeration cost

Department of Chemical Engineering, National Institute of Technology, Calicut

 DILCHILL dewaxing

Recent development of the solvent dewaxing process which is aimed at minimising

the cost of operation and to increasing the yield of dewaxed oil

DILCHILL dewaxing process

• The Dilchill Dewaxing Process was developed by Exxon
• a unique method of wax crystallisation by direct injection of cold dilution solvent
into the warm waxy feed in a highly agitated crystallizer.
• The typical solvent to feed ratio is maintained between 2.5 to 6.0
• A high filtration rate and dewaxed oil yield is obtained due to formation of highly
discrete and compact wax crystal agglomerates

Department of Chemical Engineering, National Institute of Technology, Calicut

 Exxon DilChill Dewaxing

Department of Chemical Engineering, National Institute of Technology, Calicut

 Exxon DilChill Dewaxing

Department of Chemical Engineering, National Institute of Technology, Calicut

 Propane Dewaxing
Propane dewaxing process has been mostly accepted as a versatile and economical
technique due to the following advantages

• Readily available, less expensive, and easier to recover.

• Direct chilling can be accomplished by vaporization of the solvent, thus
reducing the capital and maintenance costs of scraped-surface chillers.
• High filtration rates can be obtained because of its low viscosity at very low
temperatures.

The disadvantages of propane dewaxing

• Large differences between filtration temperatures and pour point of finished oils
(15 to 25°C).
• The process is suitable for dewaxing of residual heavier petroleum fraction (525
°C +) only

Department of Chemical Engineering, National Institute of Technology, Calicut

 Propane Dewaxing

Department of Chemical Engineering, National Institute of Technology, Calicut

 Propane Dewaxing

• The feed and propane mixture is preheated to 45-50°C under pressure for
complete dissolution of wax.
• Direct chilling of the solution by evaporation of propane to crystallise wax, at 0.4kg/
kg of wax crystallised. Chilling is controlled at 3 °C/min
• Additional liquid propane is added during chilling to control slurry viscosity.
• The final temperature was maintained at -30 to -40 °C .
• Pressure filtration at 2-15 psi is generally carried out with rotary filters.
• Washing of cake is done with fresh propane.
• Evaporation of propane is carried out in two stages .
• Initially by flash evaporation and finally by steam stripping for complete removal of
propane from the oil.

Department of Chemical Engineering, National Institute of Technology, Calicut

 Urea Dewaxing

• The process is based on the principle that n-paraffinic hydrocarbons form solid
complex adducts (solid filterable complex) with urea when a mixture of
hydrocarbons is treated in presence of a suitable activator such as acetone or
methanol.

• The n-paraffinic hydrocarbons of more than 5 carbon atoms that have little or no
branching selectively get blocked inside the hexagonal channel formed by
crystallizing 0.7 mole of urea for each carbon atom.

Department of Chemical Engineering, National Institute of Technology, Calicut

 Urea Dewaxing

Department of Chemical Engineering, National Institute of Technology, Calicut

 Urea Dewaxing

• Petroleum fraction, urea and the activator were mixed in the ratio 1:1.2:3
(vol:wt:vol ) and the mixture was stirred thoroughly for one hour at a
temperature of 30 °C.
• The urea adduct was then filtered and the residual hydrocarbons were
extracted with solvents e.g; toluene, benzene or naphtha .
• The urea adduct was decomposed in presence of the solvent or water at
temperature 60-80°C.
• The vapours evolved were condensed and sent back to the vessel.
• Paraffinic hydrocarbons were recovered after distilling the solvent from the
filtrate.

Department of Chemical Engineering, National Institute of Technology, Calicut

 Urea Dewaxing

• The urea adducting process suitable for dewaxing lighter stocks (250-400 °C)
because it contains a higher percentage of straight chain paraffins.

• Dewaxing of lube fractions is not suitable by this process because adduct

formation with the long chain paraffins becomes unstable and branched chain
paraffins of high melting point are not accessible for adduct formation

• So the decrease of pour point of the fraction are sometimes not up to the desired
level

Department of Chemical Engineering, National Institute of Technology, Calicut