SUBJECT NAME: PETROLEUM REFINING AND

PETROCHEMICALS
SEMESTER – VIII (CHEM)
CHAPTER NAME: TREATMENT TECHNIQUES

Phenol and furfural are very competitive Solvents in field. Both these solvents
accomplish the task satisfactorily:
a survey on the performance of these two solvents is presented
below:
1. Furfural extraction may require a higher temperature of extraction
and more number of stages.
2. Yield of raffinate is more with phenol.
3. Phenol treated lubes have better oxidation stability.
4. Viscosity index improvement may be same in both cases, however
solvent dosage may be slightly more for furfural on comparative
basis.
5. Phenol is more adoptable to different stocks and is unavoidable when
naphthenic acids are more.
6. The selectivity of phenol increases with Water. This is deemed to be
a great advantage over furfural.
7. Furfural is unstable, hence requires nitrogen seal, during storage
and recovery.
8. Losses can be negligible with phenol.
9. Residual solvent in treated stocks is not harmful: provided the
solvent is phenol.

LEAD DOCTORING OF GASOLINE-

In this method of treating charge stock(c/s) i.e. sour gasoline is thoroughly agitated in
(Mixer 1) with a solution of caustic plumbite. Lead becomes lead sulfide during reaction as
shown below:

This lead alkyl sulfide (a) is reacted with fresh sulfur. (Mixer 2) to free lead sulfide from
disulfide as shown in the above raction (b). Lead sulfide is converted back to sodium
plumbite by blowing air into the spent solution obtained from the settler(2).

The regenerated solution is ready for treatment. Lead consumption as is evident from the
reactions, is negligible, but alkali consumption is high.

Prepared By: Mr. Dhiraj Tatar

 SUBJECT NAME: PETROLEUM REFINING AND
PETROCHEMICALS
SEMESTER – VIII (CHEM)
CHAPTER NAME: TREATMENT TECHNIQUES

Operating Data-
Ratio of Doctor sol. to
gasoline 1:5
Time of contact- 1 min.
Sulfur addition and Stirring 5 to 15 min.
Air regeneration temp. 1000C
Pressure 1 to 5 kg/cm2

Fig: Lead doctoring of GASOLINE

There is one difference in this doctoring, that is sulphur in organic phase (gasoline) is
converted to a disulphide and it is allowed to go into the stream as a disulphide which is
less harmful than sulphide.

PROPANE DEASPHALTING

Deasphalting is another important operation and all lube oils of naphthenic base
invariably require as propane exhibits unique capacity in separation of asphalts and resins
even from highly viscous stocks, industrially, it is chosen; as as solvent.
In this operation contacting of this high viscous stock and propane under a pressure of 15
atmospheres and at a temperature between 30°C to 70°C takes place.
Higher temperatures increase the tendency of asphalt materials to separate out.
Re1ativiely 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 collect
a heavy phase.
The two phases, are i.e. separately processed for solvent, recovery as described in
dewaxing operation.
Virgin oils after treatment naturally give to light neutral or neutral oils. The quality of
asphalt obtained is very good with high; softening point.

Prepared By: Mr. Dhiraj Tatar

 SUBJECT NAME: PETROLEUM REFINING AND
PETROCHEMICALS
SEMESTER – VIII (CHEM)
CHAPTER NAME: TREATMENT TECHNIQUES

It may be true that all lighter hydrocarbons from ethane to butane are commendable as
propane in operation.
However, the rejection of the asphalts by propane to desired extent, has in fact made its
involvement indispensable.
Propane de-asphalting is quite comparable with vacuum distillation in production of
medium to cylinder stocks as shown below:

DEWAXING WITH SOLVENTS

Inordinate delay and ineffectiveness of natural chilling and

pressing process for dewaxing of lubes has given way to solvent
dewaxing.
Admirably close to required pour point of a finished lube is possible with this operation.
Three important commercial processes are in service for solvent dewaxing as given below:
(a) Barisol process (Ethylene dichloride and benzol solvents.
(b) Ketone dewaxing (Methyl ethyl. ketone methyl
propyl ketone.
(c) Propane dewaxing.

BARISOL PROCESS

This was once in good demand although. a few refineries adopt this even today. Solvent
mixture, constituting equal volumes of ethylene dichloride and benzol, is used for
dewaxing. Wax being insoluble in this mixture precipitates out and floats this permits easy
filtration by a rotary continuous vacuum filter alone or aided by a centrifuge. The chilling
temperatures are guided by the desired pour point of oil. Usual chilling of stock goes down
to 0°C or even. upto - 10°C, and that ensures pour point of oil to lie some where between
5 to 10°C, which satisfies most of the consumers. Recovery of solvent from oil and cake is
Prepared By: Mr. Dhiraj Tatar
 SUBJECT NAME: PETROLEUM REFINING AND
PETROCHEMICALS
SEMESTER – VIII (CHEM)
CHAPTER NAME: TREATMENT TECHNIQUES

done by fractionation of these phases separately. Barisol is flexible in treating different feed
stocks ranging from long residue to waxy distillates.

KETONE DEWAXING (METHYL ETHYL. KETONE METHYL

PROPYL KETONE)

KETONE DEWAXING

It is credited to be a modern process and employs methyl ethyl ketone as a solvent, hence
it is known as dewaxing.
The development of solvent dewaxing started with commercialization of acetone and
benzoyl mixtures in 1927.
These mixtures were gradually replaced by MEK-aromatic mixtures and which have
creditably retained their position till today.
Lower molecular weight ketones with low viscosity are preferred, obviously for their
noted contributions towards high filter rates and effective dewaxing.
Ketones enhance the crystals ability of wax without dissolving oil. So the lyophobic
tendency of ketone has to be counteracted with suitable hydrocarbons to keep the oil
phase in solution.
This directs the precipitation of wax at lower temperatures. Benzene and toluene mixtures
are good in dissolving oil, so a suitable mixture may be made of by mixing 60-65 parts of
ketone with 30 parts of benzene and 10 parts of toluene.
Highly naphthenic stocks are to be encountered with rich mixtures of aromatics.

Prepared By: Mr. Dhiraj Tatar

 SUBJECT NAME: PETROLEUM REFINING AND
PETROCHEMICALS
SEMESTER – VIII (CHEM)
CHAPTER NAME: TREATMENT TECHNIQUES

MEK dewaxing enjoys advantages like complete recoverability of solvent and

achievement of low pour point over acetone mixtures.

Process Description:
Wax bearing oil and solvent (1:1 to 1:4 for paraffinic to naphthenic stocks) are
proportioned and slightly warmed by outgoing streams.
This mixture is now cooled by filtrate to moderate temperatures slowly and finally chilled
by refigerant to the desired pour point.
The chilled mixture then goes to an intermediate accumulator (5) and finally to
continuous rotary filter (6) which operates under vacuum.
The scraped cake is transferred to a storage tank (7), from where it goes to evaporator (8).
Evaporation of solvent from Wax cake is done in this.
The filtrate from filter passes through heat exchangers and enters a flash tower, (12). This
contains two different sections; bottom one is low pressure flash tower and upper is high
pressure tower.
The filtrate is submitted to high pressure flashing first, later it is flashed in low pressure
section of the tower.
Most or-the solvent is expelled in this process.
After solvent evaporation is over, the remaining oil is steam stripped in a stripper (11) to
free the oil from contaminants or residues of solvent.
Cake is steam stripped separately in another stripper (9). Solvent vapours from all the
strippers are combined; and sent into a distillation column (13); where solvent is
regenerated.
It is likely that the resultant dewaxed oil may have a pour point less than the chilling
temperature.
However, chilling is continued to reach 4 to 5°C the desired pour point of oil.
Cake from this operation does not carry oil more than 6% this is a commendable
achievement over chilling and processing operations.

PROPANE DEWAXING OR PROPANE SELF-REFRIGERATION PROCESS

Propane is available in abundance in all refineries and its application for such extraction
operations has aroused the interest of refiners.
Its dual function in precipitation of wax and rejection of asphalt is considered to be
invaluable.
It has become invincible in this context as it could overcome chilling difficulties offered
by feed stocks (because the stocks are viscous at that low temperature, rendering
ineffective to heat transfer) by self-evaporation; resulting in rapid rates of chilling.
Recovery of solvent with ease and high purity cannot be substituted. For the same extent
of dewaxing, it requires only half the time than that required by an effective operation like
MEK.
Propane is ‘prized to handle all stocks with almost the same efficiency

Prepared By: Mr. Dhiraj Tatar

 SUBJECT NAME: PETROLEUM REFINING AND
PETROCHEMICALS
SEMESTER – VIII (CHEM)
CHAPTER NAME: TREATMENT TECHNIQUES

Description of operation:

Initially oil and propane mixture is warmed to 25°C by charging through a heater and
stored in a tank (1).

The charge solutioin is now chilled in series of chillers (2) by evaporation of propane it at
a controlled rate till the; filtering temperature is achieved, chilling aids in crystallization
of wax, and these crystals remain in propane-oil solution.

The solution is then filtered to remove wax. Filtration, is in a "rotary vacuum filter (3),
and simultaneous washing of cake with fresh solvent is also done. Wax free solution i.e.
filtrate is led through process heat—exchangers to evaporators (4 & 5).

In the beginning evaporation is done at low pressure and later at high pressure. Propane
evaporated from these evaporators are gathered and sent back Ito compression and
liquefaction system.

The remaining oil is finally steam stripped (6). In the same way, recovery of solvent from
wax is done. In strippers. only traces of propane are. obtained, hence by condensation
water separate out (7) leaving propane in as gas, which is sent to liquefaction section.
Dewaxing is conducted with oil and propane ratio fixed at 1: 3.

High pressure is needed to keep propane in liquid state. Warming of solution up to 25°C
is necessary before chilling, to keep all wax in solution.

Prepared By: Mr. Dhiraj Tatar

 SUBJECT NAME: PETROLEUM REFINING AND
PETROCHEMICALS
SEMESTER – VIII (CHEM)
CHAPTER NAME: TREATMENT TECHNIQUES

MEROX SWEETENING

Mercaptan oxidation (Merox) process is most appealing as it is suitable for treating

LPG,gasolines and kerosenes.

This process has shown commendable abilities in ablating mercaptans in the form of
harmless disulfides.

All modern refineries in India are bent upon using this process. C/ S and merox solution
(catalyst cobalt salt) in caustic solution are contacted in extractor (1).

Sweetened product from the top of extractor goes into MEROX separator (3) where a
fresh gust of air comes in contact with MEROX solution.

Merox is regenerated here and the solution is transferred to a settler (4).

The phases are separated in this horizontal settler (4), and the heavy MEROX is
obtained from the bottom of the tank.
This MEROX being regenerated is fed back to extractor along with fresh MEROX.
The extract containing rnercaptans is oxidised by blowing air in towers (2).
Disulfides are separated in settler (5) by decantation and regenerated MEROX is collected
for circulating into extractor.

Prepared By: Mr. Dhiraj Tatar

 SUBJECT NAME: PETROLEUM REFINING AND
PETROCHEMICALS
SEMESTER – VIII (CHEM)
CHAPTER NAME: TREATMENT TECHNIQUES

A reduction of 90% sulfur is possible in this operation. When LPG is treated, the
sweetened gas is passed through a mist eliminator to remove the MEROX entrainments.
Merox operations can be collected in fixed beds also, where the catalyst is spread
on charcoal.

CATALYTIC DESULFUILISATION
Desulfurization technique is a predecessor to hydrodesulphurisation. All fractions lighter
than diesels can be desulfurised.
Desulfurisation conducted at higher temperatures(upto400°C); hence the feed should be
vaporisable without any thermal degradation.
The reaction is brought out in catalytic reactors. Any suitable catalyst ranging from
synthetic nature to natural bauxite can be employed.
Often the gases are vented out. But, recycling is essential when hydrogen gas is a
costream.

Desulfurisation as followed in Autofining process satisfactorily operates even without

hydrogen recycle. Depending upon the nature of catalyst, 90-95% of sulfur can be
removed.

Prepared By: Mr. Dhiraj Tatar

 SUBJECT NAME: PETROLEUM REFINING AND
PETROCHEMICALS
SEMESTER – VIII (CHEM)
CHAPTER NAME: TREATMENT TECHNIQUES

CAUSTIC AOND METHANOL (UNISOL PROCESS)

The treatment is performed in a counter current extraction

tower, as shown in Fig.

The extraction tower is provided with two inlets one at the top and the other at the middle
for separately introducing solvents, viz. caustic and methanol respectively, Sour gasoline
comes into contact with these twos down flowing solvents.
‘Methanol removes some nitrogen compounds in addition to mercaptans. The temperature
operation is kept around 40°C.
The spent solvent is recovered back in two distillation columns, one for caustic and the
other for methanol.
Methanol steam-stripper separates methanol and mercaptans. The recovered streams are
again proportioned to the extractor.
This process can successfully eliminate 60% of sulphur compounds while mercaptan
removal is complete.
Caustic to methanol ratio is maintained around two and consumptions are found to vary.

Prepared By: Mr. Dhiraj Tatar