Treatment Techniques

• Impurities in petroleum products

• 1.Physical impurities-Dust,mud,moisture,catalyst
dust,solvent droplets
• 2.Chemical impurities-S,N2,O2 compounds
• Sweetening/Doctoring-removal of S
• 1.Oxidising mercaptans to disulfides
• 2.Physical extraction
• 3.In-situ destruction of sulphur bearing compound
• 4.Catalytic conversion
• 1.Oxidising mercaptans to disulphides
• A.Copper chloride process
• B.Lead doctoring process
• C. Merox treatment
• 2.Extraction process-Caustic,M.E.A,D.E.A
• 3.Destruction of Sulphur compounds
• A.Sulphuric acid
• 4.Catalytic desulphurisation-COMOX catalyst
 Oxidising mercaptans to disulphides

• Conversion of active mercaptans to inactive

disulphides. Disulphides are found to be
harmless compared to sulphides. Pollution
considerations both are equally harmful.
• 1.Copper chloride process :-
• 4 RSH + 4CuCl2-> 2R2S2 +4CuCl+4HCl
• 4CuCl + 4HCl +O2  4CuCl2 + 2H2O
• 2. Lead Doctoring Process
• Na2PbO2 + 2RSH  (RS)2Pb + 2NaOH
• (RS)2Pb +S  R2S2 +PbS
• Physical extraction process:-
• 2(OH CH2 CH2)NH2 +H2S  (OH CH2 CH2
NH3)2S
• MEA, DEA, MDEA, NaOH, Vetrocoke (Pot.
Arsenite), KOH, Methanol +KOH, Methanol.
 Destruction of Sulphur compounds by
Sulphuric acid
• Acid above 93% of strength is normally used.
• Olefins, unsaturates, sulphur, O2, N2
compounds are also removed by H2SO4.
• RSH + H2SO4  RSHSO4 + H2O
• RSH + RSHSO4 - (RS)2 SO2 + H2O
• (RS)2 SO2 - R2S2 + SO2
• Disposal of acid sludge.
 Catalytic Desulphurisation
• Sweetening operations are carried out by catalyst. In
such reactions whole molecule bearing sulphur is not
removed, as seen in extraction or acid treatment, but
only the sulphur atoms are picked up. Thus material
loss is negligible with possible recovery of Sulphur.
• CU-Cr- Al catalyst
• Cu- Cr- Va catalyst
• Co- Mo oxide catalyst – Widely used.
• Sulphides of Tungsten and Nickel.
 Production and treatment of L.P.G
• Production of L.P.G
• 1.Distillation at low temp
• 2.Absorption and desorption
• 3.Compression and expansion
• 4.Combined methods
• BIS categorised L.P.G
• A.Commercial butane
• B.Commercial butane-propane mixture
• C.Commercial propane
• Properties of L.P.G
• High C.V,Purity,V.P is one of the important
characteristics,Low sulphur,Heavier than
air,Flammability range is narrow,odourless,non
corrosive to steel.no lubricating proprty,slightly toxic
• V.P at 65 C is important property-16.8kg/cm2
• 95% volume evaporated at 2C
• Hydrogen sulphide –nill
• Sulphur-0.02% wt
• LPG production in KRL(CDU)
• Naphtha stabilizer(170C,8 kg/cm2)-Amine
treatment-caustic wash-sand filter-cooled to atm
temp-liquified gas-stored in horton sphere(8 kg/cm2
and atm temp)
• FCCU
• Compressor-Knock out drum-Absorber-stripper(70C
and 13 kg/cm2)-Debutanizer(70C and 10 kg/cm2)-
Condenser-Amine treatment-Merox-storage
 FUEL GAS
0.37 TPH

CV17/CV4 GAS
LV3
11 Kg (A)
45 C

Compressor

LPG
LPG COOLER

LV2
175 C

NAPHTHA FROM
CV-4/CV17 LH1

STAB. BOT
LPG RECOVERY NAPHTHA
LPG production by Absorption technique
• A stream of combined gases consisting of
gases from ADU, Isomerization, cracker etc is
first given a water wash to remove suspended
impurities. The gases then passed through a
Dryer containing any suitable adsorbent. The
gas is then compressed to 15 atm and chilled
and sent into absorber. Absorber always
maintain a cold lean oil circulation. CH4, C2H6,
H2, CO2 are not dissolved in this cold oil.
• Heavier gas fraction C3 and C4 are carried
along with fat oil. Small amount of light gas
absorbed in oil may be separated by
decreasing the pre is done in deethaniser.
Deethanizer bottom are taken into another
stripper called debutanizer. The top fraction
consits of mixture of butane and propane. The
bottom solvent and other heavier
hydrocarbons routed to gasoline pool.
Amine treatment of LPG
• Feed gas containing acid components is first
compressed to 10 to 15 atm and then cooled
by cold water. The cold gas is admitted into
absorber (1). Amine solution (30%) is
distributed from the top of the tower and
gases are fed counter currently. Undesirable
constituents of gases are absorbed by solution
and sweet gas leaves from the top of absorber.
The rich solution flashed in the flash tower (2).
• Here some of the dissolved gases escape due
to low pressure. The solution then later fed
into stripper/regenerator (3) where the
stripping of acid gases takes place (120C and
0.7 Kg/cm2. Heating is done by HE and
reboilers. The amine solution from the
stripper is filtered and sent back to absorber
after cooling to 30C. The off gas from the
stripper are sent for sulphur recovery.
Stretford process
• Complete removal of hydrogen sulphide and partial
removal of accompanying organic sulphur is also
achieved.
• Treating solution consist of a mixture of sodium
carbonate, sodium vanadate anthroquinone di
sulphonic acid and arsenic oxide
• Hydrogen sulphide is first removed because of its
reaction with pentavalent vanadium. Hydrogen
sulphide is completely oxidised to elemental sulphur
in one operation itself.
• In the contactor (1) sour gas comes into contact
with circulating solution. Hydrogen sulphide is
first removed because of its reaction with
pentavalent vanadium. Hydrogen sulphide is
completely oxidised to elemental sulphur in one
operation itself. Sulphur liberated in the reaction
must be freed from the solution. This can be done
by rich solution is frothing by blowing air through
the tank (2). Sulphur is removed as floating layer.
• When air is blown into fat solution
hydroquinone is oxidised back to original
disulphonic acid, which keeps the activity of
vanadium, by restoring its five valence state.
Merox process
• Merox oxidation process is most suitable process
for treating LPG, Gasoline and kerosene.
• 1. extracor- merox solution-catalyst CO in caustic
solution.
• 3. water washing
• 4. separator
• 2. air blowing tower
• A reduction of 90% sulphur is possible in this
operation.
• Merox extraction process
• RSH +NaoH – RSNa +H2O
• RSNa+1/4 O2+1/2 H2O – NaoH+1/2 RSSR
• Merox sweetening process- blowing caustic
hydrocarbon mixture with air in the presence of
merox catalyst.
• 2RSNa+1/2 O2+H2O- RSSR+2NaoH
• Merox catalyst consist of sulphonated derivative of
Cobalt phthalocyanine complex
• C/S and merox solution are contacted in extractor (1).
Sweetened product from the top of the extractor goes
into a warer wash column (3) and merox separator (3)
where air comes in contact with merox solution. Merox is
regenerated here and the solution is transferred to a
settler (4), heavy merox is obtained from the bottom of
the tank is recycled.
• The extract containing mercaptans is oxidized by blowing
air in towers (2), disulfides are separated in settler (5)
and regenerated merox is circulated into extractor.
 Gasoline, Motor spirit, Petrol
• Gasoline is a light distillate and consists of the fraction
within the boiling range of 30 to 180 C. it consists of
hydrocarbon ranging from C5 to C10. the main types
are straight chain paraffin, iso paraffin, cycloparaffin,
aromatics, olefins,
• Combustion- Octane number, Distillation range,
Hydrocarbon composition
• Handling and storage- Volatility, V.P. Copper corrosion
• Cleanliness during use- Sulphur, Gum, Stability.
Gasoline treatment-copper chloride process
• 1.Copper chloride process :-
• 4 RSH + 4CuCl2-> 2R2S2 +4CuCl+4HCl
• 4CuCl + 4HCl +O2  4CuCl2 + 2H2O
• 1. dehydrator-Nacl or Cacl2
• 2. mixer/reactor (3 to 4 hours)
• 3. water washing system
• Temp- 40 to 60C
• Circulating slurry consits of copper chloride
and clay(-200 mesh) in water.
• Gasoline free of H2S and sulphur is first passed through
a moisture remover (1). The feed is heated to temp of
40 to 60C and sent to mixer (2). Part of circulating slurry
consist of copper chloride and clay(-200 mesh) in water
is mixed with the feed. O2 is admitted into the mixer
containing slurry and gasoline. The floating layer consist
of gasoline and is taken to water washing system (3).
Water removes the trapped particles of catalyst and
acid. After settling the gasoline phase is routed through
another dehydrator to storage tank.
Caustic and methanol(Unisol process)
• Extraction tower with three inlets
• Methanol removes some nitrogen compound in
addition to mercaptans.
• Temp 40c
• Methanol steam stripper
• Caustic to methanol ratio is 2
• Process successfully eliminates 60% of sulphur
compounds while mercatan removal is complete.
Lead Doctoring of Gasoline
• Lead Doctoring Process
• Na2PbO2 + 2RSH  (RS)2Pb + 2NaOH
• (RS)2Pb +S  R2S2 +PbS
• PbS + NaOH + O2 - Na2PbO2 + Na2SO4 +
2 H2O
• Caustic plumbite solution
• Lead alkyl sulphide
• Ratio of doctor solution to gasoline-1:5
• Contact time- 0.5 min to 1 min
• Sulphur addition and stirring – 5 to 15 min
• Air regeneration temp 100C and pre 1 to 5 Kg /cm2
• Calculated amount of fresh sulphur should be
added otherwise sulphur will increase in end
producrs.
• Charge stock is agitated in a mixer (1) with
solution of caustic plumbite. Lead becomes
lead sulphide. The lead alkyl sulphide is
reacted with fresh sulphur (2) to free lead
sulphide from disulphide. Lead sulphide is
converted back to sodium plumbite by
blowing air into the spent solution obtained
from the settler.
Sulphuric acid treatment
• Acid and charge stock are proportioned and sent into
the orifice mixer. The reaction with sulphuric acid is
exothermic, hence care must be taken to temp does not
exceed 40C. After the reaction is over the contents are
sent into the settler, where a settling time of 5 to 6 hrs
is given. The acid sludge separates out and concentrate
at the bottom. The hydrocarbon layer from the top of
the settler given a water wash to scrub of acid residue.
The hydrocarbon phase is later neutralized with caustic
in a contactor and again washed with water and dried.
• RSH+ H2SO4 –RSHSO3+H2O
• RSH+RSHSO3-( RS)2 SO2+H2O
• (RS)2 SO3-R2S2 +SO2
• 1. orifice mixer
• Temp does not exceed 40C
• 2. settler (5 to 6 hours)
• Sulphur, unsaturates, metallic bodies are removed as sludge.
• 3. water wash column
• 6. caustic contactor
• Product drier
Catalytic Desulphurisation
• Feed stock along with recycle H2 rich gas is
preheated to the desired temp and the
mixture is then passed to a fixed bed reactor.
The reactor effluent after cooling go to a high
pre separator goes to a low pressure separator
where light gases are stripped off. The liquid
product from the low pre separator is
stabilized in a stabilizer.
 Process variables
• Partial pressure of hydrogen
• Process temp
• Residence time
• Catalyst :- CO- MO, Ni-MO, Ni-CO- MO. The
catalyst usually have a alumina or zeolite
support and sulphided before use by
treatment with H2S in the presence of H2.
 Typical operating condition
• Reactor temp – 360 to 390C
• Pressure – 30 to 35 Kg/cm2
• Space velocity – 2.1 m3 of feed/m3 of catalyst
• Recycle gas rate – 200 m3 pure H2/ m3 of
liquid feed.
 Hydrotreating reactions
• Desulphurisation
• RSH + H2 - RH + H2S
• Denitrogenation
• De oxygenation
• Olefin saturation
• Improvement of colour, odour etc.
 Applications of hydrotreating
• Reduction of sulphur in the feed to the CCR.
• Desulphurisation of Naphtha, Kerosene, Diesel. Fuel
oil, VGO.
• Improvement of colour, odour, oxidation stability of
lubricating oil base stock.
• Mild hydrogenation of aromatics into naphthenes in
stream like high aromatics kerosene and gas oils to
improve smoke point and cetane number.
• Hydrogenation of olefinic streams produced from
thermal cracking process.
FEED NAPHTHA

HT
C
O
Z Z S H2
N N H
M
O O I
O
F
X
T

STEAM FUEL NAPHTHA

PURGE GAS
STEAM DRUM
P
S
A
REFORMER

PG BOILER
 Kerosene
• Boiling range 150 to 250C
• Carbon number 10 to 14
• Paraffins have the least tendency towards smoke
formation and aromatics the greatest.
• Aromatics> Naphthenes> isoparaffin> Paraffin
• Stipulated flame height with out smoke
• -10C liquid SO2 , aromatics and unsaturates are
completely miscible with liquid SO2.
• SO2 also extracts cyclic sulphur compounds and nitrogen
compounds.
Treatment of Kerosene-Edeleanu
EDELEANU PROCESS
 Process description
• Straight run kerosene is passed through a column
filled with rock salt at about 40-45 C to remove
traces of free water. It is then deaerated in vacuum
column maintained at a pre of 0.04 atm. Deaerated
kerosene is cooled to about 10C and then passed
through calcium chloride drier to remove dissolved
water in it.
• Dehydrated kerosene is further chilled to -15C and
then sent to a counter current extraction column
packed with rasching rings.
• Dehydrated kerosene at -15 C sent to a
counter current extraction column.
• SO2 at -26 C , ratio 1:1
• Raffinate separators- 7, 0.2, -0.5 kg/cm2
• Extract separators- 7, 0.2, -0.5
• VDU – to obtain various distillate fraction and VR.
• Solvent Deasphalting unit-to remove asphalt from
VR.
• Solvent extraction unit –to remove undesirable
naphthenic and aromatic hydrocarbon from
distillate fraction to improve VI.
• Solvent dewaxing – to improve pour point.
• Hydrofinishing.- to improve colour, oxidation,
stability of finished lube oil base stock.
 LUBRICANTS
• LUBRICANTS = BASE OILS + ADDITIVES
• BOTH MINERAL AND SYNTHETIC BASE STOCKS AND
THEIR MIXURES ARE USED IN LUBRICANT
FORMULATION
• MINERAL OILS PRODUCED / REFINED FROM CRUDE
OILS ARE SINGLE COMMON SOURCE OF BASE STOCKS.
• LUBRICATING PROPERTIES OF BASE STOCKS ARE
INFLUENCED BY
 CRUDE SOURCE
 REFINING PROCESSES
USE OF LUBRICANTS/BASE OILS

• ENGINE OILS

• GEAR OILS

• TRANSMISSION FLUID

• INDUSTRIAL APPLICATION
 REQUISITE PROPERTIES
• APPROPRIATE VISCOSITY
• HIGH VISCOSITY INDEX
• LOW POUR POINT
• LOW VOLATILITYAND HIGH FLASH POINT
• GOOD THERMAL AND OXIDATION STABILITY
• HIGH HEAT CAPACITY GOOD THERMAL
CONDUCTIVITY
• NON CORROSIVE, OILINESS AND WETABILITY
 HYDROCARBON STRUCTURE
STRUCTURE VI POUR PT INTEREST

N-PARRAFIN VERY HIGH HIGH LOW

ISO-PARAFFIN HIGH LOW HIGH

NAPHTHENE MEDIUM LOW HIGH

AROMATICS LOW LOW LOW
 Additive Types

• Dispersants
• Detergents
• Antiwear
• Friction Modifiers
• Oxidation Inhibitors
• Rust Inhibitors
• Emulsifiers / Demulsifiers
• Antifoamants
• Vacuum distillation isolates individual raw lube oil
fractions according to desired starting viscosity.
• Deasphalting of VR is employed to produce a feed
stock for a very heavy lube oil called bright stock.
• Solvent extraction process improves the viscosity
temp characterestics
• Dewaxing improve the pour point
• Finishing improves colour, colour stability and
oxidation stability.
• Low viscosity index lube oil base stock- VI
below 30, rich in aromatics, extracted from
naphthenic crude.
• MVI- VI between 30 to 85. contains aromatics
and paraffins,
• HVI – VI more than 85. contains paraffins.
Used where good oxidation stability and high
VI are needed.Extracted from paraffinic crude
 Treatment of Lubes
• 1.Sulphuric acid treatment
• 2.Clay treatment
• 3.Solvent refining
• 4.Hydrotreatment
Clay treatment –Contact treatment
• Oil and clay are now mixed in required
proportion and thoroughly agitated in
mixer(2). The slurry is then routed through a
convection of a heater(3) to reach the temp of
200 to 225C. The hot slurry is pumped into a
contact tower (4). Usually an empty tower,
fitted with steaming arrangement. The
residence time is one hour and by that time
the decolourisation will complete.
• The slurry is now transported to filtration
equipment. Filtration is some times difficult
with highly viscous stocks, fresh addition of
diluents. Filtrate containing diluent is distilled
or flashed in a stripper (6), diluent is collected
as top product which is cooled and kept ready
for recycle. Treated oil from the stripper is also
cooled and stored.
• 1. heat exchanger
• 2. mixer
• 3. convection section of a heater
• 4. contact tower-1 hour
• 5. filtration
• 6. stripper
• Temp- 200 to 225C
• Pre- 20 atm
• Contact treatment or percolation treatment
 Solvent treatment- Viscosity index
improvement
• Solvents widely used for this purpose are
• 1. Phenol
• 2. Furfural
• 3. Mixture of propane and cresols
• Selection of suitable solvents
• 1. solubility
• 2. ease of recovery
• 3.High density
• 4.less corrosive
• 5.good stability
• 6. low viscosity
• 7.less toxic
• 8.low interfacial tension
• 9. low freezing point
• 10. low latent heat
Comparison of phenol and furfural extraction

• Furfural extraction may require a high temp of

extraction and more number of stages
• Yeild of raffinate is more with phenol
• Phenol treated lubes have better oxidation stability
• Viscosity index improvement may be same in both
case, however solvent dosage may be slightly more
for furfural on comparative basis
• Phenol is more adoptable to different stocks and is
unavoidable when naphthenic acids are more
• The selectivity of phenol increases with water
(up to 10%). This is great advantage over
furfural
• Furfural is unstable, hence requires nitrogen
seal during storage and recovery
• Losses can be negligible with phenol
• Residual solvent in treated stocks is not
harmful provided the solvent is phenol.
Solvent treatment-Phenol extraction of Lubes
• 1-H.E
• 2- SOLVENT VAPUR ABSORBER
• 3-EXTRACTION TOWER
• 4-SEPARATOR
• 5,8-FRACTIONATOR OR FLASH VESSEL
• 7,9- STEAM STRIPPER
• To remove undesirable naphthenic and aromatic
hydrocarbon from the distillate fraction so as to
improve VI of lube oil base stock.
• Plate or packed bed extractor are generally employed in
phenol extraction.
• Operating temp 60 to 100 C
• Thermal gradient of 10 to 20 C from top to bottom is
imposed on the column to enhance the internal turbulence.
• Solvent to feed ratio of 1.5 to 2.5 for processing paraffinic
and naphthenic stocks.
• An increase of viscosity index by 25 to 50 units confirmed.
• Phenol treated oil posses good oxidation stability with less
sludge forming and carbon depositing tendencies.
 Process description
• c/s heated to 80 to 100C by exchanging heat with
raffinate and extract in HE is first allowed to absorb
phenol vapours in absorber (2), these vapours are
delivered from stripper. The stock then goes to
extraction unit(3). Feed being lighter is admitted at
the bottom of the tower. Raffinate from the top is
led into separator (4) to settle any solvent drops.
Bottom product is extract, a part of this is circulated
back to extractor and the rest is processed for
recovering solvent.
• Raffinate contains less solvent, hence it is
stripped off in fractionator(8) under vacuum.
The stripped raffinate is again steam stripped
to remove remaining solvent from the oil.
• The extract is heated first and then flashed in
a fractionator (5) under pressure and then
under vacuum. The remaining solvent from
the extract is removed in the steam stripper.
Furfural extraction
• 1- RDC
• 2-FLASH TOWER CUM STEAM STRIPPER OR
EVAPORATOR
• 3-FLASH TOWER
• 4- STEAM STRIPPER
• 5- WATER SEPERATOR
• 6-FURFURAL COLUMN(RECTIFICATION VESSEL)
 Process description
• C/S is heated by passing through product HE to raise
the temp to 80C. Feed then enters the extractor RDC
at two or three points and solvent is admitted into
the upper portion. Raffinate phase being lighter
leaves from the top of the contactor. It is heated in
the heater and flashed in flash tower working at low
pre and finally steam stripped.
• Extract from the bottom of the column is heated in a
heater and then admitted into high pressure zone of
flash tower and then to low pressure zone.
• Extract is obtained as a finished product from
the bottom sent to the stripper. Furfural water
mixture forms azeotrope, so it is purified in
rectification column.
• Naphthenic stock treatment may not yield convincing result with
this solvent
• Rotating disc contactors are used
• Temp range of 75 to 125C under a gradient of 20 to 30C makes the
operation success.
• Number of stages as well as solvent feed ratio is more for same
elevation of viscosity index
• Furfural extraction is practiced not only for lubes but also gas oils,
cycle oils and removal of low cetane index components from
diesel.
• Furfural has tendency to react with oxygen leads to solvent power.
 Dewaxing
• Dewaxing is broadly classified into two.
• 1. With out solvents – Pressing and chilling
process.
• 2. With solvents
• A, Barisol process- EDC and benzol solvents
• B, Ketone dewaxing - MEK
• C, Propane dewaxing
Treatment of Wax-Chilling and pressing
• Chilling to 10 to 15 C below its pour point.
(cooling at a rate of 3C per hour)
• Pressing in a filter press at a pressure of 100
atm.
• Sweating operation.
Dewaxing with solvents-Ketone dewaxing
• Wax bearing oil and solvent are mixed and
slightly warmed by outgoing streams. This
mixture is cooled by filtrate and then by
refrigerant in a chiller to a desired pour point.
The chilled mixture then goes to intermediate
accumulator and finally goes to rotary drum
filter. The scrapped cake is transferred to
storage tank from where it is goes to
evaporator and finally wax steam stripper.
• The filtrate from the filter press pass through
HE and enters a flash tower consist of two
section. The filtrate is submitted to LP flash
section first then goes to HP flash section
using a pump. Most of the solvent is expelled
by this process. Wax free oil is steam stripped.
Solvent vapours from all the strippers are
combined and sent into a distillation column,
where solvent is regenerated.
• Methyl ethyl ketone dewaxing
• Lower molecular weight of ketones with low
viscosity are preferred.
• Ketones enhance the crystalisability of wax
without dissolving oil.
• Precipitation of wax at lower temp
• MEK dewaxing enjoys the advantages like
complete recoverability of solvent and
achievement of low pour point.
• 3-heaters
• 4-chiller
• 5- intermediate accumulators
• 6- rotary drum filter
• 7- storage of wax
• 8- evaporators
• 9- wax steam stripper
• 12- flash tower
• 11- oil steam stripper
• 13- solvent fractionator
Propane dewaxing
• Propane self refrigeration process
• Propane is available in refineries
• Its dual function of precipitation of wax and
rejection of asphalt
• Overcome the chilling difficulties by self
evaporation
• For the same extent of dewaxing, it requires only
half time than that required by MEK dewaxing
• 1-warm solution drum
• 2- self evaporation chiller
• 3- rotary drum filter
• 4,5- evaporators
• 6- oil steam stripper, wax steam stripper
• 7- seperator
• Temp- 25C, propane oil ratio 1:3
 Propane deasphalting
• Propane exhibit unique capacity in separation
of asphalts and resins.
• Asphalt rejection by propane.