PAJ PetroProc V Treatment III

PETROLEUM PROCESSING-V
Treatment Techniques-III
Dr. P. A Joshi
Dept. of Chemical Engg.,
FOT,D.D.University.
Nadiad-387001.
Treatment of Lube oils
11/11/2019 Dr P A Joshi, DDU, Nadiad 2

Lube Oils- Introduction
 Principal source of lubricating oil is the fraction
that is left after components, namely gasoline,
kerosene, diesel oil during crude distillation.
 Boiling point >350 oC
 Otained from vacuum distillation units.
 Composed of
 Paraffins
 Naphthenes
 Aromatics(poly, condensed, branched chains)
 Waxes
 Asphalts & resins
 Inorganic constituents (O, N & S compounds &
contaminants like metals)

 Paraffins are credited for high viscosity
index while aromatics for low viscosity
index & aromatics are generally more
viscous than paraffins.
 Paraffins in higher ranges are more
branched & invariably increase pour point
of oil.
 A high viscosity index oil can be produced
from paraffinic-naphthenic base or
paraffinic base crudes only.
 Wax is undesirable constituent in oil due to
its high pour point.

 The properties that considered
important
 Viscosity
 Viscosity index
 Pour point
 Oxidation resistance
 Flash point
 Boiling temperature

Lube oil Attributes
 Low volatility
 Proper viscosity
 High viscosity index (VI)
 High oxidation and thermal stability
 Low pour point
 Solubility for additives

Lube oil Processing
 Undesirable characteristics include high pour points,

large viscosity changes with temperature (low VI),
poor oxygen stability, poor color, high cloud points,
high organic acidity, and high carbon- and sludge-
forming tendencies.
 The processes used to change these characteristics
are:
 Solvent deasphalting to reduce carbon- and sludge-forming
tendencies
 Solvent extraction and hydrocracking to improve viscosity
index
 Solvent dewaxing and selective hydrocracking to lower
cloud and pour points
 Hydrotreating and clay treating to improve color and
oxygen stability

Propane Deasphalting
 Lighter feed stocks for producing
lubricating oil stocks can be sent directly
to the solvent extraction units.
 Atmospheric and vacuum still residues
require deasphalting to remove the
asphaltenes and resins before
undergoing solvent extraction.
 In some cases highest boiling distillates
also contain sufficient asphaltenes and
resins and need deasphalting.
 Propane : is usually used as the solvent in
deasphalting but it may be used with
ethane and butane in order to obtain the
desired solvent properties.
 At 40- 60 oC paraffins are very soluble in
propane, the solubility decreases with
increasing temperature, until the critical
temperature (96.8 oC ) all HC becomes
insoluble.
 (40–96.8oC) the high molecular weight
asphaltens and resins are largely insoluble
in propane.

 Feed stock is contacted with 4-8
volumes of liquid propane in a cylindrical
tower, usually RDC (rotating disc
contactor ).
 Asphalt recovered from the raffinate can
be blended with other asphalts , into
heavy fuels, or used as a feed to the
coking unit.
 Heavy oil product from vacuum
residuum is called bright stock.
Solvent for Lube Extraction
 The most widely used extraction solvents are

phenol, furfural, and cresylic acid. The last is used
with propane in the Duosol process. Other
solvents less frequently used are liquid sulfur
dioxide, nitrobenzene, and chlorex (2,2-
dichloroethyl ether).
 All lubricating oil solvent extraction processes
operate on the principle of mixing the oil with the
solvent and then allowing the solvent to settle
from the treated oil.
 The solvent carries the unwanted materials with
it.

Solvent for Lube Extraction
 The nature of the raw lubricating oil stock is important

in determining the type of process to use and the
extent to which treatment should be carried out.
 Liquid SO2 - benzene-developed by Edeleanu(1907) OH

 Phenol - Licensed by Kellogg and Exxon (1930)
 Furfural - developed by Shell(1934) & Texaco CH CH
 N Methyl Pyrrolidone (NMP) -developed by CH C-CHO
Texaco(1965) & Exxon CH2 CH2

O
CH2 C=O
N
CH3
Process Concept
 Lube treatment consists of following
units
 Solvent extraction - to remove aromatics
and improve VI
 Solvent Dewaxing - to remove wax and
improve pour point
 Hydrofinshing - to improve colour and
stability

Solvent Selection
 High Selectivity
 Good Solvency
 Easy Recovery from hydrocarbon phase
 Good thermal stability
 Low vapor pressure to minimize energy
 Non Corrosive and non toxic
 Bio-degradability
 Low Cost
Purpose - Solvent extraction
 Improve VI.
 Improve oxidation resistance and
color.
 Reduce carbon and sludge forming
tendencies of the lubricants by
separating the aromatic portion from
the naphthenic and paraffinice portion
of the feed stock.

Purpose - Solvent extraction
 solvent treatment is a physical process
in which undesirable olefin compounds,
asphaltic compounds, aromatic
compounds, and sulfur compounds are
selectively dissolved in the solvent and
removed with the solvent.
 After separation of the solvent by
distillation from both the unwanted
materials and the treated oil, the solvent
can be reused.

Process - Solvent extraction
 It is a counter current solvent extraction
process to remove undesirable poly
aromatic hydrocarbons from the lube
distillates.
 Undesirable poly aromatics are accumulated
in solvent rich Extract phase due to their
preferential solubility in solvent
 Desirable paraffinic & naphthenic
components are accumulated in lighter
raffinate phase
Packed Extraction Tower
Packings – random & structured packings
Packings – better efficiency – improved
contacting & reduced back mixing
Packing material –wetted by continuous
phase
Packings selection – nature of liquid
Packed Extraction Tower
Packing should always be of material which is
preferentially wetted by the continuous phase to
reduce the tendency of dispersed phase droplets
from coalescing on the surface thus contributing to
further loss of efficiency.
In this regard thermoplastic packing are
preferentially wetted by hydrocarbon liquids and
ceramic packing is preferentially wetted by aqueous
liquids.
Metal packings are wetted by either hydrocarbon or
aqueous liquids.
Light liquid
Interface
Heavy liquid
Packing
Light liquid
Heavy liquid
Figure: Packed extraction tower

Sieve Tray (Perforated Plate) Tower
Multistage, counter-current tower – effective for liquid handling capacity

& extraction efficiency
Suitable – corrosive system – absence of mechanical moving parts
Either heavy liquid or light liquid dispersed
Light liquid dispersed – flows thro’ perforation of each plate & dispersed
into drops thro’ continuous phase
Continuous phase flows horizontally across each plate, next plate –
down-comer
Heavy phase dispersed – column reversed – up-comer for continuous
phase
Alternative – heavy liquid dispersed in one part & light liquid another part
Principal interface – central portion
Cross flow trays – small diameter tower ( 2m)
Larger tower- multiple downspout - intervals
Light liquid out
Principal
interface Heavy liquid in
Coalesced dispersed
liquid
Perforated plate
Downspout
Light
liquid in
Heavy
liquid out
Figure- Sieve-tray extraction tower

Rotating Disk Contactor (RDC)
Mechanically agitated –counter-current extractor
Horizontal disks – agitated elements – centrally
supported shaft
Stator ring – mounted column wall & offset against
agitator disks – aperture greater than agitator disk
diameter
Rotating disk shearing action – used – inter-
disperse phases
 In this system, horizontal disks are used
as agitating elements, which are
mounted on a centrally supported shaft.
 Mounted on the column wall and offset
against the agitator disks are the stator
rings, whose have aperture is greater
than the agitator disk diameter.
 This device uses the shearing action of
the rapidly rotating disks to inter-
disperse the phases.
 Characteristics
 Reasonable capacity: 20-30 M3/M2-hr
 Limited efficiency due to axial back-
mixing
 Suitable for viscous materials
 Suitable for fouling materials
 Sensitive to emulsions due to high
shear mixing
 Reasonable turndown (40%)

Variable speed drive
Light liquid
outlet
Heavy liquid
Interface
inlet
Stator ring
Rotor disk
Light liquid
inlet
Heavy liquid
outlet
Figure: Rotating Disk Contactor

Uses:
 Petroleum industry – furfural extraction
 Separation of aromatics from aliphatic
 Desulphurization of gasoline
 Recovery of phenol from waste water
Phenol treatment process
 The phenol treatment process is the
most widely used. Phenol, also known as
carbolic acid, is a poisonous solid that
can cause serious flesh burns.
 It melts at 410C (1060F) and boils at
1830C (3610F).
 In the phenol treatment process, phenol
is used in the liquid state by maintaining
the temperature at over 350C (1000F)
 In the process, raw lubricating oil is pumped into the bottom
of the tower and phenol into the top; the phenol descends
through the oil and is mixed with the oil by means of baffles
or other mechanical mixing devices.
 The treated oil or raffinate leaves the top of the tower.
 The phenol that collects at the bottom of the tower contains
the extract (aromatic, unsaturated, asphaltic, and sulfur
compounds extracted from the raw oil) and is known as
spent phenol.
 The raffinate is heated to 2600C (5000F) and pumped to a
pair of fractional vacuum distillation towers operated in
series. Here the phenol in the raffinate is removed overhead.
 The bottom product from the second tower is the finished
product.
 The phenol is recovered from the spent phenol in a phenol recovery
unit, which consists of another pair of fractional distillation towers
and a stripper tower.
 The spent phenol is heated and passed into the primary tower,
where process water is removed as an overhead product and some
of the phenol recovered as a side-stream product.
 The bottom product from the primary tower is heated to about
2400C (4600F) and pumped into the secondary tower, where the
majority of the remaining phenol is recovered as an overhead
product.
 The extract (the bottom product) is heated to 3450C (6500F) and
pumped into a vacuum stripper tower, where steam removes the
phenol from the extract.
 The phenol obtained from the various distillation units is pumped to
a heated storage tank for reuse.
 The extract may be used
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Dr P A Joshi, special-purpose
Nadiad product when high-
32
molecular-weight aromatic hydrocarbons are needed; it may be
Furfural(Furan-2 carbaldehyde)
 Furfural is an organic compound derived
from a variety of agricultural
byproducts, including corncobs, wheat
bran, and sawdust.
 The name furfural comes from the Latin
word furfur, meaning bran, referring to
its usual source.
 Chemical formula: OC4H3CHO
 Boiling point: 161.7 °C
 Density: 1.16 g/cm³

Furfural(Furan-2 carbaldehyde)
 It has tendency to react with
atmospheric oxygen gradually
resulting in polymers of furfural; as a
consequence to this change, solvent
power is lost.
 To arrest such unwanted contacts, a
nitrogen or inert gas seal over
extractor & storage tanks is
necessary.

Processing Units
 Extractor
 Raffinate recovery
 Extract Recovery Section

Furfural Extraction
 The most important operating variables are :
 Furfural / oil ratio ( F / O ratio )
 It has the greatest effect on the quality and yield of
the raffinate.
 Range 2:1 for light stocks to 4.5 : 1 for heavy stocks.
 Extraction temperature
 is selected as a function of the viscosity of the oil and
the miscibility temperature.
 Extracted recycle ratio
 Determines to some extent the rejection point for the
oil and the sharpness of separation between the
aromatics and naphthenes and paraffins.

Pumping of waxy crude
 Important factor for pumping wax is its pour
point.
 Pour point is directly related to the wax content
of oil.
 Indian crudes are waxy and high pour points.
 Crudes from Assam are characteristically famous
for high pour points(wax content 16% and pour
point about 300C).
 Pumping such crudes, is extremely difficult.
 Such crudes can be transported only after
conditioning

Waxy crude
 Waxes which can be composed of saturates,
aromatic, polars and asphaltenes, vary in
molecular weight and composition with their
temperature of precipitation in waxy crude.
 Waxes that precipitate out of the crude oil
solution at temperature above the pour point are
of higher molecular weight and have a high
asphaltene content.
 The waxes that precipitate at lower temperature
have lower molecular weights and contain
mostly saturates.
Chemical additives
 These additives act by changing the structure
of wax and retard the crystal growth.
 Pour point of an oil can be lowered by
lowering the viscosity of the oil or by
dewaxing or by the addition of a suitable
pour point depressant.
 The depressant gets adsorbed on the
surface of the wax crystals and reduce their
size and also change the crystal structure,
thus increase the rate of flow at lower
temperature.

Chemical additives
 Modification of wax structure reduces
viscosity.
 Even small quantities of
additives(300-800ppm) can markedly
depress the pour point by 10 to 160C.
 The additives being hydrocarbons in
nature.(tetradodecyl
polymethacrylate)

Conditioning of waxy crude
 A heat-treatment process for conditioning waxy
crude oils, developed by Burmah Oil Co. and British
Petroleum Co. Ltd.
 Principal : behavior of the wax itself.
 Conditioning of crude starts with cycles of heating
and cooling.
 Firstly, heating is done up to 950C,followed by
cooling in two stages.
 First cooling goes down to 650C followed closely by
another cooling cycle to 180C at a rate of 0.50C per
minute
 This modifies the crystal structure of wax to permit
the flow.

Solvent Extraction of Lube oil
 lube oil stock is treated by a solvent,

such as phenol and furfural , which can
dissolve the aromatic components in one
phase (extract) and the rest of the oil in
another phase (raffinate).
 The solvent is removed from both phases
and the raffinate is dewaxed.

Solvent Dewaxing Unit
 In the first solvent dewaxing process (developed
in 1924), the waxy oil was mixed with naphtha
and filter aid (Fuller’s earth or diatomaceous
earth).
 The mixture was chilled and filtered, and the
filter aid assisted in building a wax cake on the
filter cloth.
 This process is now obsolete, and most of the
modern dewaxing processes use a mixture of
methyl ethyl ketone and toluene or benzene.
 Other ketones may be substituted for dewaxing,
but regardless of what ketone is used, the
process is generally known as ketone dewaxing.

 Solvent dewaxing is used to remove wax from
either distillate or residual basestocks at any
stage in the refining process.
 General steps for dewaxing
 Contacting the feedstock with the solvent,
 precipitating the wax from the mixture by chilling,
 and recovering the solvent from the wax and
dewaxed oil for recycling.
 Processes use benzene–acetone (solvent
dewaxing), propane (propane dewaxing),
ethylene dichloride–benzene (Barisol dewaxing),
and urea (urea dewaxing), as well as liquid sulfur
dioxide–benzene mixtures.

 Several pure solvents or mixtures of solvents
have been in use for solvent dewaxing.
 These include Methylisobutylketone (MIBK),
Dichloromethane, Trichlorethylene, and a mixture
of Methyl Ethyl Ketone (MEK) and Toluene and
MEK/Benzene.
 Pure Toluene is an excellent oil solvent, and, has
good solvent power for wax as well. If it is used
alone, a tight lattice of wax will form that hinders
filtration.
 In contrast, MEK shows low solvent power to
paraffinic compound (i.e., low selectivity) and as
such it precipitates the wax very well.

Wax types
 Solvent dewaxing process produces
three different waxes (also known as
crude waxes or raw waxes) depending
on whether light, intermediate, or heavy
paraffin distillate is processed.
 The wax from heavy paraffin distillate
may be sold as dark raw wax, the wax
from intermediate paraffin distillate as
pale raw wax.
 The latter is treated with lye and clay to
remove odor and improve color.

Cold press Filtration method
 The lowest viscosity paraffinic oils were
dewaxed by the cold press method to
produce oils with a pour point of 20C
(350F).
 The light paraffin distillate oils contained
a paraffin wax that crystallized into
large crystals when chilled and could
thus readily be separated from the oil by
the cold press filtration method.

 The more viscous paraffinic oils (intermediate and
heavy paraffin distillates) contained amorphous or
microcrystalline waxes, which formed small crystals
that plugged the filter cloths in the cold press and
prevented filtration.
 As the wax could not be removed from intermediate
and heavy paraffin distillates, the high-quality, high-
viscosity lubricating oils in them could not be used
except as cracking stock.
 The wax from raffinate phase of solvent extraction is
dissolved in a solvent (methyl ethyl ketone, MEK)
and the solution is gradually chilled, during which high
molecular weight paraffin (wax) is crystallized, and
the remaining solution is filtered.

 There are two types of processes in use
today
1) Uses refrigeration to crystallize the
wax and solvent to dilute the oil portion
sufficiently to permit rapid filtration to
separate the wax from the oil.
2) Uses selective hydrocracking process
to crack the wax molecules to light HC.
(using zeolite based catalyst)
 Dewaxed oil next must go through a
finishing step to improve its color and
color stability.
 Stock wax is used either for catalytic
cracker feed or undergoes a de-oiling
operation before sold as industrial
wax.
 These include mixing and heating,
cooling (chilling), filtration, and
evaporation.
 Rate of cooling (high or low) has a strong
influence on crystal formation and particle
characteristic.
 For example, a high cooling rate is found to
promote the formation of small crystals but
they are of the needle type that clogs the
filter.
 Experiments showed that the optimum
cooling rate varies between 0.56–4.4oC per
minute depending on the type of crude oil.
 The chilling or filtration temperature is
usually in the order of -20 oC

Acid clay process
 Lubricating oil is settled or filtered after collection and
is dehydrated.
 Oil is then treated with concentrated sulphuric acid to
remove polymers, asphalts, degraded additives and
other products of degradation.
 Sludge formed is allowed to settle and removed.
 Oil is neutralized with activated clay, at elevated
temperatures.
 Clay also bleaches the oil and adsorbs certain
impurities not removed by acid treatment.
 Clay-oil slurry is filtered to remove clay and other
solids.
 If the raw material contains more than one grade of
lube oil product further processing may be required.

Acid clay process
 Spent oils, which have not deteriorated
to great extent, are often clay
contracted or treated with adsorbents
without any acid treatment.
 They are generally given a preliminary
settling, filtering, centrifuging or
vacuum dehydrating treatment.
 Insulating oils and Transformer oils are
often treated in this way.
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PAJ PetroProc V Treatment III

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PETROLEUM PROCESSING-V

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 Undesirable characteristics include high pour points,

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 The most widely used extraction solvents are

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 The nature of the raw lubricating oil stock is important

 Liquid SO2 - benzene-developed by Edeleanu(1907) OH

 N Methyl Pyrrolidone (NMP) -developed by CH C-CHO

Texaco(1965) & Exxon CH2 CH2

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Figure: Packed extraction tower

Multistage, counter-current tower – effective for liquid handling capacity

Figure- Sieve-tray extraction tower

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Figure: Rotating Disk Contactor

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 lube oil stock is treated by a solvent,

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