Clay Processes

SUBTOPIC 24.2.3.4-24.5.2.3

Continous Contact
Filtration Process

This is a continuous clay treatment

process in which finely divided
adsorbent is mixed with the charge
stock and heated to 95 8C to 175 8C
(200 8F to 350 8F). The slurry is then
conveyed to a steam-stripping tower,
after which it is cooled, vacuum
filtered, and then vacuum stripped for
further product specification control.

Cyclic Adsorption Process

The cyclic adsorption process is used

for the separation of aromatics from
petroleum product streams. Like the
Arosorb process, the cyclic adsorption
process employs fixed beds of silica
gel. The various stages of the process
are

(1) extraction of the adsorbable

material from the feedstock (refining)

(2) concentration of the adsorbed

phase (enriching)

(3) stripping for recovery of the extract

and regeneration of the gel using a
light gasoline or pentane fraction.

Gray Clay Treatment

This is a continuous vapor-phase process for selectively

polymerizing the diolefin constituents of, and removing other
gum-forming agents from, thermal gasoline.

Two or more towers (10 ft in diameter and approximately 25 ft

high) are used in parallel, and the hydrocarbon vapors are
passed through the bed at temperatures (120 8C to 245 8C, 250
8F to 475 8F) just above the condensation point.

The diolefins polymerize and drain from the base of the tower or
they are separated from the gasoline by fractionation. Spent clay
is either discarded or regenerated in kilns.

Percolation Filtration Process

This is a continuous-flow cyclicregenerative liquid phase process

in which oil is filtered through a
bed (containing 10 to 50 tons of
Fullers earth) before storage. Two
or more beds are used alternately
on an operating and regenerating
cycle. The spent clay is
regenerated by washing it with
naphtha, steaming, and burning.

Thermofor continuous percolation

process

The Thermofor continuous percolation

process is a continuous regenerative
process for stabilizing and decolorizing
lubricants or waxes that have been
distilled, solvent refined, or acid
treated.

The charge stock is heated to 50 8C to

175 8C (125 8F to 350 8F), injected into
the base of a clay- filled tower, and
allowed to percolate in countercurrent
flow through the bed. Spent clay is
continuously withdrawn from the base
of the tower; regenerated clay is added
to the top of the bed to maintain a
constant level .

Oxidative Process

Oxidative treatment processes are, processes that have been

developed to convert the objectionable-smelling mercaptans to the
less-objectionable disulfides by oxidation.

However, disulfides tend to reduce the tetraethyl lead susceptibility

of gasoline, and recent trends are toward processes that are cap able
of completely removing the mercaptans.

Bender Process

The Bender process is a fixed-bed catalytic treatment method that employs a lead sulfide
catalyst. Controlled amounts of sulfur, alkali, and air are added to the product stream,
which is passed through lead sulfide catalyst beds.

In this method, the sulfur required to oxidize the mercaptides is also furnished by the air
oxidation of lead sulfide.

When larger quantities of air must be supplied for treating gasoline of high mercaptan
content, there is a tendency toward excessive plumbite formation and also excessive
sulfur formation.

In such cases, a controlled quantity of aqueous sodium sulfide is simultaneously added

to reconvert the extra plumbite back to lead sulfide. The presence of the remaining extra
sulfur is not desirable, and therefore it is advantageous to control the air oxidation
carefully. The lead sulfide is essentially a catalyst, as only oxygen is consumed in the
process; there is, however, a certain loss of alkali to sodium sulfate and thiosulfate

Copper Sweetening Process

The oxidizing power of cupric (Cu2 ) salts is also used to convert mercaptans directly into
disulfides; free sulfur is not employed, and polysulfides are not obtained. The process employs
cupric chloride in the presence of strong salt solutions, which are generally made up by dissolving
copper sulfate in an aqueous solution of sodium chloride. The cuprous chloride (CuCl) is soluble in
the salt solution, and there is no precipitation.

Under operating conditions, a certain amount of copper is retained by the sweetened petroleum
fraction but these can be remove d by washing the material with aqueous sodium sulfide. Air
blowing the cuprous chloride solution, after or during the sweetening operation, regenerates the
cupric chloride. The copper chloride solution may be employed as such, or the sour fraction may
be percolated through a porous mass saturated with the treating agent.

Alternatively, the gasoline may be mixed with a solid carrier for the reagent, dispersed as a slurry.

Three methods of mechanical application of the

copper chloride are used.
Fixed-Bed Process

Solution Process

Slurry Process

If air will not cause

the petroleum fraction to
change color or form
gum, this process may be
used. The sour material is
passed through beds of
an adsorbent that have
been impregnated with
cupric
chloride.
Air
continuously regenerates
the cupric chloride almost
simultaneously with the
sweetening react ion.

A solution of cupric
chloride is continuously
mixed in a centrifugal
pump
with
the
sour
fraction. The mixture then
enters a settling tank
where the spent treatment
solution separates from
the petroleum liquid, and
the treatment solution is
withdrawn to a tank where
blowing
with
air
regenerates
cupric
chloride.

This process makes use of clay or

a similar material impregnated
with cupric chloride. The clay is
mixed with a small amount of,
say, naphtha to form a slurry,
which is pumped into the sour
naphtha stream. Air or oxygen
gas is added with the sour stream
and continuously regenerates the
cupric chloride. The treated
material and clay slurry flow into
a settling tank and separate, and
then the clay slurry is recycled.

The Doctor Process

The doctor process is a method of treating sour distillates (Brown , 19

92)

the distillate with alkaline sodium plumbite (doctor solution) is agitated

in the presence of a small amount of free sulfur. A black precipitate of
lead sulfide is formed, and the material, which has improved odor, has
been rendered sweet.

The Doctor Process

Hypochlorite Sweetening Process

This process employs sodium or calcium hypochlorite [NaOCl or

Ca(OCl)2)]. The principal reaction produces disulfides (RS SR 0)
with some formation of sulfoxides (R2S O) and sulfonic acids
(RSO2H). When hydrogen sulfide is present, an alkaline wash
prevents the formation of elemental sulfur. An alkaline after-wash
is frequently necessary to remove undesirable chlorinated
products.

Inhibitor Sweetening Process

This is a continuous process that uses a phenylenediamine-type

inhibitor, air, and caustic to sweeten low-mercaptan-content gasoline.
The inhibitor and air are injected between the caustic washing stages,
and the mercaptan disappearance may be attributed to reaction with
the caustic and then to oxidation during both washing and storage. In
the absence of caustic, excessive peroxide formation occurs, which
leads to gasoline deterioration.

Merox Process
The

Merox process is a
combination
process
for
mercaptan
extraction
and
sweetening of gasoline
or
lower-boiling
materials
(Holbrook,
1997).

The

catalyst is a cobalt
salt, which is insoluble
in the oil and may be
used
in
caustic
solution
or
on
a
suitable solid support.

SOLVENT PROCESSES

Solvent

refining processes are of a physical nature

rather than a chemical nature.

The desirable constituents, as well as the undesirable

constituents, of the mixture can be recovered
unchanged and in the original state. In addition, the
processes that use solvent as a means of refining are
extremely versatile, insofar as both low-boiling and
high-boiling fractions can be used as feedstocks.

3 classifications of Solvent
Processes
Deasphalting
is usually applied to
such materials as gas
oils, lubricating stocks,
residua,
and
even
heavy crude oil before
further treatment. The
solvent separates the
feedstock
into
constituents that are
usually
based
on
molecular
size
and
polarity.

Solvent refining
is usually applied to
materials boiling in the
lubricating oil range,
and
it
is
a
means of selectively
removing
(by
extraction) aromatics,
naphthenes, or other
constituents
that
adversely
affect
physical
parameters,
such as the viscosity
index .

Dewaxing processes

are applied to refined feedstocks

before final treatment with clay. Wax
in a finished lubricating oil adversely
affects the properties of the oil, for
example, by increasing the pour point
and reducing the fluidity at low
temperatures
because
of
crystallization of the wax from the
lubricating oil. Dewaxing operations
are often combined with wax
production
when
low-pour-point
lubricating oil and high-melting-point
wax can be produced simultaneously.

Deasphalting

Solvent deasphalting provides an extension to vacuum distillation

and is a later addition to the petroleum refinery. In its present
form, solvent deasphalting (when employed for feedstock
preparation to catalytic cracking units) may be considered a
competitor to vacuum distillation, visbreaking, and coking.

The highest-boiling lubricating oil fractions are valuable for the

lubricating of engine parts, such as steam cylinders, which are
subjected to high temperatures. One common method of
obtaining the highest-boiling lubricating oil fractions is to treat
asphaltic crude residues with sulfuric acid, which removes the
asphaltic materials; another method of separating asphalt from
residual lubricating oil fractions is deasphalting, also often
referred to as decarbonizing.

Deasphalting

Propane deasphalting focuses on the ability of liquefied petroleum gases to

precipitate asphaltic materials from heavy feedstocks and residua whereas
the lubricating oil components remain in solution.

In propane deasphalting, the heavy feedstock and three to ten times its
volume of liquefied propane are pumped together through a mixing device
and then into a settling tank.

The temperature is maintained between 27 C (80 F) and 71 C (160 F).

The propane is maintained in the liquid state by a pressure of about 200
psi. The asphalt settles in the settling tank and is pumped to an asphalt
recovery unit, where propane is separated from the asphalt.

The upper layer in the settling tank consists of lubricating oil dissolved in a
large amount of propane, and while it is still dissolved in the propane, ore
impurities may be removed by sulfuric acid, or it may even be dewaxed.

Deasphalting
Propane fractionation

is a continuous process for the

segregation of vacuum distillation
residua into two or more grades of
lubricating oils. It is an extension
of the propane deasphalting
process. The residuum is charged
to the primary tower where it is
contacted countercurrently with
propane. The bottoms from the
primary tower are then
countercurrently extracted with
propane in a secondary tower for
production of a second propane
soluble stream (bright stock) but
at lower temperatures and
pressures.

Propane decarbonizing

is a solvent process usually used to

recover catalytic cracking feed from
residua. As butane, alone or with propane,
can also be used as the solvent, the
process is often called solvent
decarbonizing. The process and
equipment are essentially the same as
those employed for the deasphalting of
lubricating oils. Apart from the additional
use of butane, there is so little difference
between the processes that the terms
deasphalting and decarbonizing are often
used interchangeably (Hydrocarbon
Processing, 1978).

Solvent Refining

Solvent refining (solvent treatment) is a widely used method of refining

lubricating oils, as well as a host of other refinery stocks. The solvent
processes yield products that meet the desired specifications by removing
undesirable constituents (such as aromatics, naphthenes, and unsaturated
compounds) from the charge material.

There are, however, solvent refining processes in which the desirable

constituents are aromatics and are extracted by the solvent from the
petroleum fraction. Nevertheless, the original object of solvent extraction, or
solvent treatment, was to remove aromatic compounds from feedstocks, such
as lubricating oils.

In contrast to sulfuric acid treatment (which depends on chemical reaction for

a large part of its effect) , 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. The most widely used extraction solvents are phenol,
furfural, and cresylic acid.

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.

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. The greater is the extent of
treatment, the smaller the yield of treated oil but the higher the
quality.

It is possible to make oil of any desired quality from any raw

lubricating oil stock. In fact, it is possible to over-treat lubricating
oils, causing a loss in lubricating properties.

Such oils are so over-refined that they are not used as lubricating
oils; their lubricating properties are inferior to oils refined
specifically for use as lubricants. Thus, solvent extraction is a
complex operation requiring the selective removal of only those
components that reduce the lubricating qualities of the oil being
treated. The phenol treatment process is the most widely used.

In the phenol treatment process, phenol is used in the liquid state

by maintaining the temperature at over 35 C (100 F). 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.

Phenol,
also known
as carbolic
acid, is a
poisonous
solid that
can cause
serious
flesh
burns.

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 260 C
(500 F) 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 240 C
(460 F) 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 345 C (650 F) 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 feedstock is contacted with liquid sulfur dioxide and the

aromatic portion is concentrated in the extract phase, which is in
turn contacted with a wash oil (such as kerosene) to remove the
lower-boiling nonaromatic compounds. The streams are then
stripped and fractionated to recover sulfur dioxide and the wash
oil for recycling to the extraction tower.

Sulfur dioxide is used in conjunction with benzene for treating

lubricating oils. Mixing benzene with sulfur dioxide increases the
solvent capacity but at the same time retains the selectivity for
aromatic and nonparaffinic hydrocarbons.

The percentage of benzene in the solvent mixture makes it

possible to select the most advantageous treatment conditions
for any particular feedstock to produce a product with the desired
specifications. The process is carried out in the same manner as
phenol treatment, but the raffinate or treated oil has so little
furfural dissolved in it that distillation is not used to remove it;
steam stripping is all that is required.

The treatment is conducted in counterflow towers, or multistage units, which

normally operate at a temperature of 40 C to 120 C (100 F to 250 F).A hightemperature gradient in the treatment section permits a high yield of the refined oil.
Hydrogen fluoride treatment is a liquidliquid extraction process removing sulfur
and potential coke-forming materials from naphtha, middle distillates, and gas oil.

The feedstock is contacted countercurrently with liquid hydrofluoric acid in an

extraction tower, after which the overhead product is sent to a tower for removal of
hydrogen fluoride. The solvent is recovered from the extract by use of evaporators
and a stripper. The process is relatively insensitive to variations in temperature and
pressure, but normally temperatures of 50 C (120 F) and pressures below 100 psi
are employed.

The Udex extraction process is a liquidliquid recovery method for

the selective extraction of aromatic compounds from hydrocarbon
mixtures by the use of a diethylene glycol (90% o 92%), water (8%
to 10%), and solvent system. The feedstock, which may be
pretreated to eliminate high conjugated dienes or alkenyl aromatics,
rises countercurrent to the descending solvent.

The stripper recovers the solvent for recycling; the overhead from
the extractor is treated with clay and fractionated to separate the
aromatics. The temperatures employed in the process are usually
fairly low (120 C, 250 F); the pressures are just high enough to
maintain liquid-phase conditions.

Sulfolane has been used primarily for the extraction of aromatics,

such as benzene, toluene, and xylene(s). The chemicals usually arise
from catalytic reforming of various feedstocks. Thus the feedstock is
contacted with the solvent in an extractor, and the mixture is
conveyed to an extractive distillation column. The bottom product
from this column is a mixture of solvent and aromatic compounds.
Vacuum and steam stripping remove the final traces of hydrocarbons
in the bottom part of the recovery column.

Dewaxing

Dewaxing processes are designed to remove wax from lubricating oils to

give the product good fluidity characteristics at low temperatures. The
mechanism of solvent dewaxing involves either the separation of wax as
a solid that crystallizes from the oil solution at low temperature or the
separation of wax as a liquid that is extracted at temperatures above
the melting point of the wax through preferential selectivity of the
solvent. However, the former mechanism is the usual basis for
commercial dewaxing processes.

In the first solvent dewaxing process (developed in 1924), the waxy oil
was mixed with naphtha and filter aid (Fullers 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 benzene.

Other ketones may be substituted for dewaxing, but regardless

of what ketone is used, the process is generally known as ketone
dewaxing.

The process involves mixing the feedstock with one to four times
its volume of the ketone. The mixture is then heated until the oil
is in solution. The solution is then chilled at a slow, controlled
rate in double-pipe, scraped-surface exchangers.

Cold solvent, such as filtrate from the filters, passes through the
2 in. annular space between the inner and outer pipes and chills
the waxy oil solution flowing through the inner 6 in. pipe. To
prevent wax from depositing on the walls of the inner pipe,
blades or scrapers extending the length of the pipe and fastened
to a central rotating shaft scrape off the wax.

Slow chilling reduces the temperature of the waxy oil solution to 2

C (35 F), and then faster chilling reduces the temperature to the
approximate pour point required in the dewaxed oil. The waxy
mixture is pumped to a filter case into which the bottom half of
the drum of a rotary vacuum filter dips. The drum (8 ft in
diameter, 14 ft long), covered with filter cloth, rotates
continuously in the filter case.

Vacuum within the drum sucks the solvent and the oil dissolved in
the solvent through the filter cloth and into the drum. Wax
crystals collect on the outside of the drum to form a wax cake,
and as the drum rotates, the cake is brought above the surface of
the liquid in the filter case and under sprays of ketone that wash
oil out of the cake and into the drum.

A knife edge scrapes off the wax, and the cake falls into the
conveyor and is moved from the filter by the rotating scroll. The
recovered wax is actually a mixture of wax crystals with a little
ketone and oil, and the filtrate consists of the dewaxed oil
dissolved in a large amount of ketone.

Ketone is removed from both by distillation, but before the wax is

distilled, it is deoiled, mixed with more cold ketone, and pumped
to a pair of rotary filters in series, where further washing with
cold ketone produces a wax cake that contains very little oil.

The deoiled wax is melted in heat exchangers and pumped to a

distillation tower operated under vacuum, where a large part of
the ketone is evaporated or flashed from the wax. The rest of the
ketone is removed by heating the wax and passing it into a
fractional distillation tower operated at atmospheric pressure and
then into a stripper where steam removes the last traces of
ketone.

An almost identical system of distillation is used to separate the

filtrate into dewaxed oil and ketone. The ketone from both the
filtrate and wax slurry is reused.

Clay treatment or hydrotreating finishes the dewaxed oil as

previously described. The wax ( slack wax), even though it
contains essentially no oil as compared to 50% in the slack wax
obtained by cold pressing, is the raw material for either sweating
or wax recrystallization, which subdivides the wax into a number

Solvent dewaxing can be applied to light, intermediate, and

heavy lubricating oil distillates, but each distillate produces a
different kind of wax. Each of these waxes is actually a mixture of
a number of waxes.

However, heavy paraffin distillate yields a wax composed of a

series of waxes with melting points in the range of 60 C to 90 C
(140 F to 200 F), which harden into small crystals from which
they derive the name of microcrystalline wax or microwax. On the
other hand, intermediate paraffin distillates contain paraffin
waxes and waxes intermediate in properties between paraffin and
microwax.

The solvent dewaxing process produces three different slack

waxes (also known as crude waxes or raw waxes) depending on
whether light, intermediate, or heavy paraffin distillate is
processed. The slack 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.

There are several processes in use for solvent dewaxing, but all
have the same general steps, which are

The processes use benzeneacetone (solvent dewaxing), propane

(3) recovering
( propane dewaxing), trichloroethylene
(2) precipitating ( separator Nobel dewa
(1) contacting
the solvent from
the
wax
from
xing),
ethylene dichloridebenzene Barisol dewaxing),
and
urea (
the feedstock
the wax
and
the mixture by
urea
axing), as well as
liquid sulfur dioxidebenzene
with dew
the solvent
dewaxed oil for
chilling
recycling
mixtures.
Residual lubricating oils from urea dewaxing, such as cylinder oils
and bright stocks, are made from paraffinic
or mixed-base reduced crude oils and contain waxes of the
microcrystalline type. Removal of these waxes from reduced
crude produces petrolatum, a grease-like material that is known
in a refined form as petroleum jelly. This material can be
separated from reduced crude in several ways.

The original method was cold settling, whereby reduced crude was
dissolved in a suitable amount of naphtha and allowed to stand
over winter until the microwax settled out. This method is still
used, but the reduced crude naphtha solution is held in
refrigerated tanks until the petrolatum settles out.

The supernatant naphtha-oil layer is pumped to a still where the

naphtha is removed, leaving cylinder stock that can be further
treated to produce bright stock. The petrolatum layer is also
distilled to remove naphtha and may be clay treated or acid-andclay treated to improve the color.

Another method of separating petrolatum from reduced crude is

centrifuge dewaxing. In this process the reduced crude is dissolved
in naphtha and chilled to 18C (0F) or lower, which causes the
wax to separate. The mixture is then fed to a battery of centrifuges
where the wax is separated from the liquid.

However, the centrifuge method has now been largely replaced by

solvent dewaxing methods and by more modern methods of wax
removal.