Lubricant Base Oil Deasphalting Processes

Most crude oils contain varying amounts of high molecular weight hydrocarbons (asphaltenes and
resins) which are solid to semisolid in nature with high carbon to hydrogen ratios.
These asphaltenes are nonvolatile and thus tend to remain in the residue on heating. The resins are
in part volatile and may be present in some of the high boiling lube distillates. Since these fractions
contain many high viscosity components useful in the manufacture of lubricating oils, refiners have
employed many methods (adsorption, chemical treating and precipitation with alcohols, ketones and
light hydrocarbons) to remove these asphaltic materials from heavy distillates and vacuum residuum.
Propane deasphalting and the Duo-Sol process are most often used to remove these materials. The
Duo-Sol process is a combination propane-deasphalting and solvent-refining process which uses
Selecto (a mixture of phenol and cresylic acids) as the extraction solvent.

Why we remove asphaltenes &resins?

The asphalt and resins present in the very heavy distillates and residua are removed because they
are high in viscosity, seriously impede the refining action of other processes, contribute an
undesirable dark color to lube base stocks and have a tendency to form carbonaceous material and
deposits on heating.

Propane deasphalting:
 (propane deresining): when used to remove resins from Pennsylvania grade vacuum residua.
 (propane decarbonizing): is a milder "deep" deasphalting processes to prepare feedstocks for fuels
processing.
is an extractive-precipitation process which selectively precipitates asphalt, resins and hydrocarbons
on the basis of density and the invert solubility of the heavy hydrocarbons in liquefied light
hydrocarbons. Propane is preferred over the other liquefied gases used in the milder "deep"
deasphalting processes to prepare feedstocks for fuels processing, because considerably more
asphalt and resins must be precipitated to prepare a deasphalted oil (DAO) which can be used for the
manufacture of lube base stocks.
Deasphalting is an extractive-precipitation process. The purpose of the process is the removal of
asphaltenes, resins and metals from vacuum residua and very heavy vacuum gas oils. Propane can
also be used to fractionate distillates and other hydrocarbons on the basis of density. When used in
this manner it is called propane fractionation “Solvent fractionation”.
Although the process is primarily used to remove asphaltic materials from the feedstock, it also
removes other undesirable materials such as sulfur, nitrogen, aromatics and metals. It also improves
the color and viscosity index of the feedstock. Accompanying these beneficial changes one accepts
the increase in wax content of the deasphalted oil.
 The deasphalted oils from atmospheric residua and very heavy vacuum distillates are used as
feedstocks to lube processing units for the manufacture of lube base oils ranging from solvent neutral
oils to cylinder oils and bright stocks. Deasphalted oils from the deep deasphalting processes are
used as feedstocks to cat-cracking or hydrocracking units. The residue, asphaltenes and resins from
deasphalting are used as asphalt extenders, coker feed, or as a component of fuel oil.

DEASPHALTING PROCESS VARIABLES:

The more important variables are:

 the quality of the feedstock.

 the solvent.
 the deasphalting temperature.
The temperature and dosage are the process conditions which are most often varied with the quality
of the feedstock and the DA oil quality being the major determinants of these process conditions.
Although solvent dosage as high as 15 or more may be used to maximize DA oil yield, the dosage
used will depend on the quality of the feedstock and product being manufactured. The more typical
range for solvent dosage is probably about 800-1000 volume percent propane to residua for the
manufacture of bright stocks.
A. Feedstock

The effect of feedstock on yield and DA oil properties for preparation of lube feedstocks is shown
in tables below.

These data show that crude source and length of the residuum are important process variables.
Heavy neutral distillates are also sometimes produced by deasphalting the wash oil stream from
vacuum fractionation of reduced crudes. The yield of DA oil for use in bright stock and cylinder
oil manufacture can be increased by the inclusion of a higher than normal proportion of wash oil in
the vacuum residuum used as feed to the deasphalting unit.
Benefits of this technique is:
 lower investment cost.
 a higher yield of DAO.
 a lower operating cost per barrel of feed and product for both new and existing propane
deasphalting units.
The comparison of the data in Tables above shows that the carbon residue and yield for deep
deasphalting “FCCU feedstock” is higher than for lube manufacture; the high carbon residue FCCU
feeds would not be suitable for quality base oil manufacture.
B. Solvent-to-Oil Ratio and Temperature
The general effects of solvent-to-oil ratio and temperature on the yield and quality of the deasphalted
oil from virgin residua are presented below:
 Propane deasphalting at constant temperature: effect of dosage on deasphalted oil yield.

Deasphalting solvents behave like extraction solvents when the solvent dosage is increased at
constant temperature; the amount of hydrocarbon soluble in the solvent increases.

Propane deasphalting: carbon residue versus yield.

 Propane deasphalting at constant dosage: effect of temperature on deasphalted oil viscosity.

Propane deasphalting at constant dosage: effect of temperature on deasphalted oil yield.

However, the deasphalting solvents exhibit and invert solubility in comparison to extraction solvents
with an increase in temperature; the amount of hydrocarbon decreases with an increase in
temperature.
The deasphalting solvents also behave differently when both solvent and temperature is increased.
In extraction, the amount of hydrocarbon soluble in the solvent increases and with a deasphalting
solvent the solubility may increase or decrease depending on the increase in either solvent dosage
or temperature.
An increase in solvent dosage, with the appropriate increase in temperature, will almost always
improve the quality of the DA oil at a given yield. However, this may not be cost-effective when one
considers that the investment and operating costs of the deasphalting unit are proportional to the
solvent dosage. It is therefore apparent that selecting an optimum solvent-to-oil ratio depends on
the solvent and temperature used to prepare the desired DA oil from a given feedstock. Other factors
which influence the processing conditions are the site, investment and operating costs.
The information available concerning the effect of solvent-to-oil ratio indicates that the optimum
solvent dosage depends on the quality of the feedstock. Zuiderweg presents data which shows that
the quality of the deasphalted oil continues to improve with an increase in solvent-to-oil ratios as
high as 10 to 1, but that metals removal is only slightly influenced by solvent ratios above about 5 to
1. Johnson et al. report that increasing the solvent-to-oil ratio to about 15: 1 results in better quality
cracking stocks.
Control of the deasphalting tower becomes very difficult near the critical point of the solvent because
the solubility of hydrocarbons in the solvent with temperature becomes very large at the critical
point. This change in solubility results in drastic changes in the amount of oil transferred between
the raffinate and extract phases which causes flooding and DA oils of variable quality. Although no
separations are currently being made in the supercritical region, solvent is being separated from the
deasphalted oil using supercritical techniques.
Temperature gradients are used in the deasphalting devices because they create internal reflux and
increase the sharpness of the separation in the bottom of the deasphalting tower. Low temperatures
may impede mass transfer leading to inefficient operation.
C. Pressure
An increase in temperature decreases the yield and carbon residue content of the deasphalted oil.
An increase in pressure increases the density of the solvent and increases the yield and decreases
the quality of the DA oil. The effect of pressure becomes more evident as operating conditions
approach the critical point.
Pressure is normally not used for operational control of the deasphalting tower because of the
instability of the separation and quality of the DA oil near the critical point.
D. Solvent and Solvent Composition
The solubility of a vacuum residuum in various light hydrocarbons is depicted in the figure below. The
results obtained with different residua will be different at different temperatures and solvent-to-oil
ratios. It is obvious from this curve that the solvent power of the deasphalting solvent can be
controlled by selecting various mixtures of these solvents. This is done by some refiners. The lower
molecular weight hydrocarbons have the lower solvent power and will precipitate more asphalt. It
has generally been found that propane is more suited for the manufacture of lube feedstocks because
greater quantities of the asphaltenes and resins must be removed to produce a quality base oil as
compared to preparation of cracking feedstocks. Butanes and pentanes are generally used to prepare
FCCU and hydrocracker feedstocks because they provide a higher yield of DA oil, and precipitate less
of the asphalt than does propane.

Selectivity of normal hydrocarbons.

The deasphalted oil quality relationships when using different deasphalting solvents are presented
as Figures below. These deasphalting studies were conducted at a constant solvent-to-feed ratio of
about eight while increasing temperature. The data show the effect of propane, butane and pentane
on the deasphalted oil yield and quality of a mid-continent vacuum residuum. Similar data and
behavior can be developed for other feedstocks; however, the shape and location of the curves will
vary as a result of differences in the residuum composition.
PROCESS FLOW
Although mixer-settlers were used in the early deasphalting units, baffle towers of various designs
and rotating disc contractors are used in modern deasphalting units. A simplified flow diagram for a
unit using a mixer-settler is shown.

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Mixer-settler deasphalting unit.

A. Mixer-Settler Deasphalting Unit

In the older mixer-settler type of unit, the feedstock is combined with propane and mixed using a
mixing valve or static mixer and flows to the asphalt settler. The solvent rich (extract) phase
containing a partially deasphalted oil exits the top of the settler, is heated to a higher temperature
and flows into the resin settler. The solvent rich extract phase containing the DA oil exits the top of
the resin settler, is heated and flows to the solvent recovery section. Propane is separated from the
DA oil using a high pressure and low pressure evaporator followed by steam stripping. The propane
is condensed and/or compressed and flows to propane storage for reuse in the process. The
raffinate, solvent-lean phase rich in asphaltenes, settles in the asphalt settler and the solvent-lean
resin-rich phase settles in the resin settler. These phases flow from the bottom of the settlers and
are mixed with propane before entering wash settlers. The resin and asphalt wash settlers to
combine with the feedstock entering the unit. The asphaltenes and resins are heated and recovered
by flash distillation and steam stripping. The evaporated propane is condensed and/or compressed
and flows to the propane storage tank for reuse in the process.
B. Continuous Deasphalting Units
In modern deasphalting units the feedstock is combined with a small amount of propane to reduce
viscosity. The pre-diluted feedstock is then pumped to a treating tower and enters at a point located
in the upper part of the treating tower as shown in figure. The feed is counter-currently contacted
therein with propane which enters near the bottom of the treating tower. The extract or solvent-rich
phase consisting of a solution of deasphalted oil and propane leaves the top of the treating tower;
the raffinate or solvent lean phase containing a solution of the residue or asphalt and propane leaves
from the bottom of the treating tower. The solvent recovery techniques used will depend on the type
of solvent recovery system being used and if resins are being separated from the asphaltenes.

Propane deasphalting unit flow diagram.

SOLVENT RECOVERY TECHNIQUES

Although flash vaporization is the most widely used method, many new units use and several older
units have or are being revamped to use the supercritical solvent recovery techniques.

A. Multiple Effect Evaporation

For units using multiple effect evaporation, the propane is recovered from the raffinate and extract
phases using multistage flash vaporization and steam stripping. The water is removed from the
propane by condensation and the propane is recirculated in the process as is done in the older mixer-
settler units. The effluent DA oil is cooled and sent to tankage for further processing. The residue
from deasphalting is also sent to tankage for further processing or use in asphalt manufacture or fuel
oil.
 Deasphalting unit flow diagram

The main difference between the process flow of the units presented in Figures above is the number
of evaporation stages used to recover the solvent from the deasphalted oil. The unit in fig. (1) uses
two stages of evaporation as compared to three stages for the unit depicted in fig. (2). Units using
three stages of evaporation use about two-thirds of the energy required for recovery of solvent from
the DA oil mix in a two stage unit.
Single effect evaporation is used in some older deasphalting units with dual effect evaporation being
used in most deasphalting units and triple effect evaporation being used in some modern and in some
refurbished deasphalting units. The two- and three-stage flash vaporization units use about 45 to 65
percent and 40 to 50 percent of the energy of a single stage flash vaporization for solvent recovery.
These reductions in energy are obtained because the heat required to vaporize the solvent in the
higher pressure flash vaporization stages is used to vaporize solvent in the next lower pressure flash
vaporization stages. The amount of energy saved is proportional to the solvent-to-feed ratio and the
cost of steam, fuel and electrical power.
B. Supercritical Solvent Recovery
Supercritical solvent recovery methods are also being used in some deasphalting and demetallization
processes. The Kerr-McGee Residual Oil Supercritical Extraction (ROSE®) and the UOP Demex
processes are two of the processes for which considerable information has been published. The
process flows for these processes are presented in figures below.
The process flow of the supercritical solvent recovery processes is very similar and consist of mixing
the feed with solvent and separating an asphalt rich phase which flows through a heater and stripper
for recovery of the solvent in the usual manner of a conventional deasphalting unit. The extract
solution of DA oil and solvent is pumped from the settler or first extractor, is heated, and enters the
resin settler for separation of the resins. The resins are pumped to a stripper for recovery of the
solvent. The extract, DA oil-solvent, solution is pumped through a heater wherein it is heated above
the critical temperature and passes into a settler for separation of the DA oil and solvent as separate
liquids. The liquid solvent is cooled by heat exchange with the extract solution and recycled in the
process. The DA oil leaving the DA oil separator is pumped to a stripper for removal of the residual
solvent by steam stripping as is done in a conventional deasphalting unit. The solvent contained in
the resins and asphalt from the separators are recovered using the conventional flash and/or
stripping operations. The vapors from the strippers are cooled to condense the water; the solvent
vapors are compressed and recycled in the process.

Supercritical Demex Unit flow diagram.

DEASPHALTING DEVICES
The deasphalting devices used in continuous deasphalting units consist of vertical towers containing
slats, gratings, baffles or rotating discs and stators. The use of baffle towers was the first replacement
for the mixer-settlers used in the early deasphalting units. The Rotating disc contactor, RDC, was first
introduced by Shell for the furfural extraction of lubricating oil base stocks. It has also been applied
to deasphalting of residua and heavy vacuum gas oils for manufacture of base oils and feedstocks to
fluid catalytic cracking units. A sketch of a rotating disc contactor is shown in Figure.
Rotating disc contactor.