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.