U.S. patent number 3,779,902 [Application Number 05/145,662] was granted by the patent office on 1973-12-18 for preparation of mineral free asphaltenes.
This patent grant is currently assigned to Atlantic Richfield Canada Limited, Canada Cities Service, Ltd., Gulf Oil Canada Limited, Imperial Oil Limited. Invention is credited to David L. Mitchell, James G. Speight.
United States Patent |
3,779,902 |
Mitchell , et al. |
December 18, 1973 |
PREPARATION OF MINERAL FREE ASPHALTENES
Abstract
Disclosed herein is an invention directed to a method of
deasphalting in which a desired amount of asphalt is removed by
adjusting the solvent power of the solvent-feed system to obtain a
desired cotangent theta for the system. Also disclosed is the
application of the cotangent theta principle to two-stage
deasphalting of Athabasca bitumen.
Inventors: |
Mitchell; David L. (Edmonton,
Alberta, CA), Speight; James G. (Edmonton, Alberta,
CA) |
Assignee: |
Canada Cities Service, Ltd.
(N/A)
Imperial Oil Limited (N/A)
Atlantic Richfield Canada Limited (N/A)
Gulf Oil Canada Limited (N/A)
|
Family
ID: |
22514038 |
Appl.
No.: |
05/145,662 |
Filed: |
May 21, 1971 |
Current U.S.
Class: |
208/251R;
208/401; 208/424; 208/309 |
Current CPC
Class: |
C10G
21/003 (20130101); C10C 3/08 (20130101) |
Current International
Class: |
C10G
21/00 (20060101); C10C 3/08 (20060101); C10C
3/00 (20060101); C10g 021/00 () |
Field of
Search: |
;208/11,251,309 |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
Richard, Paper Presented at the 19th Canadian Chemical Engineering
Conference and 3rd Symposium on Catalysts, Oct. 19-22, 1969,
Edmonton, Alberta, 17 pages..
|
Primary Examiner: Levine; Herbert
Claims
Therefore, we claim:
1. A process for deasphalting a petroleum crude oil feedstock
containing asphaltenes and mineral contaminants which
comprises:
a. contacting said petroleum crude with hydrocarbon solvent in a
first deasphalting zone maintained at a cot .theta. solubility
parameter between about -0.3 and about -0.6, whereby between about
10 and about 25 wt. percent of the asphaltenes are precipitated
together with about 90 to 100 wt. percent of the mineral
contaminants; and
b. recovering said precipitate from said first deasphalting
zone;
c. recovering from said first deasphalting zone a heavy oil
fraction containing between about 75 and about 90 wt. percent of
the asphaltenes originally present in the feedstock and less than
10 wt. percent of the mineral contaminants present in such
feedstock;
d. contacting said heavy oil fraction from the first deasphalting
zone with hydrocarbon solvent in a second deasphalting zone wherein
the cot .theta. solubility parameter is maintained less than about
-0.8;
e. recovering from said second deasphalting zone an asphaltene
fraction containing between about 70 and about 90 wt. percent of
the asphaltenes originally contained in the feedstock together and
less than about 0.5 wt. percent of the mineral contaminants present
in such feedstock; and
f. recovering a deasphalted heavy oil fraction from the second
deasphalting zone.
2. The process of claim 1 in which the hydrocarbon solvents are
formulated as a single solvent or solvent blend selected from the
group consisting of paraffinic or isomeric hydrocarbons having from
three to eight carbon atoms, saturated substituted cycloparaffins
having five or more carbon atoms and saturated unsubstituted
cycloparaffins having five or more carbon atoms with the
concentration of the solvent or solvent blend introduced to form
the system adjusted by altering the proportions of the solvent used
according to the requisite Cot .theta. so as to yield the desired
Cot .theta. for the system.
3. The process of claim 1 in which the feedstock is bitumen
recovered from bituminous sand, which bitumen contains between
about 0.5 and about 10 wt. percent asphaltenes and at least about 3
wt. percent minerals.
4. The process of claim 3 in which the feedstock also contains
between about 5 and about 30 wt. percent water and in which at
least about 85 percent of such water is recovered in the first
asphaltene fraction.
5. A process for deasphalting a petroleum crude oil feedstock
containing asphaltenes and mineral contaminants which
comprises:
a. contacting said petroleum crude with hydrocarbon solvent in a
deasphalting zone maintained at a cot .theta. solubility parameter
between about -0.3 and about -0.6, whereby between about 10 and
about 25 wt. percent of the asphaltenes are precipitated together
with about 90 to 100 wt. percent of the mineral contaminants;
and
b. recovering said precipitate from said deasphalting zone.
6. The process of claim 5 in which the hydrocarbon solvents are
formulated as a single solvent or solvent blend selected from the
group consisting of paraffinic or isomeric hydrocarbons having from
three to eight carbon atoms, saturated substituted cycloparaffins
having five of more carbon atoms and saturated unsubstituted
cycloparaffins having five or more carbon atoms with the
concentration of the solvent or solvent blend introduced to form
the system adjusted by altering the proportions of the solvent used
according to the requisite cot .theta. so as to yield the desired
cot .theta. for the system.
7. The process of claim 5 in which the feedstock is bitumen
recovered from bituminous sand, which bitumen contains between
about 0.5 and about 10 wt. percent asphaltenes and at least about 3
wt. percent minerals.
Description
BACKGROUND OF THE INVENTION
The present invention is directed to a method of removing mineral
contaminants from petroleum fractions. More particularly, the
present invention is concerned with the deasphalting of crude
petroleum fractions and the removal of mineral contaminants during
a deasphalting operation. The invention is particularly useful in
treating bitumen recovered from bituminous sands.
Large deposits of bituminous sand are found in various localities
throughout the world. The term, bituminous sand, is used herein to
include those materials commonly referred to as oil sand, tar sand
and the like. One of the most extensive deposits of bituminous sand
occurs, for example, in the Athabasca District of the Province of
Alberta, Canada.
Typically, the composition of these sands by weight is: from about
5 percent to about 20 percent oil; from about 1 percent to about 10
percent water; and from about 70 percent to about 90 inorganic
solids. The specific gravity of the bitumen varies from about 1 to
about 1.05 at 60.degree. F. The major portion of the inorganic
solids, by weight, is a fine grain porous sand, having a particle
size greater than about 45 microns and less than 2,000 microns. The
remaining inorganic solid matter has a particle size of less than
44 microns and is referred to as fines. The fines content typically
varies from about 5 percent to about 30 percent by weight of the
solid inorganic content of bituminous sand. However, it is not
uncommon for the composition of bituminous sand to vary from the
above-mentioned ranges. Also, in mining the bituminous sand, clay,
which is found in layers of varying thickness in such sand areas,
may be mixed with the bitumen, thus increasing the inorganic solids
content, particularly the fines content of the material to be
processed. The fines portion contains minor amounts of various
metals including, for instance, titanium and zirconium. Such metals
are sometimes present in economically recoverable concentrations.
In any event, the presence of such metals in recovered bitumen is
frequently considered undesirable, especially in connection with
upgrading of the bitumen to saleable products.
In refining crude petroleum, including bitumen recovered from
bituminous sands, a variety of processes are available for
converting the lower boiling distillate portion of the crudes into
more valuable products. Materials boiling below about 750.degree.
F. are usually recovered by atmospheric distillation and materials
boiling up to 950.degree. to 1,150.degree. F., or higher, by vacuum
distillation. The remaining residuum generally contains high
concentrations of the high molecular weight organic compounds with
sulfur, nitrogen, oxygen, metals and other non-hydrogen species, as
well as high molecular weight hydrocarbons, including condensed
ring aromatics. The non-hydrocarbon compounds are often poisonous
to catalysts used in upgrading processes with metal compounds or
mineral contaminants being particularly deleterous to cracking
catalysts.
The residual portions of crude petroleum are sometimes described in
terms of relative solubility as comprising: firstly, a pentane
soluble heavy oil fraction resembling distillate except for its
high molecular weight and boiling point; secondly, a less soluble
resin or maltene fraction; and thirdly, a pentane insoluble
asphaltene fraction. The term "asphaltenes" as used herein refers
to material which is insoluble in pentane under temperature and
pressure conditions used for the extraction. When so extracted, the
asphaltenes separate as solid particles or granules. "Resins" are
less clearly defined terms in the art and the term is used herein
to describe that portion of the bitumen which adheres to the
insoluble asphaltene particles, but which may be solubilized by a
further extraction with pentane. The term "deasphalted heavy oil"
is used herein to describe that portion of the crude petroleum or
bitumen that is solubilized by the first extraction with a
solvent.
The deasphalting of petroleum crude is well known in the art.
Descriptions of deasphalting operations may be found in U. S. Pat.
No. 3,278,415, by Doberenz, et al; U. S. Pat. No. 2,188,013, by
Pilat, et al; and U. S. Pat. No. 2,853,426, by Peet. In the above
processes, the metal contaminants are normally remove together with
the resins and asphaltenes and, depending upon their origin,
generally about 60 percent of the crude, by addition to the crude
of an excess (from 2 to 10 volumes) of a low boiling liquid
hydrocarbon. Propane, propylene, normal or isobutanes, butylenes,
normal or isopentanes, hexanes, or their mixture, light straight
run naphthas, or other light aromatic free fractions of mineral oil
have been claimed to be satisfactory solvents.
However, the above art teaches that the crude or asphaltic
materials yield low recoveries of deasphalted heavy oil, generally
below 40 percent of the residuum, and it has been stated that if
high ratios of solvent to crude are utilized, to obtain oil yields
above about 60 percent, excessive amounts of metal compounds and
some asphaltenes appear in the extract phase.
It is an object of the present invention to provide a process for
the removal of metal contaminants from an Athabasca bitumen using
normally liquid or liquefied hydrocarbon solvents.
It is a further object of the present invention to provide a
process whereby hydrocarbon solvents, for example the isomeric and
paraffinic hydrocarbons having from three to eight carbon atoms,
saturated substituted or unsubstituted cycloparaffins having five
or more carbon atoms are utilized to deasphalt petroleum crude.
It is still a further object of the present invention to provide a
process for deasphalting the Athabasca bitumen whereby the
deasphalting medium is adjusted by the addition thereto of any of
the aforementioned solvents employed either individually or as
blends of two or more individual solvents.
It is still a further object of the present invention to provide a
process whereby a low mineral content asphaltene fraction is
produced which may be employed in the manufacture of high grade
metallurgical coke, electrocarbon, or other processes wherein a low
mineral content is a necessary prerequisite.
With these and other objects in mind, the present invention may be
more fully understood by specific referral to the following
discussion and drawings.
SUMMARY OF THE INVENTION
The objects of the present invention are accomplished by a process
for treating an asphaltene containing petroleum crude which may be
contaminated by both metals and water. The petroleum crude may
contain a considerable water concentration, being represented by a
froth. The process comprises the introduction, singularly or in
multiple steps, of a normally liquid or liquefied hydrocarbon
solvent into the asphaltene containing petroleum crude so as to
adjust the total asphaltene solvent power of the system. By
asphaltenes is meant those hydrocarbons which are pentane
insolubles. By solvent power of the system is meant the ability of
the total hydrocarbon system, including solvent, to dissolve and
contain the asphaltenes present.
In general, the process uses hydrocarbon solvents which may be
selected from the group consisting of one or more paraffinic or
isomeric hydrocarbons having from three to eight carbon atoms and
saturated substituted cycloparaffins and saturated unsubstituted
cycloparaffins having five or more carbon atoms. The solvent power
of the system including solvent and feed is adjusted by latering
the proportions of the solvent or the solvent type according to the
required cotangent .theta., as described hereafter, so as to yield
a desired solvent power for the total system of solvent and
petroleum crude. In general, in treating petroleum crude, for
example an Athabasca bitumen, it is preferred that from about 5.0
to about 40.0 barrels of solvent are introduced in each step of the
process per barrel of liquid to be treated.
In a two-step process, a solvent having a high solvent power is
introduced to form two fractions. The first fraction preferably
contains about 10.0 to about 25 weight percent of the asphaltenes
and resins contained within the petroleum crude, at least 85.0
weight percent of the water and at least 98.0 weight percent of the
mineral contaminants. A liquid fraction or heavy oil is formed
which contains the remaining mineral contaminants and asphaltenes
originally present in the petroleum crude. Subsequently, the two
fractions are separated and a second normally liquid or liquefied
hydrocarbon solvent forming a low solvent power system is
introduced into the liquid fraction, thereby forming two additional
liquid fractions. A first additional liquid fraction is formed
containing the remainder of the water, mineral contaminants and
asphaltene content of the heavy oil and a second additional liquid
fraction is formed consisting essentially of a mineral, water and
asphaltene free heavy oil. These two additional liquid fractions
are then separated to form the desired products of the present
invention, that is, a heavy oil significantly free of water or
mineral contaminants in a solvent phase and an asphaltene fraction
of the bitumen substantially free of mineral and water
contaminants.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention may be more fully understood by referral to
the following drawings in which:
FIG. 1 represents the relationship between as phaltene percent
recovery and the Cot .theta. of the total system for determining
solvent type and quantity of solvent introduced for use in the
process of the present invention; and
FIG. 2 represents one embodiment of a two-step process utilizing
the solvent power relationship of the present invention for
treating a petroleum crude to remove the asphaltenes therefrom and
concentrate and remove the metal contaminants and water.
DETAILED DESCRIPTION OF THE INVENTION
Solvent power is generally measured as the solubility of an oil in
a particular solvent system. As the asphaltenes are the least
soluble components of the oil, it is necessary to define solvent
power as the measurement of the critical solubility of the
asphaltenes in given oil systems containing solvents so that
deasphalting and deimineralizing of asphaltene containing oils may
be regulated. Conventional deasphalting processes for the
deasphalting of heavy oils by pentane or other paraffinic solvents
generally utilize the solvents singularly, wherein the asphalts are
all concentrated in one deasphalting tower, but in most instances
the asphaltenes recovered having a high mineral content.
It has been found that particularly useful solvent combinations may
be formed by the mixing of one or more high power solvents with
heavy oils in definite relationships, so that exact precipitation
of asphaltenes in deasphalting tower occurs. Specifically, the
yield of asphaltene precipitate obtained from the heavy oil is
related to solubility of the normally precipitating asphaltenes in
the solvent system. The major influence on precipitation is
governed by the solvent power of the single solvent or solvent
blend, in conjunction with the heavy oil system, with the
contribution of the solvent powers of the soluble oils and resins
in the heavy oil being considered. Additional information
concerning solubility characteristics may be found in "Regular
Solution" by Hildebrand and Scott, published by Prentice Hall in
1963 (Library of Congress Catalogue No. 62-11984).
The relationship of asphaltene solvent power of the heavy
oil-solvent precipitating medium may be expressed by the solubility
parameter Contangent .theta. (Cot .theta.). Cot .theta. is derived
from experimental data in which the percent asphaltenes
precipitated from a system for each solvent or solvent blend
mixture with the heavy oil is plotted against the individual
solvent concentrations or blend concentrations in the system,
thereby deriving a definite linear relationship. Cot .theta. being
the contangent of the angle .theta. formed between the X-axis or
the axis containing the solvent concentration and the linear line
formed by the experimental data. The Cot .theta. relationship and
means for determining .theta. for deasphalting system is fully
presented by J. A. Bichard, Oil Solubility, 19th Canadian Chemical
Engineering Conference and 3rd Symposium on Catalysis, Oct. 19-22,
1969, Edmonton, Alberta. As originally conceived, the Cot .theta.
relationship was intended to provide a means for insuring that
undesirable precipitation would not occur. Using this concept, it
was found that precipitation would be precluded by maintaining the
Cot .theta. of the system at a positive value. It has now been
found that by use of the Cot .theta. relationship, solvent power
relationships may be placed on a single functional graph as
illustrated by FIG. 1. One may choose the desired percent of
asphaltenes to be precipitated from FIG. 1 and thereby determine
what Cot .theta. relationship is required for the system, thus
adjusting the solvent content of the system to the exact
specifications required to obtain the necessary Cot .theta.
relationship in the system and thereby control the degree of
precipitation of asphaltenes.
The significance of selecting Cot .theta. for deasphalting becomes
apparent when one realizes that a solvent system exhibiting a
negative value yields an excellent asphaltene precipitation. If the
solvent system exhibits a very low solvent power, its respective
Cot .theta. is liable to lie close to the X-axis and exhibit a
value of minus infinity. If the system exhibits a good solvent
power, it will lie closer to the Y-axis. A good solvent has a
positive value by definition, the cotangent .theta. having a value
greater than zero. Therefore, a solvent having a cotangent .theta.
less than zero will be a relatively poor solvent. It is preferred
that the cotangent .theta. of the solvent and oil system utilized
in the deasphalting of heavy oil be less than about minus 0.3 if a
significant degree of asphaltene precipitation is desired.
To fully understand the meaning of solvent power for the Athabasca
oil systems, it is necessary first to consider the components,
composition and structure of the oil. The existence of saturates,
aromatics, resins and asphaltenes in the oil has been measured
showing the oil to be a mixture of isogels or heterogels, a
structure composed of an ordered state consisting of asphaltenes
surrounded by still higher molecular weight aromatic type
hydrocarbons with layers of resin molecules about them. These
molecules form micelles in an oil saturated environment. Weak inner
molecular attraction and repulsion forces between the nonpolar
hydrocarbons are essentially responsible for the structure. The
process of solution proceeds by the addition of solvent toward the
nucleus. These components held by the weakest association forces
dissolve first. The energy supplied to overcome the association
forces of the micelles is supplied by the solution energy of the
solvent system. The solution energy is different for different
solvent systems and is a function of chemical structure. Paraffin
containing solvent systems have the least amount of solution
energy, with solution energy decreasing with increasing molecular
size, this is due apparently to parallel self-association.
Polarizability of aromatics, such as benzene, result in greater
dispersion forces and hence, high solution energy. This is even
more prevalent with condensed aromatics with side chain
substitution. Partial moments through substitution are responsible
for the good solvent powers of chlorinated solvents. When the
solution energy of the solvent molecules is insufficient to
overcome the strong cohesive forces acting on the nucleus of the
micelle, floculation or precipitation of these nuclei occur. The
experimental end point of asphaltene solubility is a measure of the
critical cohesive energy of the system at which the solvation of
the nuclei can no longer be maintained and precipitation of the
asphaltene occurs. Therefore, in deasphalting it is desirable to
obtain the effective rate of floculation required such that the
exact Cot .theta. or solvent blend in the oil system may be chosen
whereby an exacting percent asphaltene will be precipitated in the
deasphalting tower. In multiple stage deasphalting for the
treatment of materials such as metal contaminated Athabasca
bitumens, it is preferred that the first deasphalting tower exhibit
a relatively low asphaltene precipitation with a high precipitation
of the minerals contained therein. Between about -0.3 and -0.6 Cot
.theta. would be preferred in the first deasphalting tower, while
the second and subsequent deasphalting towers would utilize a lower
Cot .theta. such as between about -0.3 and -2.0, preferably between
about -1.4 and -2.0 so that a significant precipitation of
asphaltenes, comparatively mineral-free, will be obtained with a
low asphaltene content in the oil-solvent mixture effluent produced
from the top of the deasphalting tower.
Through use of FIG. 1, in which is illustrated the relationship of
asphaltene yield and solvent power of the precipitating medium as
expressed as a solubility parameter Cot .theta., it has been shown
that the more concentrated the solution of the bitumen in the
solvent, the more limited the solvent power of the system becomes
so that the solvent cannot retain as large a quantity of the
asphaltenes. As bitumen often contains considerable aromatic
constituents, which act in a similar manner as the added solvents,
these properties must also be considered in obtaining the Cot
.theta. of the solvent system shown in FIG. 1. The Cot .theta. of
the system is a function of the type and amount of solvent
utilized, as well as the type and amount of oil being treated.
In the processing of Athabasca tar sands for the formation of
useful refinery products, one finds a residual product of
asphaltenes and ash content being made up of mineral contaminants
in a water froth mixture. This mixture is extremely difficult to
decompose into the desirable product of a heavy oil for coking or
catalytic cracking and asphaltenes free from minerals. The minerals
are recovered for their economic value and the asphaltenes
separated as a suitable source for asphalt and derivative materials
for use in commercial processes. Required is a solvent dilution
technique whereby the heavy oils and asphaltenes may be separated
and the asphaltenes then separated from the minerals contained
therein for the reduction of the bitumen froth to commercially
desirable products.
In accordance with a preferred embodiment of the invention, a heavy
crude oil such as Athabasca bitumen which is contaminated by
substantial amounts frequently exceeding 3 weight percent of
mineral contaminants is treated in a two-stage process to produce
substantially deasphalted heavy oil and an asphaltene product
sufficiently free of minerals to be useful in the manufacture of
metallurgical grade coke. In the first stage, the feedstock is
contacted with hydrocarbon solvent of a type and quantity chosen to
adjust the Cot .theta. of the system to between about -0.3 and
about -0.6. This results in two first stage product fractions, one
of which is an asphaltene fraction comprising between about 10 and
about 25 weight percent of the asphaltenes present in the feedstock
(in the case of Athabasca bitumen frequently between about 0.5 and
about 10 wt. percent of the total bitumen) and which contains more
than about 90 wt. percent, preferably more than about 98 wt.
percent, of the total minerals content of the feedstock. The second
first-stage product fraction is a heavy oil fraction which contains
the remainder of the asphaltenes and solvent. Where the feedstock
is Athabasca bitumen, this fraction usually contains between about
90 and about 98 wt. percent of the total bitumen feedstock and less
than 0.1 percent of the minerals originally present in the bitumen.
This heavy oil fraction is then subjected to a second-stage
deasphalting treatment with hydrocarbon solvent in which the
solvent power of the system is adjusted to a Cot .theta. less than
about -0.3 and preferably less than about -0.8 to produce a
second-stage asphaltene precipitate containing less than about 0.5
wt. percent minerals and which is therefore of sufficiently low
mineral content for use in the manufacture of metallurgical coke.
In order to obtain maximum yields of such substantially
mineral-free asphaltenes, it is preferred that the Cot .theta. of
the second-stage deasphalting unit be maintained less than about
-1.4, preferably between about -1.4 and -2.0 to insure
precipitation of at least 90 and preferably 98-100 percent of the
asphaltenes present in the second-stage feed. Maintaining the Cot
.theta. of the system less than about -1.6, may result in
precipitation of some materials such as resins which are soluble in
pentane in addition to precipitation of pentane-insoluble
asphaltenes. Where Athabasca bitumen is the original feed, the
second-stage asphaltene product frequently will be equivalent to
between about 5 and about 10 wt. percent of the original bitumen.
The other second stage product is, of course, a deasphalted heavy
oil fraction which is substantially free of minerals and preferably
also substantially free of asphaltenes and therefore does not
present problems during further refining operations.
In another preferred embodiment of the invention, material such as
Athabasca bitumen having a high water content, as well as a high
mineral content, is treated by a two-stage process similar to that
described above. For instance, in typical processes for recovery of
bitumen from Athabasca tar sands, the bitumen is recovered in the
form of a froth containing between about 5 and about 30 wt. percent
by water. In treating such a froth by the two-stage process
described immediately above, the majority and usually between 85
and 100 percent of the water present will be found in the
first-stage asphaltene product. It can thus be seen that the
treatment of such bituminous froth as described above has the added
advantage of removing water, as well as minerals, from the useful
products, i.e., the second stage deasphalted heavy oil product and
second-stage asphaltene product, thus eliminating the need for
separate processing steps for removal of water.
In practicing the invention, from about 0.5 to about 40 barrels per
barrel of oil treated of either isomeric paraffin hydrocarbons
having five or more carbon atoms or saturated or unsaturated
substituted cycloparaffin hydrocarbons are frequently used to
adjust the solvent power of the deasphalting system. The invention
relates to the use of any one or more of the aforementioned
hydrocarbon types to adjust the system's solvent power in the
enhancement of the deasphalting process. The deasphalting process
is preferably conducted at from about 50.degree. F. to about
140.degree. F. and at atmospheric pressure.
To more fully understand the process of the present invention, FIG.
2 is presented in which a two-step deasphalting and demineralizing
process for treating bitumen recovered from tar sands is depicted.
In the process, bitumen 101 is introduced simultaneously with a
hydrocarbon solvent 102 into a deasphalting tower 103. The solvent
power of this system is preferably adjusted to a Cot .theta. of
between about -0.3 and about -0.6. A solvent-heavy oil mixture 105,
containing the majority of the asphaltenes, is produced from the
top of the deasphalting tower 103 and an asphaltic residue 104,
preferably containing greater than 90 percent of the minerals, is
produced from the lower portion of the deasphalting tower 103. The
solvent-heavy oil stream 105 is then introduced into a second
deasphalting tower 107 simultaneously with additional hydrocarbon
solvent 106. For maximum recovery of mineral-free asphalt, the
solvent power of the second-stage deasphalting system is preferably
adjusted to a Cot .theta. between about -1.4 and -2.0. A
solvent-oil mixture 109 is produced from the top of deasphalting
tower 107 and asphalt 108, being substantially mineral-free, is
produced from the lower portion thereof. The solvent-oil mixture
109 is then fed to a fractionating tower 110 from which a mineral
free-cracking stock oil 111 is produced from the lower portion
thereof and solvent vapor 112 is produced from the upper portion
thereof. The solvent vapor is then introduced into a condensor 113
from which a liquid solvent stream 114 is produced. The liquid
solvent stream may be used for solvent 102 and solvent 106 makeup
in the first and second deasphalting towers 103 and 107,
respectively.
To exhibit the use of solvent power adjustment of the system to
control the yield of precipitated asphaltenes, the following
Examples are presented:
EXAMPLE 1
The solvent powers in terms of Cot .theta. of various systems of
solvents and oils were determined by mixing one-to-one volumes of
normally liquid or liquefied solvents with an Athabasca bitumen
containing 17 wt. percent asphaltenes. A measured amount of 100
grams of each solvent was poured into 130 grams of a water-bitumen
froth, equivalent to 100 grams of dry bitumen. The mixture was
shaken vigorously for 5-10 minutes at 0.5 hr. intervals and allowed
to settle; this procedure was conducted for approximately 8 hours.
At the end of the 8 hour period the fractions were easily separated
by decantation followed by filtration, with light suction of the
solvent/heavy oil solution.
After removal of any residual solvent by blowing, the water content
of the asphaltene fraction was determined by the standard ASTM
D-9558 method for the determination of water in petroleum products.
For the heavy oil fraction formed, the solvent was removed by
blowing followed by evaporation and the water separated
mechanically.
Results of this analytical procedure are set forth in Table I as
follows:
TABLE I
Results of Deasphalting Bitumen
Solvent Power Weight Percent of System Asphaltenes Solvent (Cot
.theta.) Precipitated Propane -(2.5 to 100 3.5) est. Butane -2 100
N-Pentane -1.5 100 Hexane Isomers -1.2 75 Heptane Isomers -1.1 67
Pentane/Hexane -1.3 83 Pentane/Heptane -1.2 75 Pentane/Cyclopentane
(1:1) -0.7 35 Pentane/Cyclohexane (1:1) -0.7 35 Cyclopentane -0.1 1
Cyclohexane 0 0 Heptane/Cyclopentane (1:1) -0.5 22
Heptene/Cyclohexane (1:1) -0.5 23
EXAMPLE 2
A solution of bi-constituent solvent consisting of liquid propane
and varsol was utilized in a sample of Athabasca tar bitumen in
order to determine the percent asphaltenes precipitated. As liquid
propane itself precipitates asphaltenes plus resins and possibly
other fraction of bitumen, initial concentrations with 100 percent
propane solvent were determined. Yields of precipitated materials
ranged from between 40 to 48 percent with liquid propane used in
large excess. The solution of the propane with varsol produced a
solvent blend of increased solvent power. Consequently, the yield
of precipitated material decreased. For example, a solvent bitumen
weight ratio of 3.5 to 1 and a propane-varsol concentration of 2.5
to 1 resulted in a 30.7 percent yield of precipitate at a Cot
.theta. of -2.6. In a similar manner, when bitumen was present in a
higher concentration, the contribution of the soluble aromatic
portion was added to the solvent power, the precipitating media in
the yield of precipitating material decreased as the Cot .theta.
value of the system increased. In the second case, an approximate
propane-varsol weight ratio of between 1.5 and 3.5 to 1 was blended
as a solvent. The bitumen ratio was between 1.0 and 1.6 to 1 as
compared to four to one in the first instance and the Cot .theta.
was -2.5. The yield of precipitating material was 18.4 percent in
this case, showing considerable decrease in precipitate as compared
to the 30.7 percent as illustrated in the first case.
Therefore, it can be seen through this experimentation and FIG. 1
that the amount of asphaltene precipitate can be varied over a wide
range, from say, approximately 0.5 percent to 100 percent of the
total asphaltene content of the system, dependent upon the adjusted
solvent power of the precipitating medium or solvent system. The
inherent advantage of this control is that subsequent crops of
asphaltenes can be precipitated as essentially mineral-free
material in a second deasphalting tower with the majority of the
minerals precipitated with a first crop of material in a first
deasphalting tower.
The process of the present invention discloses a technique whereby
suitable solvents such as paraffinic and isomeric hydrocarbons
having from three to eight carbon atoms and saturated substituted
or unsubstituted cycloparaffins having five or more carbon atoms
may be blended in exacting compositions of solvents for the use in
the deasphalting of bitumen or petroleum crudes containing mineral
and water contaminants and high asphaltene concentrations.
The present invention has been described herein with respect to
particular embodiments and aspects thereof and it will be
appreciated by those skilled in the art that various changes and
modifications can be made, however, without departing from the
scope of the present invention.
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