U.S. patent number 3,593,790 [Application Number 04/789,089] was granted by the patent office on 1971-07-20 for method for producing shale oil from an oil shale formation.
This patent grant is currently assigned to Shell Oil Company. Invention is credited to John A. Herce.
United States Patent |
3,593,790 |
Herce |
July 20, 1971 |
METHOD FOR PRODUCING SHALE OIL FROM AN OIL SHALE FORMATION
Abstract
A method for producing shale oil from a permeable zone formed
within a subterranean oil shale formation by circulating through a
well borehole in contact with said permeable zone a fluid
containing at least one phenolic compound.
Inventors: |
Herce; John A. (Houston,
TX) |
Assignee: |
Shell Oil Company (New York,
NY)
|
Family
ID: |
25146557 |
Appl.
No.: |
04/789,089 |
Filed: |
January 2, 1969 |
Current U.S.
Class: |
166/267; 166/271;
166/275; 166/272.6 |
Current CPC
Class: |
C09K
8/592 (20130101) |
Current International
Class: |
C09K
8/58 (20060101); C09K 8/592 (20060101); E21b
043/22 (); E21b 043/24 () |
Field of
Search: |
;166/247,265,267,268,271,272,275,303 ;208/11 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Calvert; Ian A.
Claims
I claim:
1. In a method for producing shale oil from a subterranean oil
shale formation comprising the steps of:
forming a permeable zone within a subterranean oil shale
formation;
extending at least one well borehole into the permeable zone within
said subterranean oil shale formation;
circulating a hot fluid containing an aromatic Bronsted acid
through said permeable zone;
recovering shale oil and a fluid containing said aromatic Bronsted
acid; and
separating the oil from the fluid containing said aromatic Bronsted
acid.
2. The method of claim 1, wherein the Bronsted acid is a monomeric
phenolic compound.
3. The method of claim 2 wherein the monomeric phenolic compound
comprises about 10 percent by volume of the circulating fluid.
4. The method of claim 2 wherein the step of circulating a fluid
containing at least one phenolic compound therein includes the step
of introducing said phenolic compound continuously into said
permeable zone while said fluid is being circulated
therethrough.
5. The method of claim 1 wherein the circulating fluid is water
containing phenol.
6. The method of claim 1 wherein the circulating fluid is an
oil-miscible fluid containing phenol.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to a process for solvent extracting shale oil
from a subterranean oil shale formation; more particularly, it
relates to a process for recovering shale oil from a permeable zone
in an oil shale formation by circulating therethrough at least one
phenolic compound.
2. Description of the Prior Art
Shale oil as kerogen, which is a bituminous material present in oil
shale formations, can be removed from oil shale by pyrolysis at
elevated temperatures. A big drawback to the retorting of oil shale
to recover shale oil is the need to remove and dispose of a
substantial amount of the shale after it has been retorted. In view
thereof, in situ retorting has found much favor in recent years as
a method of recovering shale oil, particularly from subterranean
oil shale formations. One such method is to create a large,
permeable zone within the oil shale formation by rubblizing such a
zone by an explosion within the formation, e.g., by utilizing
high-energy explosives such as nuclear bombs. One or more access
wells are then drilled into the fragmented zone and communication
is established between the permeable zone and openings into the
wells. Hot fluids are then injected, usually to start an in situ
combustion heating process which causes the shale oil (kerogen) to
become fluidized. The shale oil is then recovered from a production
well by conventional means.
SUMMARY OF THE INVENTION
It is an object of this invention to produce shale oil from a
subterranean oil shale formation more efficiently than has been
previously accomplished.
It is a further object of this invention to improve the rate of
recovery, amount of recovery and/or the nature of the petroleum
materials that are recovered from a subterranean oil shale
formation by use of at least one phenolic compound having unique
oil-extracting properties.
These objects are accomplished by extending at least one well bore
hole into a permeable zone formed within a subterranean oil shale
formation and circulating an aromatic organic Bronsted acid, such
as a phenolic compound therethrough per se or in a fluid carrier.
Shale oil and circulating extracting fluid material are then
recovered from the permeable zone and the shale oil is separated
from the extracting material. The formation should be preheated
prior to injection or the circulating fluid should be injected hot
in carrying out this process. By "aromatic Bronsted acid" is meant
an aromatic substance that loses a proton as defined in "Advanced
Organic Chemistry," pp. 491-2, by Fieser and Fieser (1961).
In situations in which it is desirable to mine portions of an oil
shale formation and pyrolyze the mined oil shale in a fluid-heated,
pressure tight, surface located retort, the pyrolytic recovery of
petroleum material is improved by incorporating an effective amount
of phenolic compound in the hot fluid with which the oil shale is
contacted. In such a process, chunks or fragments of the oil shale
are preferably contacted with a hot aqueous and/or hydrocarbon
fluid that contains at least about 10 percent by volume of at least
one phenolic compound employing a temperature of at least about
650.degree. F. under a pressure sufficient to keep a significant
proportion of the fluid in the liquid phase. Where the
oil-shale-contacting fluid predominates in hydrocarbon components,
e.g., a benzene solution of a phenolic compound, the oil shale is
preferably preheated by contacting it with hot aqueous liquid. The
contacting of chunks of oil shale with a hot aqueous liquid, (i.e.,
with hot water utilized in preheating the oil shale and/or a hot
aqueous solution containing at least one phenolic compound) tends
to exfoliate the pieces of the oil shale. The exfoliation reduces
the tendency for clinkers to be formed during the
pyrolysis-extraction operation and reduces the extent to which the
oil shale needs to be crushed in order to obtain an efficient
recovery of petroleum material.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is a vertical sectional view of an oil shale formation to
which the recovery process of this invention has been applied,
involving a single-well borehole;
FIG. 2 is a vertical sectional view of the oil shale formation of
FIG. 1 wherein a pair of well boreholes are disposed in accordance
with the teachings of my invention; and
FIG. 3 is a vertical sectional view of an alternate recovery
process of the invention applied to the single-well borehole of
FIG. 1.
DESCRIPTION OF THE PREFERRED EMBODIMENT(S)
Referring to the drawing, FIG. 1 shows a well borehole 11 extending
into subterranean oil shale formation 12. Fluid communication may
be established between points 13 and 14 in oil shale formation 12
and adjacent to borehole 11 along a vertical fracture by, for
example, a conventional hydraulic fracturing procedure. Hot,
aromatic Bronsted acid such as a phenolic compound or fluid
containing such acid is then circulated through tubing 17 past
packers 18 and 19, or the formation should be heated and the fluid
injected, until oil shale-derived fluidizable materials are
entrained in the circulating fluid. The fluid passes through
perforations 20 and 21 in casing 22. Of course, if the wellbore 11
is uncased, such perforations are unnecessary. The fluidizable
materials may then be recovered from the outflowing portions of the
circulating fluid by any known means. Thus, a single well may be
used, although it is generally preferred to use at least a pair of
wells. As seen in FIG. 1, if a single well is used, the preferred
two points may be a pair of substantially vertically separated
points that are apt to be encountered by vertical fractures within
the oil shale.
As shown in FIG. 2, a pair of wellbores 23 and 24 extend into
subterranean oil shale formation 25. Fluid communication is
established between point 26 adjacent to wellbore 23 and point 27
adjacent to wellbore 24. In a preferred embodiment, the depths of
such points may be those at which a tuffaceous streak is
encountered by a pair of well boreholes between which the streak is
continuous. The permeable channel extending through the oil shale
may be formed by the process of locating and acidizing a tuffaceous
streak as described in an application Ser. No. 619,259 filed Feb.
281967 to Prats, now U.S. Pat. No. 3,481,398. A hot phenolic
compound, such as as aromatic Bronsted acid or a fluid containing
the acid, is then circulated through tubing 29 past packer 30,
until the oil shale-derived fluidizable materials are entrained in
the circulating fluid. The circulating fluid passes through
perforation 31 in the casing 32 of wellbore 23, through points 26
and 27, and through perforation 33 in the casing 34 or wellbore 24.
Again, if the well is uncased, such perforations are unnecessary.
Fluidizable materials which are derived from the oil shale can then
be recovered from the circulated fluid by any known means.
The circulation of the hot fluid may be a long duration heating
operation, and, for some time, the amount of oil production may be
insignificant. The temperature of the circulating fluid is
preferably monitored either at the point at which the fluid flows
out of the permeable path or at the wellhead.
Oil shales are generally impermeable. Once a permeable path has
been established between a pair of wells, the permeable path will
provide substantially the only zone that can be penetrated by a
fluid injected into either of the wells. In view of this,
relatively simple equipment can be utilized to circulate the heated
fluid through the permeable path between the selected points. The
fluid can be pumped through a heating device, through the permeable
path, through a temperature-monitoring device, and then recycled
back through the heating device. The duration of the heating that
is necessary for a given oil shale can be determined by maintaining
a sample of the shale at an equivalent temperature for an
equivalent time until a suitable degree of conversion is obtained.
This can be done prior to or while circulating the fluid.
In FIG. 3, an alternate recovery process, which can be operated
with a single well, is illustrated. Here, the permeable channel
formed within oil shale formation 12 is preferably a relatively
voluminous permeable fragmented zone 35. The term "permeable
fragmented zone" refers to a multiply-fractured zone in which the
number of the fractures and the volume of the interconnected
openings within the fractures provide a void volume of from about 5
to 40 per cent of the volume of the zone.
Permeable fragmented zones can be formed by known hydraulic and/or
explosive techniques for fracturing subsurface earth formations.
One suitable fracturing technique was described in l922, in U.S.
Pat. No. 1,422,204. The streak acidizing procedure of application
Ser. No. 619,259, filed Feb. 28, 1967 which matured as U.S. Pat.
No. 3,481,398 on Dec. 2, 1969, may be used, preferably to form a
channel into which a liquid explosive is injected and subsequently
detonated to form a generally disc-shaped permeable fragmented
zone. High-power explosives, such as those produced by nuclear
devices, are particularly suitable means for forming such
fragmented zones. In general, the permeable fragmented zone formed
by a nuclear device has a vertically extensive and generally
cylindrical shape.
In circulating hot fluid through a permeable fragmented zone, the
flow paths can be vertical or horizontal and can involve a radially
expanding or line-drive type of displacement of the fluid that is
circulated through the oil shale. Generally, a substantially
vertical downward flow is preferred.
FIG. 3 illustrates a portion of a nuclear chimney type of permeable
fragmented zone 35. In treating such a zone, one or more wells 36
are drilled to near the bottom, preferably while the zone is hot,
or at least warm, from the explosion energy. In the illustrated
arrangement of FIG. 3, the well 36 is drilled and cased to near the
bottom and the casing 37 is perforated at 38 and 39 and equipped
for injecting fluid through the borehole annulus above packer 18,
and through perforations 38 into the upper portion of the
fragmented zone. Fluid is produced from near the bottom of the zone
through perforations 39 and tubing string 40.
With such an arrangement, the pressure within the permeable
fragmented zone is adjusted to one selected for the circulation of
heated fluid. The adjustment is affected by controlling the rate of
withdrawing fluid from the cavern relative to the rate of injecting
fluid into the cavern. As indicated in FIGS. 1 through 3,
conventional equipment and techniques, such as heater 41, pump 41a,
separator 42 and heat exchanger 43 may be used for pressurizing,
heating, injecting, producing, and separating components of the
fluid that is circulated through the permeable zone 35. The
production of the fluid can be aided by downhole pumping means, now
shown, or restricted to the extent necessary to maintain the
selected pressure within the zone. The pressure in the zone is
preferably maintained at a level suited for economically
transferring heat into the zone by circulating a fluid that is
economically available at the well site.
A wide variety of aromatic Bronsted acids and fluids containing
such acids may be used in this process. The main requirements are
that these acids be pumpable at a moderate temperature such as from
about 400.degree. to 600.degree. F. Carriers for the aromatic
Bronsted Acids can be oil-immiscible fluids such as water; aqueous
liquids; steams of various grades, such a low quality steam, dry
steam or supersaturated steam; or oil miscible fluids such as
relatively low-cost volatile hydrocarbons that contain or consist
essentially of volatile oil shale hydrocarbons that contain or
consist essentially of volatile oil shale hydrocarbons may be used.
The aqueous fluids, e.g., water, should be softened to inhibit
scaling at the temperatures to which they are heated.
In certain situations, it is advantageous to circulate a mixture of
relatively low-molecular weight, predominantly aromatic
hydrocarbons having relatively low critical temperatures and
pressures. With such hydrocarbons (which may include significant
proportions of shale oil hydrocarbon) the temperatures and
pressures within the permeable zone may provide conditions
approaching or exceeding the critical conditions for part or all of
the circulating hydrocarbons. In the critical or supercritical
region, such hydrocarbons have densities and viscosities that are
intermediate between their gas and liquid states and are
particularly effective in extracting organic components from oil
shale.
In a preferred feature of my invention, an aromatic Bronsted acid,
a reactive petroleum-extracting material having unique properties,
is added to the fluid being circulated through the permeable oil
shale formation of FIGS. 1 through 3 in an amount as low as about
10 per cent by volume of the injected fluid. The reactive material
may be mixed with either an oil-immiscible or an oil-miscible
fluid. The reactive materials also include phenolic or substituted
phenolic compounds, e.g., phenol or cresol, which are relatively
soluble in either oil or water. In the preferred method of my
invention disclosed herein, the reactive material containing
circulating fluid may contain the reactive material either as a
solute and/or a separate fluid phase that is introduced either
continuously or intermittently into the well boreholes of FIGS. 1
through 3.
EXAMPLE
It has been found that the addition of a phenolic or substituted
phenolic compound to a fluid (e.g., water or benzene) circulating
through a permeable oil shale formation results in the extraction
of significant amounts of organic matter from the oil shale within
the oil shale formation. Recoveries of 120 percent Fisher Assay
have been obtained with such phenolic compounds in much shorter
time periods than known prior art processes, as for example the
process disclosed in application Ser. No. 656,815, filed July 28,
1967to Deans et al. which matured as U.S. Pat. No. 3,474,863 on
Oct. 281969in which shale oil is produced by circulating a
volatile, normally liquid oil solvent through a permeable
fragmented zone within a subterranean oil shale formation under
supercritical conditions of temperature and pressure. In the Deans
et al. application, it was found that the addition of a normally
liquid hydrocarbon solvent, such as benzene, to the circulating
fluid gave results far superior to known prior art processes.
Solvent extractions utilizing aromatic Bronsted acids, e.g., phenol
or cresol, have achieved much greater recovery of oil than benzene
solvents. For example, in an eight day period, 120 percent Fisher
Assay was extracted by the circulation of pure phenol. Under very
long solvent oil shale contact times, recovery by the circulation
of phenol still attained 120 percent Fisher Assay. The phenol
solvent may be recovered by conventional distillation methods
yielding both pure phenol to be recycled back into the oil shale
formation and an organic enriched phenolic liquor. Further, a
phenolic compound miscible in water may be dissolved in water and
then flowed through the permeable oil shale formation. Tests have
shown that phenol-water solutions of from about 25 percent phenol /
75 percent water effectively recover the shale oil (kerogen) from
oil shale. The phenol water mixture of this method is sufficiently
acidic to attack the carbonates which form a portion of the
inorganic matrix of the oil shale within the oil shale formation.
These acid attacks increase the permeability of the oil shale and
lessen the resistance of the oil shale to the circulating
fluid.
The Fisher Assay method is a standard analytical method used to
determine the richness of an oil shale. The results are commonly
given in gallons of shale oil per ton of oil shale. Since this
method is essentially a retorting process, much of the organic
matter in the oil shale is converted to gas and approximately 20
percent of the kerogen is left in the residue as fixed carbon.
Thermal solution processes, such as disclosed herein, on the other
hand, may be carried out at much lower temperatures and more
organic matter may be recovered without coking it. Therefore,
recoveries by a thermal solution process, in accordance with the
teachings of my invention, resulting in a Fisher Assay greater than
100 percent are not anomalous.
Although good results in accordance with the teachings of the
present invention have been obtained with phenolic or substituted
phenolic compounds, any suitable aromatic organic Bronsted acid
having an active hydrogen proton may be used with varying degrees
of effectiveness. Examples of such organic compounds include:
phenol, cresol, catechol, resorcinol, aromatic carboxylic acids,
substituted aromatic carboxylic acids, etc.
The use of aromatic organic Bronsted acids, such as phenol or
cresol, provides a substance which donates active hydrogen ions
(protons) for attacking oil shale in situ. The active hydrogen ions
attack the acid-soluble inorganic components of the oil shale,
causing increased permeability and solution of the inorganic matrix
material. The active hydrogen ions may also attack particular
functional groups contained in the kerogen molecules in the oil
shale by breaking such molecules into smaller fragments more
amenable to solution. The remainder of the active hydrogen donor
molecule, after donation, is employed both as a solvent for the
kerogen fragments and as a transportation medium for bringing the
fragments to the earth's surface. Finally, the entire process may
take place at elevated temperature (namely above 400 .degree. F.)
and pressure conditions, but these conditions must be such that the
solvent employed exists as a liquid.
* * * * *