Note: Descriptions are shown in the official language in which they were submitted.
CA 02699764 2013-09-13
EXTRACTION OF HYDROCARBONS FROM HYDROCARBON-CONTAINING
MATERIALS
FIELD OF THE INVENTION
[0021 The = present invention relates to the field of extraction of
hydrocarbons from
hydrocarbon-containing materials.
BACKGROUND OF THE INVENTION
[0031 The liquefaction, solubilization and/or extraction of fossil fuels, also
called hydrocarbon-
containing organic matter, in solid, semi-solid, highly viscous or viscous
form (individually and
jointly referred to as fossil fuels hereafter) have proven to be extremely
challenging and
difficult. As used herein, such fossils fuels include, but are not limited to,
hydrocarbon-
containing organic matter within coal, oil shale, tar sands and oil sands
(hereinafter jointly called
tar sands), as well as crude oil, heavy crude oil, crude bitumen, kerogen,
natural asphalt and/or
asphaltene. The difficulty can in part be attributed to the fact that these
fossil fuels include
complex organic polymers linked by oxygen and sulfur bonds, which are often
imbedded in the
matrices of inorganic compounds. A need exists to produce additional liquid
hydrocarbon feed
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stock for the manufacture of liquid and gaseous fuels as well as for the
production of various
chemicals, pharmaceuticals and engineered materials as the demand and
consumption for
hydrocarbon based materials increases.
[004] Various technologies or processes have been developed to liquefy,
solubilize and/or
extract the fossil fuels. None of the prior art liquefaction, solubilization
and extraction
technologies or processes, however, has proven to be commercially viable on a
large scale for all
types of fossil fuels. This is due to the fact that all of the prior art
technologies and processes for
the liquefaction, solubilization or extraction of hydrocarbons developed to
date are expensive to
deploy and operate. Additionally, the prior art processes and technologies for
the liquefaction,
solubilization and/or extraction of hydrocarbons may be difficult to scale up,
operate and/or
control because of one or more of the following reasons: (1) operating at an
inordinately
elevated pressure; (2) operating at a very high temperature; (3) the need for
expensive processing
vessels and equipment that require the external supply of hydrogen under
extreme conditions; (4)
being subjected to a mixture, or composition, of two or more reagents,
catalysts and/or
promoters, which are frequently highly toxic and are neither renewable nor
recyclable; (5)
requiring to supply a special form of energy, e.g., microwave radiation; (6)
long process times
for partial liquefaction, solubilization or extraction; (7) requiring
extraordinarily fine particles
with a size of about 200 mesh (0.074 mm), which is profoundly difficult and
costly to
manufacture and handle; and (8) being incapable of recovering and recycling
the necessary
reagents, catalysts and/or promoters. Thus, there exists a need to provide
additional techniques
and processes for the increased recovery of hydrocarbon materials.
[005] For primary drilling operations, it would be advantageous to employ a
process that would
enhance solubilization and encourage movement of additional or trapped
hydrocarbon-
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containing organic matter that could then be recovered allowing existing
pressure gradients to
force the hydrocarbon-containing organic matter through the borehole. In
particular, it would be
useful to solubilize heavier hydrocarbons that usually remain in the reservoir
through primary
drilling operations.
[006] For secondary and tertiary or enhanced oil recovery operations, it would
be advantageous
to employ a process that would enhance solubilization of oil to recover
hydrocarbon-containing
organic matter in the reservoir in a manner that is cost effect and that does
not damage the
reservoir. While effective methods and compositions exist for tertiary
operations, current
methods suffer due to expense of operations in comparison to the value of the
produced
hydrocarbon-containing organic matter.
SUMMARY OF INVENTION
[007] In accordance with one embodiment of the present invention, a method of
extracting
hydrocarbon-containing organic matter from a hydrocarbon-containing material,
includes the
steps of providing a first liquid including a turpentine liquid and contacting
the hydrocarbon-
containing material with the turpentine liquid such that an extraction mixture
is formed, as well
as residual material. The extraction mixture contains at least a portion of
the hydrocarbon-
containing organic matter and the turpentine liquid. The residual material
includes non-soluble
material from the hydrocarbon-containing material. The residual material can
also includes a
reduced portion of the hydrocarbon-containing organic matter in the
circumstance where all such
hydrocarbon-containing material has not been solubilized by the turpentine
liquid and moved
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into the extraction mixture. The residual material is then separated from the
extraction mixture.
The extraction mixture is further separated into a first portion and a second
portion. The first
portion of the extraction mixture includes a hydrocarbon product stream that
includes at least a
portion of the hydrocarbon-containing organic matter extracted from the
hydrocarbon-containing
material.. The second portion of the extraction mixture includes at least a
portion of the
turpentine liquid. In one embodiment, substantially all of the turpentine
liquid is recovered in
the recycle stream.
[008] In another embodiment, substantially all hydrocarbon-containing organic
matter is
extracted into the extraction mixture. In such embodiment, the residual
materials are essential
oil-free and can be further used or disposed without impact to the
environment.
BRIEF DESCRIPTION OF THE DRAWINGS
[009] Figure 1 is a schematic for one embodiment of an apparatus for the
recovery of
hydrocarbons from tar sands.
[0010] Figure 2 is a schematic for one embodiment of an apparatus for the
recovery of
hydrocarbons from oil shale.
[0011] Figure 3 is a schematic for one embodiment of an apparatus for the
recovery of
hydrocarbons from coal.
[0012] Figure 4 is a schematic for the enhanced recovery of hydrocarbons from
a subsurface
reservoir.
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DETAILED DESCRIPTION OF THE INVENTION
[0013] In one aspect, the present invention relates to a readily deployed
composition for the
extraction, liquefaction and/or solubilization of fossil fuels from coal, oil
shale, tar sands and the
like, as well as from reservoirs.
[0014] According to one embodiment, a method is providing including the steps
of liquefying,
solubilizing and/or extracting hydrocarbon-containing organic matter from a
hydrocarbon-
containing material, such as for example, coal, oil shale, tar sands, or a
reservoir containing
heavy crude oil, crude oil, natural gas (which frequently coexists with crude
oils and other said
fossil fuels), or a combination thereof. Hydrocarbon-containing organic matter
includes, but is
not limited to, heavy crude oil, crude oil, natural gas and the like.
Hydrocarbon-containing
organic matter can be solid, semi-solid, liquid, sludge, viscous liquid,
liquid or gaseous form.
Other materials that are suitable hydrocarbon-containing materials for
treatment using the
method of this invention include liquid and solids that include hydrocarbon-
containing materials
as well as a residual material. Exemplary hydrocarbon-containing materials can
also include oil
tank bottoms, oil pit or pond sludge and slurry mix, discarded foods, manure,
sewage sludge or
municipal garbage. Liquefying, solubilizing and/or extracting the hydrocarbon-
containing
organic matter includes the step of providing a turpentine liquid, contacting
the hydrocarbon-
containing material with the turpentine liquid so as to extract at least a
portion of said
hydrocarbon-containing organic matter from said hydrocarbon-containing
material into said
turpentine liquid to create an extraction mixture that includes the
hydrocarbon-containing
organic matter that has been removed from the hydrocarbon-containing material
and the
turpentine liquid, and separating the extracted organic matter in the
turpentine liquid from any
residual material not extracted. Turpentine liquid can include an amount of
terpineol. Naturally
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occurring turpentine liquid includes an amount of terpene. In one embodiment,
the turpentine
liquid includes a-terpineol.
[0015] In certain embodiments, the ratio of turpentine liquid to hydrocarbon-
containing material
is greater than or equal to about 1:2 and 4:1, in some embodiments greater
than or equal to about
1:1, and in some embodiments the ratio can be greater than or equal to 2:1 In
embodiments
relating the reservoir recovery, the ratio can be greater than or equal to
about 3:1, and in other
embodiments relating to reservoir recovery the ratio can be greater than or
equal to about 4:1.
For purpose of application in a reservoir, pore volume is used to determine an
estimated measure
of the hydrocarbon-containing material. In other aspects of this invention,
such as in the use of
tar sands and coal and oil shale, volume of the hydrocarbon-containing
material can be more
directly measured.
[0016] In certain embodiments, the minimum organic matter contained in the
hydrocarbon-
containing material is greater than or equal to about 1% by weight, in other
embodiments greater
than or equal to about 10% by weight, and in still further embodiments greater
than or equal to
about 14% by weight of the hydrocarbon-containing material.
[0017] In one embodiment of the invention, a liquefaction, solubilization or
extraction reagent of
choice for the hydrocarbon-containing matter is a natural, synthetic or
mineral turpentine, which
can include a-terpineol, or a-terpineol itself.
[0018] In certain embodiments, the liquefaction, solubilization and/or
extraction of fossil fuels or
hydrocarbon-containing organic matter can be carried out at a temperature,
which is within the
range of about 2 C to about 300 C. In certain embodiments, the organic matter
or material is
contacted with a turpentine liquid at a temperature of less than about 300 C,
or less than about
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60 C. In other embodiments, the liquefaction, solubilization and/or extraction
temperatures can
be within the range of about 20 C to about 200 C. The pressure under which the
liquefaction,
solubilization and/or extraction of fossil fuels is to be carried out may
typically be within the
range of about 1.0x104 Pascals (0.1 atm) to about 5.0x106 Pascals (50.0 atm).
In certain
embodiments, the process can be conducted at a pressure between about 5.0x104
Pascals (0.5
atm) to about 8.0x105 Pascals (8.0 atm). In certain other embodiments, the
fossil fuels or
hydrocarbon-containing organic matter to be liquefied, solubilized and/or
extracted by
immersion in, or contact with, one or more turpentine liquid can be in the
form of a bed of
particles, pieces, chunks or blocks of fossil fuels whose sizes are within the
range of about 0.74
mm to about 10 mm in a liquefaction, solubilization or extraction vessel
(reactor hereafter) that
contains one or more of the said liquefaction, solubilization and/or
extraction reagents. In certain
embodiments, the sizes of the particles, pieces, chunks or blocks of fossil
fuels are within the
range of about 0.149 mm (100 mesh) to about 20 mm. In certain embodiments, the
bed of
particles, pieces, chunks or blocks of fossil fuels is agitated by passing the
liquefaction,
solubilization and/or extraction reagent or reagents in the form of liquid
through the bed of
particles, pieces, chunks or blocks by boiling the reagent or reagents. In
certain embodiments,
the duration of liquefaction, solubilization and/or extraction is between
about 1 minute to about
90 minutes. The fossil fuels can be partially or fully liquefied, solubilized
and/or extracted; the
degree of liquefaction, solubilization and/or extraction can be effected by
controlling the
operating conditions, such as temperature, pressure, intensity of agitation
and duration of
operation, and/or adjusting the type, relative amount and concentration of the
liquefaction,
solubilization or extraction reagent or reagents in the reactor.
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[0019] The basis of one aspect of the present invention is the unexpected
discovery that when
about 500 grams of the reagent, a-terpineol, were added to about 250 grams of
the 60-mesh
sample of coal from the Pittsburgh seam in Washington County of Pennsylvania
in a tray, the
reagent's color turned pitch black almost immediately, and remained so after
several hours. This
indicated that the color change was not due to the suspension of the coal
particles, but rather was
indicative of the extraction of hydrocarbon-containing organic matter from the
coal.
Subsequently, this 2:1 mixture of a-terpineol and the coal sample was
transferred from the tray
to a capped and tightly sealed jar and was maintained under the ambient
conditions of about
20 C and slightly less than about 1.01x105 Pascals (1 atm) for about 25 days.
The conversion,
(i.e., the degree of liquefaction), of the coal sample was determined to be
about 71 wt. % after
filtering, washing with ethanol, drying, and weighing. This 71 wt. %
conversion corresponds to
nearly all the solubilizable bitumen (organic matter) present in the coal
sample whose proximate
analyses are 2.00 wt. % of as-received moisture, 9.25 wt. % of dry ash, 38.63
wt. % of dry
volatile matter, and 50.12 wt. % of dry fixed carbon. A series of subsequent
experiments with
coal, as well as oil shale and tar sands under various operating conditions,
has shown that the
family of reagents that includes natural and/or synthetic turpentines
containing pinenes, and
alcohols of pinene, i.e., terpineols, are inordinately effective in
liquefying, solubilizing and/or
extracting kerogen (organic matter), bitumen (organic matter) and/or
asphaltene (organic matter)
in the fossil fuels, including coal, oil shale, tar sands, heavy crude oil
and/or crude oil, without
requiring the aid of any catalyst or alkaline metals. These reagents, except
mineral turpentine
that is derived from petroleum, are renewable and "green," i.e., low in
toxicity, and relatively
inexpensive, as compared to all other known liquefaction, solubilization
and/or extraction
reagents for the fossil fuels, such as tetraline, xylene, anthracene, and
various solutions or
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mixtures of these reagents with other compounds. Even mineral turpentine
derived from
petroleum, although not renewable, is relatively low in toxicity and is
inexpensive. It was also
found that any of the said liquefaction, solubilization and/or extraction
reagents penetrates or
diffuses into the particles, pieces, blocks or chunks of fossil fuels through
their pores at
appreciable rates, thus causing these particles, pieces, chunks or blocks to
subsequently release
the liquefiable, solubilizable or extractable fraction in them often almost
nearly completely even
under the far milder conditions, e.g., ambient temperature and pressure, than
those required by
the recent inventions pertaining to the liquefaction, solubilization and/or
extraction of the fossil
fuels, such as coal, oil shale, tar sands, crude oil and heavy crude oil.
[0020] An aspect of the present invention provides a method of liquefying,
solubilizing and/or
extracting the fossil fuels or hydrocarbon-containing organic matter from
hydrocarbon-
containing material, such as coal, oil shale and tar sands, wherein a portion
of solid or semi-solid
fossil fuels is contacted with a turpentine liquid in an extraction mixture,
which can be in an
absence of an alkali metal, catalyst, hydrogen (H2) and/or carbon monoxide
(CO). While
hydrogen and CO can be useful as a mixing agent, one embodiment of the
invention includes the
process and the composition in the absence of hydrogen and CO.
[0021] In certain embodiments, the turpentine liquid is selected from natural
turpentine,
synthetic turpentine, mineral turpentine, pine oil, a-pinene, fl-pinene, a-
terpineol, P-terpineol, y-
terpineol, polymers thereof, and mixtures thereof. In certain other
embodiments, the turpentine
liquid is selected from geraniol, 3-carene, dipentene (p-mentha-1,8-diene),
nopol, pinane, 2-
pinane hydroperoxide, terpin hydrate, 2-pinanol, dihydromycenol, isoborneol, p-
menthan-8-ol,
a-terpinyl acetate, citronellol, p-menthan-8-y1 acetate, 7-
hydroxydihydrocitronellal, menthol, and
mixtures thereof. In other embodiments, the turpentine liquid is selected from
anethole,
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camphene; p-cymene, anisaldeyde, 3,7-dimethy1-1,6-octadiene, isobornyl
acetate, ocimene,
alloocimene, alloocimene alcohols, 2-methoxy-2,6-dimethy1-7,8-epoxyoctane,
camphor, citral,
7-methoxydihydro-citronellal, 10-camphorsulphonic acid, cintronellal,
menthone, and mixtures
thereof.
[0022] According to an aspect, solid or semi-solid fossil fuels or other
hydrocarbon-containing
materials, such as coal, oil shale, tar sands and heavy crude oil, or for
example oil tank bottoms,
oil pit or pond sludge, discarded foods, manure, sewage sludge or municipal
garbage, may be
provided in any size that facilitates contact with a turpentine liquid. The
fossil fuels or
hydrocarbon-containing materials can be provided as particles, pieces, chunks,
or blocks, for
example, large fragments or pieces of coal or oil shale. According to a
certain aspect of the
invention, the fossil fuel or hydrocarbon-containing material is provided as
particles. According
to a certain aspect of the invention, the particles of fossil fuel or
hydrocarbon-containing
materials have an average particle size of from about 0.074 mm to about 100
mm. In certain
other embodiments, the particles of fossil fuel have an average particle size
from about 0.074
mm to about 25 mm.
[0023] According to an aspect of the present invention, a second liquid can be
added to the
turpentine liquid. According to a certain aspect of the invention, the second
liquid can be
selected from lower aliphatic alcohols, alkanes, aromatics, aliphatic amines,
aromatic amines,
carbon bisulfide and mixtures thereof. Exemplary mixtures include solvents
manufactured in
petroleum refining, such as decant oil, light cycle oil and naphtha, or
solvents manufactured in
dry distilling coal and fractionating liquefied coal.
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[0024] As used herein, lower aliphatic alcohols refers to primary, secondary
and tertiary
monohydric and polyhydric alcohols of between 2 and 12 carbon atoms. As used
herein, alkanes
refers to straight chain and branched chain alkanes of between 5 and 22 carbon
atoms. As used
herein, aromatics refers to monocyclic, heterocyclic and polycyclic compounds.
As used herein,
aliphatic amines refers to primary, secondary and tertiary amines having alkyl
substituents of
between 1 and 15 carbon atoms. In certain embodiments, benzene, naphthalene,
toluene or
combinations thereof are used. In another embodiment, the lower aliphatic
alcohols noted above
can be used. In one embodiment the solvent is selected from ethanol, propanol,
isopropanol,
butanol, pentane, heptane, hexane, benzene, toluene, xylene, naphthalene,
anthracene, tetraline,
triethylamine, aniline, carbon bisulfide, and mixtures thereof, at a
temperature and pressure
operable to maintain the solvent in liquid form.
[0025] In certain embodiments, the ratio of turpentine liquid to any other
turpentine-miscible
solvent contained in said fluid is greater than or equal to 1:1, in certain
embodiments greater than
or equal to about 9:4. In certain embodiments, the ratio is greater than or
equal to about 3:1. In
yet other embodiments, the ratio is greater than or equal to 4:1.
[0026] According to an aspect of the present invention, the fossil fuel and
the turpentine liquid
are contacted at a temperature of from about 2 C to about 300 C. In certain
embodiments, the
fossil fuel is contacted by the turpentine liquid at a temperature of less
than about 200 C.
[0027] According to a further aspect of the present invention, the fossil fuel
and the turpentine
liquid are contacted at a pressure of from about 1.0x104 Pascals (0.1 atm) to
about 5.0x106
Pascals (50 atm). According to an aspect, the method is executed at a pressure
of from about 0.5
atm to about 8 atm.
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[0028] According to an aspect of the present invention, the method further
includes providing an
extraction vessel within which the solid or semi-solid fossil fuel is
contacted with the turpentine
liquid. According to an aspect, agitation means can be provided whereby the
fossil fuel and the
turpentine liquid contained within the reactor or extractor vessel are mixed
and agitated.
[0029] According to an aspect of the present invention, the fossil fuel and
turpentine liquid can
be incubated in a holding tank so as to prolong their time of contact.
According to a further
aspect, the degree of liquefaction, solubilization and/or extraction is
controlled by the length of
time the solid or semi-solid fossil fuel is in contact with the turpentine
liquid and/or the
temperature of the mixture of the fossil fuel and turpentine liquid.
[0030] According to an aspect of the present invention, the fossil fuel is
contacted with a
heterogeneous liquid including a turpentine liquid and water as an agitant.
[0031] In certain embodiments, the ratio of turpentine fluid to water is
greater than or equal to
about 1:1 by volume, to avoid slurry formation, which may render separation of
the extracted
organic matter in the turpentine liquid-containing fluid difficult.
[0032] According to an aspect of the present invention, the fossil fuel is
contacted by the
turpentine liquid in the presence of an energy input selected from thermal
energy in excess of
about 300 C, pressure in excess of 50 atm, microwave energy, ultrasonic
energy, ionizing
radiation energy, mechanical shear-forces, and mixtures thereof.
[0033] According to an aspect of the present invention, a liquefaction or
solubilization catalyst is
provided to the mixture of fossil fuel and turpentine liquid.
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[0034] According to an aspect of the present invention, the reaction or
solubilization mixture is
supplemented by the addition of a compound selected from hydrogen, carbon
monoxide, water,
metal oxides, metals, and mixtures thereof
[0035] According to an aspect of the present invention, a microorganism is
included in the
reaction or solubilization mixture. Select chemical bonds, for example, sulfur
cross-links and
oxygen cross-links, in the hydrocarbons of fossil fuels and other hydrocarbon-
containing
materials are broken by biotreatment with bacillus-type thermophilic and
chemolithotrophic
microorganisms selected from naturally occurring isolates derived from hot
sulfur springs. The
breaking of these select chemical bonds facilitates the solubilization of
hydrocarbons in fossil
fuels and other hydrocarbon-containing materials.
[0036] Still other aspects and advantages of the present invention, it will
become easily apparent
by those skilled in the art from this description, wherein it is shown and
described certain
embodiments of the invention, simply by way of illustration of the best mode
contemplated of
carrying out the invention. As will be realized, the invention is capable of
other and different
embodiments, and its several details are capable of modifications in various
obvious respects,
without departing from the invention. Accordingly, the description is to be
regarded as
illustrative in nature and not as restrictive.
[0037] In accordance with one embodiment of the present invention, a method is
provided for
extracting hydrocarbon-containing organic matter from a hydrocarbon-containing
material
comprising a viscous liquid, liquid or gaseous fossil fuel material. The
method provides a first
liquid that includes a turpentine liquid. The turpentine liquid is contacted
with the hydrocarbon-
containing material in-situ in an underground formation containing said fossil
fuel material,
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thereby forming an extraction mixture so as to extract hydrocarbon-containing
organic matter
into said turpentine liquid and form an extraction liquid. The extraction
liquid is removed from
said formation, wherein the extraction liquid includes the turpentine liquid
containing the
extracted hydrocarbon-containing organic matter. The extracted hydrocarbon-
containing organic
matter is separated from a residual material not extracted. The method can
further include
separating said extracted hydrocarbon material from the turpentine liquid. The
viscous liquid,
liquid or gaseous fossil fuel material can be heavy crude oil, crude oil,
natural gas, or a
combination thereof. The underground formation may be a crude oil reservoir or
a natural gas
reservoir, for example.
[0038] The present invention can be deployed readily in-situ to liquefy and/or
solubilize directly
the fossil fuels in underground formations, and extract the resulting liquid
products from such
formations.
[0039] An extraction reagent of the present invention is a liquid, which has a
very strong physio-
chemical affinity with bituminous organic matter, including bitumen, kerogen
and/or tar, in solid
coal, oil shale and tar sands. When the extraction reagent of the present
invention and
bituminous organic matter comprising mainly hydrocarbons come into direct
contact with each
other, the organic matter dissolves into the extraction reagent of the present
invention, thereby
liquefying the organic matters. Upon contact, the hydrocarbons and the
extraction reagent of the
present invention rapidly form a homogeneous solution, i.e., a one-phase
liquid.
[0040] It is possible to take advantage of the physico-chemical affinity
between the extraction
reagent of the present invention and the bituminous matter for enhancing oil
recovery from oil
reservoirs under in-situ conditions. The prior art in-situ recovery techniques
applied to-date in
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oil reservoirs resort mostly to the so-called frontal displacement method.
This process is strictly
controlled by the characteristics of the multi-phase fluid flow in a porous
medium. This tends to
leave a large portion, often exceeding about 40% of the original oil,
unrecovered, even for the
"good" low viscosity oil reservoirs. The extraction reagent of the present
invention enhances oil
recovery by overcoming the complex behavior of the multi-phase flow prevailing
under in-situ
conditions.
[0041] The present invention takes advantage of the very strong physico-
chemical affinity of the
turpentine liquid.
[0042] One method of the present invention injects an extraction reagent of
the present invention
into an oil or natural gas reservoir through an injection well.
[0043] Oil is dissolved into the extraction reagent of the present invention
when the two come
into contact in an oil reservoir, thereby yielding a homogeneous solution,
i.e., a one-phase liquid.
The extraction reagent of the present invention does not simply displace the
oil as it travels from
the injection well to the producer well; dissolution of previously trapped oil
into the extraction
reagent of the present invention continues until the extraction reagent is
fully saturated with oil.
Thereafter, the extraction reagent becomes inactive in the additional oil
recovery process and
simply flows through the pores of the reservoir as a one-phase liquid,
eventually reaching a
production well.
[0044] The following illustrates three specific embodiments of in-situ methods
for oil recovery
of the present invention.
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[0045] In a first in-situ embodiment, about three (3.0) to seven (7.0) pore
volumes of an
extraction reagent of the present invention are injected into an oil reservoir
already water-flooded
to the residual oil saturation while producing about 51% of the original oil
in the reservoir. The
injection of the extraction reagent can unexpectedly produce about an
additional 41% of the
original oil in the reservoir. This embodiment of the method was
experimentally validated, as
described in Example 22 herein below.
[0046] In a second in-situ embodiment, about two (2.0) to five (5.0) pore
volumes of an
extraction reagent of the present invention are injected into an oil
reservoir. At the outset, the
injection causes only oil to be produced until about one-third (0.3) to three-
quarter (0.75) of pore
volume of the extraction reagent of the present invention is injected;
thereafter, the extraction
reagent of the present invention in which oil is dissolved, is produced. The
majority of the oil
present can be recovered upon injecting between about one and a half (1.5) to
three and a half
(3.5) pore volumes of the reagent. The method unexpectedly recovers about 90%
of the original
oil in the reservoir. This embodiment of the method also is experimentally
validated, as
described in Example 22 herein below.
[0047] In a third in-situ embodiment, an extraction reagent of the present
invention is injected to
improve the oil recover from oil reservoirs containing very viscous oil, e.g.,
the reservoirs of the
"Orinoco Oil Belt" in Venezuela. The recovery factor with prior art recovery
methods is low,
ranging from 10% to 15% of the original oil in such reservoirs. The unexpected
increase in the
recovery efficiency from these reservoirs with injection of the turpentine
liquid extraction
reagent of the present invention can be further enhanced by adopting
horizontal wells for both
producers and injectors, and periodic steam soaking of these wells.
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[0048] Ultimate recovery of natural gas from a large gas reservoir can be
increased with the
injection of an extraction reagent of the present invention into a reservoir.
The gas production
form such a reservoir often creates dangerously large-scale subsidence on the
surfaces of the gas
field, e.g., the "Groeningen" field in the Netherlands. As such, it is
necessary that the reservoir
pressure be maintained by water injection. The water injected into the
reservoir traps about 30%
of the gas in-situ at high pressure due to the two-phase flow of water and gas
through the
reservoir with a low permeability. With the injection of an extraction reagent
of the present
invention, the trapped gas in the reservoir is dissolved in the reagent and
flows to the producer
wells. By separating the reagent and gas at the surface, the gas is recovered
and the reagent is
recycled for reuse.
[0049] The extraction methods of the present invention can be implemented
after one or more of
the known methods for facilitating oil production, e.g., CO2 or natural gas
injection and
surfactant addition, are executed.
EXEMPLARY EMBODIMENTS FOR CARRYING OUT THE INVENTION
[0050] Coal
[0051] In certain embodiments, anthracite or bituminous coal can be ground to
sizes ranging
from about 0.841 mm (20 mesh) to about 0.149 mm (100 mesh), and subsequently
be solubilized
and/or extracted, i.e., liquefied, by immersing in a turpentine liquid under a
pressure within the
range of about 1.0x105 Pascals (1 atm) to about 2.0x105 Pascals (2.0 atm). In
certain other
embodiments, the turpentine liquid can be natural, synthetic or mineral
turpentine that includes
up to about 50-70 volume % of a-terpineol, about 20-40 volume % of 13-
terpineo1, and about 10
volume % of other components. In certain embodiments, the bed of ground
anthracite or
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bituminous coal can be agitated by passing said turpentine liquid at a
temperature in the range
between 80 C and about 130 C, or possibly up to the boiling point of said
turpentine liquid. In
certain other embodiments, the duration of solubilization and/or extraction,
i.e., liquefaction, can
be within about 10 minutes to about 40 minutes. In certain embodiments, the
contact time for
the extraction of hydrocarbon-containing organic matter from coal is less than
5 minutes.
[0052] In some embodiments, lignite, brown coal, or any other low-rank coals
can be ground to
sizes ranging from about 0.419 mm (40 mesh) to about 0.074 mm (200 mesh), and
subsequently
be solubilized and/or extracted, i.e., liquefied, by immersing in a turpentine
liquid under a
pressure within the range of about 1.0x105 Pascals (1 atm) to about 2.0x105
Pascals (2.0 atm). In
certain other embodiments, the turpentine liquid can be natural, synthetic or
mineral turpentine
that includes about 70-90 volume % of a-terpineol, about 5-25 volume % of 13-
teipineo1, and
about 5 volume % of other components. In other embodiments, the bed of ground
lignite, brown
coal, or any other low-rank coals can be agitated by passing said turpentine
liquid at a
temperature in the range between about 80 C and about 130 C, or possibly up to
the boiling
point of said turpentine liquid. In certain other embodiments, the
solubilization and/or
extraction, i.e., liquefaction, can be within about 20 minutes to about 60
minutes. In certain
embodiments, the contact time for the extraction of hydrocarbon-containing
organic matter from
coal is less than 5 minutes.
[0053] Oil Shale
[0054] In certain embodiments, oil shale can be ground to sizes ranging from
about 0.419 mm
(40 mesh) to 0.074 mm (200 mesh), and subsequently be solubilized and/or
extracted, i.e.,
liquefied, by immersing in a turpentine liquid under a pressure within the
range of about 1.0x1.05
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Pascals (1 atm) to about 2.0x105 Pascals (2.0 atm). In other embodiments, the
turpentine liquid
can be natural, synthetic or mineral turpentine that includes about 70-90
volume % of a-
terpineol, about 5-25 volume % of P-terpineol, and about 5 volume % of other
components. In
certain other embodiments, the bed ground oil shale can be agitated by passing
said turpentine
liquid at a temperature in the range between about 80 C and about 130 C, or
possibly up to the
boiling point of said turpentine liquid. In other embodiments, the
solubilization and/or
extraction, i.e., liquefaction, can be within about 30 minutes to about 60
minutes. In certain
embodiments, the contact time for the extraction of hydrocarbon-containing
organic matter from
oil shale is less than 5 minutes.
[0055] Tar sands
[0056] In certain embodiments, tar sands can be broken up to sizes ranging
from about 25.4 mm
(1 mesh) to 4.76 mm (4 mesh), and subsequently be solubilized and/or
extracted, i.e., liquefied,
by immersing in a turpentine liquid under a pressure within the range of about
1.0x1.05 Pascals
(1 atm) to about 2.0x105 Pascals (2.0 atm). In other embodiments, the
turpentine liquid can be
natural, synthetic or mineral that includes containing about 40-60 volume % of
a-teipineol, about
30-50 volume % of P-terpineol, 5 volume % of a and/or P-pinene and about 5
volume % of other
components. In another embodiment, a ground oil shale bed can be agitated by
passing said
turpentine liquid at a temperature in the range between about 60 C and about
90 C, or possibly
up to the boiling point of said turpentine liquid. In other embodiments, the
solubilization and/or
extraction, i.e., liquefaction, can be within about 10 minutes to about 30
minutes. In certain
embodiments, the contact time for the extraction of hydrocarbon-containing
organic matter from
tar sands is less than 5 minutes.
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[0057] Crude oil
[0058] In certain embodiments, light and medium crude oil can be produced in
situ, i.e.,
removed from an underground reservoir, for primary, secondary or tertiary
recovery, by injecting
about one (1.0) to about five (5.0) pore volumes of a turpentine liquid. In
other embodiments,
between about two (2.0) and about four (4.0) pore volumes of a turpentine
liquid can be injected.
In certain embodiments, the turpentine liquid can be natural, synthetic or
mineral turpentine that
includes about 40-70 volume % of a-terpineol, about 30-40 volume % of P-
terpineol, 10 volume
% of a and/or P-pinene and about 10 volume % of other components. In certain
embodiments,
the injection of a turpentine liquid can be followed by waterflooding with
about one (1.0) to
about three (3.0) pore volumes of water.
[0059] In certain embodiments, heavy and extra heavy crude oil can be produced
in situ, i.e.,
removed from an underground reservoir, for primary, secondary or tertiary
recovery, by injecting
about one (1.0) to about five (5.0) pore volumes of a turpentine liquid. In
other embodiments,
between about two (2.0) and about four (4.0) pore volumes of a turpentine
liquid can be injected.
In certain embodiments, the turpentine liquid can be natural, synthetic or
mineral turpentine that
includes about 50-70 volume % of a-terpineol, about 20-35 volume % of P-
terpineol, 10 volume
% of a and/or p-pinene and about 5 volume % of other components can be used in
conjunction
with steam injection.
[0060] Referring to Figure 1, an apparatus for the recovery of hydrocarbon-
containing organic
matter from tar sands is provided. Apparatus 100 includes turpentine liquid
supply 102, which
can optionally be coupled to a pump 104, to supply a turpentine liquid to
contacting vessel or
extraction vessel 110. In certain embodiments, the turpentine liquid supply
can include means
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for heating the turpentine liquid. In certain embodiments, the contacting
vessel can be an
inclined rotary filter or trommel. Tar sand sample 106 is provided to conveyor
108 or like
feeding apparatus for supplying the tar sands to an inlet of contacting vessel
110. Optionally,
conveyor 108 can include a filter screen or like separating apparatus to
prevent large particles
from being introduced into the process. Contacting vessel 110 includes at
least one inlet for
turpentine liquid to be introduced and contacted with the tar sands.
Contacting vessel 110 can
include a plurality of trays or fins 114 designed to retain the tar sands in
the contacting vessel for
a specified amount of time, and to increase or control contact between the tar
sand particles and
the turpentine liquid. In certain embodiments, the contacting vessel can be an
inclined rotary
filter. An extraction mixture that includes the extracting liquid and
hydrocarbon-containing
organic matter extracted from the tar sands is removed from contacting vessel
110 via outlet 116,
which can include filter 118 to prevent the removal of solids with the
extraction mixture that
includes the extracted hydrocarbon-containing organic matter. Pump 120 can be
coupled to
outlet 116 to assist with supplying the extraction mixture to holding tank
122. Line 124 can be
coupled to holding tank 112 for supplying the extraction mixture for further
processing. After
extraction of the hydrocarbon-containing organic matter, inorganic solids and
other materials not
soluble in the turpentine liquid can be removed from the contacting vessel via
second conveyor
126. Some turpentine liquids include, but are not limited to, liquids that
include a-terpineol and
13-terpineo1.
[0061] Referring now to Figure 2, apparatus 200 is provided for the recovery
of hydrocarbon-
containing organic matter from oil shale and other sedimentary rock formations
that include
recoverable hydrocarbon materials. Oil shale sample 202 is supplied to grinder
or crusher 204 to
reduce the size of the oil shale. Preferably, grinder or crusher 204 reduces
the oil shale to
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between about 0.074 and 0.42 mm in diameter. Crushed oil shale may optionally
be supplied to
a filter to ensure uniform and/or conforming particle size. First conveyor 206
provides particles
from grinder or crusher 204 to contacting vessel 208. Contacting vessel 208 is
coupled to
turpentine liquid supply 210, which may optionally be coupled to a pump, and
which supplies a
turpentine liquid to at least one inlet 212 coupled to contacting vessel 208.
In certain
embodiments, the turpentine liquid supply can include means for heating the
turpentine liquid.
Contacting vessel 208 can include a plurality of trays or fins 214 designed to
retain the tar sands
in the contacting vessel for a specified amount of time, and to increase or
control contact
between the tar sand particles and the turpentine liquid. In certain
embodiments, the contacting
vessel can be an inclined rotary filter or trommel. An extraction mixture
stream that includes the
turpentine liquid and recovered hydrocarbon-containing organic matter from the
oil shale is
collected via outlet 216 and supplied to holding tank 220. Pump 218 is
optionally coupled to
outlet 216 to assist with the supply of the extraction mixture stream to
holding tank 220. The
extraction mixture stream can be coupled to line 222 for supplying the
extraction mixture stream
to further processing. Second conveyor 224 assists with the removal of
inorganic or insoluble
materials from contacting vessel 208. Turpentine liquids can include, but are
not limited to, a-
terpineol and P-terpineol.
[0062] Referring now to Figure 3, apparatus 300 is provided for the recovery
of hydrocarbon-
containing organic matter from coal. Coal sample 302 is supplied to grinder or
crusher 304 to
reduce the size of the coal. Preferably, grinder or crusher 304 reduces the
coal to between about
0.074 and 0.84 mm in diameter, depending upon the quality of the coal sample.
In certain
embodiments, the grinder or crusher 304 can be a wet grinder. Crushed coal may
optionally be
supplied to a filter to ensure uniform and/or conforming particle size.
Crushed coal is supplied
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to first contacting vessel 306. First contacting vessel 306 is also coupled to
a turpentine liquid
supply 308, which may optionally be coupled to pump 310, and which supplies
the turpentine
liquid to first contacting vessel 306. In certain embodiments, the turpentine
liquid supply can
include means for heating the turpentine liquid. First contacting vessel 306
includes mixing
means 312 designed to agitate and improve or control contact between the solid
coal particles
and the turpentine liquid. An extraction mixture stream that includes the
turpentine liquid and
recovered hydrocarbon-containing organic matter from the oil shale is
collected via first
contacting vessel outlet 313 and supplied to second contacting vessel 316.
Pump 314 is
optionally coupled to outlet 313 to assist with the supply of the extraction
mixture stream to the
second contacting vessel 316. Second contacting vessel 316 can include a
series of trays or fins
318 designed to increase or control separation of the solids and turpentine
liquids. Optionally,
the second contacting vessel 316 can be an inclined rotary filter or trommel.
The extraction
mixture stream can be collected from second contacting vessel outlet 320,
which may optionally
be coupled to pump 322, to assist with supply of the extraction mixture stream
to holding tank
324. Liquid coal and any turpentine liquid present in holding tank 324 can be
supplied to a
liquid coal refinery or other processing step via line 326. Conveyor 328 can
be coupled to
second contacting vessel 316 for removal and recovery of the solids as a by-
product of the
process. Turpentine liquids can include, but are not limited to, a-terpineol
and P-terpineol. The
apparatus 300 can also be used to process high and low grade oil shale.
[0063] Referring now to Figure 4, process 400 is provided for the enhanced
recovery of
hydrocarbon-containing organic matter from a hydrocarbon-containing subsurface
formation.
Hydrocarbon-containing reservoir 404 is shown positioned below the surface
402. Production
well 406 is already in operation. Injection well 408 is provided for the
injection of a turpentine
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liquid via line 410. The turpentine liquid facilitates the liquefaction,
solubilization and/or
extraction of hydrocarbon-containing organic matter present in the reservoir,
as well as providing
the driving force to push the hydrocarbon-containing organic matter in the
formation toward the
production well. A hydrocarbon product stream that includes injected
turpentine liquid is
collected via line 412. Turpentine liquids can include, but are not limited
to, a-terpineol and 13-
terpineol.
[0064] In certain embodiments, the turpentine liquid for increasing production
from an oil well is
provided that includes at least 30% by volume of natural turpentine, synthetic
turpentine, mineral
turpentine, pine oil, a-pinene, (3-pinene, a-terpineol, 13-terpineol, y-
terpineol, terpene resins, a-
terpene, f3-terpene, -y-terpene, or mixtures thereof. In other embodiments,
the turpentine liquid
includes at least 30% by volume geraniol, 3-carene, dipentene (p-mentha-1,8-
diene), nopol,
pinane, 2-pinane hydroperoxide, terpin hydrate, 2-pinanol, dihydromycenol,
isoborneol, p-
menthan-8-ol, a-terpinyl acetate, citronellol, p-menthan-8-
y1 acetate, 7-
hydroxydihydrocitronellal, menthol, or mixtures thereof. In yet other
embodiments, the
turpentine liquid includes at least 30% by volume anethole, camphene; p-
cymene, anisaldeyde,
3,7-dimethy1-1,6-octadiene, isobornyl acetate, ocimene, alloocimene,
alloocimene alcohols, 2-
methoxy-2,6-dimethy1-7,8-epoxyoctane, camphor, citral, 7-methoxydihydro-
citronellal, 10-
camphorsulphonic acid, cintronellal, menthone, or mixtures thereof.
[0065] In certain embodiments, the turpentine liquid includes at least about
40% by volume a-
terpineol. In other embodiments, the turpentine liquid includes at least about
25% by volume (3-
terpineol. In yet other embodiments, the turpentine liquid includes at least
about 40% by volume
a-terpineol and at least about 25% by volume 13-terpineol. In other
embodiments, the turpentine
liquid includes at least about 50% a-terpineol, and in certain embodiments
also includes 0-
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terpineol. In certain embodiments, the turpentine liquid includes at least 20%
by volume of p-
terpineol. In certain embodiments, the turpentine liquid includes between
about 50 and 70% by
volume of a-terpineol and between about 10 and 40% by volume of13-terpineol.
[0066] In another aspect, a process for increasing production from a sub-
surface hydrocarbon-
containing reservoir undergoing enhanced recovery operations is provided that
includes injecting
a turpentine liquid into the reservoir through an injection well to stimulate
production of the
hydrocarbon-containing material. The turpentine liquid can include at least
one compound
selected from natural turpentine, synthetic turpentine, mineral turpentine,
pine oil, a-pinene, P-
pinene, a-terpineol, P-terpineol, y-telpineol, terpene resins, a-terpene, I3-
terpene, y-terpene, and
mixtures thereof. In other embodiments, the turpentine liquid can include at
least one compound
selected from geraniol, 3-carene, dipentene (p-mentha-1,8-diene), nopol,
pinane, 2-pinane
hydroperoxide, terpin hydrate, 2-pinanol, dihydromycenol, isoborneol, p-
menthan-8-ol, a-
terpinyl acetate, citronellol, p-menthan-8-y1 acetate, 7-
hydroxydihydrocitronellal, menthol, and
mixtures thereof. In yet other embodiments, the turpentine liquid can include
at least one
compound selected from anethole, camphene; p-cymene, anisaldeyde, 3,7-dimethy1-
1,6-
octadiene, isobornyl acetate, ocimene, alloocimene, alloocimene alcohols, 2-
methoxy-2,6-
dimethy1-7,8-epoxyoctane, camphor, citral, 7-methoxydihydro-citronellal, 10-
camphorsulphonic
acid, cintronellal, menthone, and mixtures thereof. A hydrocarbon-containing
organic matter
production stream that includes the turpentine liquid and recovered
hydrocarbons is recovered
from the production well associated with the hydrocarbon-containing reservoir.
The
hydrocarbon-containing organic matter production stream can be separated into
a recovered
hydrocarbons stream and a turpentine liquid recycle stream. In certain
embodiments, the method
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of further can further include the step of injecting the turpentine liquid
recycle stream into the
injection well.
[0067] In another aspect, a method for the increasing production from a
hydrocarbon-containing
sub-surface hydrocarbon formation undergoing enhanced recovery operations is
provided. The
method includes the steps of injecting a turpentine liquid into the formation
through an injection
well. In certain embodiments, the turpentine liquid includes at least 40% by
volume a-terpineol
and at least 10% by volume 13-teipineol. The turpentine liquid solubilizes,
extracts and/or
displaces the hydrocarbon-containing materials from the formation, which are
subsequently
recovered from the formation with the turpentine liquid through a production
well. In certain
embodiments, the method further includes separating the hydrocarbons from the
turpentine
liquid. In yet other embodiments, the method further includes recycling the
turpentine liquid to
the injection well. In certain embodiments, a-terpineol is present in an
amount between about 40
and 70% by volume. In certain other embodiments, a-terpineol is present in an
amount of at
least 70% by volume. In yet other embodiments, [3-terpineol is present in an
amount between
about 10 and 40% by volume. In other embodiments, the turpentine liquid
further includes up to
about 10% by volume y-terpineol. In other embodiments, the turpentine liquid
can include up to
about 25% by volume of an organic solvent selected from methanol, ethanol,
propanol, toluene
and xylenes. The method is useful for the recovery of hydrocarbon-containing
organic matter
during primary, secondary and tertiary recovery operations, including after
secondary recovery
operations that include waterflooding.
[0068] In another aspect, a turpentine liquid for the recovery of hydrocarbon-
containing organic
matter from tar sands is provided. In one embodiment, the turpentine liquid
includes at least
about 30% by volume a-terpineol and at least about 25% by volume P-terpineol.
In another
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embodiment, the turpentine liquid includes between about 30 and 70% by volume
a-terpineol,
between about 25 and 55% by volume P-terpineol, up to about 10% by volume a-
terpene, and up
to about 10% by volume P-terpene.
[0069] In another aspect, a turpentine liquid for recovering hydrocarbon-
containing organic
matter from high grade coal sources, such as for example, anthracite or
bituminous coal, is
provided. In one embodiment, the turpentine liquid includes at least about 45%
by volume a-
terpineol and at least about 15% by volume P-terpineol. In another embodiment,
the turpentine
liquid includes between about 45 and 80% by volume a-terpineol, between about
15 and 45% by
volume P-terpineol, up to about 10% by volume a-terpene, and up to about 10%
by volume P-
terpene.
[0070] In another aspect, a turpentine liquid for recovering hydrocarbon-
containing organic
matter from low grade coal sources is provided. In one embodiment, the
turpentine liquid
includes at least about 60% by volume a-terpineol and up to about 30% by
volume P-terpineol.
In another embodiment, the turpentine liquid includes between about 60 and 95%
by volume a-
terpineol, up to about 30% by volume P-terpineol, up to about 5% by volume a-
terpene, and up
to about 5% by volume f3-terpene.
[0071] In another aspect, a turpentine liquid for recovering hydrocarbon-
containing organic
matter from oil shale is provided. As used herein, oil shale generally refers
to any sedimentary
rock that contains bituminous materials. In one embodiment, the turpentine
liquid includes at
least about 60% by volume a-terpineol and up to about 30% by volume P-
terpineol. In another
embodiment, the turpentine liquid includes between about 60 and 95% by volume
a-terpineol, up
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to about 30% by volume P-terpineol, up to about 5% by volume a-terpene, and up
to about 5%
by volume P-terpene.
[0072] In another aspect, a turpentine liquid is provided for recovering
hydrocarbon-containing
organic matter from light and medium crude oil. In one embodiment, the
turpentine liquid
includes at least about 40 and 70% by volume a-terpineol and at least about 30
and 40% by
volume P-terpineol. In yet another embodiment, the turpentine liquid includes
between about 40
and 70% by volume a-terpineol, between about 30 and 40% by volume P-terpineol,
up to about
10% by volume a-terpene, and up to about 10% by volume P-terpene.
[0073] In another aspect, a turpentine liquid is provided for recovering
hydrocarbon-containing
organic matter from heavy and extra heavy crude oil. In one embodiment, the
turpentine liquid
includes at least about 50 and 70% by volume a-terpineol and at least about 30
and 40% by
volume P-terpineol. In another embodiment, the turpentine liquid includes
between about 50 and
70% by volume a-teipineol, between about 30 and 40% by volume P-terpineol, up
to about 10%
by volume a-terpene, and up to about 10% by volume P-terpene.
[0074] In another aspect, a method for recovering hydrocarbon-containing
organic matter from
tar sands is provided. The method includes mining a formation rich in tar
sands to provide a tar
sand sample, wherein the tar sand sample includes a recoverable hydrocarbon-
containing organic
matter and residual inorganic or insoluble material. The tar sand sample is
supplied to a
contacting vessel, wherein the contacting vessel includes at least one inlet
for supplying a
turpentine liquid for recovery of hydrocarbons from the tar sands. The tar
sand sample is
contacted with a turpentine liquid to extract the hydrocarbon-containing
organic matter from the
tar sands to produce a residual material and an extraction mixture. The
extraction mixture
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includes the turpentine liquid and recovered hydrocarbon-containing organic
matter, and the
residual material is separated from the turpentine liquid to produce
hydrocarbon product stream
and a turpentine liquid recycle stream. In certain embodiments, the method
further includes the
step of recycling the turpentine liquid recycle stream to the contracting
vessel. In other
embodiments, the extraction mixture can be separated by distillation to
produce the hydrocarbon
product stream and the turpentine liquid recycle stream.
[0075] In certain embodiments, the turpentine liquid can include a-terpineol.
In other
embodiments, the turpentine liquid can include at least about 40% by volume a-
terpineol and
between 10 and 40% by weight 11-terpineo1. In certain embodiments, between 0.5
and 4
equivalents of the turpentine liquid is used to contact the tar sands and
recover hydrocarbons. In
certain embodiments, between 0.5 and 2.0 equivalents of the turpentine liquid
is used to contact
the tar sands and recover hydrocarbons.
[0076] In another aspect, a method for recovering hydrocarbon-containing
organic matter from a
hydrocarbon rich oil shale is provided. The method includes mining a rock
formation that
includes hydrocarbon-containing organic matter to produce a hydrocarbon
containing oil shale
that includes a recoverable hydrocarbon material and inorganic or insoluble
material. The oil
shale is ground to produce crushed hydrocarbon-containing oil shale. The
crushed hydrocarbon-
containing oil shale is then filtered with a filter screen to prevent or
control the excessively large
particles from being supplied to the extraction process. The crushed
hydrocarbon-containing oil
shale is fed to a contacting vessel, wherein the contacting vessel includes at
least one inlet for
supplying a turpentine liquid for recovery of hydrocarbons from the crushed
hydrocarbon-
containing oil shale. The crushed hydrocarbon-containing oil shale is
contacted with the
turpentine liquid to extract the hydrocarbon-containing organic matter from
the crushed
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hydrocarbon-containing oil shale to produce inorganic solids and an extraction
mixture that
includes the turpentine liquid and recovered hydrocarbons. The inorganic or
insoluble materials
are removed from the extraction mixture, and the recovered hydrocarbons are
separated from the
turpentine liquid to produce a hydrocarbon product stream and a turpentine
liquid recycle stream.
In certain embodiments, the turpentine liquid recycle stream is recycled to
the contracting vessel.
In other embodiments, the crushed hydrocarbon-containing oil shale has a mean
particle size of
less than about 0.42 mm in diameter. In other embodiments of the method for
the recovery of
hydrocarbon-containing organic matter from oil shale, the turpentine liquid
includes at least one
compound selected from natural turpentine, synthetic turpentine, mineral
turpentine, pine oil, a-
pinene, 13-pinene, a-terpineol, f3-terpineol, 7-terpineol, terpene resins, a-
terpene, f3-terpene, y-
terpene, or mixtures thereof. In other embodiments, the turpentine liquid
includes at least one
compound selected from geraniol, 3-carene, dipentene (p-mentha-1,8-diene),
nopol, pinane, 2-
pinane hydroperoxide, terpin hydrate, 2-pinanol, dihydromycenol, isoborneol, p-
menthan-8-ol,
a-terpinyl acetate, citronellol, p-menthan-8-y1 acetate, 7-
hydroxydihydrocitronellal, menthol, and
mixtures thereof. In other embodiments, the turpentine liquid includes at
least one compound
selected from anethole, camphene; p-cymene, anisaldeyde, 3,7-dimethy1-1,6-
octadiene, isobornyl
acetate, ocimene, alloocimene, alloocimene alcohols, 2-methoxy-2,6-dimethy1-
7,8-epoxyoctane,
camphor, citral, 7-methoxydihydro-citronellal, 10-camphorsulphonic acid,
cintronellal,
menthone, and mixtures thereof. In certain embodiments, the turpentine liquid
can include a-
terpineol. In other embodiments, the turpentine liquid can include at least
about 40% by volume
a-terpineol and between 10 and 40% by weight (3-terpineol. In certain
embodiments, between
0.5 and 4 equivalents of the turpentine liquid is used to contact the oil
shale and recover
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hydrocarbon-containing organic matter. In certain embodiments, between 0.5 and
2.0
equivalents of the turpentine liquid is used to contact the oil shale and
recover hydrocarbons.
[0077] In another aspect, a method for recovering hydrocarbon-containing
organic matter from a
coal rich sub-surface formation is provided. The method includes mining the
sub-surface
formation to produce coal, wherein the coal includes a recoverable hydrocarbon-
containing
organic matter and inorganic or insoluble material. The coal is ground to
produce crushed coal
and filtered to provide a sample of uniform or desired size. The crushed coal
is fed to a
contacting vessel, wherein the contacting vessel includes at least one inlet
for supplying a
turpentine liquid for recovery of hydrocarbons from crushed coal, and
contacted with the
turpentine liquid to extract the hydrocarbons from the crushed coal to produce
inorganic solids
and an extraction mixture. The extraction mixture includes the turpentine
liquid and recovered
hydrocarbons. The inorganic or insoluble solids are separated from the
extraction mixture, and
the recovered hydrocarbons are separated from the turpentine liquid to produce
a liquid coal
product stream and a turpentine liquid recycle stream. In certain embodiments,
the method
further includes recycling the turpentine liquid recycle stream to the
contracting vessel. In yet
other embodiments, the liquid coal product stream is supplied to a liquid coal
refinery. In certain
embodiments, the coal sample includes a low grade coal having a mean particle
size of less than
about 0.42 mm. In certain embodiments, the coal sample includes a high grade
coal having a
mean particle size of less than about 0.84 mm.
[0078] In yet other embodiments of the method for recovering hydrocarbon-
containing organic
matter from coal, the turpentine liquid includes at least one compound
selected from natural
turpentine, synthetic turpentine, mineral turpentine, pine oil, a-pinene, P-
pinene, a-terpineol, 13-
terpineol, y-terpineol, terpene resins, a-terpene, 0-terpene, y-terpene, or
mixtures thereof. In
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other embodiments, the turpentine liquid includes at least one compound
selected from geraniol,
3-carene, dipentene (p-mentha-1,8-diene), nopol, pinane, 2-pinane
hydroperoxide, terpin hydrate,
2-pinanol, dihydromycenol, isoborneol, p-menthan-8-ol, a-terpinyl acetate,
citronellol, p-
menthan-8-y1 acetate, 7-hydroxydihydrocitronellal, menthol, and mixtures
thereof. In other
embodiments, the turpentine liquid includes at least one compound selected
from anethole,
camphene; p-cymene, anisaldeyde, 3,7-dimethy1-1,6-octadiene, isobornyl
acetate, ocimene,
alloocimene, alloocimene alcohols, 2-methoxy-2,6-dimethy1-7,8-epoxyoctane,
camphor, citral,
7-methoxydihydro-citronellal, 10-camphorsulphonic acid, cintronellal,
menthone, and mixtures
thereof. In certain embodiments, the turpentine liquid includes at least 60%
by volume a-
terpineol. In certain embodiments, the turpentine liquid includes at least 45%
by volume a-
terpineol and at least about 15% by volume (3-terpineol. In certain other
embodiments, the
turpentine liquid includes at least 60% by volume a-teipineol and up to about
30% by volume 13-
terpineol. In certain embodiments, between 0.5 and 4 equivalents of the
turpentine liquid is used
to contact the oil shale and recover hydrocarbon-containing organic matter. In
certain
embodiments, between 0.5 and 2.0 equivalents of the turpentine liquid is used
to contact the oil
shale and recover hydrocarbon-containing organic matter.
[0079] In another aspect, a system for recovering hydrocarbon-containing
organic material from
tar sands is provided. The tar sands recovery system includes a tank for
supplying a turpentine
liquid and a contacting vessel, wherein the contacting vessel includes at
least one inlet for
introducing the turpentine liquid and at least one outlet for recovering an
extraction mixture from
the contacting vessel. The system also includes a first conveyor for supplying
tar sands to the
contacting vessel. A holding tank that includes a line connecting the holding
tank to the
contacting vessel is provided, wherein the line connecting the contacting
vessel and the holding
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tank includes a filter to prevent the passage of solids to the holding tank.
The system also
includes a second conveyor for the recovery and transport of the solids.
[0080] In one embodiment, the contacting vessel is a rotary inclined filter
that includes a series
of fins or trays for separating and or controlling the tar sands. In another
embodiment, the fins or
trays are provided to increase or control the contact time between the tar
sands and the turpentine
liquid. In certain embodiments, the turpentine liquid can include a-terpineol.
In other
embodiments, the turpentine liquid can include between about 30% and 70% by
volume a-
terpineol and between about 25% and 55% by weight 13-terpineo1.
[0081] In another aspect, a system for recovering hydrocarbon-containing
organic matter from
oil shale is provided. The system includes a tank for supplying a turpentine
liquid and a grinder
for comminuting the oil shale to a reduced particle size. A contacting vessel
is provided that
includes at least one inlet for introducing the turpentine liquid, at least
one inlet for receiving
crushed oil shale, at least one outlet for recovering solids from the
contacting vessel and at least
one outlet for recovering an extraction mixture from the contacting vessel. A
first conveyor is
provided for supplying crushed oil shale to a contacting vessel. The system
further includes a
holding tank, wherein the holding tank includes a line connecting the holding
tank to the
contacting vessel, wherein the line includes a filter to prevent the passage
of solids to the holding
tank; a second conveyor for recovering solids. In certain embodiments, the
system further
includes a line for supplying a reaction mixture including recovered
hydrocarbons and the
turpentine liquid to a refinery for further separation and/or processing. In
certain embodiments,
the turpentine liquid can include a-terpineol. In certain embodiments, the
turpentine liquid can
include between about 60% and 95% by volume a-terpineol and up to about 30% by
weight 3-
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terpineol. In other embodiments, the turpentine liquid can include between
about 70% and 90%
by volume a-terpineol and between about 5% and 25% by weight 13-terpineo1.
[0082] In another aspect, a system for recovering hydrocarbon-containing
organic matter from
coal is provided. The system includes a tank for supplying a turpentine liquid
and a grinder for
comminuting coal to produced particulate matter of a reduced size. A
contacting vessel is
provided that includes at least one inlet for introducing the turpentine
liquid and at least one
outlet for recovering solids and liquids from the contacting vessel. The
contacting vessel
includes also stirring means for thoroughly mixing the turpentine liquid and
the comminuted coal
. A separator is provided for separating the solids and liquids, wherein the
separator includes an
inlet, an outlet and a line connecting the inlet of the separator to the
outlet of the contacting
vessel. The system also includes a holding tank, wherein the holding tank
includes a line that
connects the holding tank to the separator, wherein the line can include a
filter to prevent the
passage of solids to the holding tank.
[0083] In certain embodiments, the system further includes a filter for
selectively preventing
particles having a mean diameter greater than about 0.85 mm from being
introduced to the
contacting vessel. In certain other embodiments, the system further includes a
line for supplying
a liquid coal product to a refinery for further processing. In certain
embodiments, the system
further includes a first conveyor for supplying crushed coal to the contacting
vessel. In other
embodiments, the system further includes a second conveyor for removing solids
from the
separator. In certain embodiments, the turpentine liquid can include a-
terpineol. In
embodiments directed to the recovery of hydrocarbons from high grade coal, the
turpentine
liquid can include between about 45% and 80% by volume a-terpineol and between
about 15%
and 45% by weight 13-telpineo1. In embodiments directed to the recovery of
hydrocarbons from
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low grade coal, the turpentine liquid can include between about 60% and 95% by
volume a-
terpineol and between about 0% and 30% by weight P-terpineol.
[0084] In another aspect, a method for optimizing a turpentine liquid for
extraction of
hydrocarbon-containing organic matter from hydrocarbon containing matter is
provided.
Generally, the method includes providing a sample of the hydrocarbon-
containing material and
analyzing the hydrocarbon material to determine the type ofhydrocarbon being
extracted. A
formulation for extraction of hydrocarbon-containing organic matter from the
hydrocarbon
material is provided, wherein the formulation is a function of the type of
formation and the size
of the particulate hydrocarbon material. Generally, the formulation includes
at least about 40%
by volume a-terpineol and at least about 10% by volume 13-terpineol. The
amount of a-teipineol
and 13-terpineol in the formulation is then adjusted based upon the parameters
noted above. In
general, while the above noted method provides a good starting point for
determining the desired
formulation for extraction of various hydrocarbon containing materials, for
other hydrocarbon-
containing materials and under specified operating conditions, either a series
of statistically
designed experiments or a series of experiments according to an optimization
method can be
performed to determine the optimum composition of the liquid turpentine.
[0085] As shown in Table 1, the specific formulation for extraction,
liquefaction and/or
solubilization of hydrocarbon-containing organic matter from tar sands varies
based upon the
particle size. In certain embodiments, the method for preparing a turpentine
liquid for extracting
hydrocarbon-containing organic matter from tar sands includes adjusting the
amount of a-
terpineol and 13-terpineol in the formulation as a function of the size of the
hydrocarbon rich solid
particulate being extracted. In other embodiments, if the hydrocarbon-
containing organic
particulate matter includes low grade coal or an oil shale, the amount a-
terpineol in the
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turpentine liquid is increased and the amount of f3-terpineol in the
turpentine liquid is decreased.
In other embodiments, if the hydrocarbon-containing organic particulate matter
includes tar
sands, the amount a-terpineol in the turpentine liquid is decreased and the
amount of P-terpineol
in the turpentine liquid is increased. In other embodiments, if the
hydrocarbon-containing
organic particulate matter includes tar sands and the mean diameter of the
particulate matter is
less than about 4.76 mm, then the amount a-terpineol in the turpentine liquid
is decreased and
the amount of P-terpineol in the turpentine liquid is increased. In other
embodiments, if the
hydrocarbon-containing organic particulate matter includes tar sands and the
mean diameter of
the particulate matter is greater than about 1 inch (1 mesh), then the amount
a-terpineol in the
turpentine liquid is decreased and the amount of P-terpineol in the turpentine
liquid is increased.
Table 1. Formulations for Extraction of Tar Sands based upon Particle Size
Particle Size a-terpineol 13-terpineol a-/ fl-terpene other
(Mesh/mm
diameter)
< 4 Mesh (4.76 30-50% vol 35-55% vol 10% vol 5% vol
mm)
1 mesh (1 inch) - 40-60% vol 30-50% vol 10% vol 5% vol
4 mesh (4.76
mm)
> 1 mesh (1 inch) 50-70% vol 25-45% vol 10% vol 5% vol
[0086] Similar to what is shown above with respect to the extraction of tar
sands, as shown in
Tables 2 and 3, the formulation for extraction, liquefaction and/or
solubilization of coal depends
both on particle size and on the quality of the coal being extracted. In one
embodiment of the
method for preparing a turpentine liquid for extracting hydrocarbon-containing
organic matter, if
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the hydrocarbon-containing matter includes anthracite, bituminous coal, or
other high grade coal
and the mean diameter of the particulate matter is less than about 0.15 mm,
then the amount a-
terpineol in the turpentine liquid is decreased and the amount of 13-terpineol
in the turpentine
liquid is increased. In other embodiments, if the hydrocarbon rich particulate
matter includes
anthracite, bituminous coal, or other high grade coal and the mean diameter of
the particulate
matter is greater than about 0.84 mm, then the amount a-terpineol in the
turpentine liquid is
decreased and the amount of 13-terpineol in the turpentine liquid is
increased. In another
embodiment, if the hydrocarbon rich particulate matter includes low grade coal
and the mean
diameter of the particulate matter is less than about 0.074 mm, then the
amount a-terpineol in the
turpentine liquid is decreased and the amount of 13-terpineol in the
turpentine liquid is increased.
In another embodiment, if the hydrocarbon rich particulate matter includes low
grade coal and
the mean diameter of the particulate matter is greater than about 0.42 mm,
then the amount a-
terpineol in the turpentine liquid is decreased and the amount of 13-terpineol
in the turpentine
liquid is increased.
Table 2. Formulations for Extraction of High Grade Coal based upon Particle
Size
Particle Size a-terpineol P-terpineol a-/ P-terpene
other
(Mesh/mm
diameter)
< 100 mesh 45-65% vol 35-45% vol 10% vol 0%
vol
(0.149 mm)
20 mesh (0.841 50-70% vol 20-40% vol 10% vol 0% vol
mm) ¨ 100 mesh
(0.149 mm)
> 20 mesh (0.841 60-80% vol 15-35% vol 10% vol 0% vol
mm)
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Table 3. Formulations for Extraction of Low Grade Coal based upon Particle
Size
Particle Size a-terpineol 11-terpineo1 a-/ p-terpene other
(Mesh/mm
diameter)
< 200 mesh 60-80% vol 10-30% vol 5% vol 0% vol
(0.074 mm)
40 mesh (0.420 70-90% vol 5-25% vol 5% vol 0% vol
mm) ¨ 200 mesh
(O. 074 mm)
> 40 mesh (0.420 75-95% vol 0-20% vol 5% vol 0% vol
mm)
[0087] Similar to what is shown above with respect to the extraction of tar
sands, as shown in
Table 4, the formulation for extraction, liquefaction and/or solubilization of
oil shale depends on
particle size. In one embodiment of the method for preparing a composition for
extracting
hydrocarbon-containing organic matter, if the hydrocarbon rich particulate
matter includes an oil
shale and the mean diameter of the particulate matter is less than about 0.074
mm, then the
amount a-terpineol in the turpentine liquid is decreased and the amount of P-
terpineol in the
turpentine liquid is increased. In another embodiment, if the hydrocarbon rich
particulate matter
includes oil shale and the mean diameter of the particulate matter is greater
than about 0.42 mm,
then the amount a-terpineol in the turpentine liquid is decreased and the
amount of P-terpineol in
the turpentine liquid is increased.
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Table 4. Formulations for Extraction of Oil Shale based upon Particle Size
Particle Size a-terpineol P-terpineol a-/ p-terpene other
(Mesh/mm
diameter)
< 200 mesh 60-80% vol 10-30% vol 5% vol 0% vol
(0.074 mm)
.
40 mesh (0.420 70-90% vol 5-25% vol 5% vol 0% vol
mm) ¨ 200 mesh
(0. 074 mm)
> 40 mesh (0.420 75-95% vol 0-20% vol 5% vol 0% vol
mm)
[0088] The extraction of crude oil similarly depends on the type of crude oil
being extracted,
liquefied, and/or solubilized. As shown in Table 5, the formulation for the
extraction,
liquefaction and/or solubilization of crude oil depends is a function of both
particle size and the
quality of the density of the crude oil being extracted. The method includes
providing a
turpentine liquid formulation that includes at least 50% by volume a-terpineol
and at least 20%
by volume P-terpineol; adjusting the amount of a-teipineol and P-terpineol in
the turpentine
liquid formulation based upon the density of the liquid hydrocarbon being
extracted. In one
embodiment, if the API gravity of the liquid hydrocarbon being extracted is
greater than about
22 , then the amount a-terpineol in the turpentine liquid is decreased and the
amount of p-
terpineol in the turpentine liquid is increased. In another embodiment, if the
API gravity of the
liquid hydrocarbon being extracted is less than about 22, then the amount a-
terpineol in the
turpentine liquid is increased and the amount of P-terpineol in the turpentine
liquid is decreased.
As used herein, light oils have an API of at least about 31 , medium crude
oils have an API of
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between about 22 and about 31 , heavy oil has an API of between about 10 and
about 22 , and
extra heavy oil has an API of less than about 10 .
Table 5. Formulations for Extraction of Crude Oil based upon API Density
Crude Type a-terpineol P-terpineol a-/ P-terpene other
Light/medium 40-70% vol 30-40% vol 10% vol 10% vol
crude (API
greater than 22 )
Heavy/Extra 50-70% vol 20-35% vol 10% vol 5% vol
Heavy (API less
than 22 )
[0089] In another aspect, a method for preparing a turpentine liquid for
enhancing recovery of
liquid hydrocarbon-containing organic matter from a sub-surface formation is
provided. The
method includes providing a formulation comprising at least 50% by volume a-
terpineol and at
least 20% by volume 13-terpineo1, and adjusting the amount of a-terpineol and
P-terpineol in the
formulation based upon the geological features of the sub-surface formation.
[0090] In another aspect, a composition for cleaning and/or recovering
hydrocarbons from a
liquid hydrocarbon-containing vessel is provided, wherein the composition
includes at least one
compound selected from natural turpentine, synthetic turpentine, mineral
turpentine, pine oil, a-
pinene, 13-pinene, a-terpineol, p-terpineol, 7-terpineol, terpene resins, a-
ternene, f3-terpene, 7-
terpene, or mixtures thereof. In other embodiments, the composition for
cleaning and/or
recovering hydrocarbons includes at least one compound selected from geraniol,
3-carene,
dipentene (p-mentha-1,8-diene), nopol, pinane, 2-pinane hydroperoxide, terpin
hydrate, 2-
pinanol, dihydromycenol, isoborneol, p-menthan-8-ol, a-terpinyl acetate,
citronellol, p-menthan-
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8-y1 acetate, 7-hydroxydihydrocitronellal, menthol, and mixtures thereof. In
yet other
embodiments, the composition for cleaning and/or recovering hydrocarbons
includes at least one
compound selected from anethole, camphene; p-cymene, anisaldeyde, 3,7-dimethy1-
1,6-
octadiene, isobornyl acetate, ocimene, alloocimene, alloocimene alcohols, 2-
methoxy-2,6-
dimethy1-7,8-epoxyoctane, camphor, citral, 7-methoxydihydro-citronellal, 10-
camphorsulphonic
acid, cintronellal, menthone, and mixtures thereof. In one embodiment, the
composition includes
at least one compound from the following: a-pinene, P-pinene, a-terpineol, and
P-terpineol. In
another embodiment, the composition includes at least 25% by volume a-
terpineol or (3-
terpineol.
[0091] In another aspect, a method for cleaning and/or recovering hydrocarbons
from a liquid
hydrocarbon-containing vessel is provided. The method includes contacting the
interior of
vessel with a hydrocarbon cleaning composition that includes at least one
compound selected
from a-pinene, P-pinene, a-terpineol, and P-terpineol to create a mixture,
wherein the mixture
includes the liquid hydrocarbon residue and the hydrocarbon cleaning
composition. The mixture
is recovered and removed from the vessel. In certain embodiments, the cleaning
composition
includes at least 25% by volume of a-terpineol or P-terpineol. In certain
other embodiments, the
cleaning composition includes at least 25% by volume of a-terpineol and at
least 25% by volume
P-terpineol.
EXAMPLES
[0092] Example 1. In this example, coal from the Pittsburgh seam in Washington
County,
Pennsylvania was liquefied with reagent a-terpineol. The coal sample was
obtained from the
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Coal Bank at Pennsylvania State University, which provided the following
proximate analyses
for it; 2.00 wt. % of as-received moisture, 9.25 wt. % of dry ash, 38.63 wt. %
of dry volatile
matter, and 50.12 wt. % of dry fixed carbon. The particle size of coal sample
was about 60
mesh. About 60 grams of a-terpineol was gently added to about 30 grams of the
coal sample
placed in an extraction vessel, thus giving rise to the reagent-to-sample
ratio of 2 to 1. The
capped, but not tightly sealed, extraction vessel containing the resultant
mixture of a-terpineol
and coal was maintained at the constant temperature of about 96 C and
continually agitated.
Without boiling the a-teipineol, the pressure in the extraction vessel
remained at the ambient
pressure of slightly less than about 1.01x105 Pascals (1 atm). After about 30
minutes, the
mixture was filtered and the coal particles retained on the filter were washed
with ethanol and
dried to a constant weight. On the basis of weight loss, the conversion, i.e.,
the extent of
liquefaction, of the coal sample was determined to be about 68 wt. %.
[0093] Example 2. This example is identical to Example 1 in all aspects except
two. After
maintaining the temperature at about 96 C, for about 30 minutes, as done in
Example 1, the
extraction vessel containing the coal sample and a-terpineol was maintained at
a temperature at
about 135 C for an additional period of about 30 minutes. The pressure in the
extraction vessel
remained at the ambient pressure of slightly less than about 1.01x105 Pascals
(1 atm). The
conversion, i.e., the degree of liquefaction, of the coal sample was
determined to be about 70 wt.
%.
[0094] Example 3. The coal sample used was from the same source with the same
proximate
analyses as those used in the preceding two examples. About 31 grams of a-
terpineol were
added to about 31 grams of the coal sample in an extraction vessel. The
mixture was maintained
at about 96 C and an ambient pressure of slightly less than about 1.01x105
Pascals (1 atm) for
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about 30 minutes. The conversion, i.e., the degree of liquefaction, of the
coal sample attained
was determined to be about 71 wt. % by weighing the sample after filtering,
washing, and drying
as done in the preceding two examples.
[0095] Example 4. This example is identical to Example 3, except that about 30
wt. % of a-
temineol was replaced with hexane, providing a reagent that includes 70 wt.% a-
terpineol and 30
wt. % hexane. This reduced the conversion, i.e., the degree of liquefaction to
about 1.3 wt. %.
[0096] Example 5. The source and proximate analyses of coal sample and
experimental
conditions in terms of temperature, pressure and reagent-to-sample ratio for
this example were
the same as those of Example 3. The duration of the extraction, however, was
reduced from
about 30 minutes to about 20 minutes. Additionally, about 30 wt. % of the a-
terpineol was
replaced with 1-butanol, providing a reagent that includes 70 wt.% a-terpineol
and 30 wt. % 1-
butanol. The amount of coal liquefied was only about 0.30 gram, corresponding
to conversion of
about 1.0 wt. %.
[0097] Example 6. This example is the same as Example 3 in terms of the source
and proximate
analyses of coal sample and temperature, pressure and duration of the
extraction. The amount of
the coal sample used was, however, about 25 grams and the reagent comprised
about 24 grams
(80 wt. %) of a-terpineol and about 6 grams (20 wt. %) of xylenes, providing a
reagent that
includes 70 wt.% a-terpineol and 30 wt. % xylenes. The coal liquefied was
about 10.0 grams,
corresponding to conversion of about 40 wt. %.
[0098] Example 7. In this example, coal from the Wyodak seam in Campbell
County, Wyoming
was liquefied with reagent a-terpineol. The coal sample was obtained from the
Coal Bank at
Pennsylvania State University, which provided the following proximate analyses
for it; 26.30 wt.
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% of as-received moisture, 7.57 wt. % of dry ash, 44.86 wt. % of dry volatile
matter, and 47.57
wt. % of dry fixed carbon. The coal sample's particle size was about 20 mesh.
About 60 grams
of a-terpineol was gently added to about 30 grams of the coal sample placed in
an extraction
vessel , a reagent-to-sample ratio of about 2 to 1. The capped, but not
tightly sealed, extraction
vessel containing the resultant mixture of a-terpineol and coal was maintained
at a constant
temperature of about 96 C and continually agitated. Without boiling of the a-
terpineol, the
pressure in the extraction vessel remained at the ambient pressure of slightly
less than about
1.01x105 Pascals (1 atm). After about 30 minutes, the mixture in the
extraction vessel was
filtered and the coal particles retained on the filter were washed with
ethanol and dried to a
constant weight. On the basis of weight loss, the conversion, i.e., the degree
of liquefaction, of
the coal sample was determined to be 75 wt. %.
[0099] Example 8. The experiment in this example was carried out under the
conditions
identical to those of the preceding example except one. About 15 grams of a-
terpineol were
added, instead of about 60 grams, as done in the preceding example, to about
30 grams of the
coal sample, thus attaining the reagent-to-coal ratio of 0.5 to 1. The
conversion, i.e., the degree
of liquefaction, of the coal sample attained decreased from about 75 wt. %,
attained in the
preceding example, to about 69 wt. %.
[00100] Example 9. In this example, about 3 grams of oil shale from the
Green-river
region of Colorado was solubilized with about 9 grams of a-terpineol, thus
giving rise to the
reagent-to-sample ratio of 3 to 1, to extract kerogen (organic matter) and/or
bitumen (organic
matter) from it. The organic carbon content, including both volatile and fixed
carbon, was
determined to be about 22.66 wt. % by a certified analysis company. Two
experiments with the
oil-shale samples, having the particle size of 60 mesh, were carried out under
the ambient
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temperature and pressure of about 25 C and slightly less than about 1.01x105
Pascals (1 atm),
respectively. The weight losses of the samples were determined by weighing
after filtering,
washing with ethanol, and drying. These losses were about 9 wt. % after about
30 minutes and
about 17 wt. % after about 45 minutes. From these weight losses, the
conversion, i.e., the degree
of extraction of organic matter, i.e., kerogen and/or bitumen, was estimated
to be about 40 wt. %
for the former and was about 75 wt. % for the latter.
[00101] Example 10. This example duplicated the preceding example with the
exception
that a single experiment, lasting about 15 minutes, was carried out at the
temperature of about
96 C, instead of about 25 C. The weight loss of the oil shale sample was about
12 wt. %,
corresponding to the conversion, i.e., the degree of extraction, of kerogen
(organic matter) of
about 53 wt. %
[00102] Example 11. In this example, bitumen (organic matter) in tar sands
from Alberta,
Canada, was solubilized and extracted with commercial grade synthetic
turpentine. The tar-
sands sample was obtained from Alberta Research Council, which provided the
following
proximate analyses for it; 84.4 wt. % of dry solids, 11.6 wt. % of dry
bitumen, and 4.0 wt. % of
as-received moisture. About 30 grams of synthetic turpentine were gently added
to about 15
grams of the tar-sands sample in a capped, but not tightly sealed, extraction
vessel , utilizing a
reagent-to-sample ratio of about 2 to 1 by weight. This extraction vessel ,
containing the
resultant mixture of synthetic turpentine and tar sands, was maintained at a
constant temperature
of about 96 C and continually agitated. Without boiling of the synthetic
turpentine, the pressure
in the extraction vessel remained at the ambient pressure of slightly less
than about 1.01 x105
Pascals (1 atm). After about 20 minutes, the mixture in the extraction vessel
was filtered and the
solids (tar sands) retained on the filter were washed with ethanol and dried
to a constant weight.
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On the basis of weight loss, the conversion, i.e., the degree of extraction,
of bitumen from the
tar-sands sample was determined to be about 100 wt. %.
[00103] Example 12. In this example, about 60 grams of the tar-sands
sample from the
same source with the same proximate analyses as those of the preceding example
were extracted
by about 60 grams of a-terpineol, instead of commercial-grade synthetic
turpentine, which
includes a-terpineol. The resultant reagent-to-sample ratio was 1 to 1 instead
of 2 to 1 as in the
preceding example. The experiment lasted about 30 minutes at the temperature
of about 96 C
under the ambient pressure of slightly less than about 1.01x105 Pascals (1
atm). The conversion,
i.e., the extent of extraction, of bitumen (organic matter) in the tar-sands
sample was determined
to be about 100 wt. %.
[00104] Example 13. In this example, about 60 gams of the tar-sands sample
from the
same source with the same proximate analyses as those of the preceding two
examples were
extracted by about 60 grams of synthetic turpentine, which is of the
commercial grade. The
resultant reagent-to-sample ratio, therefore, was about 1 to 1. The experiment
was carried out for
about 30 minutes at the temperature of about 96 C under the ambient pressure
of slightly less
than about 1.01x105 Pascals (1 atm). The conversion, i.e., the degree of
extraction, of bitumen
(organic matter) in the tar-sands sample was determined to be about 70 wt. %.
[00105] Example 14. The experiment in this example duplicated that in
Example 8 in all
aspects except that the reagent-to-sample ratio was reduced from about 2 to 1
to about 0.5 to 1:
About 60 grams to the tar-sands sample was extracted by about 30 grams of
synthetic turpentine,
which is of the commercial grade. The conversion, i.e., the degree of
extraction, of bitumen
(organic matter) decreased from about 100 wt. % attained in Example 9 to about
70 wt. %.
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[00106] Example 15. The experiment in this example repeated that of the
preceding
example with a-terpineol instead of the commercial-grade synthetic turpentine.
The conversion,
i.e., the degree of extraction, of bitumen (organic matter) in the tar-sands
sample was about 70
wt. % as in the preceding example.
[00107] Example 16. The experiment in this example was carried out under
the ambient
pressure of slightly less than about 1.01x105 Pascals (1 atm) with the tar-
sands sample from the
same source with the same proximate analyses as those in the preceding
examples with tar sands.
About 60 grams of commercial-grade synthetic turpentine was added to about 60
grams of the
tar-sands sample, thus giving rise to the reagent-to-sample ratio of about 1
to 1. The temperature
of the sample and commercial-grade synthetic turpentine was maintained at
about 65 C for about
30 minutes followed by cooling to about 15 C within about 5 minutes.
Subsequently, the tar-
sands sample was filtered, washed, dried and weighed. On the basis of weight
loss, the
conversion, i.e., the degree of extraction, of bitumen (organic matter) in the
tar-sands sample was
determined to be about 70 wt. %.
[00108] Example 17. The experiment in this example repeated that of the
preceding
example with a-terpineol instead of commercial grade synthetic turpentine. The
conversion, i.e.,
the degree of extraction, of bitumen (organic matter) increased to about 90
wt. % from about 70
wt. % of the preceding examples.
[00109] Example 18. In this example, a tar-sands sample, weighing about 30
grams, from
the same source with the same proximate analyses as those in Examples 11
through 17, was
extracted with a liquid that included about 20 grams (80 wt. %) of a-terpineol
and about 5 grams
(20 wt. %) of toluene at the temperature of about 96 C under the ambient
pressure of slightly less
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than about 1.01x105 Pascals (1 atm). The duration of the experiment (reaction
or extraction
time) was about 30 minutes. The weigh loss of the sample was about 10.2 grams.
From this
weigh loss, the conversion, i.e., the degree of extraction, of bitumen
(organic matter) was
estimated to be about 33 wt. %.
[00110] Example 19. Three tar-sands samples, all from the same source with
the same
proximate analyses as those used in all preceding examples with tar sands were
extracted by
reagents comprising various amounts of a-terpineol and ethanol at the
temperature of about 15 C
under the ambient pressure of slightly less than about 1.01x105 Pascals (1
atm). The duration of
each experiment (reaction or extraction time) was about 15 minutes for each
tar-sands sample.
The first sample was extracted with a mixture comprising about 0 gram (0 wt.
%) of a-terpineol
and about 15 grams (100 wt. %) of ethanol, i.e., with pure ethanol. The second
sample was
extracted with a mixture comprising about 7.5 grams (50 wt. %) of a-terpineol
and about 7.5
grams (50 wt. %) of ethanol. The third sample was extracted with a mixture
comprising about
12 grams (80 wt. %) of a-terpineol and about 3 grams (20 wt. %) of ethanol.
The weight losses
and the estimated conversions, i.e., the degrees of extraction, of bitumen
(organic matter) in the
three samples were about 0.2 gram (1.0 wt. %), 0.6 gram (3.0 wt. %) and 0.9
gram (4.5 wt. %),
for the first, second and third sample, respectively.
[00111] Example 20. Irregular-shaped pellets of commercial-grade asphalt
whose average
size was about 15 mm were solubilized and extracted with a-terpineol and at
the ambient
temperature of about 22 C under the ambient pressure of slightly less than
about 1.01x105
Pascals (1 atm). The first sample weighing about 20 grams was solubilized and
extracted with
about 40 grams of a-terpineol, and the second sample also weighing about 20
grams was
solubilized and extracted with about 20 grams of a-terpineol. Both samples
were completely
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dissolved after 30 minutes. These experiments were carried out to simulate the
solubilization
and extraction of heavy crude oil, which tends to be rich in asphaltenes like
asphalt.
[00112] Example 21. In this example, bitumen (organic matter) in tar-sands
from the
same source with the same proximate analyses as those used in all previous
examples with tar
sands was solubilized and extracted with two varieties of vegetable oils,
soybean oil and corn oil.
The vegetable oils are completely miscible with turpentine liquid. In the
first experiment, a tar-
sands sample weighing about 15 grams was blended and agitated continually with
about 30
grams of soybean oil for about 20 minutes at the temperature of about 96 C
under the ambient
pressure of slightly less than about 1.0 1 x105 Pascals (1 atm). The weight
loss was about 0.5
gram from which the conversion, i.e., the degree of extraction, of bitumen in
the sample was
estimated to be about 3.3 wt. %. In the second experiment, a tar-sands sample
weighing about
30 grams was blended and agitated continually with about 60 grams of corn oil
for about 30
minutes at the temperature of about 175 C under the ambient pressure of
slightly less than about
1.01x105 Pascals (latm). The weight loss was about 4.8 grams from which the
conversion, i.e.,
the degree of extraction, of bitumen in the sample was estimated to be about
12 wt. %.
[00113] Example 22. Two tests were performed on Berea sandstone plug core
samples to
determine the effect of reagent injection on oil recovery from core. The first
test was designed to
determine the increment oil recovery due to a- terpineol injection after a
field had already
undergone waterflooding to the limit. The selected core contained 9.01 mL of
laboratory oil
simulating crude oil. The waterflooding with aqueous solution containing 3.0%
of potassium
chloride produced 4.6 mL of oil. Five (5) pore volumes of a-terpineol
injection produced
additional 3.61 mL of oil, thereby leaving the core with less than 8.0% of oil
remaining in the
original volume. The second test was designed to represent the increased
recovery that could be
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expected from a virgin reservoir with a-terpineol injection. The selected core
contained 8.85 mL
of laboratory oil simulating crude oil. Oil production began after
approximately 0.5 pore
volumes of a-terpineol injection, which was continued until 3.5 pore volumes;
however, the
majority of the oil was recovered after only 2.5 pore volumes of a-terpineol
injection. A total of
7.94 mL of laboratory oil was recovered, thereby leaving the core with less
than 7.5% of oil
remaining in the original volume.
[00114] In one experiment, various different ratios of a turpentine liquid
to tar sand
sample were tested. The turpentine liquid for each of the experiments provided
below had the
same formulation, wherein the composition included about 60% by volume a-
terpineol, about
20% by volume P-terpineol, and about 20% by volume y-terpineol. The tar sands
were a
different mix of ores from Alberta, Canada, having a bitumen content of
approximately 12% by
weight and a water content of between about 4-5% by weight. The experiments
were all
performed at atmospheric temperature.
[00115] As shown in Table 6 below, recovery of hydrocarbons from tar sands
across all
ratios provided below (i.e., ratios of turpentine liquid to tar sands ranging
from 1:2 to 2:1)
resulted in good recovery of hydrocarbons and little discernible difference.
With respect to the
temperature at which the extraction is carried out, it is believed that the
optimum temperature for
the extraction, solubilization and/or liquefaction of hydrocarbons from tar
sands is 65 C. As
shown in the table, at about 130 C, the amount of hydrocarbons recovered is
reduced. It is noted
however, that for certain solids from which it is particularly difficult to
recover hydrocarbons,
increasing the temperature of the extraction solvent can increase the amount
of hydrocarbons that
are recovered. Finally, it is shown that exposure time had very little effect
on the amount of
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materials that were extracted. This is likely because the shortest extraction
time was 20 minutes,
which is believed to be more than adequate for the extraction of the
hydrocarbons from tar sands.
Table 6
Tar Extractable Weight Ratio of Amount Percent Temp, Exposure
Sand HC of tar sand of HC HC C Time,
Weight, weight, g extraction to extracted, extracted minutes
g solvent solvent g
15 2.0 30.0 1:2 3.2 161 96 20
60 7.8 120.0 1:2 5.4 69 96 30
60 7.8 31.6 - 2:1 9.6 123 96 30
60 7.8 60.0 1:1 7.6 97 65 30
60 7.8 60.0 1:1 4.0 51 130 30
60 7.8 60.0 1:1 6.3 80 65 30
[00116] Additional experiments were conducted using alternative solvents,
namely
ethanol and corn oil, which was compared with the composition that included
about 60% by
volume a-terpineol, about 20% by volume 13-terpineo1, and about 20% by volume
y-terpineol.
As noted in Table 7 provided below, the performance of ethanol and corn oil
were unexpectedly
substantially lower than the composition that included 60% by volume a-
terpineol, about 20% by
volume f3-terpineol, and about 20% by volume y-terpineol. For example, whereas
the terpineol
composition achieved complete or nearly complete extraction of extractable
hydrocarbons,
ethanol yielded only 10% of the recoverable hydrocarbons and heated corn oil
yielded only 33%
of the recoverable hydrocarbons.
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Table 7
Chemical Tar Extractable Weight Ratio Amount Percent Temp, Exposure
Sand HC of of tar of HC HC C Time,
Weight, weight, g extraction sand to extracted, extracted minutes
solvent solvent g
Ethanol 15 2.0 15.0 1:1 o.2 10 15 15
Corn oil 30 3.9 60.0 2:1 1.3 33 175 30
60/20/20 60 7.8 60.0 1:1 7.6 97 65 30
terpineol
60/20/20 60 7.8 31.6 2:1 9.6 123 96 30
terpineol
[00117] As shown in Table 8 below, the performance of various turpentine
liquid
formulations, including turpentine liquid formulations that include only a-
terpineol and a-
terpineol in combination with various known organic solvents, are provided.
The first three
compositions presented in the table include a-terpineol, 13-terpineo1, and y-
terpineol. For
example, the first same includes about 60% by volume a-terpineol, about 30% by
volume 13-
terpineol, and about 10% by volume y-terpineol. The results unexpectedly show
that as the
concentration of the a-terpineol increases, performance of the turpentine
liquid increases to the
point that when the turpentine liquid includes approximately 70% a-terpineol,
full extraction of
the hydrocarbon material from the tar sand sample is achieved.
[00118] The second set of data is presented for extraction of hydrocarbon
bearing tar
sands with pure a-terpineol. As shown, extraction of greater than 100% is
achieved, likely due
to inconsistencies in the hydrocarbon content of the samples. However, the
results generally
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demonstrate the unexpected result that a-terpineol is capable of extracting
substantially all of the
recoverable hydrocarbon from a tar sand sample.
[00119] Finally, the last data provided in Table 8 illustrates the
effectiveness of mixed
systems of a-terpineol and known organic solvents. As shown, substantially
complete recovery
of recoverable hydrocarbons is achieved with a composition that includes a 1:1
ratio of a-
terpineol to ethanol. This is unexpected as pure ethanol only removed about
10% of the total
recoverable hydrocarbons. Additionally, mixed systems that include either a
1:1 or a 3:1 ratio of
a-terpineol to toluene still resulted in the recovery of 77% and 92% of the
total recoverable
hydrocarbons. This was an unexpected result.
Table 8
Chemical Tar Extractable Wt. of Ratio of Amount Percent Temp,
Exposure
comp. Sand HC wt., g solvent tar sand of HC
HC C Time,
wt., g to solvent extracted, extracted minutes
g
60/30/10 60 2.0 60.0 1:1 7.1 91 96 30
terpineol
40/30/20 60 7.8 60.0 1:1 4.7 60 96 30
terpineol
70/20/10 60 7.8 60.0 1:1 7.9 101 96 30
terpineol
100/0/0 60 7.8 60.0 1:1 10.0 128 96 30
terpineol
100/0/0 60 7.8 120.0 1:2 8.7 111 96 30
terpineol
100/0/0 60 7.8 31.0 2:1 9.6 123 96 30
terpineol
50% a- 15 2.0 15.0 1:1 8.1 103 65 30
terpineol/
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Chemical Tar Extractable Wt. of Ratio of Amount Percent Temp,
Exposure
comp. Sand HC wt., g solvent tar sand of HC HC *C Time,
wt., g to solvent extracted, extracted minutes
50% ethanol
80% a- 15 2.0 15.0 1:1 1.2 62 15 15
terpineol/
20% ethanol
75% a- 30 3.9 25.0 1:0.8 1.8 92 15 15
terpineol/
25% toluene
50% a- 30 3.9 26.0 1: 0.9 3.0 77 96 30
terpineol/
50% toluene
50% a- 30 3.9 26.0 1:0.9 2.4 61 96 30
terpineol/
50% xylenes
1001201 The results for the extraction of hydrocarbon-containing organic
matter from
hydrocarbon-containing material described in the specification, and especially
in the Examples
above, were unexpected.
1001211 As used herein, the terms first, second, third and the like should
be interpreted to
uniquely identify elements and do not imply or restrict to any particular
sequencing of elements
or steps.
1001221 As used herein, the terms about and approximately should be
interpreted to
include any values which are within 5% of the recited value. Furthermore,
recitation of the term
about and approximately with respect to a range of values should be
interpreted to include both
the upper and lower end of the recited range. As used herein, the terms first,
second, third and
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the like should be interpreted to uniquely identify elements and do not imply
or restrict to any
particular sequencing of elements or steps.
[00123] While the invention has been shown or described in only some of
its
embodiments, it should be apparent to those skilled in the art that it is not
so limited, but is
susceptible to various changes without departing from the scope of the
invention.
