Note: Descriptions are shown in the official language in which they were submitted.
MIXTURES OF ALCOHOL, FLUOROCARBON,
AND STEAM FOR HYDROCARBON RECOVERY
BACKGROUND OF THE INVENTION
1. Field of the Invention
The disclosure pertains to hydrocarbon production, extraction or recovery. In
particular,
the disclosure pertains to hydrocarbon production, extraction or recovery
methods incorporating
steam, water and/or additives.
2. Description of the Related Art
At or beneath its surface, the earth contains deposits of crude oil and
bituminous sands,
known as tar sands or oil sands. If these deposits are located sufficiently
close to the earth's
surface, they can be recovered using surface or strip mining techniques. The
mined ore typically
contains about 10-15% bitumen, 80-85% mineral matter with the balance being
water, and
requires separation of the valued bitumen product from the mineral matter.
This bitumen
liberation process begins by initially mixing or slurrying the ore with warm
water in a
hydrotransport line. The resultant slurry is then fed to a primary separation
vessel or cell. In this
separation process, additional warm water is added and the majority of the
liberated bitumen will
become attached to air bubbles where it is recovered by flotation. The bitumen
liberation and
recovery process generally occurs at a pH of about 8.5, which is generally
obtained with the
assistance of caustic soda. The coarse mineral matter is removed from the
bottom of the vessel
and a middlings portion, containing water, fine mineral matter, and suspended
bitumen is sent for
further bitumen recovery.
If the crude oil or bituminous sands are located sufficiently below the
surface of the earth,
oil wells can be drilled to assist in the extraction of these materials.
However, heavy
hydrocarbons can prove difficult to recover or produce due to their high
viscosities. Various
extraction, recovery, or production methods are known in the art such as
flooding the formation
with steam in an attempt to reduce the viscosity of the hydrocarbons to enable
flow and aid in
production.
One such method known as Cyclic Steam Simulation or the "huff-and-puff" method
involves stages of injecting high pressure steam, soaking the formation, and
production. The
initial stage involves steam injection for a period of weeks to months to heat
the hydrocarbon,
1 =
CA 2821184 2019-10-11
CA 02821184 2013-07-16
bitumen or heavy oil resource in the reservoir, thereby reducing its viscosity
such that it will be
able to flow. Following injection, the steam is allowed to soak in the
formation for a period of
days to weeks to allow heat to further penetrate the formation. The heavy oil,
sufficiently
reduced in viscosity, is then produced from the same well until production
begins to decline upon
which time the three step cycle is repeated.
Another recovery or production method used in the art is referred to as steam
assisted
gravity drainage (SAGD)_ The SAGD recovery method relies on two parallel,
horizontal wells
approximately 1 km in length. An upper "injector well" resides above a lower
"producing well."
The producing well is situated as close as possible to the bottom of the
reservoir. Initially, steam
.. is injected into both wells to begin heating the formation. After a period
of time, the formation is
sufficiently heated such that the viscosity of the hydrocarbons or bitumen is
reduced and the
hydrocarbons or bitumen are now able to enter the production well. Once this
occurs, steam
injection into the production well is ceased.
Low pressure steam is continuously injected into the injector well, resulting
in the
formation of a steam chamber, which extends laterally and above as the process
continues. At
the edge of the steam chamber, the steam releases its latent heat into the
formation. This process
heats the hydrocarbons and/or bitumen causing it to be sufficiently reduced in
viscosity to drain
along the edge of the steam chamber under the influence of gravity to the
lower producing well.
It can then be pumped to the surface along with the resultant steam
condensate. At that point, the
formed water and bitumen emulsion is separated.
In addition to imparting a viscosity reduction on the hydrocarbons and/or
bitumen, the
steam condenses and a hydrocarbon-in-water emulsion forms allowing the
hydrocarbon to travel
more readily to the producing well. SAGD processes typically recover about 55%
of the original
hydrocarbon or bitumen-in-place over the lifetime of the well.
Although this process has advantages, there are drawbacks as well. For
example, with
respect to bitumen production, the SAGD process relies on the energy intensive
production of
steam to assist with bitumen recovery. It requires natural gas, significant
amounts of fresh water,
and water recycling plants. Further, as the method relies upon gravity
drainage, production rates
can be limited due to the high viscosity of the bitumen. Although the prior
art has contemplated
different variations to the SAGD process, such as the addition of certain
additives, the additives
have not been successful and their presence has resulted in, for example,
emulsions of additive,
2
CA 02821184 2013-07-16
water, and bitumen that cannot be broken because the additives have caused the
emulsion to be
stable.
Therefore, seeking out additives that could increase the amount of bitumen
produced for
the same steam input is highly desirable. Additives could possess properties
such as directly
improving the heat efficiency within a formation as well as reducing the oil-
water interfacial
tension. Moreover, successful additives will lower the steam to oil ratio
meaning less steam will
be necessary to produce the same amount of bitumen due to the presence of the
additive. Also,
desirable additives will not interfere with the resulting emulsion such that
it cannot be broken.
Finally, a successful additive should be volatile enough to be carried with
the steam through the
sand pack to reach the bitumen pay.
BRIEF SUMMARY OF THE INVENTION
A process for recovering a hydrocarbon from a subterranean formation is
disclosed. The
subterranean formation can include any number of wells, such as two wells,
three wells, etc. The
disclosed process includes the steps of contacting a hydrocarbon from a
subterranean formation
with steam or water, contacting the hydrocarbon with one or more alcohols, or
one or more
fluorinated hydrocarbons, or a combination of one or more alcohols and one or
more fluorinated
hydrocarbons, and recovering the hydrocarbon. The hydrocarbon can be contacted
by the steam
.. or water and/or the one or more alcohols, or one or more fluorinated
hydrocarbons, or
combination of one or more alcohols and one or more fluorinated hydrocarbons,
at any time
during recovery of the hydrocarbon. The hydrocarbon is selected from the group
consisting of
light or heavy crude oil, bitumen, an oil sand ore, a tar sand ore, and
combinations thereof. The
hydrocarbon can be contacted with the steam or water and one or more alcohols,
or one or more
fluorinated hydrocarbons, or a combination of one or more alcohols and one or
mare fluorinated
hydrocarbons, inside of the subterranean formation or outside of the
subterranean formation. The
steam and the one or more alcohols, or one or more fluorinated hydrocarbons,
or combination of
one or more alcohols and one or more fluorinated hydrocarbons, can be injected
into the
subterranean formation independently or as a mixture. The process can be a
SAGD process that
incorporates the addition of the one or more alcohols, or one or more
fluorinated hydrocarbons,
or a combination of one or more alcohols and one or more fluorinated
hydrocarbons.
3
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A process for the recovery of bitumen from a subterranean formation is also
disclosed.
The subterranean formation can include any number of wells, such as two wells,
three wells, etc.
The process includes the steps of contacting the bitumen with steam or water,
contacting the
bitumen with one or more alcohols, or one or more fluorinated hydrocarbons, or
a combination of
one or more alcohols and one or more fluorinated hydrocarbons, and recovering
the bitumen.
The bitumen can be contacted by the steam or water and/or the one or more
alcohols, or one or
more fluorinated hydrocarbons, or combination of one or more alcohols and one
or more
fluorinated hydrocarbons, at any time during recovery of the bitumen. The
bitumen can be
contacted with the steam or water and one or more alcohols, or one or more
fluorinated
hydrocarbons, or combination of one or more alcohols and one or more
fluorinated
hydrocarbons, inside of the subterranean formation or outside of the
subterranean formation. The
steam and the one or more alcohols, or one or more fluorinated hydrocarbons,
or combination of
one or more alcohols and one or more fluorinated hydrocarbons, can be injected
into the
subterranean formation independently or as a mixture, The process can be a
SAGD process that
incorporates the one or more alcohols, or one or more fluorinated
hydrocarbons, or a combination
of one or more alcohols and one or more fluorinated hydrocarbons.
A composition or mixture of components is also disclosed. The composition or
mixture
includes a hydrocarbon, water or steam, and one or more alcohols, or one or
more fluorinated
hydrocarbons, or a combination of one or more alcohols and one or more
fluorinated
hydrocarbons. The hydrocarbon can be selected from the group consisting of
light or heavy
crude oil, bitumen, an oil sand ore, a tar sand ore, and combinations thereof.
The foregoing has outlined rather broadly the features and technical
advantages of the
present invention in order that the detailed description of the invention that
follows may be better
understood. Additional features and advantages of the invention will be
described hereinafter
that form the subject of the claims of the invention. It should be appreciated
by those skilled in
the art that the conception and the specific embodiments disclosed may be
readily utilized as a
basis for modifying or designing other embodiments for carrying out the same
purposes of the
present invention, It should also be realized by those skilled in the art that
such equivalent
embodiments do not depart from the spirit and scope of the invention as set
forth in the appended
claims.
4
CA 02821184 2013-07-16
BRIEF DESCRIPTON OF THE SEVERAL VIEWS OF THE DRAWINGS
A detailed description of the invention is hereafter described with specific
reference being
made to the drawings in which:
Figure 1 is a one-way analysis of bitumen extracted (%) vs. blank and
trifluoroethanol.
Figure 2 is a one-way analysis of bitumen extracted (%) vs. ethanol and
trifluoroethanol.
Figure 3 is a one-way analysis of bitumen extracted (%) vs. blank, ethanol
(1,000 ppm),
and trifluoroethanol (1,000 ppm).
Figure 4 shows comparative data for the blank, methanol, ethanol and n-
alcohols,
propanol, butanol and pentanol. All alcohols were dosed at 1,000 ppm.
Figure 5 shows comparative data for the C5 alcohol derivatives. All additives
were dosed
at 1,000 ppm.
DETAILED DESCRIPTION OF THE INVENTION
This disclosure relates to methods of producing or recovering hydrocarbons,
such as light
or heavy crude oil, bitumen, and oil or tar sand ores. Compositions and
mixtures including the
produced or recovered hydrocarbons are also disclosed herein.
It has been found that addition of additives, such as fluorinated
hydrocarbons, greatly
enhances hydrocarbon extraction. In the present application, hydrocarbon is
understood to mean
viscous or heavy crude oil, light crude oil, tar sands or oil sands oil, or
bitumen.
It has also been found that addition of additives, such as one or more
alcohols, greatly
enhances hydrocarbon extraction.
Further, it has been found that addition of additives, such as certain
combinations of one
or more alcohols or combinations of one or more alcohols and one or more
fluorinated
hydrocarbons greatly enhances hydrocarbon extraction.
A process for recovering a hydrocarbon is disclosed involving two parallel,
horizontal
wells. The wells can be, for example, approximately 1 km in length, but other
lengths are
acceptable as well. The process can be an SAGD process or any other suitable
process. An
upper injector well resides above a lower producing well in the SAGD process.
The wells can be
separated by any suitable distance, for example, approximately 4-6 meters.
Initially, steam is
5
CA 02821184 2013-07-16
injected downhole into one or both of the wells where it condenses and begins
heating the
formation and the hydrocarbon(s) therein, Generally, steam is injected into
the well head and
this process is readily understood by those skilled in the art. The steam can
be injected at high
pressures and can be at a temperature of about 500 C. After a period of time,
the formation is
sufficiently heated such that the viscosity of the hydrocarbon is reduced.
Over time, low pressure steam can be continuously injected into the injector
well,
resulting in the formation of a steam chamber, further heating the hydrocarbon
causing it to be
sufficiently reduced in viscosity to drain along the edge of the steam chamber
to the lower
producing well by way of gravity where it can be pumped to the surface along
with the
condensed steam and/or the additive(s). At that point, the water and/or
additive(s) are separated
from the hydrocarbon in water emulsion and the hydrocarbon can be recovered
using various
known methods in the art such as "breaking" the emulsion.
An additive according to the present disclosure, such as a fluorinated
hydrocarbon, one or
more alcohols, or combinations of one or more alcohols and one or more
fluorinated
hydrocarbons, can also be injected into either one of the wells, or both of
the wells. The
additive(s) can be injected independently of the steam or it can be added as a
mixture with the
steam. The steam may be injected continuously or intermittently into one or
both of the wells.
Moreover, the additive(s) may be injected continuously or intermittently into
one or both of the
wells. Also, if the steam and additive(s) are added as a mixture, the mixture
can be added either
continuously or intermittently into one or both of the wells.
Additive(s) addition may occur at, but is not limited to, the steam header, at
the well head,
or it can be added into the boiler feed water.
The additive(s) can be injected into one or both of the wells at any point
during
production such as when production begins or when production begins to
diminish. For example,
when hydrocarbon production begins to decline in the well, the additive(s)
described herein can
be added. By adding the additive(s) after production has begun to decline, the
recovery level can
be brought back to or near an optimal or peak hydrocarbon recovery level.
A process for the recovery of bitumen from a subterranean formation is also
disclosed.
The process can be a SAGO process and the bitumen can be recovered from a
hydrocarbon
bearing ore, such as oil sands or tar sands. The process may involve two
parallel, horizontal
wells, which are drilled in an oil sand or tar sand formation. The wells can
be, for example,
approximately 1 km in length, but other lengths are acceptable as well. An
upper injector well
6
CA 02821184 2013-07-16
resides above a lower producing well. The wells can be separated by any
suitable distance, for
example, approximately 4-6 meters. Initially, steam is injected downhole into
one or both of the
wells where it condenses and begins heating the formation and the bitumen
therein. Generally,
steam is injected into the well head and this process is readily understood by
those skilled in the
art. The steam condenses and heats the formation and the bitumen residing
therein. The steam
can be injected at high pressures and can be at a temperature of about 500 C.
After a period of
time, the formation is sufficiently heated such that the viscosity of the
bitumen is reduced.
Over time, low pressure steam can be continuously injected into the injector
well,
resulting in the formation of a steam chamber, further heating the bitumen
causing it to be
sufficiently reduced in viscosity to drain along the edge of the steam chamber
to the lower
producing well by way of gravity where it can be pumped to the surface along
with the
condensed steam and/or the additive(s). At that point, the water and/or
additive(s) are separated
from the bitumen in water emulsion and the bitumen can be recovered using
various known
methods in the art such as "breaking" the emulsion.
An additive according to the present disclosure, such as one or more
fluorinated
hydrocarbons, one or more alcohols, or combinations of one or more alcohols
and one or more
fluorinated hydrocarbons, can also be injected into either one of the wells,
or both of the wells, to
contact the bitumen. The additive(s) can be injected independently of the
steam or can be added
as a mixture with the steam. The steam may be injected continuously or
intermittently into one
or both of the wells. Moreover, the additive(s) may be injected continuously
or intermittently
into one or both of the wells. Also, if the steam and additive(s) are added as
a mixture, the
mixture can be added either continuously or intermittently into one or both of
the wells.
Additive(s) addition may occur at, but is not limited to, the steam header, at
the well head,
or it can be added into the boiler feed water.
The additive(s) can be injected into one or both of the wells at any point
during recovery
such as when production begins or when production begins to diminish. For
example, when
bitumen production begins to decline in the well, the additive(s) described
herein can be added.
By adding the additive(s) after production has begun to decline, the recovery
level can be brought
back to or near an optimal or peak bitumen recovery level.
It is noted that when carrying out the recovery or production methods
disclosed herein,
any number of wells, such as two wells, three wells, even a single well, can
be used. No matter
the number of wells selected, the steam and additive(s) described herein can
be injected into any
7
CA 02821184 2013-07-16
of the wells, or all of the wells. The additive(s) can be injected
independently of the steam or it
can be added as a mixture with the steam into any of the wells. The steam may
be injected
continuously or intermittently into any of the wells. Moreover, the
additive(s) may be injected
continuously or intermittently into any of the wells. Also, if the steam and
additive(s) are added
as a mixture, the mixture can be added either continuously or intermittently
into any of the wells.
Also, hydrocarbons can be mined or extracted from a formation and the
hydrocarbon can
be separated outside of the formation using any known method in the art such
as, for example, a
primary separation vessel. Such a separation process can be carried out with
the assistance of
heated water, the additive(s) disclosed herein, and optionally other
additives, such as caustic
soda. In certain variations, the hydrocarbons are fed into hydrotransport
lines and contacted
therein by the heated water and optionally the additive(s), which conditions
the ore and starts the
bitumen liberation process. The resultant slurry can then be fed into one or
more primary
separation vessels. A hydrocarbon primary froth is separated at the top of the
vessel while the
sand settles at the bottom. The hydrocarbon froth is then subjected to further
processing.
The contents other than those in the hydrocarbon primary froth can go through
secondary
separation processes where further hydrocarbon can be recovered.
The additive(s) disclosed herein can be added either separately, or as a
mixture with the
heated water, at any time during primary, secondary, and/or tertiary
separation or recovery, to
enhance the hydrocarbon recovery and/or minimize the amount of water used.
Further, bitumen can be mined or extracted from a formation and the bitumen
can be
separated from, for example, oil or tar sand, outside of the formation using
any known method in
the art such as, for example, a primary separation vessel. Such a separation
process can be
carried out with the assistance of heated water, the additive(s) disclosed
herein, and optionally
other additives, such as caustic soda. In certain variations, the oil or tar
sand bitumen is fed into
hydrotransport lines and contacted therein by the heated water and optionally
the additive(s),
which conditions the ore and starts the bitumen liberation process. The
resultant slurry can then
be fed into one or more primary separation vessels. A bitumen primary froth is
separated at the
top of the vessel while the sand settles at the bottom. The bitumen froth is
then subjected to
further processing.
The contents other than those in the bitumen primary froth can go through
secondary
separation processes where further bitumen can be recovered.
8
CA 02821184 2013-07-16
The additive(s) disclosed herein can be added either separately, or as a
mixture with the
heated water, at any time during separation or secondary separation, to
enhance the bitumen
recovery and/or minimize the amount of water or used.
Compositions are also disclosed herein. The compositions can include one or
more
.. hydrocarbons, water or steam, and one or more additive(s). The additive(s)
can be the additives
described in the present application, such as the fluorinated hydrocarbon
additives, one or more
alcohol additives, or combinations of one or more alcohols and one or more
fluorinated
hydrocarbons. Such a composition can be obtained from a subterranean formation
by contacting
one or more hydrocarbons in a subterranean formation with heated water or
steam, contacting the
.. one or more hydrocarbons in the subterranean formation with additive(s),
such as one or more
fluorinated hydrocarbons, one or more alcohols, or combinations of one or more
alcohols and one
or more fluorinated hydrocarbons, as described herein, and recovering the
resulting emulsion
from the formation. Such a composition can also be obtained by contacting the
hydrocarbon with
water or steam, as well as additive(s), such as one or more fluorinated
hydrocarbons, one or more
.. alcohols, or combinations of one or more alcohols and one or more
fluorinated hydrocarbons, as
described herein, outside of the subterranean formation.
Also disclosed is a composition including water or steam, an additive, such as
one or
more fluorinated hydrocarbons, one or more alcohols, or combinations of one or
more alcohols
and one or more fluorinated hydrocarbons, as described herein, and bitumen.
Such a
.. composition can be obtained from a subterranean formation by contacting
bitumen in a
subterranean formation with heated water or steam, contacting the bitumen in
the subterranean
formation with the additive(s), and recovering the resulting emulsion from the
formation. The
water or steam and additive can be added independently of each other or can be
added as a
mixture. Such a composition can also be obtained by contacting the bitumen
with water or
.. steam, as well as an additive, outside of the subterranean formation.
Various additives are contemplated by the present disclosure. The additive
disclosed
herein can be, for example, one or more fluorinated hydrocarbons. Typically,
unless surface or
strip mining techniques are being used, the fluorinated hydrocarbon has an
atmospheric boiling
point of less than or equal to about 300 C. The fluorinated hydrocarbon
should have volatility
sufficient to allow for delivery to the production front unless surface or
strip mining techniques
are being used. Examples of fluorinated hydrocarbon additives useful in
connection with the
present disclosure include, but are not limited to, trifluoroethanol,
trifluoropropanol,
9
CA 02821184 2013-07-16
trifluorobutanol, allyIhexafluoroisopropanol, hexafluoroisopropanol,
trifluoroacetic acid, methyl
trifluoroacetate, ethyl trifluoroacetate, isopropyl trifluoroacetate,
trifluoroacetaidehydemethyl
hem iacetal, trifluoroacetaldehyde ethyl hemiacetal, trifluoroacetic
anhydride, trifluoroacetone,
fluorotoluene, and any combination or mixture thereof. Typically, the one or
more fluorinated
hydrocarbons are added at a concentration from about 25 to about 50,000 ppm by
weight of the
fluorinated hydrocarbon in the steam (wtts,vt fluorinated hydrocarbon additive
to steam basis).
Another possible dosage of the fluorinated hydrocarbon is from about 1,000 ppm
to about 5,000
ppm, and another possible dosage is from about 100 to about 1,000 ppm.
Even further, other additives are contemplated by the present disclosure. The
additives
disclosed herein can be, for example, one or more alcohols. Typically, unless
surface or strip
mining techniques are being used, the one or more alcohols have an atmospheric
boiling point of
less than or equal to about 300 C. The one or more alcohols should have
volatility sufficient to
allow for delivery to the production front unless surface or strip mining
techniques are being
used. Examples of alcohol additives useful in connection with the present
disclosure include, but
are not limited to, Ci alcohols (i.e. methanol), C2 alcohols, C3 alcohols, C4
alcohols, C5 alcohols,
C6 alcohols, C7 alcohols, C8 alcohols, C9 alcohols, or C10 alcohols, C11
alcohols, C12 alcohols, C13
alcohols, C14 alcohols, C i5 alcohols, and any combination, mixture, or isomer
thereof. For
example, the alcohol additives could be any combination of C1-C15 alcohols, or
any combination
of C2-C7 alcohols, or any combination of C8-C15 alcohols, or any combination
of C2-05 alcohols,
etc. Useful additives in accordance with the present disclosure can also be
defined as methanol,
ethanol, 1-propanol, 1-butanol, 1-pentanol, 2-pentanol, 3-methyl-1-butanol, 2-
methyl- I -butanol,
2-methyl-2-butanol, or any combination thereof. Further, any of the
aforementioned alcohol
additives can be added together as a mixture and any of the aforementioned
fluorinated
hydrocarbon additives can also be added into the mixture.
For example, in an aspect, the additive used in the disclosed process can be
ethanol. In
another aspect, the additive used can be 1-butanol. In another aspect, the
additive used can be 2-
pentanol. In another aspect, the additive used can be a mixture of propanol,
butanol, and 1-
pentanol. In another aspect, the additive used can be a mixture of
trifluoroethanol (TFE) and
ethanol. In another aspect, the additive used can be a mixture of
trifluoroethanol (TFE) and
butanol. In another aspect, the additive used can be a mixture of ethanol and
1-pentanol. As
previously noted, any combination of one or more alcohols or any combination
of one or more
fluorinated hydrocarbons can be used in accordance with the processes
disclosed herein, and
'10
CA 02821184 2013-07-16
even further, any combination of one or more alcohols combined with one or
more fluorinated
hydrocarbons can be used.
Typically, the one or more alcohols are added at a concentration from about 25
to about
50,000 ppm by weight of the one or more alcohols, or combination of one or
more alcohols and
.. one or more fluorinated hydrocarbons, in the steam (wt/wt additive
(alcohol, combination of
alcohols, or combination of one or more alcohols with one or more fluorinated
hydrocarbons)
additive to steam basis). One possible dosage of the one or more alcohols
additive, or the one or
more alcohols combined with one or more fluorinated hydrocarbons additive, is
from about 500
ppm to about 2,000 ppm, and another possible dosage is about 1,000 to about
2,000 ppm. Also,
it is possible to add the additive at a dosage of 1,000 ppm by weight of the
additive in the steam.
The foregoing additives or combinations of additives increase the amount of
bitumen
produced for the same steam input. Without wishing to be bound by any theory,
it is considered
that these additives or combinations of additives could possess properties
such as directly
improving the heat efficiency within a formation as well as reducing the oil-
water interfacial
.. tension. Moreover, the disclosed additives or combinations of additives
will lower the steam to
oil ratio meaning less steam will be necessary to produce the same amount of'
hydrocarbon or
bitumen, or additional hydrocarbon or bitumen will be produced for the same
steam input, due to
the presence of the additive(s). Further, these additives or combinations of
additives will not
interfere with the resulting emulsion such that it cannot be broken. When the
emulsion product is
recovered from the formation, it must be broken to obtain the desired
hydrocarbons. It has been
found that certain amine additives can interfere with this process such that
the produced emulsion
cannot be broken and therefore, the desired hydrocarbon(s) cannot readily be
obtained. The
additive(s) of the present disclosure overcome this problem. Finally, the
presently disclosed
additives or combinations of additives are volatile enough to be carried with
the steam through
.. the sand pack to reach the bitumen pay.
Processes wherein the additive(s) or combinations of additives of the present
disclosure
can be beneficial to the hydrocarbon recovery include, but are not limited to,
cyclic steam
stimulation, steam assisted gravity drainage, vapor recovery extraction
methods, mining or
extraction techniques, and the like.
The foregoing may be better understood by reference to the following examples,
which
are intended only for illustrative purposes and are not intended to limit the
scope of the invention.
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Example 1
A sample of oilsands ore (15 g) was charged into a pre-weighed stainless steel
holder
containing several holes. The oilsands ore contained 13.51% bitumen, 83.45%
solids and 3.04%
water. A cellulose thimble to account for any solids extracted as a
consequence of the method,
approximately 4 cm in length, was placed beneath the stainless holder and the
two were placed
into a jacket Soxhlet extractor. Deionized water or process boiler feed water
(BFW), as
specified, (300 mL) and trifluoroethanol were charged into a 500 mL round
bottom flask beneath
the extractor unit. Blank runs were additionally conducted in the same manner
excluding
trifluoroethanol. The extractor and round bottom flask were wrapped with
insulation and
aluminum foil, and the extraction run at high temperature for 4 hours. The
extraction was then
allowed to cool, the stainless holder removed, wiped of any extracted bitumen,
and allowed to
dry in a 105 C oven for 2 days. The cellulose thimble containing any solids
extracted as a
consequence of the extraction process was placed in the oven to dry overnight.
Following drying in the oven, the stainless holder and cellulose thimble were
allowed to
cool to room temperature and weighed. The amount of bitumen extracted was
determined based
on the amount of bitumen initially present in the ore, accounting for solids
losses in the
extraction process and water losses in the oven. To determine the amount of
bitumen extracted,
it was assumed that 66% of the connate water in the original ore sample would
be lost over a 2
day period in the oven (Equation 1).
Ore assuming 66% of
- (Final ore (g) + Dried solids extracted (4
Bitumen Extracted (%) connate H20 lost (g) x 100%
Initial bitumen in ore (g)
Equation 1. Bitumen extracted (%) using Test Method A.
Dosages of 500 or 1,000 ppm of trifluoroethanol (based on the water) were
tested (FIG I
and Table 1). The mean bitumen extracted for the blank (n=5) was 15.06%
(SD=1.87%), the 500
ppm dose (n=8) was 26.53% (SD=5.99), 1,000 ppm dose in deionized water (n=3)
was 29.11 %
(SD=8.20%), and 1,000 ppm in BFW was 37.38% (SD=6.37%) (Table 1). All of the
trifluoroethanol additions resulted in p-values of less than 0.05 when
compared to the blank, and
were considered to be statistically significant (Table 2).
12
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Number of Mean Bitumen
Level Std Dev
Runs Extracted (%)
Blank 5 15.06 1.87
Trifluoroethanol 1,000 ppm 3 29.11 8.20
Trifluoroethanol 1,000 ppm SEW 3 37.38 6.37
Trifluoroethanol 500 ppm 8 26.53 5.99
Table 1. Mean, standard deviation and number of runs for the trifluoroethanol
runs.
Level - Level p-Value
Trifluoroethanol 1,000 ppm BFW Blank <.0001*
Trifluoroethanol 1,000 ppm Blank 0.0040*
Trifluoroethanol 500 ppm Blank 0.0029*
Table 2. p-values comparing the trifluoroethanol and blank runs.
Example 2
A comparison between ethanol and trifluoroethanol was carried out (both dosed
at 500
ppm). Ethanol (n=6) resulted in a mean bitumen extracted of 21.04% (SD=3.88%)
while the
same dose of trifluoroethanol (n=8) resulted in 26.53% (SD=5.99%) bitumen
extracted (FIG 2
and Table 3). The blank values were as above. Considering this data,
trifluoroethanol
outperforms both ethanol and the blank, with p-values of less than 0.05 in
both cases (Table 4).
Level Number of Mean Bitumen Sid Dev
Runs Extracted (/0)
Blank 5 15.06 1.87
Ethanol 6 21.04 3.88
Trifluoroethanol 8 26.53 5.99
Table 3. Mean, standard deviation, and number of runs for the ethanol and
trifluoroethanol runs.
Level - Level p-Value
Trifluoroethanol Blank 0.0005*
Ethanol Blank 0.0482*
Trifluoroethanol Ethanol 0.0428*
Table 4. p-values for the trifluoroethanol and blank runs.
Example 3
13
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Oi'sands ore (15 g) was charged into a stainless holder containing several
holes on the
bottom and an open top. For these experiments, extraction glassware that
enabled direct contact
of steam and volatilized additive with the ore was used. Deionized water (200
mL,) and
trifluoroethanol (1,000 ppm based on the water) were added to the round bottom
portion of
extraction glassware. Directly above the round bottom portion of the
extraction flask sat a coarse
stainless steel grid to support the holder containing the oilsands ore sample.
The extraction flask
was wrapped with insulation and aluminum foil and the experiment was refluxed
for 4 h. The
collected bitumen in water was separated using a rotary evaporator (rotovap)
and subsequently
extracted with toluene into a 100 mL volumetric flask. Bitumen adhered to the
sides of the flask
was extracted with toluene and added to the bitumen obtained following rotovap
separation. The
bitumen on the sides of the stainless holder was accounted for by collecting
with a pre-weighed
cleaning tissue. The pH of the water following rotovap separation was
measured.
Following this initial extraction, the same stainless holder with ore was
added back to
extraction vessel along with fresh deionized water (200 inL) and
trifluoroethanol (1,000 ppm).
The experiment was carried out in the same manner as the first incremental
extraction. This test
was repeated a third time with the same stainless holder and ore. Following
the three incremental
recoveries, the remaining bitumen in the ore was determined by Dean-Stark
extraction with
toluene. A blank was also run in the same manner without trifluoroethanol.
The bitumen extracted with steam for each increment (runs 1-3) was compared to
the total
bitumen extracted and expressed as % bitumen extracted (Equation 2). The total
bitumen
extracted with steam for the three runs was compared to the total bitumen
extracted and
expressed as % total bitumen extracted (Equation 3).
Bitumen extracted
Bitumen Extracted Run! (%) = with steam run 1(g) x 100%
Total bitumen extracted + Bitumen extracted
with steam runs 1-3 (g) with toluene (g)
Equation 2. Incremental bitumen extracted calculation for runs 1-3.
14
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Total Bitumen extracted
Total Bitumen Extracted (%) = with steam runs 1-3 (g) x 100%
Total bitumen extracted Bitumen extracted
with steam runs 1-3 (g) with toluene (g)
Equation 3. Total bitumen extracted calculation for incremental recovery test.
Following the first run, the blank extracted 28.60% of the bitumen in the
sample whereas
the trifluoroethanol extracted 26.40%.
Considering this test method, the efficacy of
trifluoroethanol can be seen in the second and third runs. The bitumen
extracted for the blank
runs 2 and 3 was 11.79% and 5.46%, respectively. The bitumen extracted when
using
trifluoroethanol does not decline as rapidly, with 17.80% and 14.05% bitumen
being extracted
for runs 2 and 3, respectively. The overall bitumen extracted for the blank
was 45.84% and with
trifluoroethanol was 58.25%. Results are shown in Table 5.
Bitumen Bitumen Bitumen Total
PH p11 pH
Extracted Extracted Extracted Bitumen
Additive (Run (Run (Run
Run 1 Run 2 Run 3 Extracted
1) 2) 3)
(%) (%) (%) (%)
Blank 8.94 8.65 9.19 28.60 11.79 5.46
45.84
Trifluoroethanol 8.78 8.87 8.79 26.40 17.80 14.05 58.25
Table 5. Incremental bitumen extracted results for the blank and
trifluoroethanol (1,000 ppm).
Example 4
Deionized water (100 rnL) and trifluoroethanol (1,000 ppm based on the water)
were
charged into a laboratory autoclave reactor with a volume capacity of 600 m L
and fit with a glass
liner. A 15 g oilsands ore sample, with the same composition as in Example 1,
was added to a
stainless holder with several holes on the bottom and an open top. The sample
was placed above
the water/trifluoroethanol mixture so as to not directly contact the water and
trifluoroethanol
prior to the start of the experiment. The reactor was sealed and heated to 200
C to 5 hours.
During this time, the internal pressure of the vessel reached 200 psig. The
reactor was then
allowed to cool to room temperature, opened, and the water was separated from
the bitumen.
The resulting bitumen was extracted with toluene into a 100 mL volumetric
flask. Any bitumen
CA 02821184 2013-07-16
remaining on the outside of the stainless holder was accounted for by
collecting onto a pre-
weighed cleaning tissue. The remaining bitumen in the ore sample was then
determined by
Dean-Stark extraction with toluene. A blank was also run in the same manner
without
trifluoroethanol. The resulting bitumen extracted for the blank was found to
be 6.42% and with
the addition of trifluoroethanol, extraction increased to 13.05%.
Example 5
Bitumen extraction studies for Examples 5-8 were carried out according to the
following
procedures. These examples used a glass laboratory extraction vessel that
enabled steam and
volatilized additive to directly contact the core sample. For these
experiments, 15 g of core
sample was added to a stainless holder containing several holes and a closed
top. Previous
experiments using this extraction vessel were run with the stainless holder
having an open top.
The core sample had a composition of 15.23% bitumen, 83.58% solids, and 1.37%
water (based
on the average of five Dean-Stark runs). Deionized water (200 mL) and/or
additive(s) were
added to the round bottom portion of the extraction vessel. The vessel was
fitted with insulation
and sufficient heat was applied to allow the contents to reflux for 4 hours at
ambient pressure.
The additive(s) dosage was based on the concentration in water. Following the
experiment, the
water was separated from the collected bitumen. The bitumen component remained
in the vessel,
was removed with toluene, and subsequently placed into a 100 mL volumetric
flask. The
bitumen on the sides of the stainless holder was accounted for by collecting
with a pre-weighed
cleaning tissue. The amount of bitumen remaining in the core following steam
extraction was
determined by Dean-Stark extraction with toluene. The bitumen recovered with
steam, or steam
together with additive(s), was compared to the total bitumen in the sample and
expressed as %
bitumen extracted (Equation 4).
Bitumen extracted
)
Bitumen Extracted (%)= with steam (g x T00%
Bitumen extracted Bitumen extracted
with steam (g) with toluene (g)
Equation 4, Bitumen extraction calculation for examples 5-8.
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In Example 5, using just water for reflux (blank) resulted in a mean bitumen
extracted of
6.2% (Table 6). Addition of the alcohol additives significantly improved the
bitumen extraction.
The majority of the studies were carried out at a dosage of 1,000 ppm (based
on the water
fraction). When blends were studied they were also conducted to total 1,000
ppm product
dosage, however some runs were carried out at a total product dosage of 1,500
or 2,000 ppm in
subsequent examples.
Experimental runs were carried out to compare the performance of ethanol (200
proof) to
trifluoroethanol. Runs without additive (n=5) resulted in a mean bitumen
extraction of 6.2 1.7
%. Addition of 1,000 ppm of ethanol (n=3) resulted in a mean bitumen
extraction of 25.6 1.3
% and 1,000 pm trifluoroethanol (n=3) resulted in an extraction of 15.8 4.0%
(Figure 3, Table
6). Both additives outperform the blank, and additionally, ethanol displayed
enhanced
performance compared to trifluoroethanol (student's t test, p=0.001).
Number Mean Bitumen
Level Std Dev
of Runs Extraction (%)
Blank 5 6.23 1.65
Ethanol 3 25.58 1.28
Trifluoroethanol 3 15.76 3.95
Table 6. Mean bitumen extraction, standard deviation, and number of runs for
the blank, ethanol
(1,000 ppm) and trifluoroethanol (1,000 ppm).
Level - Level p-Value
Ethanol Blank <.0001*
Ethanol Trifluoroethanol 0.0010*
Trifluoroethanol Blank 0.0006*
Table 7. Comparative data with p-values for the blank, ethanol, and
trifluoroethanol.
Example 6
A comparative study was undertaken looking at CI-05 (methanol-pentanol)
straight chain
alcohols for their efficacy in enhancing bitumen extraction. All of the
alcohols tested were dosed
at 1,000 ppm and displayed enhanced bitumen extraction over the blank (Figure
4, Table 8). In
addition, methanol was outperformed by the other alcohols studied. From this
data set, no
17
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statistically significant differences in bitumen extraction were observed
between ethanol, 1-
propanol, 1-butanol and 1-pentanol.
Number of Mean Bitumen
Level Std Dev
Runs Extracted (%)
1-Butanol 3 29.25 7.28
I-Pentanol 3 22.82 2.53
1-Propanol 2 24.65 4.65
Blank 5 6.23 1.65
Ethanol 3 25.58 1.28
, Methanol 2 14.58 3.05
Table 8. Mean bitumen extraction, standard deviation and number of
experimental runs
completed for CI-05 alcohols.
Level - Level p-Value
1-Butanol Blank <.0001*
Ethanol Blank <.0001*
1-Propanol Blank <0001*
1-Pentanol Blank <.0001*
I -Butanol Methanol 0.0009*
Ethanol Methanol 0.0068*
1-Propanol Methanol 0.0185*
Methanol Blank 0.0193*
1-Pcntanol Methanol 0.0310*
1-Butanol 1-Pentanol 0.0546
Table 9. Comparative data with p-values for additives tested.
Example 7
A study was conducted looking at various isomers of C5 alcohols to determine
if any
performance difference could be observed. In addition to 1-pentanol previously
tested, 2-
pentanol, 3-methyl-1 -butanol, 2-methyl-I -butanol and 2-methyl-2-butanol were
run at a dosage
of 1,000 ppm. No statistically significant performance difference between
these additives was
observed (Figure 5, Tables 10 & 11).
18
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Number of Mean Bitumen
Level Std Dev
Runs Extracted (1)/0)
1-Pentanol 3 22.82 2.53
2-methyl-1-butanol 2 22.57 0.021
2-methyl-2-butanol 4 22.83 4.41
2-Pentanol 3 26.51 6.02
3-methyl-1-butanol 2 19.95 0.028
Table 10. Mean bitumen extracted, standard deviation and number of
experimental runs
completed for the C5 alcohol isomers.
Level - Level p-Value
2-Pentanol 3-methyl- I -butanol 0.1058
2-Pentanol 2-methyl- I -butanol 0,3077
2-Pentanol 1-Pentanol 0.2878
2-Pentanol 2-methyl-2-butanol 0.2588
2-methyl-2-butanol 3-methyl- 1-butanol 0.4269
1-Pentanol 3-methyl-l-butanol 0.4512
2-methyl-l-butanol 3-methyl- I -butanol 0.5293
2-methyl-2-butanol 2-methyl- -butane! 0.9407
I -Pentanol 2-methyl- 1-butanol 0.9451
2-methyl-2-butanol I -Pentane' 0.9983
Table 11. Comparative data with p-values for additives tested.
Example 8
Experimental runs were also completed studying alcohol blends (Table 12). All
of the
blends outperformed the blank (mean bitumen extracted of 6.2 %). Alcohols were
also blended
with trifluoroethanol (TFE) which also resulted in enhanced bitumen extraction
(Table 13).
Bitumen
Additive Dose (ppm)
Extracted (%)
Ethanol/Propanol/Butanol 400/400/200 12.68
Ethanol/Propanol/Butanol 400(400/200 13.79
Propanol/Butano1/1-Pentanol 400/400/200 22.99
Propanol/Butano1/1-Pentanol 400/400/200 20.77
19
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Table 12. Bitumen extracted for a blend of three alcohols added in a combined
dose
of 1,000 ppm.
Bitumen
Additive Dose (ppm)
Extracted (A)
TFE/Ethanol 500/500 19.05
TFE/Ethanol 500/500 18.06
TFE/Ethanol 200/800 22.53
TFE/Ethanol 200/800 25.97
TFE/Butanol 1000/1000 32.08
TFE/Ethanol/Propanol 200/400/400 18.63
TFE/Ethanol/Propanol 200/400/400 20.62
TFE/Pentanol 500/500 21.49
TFE/Pentanol 500/500 14.91
Ethano1/1-Pentanol 500/500 23.81
TFE/Ethanol 1000/500 19.94
TFE/Ethanol 500/1000 14.75
TFE/Ethanol 1000/1000 26.23
TFE/Ethano1/1-Pentanol 167/667/167 14.64
TFE/Ethano1/1-Pentanol 667/167/167 21.22
TFE/Ethanol/1-Pentanol 333/333/333 11.53
TFE/Ethanol/ I -Pentanol 167/167/667 15.06
TFE/Ethanol 100/900 15.50
TFE/Ethanol 750/250 21.70
TFE/Ethanol 250/750 19.43
Table 13. Bitumen extracted for alcohols blended with trifluoroethanol (TFE).
All of the compositions and methods disclosed and claimed herein can be made
and
executed without undue experimentation in light of the present disclosure.
While this invention
may be embodied in many different forms, there are described in detail herein
specific preferred
embodiments of the invention. The present disclosure is an exemplification of
the principles of
the invention and is not intended to limit the invention to the particular
embodiments illustrated.
In addition, unless expressly stated to the contrary, use of the term "a" is
intended to include "at
least one" or "one or more." For example, "a device" is intended to include
"at least one device"
or "one or more devices."
Any ranges given either in absolute terms or in approximate terms are intended
to
encompass both, and any definitions used herein are intended to be clarifying
and not limiting.
Notwithstanding that the numerical ranges and parameters setting forth the
broad scope of the
CA 02821184 2013-07-16
invention are approximations, the numerical values set forth in the specific
examples are reported
as precisely as possible. Any numerical value, however, inherently contains
certain errors
necessarily resulting from the standard deviation found in their respective
testing measurements.
Moreover, all ranges disclosed herein are to be understood to encompass any
and all subranges
(including all fractional and whole values) subsumed therein.
It should also be understood that various changes and modifications to the
presently
preferred embodiments described herein will be apparent to those skilled in
the art within the
scope of the appended claims.
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