Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
CA 02790267 2014-03-04
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CA2790267
OIL THINNING COMPOSITIONS AND RETRIEVAL METHODS
FIELD OF THE INVENTION
The present invention relates to compositions of plant oil-based biodegradable
crude
oil thinning fluids having a performance especially suitable to reducing crude
oil viscosity in
extraction and retrieval operations.
BACKGROUND OF THE INVENTION
With ever increasing environmental pressures being placed on the oil industry
it has
become necessary to develop and employ products and methods of well treatment
which
can perform in a timely fashion, be cost effective and conform to the stricter
controls now in
place.
It is known in the art that oil fields can become extremely viscous due to a
heavy
concentration of paraffin, asphaltene, or a combination of both and other
organics in the
formation. Paraffin plugs stop oil recovery completely until they are cleared.
Indeed, these
deposits can result in reduced oil production, fouling of flow lines and down
hole piping,
under deposit corrosions, reductions in gas production, and increased pumping
costs due to
pumping a high viscosity fluid. Each of these conditions individually can
result in lost
revenue. The combination of two or more of these conditions will lead to a
significant
revenue loss to the well owner, as well as additional income spent due to
clean up of oil
spills caused by under
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deposit corrosion or other flow restrictions. Moreover, the differing oxygen
concentrations (and
other corrosive compounds which may be present and intensify the corrosiveness
of the oil) in
bulk oil with respect to the oxygen levels extant beneath the deposit result
in localized, rapid
corrosion of the piping and eventual oil leaks. What is needed is a
environmentally friendly,
recyleable composition and methods for reducing the viscosity of crude oils in
the field to
facilitate extraction.
SUMMARY OF THE INVENTION
The present invention relates to compositions of plant oil-based biodegradable
crude oil
thinning fluids, having a performance especially suitable to reducing crude
oil viscosity in
extraction and retrieval operations.
In one embodiment, the present invention comprises formulations and methods to
enhance recovery from an oil well field. In one embodiment, the applicant's
method supplies a
mixture of terpenoid compounds derived from d-limonene, soy methyl esters, and
non-toxic
glycol ether esters reacted in a specific sequence with inorganic catalyst to
yield a mixture the
effectively reduces the viscosity of crude oil and oil sands. In one
embodiment, the method
continues the extraction of materials from the oil well or oil sands wth the
mixture of -limonene,
soy methyl esters, and non-toxic glycol ether esters into the oil well or
sands reducting the
material's viscosity. In one embodiment, the method recirculates the oil well,
and then returns
the oil well to service enabling extraction of additional oil with reduced
effort.
In one embodiment, the invention relates to a method to recover oil from an
oil well,
comprising the steps of: a) providing a formulation comprising: one or more
terpenoid
compounds, soy methyl esters, and glycol ether esters; b) introducing a said
formulation into
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said oil well; and c) recovering a mixture from said oil well, said mixture
comprising at least a
portion of said formulation and oil from said oil well. In one embodiment, the
invention relates
to a method to recover oil from an oil well, comprising the steps of: a)
providing a formulation
comprising: one or more terpenoid compounds, soy methyl esters, and glycol
ether esters; b)
introducing a first portion of said formulation into said oil well; and c)
recovering a mixture
from said oil well, said mixture comprising at least a portion of said
formulation and oil from
said oil well. In one embodiment, said oil well is not producing oil using
standard extraction
techniques. In one embodiment, said oil well is producing oil using standard
extraction
techniques. In one embodiment, the method further comprises, prior to said
introducing of step
b), the step of discontinuing extraction of materials from said oil well by
said standard
extraction techniques. In one embodiment, the method further comprises, after
said recovering
of step c), the step of recirculating said oil well. In one embodiment, the
method further
comprises, after said recirculating, the step of returning said oil well to
service and extracting
oil by standard extraction techniques. In one embodiment, said formulation
comprises
approximately 30-35 or even 30-45 weight percent of said one or more terpenoid
compounds,
approximately 30-35 or even 30-45 weight percent of said methyl esters, and
the balance of
weight percent of said glycol ether esters. In one embodiment, said one or
more terpenoid
compounds comprise one or more of pinene, menthene, menthane, and limonene. In
one
embodiment, said one or more terpenoid compounds comprises at least D-
limonene. In one
embodiment, the present invention contemplates making monoterpenes from
soybean oil and
their derivatives. In one embodiment, the method further comprises after said
recirculating
step the steps of: introducing a second portion of said formulation into said
oil well. In one
embodiment, said second portion is introduced under pressure (e.g. greater
than ambient
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atmospheric pressure). In another embodiments, different pressures are used
over time (e.g.
24 to 72 hours). In one embodiment, said first pressure is between about 200
psi and about
1000 psi, and wherein said second pressure is between about 400 psi and about
1200 psi, and
wherein said third pressure is between about 600 psi and about 1400 psi.
In one embodiment, the invention relates to a formulation comprising one or
more
terpenoid compounds, soy methyl esters, and glycol ether esters. In one
embodiment, the
formulation comprises approximately 30-35 weight percent of said one or more
terpenoid
compounds, approximately 30-35 weight percent of said methyl esters, and about
30 weight
percent of said glycol ether esters. In one embodiment, the formulation is
subtantially
non-toxic.
In one embodiment, the invention relates to a method for producing a
formulation to
dispose in an oil well to enhance recovery therefrom, comprising: a. providing
i) a solution of
one or more terpenoid compounds, ii) soy methyl esters, iii) glycol ether
esters, iv) a first
inorganic catalyst, v) a second inorganic catalyst, and vi) a reactor; b.
placing said solution of
one or more terpenoid compounds in said reactor; c. suspending said first
inorganic catalyst in
said solution in said reactor; d. adding said soy methyl esters to the reactor
to create a first
reaction mixture; e. agitating said first reaction mixture; and f. adding said
glycol ether esters
to said reaction mixture in the presence of said second inorganic catalyst to
create a second
reaction mixture; and g. agitating said second reaction mixture so as to
produce a formulation
for recovering oil. In one embodiment, said reactor is a stainless steel
reactor. In one
embodiment, said reactor is a glass reactor with an added source of steel. In
one embodiment,
said reactor is a plastic reactor with an added source of steel. In one
embodiment, agitating
comprises stirring the mixture for at least 30 minutes at 1700-3500 rpm. In
one embodiment,
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said reactor is grounded. In one embodiment, agitating comprises stirring the
mixture until the
solution is clear. In one embodiment, the invention is the composition
produced according to
the method above. In one embodiment, the composition can be used to reduce the
viscosity of
oil in pipes. In one embodiment, the composition can be used to increase the
extraction of oil
from oil sands. In one embodiment, the composition is subtantially non-toxic.
In one embodiment the invention relates to a method to enhance recovery from
an oil
well, comprising the steps of: supplying a mixture of compounds comprising: a
mixture of one
or more terpenoid compounds, soy methyl esters, and glycol ether esters;
discontinuing the
extraction of materials from said oil well; disposing said mixture of
compounds into said oil
well; recirculating said oil well; returning said oil well to service. In one
embodiment, said
supplying a mixture of compounds further comprises supplying a mixture
comprising about
30-35 or even 30-45 weight percent of said a mixture of one or more terpenoid
compounds,
about 30-35 or even 30-45 weight percent of said methyl esters, and the
balance of weight
percent of said glycol ether esters. In one embodiment, said one or more
terpenoid
compounds comprise one or more of pinene, menthene, menthane, and limonene. In
one
embodiment, said mixture of one or more terpenoid compounds comprises at least
D-limonene.
In one embodiment, the method further comprising after said recirculating step
the steps of:
injecting said mixture of compounds into said oil well using a first pressure,
wherein said first
pressure is greater than ambient atmospheric pressure; wherein said second
pressure is greater
than ambient atmospheric pressure; maintaining a third pressure in said well
for 24 to 72 hours,
wherein said third pressure is greater than ambient atmospheric pressure. In
one embodiment,
said first pressure is between about 200 psi and about 1000 psi, and wherein
said second
pressure is between about 400 psi and about 1200 psi, and wherein said third
pressure is
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between about 600 psi and about 1400 psi.
In another embodiment, the invention relates to a formulation to dispose in an
oil well
to enhance recovery therefrom, comprising a mixture of mixture of compounds
comprising a
mixture of one or more terpenoid compounds, soy methyl esters, and glycol
ether esters. In
one embodiment, the mixture of compounds further comprises about 30-35 or even
30-45
weight percent of said a mixture of one or more terpenoid compounds, about 30-
35 or even
30-45 weight percent of said methyl esters, and the balance of weight percent
of said glycol
ether esters.
In another embodiment, the invention relates to a method for producing a
formulation to
dispose in an oil well to enhance recovery therefrom, comprising: a) one or
more terpenoid
compounds, soy methyl esters, glycol ether esters, a first inorganic catalyst,
a second inorganic
catalyst, b) 30-35% weight by weight of the terpenoid compound d¨ limonene is
placed in a
reactor and said first inorganic catalyst is suspended in the solution of d-
limonene; c) addition
of 30-35% soy methyl esters to the reactor and subsequent agitation of the
resulting mixture;
and d) slow addition of glycol ether esters by weight to make up the balance
of the mixture in
the presence of said second inorganic catalyst and subsequent agitation of the
solution. In one
embodiment, said reactor is a stainless steel reactor. In one embodiment, said
reactor is a
glass reactor with an added source of steel. In one embodiment, said reactor
is a plastic
reactor with an added source of steel. In one embodiment, said first inorganic
catalyst is a
copper/iron catalyst. In one embodiment, agitation comprises stirring the
mixture for at least
minutes at 1700-3500 rpm. In one embodiment, said reactor is grounded. In one
embodiment, step d further comprises stirring the mixture until the solution
is clear. In one
embodiment, said second inorganic catalyst is a copper/iron catalyst. In one
embodiment, the
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invention is the composition produced according to method described above. In
all instances,
the reactions are endothermic.
In one embodiment, the invention relates to crude oil thinning formulations
including,
but not limited to:
1. In one embodiment, a family of formulations which use the solvent
discoveries and
other organic compounds to increase the recovery or crude oil form the
geologic formation, the
reservoir, and the oill tar sands. In one embodiment, this includes the
chemistry and methods
of oil recovery in the tar sands and oil rock/shale. We have experimentally
increased the yield
of oil by up to 10 times, and maintained that flow for 6-12 weeks.
2. In one embodiment, viscosity reducers which work outside the oil molecule
which
allows for at least 80% recovery, more preferably at least 90% recovery, and
most preferably up
to 100% recovery of our formulations with either mechanical or simple low
temperature
distillation techniques. In one embodiment, charged particle theory using the
outermost ring
of electrons to separate the oil molecules, reducing the cohesive properties
of oil.
3. In one embodiment, pipeline thinning agents which reduce the viscosity and
the
operating temperature requirements, and eliminate the need for corrosion
preventatives,
synthetic oil additions and sub-sequent separation, and readily allow for the
addition of
condensates, which can be separated and recovered though either physical
mechanical
separation or distillation.
4. In one embodiment, paraffin plug treatment agents to resume or restore
flow.
In one embodiment, the invention relates to a method to improve oil flow from
an oil
pipe, comprising the steps of: a) providing a formulation comprising: one or
more terpenoid
compounds, soy methyl esters, and glycol ether esters; b) introducing a first
portion of said
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formulation into said oil pipe; and c) recovering a mixture from said oil
pipe, said mixture
comprising at least a portion of said formulation and oil from said oil pipe.
In one
embodiment, the mixture can be added to oil field pipes in order to increase
flow. In one
embodiment, the mixture can be added to oil field pipes in order to clear a
blockage. In one
embodiment, the blockage comprises a paraffin plug. In one embodiment, the
mixture
comprises a paraffin plug treatment. In one embodiment, the pipes are buried.
In one
embodiment, the pipes are remotely located. In one embodiment, the pipes are
exposed to
extreme temperatures (e.g. -60 C to +40 C). In one embodiment, the pipes are
exposed to
very low temperatures. In one embodiment, the mixture is added to said oil
pipe to enable the
recovery of otherwise uncapturable oil.
In one embodiment, the invention relates to a method of separating the oil
from the
mixture. In one embodiment, a large portion of the mixture is substantially
recovered. In
one embodiment, the recovery of the mixture is at least 80%, and more
preferably at least 90%.
In one embodiment, the recovered mixture is substantially nontoxic. In one
embodiment, the
recovered mixture is nontoxic. In one embodiment, the recovered mixture is
recovered though
a combination of physical mechanical separation and distillation. In one
embodiment, the
recovered mixture is recovered though physical mechanical separation. In one
embodiment,
the recovered mixture is recovered though distillation. In one embodiment, the
recovered
mixture may reused in the same fashion as the original mixture with little or
no reduction in
performance.
In one embodiment, the invention relates to a method to recover oil from an
oil sands,
comprising the steps of: a) providing a formulation comprising: one or more
terpenoid
compounds, soy methyl esters, and glycol ether esters; b) introducing a first
portion of said
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formulation into said oil sands; and c) recovering a mixture from said oil
sands, said mixture
comprising at least a portion of said formulation and oil from said oil sands.
In one
embodiment, said oil sands is not producing oil using standard extraction
techniques. In one
embodiment, said oil sands is producing oil using standard extraction
techniques. In one
embodiment, the method further comprises, prior to said introducing of step
b), the step of
discontinuing extraction of materials from said oil sands by said standard
extraction techniques.
In one embodiment, the method further comprises, after said recovering of step
c), the step of
recirculating said oil sands. In one embodiment, the method further comprises,
after said
recirculating, the step of returning said oil sands to service and extracting
oil by standard
extraction techniques. In one embodiment, said formulation comprises
approximately 30-35
or even 30-45 weight percent of said one or more terpenoid compounds,
approximately 30-35
or even 30-45 weight percent of said methyl esters, and the balance of weight
percent of said
glycol ether esters. In one embodiment, said one or more terpenoid compounds
comprise one or
more of pinene, menthene, menthane, and limonene. In one embodiment, one or
more
terpenoid compounds comprises at least D-limonene. In one embodiment, further
comprises
after said recirculating step the steps of: introducing a second portion of
said formulation into
said oil sands using a first pressure, wherein said first pressure is greater
than ambient
atmospheric pressure; wherein said second pressure is greater than ambient
atmospheric
pressure; maintaining a third pressure in said well for 24 to 72 hours,
wherein said third
pressure is greater than ambient atmospheric pressure. In one embodiment, said
first pressure
is between about 200 psi and about 1000 psi, and wherein said second pressure
is between
about 400 psi and about 1200 psi, and wherein said third pressure is between
about 600 psi and
about 1400 psi. In one embodiment, the mixture is added to oil sands to enable
the recovery
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of otherwise uncapturable oil.
DEFINITIONS
To facilitate the understanding of this invention, a number of terms are
defined below.
Terms defined herein have meanings as commonly understood by a person of
ordinary skill in
the areas relevant to the present invention. Terms such as "a", "an" and "the"
are not intended
to refer to only a singular entity, but include the general class of which a
specific example may
be used for illustration. The terminology herein is used to describe specific
embodiments of
the invention, but their usage does not delimit the invention, except as
outlined in the claims.
Asphalt is a black bituminous material used for paving roads or other areas;
usually
spread over crushed rock. Asphalt is also a dark bituminous substance found in
natural beds
and as residue from petroleum distillation; comprised mainly of hydrocarbons.
Asphalt is also
a mixed asphalt and crushed gravel or sand; used especially for paving but
also for roofing.
Asphalts, as used herein, include cementitious materials in which the
predominating
constituents are bitumens that occur in nature or are obtained in petroleum
processing. Bitumen
is a term which encompasses cementitious substances, natural or manufactured,
composed
principally of high molecular weight hydrocarbons, of which asphalts, tars,
pitches, and
asphalitites are typical. Asphalts are often classified as solids, semisolids,
or liquids. They are
often defined as the manufactured materials that are produced during petroleum
processing.
Asphalts characteristically contain very high molecular weight molecular polar
species, called
asphaltenes, which are soluble in carbon disulfide, pyridine, aromatic
hydrocarbons,
chlorinated hydrocarbons, and tetrahydrofuran (THF). Asphalts produced from
the refining of
petroleum have been used primarily in paving and roofing applications.
In one embodiment, natural gas condensate or condensate is a low-density
mixture of
CA 02790267 2012-09-13
hydrocarbon liquids that are present as gaseous components in the raw natural
gas produced
from many natural gas fields. In one embodiment, it condenses out of the raw
gas if the
temperature is reduced to below the hydrocarbon dew point temperature of the
raw gas. In
one embodiment, the natural gas condensate is also referred to as simply
condensate, or gas
condensate, or sometimes natural gasoline because it contains hydrocarbons
within the gasoline
boiling range. Raw natural gas may come from any one of three types of gas
wells: In one
embodiment, such as crude oil wells, raw natural gas that comes from crude oil
wells is called
associated gas. In one embodiment, this gas can exist separate from the crude
oil in the
underground formation, or dissolved in the crude oil. In one embodiment, such
as dry gas
wells, these wells typically produce only raw natural gas that does not
contain any hydrocarbon
liquids. In one embodiment, such gas is called non-associated gas. In one
embodiment, such
as condensate wells, these wells produce raw natural gas along with natural
gas liquid. In one
embodiment, Such gas is also non-associated gas and often referred to as wet
gas.
A preferred rubber is at least a poly(conjugated diene). Exemplary conjugated
diene
contributed monomer units include 1,3-butadiene, isoprene, 2,3-dimethy1-1,3-
butadiene, and
1,3-pentadiene. Preferred conjugated diene contributed monomer units are 1,3-
butadiene and
isoprene. The rubber may include more than one conjugated diene contributed
monomer unit,
such as, for example, the rubber may be a poly(1,3-butadiene-co-isoprene).
In addition, the rubber may also contain additional monomer contributed units.
Exemplary monomer contributed units include vinyl-substituted aromatic
hydrocarbons.
Suitable vinyl-substituted aromatic hydrocarbons include styrene, a-
methylstyrene,
1 -vinylnaphthalene, 2 -vinylnaphthalene, 1 -a-methyl
vinylnaphthalene, 2-a-methyl
vinylnaphthalene, as well as alkyl, cycloalkyl, aryl, alkaryl, and aralkyl
derivatives thereof, and
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di-or tri-vinyl aromatic hydrocarbons. A preferred vinyl-substituted aromatic
hydrocarbon is
styrene. The rubber is preferably any of poly(1,3-butadiene), styrene-
butadiene diblock
polymers, as well as any styrene-butadiene block or random polymers, and
mixtures thereof.
Limonene is a colourless liquid hydrocarbon classified as a cyclic terpene
possessing a
strong smell of oranges. D-limonene has the structure as shown below:
Limonene is a chiral molecule, and biological sources produce one enantiomer:
the principal
industrial source, citrus fruit, contains D-limonene ((+)-limonene), which is
the (R)-enantiomer.
Racemic limonene is known as dipentene [1]. D-Limonene is obtained
commercially by
extraction from orange peel with supercritical CO2.
The term "effective," as that term is used in the specification and/or claims,
means
adequate to accomplish a desired, or hoped for result.
DESCRIPTION OF THE FIGURES
Figure 1 shows a graphical representation of a well head 41 from the Kern
River Field
demonstrating a significant decrease in the viscosity, and an increase in the
oil produced with
the formulation.
Figure 2 shows a graphical representation of a well head 47 from the Kern
River Field
demonstrating a significant decrease in the viscosity, and an increase in the
oil produced with
the formulation.
Figure 3 shows a graphical representation of a well head 72 from the Kern
River Field
demonstrating a significant decrease in the viscosity, and an increase in the
oil produced with
the formulation.
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Figure 4 shows an FTIR spectrum analysis of the Formula "A" also known as
Prodigen X.
Figure 5 shows an FTIR spectrum analysis of the Formula "B"
Figure 6 shows an FTIR spectrum analysis of the Formula "C"
Figure 7 shows an FTIR spectrum analysis of the AR 3600 asphalt remover.
DESCRIPTION OF THE INVENTION
Crude oils of various composition and viscosities are hydrophobic and are
difficult
to remove due the high surface tension and the general insolubility with many
inorganic and
organic solvents. Detergent systems designed to reduce the surface tension
have met with
limited success; however, the resulting mixtures are often surface
contaminants, or may
cause rusting or other forms of corrosion. Generally, the solvents used to
thin crude oil
come form distillation fractions of crude oil, and carry the same toxic
compounds present in
the crude oil. In addition, these agents can destroy the integrity of the
crude oil and its
soluates, thus preventing the recovery and use of the materials removed.
Further, these
materials make it extremely difficult or impossible to recover the crude oil
due to physical
destruction of the crude.
There are several other needs for effective oil thinning agents. They are:
1.In Situ: There is a significant need for crude oil thinning in the geologic
formation containing the oil. Approximately 40-60% of the available crude in a
well is left
due to viscosity and surface tension of the crude oil. The oil molecules
"stick together"
and on the
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surfaces of the formation, holding the oil back from flowing into the
reservoir of the well. Oil
wells are drilled into a geologic formation, which contains sufficient
quantities of crude oil (or
natural gas) to make it economically viable. Either a reservoir is present, or
one is established
to collect the crude oil so it can be pumped to the surface. Various
technologies are used to
"enhance" the oil to flow into the reservoir, including CO2 injection under
pressure,
superheated steam, propane, detergents and acids, and forced air. Further,
chemical and
physical "fracing" (also called fraccing or fracking) or fracturing the
formation is a common
practice to open the formation for more oil to flow into the collection
reservoir. There are major
issues with the use detergents and acids because of the chemical alteration of
the crude oil, and
additional pollution. Similar issues exist with the use of superheated steam
(water discharge),
and the depletion of the water table.
Opponents of fraccing point to the negative impact on the environment and
health,
including contamination of pound water and the migration of gases and
hydraulic fracturing
chemicals to the surface, as well as surface contamination from spills.
Importantly, the
plant-derived formulations described herein can be an aid to fraccing, since
they are non-toxic,
thereby reducing the potential for environmental damage.
2. Oil or tar sands oil recovery. Current technologies use high superheated
steam to
force the oil to be released from the 'Mud" or sands. In most areas this is
achieved by mining
the oil mud, placing it on trucks, and carrying the mud to a processing site.
No In Situ
processing is conducted. Similar problems are created using steam for this
use.
3. Crude oil transport via pipelines. Crude oil is transported from the well
head to the
storage area, refinery, or ship via large, heated pipes. Generally, the oil
has been diluted with
condensate (a hydrocarbon liquid/gas) present in all wells. The condensate
gases are usually
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burned off, and the liquid is used to thin the crude. The amount of condensate
to crude oil
may be anywhere from very liitte condensate to as much as 50 %. In some
instances, a 50%
blend of synthetic oil is added to reduce the viscosity and thus, the surface
tension to allow oil
to flow. Heat is always present in the transport pipes. Generally, the oil is
heated to 90 C to
allow it to flow freely. This represents additional energy consumption to
allow oil to flow. A
corrosion inhibitor is always added (1-2%) to reduce the chemical attack of
the crude on the
pipeline walls.
This invention is described in preferred embodiments in the following
description with
reference to the Figures, in which like numbers represent the same or similar
elements.
Reference throughout this specification to "one embodiment," "an embodiment,"
or similar
language means that a particular feature, structure, or characteristic
described in connection
with the embodiment is included in at least one embodiment of the present
invention. Thus,
appearances of the phrases "in one embodiment," "in an embodiment," and
similar language
throughout this specification may, but do not necessarily, all refer to the
same embodiment.
The described features, structures, or characteristics of the invention may be
combined
in any suitable manner in one or more embodiments. In the following
description, numerous
specific details are recited to provide a thorough understanding of
embodiments of the
invention. One skilled in the relevant art will recognize, however, that the
invention may be
practiced without one or more of the specific details, or with other methods,
components,
materials, and so forth. In other instances, well-known structures, materials,
or operations are
not shown or described in detail to avoid obscuring aspects of the invention.
As a result of the problems described, I was able to discover and perfect
novel
formulations which can be used to extract, retrieve and recover the following:
Thin crude oils,
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oil based tar sands, and allow the recovery of crude oil from "oil rock " (
oils impregnated or
bound by sandstone or other naturally occurring aggregates with economically
viable
formulations that: a) require no heat, b) use no water, c) offer recovery of
the formulations up to,
and inclusive of 94% of the original amount used through physical or
mechanical separation, d)
convert to polyols if no recovery is required, e) are either the majority or
completely biobased
in content (non-toxic, thus non¨ polluting), f) combine readily with all types
of crude oil, g)
increase the well head yield of crude oil from 200-1,000%, h) free oil lodged
in formations
allowing total recovery of available oil reserves in a well from 50-60% to 80
% plus, i).
Separate oil from water based emulsions and mixtures, allowing greater oil
recovery
In one embodiment, the preferred chemistry comprises of a non-saponifiable
cyclic
monoterpene containing 2 isoprene units, with the "d" configuration,
specifically d-limonene
reacted with soy methyl esters and non-toxic glycol ether esters added in a
specific sequence in
the presence of an inorganic catalyst. (Other monoterpines including pinene,
menthol, and
turpentine, do not work, nor do additional isoprene units making up the
sesquiterpenes,
diterpines, triterpenes, and tetraterpenes respectively. The "L" forms of all
structures,
including 1-limonene do not react to form the end products.)
The reaction is a series of endothermic reactions resulting in a clear, water
white to hazy
yellow thin liquid. Each of the reactants can be varied in concentration
within limits in order
to produce a slightly altered material formulated to achieve the specific
functional result of
thinning crude oil per environmental application (Injection or gravimetric
application into the
formation, injection (In situ or under pressure in the formation or
reservoir), continuing drip or
single charge into the reservoir application, or combining with the crude oil
post well for
transport, or spray or flooding on oil sands to release the bound oil.
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The reaction steps are very specific. We tried other ways to react the
materials but the
end product did not work very well.
PREFFERED EMBODIMENTS: REACTION SEQUENCE
In one embodiment, 30-35% or even 30-45% (by weight) of d¨ limonene is placed
in a
stainless steel reactor. An inorganic (e.g. iron/copper) catalyst is suspended
in the solution.
Note: the catalyst must extend to the full length of the reactant results (it
has got to be as long
as the tank or vessel). In one embodiment, the reaction must be run in a
stainless or other steel
tank in order to set up an electrolytic reaction between the dissimilar
metals. We have
repeatedly try to achieve the same results in glass and plastic containers
with just the copper
catalyst, the results are solutions that don't work any where near as well on
oil thinning.
When we add a steel rod, strip, or other source of steel to the glass or
plastic vessel, we get
great end product that works well. A 30-35% addition of soy methyl esters
(methyl soyate
derived from soybean oil) is added and the resulting mixture is stirred at
1700-3500 rpm for 30
minutes. The reactor must be grounded.
The intermediate solution will gradually change color from a clear to slightly
yellow
color to a golden yellow, have a pH of between 4.0-5.0 depending on the
specific ratio of the
two starting materials. A slight haze will form in the solution.
Glycol ether esters are the added (to make up the balance) and the solution is
stirred (in
the presence of the catalysts) for 1 hour or until the solution clears, hl one
embodiment, The
temperature of the final solution will be at least 10 degrees lower than the
surrounding ambient
conditions.
Physical and Chemical Properties: (at STP)
pH: 4.3-4.8
17
CA 02790267 2012-09-13
Specific gravity: 0.8810-0.8900 (water =1.000)
Density:7.09-7.10 #/ US Gallon
Surface tension: 10.5-11 dynes/cm2
Odor: Aromatic, sweet fruity
Boiling Point: 185-190 F
Flash Point: 140 F (Tag Closed Cup), 70 F (Penske, open cup)
Solubility in water: Insoluble
Oil Thinning
A ratio of 30 % d¨ limonene, 30% methyl soyates, 40% glycol ether esters
applied to
heavy crude oil at STP, having a viscosity of 22,500 cTs.
Start viscosity of Crude Oil 22,500 (all applications done on a weight/weight
basis,
mixed for 2 minutes by hand) the viscosity results are shown in figure 8:
Table 1.
Crude oil cannot be efficiently pumped through pipelines unless the viscosity
is reduced
to a minimum high measurement of 350 cTs. This is the international standard
used for all
pipeline transport of crude oil. The viscosity is lowered with the assistance
of heat and the
inclusion of condensates.
The attached study performed by (Enbridge) clearly describes the performance
of the
solution, which includes the variable range of raw reactants. Formula "A" is
the final
formulation which uses the Bituminous Substance Removal formulation as a
primary building
block of the cyclic monoterpene and the surfactant, The addition of the other
primary raw
materials previously identified in this document are essential for the
viscosity and surface
tension reduction to occur.
A study performed on a sample of crude oil obtained from Cushing, Oklahoma was
evaluated using "formula A" for viscosity reduction, recovery of the solution,
and surface
tension.
18
CA 02790267 2012-09-13
The results are as follows:
Original viscosity 4,500 cTs surface tension: 31
dynes/cm2
Add 3.5% "A" 375 cTs surface tension: 18
dynes/cm2
Oil Thinning Agent-Distillation/Recovery
The following steps were used to recover up to 94% of the original Solution. A
simple.
Low temperature distillation of the oil/solution mixture was employed. Water
was removed by
one of two methods. The first method was tested at a well site in OK.
The first method used a simple skimming operation whereby the crude oil/our
formula
"A" mixture was separated from the water phase by gravimetric separation. The
oil phase
always floats above the water phase. When this method was utilized, our
material helped
separate the phases significantly better than all other separation methods,
and helped remove
suspended salts from the crude.
The second method was performed in a laboratory. This method used simple
centrifugation, whereby the crude oil/formulation "A" mixture was separated
from the water
phase. The problem with centrifugation is that there was some oil/
"formulation "A" loss, and
the residual fluid was processed through a gravimetric separator to eliminate
toxic material
discharge back into the watershed.
Once the oil/formulations "A", "B", and "C" were separated from the water
phase, a
low temperature, simple distillation/ condensing recovery system was used to
separate the
crude oil from the oil phase. A mean temperature of less than 150 C allowed
intact recovery
of almost all of the formulations. Recovery averages ranged from a low of 85%
(Formulation
"C") to a High of 97%+ (Formulation "A"). Mean recovery levels of 94% were the
target
level, with solutions "A and B" were recovered and tested for reuse in
thinning fresh crude.
19
CA 02790267 2014-03-04
CA2790267
EXPERIMENTAL FIELD RESULTS
The study of formulation "A", referred to as AR-OT demonstrates the increased
flow
of crude oil from the well following the introduction of our material. The
data, following
a 1 month experimental trial, speaks for itself with the increased output
derived in situ.
Well head studies on wells # 37, 41,47-72 from the Kern River Field
demonstrate a
significant decrease in the viscosity, and an increase in the oil produced
with the
formulation (shown in Figure 1, Figure 2, and Figure 3).
With respect to Figure 1:
Wdil 4 I Well 41 T well
Start af TesiT ¨2i1õ39 23:02 2:16.611 2,11709 12:36
Eid Tel 9.: 12 2117/09 8:55 2.1&IN
055
,
esw % 96.6 97 .25.3
EGLPD 71.2 182.7 145,8
BWPD 58.9W 177.2' 1381
44.111111110.1
BOPC) 2,3 5.51 6,a
IP1CraI .15
Waer Al); 9,71 10.3 9_8
Wel 41; 1,016141 Well it 1
0 9 23.'..02 2i1ELU9 11:30 2/17.9 12:36,
2, 1 elin 9:12 2117. 1.'9 a ;65 2/16;09 BS W% 96,8 07 95,3
BG LPL) 71.2 B1.7 145 104%
EWPD 177,2T3,,5.,7 101%
80PD 2,3 15.8
15.9
Water P. 71 9,7 10.3 9,6
CA 02790267 2014-03-04
CA2790267
With respect to Figure 2:
el 47 -WO 47
Start or Test 2/13,'OR 16:15. 2/18:09 11::35!
End ,of Tes1 214.,0 918 2i1 7/09
B-SW
BGLPD 64.5 82.4
1810113D I _ 62.2 79.1
BOPD 2 3,3'
,AFR3ra'iIJ 13,5 15.7
rWa".er API 10õ1
VI=if,1 47 Wel 47
210/09 16:15 2/1600 1125
211408 8:18 2:17,09 8;24 yt Cnaelf;
t,SW % 9t3,5
RGI.PD 6-11.E 82.4 28'.4
B1NPU 62.2 70.1
BOP D 2.3 3.3 43%
Grav11y 13,5 15.7 15%
nier API 10,1
With respect to Figure 3:
õ
Wcdi 72 I weti 72
151art
Test 2,17:19 14:00 .-1211.6,V9 12T,.17)
End of Tes1 2114/450 9:05 2117.'09 9:116
B-SW % 98 87.5
BGLPD ____________________________ 92 727r6
BWPD 91.4 1216.5
BOPD .8 2,2
AP i Gray ly 15,6
Wwer API_ 96L __________ 1(.
20a
CA 02790267 2014-03-04
CA2790267
we :I 72 Wo'l 72
2.(13.`DS 14:00 2'16:09 12:10
2i 4'C9 9;05 2i1710.S -9:C4 % CI-mu.*
B$'y'i % 98
BOLPD 93.2 12118 89%
r3WPD :91A 16.f.-; '39%
BOPD 1,9 3.2 68%
.1;Pi Gray 15.8
.
Ma1er API 9,8 10
The Glen Rose study and the Mega West data on " Prodigen X (which is
Formulation "A"), clearly shows the significant improvements in flow and stem
injection in
the wells and in the formation with the use of our material.
FT-IR scans of Formulation "A," "B," and "C" (shown in Figure 4, Figure 5, and
Figure 6, respectively) attached and a scan of AR3600 (Bituminous Substance
Removal
product), shown in Figure 7 is included for comparative use.
With respect to Figure 4:
n- __ Peak intensity Corr. Intensity Base (14) Base (L) Area
COM. Area
...._ .. õ .. .. .... õ . .
... _ ...
1 798.53 93.542 4,157 815 89 792.74 0334 0 169 __
2- 887.26- 80.1.5 17.567 906.4 86025 1.731 1.349
. _
3 914.26 92.977 3.505 925.83 908.47 ____ 0 361 0.104
4 966.34 95.015 0.943 970.19 947.05 0.401 4,054
977.91 95.418 0.896 991.41 972.12 0.312 0.026
6 1016.49 90.397 ,
6,067 1031.92 993.34 0.965 0.401
7 1049_28 91.323 3.374 1056.99 1033.85 0.703 0.189
8 1068.56 90.72 3.063 1087_85 1058.92 1,01 0.175
9 1101.35 88.004 1.709 1105.21 1089.78 0.704 0.069
1116.78 82_868 8.385 1138 1107.14 1.466 0.43
11 1155.36 92.585 4.635 1182.36 1139.93 0.877 0.381
12 1203.58 91.84 3.381 1211.3 118429 0.612 0.154
13 1240.23 62.905 32.37 1305.81 1213.23 5.528 3.896
14 1371,39 84.828 12.137 1386.82 1338.6 1_36 0.853
1438.9 89.541 2.374 1444.68 1417.68 0.848 0.163
16 1450.47 89.944 1,721 1473.62 1446.61 0.776 0.072
17 1643.35 93.922 5.307 1653 1635.64 0.281 0.223
18 1739.79 73.178 25,65 1770.65 1716.65 2.642 2.371
19 2833.43 93.21 2.829 2546.93 2111_5 0.94 0.184
2856.58 94.258 0.546 2862.36 2848.86 0.323 0.018
21 2889.37 91,389 0.947 2897_08 2864.29 1.124 0,11
22 2916.37 90.535 2.582 2951.09 2899.01 1.823 0.357
23 2964.59 93.709 2.731 3030.17 2953.02 1.223 0.383
20b
CA 027 902 67 2014 -03 -04
,
, .
, = .
.
CA2790267
With respect to Figure 5:
Peak . intensity ! Corr. Intensity Base (H) ' Base (1.)-
- -Area ' Corr. Area
1 796.6 932615 4.158 815.89 ' 792.74
0.375 0.195
2 887.26 80.491 16,943 906.64 860.25
1.843 1.396
3 914,26 93.418 3.066 927.76 908.47
0361 0.089
4 966.34 95.684 0.68.8 972.12 943.19 0.435
0.042
1018.41 91.181 3222 1028.06 993.34 0.867 0,186
6 1049.28 84.5 7.522 1060.85 1029.99
1.607 0.534
r 1070.49 89.653 0.608 1074.35 1062,78
0.51 0.023
8 1085.92 89.219 _ 0.273 11389.78 1076.28
6.648 0,01
9 1097.5 88,571 0,892 110521 1091.71 0.688
0.035
1116_78 87.134 5.021 1138 /107.14 1.151 0.236
11 1155.36 93.901 3.643 , 1182.36
1139.93 0714 0.28
12 1203.58 93.682 2.619 1211.3 1184,29
0.478 0.122
13 124023 71814 23.155 1300.02 1213.23
4_6 3.144
14 1373.32 86.606 9295 1386.82 1340.53
1.338 0.656
1438.9 89.737 2.64 1446.61 1417.68 0.959 0.179
16 1643.35 94.052 4.998 1653 1635.64
0.284 0.212
17 1741,72 83.535 16.189 1770_65 1699-29
2,122 2033,
18 2835.36 93.314 2.507 2846.93 2773.64
1,007 0.186
19 2889,37 90.998 1.412 2902,87 2848,86
1,796 0,198
2916.37 90.758 1.755 2949.16 2904_8 1.558 0.237
21 2966.52 92.182 4.049 3030.17 2561,09
1.48 0.51
With respect to Figure 6:
Peak intensity Con. intensity Base fill Base (L) .. Area .. Corr.
Area
1 798.53 94.43.4 4.196 815,89 19274 0244
0,161
2 .387,26 82.394 15.953 938.54 36025 1402
1111
2 9t1.2694.441 3.274 929.69 08470 0.278 0
004
4 956.69 97.807 1.081 968 27 945 12 0-15
0,048
5 1015.49 95.529 2.563 1035.77
999.13 0.486 0.179
1051.2 56201 0.773 105629 1043.49
0,152 0,025
107).49 96225 0.396 1074.35 1053.92 0.1136
0.018
E 1113.78 02.422 .. 3.324 1130.20
/07523 1.244 0.346
5 114755 92.974 0.405 1145.57
113107 0.343 0.006
10 116186 92.349 1.144 1784.29
1163.08 0.647 0.061
11 1197.79 92931 2.065 1217.08
1185.22 0.824 0.143
12 1'24).23 ts/3114 t1.2.4:1 129t.15
IZ1I.C.1! Z_U:39 0.301
13 1325.1 97.006 0,36 1336,67 1313,31
0.157 0,022
14 1357.89 96 634 0 go 11 74 1.133 A n
275 0 Mc
15 137525 93.053 4.42 1336.82 1361.74
0.551 0.27
16 1435.04 88,795 5.324 1446.61 1417.68
0.946 0.298
17 1643.35 951106 4.981 1553 1635.64
0.211 0.21
18 1741.72 83.423 16.932 1770,05 1715,95
1.421 1.002
19 2854.65 89765 3.612 2366.22
2773,42 1.635 0.303
20 2875.86 91.867 0.115 2977_79 2863.15
0.346 0.005
21 2922.16 84.816 7 642 2949.16 2877,79
3.561 1,06
22 2962.66 92.565 1.596 2995.45 255102
0.933 0.082 .
23 1003.95 96.745 1.326 3035.96 2997.38
0.352 0.088
20c
CA 02790267 2014-03-04
CA2790267
Table 1 shows the viscosity of a crude oil sample with the addition of
corresponding % of solution "A"
from the present invention.
TABLE 1
Viscosity % Solution
22,500 0.00
19,500 1.00
17,600 1.50
15,900 2.00
14,700 2.50
12,300 3.00
11,000 3.50
9,500 4.00
8,000 4.50
6,770 5.00
5,100 5.50
4,000 6.00
2,950 6.50
1,800 7.00
950 7.50
951 8.00
952 8.50
270 9.00
Samples of raw MacKay River Bitumen (MKB), and Coid Lake heavy crude oil were
provided
by Enbridge for evaluation and testing. Condensate was also supplied since
this is used as the primary
diluent Synthetic oil was not supplied
The primary objective with the MacKay River Bitumen were to reduce the
viscosity of the MKB
with a limited amound of BioSpan material, eliminating the need to heat the
bitumen to 90 C for
transport to the blending facility where it is blended with a synthetic oil at
a 50:50 ratio, and to further
reduce the amound of diluent to achieve a target of 350 centistokes at a
temperature of 11.9 C.
The second set of objectives were to reduce the Cold Lake blended crude
viscosity
20d
CA 02790267 2012-09-13
below 350 cSt with a small amound of the same BioSpan solution used to reduce
the viscosity
of the MKB, if possible.
There were secondary objectives as follows:
1. Reduce, or eliminate the need for corrosion inhibitors added to the crude
oil flowing
through the pipelines.
2. Be able to recover the BioSpan diluent solution at a minimal 80% level,
with
85-90% recovery preferred.
3. Maintain the NON-TOXIC nature of the BioSpan solution(s).
4. Reduce the toxicity of the final diluent when condensate is incorporated
into the
formulation
5. Availability of raw materials to meet demand.
EXPERIMENTAL LABORATORY METHODS:
All testing was conducted using currently accepted scientific methods. Hot and
cold
water bath were used to maintain constant temperature during testing. A
Brookfield
viscometer was used to measure viscosity and a distillation set u was used to
replicate the initial
recovery of the BioSpan Material at the refinery or other processing facility.
GC/MS was
used to determine if there were any changes in the chemical structure,
comparing the recovered
crude or bitumen versus the undiluted material, and the BioSpan solution(s). A
Hewlett
Packarad 5988A GC/MS was used. Initial substrate compatibility was evaluated
using black
steel pipe following an accepted FDA protocol for corrosion resistance.
Over 60 different formulation modifications were evaluated for MKB viscosity
reduction, staring at a temperature of 90 C, and sequentially reducing the
temperature by
21
CA 02790267 2012-09-13
C on those formulations expressing significant viscosity reduction as the
temperature was
reduced. The concentration level of test solutions started at 10% and was
adjuste dupwar to
reach the end point goals of the project It was our goal to incorporate the
condensate as part of
the diluent, since this material is already been recovered and must be
disposed of
5 Condensate diluent was used at the 70% MKB: 30% condensate level as a
standard.
Final testing and all other analysis were performed once the 11.9 C viscosity
level was
achieved on the MKB samples. Recovery of the BioSpan diluent was done on these
materials,
as were the GC/MS tests.
Similar testing was performed on the Cold Lake material, but at a much lwer
level,
10 since our target was to come up with a diluent reducer, or replacement.
All testing was done on a weight/weight basis.
RESULTS:
1. Three formulations demonstrated that the targeted viscosity of 350 cSt or
less is
achievable at 11.9 C.
2. The amount of BioSpan material to achieve this goal ranges from 11.45%
to 18.0%.
3. Condensate may be combined with BioSpan materials at a ratio of 50:50 or
higher
depending on the desired viscosity/temperature ratio.
4. All formulations tested are completely hydrophobic.
5. All formulations are recoverable at a range of 85% or higher.
FORMULA "A"
Formula "A" is a non-toxic formulation that eliminates the need for
condensate. An
22
CA 02790267 2012-09-13
18% (by weight) use level of Formula "A" completely solubilizes MKB at 19 C
resulting in a
viscosity of 200-225 cSt, and at 11.9 C the viscosity was 250-275 cSt.
Solubilization speed is
much better than other formulations. Slightly increased temperatures of
between 30 and
40 C result in almost immediate dissolution. At 60 C, the dissolution is
immediate, with
little or no agitation needed.
Distillation recovery of this formulation is between 90 and 94% with no
apparent
change in the structure. The formulation is a corrosion protectant, and a
version of the base
formulation is marked for this use on salt trucks and other heavy equipment
exposed to
chlorides and moisture.
Serial reductions of this formulation at a ratio of 1 part "A" to 3 parts
condensate
provides a similar viscosity reduction level with MKB; however, a linear
increase in mixing
temperature is necessary to easily combine the diluent since the initial
solubility of the
condensate/Formulat"A" is not as quick at 11.9 C as a straight Formula "A."
Toxicity
becomes an issue when condensate is combined with Formula "A" due to the
inherent nature of
the condensate.
An equal belend of Formula "A" and condensate at the 9% condentration level of
each
came closest to using a 18% concentration of Formula "A."
FORMULA "B"
Formula "B" is a modification of Formula "A." The use level of this
formulation is
approximately 15%, with a 15% addition of condensate. It rapidly solubilizes
the MKB at
50 C. The viscosity at 11.9 C is 350 cST, and has similar (but not quite as
good as Formula
"A") corrosion protection characteristics. The ratio of Formula "B" to
condensate is roughly
23
CA 02790267 2012-09-13
1:4. The base solution is non-toxic, but will exhibit similar toxicity
characteristics as "A"
when combined with condensate.
One advantage is that it reduces the viscosity of the Cold Lake material to
¨250 cSt with
a 3-4% addition at 11.9 C. It mixes immediately into a uniform liquid and is
recoverable at a
rate of approximately 85-90%. No significant observable changes were seen on
the GC/MS
scans.
FORMULA "C"
Formula "C" has a different formula than "A or B." It is non-toxic, but has a
higher
boiling point that the other two formulations. At a use concentration of
11.45%, the viscosity
measured 350 cSt, at 19 C. When the temperature was lowered to 11.9 C, the
viscosity
jumped to almost 500 cSt. We attempted to reduce the viscosity by altering the
formulation
components without success; however this formulation did combine with the Cold
Lake
samples reducing the viscosity to 300 cSt with a 5% addition to the Cold Lake
product.
Recovery through distillation was as the 80-85% level.
CONCLUSIONS:
1. Of the 67 formulations evaluated under the criteria set forth by Enbridge,
three (3)
formulations were identified as potential candidates that met most, if not all
the
performance needs.
2. Formulat "A" met all the criteria set forth this far. It is non-toxic,
equipment
friendly, environmentally friendly, and does not alter the structural
integrity of the
crude oil while liquefying the MKB, and reducing the viscosity of the Cold
Lake
24
,
CA 02790267 2012-09-13
material. It is recoverable, and may be reusable if desired. It combines
readily
with condensate, and the resulting mixture offers a significant energy savings
by
reducing the need for elevated temperature when liquefying the MKB. Sufficient
raw materials are available to keep us with demand, and provide secondary
benefits
in maintaining the pipelines with reduced corrosion.
3. Formula "B" provided similar results as Formula "A" but used more materials
and
requires a higher mix temperature. It combines readily with the Cold Lake
crude,
and sufficien raw materials are available to meet future needs. It is
recoverable
without significant changes to the integrity of the crude. It mixes with
condensate,
but requires more condensate use than Formula "A" to achieve similar results.
4. Formula "C" offers the lowerst use concentration, but requires higher mix
temperatures and does not provide the same kind of corrosion protection as the
other
formulations. Of the three, this formulation would require additional
extensive
research on MKB in order to achieve the desired performance characteristics.
REFERENCES:
1. Simonsen, J. L. (1947) The Terpenes, Vol. 1, 2nd ed., Cambridge
University Press.
25
