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WO2010148204A2 - Émulsions stabilisées par des particules pour extraction d'hydrocarbures à partir de sables bitumineux et de schiste bitumineux - Google Patents

Émulsions stabilisées par des particules pour extraction d'hydrocarbures à partir de sables bitumineux et de schiste bitumineux Download PDF

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Publication number
WO2010148204A2
WO2010148204A2 PCT/US2010/038998 US2010038998W WO2010148204A2 WO 2010148204 A2 WO2010148204 A2 WO 2010148204A2 US 2010038998 W US2010038998 W US 2010038998W WO 2010148204 A2 WO2010148204 A2 WO 2010148204A2
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WO
WIPO (PCT)
Prior art keywords
component
particles
emulsion
hydrocarbon
carbon dioxide
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PCT/US2010/038998
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English (en)
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WO2010148204A3 (fr
Inventor
David K. Ryan
Dan S. Golomb
Eugene F. Barry
Michael J. Woods
Peter A. Swett
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University Of Massachusetts
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Priority to CA2765788A priority Critical patent/CA2765788A1/fr
Publication of WO2010148204A2 publication Critical patent/WO2010148204A2/fr
Publication of WO2010148204A3 publication Critical patent/WO2010148204A3/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/04—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by extraction
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/04—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by extraction
    • C10G1/047—Hot water or cold water extraction processes

Definitions

  • Oil sands also known as tar sands, and oil shales are large deposits of energy rich bitumen or kerogen found immobilized in sand or rock strata at numerous locations around the world.
  • the most notable oil sand reserves are located in Alberta, Canada, and Venezuela.
  • the largest oil shale deposits are in North America, but the Middle East, Australia and Europe (e.g. Estonia) all have significant deposits.
  • Bitumen and kerogen are high carbon content materials produced as a result of fossilization of primeval fauna and flora. In order to use such hydrocarbons as energy sources and feed stocks for oil refineries, initial extraction from the mineral matter (sand and shale) is necessary.
  • Such a method can comprise providing a subterranean formation comprising a hydrocarbon component, such a component as can be selected from a tar, an oil and/or bitumen and kerogen precursors thereof; contacting the material content of such a subterranean formation with a fluid medium comprising an emulsion comprising a liquid carbon dioxide and/or supercritical carbon dioxide component, an aqueous component and a particulate component selected from hydrophilic components and/or combinations thereof and hydrophobic components and/or combinations thereof, such particulate component(s) in an amount sufficient for at least partial emulsification, such contact for a time and/or at a pressure at least partially sufficient to displace the hydrocarbon component from the formation; and recovering the hydrocarbon component and, optionally, at least a portion of the fluid medium and/or emulsion.
  • a hydrocarbon component such a component as can be selected from a tar, an oil and/or bitumen and kerogen precursors thereof
  • a fluid medium comprising an
  • the fluid medium can comprise an emulsion comprising a dispersed phase comprising an aqueous component, a continuous phase comprising one or more such carbon dioxide components and one or more hydrophobic particulate components, such hydrophobic particles can include but are not limited to those described elsewhere herein or as would be otherwise known to those skilled in the art made aware of this invention.
  • the fluid medium can comprise an emulsion comprising a dispersed phase comprising one or more such carbon dioxide components, a continuous phase comprising an aqueous component and one or more hydrophilic particulate components.
  • hydrophilic particulate components can include but are not limited to those described elsewhere herein or as would otherwise be known skilled in the art skilled made aware of this invention.
  • the subterranean formation can comprise but is not limited to a oil sand and/or oil shale deposit.
  • a hydrocarbon component can be selected from a tar and an oil and bitumen and/or kerogen precursors thererof.
  • the material content of such a formation can be excavated and contact with a fluid medium of the sort discussed above can be ex situ and/or above ground with regard to the subterranean formation. In certain other embodiments, the material content can be contacted in situ and/or under ground with respect to the subterranean formation.
  • such a fluid medium can comprise an emulsion comprising a liquid carbon dioxide and/or supercritical carbon dioxide component, an aqueous component and a particulate component selected from hydrophilic components and/or combination thereof and hydrophobic components and/or combinations thereof.
  • such a fluid medium can comprise an emulsion comprising a dispersed phase comprising an aqueous component, a continuous phase comprising one or more such carbon dioxide components and one or more hydrophobic particulate components.
  • such a fluid medium can comprise an emulsion comprising a dispersed phase comprising one or more such carbon dioxide components, a continuous phase comprising an aqueous component and one or more hydrophilic particulate components.
  • a carbon dioxide component of an emulsion used in conjunction with this invention can be present in an amount greater than about 1 wt. % of the emulsion.
  • particles utilized in conjunction with such an emulsion can be dimensioned from about 5 nanometers or less to about 100 ⁇ m or more. With correlation to a dispersed phase of such an emulsion, particulate dimension can be about 5x to about 50x smaller than a dimensional aspect of any such dispersed phase.
  • such a method can comprise contact of said formation with an organic component at least partially immiscible with an aqueous component of such a fluid medium.
  • an organic compound can be selected from C 2 to about C 20 hydrocarbon compounds, C 2 to about C 4 o ether compounds and combinations of such hydrocarbon and/or ether compounds, such compounds of the sort illustrated below or as would otherwise be understood by those skilled in the art made aware of this invention.
  • such contact can be prior to either such in situ or ex situ contact and can be considered as an optional pre-treatment aspect or component of the present methodologies.
  • the present invention can also be directed to a method of using a particulate-stabilized emulsion for hydrocarbon extraction from oil sand/oil shale.
  • a method can comprise providing a oil sand, oil shale or a related formation comprising a hydrocarbon; contacting the material content of such a formation, whether in situ or ex situ, with a fluid medium comprising an emulsion comprising an aqueous component, a component at least partially immiscible with such an aqueous component and a particulate component selected from hydrophilic components and/or combinations thereof and hydrophobic components and/or combinations thereof, such a particulate component(s) in an amount sufficient for at least partial emulsification, such contact for a time and/or at a pressure at least partially sufficient to displace the hydrocarbon deposit from the formation; and recovering the hydrocarbon component and at least a portion of the emulsion.
  • a hydrocarbon component can be selected from a tar, an oil, a bitumen, a kerogen and/or combinations thereof.
  • a fluid medium can comprise an emulsion comprising a dispersed phase comprising an aqueous component, a continuous phase comprising one or more components at least partially immiscible with such an aqueous component and one or more hydrophobic particulate components.
  • a continuous phase can comprise a liquid carbon dioxide component, a supercritical carbon dioxide component, an organic component at least partially immiscible with an aqueous component and/or combinations thereof.
  • such an organic component can, without limitation, be selected from about C 2 to about C 2 o hydrocarbons, from about C 2 to about C 40 ethers and from combinations thereof.
  • a dispersed phase can comprise water, water-miscible components and combinations thereof.
  • Such hydrophobic particulate components can be selected from those described elsewhere herein or as would otherwise be understood by those skilled in the art made aware of this invention.
  • such a fluid medium can comprise an emulsion comprising a continuous phase comprising an aqueous component, a dispersed phase comprising one or more components at least partially immiscible with such an aqueous component and one or more hydrophilic particulate components.
  • a continuous phase can comprise an aqueous component comprising water, water-miscible components and combinations thereof.
  • water-miscible components can, without limitation, be selected from Ci to about C 6 alcohols, Ci to about C 6 ketones, C 2 to about C 6 glycols, such components as can comprise one or more ionic and/or non-ionic components and/or solutes therein.
  • such a dispersed phase can comprise a liquid carbon dioxide component, a supercritical carbon dioxide component, an organic component at least partially immiscible with such an aqueous component and combinations thereof.
  • hydrophilic particulate components can be selected from those described elsewhere herein or as would otherwise be understood by those skilled in the art made aware of this invention.
  • hydrophobic particulate components can include but are not limited to coal particles, carbon black particles, petrocoke particles, Teflon R particles, latex particles, polymer bead particles, protein particles, modified cellulose particles, chitosan particles, clay particles, and various other hydrophobic particles known to those skilled in the art, whether naturally-available or prepared by grinding, pulverizing, crystallizing, chemical synthesis, chemical coating and/or surface modification, pyrolysis or petroleum refining.
  • hydrophilic particulate components can include, but are not limited to carbonate mineral particles, silicate mineral particles, clay mineral particles, latex particles, polymer bead particles, protein particles, cellulosic particles, modified cellulose particles, chitin particles, chitosan particles, iron particles, iron oxide particles, cadmium selenide particles and various other hydrophilic particles known to those skilled in the art, whether prepared by grinding, pulverizing, crystallizing, chemical coating and/or surface modification or chemical synthesis.
  • such an emulsion can comprise one or more carbon dioxide components.
  • a carbon dioxide component whether part of a continuous phase or dispersed phase, can be present in an amount greater than about 1 wt. % of the emulsion.
  • particulates utilized in conjunction with such an emulsion—whether hydrophobic or hydrophilic— can be dimensioned from about 5 nanometers or less to about 100 ⁇ m or more.
  • nanometer-dimensioned particulates i.e., nanoparticles
  • particulate dimension can be about 5 x to about 50 x smaller than a dimensional aspect of any such dispersed phase.
  • the steps and components thereof can suitably comprise, consist of, or consist essentially of any of the steps or components disclosed herein.
  • Each such method or step and emulsion or component thereof is distinguishable, characteristically or functionally contrasted and can be practiced in conjunction with the present invention separate and apart from another.
  • inventive methods and/or emulsions as illustratively disclosed herein, can be practiced or utilized in the absence of any one component or step which may or may not be disclosed, referenced or inferred herein, the absence of which may or may not be specifically disclosed, referenced or inferred herein.
  • FIG. 1 shows a schematic diagram of a particle stabilized emulsion according to one embodiment of the invention
  • FIG. 2 shows droplets of water in a dodecane continuous phase stabilized by carbon black particles according to another embodiment of the invention
  • FIG. 3 shows a schematic diagram of a high-pressure batch reactor for forming an emulsion according to another embodiment of the invention
  • FIG. 4 shows a static mixer that can be used to form an emulsion according to another embodiment of the invention
  • FIG. 5 shows a static mixer emulsion apparatus according to another embodiment of the invention.
  • FIG. 6 shows a system for recovering hydrocarbon from a subterranean formation according to another embodiment of the invention.
  • FIG. 7 shows one particular system for extracting hydrocarbon(s) from excavated oil sand/oil shale, according to another embodiment of the invention.
  • FIGS. 8A-8B illustrate oil extraction from sand, in accordance with one embodiment of this invention.
  • Particle stabilized emulsions and more specifically, particle stabilized emulsions for extraction of hydrocarbons from oil sand and/or oil shale formations are provided. While certain embodiments are discussed, it will be understood by those skilled in the art made aware of this invention that any such embodiment can independently pertain to the other or another such recovery process with corresponding revision or adaptation to a particular recovery, subterranean formation and/or particular end-use application, and can be applied thereto with comparable effect.
  • One aspect of the invention relates to a process for recovering hydrocarbons from a subterranean formation by contacting or injecting an emulsion of aqueous liquid in liquid or supercritical carbon dioxide (aqueous-in-CO 2 [A/C] emulsion more commonly referred to as water-in-CO 2 emulsion [W/C]) stabilized by fine hydrophobic particles, with or into the formation.
  • aqueous-in-CO 2 [A/C] emulsion more commonly referred to as water-in-CO 2 emulsion [W/C]
  • Another aspect of the invention relates to the process for recovering hydrocarbons from a subterranean formation by contacting or injecting an emulsion of liquid or supercritical carbon dioxide (CO 2 -in- aqueous [C/A] emulsion more commonly referred to as CO 2 -in-water emulsions [CAV]) stabilized by fine hydrophilic particles, with or into the formation.
  • CO 2 -in- aqueous [C/A] emulsion more commonly referred to as CO 2 -in-water emulsions [CAV]
  • an “emulsion” is a stable mixture of at least two immiscible liquids.
  • mixing or dispersing immiscible liquids creates an unstable dispersion, which tends to separate back into two distinct phases.
  • An emulsion is thus stabilized by the addition of an "emulsifying agent" which functions to reduce surface tension between at least two immiscible liquids.
  • an "emulsifying agent” defines a substance that, when combined with a first component defining a first phase, and a second component defining a second phase immiscible with the first phase, will facilitate assembly of a stable dispersion of the first and second phases.
  • Emulsions described herein may be stabilized by particles.
  • the particles may orient themselves around the droplets according to their hydrophilicity or hydrophobicity. For instance, in A/C emulsions, a part of the hydrophobic particles may be wetted by the continuous carbon dioxide phase. Conversely, with C/A emulsions, the hydrophilic particles may be wetted by an aqueous continuous phase. The sheath of particles surrounding the droplets can prevent the coalescence of either carbon dioxide or water droplets into a continuous phase. In C/A emulsions, a larger part of the hydrophilic particles may be wetted by the continuous aqueous phase.
  • the invention comprises many types of aqueous systems including water that is distilled, deionized, artesian, sea, waste, brine, oil- and gas-well associated or formation water.
  • the invention comprises all sorts of carbon dioxide, pure liquid and supercritical carbon dioxide, as well as complex mixtures and complex liquids, such as liquid hydrogen sulfide, organic and inorganic solvents freely miscible with carbon dioxide.
  • the emulsion upon injection into a subterranean formation, the emulsion disperses and disintegrates. If, for example, an A/C emulsion is injected, the liquid or supercritical carbon dioxide released therefrom can interact with the hydrocarbon component of the formation, dissolve at least a portion of it, at least partially reduces its viscosity and leave behind a slurry of fine particles in water. Further, as sand or other similar granules of the formation may be hydrophilic, there may be a preferential interaction with water rather than the hydrophobic hydrocarbon component, thereby allowing release of the tar, oil, bitumen and/or kerogen from the granules. As a result, water can displace the hydrocarbon component from the formation, mobilizing it for extraction and recovery.
  • liquid carbon dioxide is very sparingly soluble in water (e.g., less than about 5 wt. % at low temperatures and relatively high pressures)
  • up to about 50 wt. % or more of a carbon dioxide component can be dispersed in water with an emulsion system of the sort described herein, using hydrophilic particulate components.
  • interaction of such a carbon dioxide (and/or organic) component with an oil sand/oil shale formation can be used to promote hydrocarbon extraction and recovery.
  • a method of recovering or extracting a hydrocarbon from an oil sand and/or oil shale formation comprises introducing an emulsion comprising supercritical CO 2 , an aqueous liquid, and an emulsifying agent comprising particles, into such formation or in contact with sand or shale excavation therefrom, and extracting hydrocarbon.
  • the emulsion comprises supercritical CO 2 and an aqueous liquid.
  • the emulsion may comprise a continuous phase comprising supercritical CO 2 and a dispersed phase comprising an aqueous liquid.
  • such a method comprises contacting an emulsion comprising a continuous phase including greater than about 1% by weight of liquid CO 2 , a dispersed phase comprising an aqueous liquid, and an emulsifying agent comprising particles, with oil sand and/or oil shale, and extracting hydrocarbon deposit(s) therefrom.
  • a related system comprises supercritical CO 2 , an aqueous liquid, and particles in fluid communication with an emulsion forming apparatus for forming an emulsion comprising the CO 2 component, aqueous liquid, and particles.
  • the system also includes an apparatus for introducing the emulsion into a formation or contacting material excavated therefrom and an apparatus for recovering hydrocarbons.
  • the emulsion formed by such a system comprises a continuous phase comprising supercritical CO 2 and a dispersed phase comprising an aqueous liquid.
  • a related system comprises liquid CO 2 , an aqueous liquid, and particles in amounts sufficient to form an emulsion comprising a continuous phase including greater than about 1% by weight of liquid CO 2 , a dispersed phase comprising an aqueous liquid, and an emulsifying agent comprising particles.
  • the liquid CO 2 , aqueous liquid, and particles may be in fluid communication with an emulsion forming apparatus.
  • the system also includes an apparatus for introducing the emulsion into a formation or contacting an excavation thereof and an apparatus for recovering hydrocarbon.
  • the emulsion formed by such a system comprises a continuous phase comprising greater than about 1% by weight of liquid CO 2 and a dispersed phase comprising an aqueous liquid.
  • the emulsion comprises a plurality of droplets of an aqueous liquid suspended in a continuous phase comprising supercritical CO 2 , and an emulsifying agent comprising particles.
  • an emulsion comprises a plurality of droplets of an aqueous liquid suspended in a continuous phase comprising greater than about 1% by weight of liquid CO 2 , and an emulsifying agent comprising particles.
  • a method of this invention comprises extracting a hydrocarbon component from a mixture.
  • the method comprises introducing an emulsion comprising supercritical CO 2 , an aqueous liquid, and an emulsifying agent comprising particles, into a mixture containing a hydrocarbon, and extracting the hydrocarbon from the mixture.
  • the emulsion comprises supercritical CO 2 and an aqueous liquid.
  • the emulsion may comprise a continuous phase comprising supercritical CO 2 and a dispersed phase comprising an aqueous liquid.
  • such a method of extracting a hydrocarbon from a mixture comprises introducing an emulsion comprising a continuous phase including greater than about 1% by weight of liquid CO 2 , a dispersed phase comprising an aqueous liquid, and an emulsifying agent comprising particles, into a mixture of components, and extracting a hydrocarbon component from the mixture.
  • the emulsion comprises a continuous phase comprising greater than about 1% by weight of liquid CO 2 and a dispersed phase comprising an aqueous liquid.
  • a related system for recovering a hydrocarbon component from a mixture comprises supercritical CO 2 , an aqueous liquid, and particles in fluid communication with an emulsion-forming apparatus for forming an emulsion comprising the supercritical CO 2 , aqueous liquid, and particles.
  • the system also includes an apparatus for introducing the emulsion into a mixture of components, and an apparatus for recovering a hydrocarbon component from the mixture.
  • the emulsion of such system comprises supercritical CO 2 and an aqueous liquid.
  • the emulsion may comprise a continuous phase comprising supercritical CO 2 and a dispersed phase comprising an aqueous liquid.
  • a related system for recovering a hydrocarbon component from a mixture comprises liquid CO 2 , an aqueous liquid, and particles in amounts sufficient to form an emulsion comprising a continuous phase including greater than about 1% by weight of liquid CO 2 .
  • the system also includes a dispersed phase comprising an aqueous liquid, and an emulsifying agent comprising particles.
  • the liquid CO 2 , aqueous liquid, and particles are in fluid communication with an emulsion-forming apparatus, an apparatus for introducing the emulsion into a mixture of components, and an apparatus for recovering a hydrocarbon component from the mixture.
  • the emulsion comprises a continuous phase comprising greater than about 1% by weight of liquid CO 2 and a dispersed phase comprising an aqueous liquid.
  • an emulsion 8 includes droplets 10 (also known as "globules") of a dispersed phase 14 (i.e., the isolated phase stabilized by an emulsifying agent).
  • the dispersed phase can comprise an aqueous liquid (e.g., water or aqueous solutions).
  • a continuous phase 18 can comprise supercritical or liquid carbon dioxide (i.e., an AIC- type emulsion).
  • Some emulsions may also include an oil or lipid component forming all, or portions, of a continuous phase (e.g., aqueous-in-oil [A/O] type emulsions). Examples of such emulsions are provided below.
  • the droplets of the emulsion are stabilized by particles 22, which may include, for example, solid particles such as pulverized coal. The particles form a particle sheath at the interface of the two phases, preventing their coalescence into a bulk phase.
  • particle stabilized emulsions can be referred to or are commonly known as "Pickering emulsions”.
  • liquid or supercritical CO 2 may form substantially all of the continuous phase of A/C emulsions
  • the invention is not so limited, and it should be understood that A/C emulsions described herein can have other compositions.
  • A/C emulsions can also include other fluids in the continuous phase in addition to liquid or supercritical CO 2 (e.g., to form a ternary mixture).
  • the continuous phase can include greater than about 1% by weight of liquid or supercritical CO 2 .
  • the continuous phase can include between about 1- about 20%, about 20- about 50%, or about 50-100% by weight of liquid or supercritical CO 2 .
  • droplet means an isolated phase having any shape, for example cylindrical, spherical, ellipsoidal, tubular, irregular shapes, etc. Droplets may have an average cross-sectional dimension of greater than or equal to about 25 nm, greater than or equal to about 50 nm, greater than or equal to about 100 nm, greater than or equal to about 250 nm, greater than or equal to about 500 nm, greater than or equal to about 1 micron, greater than or equal to about 5 ⁇ m, greater than or equal to about 10 ⁇ m, greater than or equal to about 50 ⁇ m, greater than or equal to about 100 ⁇ m, greater than or equal to about 200 ⁇ m, greater than or equal to about 350 ⁇ m, greater than or equal to about 500 ⁇ m, greater than or equal to about 700 ⁇ m, greater than or equal to about 800 ⁇ m, or greater than or equal to about 900 ⁇ m.
  • the droplet size of a particular emulsion may depend, at least in part, on the size and type of the emulsifying particles, inter-particle interactions (e.g., steric interactions), concentration and composition of the continuous and dispersed phases, as well as the rate of shearing/mixing when forming the emulsion, as described in more detail below.
  • emulsions described herein have a CO 2 continuous phase and an aqueous dispersed phase.
  • an emulsion comprises a plurality of droplets of an aqueous liquid (e.g., water and seawater) suspended in continuous phase comprising greater than 1% by weight of liquid CO 2 , and an emulsifying agent comprising particles.
  • the continuous phase can include between 1-20%, 20-50%, or 50-100% by weight of liquid CO 2 .
  • the continuous phase consists essentially of liquid CO 2 .
  • particle stabilized aqueous-in-oil (A/O) emulsions are contemplated.
  • A/O aqueous-in-oil
  • an "oil" can include any liquid that is immiscible with an aqueous liquid such as water; that is, any liquid that, when admixed with an aqueous liquid, can form a two-phase mixture.
  • an emulsion may include a continuous phase comprising an oil (e.g., a hydrocarbon or fluorocarbon) and a dispersed phase comprising an aqueous liquid (e.g., water).
  • Such emulsions may optionally comprise liquid or supercritical carbon dioxide with respect to a continuous phase thereof.
  • An example of a particle stabilized aqueous-in-oil emulsion is shown in FIG. 2.
  • emulsion 40 including droplets 42 of water in a dodecane continuous phase 44.
  • the droplets are stabilized by carbon black particles 48.
  • the droplets have an average size of 10-20 ⁇ m.
  • the aqueous liquid of an emulsion can be any liquid miscible with water; that is, any liquid that, when admixed with water, can form a single-phase solution.
  • the aqueous liquid can comprise one or more additives, such as salts (e.g., salts of alkali and/or alkali earth metals).
  • Non-limiting examples of aqueous phase materials include, for example, water (e.g., purified water, unpurified water, distilled water, deionized water, artesian water, seawater, ground water, well water, waste water, brackish water, brine, oil- and gas-well associated water, formation water, natural sources of water that may or may not contain dissolved salts or contaminants, etc.), methanol, ethanol, DMF (dimethylformamide), or DMSO (dimethyl sulfoxide).
  • water e.g., purified water, unpurified water, distilled water, deionized water, artesian water, seawater, ground water, well water, waste water, brackish water, brine, oil- and gas-well associated water, formation water, natural sources of water that may or may not contain dissolved salts or contaminants, etc.
  • methanol ethanol
  • DMF dimethylformamide
  • DMSO dimethyl sulfoxide
  • the oil portion of an emulsion can be any liquid that is immiscible with an aqueous liquid such as water.
  • the oil may include one or more additives such as a surfactant.
  • Two classes of oils that may be used in emulsions described herein include hydrocarbons and halocarbons (e.g., fluorocarbons).
  • the emulsion can be stable at any suitable temperature depending on the particular application.
  • a hydrocarbon may include a linear, branched, cyclic, saturated, or unsaturated hydrocarbon.
  • the hydrocarbon can optionally include at least one heteroatom (e.g., oxygen in the backbone of the compound to provide a corresponding ether).
  • heteroatom e.g., oxygen in the backbone of the compound to provide a corresponding ether.
  • hydrocarbons include methane, ethane (and, e.g., dimethyl ether), propane, butane, pentane, hexane, heptane, octane, nonane, decane, undodecane, dodecane, and the like and corresponding available ethers.
  • Higher-order hydrocarbons such as Ci 0 -C 2O hydrocarbons can also be used.
  • a continuous or dispersed phase of an emulsion can include mixtures of hydrocarbons of various chain lengths.
  • the hydrocarbon may be, for example, a petroleum hydrocarbon.
  • hydrocarbons recovered from an oil sand/oil shale formation can be used in continuous phases of emulsions described herein.
  • use of such water immiscible solvents such as dimethyl ether, dodecane or similar such organic solvents, can facilitate hydrocarbon extraction from a particular formation.
  • use of such components whether in conjunction with a dispersed or continuous phase, can enable extraction at lower (e.g., atmospheric) pressures, thereby improving extraction efficiencies.
  • such organic components can be used with good effect for in situ extraction.
  • a fluorocarbon may include any fluorinated compound such as a linear, branched, cyclic, saturated, or unsaturated fluorinated hydrocarbon.
  • the fluorocarbon can optionally include at least one heteroatom (e.g., in the backbone of the component).
  • the fluorocarbon compound may be highly fluorinated, i.e., greater than 50% of the hydrogen atoms of the component are replaced by fluorine atoms. In other cases, the fluorocarbon is perfluorinated.
  • Halocarbons including, for example, bromine or chlorine atoms, are also contemplated.
  • emulsions described here include liquid or supercritical carbon dioxide in the continuous phases.
  • Gaseous carbon dioxide can become liquid carbon dioxide when compressed or pressurized (e.g., above 5.1 atm).
  • Supercritical carbon dioxide can form when the carbon dioxide is brought above its critical temperature (31.1° C) and pressure (78.3 atm).
  • Supercritical carbon dioxide behaves like a gas with respect to viscosity, and can expand to fill its container like a gas, but behave like a liquid with respect to density.
  • liquid and supercritical carbon dioxide can diffuse through solids like a gas, and dissolve materials like a liquid, because of their properties such as low viscosity, high diffusion rate, and little or no surface tension.
  • the viscosity of supercritical carbon dioxide is typically in the range of 20 to 100 ⁇ Pa-s, whereas typical liquids have viscosities of approximately 500 to 1000 ⁇ Pa-s. Such properties make supercritical and liquid carbon dioxide useful for extraction processes.
  • the invention comprises all sorts of carbon dioxide, pure liquid and supercritical carbon dioxide, complex mixtures, complex liquids, as well as binary liquids, such as liquid hydrogen sulfide, organic and inorganic solvents freely miscible with carbon dioxide.
  • continuous or dispersed phases described herein may include one or more of the following non-limiting examples of supercritical fluids: water, methane, ethane, propane, ethylene, propylene, methanol, ethanol and acetone. Additionally and/or alternatively, the continuous or dispersed phase can also include liquids such as liquid nitrogen, liquid oxygen, liquid hydrogen, liquid argon, liquid helium, or other cryogenic liquids (i.e., liquefied gases at very low temperatures).
  • Liquids forming continuous and dispersed phases may have a range of viscosities suitable for forming emulsions described herein.
  • the viscosity of the liquid may be in the range of, e.g., between 10-200 ⁇ Pa-s.
  • a continuous and/or dispersed phase consisting essentially of a supercritical or cryogenic liquid may have a viscosity in the above range.
  • a continuous and/or dispersed phase comprising a supercritical or cryogenic liquid may have a viscosity in the range of between 200-1,500 ⁇ Pa-s.
  • a continuous and/or dispersed phase comprising a liquid, but which does not comprise a supercritical or cryogenic liquid therein may have a viscosity in the range of between 200-1,500 ⁇ Pa-s. It should be understood, however, that any suitable viscosity of a continuous and/or dispersed phase can be used to form emulsions described herein and that the invention is not limited in this respect.
  • the dispersed and/or continuous phase of an emulsion may include one or more additives such as organic substances, microbial components (e.g., bacteria), minerals, undissolved particles, various dissolved species, gases, solvents, salts, and the like. Accordingly, in some embodiments, emulsions described herein include ternary or higher mixtures.
  • emulsions described herein are stabilized at least in part by fine particles.
  • Suitable particles include solid particles that are at least partially undissolved in the emulsion.
  • the particles may be, for example, naturally occurring, synthetic, or modified.
  • Particles can be held at the interface between the two phases of the emulsion by, e.g., van der Waals forces, hydrophobic/hydrophilic interactions, hydrogen bonding, ionic interactions, and the like.
  • the surface properties of the particles determines, at least in part, use in conjunction with an aqueous-in-CO 2 emulsion, in the case of a mixture of carbon dioxide (e.g., supercritical or liquid carbon dioxide) and an aqueous liquid.
  • Particles having some hydrophobic character e.g., ground Teflon ® , activated carbon, carbon black, and pulverized coal
  • the hydrophobic character of the particles is naturally occurring or inherent in the material.
  • particles can be treated by a process such as heating or coating, which can change the surface characteristics of the materials.
  • particles can be partially, completely, or uniformly coated with a substance (e.g., a surfactant or polymer).
  • Applicable surface properties of the particles can be measured by those of ordinary skill in the art by techniques such as contact angle measurements between, for example, particle, aqueous and carbon dioxide three-component systems. Numerous representative particulate materials are summarized, below, with respect to type, preparation and source.
  • Particles described herein may have a variety of shapes and sizes.
  • particles may be cylindrical, spherical, rectangular, triangular, ellipsoidal, tubular, rod-like, or irregularly shaped. Suitable sizes of the particles may depend on factors such as the particulate type of emulsion (e.g., a water-in-carbon dioxide emulsion), the components of the continuous and dispersed phases, and the size of the dispersed droplets in the medium.
  • the size of the particles refers to the length of the shortest line (e.g., cross-sectional dimension) connecting two end points of the particle and passing through the geometric center of the particle.
  • the average size of the particles used to form an emulsion is less than 100 ⁇ m, less than 50 ⁇ m, less than 25 ⁇ m, less than 10 ⁇ m, less than 5 ⁇ m, less than 1 ⁇ m, less than 500 nm, less than 250 nm, less than 100 nm, less than 50 nm, less than 10 nm, or less than 5 nm.
  • the average size of the particles used to form an emulsion is chosen, at least in part, by the desired size of the dispersed droplets of the emulsion. For instance, in some embodiments, very small particles may not be suitable for large droplets, as the particles may be dislodged from the surface of large droplets by Brownian motion. In other embodiments, large particles may not be suitable for small droplets, as the particles may not be able to pack onto small droplets. Accordingly, in some cases, the particle size is adjusted to the dispersed droplet diameter. In certain embodiments, the average size of the particles may be 5-50 times smaller than the average size of the dispersed droplets of the emulsion.
  • the average size of the particles may be at least 5, 15, 25, or 50 times smaller than the average size of the dispersed droplets of the emulsion.
  • the ratio of particle size to droplet size may be, for example, between 1 : 10 and 1 :30 (e.g., between 1 : 10 and 1 :20 or between 1 :20 and 1 :30). Of course, other ratios of particle size to droplet size may also be used.
  • Particles may include elemental metals (e.g., gold, silver, copper), semi- metals and non-metals (e.g., antimony, bismuth, graphite, sulfur), and/or ceramics.
  • particles can include, but not limited to, oxides, sulfides, sulfates, carbonates, silicates.
  • Particles can also include, but not limited to, polymer particles (e.g., plastics) such as polycarbonates, polyethers, polyethylenes, polypropylenes, polyvinyl chloride, polystyrene, polyamides, polyacrylates, polymethacrylates, polytetrafluoroethylene (Teflon R ) and the like.
  • polymer particles e.g., plastics
  • plastics such as polycarbonates, polyethers, polyethylenes, polypropylenes, polyvinyl chloride, polystyrene, polyamides, polyacrylates, polymethacrylates, polytetrafluoroethylene (Teflon R ) and the like.
  • particles from the following group of materials can be used: carbon black, petrocoke, Teflon ® , shale, surface-coated clays, silica and pulverized coal. It should be understood that the invention is not limited to the above mentioned particles, but any particle or group of particles that facilitates the generation of an A/C and/or C/ A emulsion as desired can be used in accordance with the invention.
  • an emulsion can be stabilized by both particles and a surfactant, which act as emulsifying agents to stabilize at least two immiscible phases.
  • a surfactant which act as emulsifying agents to stabilize at least two immiscible phases.
  • a variety of surfactants is known in the art and may include, for example, anionic, cationic, zwitterionic, and non-ionic species.
  • emulsifying agent by, for example, choosing the components used to form the continuous and dispersed phases of the emulsion and knowing the surface properties (e.g., wettability) and/or likelihood of reactivity between the emulsifying agent and the two phases, and/or by a simple screening test.
  • a suitable emulsifying agent e.g., particles
  • One simple screening test may include mixing one set of components in a vial to form the emulsion and determining the stability of the emulsion. Either the material composition, quantities, and/or concentration of one component can then be varied while keeping the others constant, and the stability of this emulsion can then be measured. Other simple tests can be conducted by those of ordinary skill in the art.
  • Emulsions described herein are, according to some embodiments, stable for at least about 1 minute. Emulsions that are stable over time are useful because they allow for the time necessary to transport, place, and/or use the emulsion before coalescence or disintegration. For example, emulsions may be stable for more than 1 minute, 1 hour, 1 day, 1 week, 1 month, or 1 year.
  • a "stable emulsion" means that droplets of the emulsion do not coalesce, e.g., to form larger droplets, at a particular temperature and pressure resulting in two bulk phases with a meniscus between them.
  • an emulsion that can be used for hydrocarbon extraction from oil sand/oil shale is stable from the time of formation to the time of injection into or contact with the sand/shale.
  • Emulsions described herein can have any suitable ratio of continuous and dispersed phases.
  • the volume of the continuous phase is greater than that of the dispersed phase.
  • the ratio of the volumes of the continuous phase to dispersed phase may be greater than or equal to 1 : 1 up to 20: 1 (e.g., between 1 : 1 and 5: 1, between 5:1 and 10: 1, or between 10: 1 and 20: 1). It should be understood, however, that any suitable ratio of volumes of continuous phase to dispersed phase can be used to form emulsions described herein and that the invention is not limited in this respect.
  • the amount of particles necessary for forming an emulsion may depend on one or more of the following parameters: particle size, droplet size, type of emulsion formed, shape of the particles (which, in turn, may effect inter-particle or steric interactions), concentration and composition of the continuous and dispersed phases, and physical parameters associated with forming the emulsion (e.g., shear force, temperature, and pressure). Accordingly, various amounts of particles relative to the amount of dispersed and/or continuous phase may be used to form emulsions described herein.
  • the mass ratio of particle to carbon dioxide may be, for example, greater than or equal to 0.005: 1 up to 1.0: 1 (e.g., between 0.005: 1 and 0.2: 1, between 0.2:1 and 0.6: 1, or between 0.6: 1 and 1.0: 1).
  • the amount of particles added to two immiscible phases of an emulsion can be greater than that which is necessary to form the emulsion, and a portion of the particles can accumulate, for example, at the bottom of a reactor.
  • the particles are of uniform size and may, in fact, include a distribution of sizes (e.g., some may be too small to adhere to the interface of the continuous and dispersed phases, and some may be too big), higher mass ratios of particles to dispersed phase material may be used.
  • the amount of particles necessary for emulsion formation can be estimated from a particle sheath model (e.g., a monolayer or multilayer sheath model).
  • a particle sheath model e.g., a monolayer or multilayer sheath model.
  • An example is given for liquid CO 2 droplets in an aqueous continuous phase and particles comprising CaCO 3 .
  • a sheath thickness of 2 ⁇ m corresponding to a monolayer of Hubercarb CaCO 3 Q6 particles with mean size 2 ⁇ m
  • a liquid CO 2 density at 15° C and 17 MPa of 0.93 g/cm 3 a CaCO 3 bulk density of 2.7
  • the mass ratio of CaCO 3 /CO 2 is estimated at 0.2: 1.
  • ratios of CaCO 3 /CO 2 may be used. For example, 0.4: 1, that is, for every 1 kg of CO 2 , 0.4 kg of pulverized limestone may be used as well as ratios down to 0.002:1.
  • Emulsions described herein may be formed using any suitable emulsification procedure known to those of ordinary skill in the art.
  • the emulsions can be formed using methods/systems such as micro fluidic systems (e.g., a micro fluidizer), ultrasound, high pressure homogenization, using a static mixer, shaking, stirring, spray processes, and membrane techniques.
  • emulsions described herein are formed by shear forces.
  • suitable materials, techniques, conditions e.g., temperature and pressure
  • emulsions described herein are formed using a high-pressure batch reactor, as shown in FIG. 3.
  • high-pressure batch reactor 50 can be used to form an emulsion comprising water and liquid or supercritical carbon dioxide as the continuous or dispersed phases.
  • the reactor includes source of water 54 in fluid communication with vertical batch reactor 58.
  • Electrical pump 60 can transport water from the source to the reactor via pipe 62, and this process which can be controlled at least in part by check valve 64 and/or release valve 66.
  • source of carbon dioxide 70 is also in fluid communication with the reactor via pipe 72. Introduction of carbon dioxide into the reactor can be controlled by manual piston screw pump 74, shut off valves 76 and 78, and relief valve 80.
  • the pressures in the pipes can be measured by gauges 82 and 86.
  • magnetic mixer assembly 88 can mix the components and form an emulsion.
  • the temperature inside the reactor can be measured by thermal couple and panel meter 90.
  • Particles can be introduced into the reactor via an opening (not shown) in the form of a slurry or particles alone.
  • System 100 or a similar system, can be used to form a variety of emulsions including, but not limited to, CO 2 -in-aqueous, aqueous-in-CO 2 , aqueous-in-oil, and oil-in-aqueous emulsions.
  • a microfluidizer is used to form an emulsion.
  • the size and stability of the droplets produced by this method may vary depending on, for example, capillary tip diameter, fluid velocity, viscosity ratio of the continuous and dispersed phases, and interfacial tension of the two phases.
  • a static mixer is used to form an emulsion.
  • An example of a static mixer is illustrated in FIG. 4.
  • static mixer 92 is tubular and includes alternating helical mixing blades 96 with no moving parts.
  • the static mixer is a Kenics-type static mixer.
  • the components of an emulsion e.g., liquid or supercritical CO 2 , particles, and an aqueous liquid
  • a static mixer can be incorporated into a static mixer emulsion apparatus, e.g., as shown in FIG. 5.
  • the size and stability of the droplets produced by a static mixer may vary depending on, for example, the pressure differential between the up- and down-stream portions of the static mixer, the length of the mixer, the number of baffles per unit length of the mixer, and other variables (e.g., temperature).
  • emulsions described herein are used for extracting a component from a mixture of at least two components.
  • the component to be extracted may be in the form of a solid (e.g., particles), a liquid (e.g., oil), or a gas (e.g., methane).
  • the component may include impurities and/or can include more than one phase (e.g., solid contaminants in a liquid).
  • the at least two components of the mixture may be of the same phase (e.g., both solid, both liquid, or both gaseous) or may include different phases (e.g., a solid and a liquid, a solid and a gas, or a liquid and a gas).
  • FIG. 6 schematically illustrates a system and one or more associated methods that can be used to recover a hydrocarbon from a subterranean formation in situ, that is, underground without removing the overground burden.
  • system and related method(s) 100 include particles 102, supercritical or liquid CO 2 104 and aqueous liquid (e.g., water), which can be in fluid communication with emulsion forming apparatus 112 for forming, for example, aqueous-in-CO 2 , or aqueous-in-oil emulsions.
  • injection apparatus 118 e.g., an injection well or pump
  • Well 123 may be drilled from top layer 124 to bottom layer 125 of a subterranean formation, and the intermediate layer may include oil sand and/or oil shale deposits 126 containing mixtures of bitumen and/or kerogen components.
  • the intermediate layer may include oil sand and/or oil shale deposits 126 containing mixtures of bitumen and/or kerogen components.
  • the carbon dioxide (or other oil) component can dilute the hydrocarbon component, reduce its density and/or increase its mobility, thereby mobilizing the hydrocarbon component in the direction of arrows 128.
  • the remaining slurry of fine particles in water pushes out the diluted hydrocarbon.
  • water has a greater affinity for hydrophilic sand particles, than for oil.
  • the aqueous component of the emulsion is exchanged with the hydrocarbon component on the sand or shale of the formation.
  • the hydrocarbon extracted from formation/deposits 126, along with portions of the continuous and/or dispersed phases of the emulsion, can flow in the directions of arrows 132 to receiver 142 (e.g., a producing well).
  • the resulting extracted mixture may include carbon dioxide, a hydrocarbon and water (e.g., in the case of a water-in-CO 2 emulsion being injected), separation of the components may be necessary or desired.
  • a first separation process can include the use of separator 146, which may separate carbon dioxide from the hydrocarbon and water.
  • the carbon dioxide which may now be in the form of a gas, can be recovered in container 154. If desired, this carbon dioxide can be recycled by transporting it to compressor/condenser 158, which can compress and/or condense the carbon dioxide to form supercritical or liquid CO 2 . This compressed carbon dioxide can act as, or be added to, source of carbon dioxide 104.
  • separator 164 can separate water from the hydrocarbon component.
  • Water separated from the mixture can be transported to container 168, and can act as, or be added to, source of water 108 used in forming the emulsion. Additionally and/or alternatively, at least a portion of the water can be transported to a water disposal well.
  • the hydrocarbon separated from separator 164 can be transported to storage facility 174 for future use or consumption.
  • at least a portion of the oil can act as, or be added to, source of oil 109 used to form the emulsion.
  • Carbon dioxide 104 may be obtained commercially from sources such as natural CO 2 deposits, gas wells, CO 2 separated from natural gas wells, from separating CO 2 in the flue gas of fossil fuel combustion, from cement manufacturing, from fermentation, from combustion of carbonaceous fuels, and as a by-product of chemical processing where CO 2 is a major by-product.
  • sources such as natural CO 2 deposits, gas wells, CO 2 separated from natural gas wells, from separating CO 2 in the flue gas of fossil fuel combustion, from cement manufacturing, from fermentation, from combustion of carbonaceous fuels, and as a by-product of chemical processing where CO 2 is a major by-product.
  • CO 2 may be obtained as a by-product from steam-hydrocarbon reformers used in the production of ammonia, gasoline, and other chemicals.
  • CO 2 may be obtained from a new generation of coal based power plants.
  • the new plants may use the principle of integrated coal gasification combined cycle (IGCC) with CO 2 capture.
  • coal is gasified to produce a synthetic gas comprising a mixture of carbon monoxide (CO) and hydrogen (H 2 ).
  • the CO is further reformed with steam to produce more H 2 and CO 2 .
  • the CO 2 is separated from H 2 by one of several known technologies, such as physical absorption, chemical absorption, or membrane separation.
  • the H 2 is used for power generation in a combined cycle.
  • the separated gaseous CO 2 is liquefied under pressure and may be sequestered in subterranean formations, called geologic sequestration. However, a part of the separated CO 2 may become available to form the particle stabilized emulsions to be used for oil sand and/or oil shale extraction as described in this invention.
  • carbon dioxide 104 may be recycled or recovered from the extraction process.
  • Carbon dioxide may be treated by processes such as, for example, amine (MEA) treatment, adsorption processes, extractive distillation techniques, and membrane systems.
  • Crude CO 2 e.g., containing at least 90% CO 2
  • the carbon dioxide can then be placed in an insulated storage vessel.
  • CO 2 is imported to the oil sand/oil shale extraction site, it is most economical to transport the liquid carbon dioxide by pipeline.
  • the carbon dioxide can be transported, for example, in high-pressure un-insulated steel cylinders, as a high-pressure liquid in insulated truck trailers or rail tank cars, or as dry ice in insulated boxes, trucks, or boxcars.
  • aqueous liquids can be used in emulsions described herein.
  • water from a well on site of the subterranean formation can be used.
  • well water, sea water, or other sources of water can be imported.
  • waste water from an oil refinement process may be used in forming emulsions described herein.
  • the water may be purified (e.g., filtered) to remove waste materials, contaminants, and the like, prior to formation of the emulsion.
  • particles 102, carbon dioxide 104, and aqueous liquid 108 are shown as separate sources.
  • one or more materials can be premixed prior to forming an emulsion.
  • the particles are mixed with water to form a slurry prior to formation of an emulsion with carbon dioxide.
  • the particles are mixed with carbon dioxide to form a slurry prior to formation of an emulsion with another liquid.
  • Other pre-mixtures of components can also be used. Regardless, such a methodology can be used for in situ extraction of hydrocarbons from a subterranean formation, e.g., oil sand or oil shale.
  • a stabilized emulsion can be injected directly into the formation.
  • injection depth should be greater than about 200 meters.
  • vaporization of a liquid carbon dioxide component would disintegrate the emulsion.
  • A/O emulsions using an alternative organic continuous phase e.g., dimethyl ether, dodecane, etc.
  • an alternative organic continuous phase e.g., dimethyl ether, dodecane, etc.
  • an organic component at least partially immiscible with an aqueous component can be injected into the oil sand or oil shale formation prior to the injection of the particle stabilized emulsion of an aqueous fluid in carbon dioxide (AJC) or carbon dioxide in aqueous fluid (C/ A).
  • the organic component can, without limitation, be selected from about C 2 to about C 20 hydrocarbons (e.g., straight-chain, branched and/or cyclic aliphatic and aromatic compounds - - whether substituted or unsubstituted, saturated or unsaturated), from about C 2 to about C 4 o ethers and from combinations thereof.
  • the prior injection of the said hydrocarbons or ethers can reside in the formation from about 1 hour, 1 week, 1 month to about 1 year before injection of the particle stabilized emulsion.
  • This embodiment may lead to greater petroleum extraction efficiency compared to the co-injection of such an organic component together with or as a component of the AJC or C/A emulsion.
  • This embodiment can be designated "soak&puff.”
  • FIG. 7 One particular system for recovering hydrocarbons ex situ from excavated oil sand and/or oil shale is shown in FIG. 7.
  • an AJC or C/A emulsion can be contacted with excavated sand/shale.
  • a crusher 1 comminutes the oil sand or oil shale into beach sand size granules.
  • the granules are fed via a hermetic feeder 2 into the contact tower 3.
  • the contact tower must be kept under a sufficiently high pressure in order for the emulsion not to phase separate, and the liquid or supercritical CO 2 flash into a gas.
  • the particle stabilized AJC or C/A emulsion is prepared in the particle-water mixer 4.
  • the emulsion is injected into the contact tower via an emulsion forming apparatus 5, where it flows counter-current to the oil sand or oil shale granules.
  • the residual tailings are discharged via a hermetic discharger 6 into a hopper 7, from whence they are transported away by truck or rail.
  • the upward flowing emulsion extracts and dissolves the oil from the sand or shale granules and exits the top of the contact tower into a flash separator 9. where liquid or supercritical CO 2 is flashed into gaseous CO 2 , which is liquefied in compressor 10 for eventual re-use.
  • the extracted oil is stored in tank 11 for transport to the refinery.
  • a liquid CO 2 tank 12 stores the necessary make- up liquid CO 2 .
  • the emulsifying particles are stored in hopper 13.
  • the necessary water for forming the emulsion comes from municipal water, surface water (river, lake, ocean) or associated water from oil and natural gas production.
  • an organic component at least partially immiscible with an aqueous component can be contacted with the excavated oil sand or oil shale in a contact tower, as illustrated in FIG. 7, prior to contact in the tower of the particle stabilized emulsion of an aqueous fluid in carbon dioxide (AJC) or carbon dioxide in aqueous fluid (C/ A).
  • AJC carbon dioxide
  • C/ A carbon dioxide
  • the organic component can, without limitation, be selected from about C 2 to about C 20 hydrocarbons (e.g., straight-chain, branched and/or cyclic, aliphatic and aromatic compounds - - whether substituted or unsubstituted, saturated or unsaturated), from about C 2 to about C 4 o ethers and from combinations thereof.
  • the prior contact of the said hydrocarbons or ethers can reside in the tower from about 1 minute, 1 hour, to about 1 week before contact in the tower of the particle stabilized emulsion.
  • This embodiment may lead to greater petroleum extraction efficiency compared to the co-injection of such an organic component together with or as a component of the AJC or C/A emulsion.
  • This embodiment can be designated "soak&extract.”
  • Figure 7 is but one of the possible ex situ extraction processes, and is not limited to this invention.
  • a batch reactor can be used for the extraction procedure. It is understood by those skilled in the art of ex situ oil extraction that either a continuous process, such as illustrated in FIGURE 7, or a batch reactor, or a combination thereof, using the extraction process based on AJC or C/A emulsions is part and parcel of this invention.
  • water-immiscible solvents such as dimethyl ether, dodecane or other such solvents of the sort described herein
  • conventional, atmospheric pressure vessels can be used with good effect for hydrocarbon extraction from oil sand or oil shale.
  • Particle stabilized aqueous liquid- in-CO 2 (A/C) macroemulsions were formed in a high pressure batch reactor (HPBR) with view windows using an apparatus similar to the one shown in FIG. 3.
  • the reactor included a stainless steel pressure cell of 85 mL internal volume equipped with tempered glass windows (PresSure Products G03XC01B).
  • the windows were placed 180° apart, with one illuminated with a 20 W, 12 V compact halogen bulb and the other allowing observation with a video camera.
  • the view window diameter was 25 mm.
  • the window diameter was used as a scale for determining droplet diameter sizes.
  • the reactor was equipped with a pressure-relief valve (Swagelok R3 " A), a thermocouple (Omega KMQSS- 125G-6), a pressure gauge (Swagelok PGI-63B), a bleed valve (Swagelok SS-BVM2), and a 3.2 mm port for admitting CO 2 .
  • a cylindrical magnetic stir bar with a cross shape on top (VWR Spinplus) was utilized for internal mixing. Unless otherwise indicated, the stir bar rotated at 1300 rpm. Reactor temperature was adjusted by application of hot air from a heat gun or solid dry ice chips.
  • A/C macroemulsions For preparation of A/C macroemulsions, the following procedure was carried out: dry hydrophobic particles were added to the HPBR, followed by injection of liquid CO 2 . After agitation, a high-pressure syringe pump was used to inject water to a set pressure of 17.2 MPa. For the A/C emulsions, a proportion of -65 mL of CO 2 /20 mL OfH 2 O was used.
  • the particle size was determined from SEM images. In each frame, nearly all particles were counted and measured. For spherical particles, their diameter was measured; for crystalline or irregular particles, the average of two dimensions was taken, one along the long axis and the other along the short axis. The mean diameter was estimated as
  • (dp)mean [ ⁇ n, (dp) X d p ]/N t (1)
  • n, (d v ) is the number of particles counted that have a size d v
  • N 1 is the total number of particles counted.
  • the mean size, (d v ) msaa , and standard deviation of the particles used in this study are tabulated in Table 1.
  • the HPBR window diameter 25 mm was used as a scale. The diameter of droplets near the window was measured under magnification and compared with the window diameter.
  • a C/A macroemulsion stabilized by Hubercarb Q6 particles with mean particle size of 2 (1.7) ⁇ m was formed. After thorough mixing and a rest period, most globules settled in the bottom of the pressure cell, indicating that the globules were heavier than the surrounding water. The globule diameter was in the range of 200-300 ⁇ m.
  • Macroemulsions were also formed with supercritical CO 2 and Q6 particles.
  • the pressure in the cell was 17.2 MPa at a temperature of 45-47° C.
  • a stable macroemulsion formed with a globule diameter in the 100-150 micron range, smaller than that with liquid CO 2 under the same pressure and mixing conditions. Most globules settled in the bottom of the cell. Even though the density of supercritical CO 2 (-800 kg m "3 ) is smaller than that of liquid CO 2 (-930 kg m "3 at 17.2 MPa and 15° C), the gross density of the supercritical globules was greater than that of the surrounding water.
  • Macroemulsions were also formed with Fisher Chemical C-65 reagent-grade CaCO 3 (mean particle size 3.1 (1.6) ⁇ m). Under mild mixing conditions (400-500 rpm), rather large globules were formed, in the 500-800 micron diameter range. The sheath of crystalline particles adhering to the surface of CO 2 droplets was clearly visible.
  • the milled and sieved sand particles had a mean particle size of 4.3 (5.7) ⁇ m. The large standard deviation indicates a wide distribution of particle size.
  • the sand particles produced a stable C/A macroemulsion, probably due to the hydrophilic silica content of sand.
  • the globule diameter was in the 200-300 micron range.
  • fly ash The unprocessed flyash particles had a mean particle size of 2.5 (3.1) ⁇ m. The large standard deviation indicates a wide distribution of sizes, but most particles were in the submicron to a few micron size range. The size of the particles, plus their hydrophilic character (similar to sand), was conducive for the formation of a stable C/A macroemulsion. The globule diameter was in the 80-150 micron range.
  • the pulverized shale had a mean particle size of 4.2 (6.0) ⁇ m with a wide distribution of sizes. Pulverized shale produced a stable C/A macroemulsion, probably due to the hydrophilic character of shale's major ingredients, clay minerals and quartz. The globule diameter was in the 80-150 micron range. Because of the small bulk density of shale (2.0-2.2 g/cm 3 ), most pulverized shale- sheathed globules floated on top of the water column.
  • Magnesium Silicate The pulverized lizardite had a mean particle size of 4.8 (3.9) ⁇ m. The appropriate particle size and the hydrophilic character of magnesium silicate produced a stable C/A macroemulsion. The globule diameter was in the 80-130 micron range.
  • Teflon ® Teflon ® powder is strongly hydrophobic.
  • One gram of the powdered resin produced an aqueous liquid-in-carbon dioxide (AJC) macroemulsion, where water is the dispersed phase and CO 2 is the continuous phase. Water droplets sheathed with Teflon ® particles were evident, and no phase separation occurred during several hours of observation, which indicates that a stable AJC macroemulsion was formed.
  • AJC liquid-in-carbon dioxide
  • Activated Carbon When activated carbon (AC) was dispersed in liquid CO 2 under pressure, the AC agglomerated into clumps. Under the conditions employed, upon addition of water and stirring, a black mass ensued in which it was difficult to discern distinct globules.
  • AC activated carbon
  • Carbon Black did disperse in liquid CO 2 without agglomeration. Upon addition of water with stirring, a black, inscrutable liquid ensued. However, no phase separation occurred after several hours of observation, suggesting that a stable AJC emulsion was formed.
  • Example 3d [00113] Coal. Pulverized coal also dispersed readily in liquid CO 2 without agglomeration. Upon addition of water with stirring, a A/C macroemulsion was formed where water droplets were sheathed with coal particles dispersed in CO 2 .
  • embodiment 200 includes a mixture of oil and sand.
  • a water-in-oil emulsion comprising a dodecane continuous phase (having an average droplet size of 50-100 ⁇ m) and a water dispersed phase stabilized by Teflon ® particles (average size of 1.8 ⁇ m) was injected into tube 206 in the direction of arrow 208.
  • Tube 206 extended to the bottom of column 207.
  • oil was extracted from the mixture of sand and oil. This extraction process resulted in a relatively clean sand 212 (i.e., substantially free of oil), and extracted oil phase 214 as a mixture of oil and dodecane.
  • This example shows that particle stabilized dodecane and water emulsions are more effective in extracting oil from sand and oil mixtures than non- emulsions comprising dodecane and water.
  • Emulsions of Water- in-CO 2 (W/C) or Water- in-Oil (W/O) stabilized by fine particles can disperse as much as 50% by volume water in liquid or supercritical CO 2 or other solvents, whereas less than a few percent by volume water can be dissolved in liquid or supercriticalCO 2 or other solvents.
  • Laboratory experiments showed that crude oil is readily displaced from the pores of oil sand or oil shale when using particle stabilized W/C or W/O emulsions.
  • Particle stabilized emulsions of Water-in-CO 2 provide greater extraction efficiencies than water alone, CO 2 alone, or Water- Alternate-Gas (WAG) methods.

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Abstract

L'invention porte sur des émulsions stabilisées par des particules, de la sorte qui peut utiliser du dioxyde de carbone liquide et/ou du dioxyde de carbone supercritique en tant que phase continue ou phase dispersée, pour l'extraction d'hydrocarbures.
PCT/US2010/038998 2009-06-17 2010-06-17 Émulsions stabilisées par des particules pour extraction d'hydrocarbures à partir de sables bitumineux et de schiste bitumineux WO2010148204A2 (fr)

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US9169446B2 (en) 2013-12-30 2015-10-27 Saudi Arabian Oil Company Demulsification of emulsified petroleum using carbon dioxide and resin supplement without precipitation of asphaltenes
EP2978919A4 (fr) * 2013-03-27 2016-11-23 Halliburton Energy Services Inc Procédés d'atténuation de l'adhérence de matière bitumineuse en utilisant de nanoparticules
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CN112431576B (zh) * 2020-10-15 2023-01-06 中国石油天然气股份有限公司 一种评价二氧化碳驱沥青质沉淀对采收率影响的方法
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CN113699809A (zh) * 2021-08-30 2021-11-26 苏州赫伯特电子科技有限公司 用低成本Pickering型乳化剂制备W/C反相胶束的方法及染色方法
CN113861329A (zh) * 2021-08-30 2021-12-31 苏州赫伯特电子科技有限公司 一种低成本W/C反相胶束及其反相Pickering乳液聚合的制备方法
CN113861329B (zh) * 2021-08-30 2022-12-02 苏州赫伯特电子科技有限公司 一种低成本W/C反相胶束及其反相Pickering乳液聚合的制备方法
CN113699809B (zh) * 2021-08-30 2023-12-01 苏州赫伯特电子科技有限公司 用低成本Pickering型乳化剂制备W/C反相胶束的方法及染色方法

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