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WO2005115603A2 - Dispersants pour nappes de pétrole et processus de dispersion - Google Patents

Dispersants pour nappes de pétrole et processus de dispersion Download PDF

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Publication number
WO2005115603A2
WO2005115603A2 PCT/US2005/016043 US2005016043W WO2005115603A2 WO 2005115603 A2 WO2005115603 A2 WO 2005115603A2 US 2005016043 W US2005016043 W US 2005016043W WO 2005115603 A2 WO2005115603 A2 WO 2005115603A2
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WO
WIPO (PCT)
Prior art keywords
dispersant
matrix component
oil
component includes
matrix
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2005/016043
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English (en)
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WO2005115603A3 (fr
Inventor
Timothy J. Nedwed
Patrick Brant
Gerard P. Canevari
James R. Clark
Herman W. Schlameus
Niraj Vasisht
Herbert G. Wheeler, Jr.
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ExxonMobil Upstream Research Co
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ExxonMobil Upstream Research Co
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Publication of WO2005115603A2 publication Critical patent/WO2005115603A2/fr
Publication of WO2005115603A3 publication Critical patent/WO2005115603A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/32—Materials not provided for elsewhere for absorbing liquids to remove pollution, e.g. oil, gasoline, fat
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
    • C02F1/682—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water by addition of chemical compounds for dispersing an oily layer on water
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/017—Mixtures of compounds

Definitions

  • Embodiments of the present inventions relate to dispersion of oil spills. At least one embodiment involves dispersing oil located on the surface of a body of water by a method that includes providing solid particles that include a matrix component and an effective amount of a dispersant component; and contacting the solid particles with the oil on the body of water in an amount sufficient to disperse at least a portion of the oil.
  • Each invention claimed herein relates to oil dispersion.
  • a method of dispersing oil located on the surface of a body of water comprising (including) providing solid particles that include a matrix component and an effective amount of a dispersant component; and contacting the solid particles with the oil on the body of water in an amount sufficient to disperse at least a portion of the oil.
  • One or more other specific embodiments include a method of treating an oil spill, comprising providing solid particles, wherein each particle includes a matrix component and an effective amount of a dispersant component; and placing the solid particles on a vehicle, the solid particles on the vehicle being in an amount sufficient to disperse oil forming part of an oil spill located on the surface of a body of water when the solid particles are placed in contact with the oil.
  • a method of dispersing oil located on the surface of a body of water includes placing on an airplane an oil spill treatment agent that includes a plurality of solid particles that each include a matrix component and an effective amount of a dispersant component, wherein the plurality of solid particles has an average particle size of 500 microns or more; flying the airplane over oil located on the surface of a body of water; and dropping the oil spill treatment agent onto the upper surface of the oil spill from the airplane when the airplane is flying at an altitude of 200 feet or more (higher), 500 feet or more, or 750 feet or more, or 1,000 feet or more over the oil spill, wherein the dispersant component is released from the solid particles, resulting in dispersion of some or all of the oil spill.
  • the airplane can be flown at lower altitudes, e.g., 100 feet or more.
  • the method can be flown at higher altitudes, e.g., 1,500 feet or more, or 2,000 feet or more, or 2,500 feet or more, or 3,000 feet or more.
  • one or more specific embodiments are directed to a dispersant for treating oil spills, comprising a solid particle that includes a dispersant component and a solid matrix component.
  • One or more of the dispersants described above or elsewhere herein includes a solid particle that includes a dispersant component and one or more gas bubbles.
  • One or more of the dispersants described above or elsewhere herein includes a solid particle that includes a dispersant component and one or more microballoons.
  • One or more of the dispersants described above or elsewhere herein includes a solid particle that includes a dispersant component and a matrix component selected from the group consisting of: a tackifier; a rosin or rosin containing compound; a resin or resin containing compound; a rosin-substituted ester; a resin-substituted ester; pentaerythritol ester; a rosin substituted pentaerythritol ester; a resin substituted pentaerythritol ester; a fully dimerized rosin; a fully dimerized resin; a rosin maleated with glycerol ester; an ester; a fatty acid; a fatty acid derivative; a fatty acid amide; stearic acid or palmitic acid, or a mixture thereof; an oleamide; and a polymer.
  • a tackifier a rosin or rosin containing compound
  • oil means hydrocarbon-based oil, including but not limited to crude oil, such as Arab Medium Crude, Alaska North Slope, or Chayvo Crude and refined crude oil products including but not limited to Intermediate Fuel Oils.
  • crude oil such as Arab Medium Crude, Alaska North Slope, or Chayvo Crude and refined crude oil products including but not limited to Intermediate Fuel Oils.
  • oil does not include animal or vegetable oil. Different crude oils typically have different characteristics, viscosities, solubilities and compositions, so that their dispersing properties are often different.
  • oil spill means any volume of "oil” that occupies at least a portion of the surface of some "body of water.”
  • the oil spills discussed herein can be oil spills that are located far offshore, at a substantial distance from land, or from an airport, or from an airport that includes a supply of any oil spill treatment agent, preferably one of the oil spill treatment agents described herein.
  • Such "substantial distance” can be over 100 miles; or over 200 miles; or over 500 miles; or over 1,000 miles; or over 1,500 miles; or over 2,000 miles; or over 2,500 miles; or over 3,000 miles.
  • the substantial distance can be a distance that requires an airplane, which can be a jet airplane, to deliver the oil spill treatment agent, e.g., the solid particles described herein, to an oil spill.
  • body of water means a large body of water, such as an ocean, sea, gulf, bay, or inlet, and includes anybody of water that is connected to an ocean, sea, gulf, bay, or inlet.
  • the term also includes smaller bodies of water, e.g., lakes or rivers, but refers only to bodies of water having a relatively large uninterrupted upper surface area, e.g., at least 1,000 square meters, or even at least 2 square miles.
  • the term does not, for example, include small volumes of water, e.g., water in cups, beakers, or other small containers.
  • body of water refers to a volume of water that, when an oil spill occurs on such body of water, an airplane is a possible vehicle used to deliver the treatment agent, which in embodiments described herein is a collection of solid particles.
  • providing should be given its broadest recognized meaning, and includes, but is not limited to, supplying, making, delivering, combining and forming.
  • solid is defined to encompass any material considered “solid” by an ordinary layperson, including granular material, and also including particulate material that is porous.
  • the term is to be defined to include any material (e.g., matrix component) or physical object (e.g., particle) that is considered to be neither gas nor liquid nor an emulsion at room temperature (herein considered to be 25 °C).
  • solid particle that includes a matrix component and a chemical dispersant
  • the term “solid” may for certain embodiments refer to the matrix component itself, which in certain embodiments herein is a continuous solid phase occupying the outer surface of the particle as well as the inside of the particle, and in other embodiments may refer to the entire particle itself, even though that entire particle may include a chemical dispersant, which in some cases may be liquid at room temperature.
  • certain materials that are described herein as “solid particles” are porous, and/or include interstices or openings, and/or include microballoons (described in greater detail below) and/or include one or more minor phases or portions that are not themselves solid at room temperature, but rather may be liquid or gaseous (vapor).
  • At least some or all of the pores, or interstices or microballoons may be occupied by a chemical dispersant, e.g., the dispersant component, which may be a liquid.
  • the dispersant component which may be a liquid.
  • solid particles formed from a mixture of Pentalyn K (used to form the matrix component) and a liquid dispersant component result in a somewhat heterogenous material, in that a "husk" (or outer shell) rich in Pentalyn K is formed, and an inner core rich in the dispersant component is also formed.
  • the inner core shrinks to a smaller diameter than the inner surface of the husk, resulting in a void space between the husk and core.
  • the entire husk/core composite material is regarded herein as "solid,” regardless of whether there is gas or even liquid present.
  • the solid particles are more homogenous, and were not observed as having void spaces.
  • solid particle refers to any object that is “solid” and that would be considered a "particle” by an ordinary layperson.
  • the term “solid particle” also includes any item that would also be referred to as a particulate, grain, dust, powder, pill, pellet, microbead, or granular material.
  • a plurality of any of the solid particles described below preferably are useful as an oil spill treatment or dispersion agent that can be delivered via airplane or marine vessel to an oil spill.
  • microbeads refers to solid particles having an average diameter less than 500 microns, e.g., 300 microns or less; 200 microns or less; or 100 microns or less.
  • matrix component means the portion of the solid particle that is not the “dispersant component.”
  • matrix material refers herein to a substance before it is formed into a part of the solid particle, after which the matrix material is considered to become the “matrix component.
  • the matrix component provides structural or mechanical support to the solid particle.
  • the matrix component can include fillers or inert materials that do not necessarily themselves provide any or substantial structural or mechanical support, or that may provide some function other than dispersion.
  • the "matrix component” is any portion of the solid particle that is not liquid or gaseous at room temperature.
  • a "matrix component" in at least one or more of the specific embodiments described herein is porous and/or includes interstices and/or includes microballoons.
  • dispenser means any material regarded as a dispersant by persons skilled in the art of oil spill dispersion, and includes any material (solid or liquid) that is capable of causing oil, including particularly a crude oil or a refined oil, to begin dispersing upon making contact with that oil, or shortly after making such contact.
  • the term “dispersant” herein refers to a solid material that includes an effective amount of a dispersant component.
  • any material that is a herding agent when applied to oil on a body of water is not a "dispersant.”
  • the term “dispersant” includes, but is not limited to, any material that is classified as a “dispersant” under the NCP Product Schedule published by the United States Environmental Protection Agency. It is contemplated that many chemicals exist that are or might be useful in treating oil spills that are not “dispersants.” For example, under the NCP Product Schedule certain materials may qualify as “surface washing agents,” “surface collecting agents” (also referred to as “herding agents”), “bioremediation agents,” or “miscellaneous oil spill control agent,” but not as “dispersants,” to the extent they do not cause oil dispersion.
  • any of such materials would be considered a “dispersant” herein.
  • the term “dispersant” also encompasses any material (e.g., a solid particle) that includes both an effective amount of a dispersant component and an effective amount of a matrix component, e.g., where the two components are mixed, blended, or in some manner combined with each other.
  • a solid particle that includes both an effective amount of a dispersant component and an effective amount of a matrix component, e.g., where the two components are mixed, blended, or in some manner combined with each other.
  • a solid particle that includes an effective amount of a "dispersant component” might itself be referred to as a “dispersant” herein even though some portion of the solid particle (e.g., the matrix component) has no dispersion properties.
  • a preferred dispersant is one that is capable of breaking up the oil on the water's surface, causing the oil to form droplets and to disperse down into the water column where natural forces can degrade the oil droplets.
  • dispenser component includes any material that qualifies as a “dispersant” (as defined above) and is part of a “solid particle,” but that does not qualify as a “matrix component” (as defined above) except as expressly stated otherwise.
  • an effective amount as used herein with reference to solid particles means any amount of solid particles sufficient to result in dispersion of oil on a body of water when that amount of solid particles is applied in any manner to the oil. Preferred amounts of solid particles are described in greater detail below.
  • an effective amount as used herein with reference to a dispersant component that occupies at least part of a solid particle means any amount sufficient to result in dispersion of oil on a body of water when an effective amount of solid particles containing such a dispersant component is applied in any manner to the oil. Preferred amounts of dispersant component are described in greater detail below.
  • particle size is a term that encompasses any recognized measurement of the size of a single solid particle, e.g., the maximum diameter of an individual solid particle when that term is used in reference to a single solid particle.
  • particle size and average particle size refer to an average particle size for a plurality of solid particles. Unless otherwise indicated, the term particle size or average particle size refers to microns.
  • mesh particle size or “particle size” (when using “mesh” as a unit) as used herein is based on the recognized “mesh” technique for quantifying sizes for collections of particles.
  • a preferred average particle size for a collection (e.g., a load) of solid dispersant particles is greater than 500 microns; or 600 microns or more; or 700 microns or more; or 800 microns or more; or 900 microns or more; or 1.0 millimeters or more; or 1.5 millimeters or more; or 2.0 millimeters or more; or 2.5 millimeters or more; or 3.0 millimeters or more; or 3.5 millimeters or more.
  • oleophilic means having an affinity (physical or chemical attraction) to oil that is greater than affinity to water.
  • the matrix component of the solid oil spill treatment particle described herein is oleophilic.
  • the solid particles herein are themselves preferably oleophilic, at least when they make initial contact with the oil.
  • a preferred oleophilic solid treatment particle is one that adheres to the oil when it initially contacts that oil.
  • a preferred oleophilic solid particle is one that adheres to the oil even when it is first placed in water next to an oil spill. That is, when placed in the water close to an oil spill, it "sticks" to the surface of the oil spill when the waves or currents cause it to brush up against the oil spill.
  • a solid particle (or a matrix component) that is “oleophilic” may also be “lipophilic,” as that term is used in the literature, e.g., U.S. Patent No. 5,348,803, the portions of which that disclose lipophilic materials being hereby incorporated by reference.
  • fatty acid means any carboxylic acid derived from or contained in an animal or vegetable fat or oil, alone or in combination with others, and that term is herein considered to have the definition for that term in the Condensed Chemical Dictionary 507-08 (Hawley, 11th Ed). Specific examples of fatty acids are stearic acid and palmitic acid, alone or in combination.
  • density refers to the mass per unit volume of a material, and is expressed herein in terms of grams per cubic centimeter (g cc) or grams per milliliter (g/ml), although other ways of quantifying density are also contemplated.
  • microballoon includes any spherical or particulate material that is solid and is capable of existing within and/or forming part of a solid "dispersant particle” as defined below. That is, the microballoons preferably form part of the matrix component. Each microballoon (sphere or particle) is preferably smaller than each solid dispersant particle. Quantitatively speaking, the average diameter of the microballoons that are incorporated into a collection of solid dispersant particles is preferably less than 20%, or less than 10%, or less than 5%, or less than 2%, or even less than 1% of the average diameter of the solid dispersant particles of which they form a part.
  • a single solid dispersant particle is randomly selected from a collection of solid dispersant particles and examined, that solid dispersant particle should include at least 5 microballoons, or at least 10 microballoons, or at least 15 or 20 microballoons.
  • a preferred type of microballoon is a "glass bubble," more preferably a ScotchliteTM brand glass bubble manufactured and sold by 3M (Minnesota Mining and Manufacturing Company).
  • each microballoon described above and elsewhere herein has a density (or a collection of such microballoons have an average density) of at least 0.05 g cc, or 0.10 g/cc, or 0.15 g/cc, and no more than 0.40 g/cc, or 0.45 g/cc, or 0.50 g/cc.
  • the average particle size of the microballoons that are incorporated into a collection (plurality) of solid dispersant particles is 50 microns or less; or 75 microns or less; or 100 microns or less; or 125 microns or less.
  • the "matrix component” includes one or more microballoons plus another material, e.g., a polymer, which is preferably a material that is oleophilic.
  • a polymer which is preferably a material that is oleophilic.
  • the microballoons lower the density to the desired level.
  • solubility means the general ability, capacity, or tendency of one material to dissolve or blend uniformly with another material, preferably to form a homogenous system, although formation of certain types of emulsions may also be acceptable in certain cases.
  • a preferred type of "solubility" of a material refers to an ability, capacity, or tendency to form a single phase system with another material, e.g., water or oil.
  • a material e.g., a solid particle, a dispersant component, or a matrix component
  • water solubility e.g., a solid particle, a dispersant component, or a matrix component
  • such material may have a low degree of water solubility (either salt water solubility or fresh water solubility), in that it does not dissolve easily in the water, particularly at low water temperatures that might range from freezing or sub-freezing temperatures (e.g., 0 °C) up to 5 °C, or 10 °C, or 15 °C, or 20 °C, or 25 °C.
  • a material may be considered to have a particular degree of "oil solubility" at a given temperature.
  • a material may have a high degree of oil solubility, in that it dissolves readily in oil (or at least a particular type of oil) at a particular temperature (e.g., any of the ranges indicated above).
  • certain preferred materials e.g., certain solid particles
  • have higher oil solubility than water solubility meaning that at a given temperature they have a greater tendency to become part of the oil phase rather than the water phase.
  • a solid particle used in treating oil spills preferably includes a dispersant component and a matrix component.
  • the dispersant component may include any chemical dispersant that is capable of dispersing oil, when applied alone or in combination with some liquid carrier.
  • the dispersant component is preferably more soluble in the oil to which it is being applied than in the water surrounding and supporting the oil.
  • any known and/or appropriate chemical dispersant can be used for the dispersant component.
  • Examples of chemical dispersants useful as a dispersant component are any of the components identified in U.S. Patent No. 3,793,218, or U.S. Patent No. 5,618,468, alone or in combination. The portions of those patents referring to the dispersants, including particularly the chemical formulas of the dispersants, are hereby incorporated by reference, as examples of the "dispersant component" discussed herein.
  • the dispersant component may also be a combination, e.g., a blend or mixture, of different chemical dispersants. Some of these chemical dispersants are sold under known trademarks, have established proportions, and may be formulated in a carrier solvent. At least one example of a dispersant component is any of the dispersant chemicals in Corexit® 9500 or Corexit®9527, sold by Ondeo Nalco Chemical Company.
  • At least one formulation of those products is composed of 9.7 wt% Span® 80 (sorbitan monooleate); 19.4 wt% Tween®80 (polyoxyethylene sorbitan monooleate); 28.6 wt% Tween ®85 (polyoxyethylene sorbitan trioleate), and 42.3 wt% Aerosol OT (aqueous sodium dioctyl sulfosuccinate).
  • an exemplary useful dispersant component may include: (a) sorbitan monooleate (from 5-15 wt%), (b) polyoxyethylene sorbitan monooletae (from 15 to 25 wt%),
  • a dispersant component may include: (a) sorbitan monooleate (10 wt%), (b) polyoxyethylene sorbitan monooletae (20 wt%), (c) polyoxyethylene sorbitan trioletae (30 wt%) and
  • the matrix component is a non-liquid component of the solid particles that are the "dispersants” discussed herein, and the matrix component is preferably solid (as "solid” is defined above) at temperatures ranging from 30°C (or higher) and below, and in certain embodiments the matrix component is liquid at elevated temperatures, e.g. 50°C and above, or 80°C and above, or 100°C and above, or 120°C and above.
  • the liquid matrix material can be mixed with the dispersant component at those elevated temperatures, then cooled to form a solid particle formed of a solid matrix component and a dispersant component that may in certain cases remain as a liquid.
  • the dispersant particle includes both a matrix component as well as a dispersant component. At least when it is part of the dispersant particle (e.g., after formation of the particle), the matrix component may have a portion of its internal volume occupied by a gas (vapor), e.g., air or nitrogen, even though certain materials might not have that characteristic until after being manipulated to form the particle. Also, as noted above, the matrix component may include one or more microballoons that are not oil soluble or water soluble, as well as a material that is soluble in oil, e.g. Pentalyn K.
  • a gas vapor
  • the matrix component may include one or more microballoons that are not oil soluble or water soluble, as well as a material that is soluble in oil, e.g. Pentalyn K.
  • the matrix component (which may include microballoons) preferably has an overall density that is lower than the density of water, e.g., the water forming the body of water to which the dispersant is to be applied, at least when it is part of the dispersant particle. For that reason, the inclusion of microballoons is particularly advantageous, in at least certain embodiments, particularly if the remaining portions of the matrix component do not have a density lower than the density of water.
  • the density of that water will be greater than 1.0 g/ml (e.g., 1.02 g/ml).
  • the overall density of the matrix component should be such that the density of the entire dispersant particle (including the dispersant component) is less than 1.02 g/ml, or in certain embodiments even less than 1.00 g/ml, so that the dispersant particles do not sink, but rather float on the surface of the body of water.
  • the matrix component (or a particle that includes the matrix component) has a density that ranges from a low of 0.85 g/ml, or 0.90 g/ml, or 0.93 g/ml, or 0.95 g/ml, to a high of 0.95 g/ml, to 0.98 g/ml, to 0.99 g/ml, to 1.00 g/ml, to 1.01 g/ml.
  • the matrix component or the solid particle or both has a density that falls below 1.02 (g/ml), so that it is at least capable of floating on salt water.
  • the matrix component is oleophilic as a whole, even though it may include (for at least certain embodiments) microballoons that are not themselves oleophilic, e.g., glass microballoons.
  • at least a portion of the matrix component e.g., the part that is not the microballoons
  • the oil solubility of at least that portion of the matrix component is preferably higher than its water solubility.
  • that portion of the matrix component is soluble in oil but has limited solubility in water.
  • a determination of the relative oil and water solubilities can be made at selected temperatures, e.g., 35 °F or 70 °F, even though actual use conditions may be different from those temperatures.
  • the matrix component includes a compound that has a standard glass transition temperature above 30°C and a modified glass transition temperature below 25 °C when in contact with oil.
  • a standard glass transition temperature refers to a materials glass transition temperature in a vacuum, in an inert gas, or in air.
  • a modified glass transition temperature refers to a materials glass transition temperature when in contact with an oil. If the matrix component has a lower modified glass transition temperature, it can be determined by observing the time that it takes for a quantity of the matrix compound to dissolve in a quantity of the desired oil or through observation under a microscope.
  • a preferred matrix compound will dissolve very rapidly in the oil when its glass transition temperature is reduced below the temperature of the test compared to the dissolution rate of the matrix compound in a pure component hydrocarbon such as decane.
  • the oil used in evaluating the modified glass transition temperature is crude oil.
  • the oil used in evaluating the modified glass transition temperature is Arab Medium Crude, Alaska North Slope Crude, or Chayvo Crude.
  • the matrix component may have a standard glass transition temperature above 35°C, 40°C or 45°C.
  • the matrix component may have a modified glass transition temperature below 35°C, 30°C, 20°C or 15°C.
  • rosin materials defined broadly herein to mean rosins, derivatives of rosins, rosin-containing compounds, e.g., compounds substituted with rosin groups.
  • rosin in the Hawley's Condensed Chemical Dictionary (11 th ed) is adopted herein, and incorporated by reference.
  • Other examples of materials useful as matrix components are esters, particularly pentaerythritol esters of rosin, e.g., materials sold under the trademark PENTALYN®, sold by Eastman Chemical Company. More specific examples of PENTALYN® materials are those sold as PENTALYN®X, PENTALYN®C, or PENTALYN®K.
  • a rosin containing material is a fully dimerized rosin, e.g., DYMEREX®, also available from Eastman Chemical.
  • another matrix component material is a rosin maleated with glycerol ester, e.g., PENTREX® from Eastman Chemical.
  • matrix components are "resin materials” defined broadly herein to mean resins, derivatives of resins, resin-containing compounds, e.g., compounds substituted with resin groups.
  • resin materials defined broadly herein to mean resins, derivatives of resins, resin-containing compounds, e.g., compounds substituted with resin groups.
  • the definition of "resin” in the Hawley's Condensed Chemical Dictionary (13 th ed) is adopted herein, and incorporated by reference.
  • tackifier materials are "tackifier materials.”
  • the definition of tackifier in the Hawley's Condensed Chemical Dictionary (11 th ed) is adopted herein, and incorporated by reference.
  • matrix components are (or include) polymers, e.g., CERAMER® 5005 polymer or PETROLITE® E-2000 polymer, or PETROLITE® E-2020 polymer, each of which is available commercially from Baker Petrolite.
  • polymer matrix components are POLYWAX® 3000, an ethane copolymer available from Baker Hughes; and ESCOREZ® 1102 and ESCOREZ® 310, both available from ExxonMobil.
  • matrix components are (or include) fatty acids or derivatives thereof.
  • a matrix component may be either stearic acid or palmitic acid, alone or in combination.
  • Another matrix component is a fatty acid amide such as estearamide (e.g., ATMER SA 1750) or an oleamide (e.g., ATMER SA 1759), both available from Unichema.
  • Still other examples of matrix components are non-polymer organic materials, such as dimers or trimers of polyolefins.
  • a matrix component may also be an aliphatic hydrocarbon resin, e.g., NENTAC® 100.
  • the dispersant particle (also referred to herein as the solid particle) includes both a matrix component and a dispersant component.
  • the relative amounts of each component can be varied. At least one version of the dispersant particle contains 50 wt% matrix component and 50 wt% dispersant component. Another version contains 50 vol% matrix component and 50 vol% dispersant component. In yet another version, the dispersant particle contains more dispersant component than matrix component.
  • the weight percentage or volume percentage of dispersant component can range from a low of 10, or 15, or 20, or 25 or 30, or 35, or 40, or 45, or 50, or 55, or 60, or 65, or 70, or 75, or 80, or 85, or even 90 percent (weight or volume) to a high of 90, or 85, or 80, or 75, or 70, or 65, or 60, or 55, or 50, or 45, or 40, or 35 percent (weight or volume) with the remainder being the matrix component.
  • the weight percentages can fall between or within any of the aforementioned low points and high points.
  • the dispersant component ranges from a low of 10 wt% to a high of 90 wt%.
  • the dispersant component in liquid form
  • the solid shell is (or becomes) the "matrix component” (after the particle is formed).
  • the material that will form all or part the matrix component herein referred to as "matrix material”
  • matrix material the material that will form all or part the matrix component
  • microballoons are then added to that melted matrix material.
  • the desired amount of dispersant preferably liquid dispersant is introduced to the melted matrix material.
  • That matrix/dispersant mixture is then placed onto the center of a spinning disk, and the spinning action causes the mixture to spread out as a thin sheet on the disk as it moves closer to the edge of the disk.
  • the mixture then flies off the disk in the form of multiple stringers that then break into small droplets. As the droplets fall through the air, they cool and harden before falling onto a surface below the disk, where they are recovered, e.g., collected or gathered in the form of "solid dispersant particles.”
  • This collection surface may be pre-coated with a flow aid such as starch; pre-coated with no flow aid; or pre-coated with microballoons used as a flow aid.
  • At least one encapsulation method that may be followed to form the solid dispersant particles herein is described in U.S. Patent No. 4,675,140, which is incorporated by reference at least to the extent methods of encapsulation and other methods of forming particles are described.
  • Another particle formation method includes formation of a solid particle, using a polymer that preferably has a low melting point and acts as a carrier. In that method, the polymer is melted, and then mixed with the dispersant component (in liquid form). The mixture is then solidified and processed to form solid particles and/or cooled and crushed to form particles in the form of a powder.
  • An alternative method of manufacture and delivery of the solid dispersant includes a method of preparing the solid dispersant particles on an airplane.
  • the alternative method consists of loading the raw materials for the solid dispersant, i.e., the matrix compound, the dispersant, and the microballoons on an airplane (or other delivery vehicle), melting and mixing the compounds on the airplane, and then forming the solid particles by dispensing the melt through nozzles on the exterior of the airplane.
  • the method could have the matrix compound, dispersant, and microballoons premixed and solidified in a large volume and loaded onto an airplane (or other delivery vehicle), melted, and dispensed through nozzles on the exterior of the airplane.
  • This method may have the following characteristics: (1) long-term storage of tiny particles is not needed and (2) the payload may be increased because it would not lose the volume associated with the porosity of solid particles. Dispersion Effectiveness
  • the effectiveness of a dispersant in relation to its ability to remove oil spills from the water surface can be measured qualitatively, or in different more quantitative ways.
  • a qualitative technique for measuring dispersion effectiveness is the Paddle Mixer Dispersant Efficiency Test, described below in the examples.
  • a quantitative dispersion effectiveness test is the EXDET Dispersant Effectiveness Test (Becker, K. W., Walsh, M. A., Fiocco, R. J., Curran, M. T., "A New Laboratory Method for Evaluating Oil Spill Dispersants" International Oil Spill Conference pp.
  • a preferred method includes loading a quantity of solid particles (which are described elsewhere herein) onto an airplane, in order to fly the airplane over the oil spill and deliver the particles onto the surface of the oil spill.
  • the solid particles can be loaded onto any type of vehicle, such as a small boat or a larger ship.
  • the delivery method includes dropping or otherwise dispensing the particles onto the oil spill, from above the oil spill, most preferably from an airplane.
  • the particles are delivered using pneumatic eductors located on the exterior of an airplane and connected to a central reservoir located on the interior, wherein the central reservoir holds the particles.
  • the delivery system evenly distributes the dispersant over a portion or all of an oil spill as the plane flies over.
  • the particles are dropped all at once, e.g., by opening a bay door of the airplane.
  • the particles are dropped in batches or "slugs" over the oil spill.
  • each of the solid particles has a size and weight such that it can be accurately dropped from a high altitude and still hit the desired location on the oil spill, even in inclement weather, e.g., rain, high winds, or storms.
  • the particle size of the load of particles is described elsewhere herein.
  • propeller driven planes are currently used for areal delivery of dispersants
  • at least one version of the delivery method includes use of a jet airplane, which is capable of flying at higher speeds than propeller driven planes, and thus is capable of providing a quicker delivery of dispersant particles than provided by propeller driven planes (measured timewise from airplane take-off).
  • the solid dispersant particles described herein can be accurately dropped onto an oil spill from a higher altitude than can liquid dispersants, since the wind does not diffuse or alter the downward trajectory of the solid dispersants to the extent it does the liquid dispersants, primarily due to the fact that larger particle sizes are possible when using solid dispersants.
  • Particles may also be delivered to a marine oil spill using marine vessels (e.g., boats or ships).
  • a number of advantages are contemplated in an oil dispersant delivery method that utilizes a jet airplane.
  • the jet airplanes are faster than propeller driven planes.
  • jet airplanes can typically hold larger payloads (more dispersant particles) than propeller planes.
  • At least one reason propeller driven planes are currently used to deliver dispersants to oil spills is because the dispersants are liquid, and there is a need for liquid dispersants to be delivered at relatively low altitudes, e.g., 500 feet or less above the water surface. At least one reason for such low altitudes is the need (or desire) to ensure the liquid dispersants find their target after being discharged from the airplane.
  • the liquid dispersants should be delivered as very small droplets, e.g., 500 microns or less in diameter. Such small diameters are beneficial, even necessary, because larger droplets tend to penetrate the oil film and interact with the seawater by either passing into the water column or "herding" the oil. Herding refers to a situation where surfactant molecules spread in a monolayer over the surface of the water and move the oil slick across the surface rather than dispersing the oil into the water column as desired, e.g., by forming droplets.
  • a lighter-than- water solid dispersant is bound within the matrix which will prevent, or at least inhibit, "herding" by keeping the dispersant encapsulated until it contacts oil. That is, the solid dispersant particles can be manufactured with a sufficiently large average particle size so that they can experience high falling velocities in the air following discharge from an airplane. The solid particles penetrate the oil slick (due in part to the velocity and force upon striking the oil surface), but their buoyancy causes them to float back to the surface where they can interact with the oil film.
  • the solid matrix component is oleophilic, and has higher oil solubility than water solubility, the solid matrix component tends to dissolve in the oil and release the liquid dispersant in the oil. Accordingly, by providing larger particles than the droplets of liquid dispersants, solid dispersants are more amenable to delivery from jet airplanes which are capable of flying at higher speeds and altitudes than propeller planes.
  • An example of a delivery method includes placing on an airplane an oil spill treatment agent that includes a plurality of solid particles, each of which includes a matrix component and a dispersant component, as described elsewhere herein.
  • the plurality of solid particles has an average particle size of 500 microns or more, although the particle may alternatively have one of the particle size ranges identified above, e.g., 1.0 millimeter or more.
  • the method preferably includes flying the airplane over oil located on the surface of a body of water (e.g., an oil spill); and dropping the oil spill treatment agent onto the upper surface of the oil spill from the airplane.
  • the airplane is flying at an altitude that allows for safe yet effective delivery of the dispersant particle to the oil spill, e.g., 500, or 700, or 1,000 feet or more over the oil spill.
  • the dispersant component is released from the solid particles, resulting in dispersion of some or all of the oil spill.
  • Each invention claimed herein relates to oil dispersion.
  • a method of dispersing oil located on the surface of a body of water comprising (including) providing solid particles that include a matrix component and a dispersant component (preferably in an effective amount); and contacting the solid particles with the oil on the body of water, preferably in an amount sufficient to disperse at least a portion of the oil.
  • One or more other specific embodiments include a method of treating an oil spill, comprising providing solid particles, wherein each particle includes a matrix component and a dispersant component (preferably in an effective amount); and placing the solid particles on a vehicle, the solid particles on the vehicle preferably being in an amount sufficient to disperse oil forming part of an oil spill located on the surface of a body of water when the solid particles are placed in contact with the oil.
  • a method of dispersing oil located on the surface of a body of water includes placing on an airplane an oil spill treatment agent that includes a plurality of solid particles that each include a matrix component and a dispersant component (preferably in an effective amount), wherein the plurality of solid particles has an average particle size of 500 microns or more; flying the airplane over oil located on the surface of a body of water; and dropping the oil spill treatment agent onto the upper surface of the oil spill from the airplane when the airplane is flying at an altitude of 200 feet or more over the oil spill, wherein the dispersant component is released from the solid particles, resulting in dispersion of some or all of the oil spill.
  • the dispersant component includes a mixture of different chemical dispersants.
  • the dispersant component includes (a) sorbitan monooleate, (b) polyoxyethylene sorbitan monooletae, (c) polyoxyethylene sorbitan trioletae and (d) aqueous sodium dioctyl sulfosuccinate.
  • the dispersant component includes (a) sorbitan monooleate (from 5-15 wt%), (b) polyoxyethylene sorbitan monooletae (from 15 to 25 wt%), (c) polyoxyethylene sorbitan trioletae (from 20 to 40 wt%) and (d) aqueous sodium dioctyl sulfosuccinate
  • the dispersant component occupies 40 % or more by volume of the solid particle. In other methods, the dispersant component occupies 50 % or more by volume of the solid particle. In other methods, the dispersant component occupies 70 % or more by volume of the solid particle. In still other methods, the dispersant component occupies 90% or more by volume of the solid particle.
  • the matrix component is solid.
  • the matrix component is a porous solid.
  • the matrix component is solid and includes interstices.
  • the matrix component includes microballoons.
  • the matrix component (as a whole) is oleophilic, even though in certain embodiments the microballoons or other portions of the matrix component are not oleophilic.
  • the oil solubility of the matrix component at 35 °F (a relatively low temperature) is higher than the water solubility of the matrix component at that temperature.
  • the oil solubility of the matrix component at 70 °F (a higher temperature) is higher than the water solubility of the matrix component at that temperature.
  • the oil solubility of the matrix component at both 35 °F and at 70 °F remains higher than the water solubility of the matrix component at each of those temperatures, and at temperatures between 35 °F and at 70 °F.
  • the matrix component includes a rosin material.
  • the matrix component includes a resin material.
  • the matrix component includes a tackifier material.
  • the matrix component includes a rosin substituted ester.
  • the matrix component includes a resin substituted ester.
  • the matrix component includes a pentaerythritol ester.
  • the matrix component includes a rosin-substituted pentaerythritol ester.
  • the matrix component includes a resin-substituted pentaerythritol ester. [0075] In one or more of the methods described above or elsewhere herein, the matrix component includes a fully dimerized rosin.
  • the matrix component includes a fully dimerized resin.
  • the matrix component includes a rosin maleated with glycerol ester.
  • the matrix component includes an ester.
  • the matrix component includes a fatty acid.
  • the matrix component includes a fatty acid derivative.
  • the matrix component includes a fatty acid amide.
  • the matrix component includes stearic acid or palmitic acid, or a mixture thereof.
  • the matrix component includes an oleamide.
  • the matrix component includes a polymer.
  • the matrix component includes a compound that has a standard glass transition temperature above 30°C and a modified glass transition temperature below 25°C when in contact with oil. [0086] In one or more of the methods described above or elsewhere herein, the matrix component has a density less than 1.00 g/ml.
  • the matrix component has a density less than 1.02 g ml.
  • the matrix component has a density of from 0.80 to 1.02 g/ml.
  • At least one specific embodiment is directed to a dispersant for treating oil spills, comprising a solid particle that includes a dispersant component and a solid matrix component.
  • One or more of the dispersants described above or elsewhere herein includes a solid particle that includes a dispersant component and one or more microballoons.
  • One or more of the dispersants described above or elsewhere herein includes a solid particle that includes a dispersant component and a matrix component selected from the group consisting of: a tackifier, a resin or resin containing compound; a rosin or rosin containing compound; a rosin-substituted ester; a resin substituted ester; a pentaerythritol ester; a rosin substituted pentaerythritol ester; a resin substituted pentaerythritol ester; a fully dimerized rosin; a rosin maleated with glycerol ester; an ester; a fatty acid; a fatty acid derivative; a fatty acid amide; stearic acid or palmitic acid, or a mixture thereof; an oleamide; and a polymer.
  • a tackifier a resin or resin containing compound
  • a rosin or rosin containing compound a
  • the matrix component may be any one of the above-described groups or any combination of the above-described groups. In alternative embodiments, the matrix component may be any one or combination of compounds which fall within the above-described groups. [0093] In one or more of the dispersants described above or elsewhere herein, the matrix component includes one or more gas bubbles.
  • the matrix component includes one or more microballoons.
  • the matrix component is oleophilic.
  • the matrix component includes an oleophilic portion and one or more gas bubbles.
  • the matrix component includes an oleophilic portion and one or more microballoons.
  • the oil solubility of at least a portion of the matrix component at a temperature of 35 °F or 70 °F, or both is higher than the water solubility of that portion of the matrix component at the same temperature.
  • the dispersant component includes a mixture of different chemical dispersants.
  • the dispersant component includes (a) sorbitan monooleate, (b) polyoxyethylene sorbitan monooletae, (c) polyoxyethylene sorbitan trioletae and (d) aqueous sodium dioctyl sulfosuccinate.
  • the dispersant component includes (a) sorbitan monooleate (from 5 to 15 wt%), (b) polyoxyethylene sorbitan monooletae (from 15 to 25 wt%), (c) polyoxyethylene sorbitan trioletae (from 20 to 40 wt%) and (d) aqueous sodium dioctyl sulfosuccinate (from 30 to 50 wt%).
  • the dispersant component occupies 40 % or more by volume of the solid particle.
  • the matrix component includes any of the following, alone or in combination with one another or another material: a tackifier; a rosin or rosin containing compound; a resin or resin containing compound; a rosin-substituted ester; a resin substituted ester; pentaerythritol ester; a rosin substituted pentaerythritol ester; a resin substituted pentaerythritol ester; a fully dimerized rosin; a fully dimerized resin; a rosin maleated with glycerol ester; an ester; a fatty acid; a fatty acid derivative; a fatty acid amide; stearic acid or palmitic acid, or a mixture thereof; an
  • the matrix component may have a density less than 1.00 g/ml; or a density less than 1.02 g/ml; or a density of from 0.80 to 1.02 g/ml.
  • each matrix material for forming dispersant particles was determined by assessing the interaction of each with a COREXIT® dispersant product. Subsequently, if those tests were positive (i.e., the materials were miscible), each matrix material was tested separately for temperature stability (tackiness), and solubility in crude oil (without the presence of the COREXIT® dispersant).
  • each matrix component for forming solid particles was melted, and the dispersant component (COREXIT® 9500 or 9527) was mixed into the melted matrix material to form a mixture, such that the polymer and dispersant each occupied approximately 50 % (by weight) of the mixture.
  • the miscibility of each mixture was assessed, and the matrix materials found to be immiscible with the COREXIT® dispersant were not tested further.
  • the immiscible matrix compounds were PENTALYN® X, PICOLYTE® SI 15, PICOLYTE® SI 35, ESCOREZ® 1102 AND ESCOREZ® 1310LC.
  • the remaining materials were tested for their temperature stability, i.e., ability to exist in a solid state at room temperature. That is, each of those materials was allowed to cool and the tackiness of the resulting solid was assessed. Materials determined to be too tacky at 50% COREXIT® loading were retested at lower loading levels. The stearic acid and palmitic acid matrix compounds required 40% COREXIT® loading to avoid undesirable tackiness.
  • PENTREX® 28 POLYWAX® 3000, PENTALYN® C, DYMEREX, and PETROLITE® E2000.
  • the loading of dispersant component was based on the tackiness of the final product, but a loading that approached 50% was desired (and attempted).
  • the stearic acid and palmitic acid particles required a lower loading (40%>) to achieve the appropriate (low) tackiness.
  • the matrix materials that had acceptable miscibility and low tackiness were then qualitatively tested for oil solubility in Arab Medium Crude, or Chayvo Crude, or both.
  • Small particles of selected matrix materials (alone, i.e., without dispersant compound) were placed into a small quantity of the desired crude oil. After 24 hours, observations were made to determine if the particles had dissolved.
  • Particles made of Ceramer® 5005 were found to readily dissolve in Arab Medium Crude oil, but not in Chayvo Crude oil.
  • Particles made of Pentalyn® K were found to readily dissolve in Chayvo Crude but slowly dissolve in Arab Medium.
  • Pentalyn® K dissolved in Chayvo Crude in a matter of minutes at room temperature; and dissolved in two hours at freezing temperature (0.0 °C).
  • Stearic acid and palmitic acid likewise dissolved in both Arab Medium Crude and Chayvo Crude at room temperature, but such room temperature dissolutions were much slower than that of Pentalyn® K.
  • Stearamide and oleamide did not readily dissolve in Chayvo Crude at room temperature.
  • Permalyn® 6110 particles rapidly dissolved in Chayvo Crude oil samples at both room temperature and freezing; however, microbeads made with a 40% loading of COREXIT ® were too tacky and not tested further.
  • dispersant particles were formed using each of the following matrix materials: CERAMER® 5005 polymer, PETROLITE® E-2020 polymer, Pentalyn® K, stearic acid, palmitic acid. Dispersant particles using PERMALYN® 6110 were scheduled to be formed.
  • Each dispersant particle was tested for dispersion effectiveness using a Paddle Mixer Dispersant Efficiency Test. Two 1000 ml beakers were filled with synthetic seawater (750 ml water per beaker). The tests were performed at room temperature. Oil (2 grams of the desired crude oil) was then poured into each beaker, onto the center of the surface of the water in each beaker. A paddle mixer was inserted into each beaker, and activated to cause the oil to collect around the mixer shaft. Then, 0.1 g of the desired dispersant particles were placed on the surface of the oil to give a weight ratio of 1 part dispersant to 20 parts oil.

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Abstract

Est présenté ici, un processus pour la dispersion du pétrole localisé sur la surface d'un corps d'eau, qui inclut le dépôt de particules solides qui comprennent un composant matriciel et une quantité efficace de composant dispersant ; et la mise en contact des particules solides avec le corps d'eau en une quantité suffisante pour disperser au moins une partie du pétrole. Est également présenté, un dispersant pour le traitement des nappes de pétrole, comprenant une particule solide qui inclut composant dispersant et un composant matriciel solide.
PCT/US2005/016043 2004-05-17 2005-05-06 Dispersants pour nappes de pétrole et processus de dispersion Ceased WO2005115603A2 (fr)

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WO2008094236A1 (fr) * 2007-01-30 2008-08-07 Exxonmobil Upstream Research Company Pâte dispersante flottante
US8708600B2 (en) 2010-09-20 2014-04-29 Wild Well Control, Inc. Subsea injection of oil dispersant
US8784004B2 (en) 2011-04-28 2014-07-22 Bp Corporation North America Inc. Subsea dispersant injection systems and methods
US9096984B2 (en) 2010-12-07 2015-08-04 The Trustees Of Columbia University In The City Of New York Network material devices, methods, and systems
CN109370528A (zh) * 2018-10-09 2019-02-22 浙江海洋大学 一种含有甘油基选择性超分子的凝油剂及其制备方法和应用
GB2565891A (en) * 2017-06-23 2019-02-27 Fung Ming Chiang Method of enhanced treatment of spilled oil on water, land, and biological organisms
RU2691716C1 (ru) * 2018-12-28 2019-06-17 федеральное государственное автономное образовательное учреждение высшего образования "Российский государственный университет нефти и газа (национальный исследовательский университет) имени И.М. Губкина" Способ получения композиции для ликвидации нефтеразливов
RU2719174C1 (ru) * 2019-06-19 2020-04-17 федеральное государственное автономное образовательное учреждение высшего образования "Российский государственный университет нефти и газа (национальный исследовательский университет) имени И.М. Губкина" Состав для ликвидации нефтеразливов
RU2744568C1 (ru) * 2020-07-21 2021-03-11 Публичное акционерное общество "Нефтяная компания "Роснефть" (ПАО "НК "Роснефть") Диспергент для ликвидации разливов нефти
US11162053B2 (en) 2017-06-09 2021-11-02 Ecolab Usa Inc. Nonylphenol ethoxylate-free oil dispersant formulation
RU2764306C1 (ru) * 2020-07-21 2022-01-17 Публичное акционерное общество "Нефтяная компания "Роснефть" (ПАО "НК "Роснефть") Способ ликвидации аварийных разливов нефти

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Cited By (16)

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WO2008094236A1 (fr) * 2007-01-30 2008-08-07 Exxonmobil Upstream Research Company Pâte dispersante flottante
EP2118382A4 (fr) * 2007-01-30 2012-09-12 Exxonmobil Upstream Res Co Pâte dispersante flottante
AU2007345718B2 (en) * 2007-01-30 2013-09-19 Exxonmobil Upstream Research Company Floating dispersant paste
US9937474B2 (en) 2007-01-30 2018-04-10 Exxonmobil Upstream Research Company Floating dispersant paste
US8708600B2 (en) 2010-09-20 2014-04-29 Wild Well Control, Inc. Subsea injection of oil dispersant
US9096984B2 (en) 2010-12-07 2015-08-04 The Trustees Of Columbia University In The City Of New York Network material devices, methods, and systems
US8784004B2 (en) 2011-04-28 2014-07-22 Bp Corporation North America Inc. Subsea dispersant injection systems and methods
US11162053B2 (en) 2017-06-09 2021-11-02 Ecolab Usa Inc. Nonylphenol ethoxylate-free oil dispersant formulation
GB2565891A (en) * 2017-06-23 2019-02-27 Fung Ming Chiang Method of enhanced treatment of spilled oil on water, land, and biological organisms
GB2565891B (en) * 2017-06-23 2022-07-13 Fung Ming Chiang Method of enhanced treatment of spilled oil on water, land, and biological organisms
CN109370528B (zh) * 2018-10-09 2021-05-18 浙江海洋大学 一种含有甘油基选择性超分子的凝油剂及其制备方法和应用
CN109370528A (zh) * 2018-10-09 2019-02-22 浙江海洋大学 一种含有甘油基选择性超分子的凝油剂及其制备方法和应用
RU2691716C1 (ru) * 2018-12-28 2019-06-17 федеральное государственное автономное образовательное учреждение высшего образования "Российский государственный университет нефти и газа (национальный исследовательский университет) имени И.М. Губкина" Способ получения композиции для ликвидации нефтеразливов
RU2719174C1 (ru) * 2019-06-19 2020-04-17 федеральное государственное автономное образовательное учреждение высшего образования "Российский государственный университет нефти и газа (национальный исследовательский университет) имени И.М. Губкина" Состав для ликвидации нефтеразливов
RU2744568C1 (ru) * 2020-07-21 2021-03-11 Публичное акционерное общество "Нефтяная компания "Роснефть" (ПАО "НК "Роснефть") Диспергент для ликвидации разливов нефти
RU2764306C1 (ru) * 2020-07-21 2022-01-17 Публичное акционерное общество "Нефтяная компания "Роснефть" (ПАО "НК "Роснефть") Способ ликвидации аварийных разливов нефти

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