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WO2015061262A1 - Procédés et formulations pour le traitement de fluides à base d'huile - Google Patents

Procédés et formulations pour le traitement de fluides à base d'huile Download PDF

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Publication number
WO2015061262A1
WO2015061262A1 PCT/US2014/061492 US2014061492W WO2015061262A1 WO 2015061262 A1 WO2015061262 A1 WO 2015061262A1 US 2014061492 W US2014061492 W US 2014061492W WO 2015061262 A1 WO2015061262 A1 WO 2015061262A1
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WIPO (PCT)
Prior art keywords
oil
emulsion
destabilizing
formulation
surfactant
Prior art date
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PCT/US2014/061492
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English (en)
Inventor
David S. Soane
Robert P. Mahoney
Eric A. VERPLOEGEN
Matthew A. BOSLEY
Rosa Casado Portilla
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Soane Energy LLC
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Soane Energy LLC
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Publication of WO2015061262A1 publication Critical patent/WO2015061262A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B21/00—Methods or apparatus for flushing boreholes, e.g. by use of exhaust air from motor
    • E21B21/06—Arrangements for treating drilling fluids outside the borehole
    • E21B21/068—Arrangements for treating drilling fluids outside the borehole using chemical treatment
    • 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
    • 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
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • 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
    • C02F1/02—Treatment of water, waste water, or sewage by heating
    • C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • 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
    • C02F1/26—Treatment of water, waste water, or sewage by extraction
    • 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
    • C02F1/38—Treatment of water, waste water, or sewage by centrifugal separation
    • 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
    • C02F1/38—Treatment of water, waste water, or sewage by centrifugal separation
    • C02F1/385—Treatment of water, waste water, or sewage by centrifugal separation by centrifuging suspensions
    • 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
    • C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
    • 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
    • C02F2001/007—Processes including a sedimentation step
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/32—Hydrocarbons, e.g. oil
    • C02F2101/325—Emulsions
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
    • C02F2103/365—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds from petrochemical industry (e.g. refineries)
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/12—Inert solids used as ballast for improving sedimentation

Definitions

  • This application relates generally to treating spent oil-based muds and breaking water-in-oil emulsions.
  • Waste products from various industrial and transportation-related processes can take the form of inverse emulsions in which a variety of solid materials (e.g., carbonaceous matter, mineral material, clays, rust scales, drilling fines, and the like) are suspended.
  • solid materials e.g., carbonaceous matter, mineral material, clays, rust scales, drilling fines, and the like
  • Emulsions are generally mixtures of two immiscible liquid phases, where one liquid is the continuous phase and the second liquid is dispersed as small droplets therein.
  • an oleaginous fluid forms the continuous phase and a non-oleaginous fluid forms the discontinuous phase, such as a water-in-oil (W/O) emulsion.
  • Emulsions are often stabilized against coalescence by surfactants that reduce interfacial tension between the two phases, and the disruption of emulsion stability is known as emulsion breaking. When an emulsion is broken, the dispersed phase droplets can coalesce and separate from the continuous phase.
  • Waste products comprising inverse emulsions can result from industrial processes such as drilling operations, oil refining or transporting, and the like; additionally, waste motor oil often exists in the form of an inverse emulsion containing suspended solids.
  • waste products may be classified as hazardous, or may otherwise require specialized disposal protocols that are complicated or expensive.
  • As an alternative to disposal it would be advantageous to treat these waste products so that useful components can be recycled and the total disposal volume can be reduced. This is of particular concern in the petroleum industry, where refinery wastes, production wastes, and drilling wastes can take the form of difficult-to-break inverse emulsions containing surfactants that support the persistence of the emulsion.
  • Such emulsions further contain fine particulate matter that should be removed if the material is to be reused.
  • inverse emulsions can be formulated by suspending a non-oleaginous fluid in an oleaginous continuous phase, forming a so-called "oil-based drilling mud.”
  • Diesel oil is a common fluid used as the continuous phase for oil based drilling fluids, although other hydrocarbons are also in general use.
  • Other hydrocarbons used in drilling muds include mineral oil, paraffins, alpha-olefins, and internal olefins.
  • the hydrocarbons of C14 through C24 chain length are also familiar in the industry, typically using a saturated or unsaturated hydrocarbon (e.g., C16-C18) as the continuous phase.
  • the drilling mud can be used during the drilling process to lubricate and cool the drill bit and the downhole environment, to transport proppants, fluid loss controllers, viscosity regulators, and other additives, and to convey the drill shavings or "cuttings" to the surface as the drilling progresses.
  • the drilling mud also provides a hydrostatic head pressure to counterbalance the naturally occurring pressure of the downhole environment.
  • fresh drilling mud an inverse emulsion carrying a designated set of particulate additives, is introduced into the wellbore; spent drilling mud carrying residual additives, cuttings and fine particulate detritus, is evacuated from the wellbore.
  • the oil- based drilling mud becomes contaminated with water and picks up particulate fines that need to be separated out if the spent mud is to be recycled.
  • this is difficult to accomplish, so that the spent drilling mud is treated simply as a waste product of the drilling process.
  • spent drilling mud is diluted with additional oil and surfactants to reduce the concentration of finely divided particulates; however, this dilution can produce an undesirable or excessive volume of contaminated drilling mud. It would be advantageous to treat this waste product so that either the spent mud or its components could be reused productively, and/or so that it could be disposed of in a less burdensome manner.
  • Emulsions are understood to be intimate mixtures of two immiscible fluids, such as an oleaginous fluid and a non-oleaginous fluid. Emulsions can be stabilized by surfactants, for example nonionic types or those carrying charges that can reinforce the interfacial stability of the emulsified droplets. Surfactants are known to reduce the interfacial tension between the oil and water phases of an emulsion, leading to a more stable emulsion. Fine particles, too, can adsorb at the oil/water interface, reinforcing the interfacial stability and preventing the coalescence of the discontinuous-phase droplets.
  • surfactants for example nonionic types or those carrying charges that can reinforce the interfacial stability of the emulsified droplets.
  • surfactants are known to reduce the interfacial tension between the oil and water phases of an emulsion, leading to a more stable emulsion. Fine particles, too, can adsorb at the oil/water interface, reinfor
  • Oil-based muds typically contain a variety of emulsifiers/surfactants intended to stabilize the emulsion, along with particulate materials intended for other purposes
  • a representative oil-based mud can contain, for example, diesel as the base oil, along with a primary emulsifier, a secondary emulsifier, a weighting agent like barite, wetting agents, modified clay viscosity modifiers (e.g., organophilic hectorite clay), calcium chloride (a viscosity modifier and weighting agent), and lime.
  • spent mud comprises the residua of the aforesaid ingredients, along with inorganic particulate matter derived from the drilling operation itself.
  • Particles in the mud can vary in size, from larger particles that can be removed by a shale shaker or hydrocyclone, to fine particles that remain suspended despite such processing.
  • Spent mud can also contain additional water and crude oil that originate from the formation or wellbore environment.
  • Breaking an emulsion can take place by physical or chemical means.
  • a variety of chemical methods are known in the art, resulting in separation of the emulsion components.
  • two fluid phases can be formed that represent, respectively, a hydrocarbon phase comprising recovered oil, and a sludge phase comprising a fluid within which are entrained various inclusions such as suspended solids, water, oil, surfactants, and water-wet fine clay particles.
  • a distinct water phase can also be formed after emulsion breaking.
  • this adjunctive process is suitable for use with mechanical separation devices, such as centrifuges, hydrocyclones, filters, sieves, screens, belt presses, rakes, clarifiers, thickeners and the like.
  • destabilizing formulations for an inverse emulsion comprising a treatment additive, wherein the treatment additive is selected from the group consisting of hygroscopic materials, surfactant deactivators, and modifier polymers.
  • the treatment additive is a hygroscopic material.
  • the hygroscopic material is a water-absorbing material.
  • the water-absorbing material comprises a super-absorbent polymer.
  • the super- absorbent polymer is modified with a formulation that associates with surfactants to inactivate them.
  • destabilizing formulations for an inverse emulsion comprising a treatment additive, wherein the treatment additive is an emulsion destabilizer.
  • the emulsion destabilizer comprises a tunable surfactant.
  • the emulsion destabilizer comprises a surfactant or blend of surfactants with a hydrophilic-lipophilic balance range of about 8 - 11.
  • a surfactant- containing water-in-oil emulsion comprising: adding to the invert emulsion an effective amount of the treatment additive formulation described above, and mixing the formulation with the emulsion, wherein contact between the treatment additive and a surfactant in the surfactant-containing water-in-oil emulsion inactivates the surfactant, thereby destabilizing the surfactant-containing water-in-oil emulsion.
  • the method may further comprise adding to the invert emulsion a quantity of clean oil.
  • the invert emulsion comprises a spent oil-based mud.
  • methods for destabilizing a fine-particle-containing water-in-oil emulsion, comprising: providing a formulation comprising a treatment additive and a modifying polymer having affinity for fine particles, and mixing the formulation with the emulsion, wherein contact between the modifying polymer and the fine particles in the emulsion attracts the fine particles, thereby destabilizing the fine-particle-containing water-in-oil emulsion.
  • methods for processing a spent oil-based mud comprising a water-in-oil emulsion, comprising: providing a formulation comprising a treatment additive for destabilizing the water-in-oil emulsion, treating the spent oil-based mud with the formulation to form treated oil-based mud, and separating the treated oil-based mud into two or more phases, wherein one phase comprises a recovered oil.
  • the method also comprises treating the spent oil-based mud with an adjunctive separation process before the step of separating the treated oil-based mud into two or more phases, and the method may further include subjecting the oil-based mud that is treated in this manner to an in-line separation mechanism.
  • a demulsifier comprising a treatment chamber and an additive circuit, wherein the treatment chamber exposes the spent oil-based mud to a treatment formulation delivered through an additive circuit, thereby producing a demulsified oil-based mud; and a separator system, comprising separator apparatus.
  • the system may further comprise a recovered oil treatment subsystem.
  • methods are disclosed herein, in embodiments, for separating a sludge phase and a hydrocarbon phase of a two-phase fluid system, wherein the two-phase fluid system is derived by destabilizing a fine-particle-containing water-in-oil emulsion.
  • the method comprises treating the fine-particle-containing water-in-oil emulsion with a substrate, destabilizing the fine-particle-containing water-in-oil emulsion to obtain the two-phase fluid system, and applying a physical mechanism to the two-phase fluid system, wherein the physical mechanism separates the sludge phase and the hydrocarbon phase of the two-phase fluid system from each other.
  • the substrate can comprise fiber additives or particulate additives.
  • the substrate is an organic substrate.
  • the substrate can be modified with one or more modifiers, and the modifier can be selected from the group consisting of cationic polymers, cationic surfactants, and cationic covalent modifiers.
  • the physical mechanism can comprise an in-line mechanism, and the in-line mechanism can be selected from the group consisting of a centrifuge, a hydrocyclone, a filter, a sieve, a screen, a belt press, a rake, a clarifier, and a thickener.
  • FIG. 1 shows a vial (L) containing spent mud diluted with diesel and a vial (R) containing spent mud diluted with diesel and mixed with crosslinked polyacrylamide particles.
  • FIG. 2 shows a vial (L) containing spent mud diluted with diesel, and a series of vials (R) containing spent mud diluted with diesel containing increasing amounts of polyethylenimine oligomer.
  • FIG. 3 shows a vial (L) containing spent mud diluted with diesel, and a series of vials (R) containing spent mud diluted with diesel containing increasing amounts of Jeffamine XTJ-542.
  • FIG. 4 shows a vial (extreme L) containing spent mud diluted with diesel, a second vial (L) containing spent mud diluted with diesel and mixed with crosslinked polyacrylamide particles, and a series of vials (R) containing spent mud diluted with diesel containing increasing amounts of polyethylenimine oligomer.
  • FIG. 5 shows a vial (extreme L) containing spent mud diluted with diesel, a second vial (L) containing spent mud diluted with diesel and mixed with crosslinked polyacrylamide particles, and a series of vials (R) containing spent mud diluted with diesel containing increasing amounts of Jeffamine XTJ-542.
  • FIG. 6 shows a series of vials containing diesel, polyethylenimine oligomer, and spent mud.
  • FIG. 7 shows a series of vials containing diesel, Jeffamine XTJ-542, and spent mud.
  • FIG. 8 shows a series of vials containing untreated spent mud (8-a), and spent mud in combination of selected treatment additives.
  • FIG. 9 shows two vials, the (R) vial containing spent mud and the left vial containing spent mud treated with a tunable surfactant.
  • a two-phase fluid system which includes a first fluid phase comprising oil, water, or a combination thereof, within which are entrained various inclusions such as suspended solids and water-wet fine clay particles (the "sludge phase"), and a hydrocarbon phase comprising the oil from the OBM that is to be recovered.
  • Representative mechanisms for in-line separation of two-component fluid systems include centrifuges, hydrocyclones, filters, sieves, screens, belt presses, rakes, clarifiers, thickeners, and the like. These mechanisms typically take advantage of the difference in density or viscosity between the two components of the system, using for example gravity or centrifugal force to separate the two components.
  • the substrate can be fibrous or particulate.
  • the fibrous materials suitable for this use can include inorganic or organic fibers.
  • the substrates can be modified to form substrate/modifier systems.
  • Solid materials useful as substrates include materials denser than the fluid suspending the contaminants, or materials that are less dense than that fluid.
  • substrates include quartz sand, diatomaceous earth (DE), cellulose acetate fibers, -20/+60 mesh rice hulls, -80 mesh rice hulls, polystyrene beads, bagasse, and the like.
  • Exemplary substrates, whether organic or inorganic, can be formed in any morphology, whether regular or irregular, plate-shaped, flake-like, cylindrical, spherical, needle-like, fibrous, etc.
  • Substrate particles can include natural materials or synthetic materials, either as a single substance or as a composite.
  • the substrates can include ferromagnetic materials and the separation of the phases can be enhanced with the use of magnetic separation equipment.
  • fibers used can be 3-4 denier fibers, 1 cm long.
  • particles may be used that are between 100 microns and 2 mm in size.
  • Organic substrates can include fibrous material, particulate matter, amorphous material or any other material of organic origin.
  • Organic substrates can include natural materials or synthetic materials.
  • synthetic organic substrates can include a variety of plastic materials. Both thermoset and thermoplastic resins may be used to form plastic substrates.
  • Plastic substrates may be shaped as solid bodies, hollow bodies or fibers, or any other suitable shape.
  • Plastic substrates can be formed from a variety of polymers.
  • a polymer useful as a plastic substrate may be a homopolymer or a copolymer. Copolymers can include block copolymers, graft copolymers, and interpolymers.
  • suitable plastics may include, for example, addition polymers (e.g., polymers of
  • Addition polymers can include, for example, polyolefins, polystyrene, and vinyl polymers.
  • Polyolefins can include, in embodiments, polymers prepared from C2-C10 olefin monomers, e.g., ethylene, propylene, butylene, dicyclopentadiene, and the like.
  • poly(vinyl chloride) polymers, acrylonitrile polymers, and the like can be used.
  • useful polymers for the formation of substrates may be formed by condensation reaction of a polyhydric compound (e.g., an alkylene glycol, a poly ether alcohol, or the like) with one or more polycarboxylic acids.
  • a polyhydric compound e.g., an alkylene glycol, a poly ether alcohol, or the like
  • Polyethylene terephthalate is an example of a suitable polyester resin.
  • Polyurethane resins can include, e.g., polyether polyurethanes and polyester polyurethanes.
  • Plastics may also be obtained for these uses from waste plastic, such as post-consumer waste including plastic bags, containers, bottles made of high density polyethylene, polyethylene grocery store bags, and the like.
  • elastomeric materials can be used as substrates. Substrates of natural or synthetic rubber can be used, for example.
  • Fibers of polyethylene, polypropylene, polyester, polyamide and the like can be in the form of a chopped fiber, or a fiber with length of about 0.01 mm to about 100 mm. In embodiments, fibers can have a length of about 1 to 50 mm.
  • Natural organic substrates can comprise materials of vegetable or animal origin.
  • Vegetable substrates can be predominately cellulosic, e.g., derived from cotton, jute, flax, hemp, sisal, ramie, and the like.
  • Vegetable sources can be derived from seeds or seed cases, such as cotton or kapok, or from nuts or nutshells.
  • Vegetable sources can include the waste materials from agriculture, such as corn stalks, stalks from grain, hay, straw, or sugar cane (e.g., bagasse).
  • Vegetable sources can include leaves, such as sisal, agave, deciduous leaves from trees, shrubs and the like, leaves or needles from coniferous plants, and leaves from grasses.
  • Vegetable sources can include fibers derived from the skin or bast surrounding the stem of a plant, such as flax, jute, kenaf, hemp, ramie, rattan, soybean husks, vines or banana plants. Vegetable sources can include fruits of plants or seeds, such as coconuts, peach pits, mango seeds, and the like. Vegetable sources can include the stalks or stems of a plant, such as wheat, rice, barley, bamboo, and grasses. Vegetable sources can include wood, wood processing products such as sawdust, and wood, and wood byproducts such as lignin.
  • Animal sources of organic substrates can include materials from any part of a vertebrate or invertebrate animal, fish, bird, or insect. Such materials typically comprise proteins, e.g., animal fur, animal hair, animal hoofs, and the like.
  • Animal sources can include any part of the animal's body, as might be produced as a waste product from animal husbandry, farming, meat production, fish production or the like, e.g., catgut, sinew, hoofs, cartilaginous products, etc.
  • Animal sources can include the dried saliva or other excretions of insects or their cocoons, e.g., silk obtained from silkworm cocoons or spider's silk. Animal sources can be derived from feathers of birds or scales of fish.
  • Inorganic substrates useful in accordance with these systems can include one or more materials such as calcium carbonate, dolomite, calcium sulfate, kaolin, talc, titanium dioxide, sand, diatomaceous earth, aluminum hydroxide, silica, other metal oxides and the like.
  • examples of inorganic substrates include clays such as attapulgite and bentonite.
  • the inorganic substrate can include vitreous materials, such as ceramic particles, glass, fly ash and the like.
  • the substrates may be solid or may be partially or completely hollow.
  • glass or ceramic microspheres may be used as substrates.
  • Vitreous materials such as glass or ceramic may also be formed as fibers to be used as substrates.
  • Cementitious materials such as gypsum, Portland cement, blast furnace cement, alumina cement, silica cement, and the like, can be used as substrates.
  • Carbonaceous materials including carbon black, graphite, lignite, anthracite, activated carbon, carbon fibers, carbon microparticles, and carbon nanoparticles, for example carbon nanotubes, can be used as substrates.
  • inorganic materials are desirable as substrates.
  • substrate materials to enhance surface area are advantageous.
  • finely divided or granular mineral materials are useful.
  • Materials that are porous with high surface area and permeability are useful.
  • Advantageous materials include zeolite, bentonite, attapulgite, diatomaceous earth, perlite, pumice, sand, and the like.
  • the substrate can be created in situ by precipitation of a chemical additive such as a metal salt.
  • the substrate can be created in situ by precipitation of components of the waste mud or waste oil stream.
  • the components can be precipitated by adjusting pH, the presence of counterions, or the presence of solvents or cosolvents.
  • the addition of the solid material substrate to the sludge phase or to the oil-based mud prior to or simultaneous with its separation into the sludge phase and the hydrocarbon phase can form a fibrous matrix that is responsive to the centrifugal forces in a centrifuge, or that allows cohesion of the sludge phase so that it can be separated from the more free-flowing hydrocarbon phase through use of gravity.
  • the use of synthetic fibers such as polypropylene (PP), polyester (PE), polyamide, and derivatives is advantageous.
  • PP polypropylene
  • PE polyester
  • polyamide polyamide
  • the sludge phase combined with a biodegradable or natural fiber can be suitable for disposal in environmentally sensitive areas, or can be used as landfill.
  • the processes disclosed herein represent adjunctive processes to be used prior to, during, or following the separation of an OBM into a two-phase component system. These adjunctive processes are useful in facilitating the disposal of the fine particulate matter ("fines") that are suspended in such inverse emulsions when such removal is accompanied by breaking the water- in-oil emulsion.
  • finely divided suspended solids, or "fines" in OBMs are generally oil-wet, and it is understood that they are preferentially attracted to the interfacial film between the suspended non-oleaginous droplets and the continuous oleaginous phase. Destabilizing the emulsion in which the fines are suspended can facilitate removal of fines from the materials to be recovered from the spent OBM.
  • substrate materials can act as platforms for the attachment of modifiers that improve the rate of separation, the yield of recovered oil, the quality of the recovered oil, and the like.
  • Modifiers useful in the removal of suspended solids according to these systems and methods include cationic polymers, cationic surfactants and cationic covalent modifiers. Examples of cationic polymers include linear or branched
  • cationic surfactants include cetyltrimethylammonium bromide (CTAB), alkyldimethylbenzyl quats, dialkylmethylbenzylammonium quats, and the like.
  • cationic covalent modifiers include quaternization reagents like Dow Q- 188 or organosilicon quaternary ammonium compounds.
  • organosilicon quaternary ammonium compounds are 3-trihydroxysilylpropyldimethylalkyl (C6-C22) ammonium halide, 3-trimethoxysilylpropyldimethylalkyl (C6-C22) ammonium halide, 3- triethoxysilylpropyldimethylalkyl (C6-C22) ammonium halide, and the like.
  • adjunctive processes are useful, further, in facilitating the removal of entrained water and associated solids, both dissolved and suspended, from hydrocarbons and sequestering them in a phase that can be disposed of more readily.
  • the removal of entrained water from produced oil before refining activities is generally known as desalting since the removal of water causes removal of associated salts that can cause corrosion or interfere with processing or refining.
  • These adjunctive processes are useful, further, in facilitating the purification and recovery of the oil phase and minimizing the volume of wastes requiring management or disposal.
  • adjunctive processes disclosed herein can be implemented once the OBM emulsion has been destabilized, with the resultant production of two discrete phases, a hydrocarbon phase and a sludge phase, or can be implemented before the OBM is destabilized to produce the two discrete phases, a hydrocarbon phase and a sludge phase.
  • These adjunctive processes can be used in combination with a variety of methods for destabilizing the OBM emulsion. Exemplary methods of OBM emulsion destabilizing are described below.
  • the formulations and methods disclosed herein are particularly useful for destabilizing those oil-based drilling muds in which diesel is the base oil.
  • these formulations and methods can be used for treating other oil-based muds, such as those formed using 16-18 carbon synthetic base oils, alpha olefins, or internal olefins.
  • these formulations and methods can be used for treating used motor oil or other waste hydrocarbons.
  • treatment additives are provided to counteract the efficacy of the surfactants that maintain such emulsions, thereby facilitating emulsion- breaking, improving the recovery of valuable components of the emulsion, and minimizing waste volume.
  • a treatment additive can comprise hygroscopic materials, surfactant deactivators or modifier polymers, as described below.
  • a treatment additive can comprise emulsion destabilizers, including tunable surfactants, as described below.
  • treatment additives such as formulations comprising hygroscopic water-absorbing materials, for example super-absorbent polymers (SAPs) such as crosslinked poly(acrylic acid) or crosslinked polyacrylamide or partially hydrolyzed poly(acrylamide), or cellulose-based SAPs can be introduced into the inverse emulsion to interact with the water phase, and/or to interact with the hydrophilic surfactants entrained therein.
  • SAPs super-absorbent polymers
  • Other hydroscopic materials useful for this purpose include hydrogels,
  • water-absorbent, non-polymeric treatment additives can be used for this purpose, for example inorganic desiccants, hygroscopic materials such as silica gel, activated charcoal, calcium sulfate, calcium chloride, calcium oxide, magnesium oxide, activated silica, activated alumina, magnesium sulfate, montmorillonite clay, and aluminosilicate molecular sieves.
  • hygroscopic materials or SAP particles can be modified with formulations that associate with surfactants and inactivate them.
  • the formulations that inactivate surfactants comprise polyamines, polycations, polyanions, and the like. Whether unmodified or modified, the SAPs facilitate breaking the inverse emulsion, releasing the fines.
  • the amount of SAP used to treat the waste emulsion or OBM can be from about 0.1% to about 10% by weight of the OBM emulsion.
  • the amount of SAP required will be dependent upon the level of impurities, water, and stabilizers in the waste emulsion or OBM.
  • the spent SAPs can be separated from the base oil so that the base oil can be retrieved and recycled.
  • the fines, too, can be separated from the base oil so that clarified base oil can be recovered.
  • an amount of base oil dilution can range from ⁇ 10% (based on the spent emulsion volume) to over 200%. In embodiments, the amount of dilution can range from about 10% to about 200%. In embodiments, the amount of dilution can range from about 20% to about 100%. In embodiments, this dilution can reduce the viscosity of the inverse emulsion, allowing the treatment additives more ready access to the suspended aqueous droplets, and also allowing the liberated fines to settle out of the oil phase more rapidly. In embodiments, the added oil can be recovered in subsequent processing steps for recycling or reuse.
  • emulsion destabilization as disclosed herein can involve one or more mechanisms of action.
  • One mechanism of action is based on surfactant sequestration, where a treatment additive such as a SAP introduced into the OBM can absorb or adsorb one or more surfactants that serve to stabilize the inverse emulsion. When the one or more surfactants are sequestered, the emulsion becomes unstable, so that it can be more readily broken.
  • Another mechanism of action is based on surfactant deactivation, where the amine functional groups of the agents carried by the SAPs can complex with one or more surfactants, thereby changing their effective chemical structure and deactivating them.
  • additives comprising polyethylenimine may reflect this mechanism of action.
  • polyetheramines have amine functional groups on the ends that can act in accordance with this mechanism.
  • another postulated mechanism of action involves the destabilization of the Pickering emulsion contained in the OBM.
  • a Pickering emulsion is characterized by solid particles that stabilize an interface between an aqueous phase and an oil phase; for OBM, for example, fine solid particles (i.e., the fines) collect at the oil-water interface to stabilize the emulsion.
  • a treatment additive comprising a polymer having an affinity for the fines in the OBM can attract the fines away from the interface, or coagulate the fines, destabilizing the association between the fines and the oil/water interface.
  • a modifying agent such as ethylene oxide / propylene oxide (EO/PO) copolymers and polyetheramines and the like can operate in accordance with this mechanism, destabilizing the interaction between the fines and the emulsion interface, allowing the fines and the water droplets to separate more readily from the continuous oleaginous fluid.
  • a modifying agent can be used alone, or in combination with SAPs such as have been disclosed above.
  • a tunable surfactant such as poly(oxy- l,2-ethanediyl),"alpha"-hydro-"omega" -hydroxy-, hydrogen 2-C15-20-alkenylbutanedioates can be used to destabilize the emulsion, resulting in three phases that can be recovered from the destabilized emulsion.
  • the first phase is predominately oil (> 90% oil), suitable, for example, for reuse in drilling mud applications, for refining, or burning as a fuel.
  • the second phase is a predominantly aqueous phase
  • the third phase is a sludge comprising oil, water, and solids.
  • various surfactant blends can be used to destabilize the emulsion, resulting in three phases that can be recovered from the destabilized emulsion.
  • the first phase is a predominately oil (> 99% oil) phase, suitable, for example, for reuse in drilling mud applications, for refining, or burning as fuel.
  • the second phase is a predominantly aqueous phase, and the third is a sludge comprising oil, water, and solids.
  • the ratio of the various components in the surfactant blend can be manipulated to optimize the efficacy of the chemical treatment for any given emulsion.
  • the surfactant blends can be added in amounts of about 1 - 5% based on the weight of the emulsion, or preferably about 2 - 4% based on the weight of the emulsion.
  • breaking an OBM emulsion that contains suspended fines can release the fines from suspension so that they settle out and can be removed.
  • Fines are initially suspended in the OBM as a consequence of various wetting agents or organic modifiers used as viscosity modifiers.
  • additional fines become entrained in the OBM emulsion in an oil-wet state.
  • a typical oil-based drilling mud aims to provide system components with an oil-wet status by introducing disproportionate amounts of surfactants, wetting agents and the like.
  • the fine particulate residual in the spent mud also become oil-wet, so that they are highly stabilized in suspension and are thus difficult to remove. Deactivation of such wetting agents or organic modifiers impairs the oil-wet status of the fines, allowing them to settle out.
  • the settling of fines can be improved by counteracting the residual surfactants, wetting agents, and the like.
  • the settling of fines can be improved by counteracting the residual surfactants, wetting agents, etc., using treatment additives comprising SAPs.
  • this can be accomplished by modifying the SAP system with appropriate polymeric modifiers, leading to more complete fines separation and/or faster separation rate.
  • polymeric modifying agents are selected with specific affinity for surfactants residing within the spent oil.
  • SAPs for use in treatment additive formulations can be selected based on their capacity to absorb water and/or brine.
  • the removal of a portion of the emulsified water by absorption via SAP results in the removal of the aqueous emulsion phase from the oil continuous emulsion.
  • the aqueous phase contributes to the stabilization of the fines in the emulsion, the removal of the emulsified water will enhance the ability for the fines to be removed.
  • a polyacrylic acid (PAA) SAP or a partially hydrolyzed poly(acrylamide) (PHP A), or a cellulose-based SAP can be used.
  • the conventional SAP polymers are generally crosslinked by reaction with multifunctional monomers.
  • PAA and PHPA SAPs can absorb from about 10 times to over 100 times their weight in tap water.
  • PAA particles did not exhibit noticeable swelling, due to charge shielding from the salt.
  • the PHPA particles can absorb over 10 times their weight in the CaC3 ⁇ 4 brine.
  • Cellulose-based SAPs can absorb about half as much liquid as PHPA particles, both in water and in brine.
  • SAPs can be modified with a modifier polymer such as a polyethylenimine (PEI) oligomer.
  • a modifier polymer such as a polyethylenimine (PEI) oligomer.
  • molecules containing shorter ethylene imine repeating units such as alkylenepolyamines such as tetraethylenepentamine (TEPA), pentaethyleneheptamine (PEHA), ethylene diamine (EDA), diethylenetriamine (DETA), and triethylenetetramine (TETA) are effective modifiers.
  • Exemplary modifier polymers can include, in embodiments, any cationic polymer, e.g., poly diallyldimethylammonium chloride, or other polymers such as polyacrylates, polyacrylamides, polyesters, and the like.
  • polyvinyl alcohol, poly maleic anhydride, and polyethers can also be added as modifier polymers.
  • any hydrophobic medium can be used as a suspending medium for the modifier polymer.
  • such polymers can be suspended in a hydrophobic medium, e.g., diesel, which suspension can be combined with the SAP to form a modified SAP.
  • a hydrophobic medium e.g., diesel
  • suitable hydrophobic media could include any low viscosity hydrocarbon (e.g., naphtha). Diesel is advantageous as a suspending medium because of its similarity to the material recovered in the oil phase from the destabilized OBM emulsion.
  • a lighter (i.e. lower viscosity or lower boiling point) suspending medium like naphtha can be used.
  • the base oil used as a suspending medium is selected so that it is compatible with the synthetic oil in the target material and does not introduce contamination.
  • Exemplary suspension media can include any low viscosity oil such as naphtha, diesel, gasoline, polyolefins, alkanes, alkenes, alpha-olefins, internal olefins, pentane, hexane, cyclohexane, toluene, xylenes, chloroform, tetrahydrofuran, diethyl ether.
  • an emulsion can be formed by adding a minimal amount of water to the hydrophobic medium, and an amphiphilic modifier polymer can be added.
  • the emulsion containing the modifier polymer can be used to modify the SAP to form the modified SAP.
  • the modifier polymer for example, propylene oxide - ethylene oxide (PO/EO) copolymers can be used as modifier polymers, for example block copolymers or random copolymers.
  • a modifier polymer like a high molecular weight PEI can be used.
  • low molecular weight modifier polymers can be particularly advantageous. Not to be bound by theory, it is envisioned that the low molecular weight modifier polymer may penetrate the SAP itself, thereby providing sites within the SAP for interacting with the surfactant and potentially deactivating or trapping it. In embodiments, a decreased particle size for the SAP can be advantageous, as it provides a greater surface area for interacting within in the inverse emulsion. (b) Emulsion Destabilizers and Tunable Surfactants
  • emulsion destabilizers suitable for use to destabilize inverse emulsions such as oil-based drilling muds, used motor oil, and waste oil emulsions, and the like.
  • the emulsion destabilizer may be described as a tunable surfactant, as defined below.
  • the term "tunable surfactant” refers to a structural class of molecules whose surface active properties can be increased or decreased by application of a trigger.
  • the trigger to change the properties of tunable surfactants is a change of environmental conditions like pH, temperature, salinity, ionic strength, and the like, or the presence of oil or a 'breaker' material.
  • the emulsion destabilizer may be a compound lacking the tunable properties of a tunable surfactant, but acting nonetheless to destabilize an inverse emulsion such as oil-based drilling muds.
  • the emulsion destabilizers comprise surfactants or blends of surfactants with a hydrophilic-lipophilic balance (HLB) range of about 8 - 11 or preferably a HLB range of 9-10.
  • HLB hydrophilic-lipophilic balance
  • the emulsion destabilizers can be added in amounts of about 1 - 5% based on the weight of the emulsion, or preferably about 2 - 4% based on the weight of the emulsion.
  • emulsion destabilizers can include compounds such as the following, and blends thereof: Sorbitan monooleates such as Span 80 sorbitan monooleate (Croda); ethoxylated nonyl phenols such as Triton X-l 14 (Dow); primary and secondary alcohol ethoxylates such as Tergitol 15-S-7 (BASF); and polysorbates and ethoxylated polysorbates such as Tween family (Croda) of surfactants.
  • Sorbitan monooleates such as Span 80 sorbitan monooleate (Croda)
  • ethoxylated nonyl phenols such as Triton X-l 14 (Dow)
  • primary and secondary alcohol ethoxylates such as Tergitol 15-S-7 (BASF)
  • polysorbates and ethoxylated polysorbates such as Tween family (Croda) of surfactants.
  • the emulsion destabilizer can comprise a tunable surfactant.
  • tunable surfactant refers to compositions such as those described below and as set forth in U.S. Patent Application Serial No's. 12/635,241 (U.S. Patent Application Serial No's. 12/635,241 (U.S. Patent Application Serial No's. 12/635,241 (U.S. Patent Application Serial No's. 12/635,241 (U.S. Patent
  • A is an alkyl, alkenyl, alkadienyl, alkynyl, cycloalkyl, or cycloalkenyl, each optionally substituted;
  • p is 1 or 2; preferably 2;
  • m and n are independently 0, 1, 2, 3, 4, or 5;
  • each of Gi and G 2 are independently absent, O, S, NR 2 ., (CO)O, O(CO), CO, CONR 2 , or NR 2 CO; each R 2 is independently H or a lower alkyl;
  • G 3 is absent, (CH 2 ) q or d; q is 1, 2, 3, 4 or 5;
  • R is a hydrophilic group, or absent; and
  • Ri is a saturated or unsaturated hydrophobic aliphatic group.
  • m is 1 or 2 and n is 0 or 1.
  • at least one of Gi and G 2 are present.
  • the methods disclosed herein use surfactant formulations that comprise com ounds having the Formula (la):
  • the methods disclosed herein use surfactant formulations that com rise compounds having the Formula (II):
  • D is an aliphatic polymer
  • p is 1 or 2; preferably 2; m and n are independently 0, 1, 2, 3, 4, or 5; each of Gi and G 2 are independently absent, O, S, NR 2 , (CO)O, O(CO), CO, CONR 2 , or NR 2 CO; each R 2 is independently H or a lower alkyl; G 3 is absent, (CH 2 ) q or d; q is 1, 2, 3, 4 or 5; R is a hydrophilic group; and Ri is a saturated or unsaturated hydrophobic aliphatic group, or an aryl, heteroaryl, cycloalkyl, or cycloalkenyl group.
  • the methods disclosed herein use surfactant formulations that comprise compounds having the Formula (Ha): wherein t is 0 or 1 ; G 4 is O or NH; and D and Ri are as defined above. In certain embodiments, the methods disclosed herein use surfactant formulations that comprise compounds having the Formula (lib):
  • each t group is independently 0 or 1 or 2; G4 is O or NH or is absent; R2 is a COOH group or salts of COO or is absent, and D and Rl are as defined above.
  • the invention relates to a compound of Formula III:
  • E is alkyl, alkenyl, alkadienyl, alkynyl, cycloalkyl, cycloalkenyl, aryl and heteroaryl;
  • G5 is CONH;
  • D2 is a hydrophilic aliphatic polymer; and
  • p is 1 or 2.
  • the methods disclosed herein use surfactant formulations that comprise compounds having the Formula (IV):
  • D2 is a hydrophilic aliphatic polymer
  • each J is independently selected from the group consisting of hydrogen and the Fragment (A) having the structure shown below: wherein E is a hydrophobic group selected from the group consisting of alkyl, alkenyl, alkadienyl, alkynyl, cycloalkyl, cycloalkenyl, aryl and heteroaryl; and wherein at least one J is the Fragment (A).
  • the methods disclosed herein use surfactant formulations that comprise compounds having the Formula (V):
  • D2 is a hydrophilic aliphatic polymer
  • each J is independently selected from the group consisting of H and the Fragment (A):
  • compositions of particular use in these systems and methods can include at least one compound of the Formula (I), Formula (la), Formula (II), Formula (Ila), Formula (III), Formula (IV) or Formula (V) as described above.
  • the surfactant formulations disclosed herein comprise a compound that has the Formula (I), (la), (II) or (Ila).
  • the surfactant formulations encompass compounds having the Formula (I) or Formula (la), wherein A is an alkyl (e.g., a C3-C8 alkyl) or cycloalkyl, each optionally substituted.
  • A is an alkyl-substituted cyclopentyl or cyclohexyl. Examples of alkyl-substituted cyclohexyl are propylcyclohexyl and ethylcyclohexyl.
  • the surfactant formulations comprise a compound has the Formula (I), wherein Gi is selected from the group consisting of O, S, NR 2 , C(0)0, OC(O), C(O), C(0)NR 2 and R 2 C(0).
  • the surfactant formulations comprise a compound that has the Formula (I), wherein Gi is selected from the group consisting of C(0)0, OC(O), C(O), C(0)NR 2 and NR. 2 .C(0).
  • Gi is selected from C(0)0 and C(0)NR 2 .
  • the compound has the Formula (I) wherein p is 1.
  • the compound has the Formula (I) wherein p is 2.
  • the compound has the Formula (I) wherein m is 1 or 2. In yet additional aspects, the compound has the Formula (I), wherein n is 0 or 1. In yet another aspect, the compound has the Formula (I), wherein R is C(0)OH. In a further aspect, the compound has the Formula (I), wherein Ri is selected from the group consisting of Cs-C 2 o alkyl, Cs-C 2 o alkenyl, and Cs-C 2 o alkadienyl.
  • the compound has the Formula (II) or (Ila), wherein D is selected from the group consisting of polyethylene glycol, poly(ethylene glycol), poly(ethylene glycol), and
  • glycol /poly(propylene glycol) copolymers, polyethylene glycol methyl ether,
  • the compound has the Formula (II), wherein p is 1. In a further aspect, the compound has the Formula (II), wherein p is 2. In yet an additional aspect, the compound has the Formula (II), wherein m is 1 or 2, or n is independently 0 or 1, or a combination thereof. In another aspect, the compound has the Formula (II), wherein each Gi is independently OC(O),
  • compounds of Formula (I), (la), (II) and (Ila) comprise a hydrophilic portion (substituent R) and a hydrophobic aliphatic group (substituent Ri).
  • the aliphatic groups include saturated or unsaturated carbon chains, preferably between five and twenty units in length, or five and eighteen units in length, or eight and twenty units in length, or hydrogen.
  • the carbon chains can optionally be unsaturated and, when present, reside anywhere along the carbon chain.
  • the hydrophilic portion of the inventive compounds can comprise one or more hydrophilic groups or substituents. Hydrophilic portions or groups can be an ionizable groups, including, for example, amines and carboxylic acids. In certain aspects of the invention, the hydrophilic group is C(0)OH. Hydrophilic groups also include hydrophilic polymers, including, but not limited to, polyalkylamine, poly(ethylene glycol) or poly(ethylene glycol)/poly(propylene glycol) copolymers. Nonionic hydrophilic materials such as polyalkylamine, poly(ethylene glycol) or poly(ethylene glycol)/poly(propylene glycol) copolymers can be used to increase hydrophilicity or aid stability in salt solutions.
  • the surfactant compound has the Formula (III).
  • D 2 is a polymer or copolymer containing ether groups.
  • Compounds having Formula (III) may be prepared by reacting an aliphatic or aromatic diacid with a polyetheramine.
  • the compound has the Formula (III), wherein E is C1-C6 alkyl.
  • the surfactant compound has the Formula (IV) or Formula (V) as described above, wherein D 2 is a polyether.
  • D 2 is a polyether.
  • E is a C5-C2 0 alkyl, C5-C20 alkadienyl or C5-C20 alkenyl.
  • a tunable surfactant can be obtained by reaction of a polyethylene glycol with a hydrophobic succinic anhydride.
  • This tunable surfactant compound can be dissolved in water along with alkali such as sodium hydroxide, where two moles of alkali are added per mole of the tunable surfactant.
  • alkali such as sodium hydroxide
  • the tunable surfactant can have a structure represented as follows, shown in the acid form:
  • a number of systems and methods exist for separating fines from a fluid stream including filtration systems, gravitational settling, clarification vessels, hydrocyclones, highspeed centrifugation, liquid-liquid extractions, and the like, any of which may be termed a "separator.”
  • formulations as described above can be used as treatment additives to treat OBM emulsions and other analogous emulsions. Treatment with such treatment additives can destabilize the emulsion forming the OBM. Following this destabilization, the treated OBM can be separated into its components by a chemical or mechanical separation process or separator, including processes as described above.
  • Adjunctive processes can be employed to facilitate this separation.
  • a treatment additive can be combined with the spent OBM and allowed to react with the spent OBM fluid for a period of time, varying from less than a minute to over a day.
  • the resulting treated fluid can be further treated with an adjunctive process, for example adding fibers or particulate separation adjuncts.
  • the processed treated fluid can then be processed with separator apparatus such as filtration systems, clarification vessels, gravitational settling, hydrocyclones, high-speed centrifugation, liquid-liquid extractions, and the like, so that the sludge phase is separated discretely from the hydrocarbon phase.
  • a treatment system for treating a spent oil-based mud can comprise a demulsifier comprising a treatment chamber that exposes the spent oil-based mud to a treatment formulation comprising a treatment additive for destabilizing water-in-oil emulsions as have been described above.
  • the treatment additive can be delivered into the treatment chamber directly or through an additive circuit in which one or more treatment additives are blended with other formulation components, including clean oil diluents.
  • the fiber or particulate additives of the adjunctive process can be added as a slurry or as a dry material. The materials can be fed continuously or batch wise into the process.
  • the treated (i.e., demulsified) oil- based mud can be separated into phases in a separator system, comprising separator apparatus.
  • the oil separated in the oil phase from the demulsified oil-based mud is thus recovered from the spent oil-based mud and can be further treated.
  • Treatments for recovered oil include filtration, sedimentation, washing, centrifugation, distillation, and the like.
  • a treatment system may include a recovered oil treatment subsystem as described above, which subsystem(s) can include apparatus for filtration, sedimentation, washing, centrifugation, distillation, and the like, for the recovered oil.
  • Crosslinked polyacrylamide particles (1 g) were mixed with 10 mL of diesel. Spent oil-based mud from an oilfield drilling rig (0.1 mL) was added to the mixture and shaken for 2 hours. The resulting mixture was allowed to settle for 36 hours. Following settling, the results are seen in FIG. 1, right. This result can be compared to a mixture of spent oil-based mud (0.1 mL) and 10 mL of diesel, shown in FIG. 1, left. As the Figure shows, the diesel layer was significantly less opaque and turbid with the addition of the crosslinked polyacrylamide particles. [0075] Example 2
  • Ethylene oxide / propylene oxide copolymers (Pluronic L35) ethylene oxide and propylene oxide block copolymer (100 ⁇ ) was mixed with 100 mL diesel. After mixing the above solution and settling for > 1 hour, 2 equal sets of 10 mL solutions were made by adding 0.5, 1, 2, 5, and 10 mL of the Pluronic L35 in diesel solution (aliquot taken from the top of the solution without removing the precipitate) to 9.5, 9, 8, 5, and 0 mL of diesel. Spent oil-based mud (0.1 mL to the first set and 0.5 mL to the second set) was added to the mixtures and mixed for 6.5 hours. The resulting mixture was allowed to settle for 62 hours. Compared to mixtures of spent oil-based mud (0.1 mL and 0.5 mL respectively) and 10 mL diesel, the diesel layer was significantly less turbid as the concentration of Pluronic L35 increased.
  • Ethylene oxide / propylene oxide copolymers (Pluronic L64), ethylene oxide and propylene oxide block copolymer (100 ⁇ ) was mixed with 100 mL diesel. After mixing the above solution and settling for > 1 hour, 2 equal sets of 10 mL solutions were made by adding 0.5, 1, 2, 5, and 10 mL of the Pluronic L64 in diesel solution (aliquot taken from the top of the solution without removing the precipitate) to 9.5, 9, 8, 5, and 0 mL of diesel. Spent oil-based mud (0.1 mL to the first set and 0.5 mL to the second set) was added to the mixtures and mixed for 5.25 hours. The resulting mixture was allowed to settle for 62 hours. Compared to mixtures of spent oil-based mud (0.1 mL and 0.5 mL respectively) and 10 mL diesel, the diesel layer was significantly less turbid as the concentration of Pluronic L64 increases.
  • Polyethylenimine oligomer 100 ⁇ was mixed with 100 mL diesel. After mixing the above solution and settling for > 1 hour, 2 equal sets of 10 mL solutions were made by adding 0.5, 1, 2, 5, and 10 mL of the polyethylenimine oligomer in diesel solution (aliquot taken from the top of the solution without removing the precipitate) to 9.5, 9, 8, 5, and 0 mL of diesel. Spent oil-based mud (0.1 mL to the first set and 0.5 mL to the second set) was added to the mixtures and shaken for 2 hours. The resulting mixture was allowed to settle for 62 hours. Compared to mixtures of spent oil-based mud (0.1 mL and 0.5 mL
  • Pluronic L35 ethylene oxide / propylene oxide copolymers (0.21 g) was added to 210 mL diesel followed by an addition of 2.5 mL water and mixing to form an emulsion.
  • 4 sets of 5 solutions are made by adding 10, 5, 2, 1, and 0.1 mL of the Pluronic L35 emulsion solution (aliquot taken from the top of the solution without removing the precipitate) to 0, 5, 8, 9, and 9.9 mL of diesel.
  • Crosslinked polyacrylamide particles (0.2 g) were added to each solution and mixed for 2 hours. Diesel (8 mL) was removed from the top of the 3 rd and 4 th set of solutions.
  • Pluronic L64 (ethylene oxide / propylene oxide copolymers) (0.21 g) was added to 210 mL diesel followed by an addition of 2.5 mL water and mixing to form an emulsion. 4 sets of 5 solutions are made by adding 10, 5, 2, 1, and 0.1 mL of the Pluronic L64 emulsion solution (aliquot taken from the top of the solution without removing the precipitate) to 0, 5, 8, 9, and 9.9 mL of diesel.
  • Crosslinked polyacrylamide particles (0.2 g) were added to each solution and mixed for 2 hours. Diesel (8 mL) was removed from the top of the 3 rd and 4 th set of solutions.
  • Spent oil-based mud (0.1 mL for 1 st and 3 rd set, 0.5 mL for 2 nd and 4 th set) was added to the solutions, which were mixed for 18 hours and then allowed to settle. After one week, these solutions looked somewhat better (less turbid) than the controls treated only with diesel.
  • Polyethylenimine oligomer (2.4 g) was mixed with 210 mL diesel. 4 sets of 5 solutions are made by adding 10, 5, 2, 1, and 0.1 mL of the polyethylenimine oligomer in diesel solution (aliquot taken from the top of the solution without removing the precipitate) to 0, 5, 8, 9, and 9.9 mL of diesel.
  • Crosslinked polyacrylamide particles (0.2 g) were added to each solution and mixed for 2 hours.
  • Diesel (8 mL) was removed from the top of the 3 rd and 4 th set of solutions. Spent oil-based mud (0.1 mL for 1 st and 3 rd set, 0.5 mL for 2 nd and 4 th set) was added to the solutions, which were mixed for 18 hours and then allowed to settle.
  • FIG. 4 The results of this Example after two days are shown in FIG. 4.
  • the spent oil-based mud diluted with diesel can be compared with the diesel-diluted oil-based mud to which crosslinked polyacrylamide particles were added (near left).
  • These samples can be compared to those where increasing concentrations of PEI oligomer were added to the diesel-diluted mud with crosslinked polyacrylamide particles.
  • Increasing amounts of PEI oligomer correlated with less turbidity in the diesel layer.
  • Spent oil-based mud (0.1 mL for 1 st and 3 rd set, 0.5 mL for 2 nd and 4 th set) was added to the solutions, which are mixed for 20 hours and then allowed to settle. Compared with a similar sample treated with diesel alone, these samples show less turbidity in the diesel layer.
  • FIG. 5 The results of this Example are shown in FIG. 5. As seen in FIG. 5, the spent oil- based mud diluted with diesel (far left) can be compared with the diesel-diluted oil-based mud to which crosslinked polyacrylamide particles were added (near left). These samples can be compared to those where increasing concentrations of Jeffamine XTJ-542 were added to the diesel-diluted mud with crosslinked polyacrylamide particles. Increasing amounts of the Jeffamine correlate with less turbidity in the diesel layer.
  • the 4.3 mL of oil extracted from the spent oil-based mud represents a 43% recovery of the oil originally present in the spent oil-based mud (the spent oil-based mud consists of 64% oil).
  • 15 mL of spent oil-based mud was added to 15 mL of diesel and centrifuged at 2500 rpm for 2 hours.
  • the resulting liquid layer (15.9 mL) had a turbidity above the instrument capabilities (>1000 NTU).
  • the 0.9 ml of oil extracted from the oil-based mud represents 9% of the oil originally present in the spent oil-based mud.
  • Varying amounts (10, 20, 50, 100, 200, and 400 mg) of polyethylenimine oligomer were mixed with 20 mL diesel. After vigorously shaking each of these solutions for > 1 minute, 1 mL of spent oil-based mud was added to the mixtures and further mixed for > 16 hours. The resulting mixtures were allowed to settle for > 6 days. Inspection revealed that the diesel layer was significantly less turbid as the concentration of polyethylenimine oligomer was increased. The results for each sample are shown in FIG. 6.
  • a blend of surfactants was prepared by mixing together 4.198 g of sorbitan monooleate (Span 80) and 5.802 g of Triton X-l 14 (ethoxylated nonyl phenols). Increasing amounts of this blend were added to a series of 10 samples each containing 30 g of spent oil- based mud. The first sample received 0.1 g of the blend, the second sample received 0.2 g of the blend, and each iterative sample received an additional 0.1 g of blend until 1.0 g was added to the tenth sample. Each sample was shaken by hand, mixed via vortex, and then left alone to settle overnight.
  • sorbitan monooleate Span 80
  • Triton X-l 14 ethoxylated nonyl phenols
  • the samples were observed the next day and showed that the blend caused a phase separation with two phases, an oil phase as the top phase and a mixture of oil, solids, and water in the bottom phase.
  • the blend concentration increased, the amount of free oil in the top phase increased, reaching a plateau when 0.7 g of the surfactant blend was added.
  • the top oil layer was analyzed via standard API retort method to determine the volume % of oil, water, and retort solids in a sample; the top oil was found to contain >99% oil by retort analysis.
  • a blend of surfactants was prepared by mixing together 0.397 g of Span 80
  • the fourth of the five samples received 0.7 g of a blend prepared by mixing 0.403 g of Span 80 (sorbitan monooleate) and 4.597 g of Tergitol 15-S-5 (secondary alcohol ethoxylates) (FIG. 8d).
  • the last of the five samples received 0.9 g of a blend prepared by mixing 2.944 g of Span 80 (sorbitan monooleate) and 2.056 g of Tergitol 15-S-9 (secondary alcohol ethoxylates) (FIG. 8e). Samples were mixed vigorously by hand and vortex before being left to react overnight. The next day the samples were observed.
  • the first sample looked the same as when the spent oil-based mud was first added: only one dark phase of a water-in-oil emulsion was visible.
  • the four samples treated with surfactant blends all had two distinct phases to them, a top phase with free oil and a bottom phase with oil, solids, and water.
  • the second and third samples each showed about 10 mL of oil in the top phase, while the fourth and fifth both had about 8 mL of oil in the top phase.
  • the third, fourth, and fifth samples also show a more pronounced color gradient in the bottom phase, starting from light grey at the top to a darker grey towards the bottom.
  • a tunable surfactant was synthesized in the following manner: a reactor was charged with poly(ethylene glycol) (12.82 g, 32 mmol) and Eka SA 210 (22.58 g, 64 mmol). The mixture was stirred for about 3 hours at 130 degrees Celsius under nitrogen, then cooled to ambient temperature. [00109] Example 17
  • Sample 2 showed clear separation into three phases: the top phase ( ⁇ 15 mL) was an oily phase that consisted of 90% oil; the middle phase ( ⁇ 5 mL) was an aqueous phase, the bottom phase is a thick oily sludge, containing oil, water and solids (right vial in FIG. 9).
  • the fourth sample was left to settle for three hours after mixing and then put in the centrifuge (2000 RPM for 2 minutes).
  • the oil-based mud separated into two phases for each sample, one phase with just free oil on the top and a second phase that was a thicker mix of oil, solids, and water.
  • the reaction of the blend with the mud stopped, showing no new liberated oil when left to react. This may be explained by the centrifuge's separating the components of the surfactant blend from each other, so that they could not continue reacting with the mud.
  • Each sample received 0.6 g of a surfactant blend prepared by mixing 14.691 g of Span 80 and 20.309 g of Triton X-l 14. Each sample was shaken vigorously by hand and then left to settle. The first sample was allowed to settle for only 1 minute before being put in the centrifuge (1000 RPM for 1 minute). The second sample was allowed to settle for about 15 minutes before being put in the centrifuge (1000 RPM for 1 minute). The third sample was allowed to settle for 15 minutes longer than the second sample before being put in the centrifuge (1000 RPM for 1 minute). Each consecutive sample was allowed to settle 15 to 45 minutes longer than the previous sample before being put in the centrifuge (1000 RPM for 1 minute each).
  • the resulting effects were that the oil-based mud separated into two phases, one phase with just free oil on the top, and a second phase that was a thicker mix of oil, solids, and water.
  • the reaction of the blend with the mud stopped, showing no new liberated oil when left to react. This may be explained by the centrifuge's separating the components of the surfactant blend from each other, so that they could not continue reacting with the mud.
  • a blend of surfactants was prepared by mixing together 397 g of Span 80 and 603 g of Tergitol 15-S-7. 2.9 mL of this blend were added to each of 6 different containers of the same spent oil-based mud. All 6 samples contained 200 g of spent oil-based mud. After the blend was added the samples were mixed with an overhead mixer for 1 minute and then left to sit for 10 minutes.
  • the 1st sample then received 2 g of polypropylene fibers, the 2nd sample received 1 g of polypropylene fibers, the 3rd sample received 0 g of polypropylene fibers, the 4th sample received 2 g of polypropylene fibers, the 5th sample received 1 g of polypropylene fibers, and the 6th sample received 0 g of polypropylene fibers.
  • the fibers were added to the samples while being mixed with an overhead mixer. Once the fibers were completely mixed into the sample the overhead mixer remained on and a polymer solution was added to each sample.
  • the polymer solution was prepared by dissolving 1% of SNF EM640CT emulsion polymer in water.
  • the 1st sample, the 2nd sample, and the 3rd sample received 9.1 mL of 1% EM640CT.
  • Each sample was mixed aggressively for 10 seconds after the polymer solution was added and then mixed slowly for another 30 seconds. The mixer was then removed and the samples observed.
  • An aqueous surfactant solution was prepared by mixing 5 g of Igepal CO-520 with 95 g of water. This surfactant solution was added to two separate oil-based drilling fluid samples.
  • the 1st sample was prepared by adding 20 g of an oil-based drilling fluid to a vial.
  • the 2nd sample was prepared by adding 20 g of an oil-based drilling fluid and then 0.2 g of polypropylene fibers to the vial. Both sample vials were shaken aggressively before and after adding 10 g of the surfactant solution to each sample vial. Each sample then received 0.2 mL of 6% EM640CT polymer solution and was mixed via vortex. The samples were observed overtime as they reacted.

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Abstract

La présente invention concerne le traitement de boues à base d'huile épuisées et la séparation d'émulsions d'eau dans l'huile. L'invention concerne la déstabilisation de formulations pour émulsion inverse, comprenant un additif de traitement, l'additif de traitement étant choisi dans le groupe composé de substances hydroscopiques, de désactivateurs de tensioactifs et de polymères modificateurs. L'invention concerne également des procédés de déstabilisation d'une émulsion d'eau dans l'huile contenant un tensioactif et des procédés de traitement d'une boue à base d'huile épuisée comprenant une émulsion d'eau dans l'huile.
PCT/US2014/061492 2013-10-21 2014-10-21 Procédés et formulations pour le traitement de fluides à base d'huile Ceased WO2015061262A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020257099A1 (fr) 2019-06-20 2020-12-24 Baker Hughes, A Ge Company, Llc Additif de microémulsion à phase unique pour la séparation d'huile et d'eau
CN113939481A (zh) * 2019-01-29 2022-01-14 施化技术有限公司 一种从废污泥中回收烃类化合物的方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4525496A (en) * 1981-07-17 1985-06-25 The Dow Chemical Company Self-inverting water-in-oil emulsions of water-soluble polymers
US7033493B2 (en) * 2000-12-27 2006-04-25 Stockhausen, Inc. Method and apparatus using super absorbent polymers for dehydration of oil
US7273892B2 (en) * 2001-11-16 2007-09-25 Institut Francais Du Petrole Reversible stabilized emulsion and method for stabilizing and/or destabilizing an emulsion
US20110100402A1 (en) * 2009-10-20 2011-05-05 David Soane Tunable polymeric surfactants for mobilizing oil into water

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4525496A (en) * 1981-07-17 1985-06-25 The Dow Chemical Company Self-inverting water-in-oil emulsions of water-soluble polymers
US7033493B2 (en) * 2000-12-27 2006-04-25 Stockhausen, Inc. Method and apparatus using super absorbent polymers for dehydration of oil
US7273892B2 (en) * 2001-11-16 2007-09-25 Institut Francais Du Petrole Reversible stabilized emulsion and method for stabilizing and/or destabilizing an emulsion
US20110100402A1 (en) * 2009-10-20 2011-05-05 David Soane Tunable polymeric surfactants for mobilizing oil into water

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113939481A (zh) * 2019-01-29 2022-01-14 施化技术有限公司 一种从废污泥中回收烃类化合物的方法
WO2020257099A1 (fr) 2019-06-20 2020-12-24 Baker Hughes, A Ge Company, Llc Additif de microémulsion à phase unique pour la séparation d'huile et d'eau
EP3986589A4 (fr) * 2019-06-20 2023-03-08 Baker Hughes, a GE company, LLC Additif de microémulsion à phase unique pour la séparation d'huile et d'eau

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