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    • 专利摘要:
    reuse of fluids containing surfactant. components of fluids loaded with surfactant, such as those used in hydrocarbon recovery operations such as for stimulation, for example, hydraulic fracture, can be reused and recycled into components for subsequent use in a wide range of different or similar operating fluids. in particular, aqueous fluids gelled with viscoelastic surfactants and having components there for pseudo-crosslinking of elongated micelles and for internal disruption can be separated into their component parts through relatively baroque processes such as filtration. a filtration process includes contacting a fluid containing a surfactant with a particle package having a particulate additive there that filters or extracts fine solids from the fluid. in an alternative embodiment the fluid charged with surfactant is a nano- and / or micro-emulsion well cleaning fluid.
    公开号:BR112012017732B1
    申请号:R112012017732
    申请日:2010-12-21
    公开日:2019-12-17
    发明作者:B Crews James；Huang Tianping
    申请人:Baker Hughes Inc；
    IPC主号:
    专利说明:

    Descriptive Report of the Invention Patent for PROCESS FOR FILTERING A FLUID UNDERSTANDING WATER, AT LEAST ONE SURFACTANT AND FINE SOLIDS.
    Technical Field [001] The present invention relates to processes and compositions for reusing components of fluids containing surfactants and other components, and more particularly, in a non-limiting embodiment, to processes and compositions for separating and reusing components of fluids containing surfactant, such as by passing fluid through a particle pack to filter at least one component of it.
    Background [002] Operating fluids are well known to be used in a variety of functions including, but not necessarily limited to, hydrocarbon recovery operations. For example, the DIAMOND FRAQ fluid system available from Baker Oils Tools is a water-based fluid that is gelled or increased in viscosity using a non-ionic viscoelastic surfactant (VES). This fluid is designed for hydraulic fracturing of dry gas and oil sandstone reservoirs where minimizing damage formation and maximizing permeability retained in gravel and proppant gravel (proppant) is of importance. The DIAMOND FRAQ fluid system contains additives for pseudo-crosslinking of elongated VES micelles that render the fluid its viscosity, as well as internal breakers to reduce fluid viscosity after fracture is complete. CLEARFRAC is a polymer free of fracture fluid available from Schlumberger that also contains viscoelastic surfactants.
    [003] Other charged fluids - surfactant for use in hydrocarbon recovery operations include, but are not necessarily limited to, Baker Hughes Drilling Fluids MICRO-WASH
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    High Definition Remediation (HDR) system that are used to treat seriously damaged reservoirs, where production or injection rates often decline to the point where the well is no longer a viable property. Many of these reservoirs have been damaged by natural emulsions, fine particles or interaction with oil-based drilling fluids. Regardless, the result is often a deficit in production and a lack of return on investment.
    [004] The Baker Hughes Drilling Fluids MICROPRIME spacer system is technology designed to optimize the well cleaning process when displacement drilling fluids are used before the completion process. Competent well cleaning is required since the removal of mud and solids is essential for successful completion of the well. The spacer system uses advanced mesophase technology that will clean and moisten all surfaces with water, even at high levels of contamination with synthetic mud or oil. The MICRO-PRIME spacer system also contains surfactants, and like the other fluids containing surfactants discussed, you can benefit from a process for reusing some or all of the components in them.
    [005] Many methods and processes are known to clean, purify, lighten and otherwise treat fluids to separate their components for reuse, proper disposal of components that cannot be reused, consumption, use, and other needs. These processes include, but are not necessarily limited to, centrifuging and filtration to remove particles, chemical treatments to sterilize water, distillation to purify liquids, decantation to separate two phases of fluids, reverse osmosis to desalinate liquids, electrodialysis to desalinate liquids, pasteurization to sterilize food, and catalytic processes to convert unwanted reagents into useful products. Each of these products is well suited
    Petition 870190094064, of 9/19/2019, p. 8/38
    3/25 for particular applications and typically a combination of processes is used to reuse or recover fluid components. [006] Industrial liquids containing viscoelastic surfactant compositions can be reversibly thickened and broken according to US patent 4 735 731. For example, a thickened industrial liquid can exhibit good capacity for transporting solids, and after the liquid's viscosity is broken, using techniques like changing pH, adding a hydrocarbon, changing temperature, etc., solids can be easily removed from it. The viscosity can be fed back to the industrial liquid without the need to add substantial amounts of additional thickener. Removal of liquid solids by filtration for liquid reuse or use of solids is shown.
    [007] It has also been found that packets of particles treated with nanoparticles, such as sand beds, can effectively filter and purify liquids such as wastewater. These packages and beds and processes for using them are described in US patent application publication 2009/0266766 (the patent application related to this). When fine contaminant particles in dumping water flow through the particle pack, the nanoparticles in the pack will capture and retain the fine contaminant particles within the pack due to surface forces from nanoparticles, including, but not necessarily limited to, van der Waals and electrostatic. Coating agents such as water, brine, alcohols, glycols, polyols, solvents, vegetable oil, mineral oils can help apply nanoparticles to particle surfaces in the beds or filter packs.
    [008] However, it can be advantageous if fluids loaded with surfactants that were used once can be reused and the components recycled in similar or different fluids with subsequent utility.
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    4/25
    SUMMARY [009] A process for filtering a fluid comprising water, at least one surfactant and fine solids is provided, in a non-limiting way, where the process includes contacting the fluid with substrate particles transporting or supporting over the same additives in comparatively smaller particles. The substrate particles (with the particulate additives on them) are optionally formed in a particle package, such as a bed of sand, in a non-limiting embodiment. At least a portion of the fine solids can be removed to yield a filtered fluid containing the surfactant. Particle additives are present in an effective amount to remove at least a portion of the fine solids.
    Representative but not restrictive forms of particle packs for fluid purification include a plurality of substrate particles that have been treated with a particulate additive, which are comparatively or relatively smaller than the substrate particles. The particles in the particle pack may include, but are not necessarily limited to, sand, gravel, ceramic beads, glass beads, and combinations thereof. The particulate additive can have an average particle size of 1000 nm or less, and are therefore sometimes called nanoparticles or nanoparticles. The nanoparticle additive may include, but is not necessarily limited to, alkaline earth metal oxides, alkaline earth metal hydroxides, transition metal oxides, transition metal hydroxides, post-transition metal oxides, postransition metal hydroxides, crystals piezoelectric, and / or pyroelectric crystals. The nanoparticles can be present in an amount ranging from about 1 part of particulate additive to 200 to 5000 parts by weight of substrate particles in the particle pack.
    Petition 870190094064, of 9/19/2019, p. 10/38
    5/25 [0011] Particulate additives, here also referred to as nano-sized particles, or nanoparticles (for example, MgO and / or Mg (OH) 2, and the like), appear to fix, bind, or otherwise capture fine solids in the fluid charged with surfactant, such as clay and non-clay particles, including charged and uncharged particles, and organic and inorganic particles. Due to their small size, at least in part, the surface forces (eg van der Waals and electrostatic forces) of nanoparticles help them to associate, group or flocculate fine solids together in larger collections, associations or agglomerations, that are retained in the particle pack. These surface forces are large in relation to the small volumes of particulate additives. Such clusters or associations help to capture the fine solids and contaminants in place and prevent them from moving and passing through the liquid, resulting in a separate liquid, which nevertheless still contains the surfactant. Thus, in many cases, the ability to filter or separate the particle pack can be improved through the use of nano-sized particulate additives that can be relatively much smaller in size than the fine filtered solids.
    [0012] The addition of alkaline earth metal oxides, such as magnesium oxide; hydroxides of alkaline earth metals, such as calcium hydroxide; transition metal oxides, such as titanium oxide and zinc oxide; transition metal hydroxides; oxides of post-transition metals, such as aluminum oxide; post-transition metal hydroxides; piezoelectric crystals and / or pyroelectric crystals like ZnO and AlPO4, to an aqueous fluid, a solvent-based fluid such as glycol, or oil-based fluid, for example, mineral oil, can be used to treat substrate particles, such as a bed of sand to create a package of particles, which in turn is expected to filter and separate the fine solids from the fluid charged with surfactant passing through the
    Petition 870190094064, of 9/19/2019, p. 11/38
    6/25 even.
    DETAILED DESCRIPTION [0013] It has been found that fluids loaded with surfactants, such as the DIAMOND FRAQ fluid system gelled with a VES and containing internal breakers and additives for pseudo-cross-linking of elongated VES micelles, can further be reusable, created by VES . The agents added to the VES fluid can be separated from a recovered gelled - VES fluid, particularly through inexpensive filtration processes. For example, internal breakers such as mineral oil products can be selectively removed by filtration from a recovered DIAMOND FRAQ fluid system, where with removal, the fluid containing VES can be returned for use again. This use process can be particularly economical for packages - fract and conventional fracture, where large volumes of fluids containing VES are used. The VES fluid can also be polished to remove other solids and hydrocarbons, if necessary. Reuse can possibly be more selectively economical where repeated fracture treatments over the same well will be carried out, and / or for wells close to being hydraulically fractured. This technology differs from previous processes by allowing internal breakers and pseudo-crosslinking particles to perform their particular function, and where the broken VES fluid is made more easily recoverable from the treated reservoir, that is, it is in its broken state of viscosity. similar to water. Furthermore, agents, such as internal breakers, can be easily absorbed through selective filtration to allow the fluid containing VES to be reused.
    [0014] Similarly, other fluids containing surfactants such as ClearFRAC fracture fluid, ClearPAC gravel pack fluid, sis
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    7/25 high definition remediation (HDR) theme, and MICRO-PRIME spacer system can also have its components recovered and processed and engineered to have a wider range of reuse. As fluids containing VES, a large amount of surfactants are present in the counterflow fluid from the use of MICROWASH and MICRO-PRIME systems, even though these are not viscoelastic fluids but aqueous cleaning fluids. In other non-limiting examples, well forming solids and other components can be removed from fluid loss control pills, gravel pack fluids, drilling fluids, formation and well cleaning fluids, autoswitch acids, and fluids. acid diversion, bottom cleaning equipment cleaning fluids, cementation spacers, spiral pipe washes, and similar fluid systems containing surfactant. Various filtration and separation processes can be used to recondition these fluids. Additional components can then be added before reuse according to known processes and technologies. Engineering of reusing fluids loaded with surfactant can also help to reduce the concepts of environmental disposal and net cost for operators. That is, less total material requiring disposal.
    [0015] The processes described here can also be used to filter fluids containing surfactants where the surfactant is different from a viscoelastic surfactant, for example, a detergent. Such aqueous fluids containing detergents and fine solids (the latter of which are to be removed) include, but are not necessarily limited to, well fluids, reservoir cleaning fluids, and the like. The surfactant may alternatively be or additionally be or additionally include emulsifiers.
    [0016] Filtration may or may not be a process for conditioning fluid for reuse, but in most cases it is expected
    Petition 870190094064, of 9/19/2019, p. 13/38
    8/25 be a part of conditioning by removing fine solids that can create formation damage. In particular, any formation fines that may create formation damage in a subsequent treatment or application can be removed. Use of nano-sized particles to fix formation fines within an underground formation is shown in U.S. patent application 2009/0312201. A somewhat related technology for fixing formation fines within proppant packages using nano-sized particle-coated propellants is shown in U.S. Patent 7,721,803.
    [0017] The processes here can use filtration mechanisms such as those described in the immediately preceding paragraph on packages or beds of sand, ceramic particles or diatomaceous earth (DE unit). For example, if a fine solid type nanoparticle fixation filtration process is used, a counterflow fluid charged with a nano- and / or micro-emulsion surfactant may have an altered composition. For example, removing components possibly added to the fluid during use as a drilling mud cleaning fluid (for example, bentonite, calcium carbonate, and barite). The nano- and / or micro-emulsion components can be engineered or reshaped into fluids for other applications at the well site including, but not limited to, a) second use as a spacer / wash ahead of cement during casing cementation; b) adding acid and using the resulting composition as an acidulating matrix fluid; c) addition of acid and use of the resulting composition for acid fracture of carbonate reservoirs; d) adding acid and using the resulting fluid when drilling to assist drilling and the region near the well (or just a fluid that is easier to flow back after a super-balanced drilling operation);
    e) dilution of fluid, and use of the resulting composition with a slickwater; or f) as a pre-wash and / or post-wash in front of and / or behind,
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    9/25 respectively, of a crosslinked polymer fluid or treatment with VES fluid. (Slickwater can also be used as a lower-friction-pressure placement fluid or slick water fracture, any of which involves adding chemical compounds to increase fluid flow and fluid recovery; slickwater formulation may involve injection of a or more components such as friction reducers, fluid loss control agents, viscosity builders, viscosity breakers, biocides, clay stabilizers, surfactants, microemulsions, and scale inhibitors). Generally speaking, these are engineering reuse applications.
    [0018] Alternatively, in some embodiments, even those using a viscoelastic surfactant to gel the fluid, it is not necessary to have an internal breaker to break the fluid, that is, there is an absence of an internal breaker. Such fluids can be disrupted by diluting with aqueous fluids from the formation or otherwise, or through contact with forming hydrocarbons, or through some other process.
    [0019] As discussed earlier, U.S. Patent 7,721,803 demonstrates that some nanoparticles coated on propellants through mineral oil or glycol can fix formation fines in the fracture proppant bed or gravel package. In a somewhat similar manner, U.S. patent application 2009/0266766 shows a process and composition for using a nanoparticle-treated sand bed to purify wastewater.
    [0020] In more detail, nano-sized particles like magnesium oxide (MgO) can be used to fix or filter fine solids like clay, feldspars, calcium carbonate, barite, and quartz in packages or beds of particles to inhibit, restrict or prevent them from moving with the fluid loaded with surfactant. Some nano-sized particles, here also called nanoparticles, not only have high
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    10/25 compared surface areas and their small sizes, but they also have relatively high surface charges that allow them to associate or connect other particles together, including other charged particles, but also other uncharged particles. In a non-limiting embodiment, these associations or connections between fines and nano-sized particles are due to electrical attractions and other intermolecular forces or effects.
    [0021] Laboratory tests have shown that relatively small amounts of MgO nanoparticles can fix and flocculate dispersed clay particles and charged and unloaded colloidal silicas. Other nanoparticles such as ZnO, AbO3, zirconium dioxide (ZrO2), TiO2, cobalt (II) oxide (Côo), nickel (II) oxide (NiO), and piezoelectric and pyroelectric crystals can also be used in the present processes and compositions.
    [0022] The nanoparticles can be directly placed or coated dry on particles of substrate or sand in a package or bed or coated on the substrate using a coating agent to filter out fine solids during these separation and recycling procedures. In one embodiment, a mixture of a coating agent and nanoparticles at least partially coats the selected substrate particles to filter out fine solids within a particle package or other porous media, or to separate the fine moving solids with the surfactant-containing fluid being filtered. If substrate particles are at least partially coated with the coating agent and the nanoparticles, then the fine solids can be kept within the particle package and thus filtered from the treated fluid.
    [0023] The base fluid or fluid carrier of the fluid being treated by the present processes (that is, spent or used treatment fluids
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    11/25 such as fracture fluids, gravel pack fluids, spacer fluids, well cleaning fluids, proppant cleaning fluids, filtration bed cleaning fluids, and the like) can be based on water, alcohol-based, solvent-based or oil-based, but in more expected realizations it is expected to be water-based. The carrier fluid or water-based fluid can be brine. In non-limiting embodiments, brines can be prepared using salts including, but not necessarily limited to, one or more of NaCl, KCl, CaCl2, MgCl2, NH4Cl, CaBr2, NaBr, sodium formate, potassium formate, and other brine salts of commonly used stimulation and completion. The concentration of salts to prepare the brines can be from about 0.5% by weight of water to near saturation for a given salt in fresh water, such as 10%, 20%, 30% and a higher percentage of salt by weight of water. The base fluid or carrier fluid may also include components typical for treatment fluids, such as salts, oxidants, enzymes, polymers, crosslinkers, pH buffers, surfactants, viscoelastic surfactants, corrosion inhibitors, scale inhibitors, chelators, biocides, preservatives , dispersants, antioxidants, reducing agents, sugars, alcohols, mutual solvents, defoamers, friction reducers, metals, resins, curing agents, non-emulsifiers, relative permeability modifiers, gas hydrate inhibitors, and the like.
    [0024] Suitable nanoparticle coating agents, optionally used to assist particulate additives (eg, nanoparticles) to adhere to substrate particles (eg, sand) include, but are not necessarily limited to, water, brine, alcohols , glycols, solvents, mineral oil or other hydrocarbons that accomplish the purposes of the processes and compositions described herein. Specific, non-limiting examples of suitable mineral oils include ConocoPhillips PURE PERFORMANCE Base Oil, such as 225N oils
    Petition 870190094064, of 9/19/2019, p. 17/38
    12/25 and 600N; ConocoPhillips ULTRA-S oils, such as ULTRA-S 2, and ULTRA-S 4; Penreco DRAKEOL oils, such as DRAKEOL 21, DRAKEOL 35 and DRAKEOL 600; and mineral oils ExxonMobil EXXSOL and NORPAR, such as EXXSOL 80, EXXSOL 110, NORPAR 12 and NORPAR 15. Non-limiting examples of alcohols include, but are not necessarily limited to, methanol, ethanol, propanol and the like. Non-limiting examples of glycols include, but are not necessarily limited to, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, and the like. Non-limiting examples of polyols include, but are not necessarily limited to, solutions of sorbitol, mannitol, fructose, glucose, galactose, lactose, sucrose, xylitol, maltitol, glycerol, and the like. Examples of alkyl carbonates include, but are not necessarily limited to, propylene carbonate and ethylene carbonate. Examples of organic solvents include, but are not necessarily limited to, xylene, toluene, acetone, methyl acetate, ethyl benzoate, limonene, and the like. It is expected that a package of sufficient filtration particles will include nanoparticles in the coating agent oil, for example, about 1 to 15% by weight of nano-sized MgO particles in the 600N mineral oil. This coating composition can be used alone or can be added to an aqueous based fluid in a relatively small amount, in a non-limiting embodiment, from about 5 to about 100 gptg. It has been found that during mixing, the particulate additive composition (for example, nanoparticles in oil) will at least partially coat or coat the substrate particles, such as sand. That is, in cases where the base fluid is aqueous, the hydrophobic oil will be repelled by water and will coat the substrate particles (for example, gravel, ceramic beads, etc.). How much particle coating occurs is dependent on concentration, base
    Petition 870190094064, of 9/19/2019, p. 18/38
    In both, the amount of substrate particles used and the amount and type of the relatively smaller particulate additive used. In a non-limiting example the coating composition may additionally have a surfactant present, such as a humectant surfactant - oil such as sorbitan monooleate (i.e. SPAN 80 from Uniqema), to improve and / or increase wetting - oil of the substrate particles through particulate additives. In another non-limiting example, the presence of a surfactant can preferably reduce the thickness of the 600N mineral oil layer on the substrate particles. A reduced oil layer thickness can improve exposure of nanoparticles on substrate particles. Agents other than SPAN 80 can be employed for coating optimization or oil wetting on substrate particles, agents including, but not necessarily limited to: sorbitan esters, ethoxylated sorbitan esters, ethoxylated alcohols, ethoxylated alkyl phenols, dicarboxylic alkyls, sulfo succinates, phospholipids, alkyl amines, quaternary amines, alkyl siloxanes, and the like. It is not necessary for a resin to be used as a coating or binder, and in a non-limiting embodiment, no resin is used.
    [0025] For bed or particle pack refill, there may be cases where an oil, even the most environmentally acceptable oils, such as pharmaceutical grade mineral oil or food grade plant oils, may not be desired for retreatment (ie, new coating) ) of a bed or package of particles with nano particles. In such cases other coating agents can be used, which include, but are not limited to: water, brines, glycols, alcohols, polyols, syrups, and combinations thereof. In non-limiting examples, brines including KCl 2% bw, KCl 9% bw, CaCl2 21% bw and the like can be used. Non-limiting examples of glycols include monopropylene glycol,
    Petition 870190094064, of 9/19/2019, p. 19/38
    14/25 dipropylene glycol, monoethylene glycol, and the like. Non-limiting examples of alcohols include propanol, ethanol, methanol and the like. Non-limiting examples of polyols include mannitol, sorbitol, glycerol, xylitol and the like. Non-limiting examples of syrups include corn syrup, cane syrup, sorghum syrup, and the like.
    [0026] It is theorized that nanoparticles remain on substrate particles mainly through electrostatic charges and others between the surfaces of substrate particles and nanoparticles, however, other attractions or coupling forces may exist to initially and over the long term maintain the nanoparticles coated on the substrate particles. The inventors do not wish to be limited to any particular theory. It is suspected that in most conditions the oil carrier fluid only assists the initial coating process of the nanoparticles on the substrate particles. However, other agents can be added to the carrier fluid, oil that can further improve the initial and / or long-term attraction of nanoparticles for the composition of quartz, glass, ceramic and similar substrate particles. In addition, the surface of the substrate particles, or a selected amount of substrate particles, can be treated with agents that can enhance the total attraction of nanoparticles to the substrate particles.
    [0027] Nano-sized particles of alkaline earth metal oxides, alkaline earth metal hydroxides, transition metal oxides, transition metal hydroxides, post-transition metal oxides, and post-transition metal hydroxides, piezoelectric crystals, pyroelectric crystals, and their mixtures have been found to have particular advantages for at least partial removal of fine solids from the fluid being filtered. Specific types of particles in each of these categories are noted below and elsewhere, but it will be appreciated that any compound in these categories that can perform the functions
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    15/25 required is included here although it was not specifically mentioned.
    [0028] Magnesium oxide particles and sprays have been appropriately used to remove fine solids. However, it will be appreciated that although MgO particles are noted throughout the present description as a representative or appropriate type of alkaline earth metal oxide and / or alkaline earth metal hydroxide, other alkaline earth metal oxides and / or hydroxides of alkaline earth metals and / or transition metal oxides, transition metal hydroxides, post-transition metal oxides, and post-transition metal hydroxides, piezoelectric crystals, pyroelectric crystals, can be used in the present processes and compositions. In addition, alkali metal oxides and / or hydroxides can be used alone or in combination with alkaline earth metal oxides and hydroxides, and / or together with one or more transition metal oxides, transition metal hydroxides, post-transition metals, post-transition metal hydroxides, piezoelectric crystals and pyroelectric crystals.
    [0029] For post-transition metal, one or more aluminum, gallium, indium, tin, thallium, lead and bismuth are intended. In another non-limiting realization, the nano-sized particles are oxides and hydroxides of elements from groups IIA, IVA, IIB and IIIB from the previous notation of Grupo Americano IUPAC. These elements include, but are not necessarily limited to, Mg, Ca, Ti, Zn and / or Al.
    [0030] The nano-sized particle additives here can also be particles of piezoelectric crystals (which include particles of pyroelectric crystals). Pyroelectric crystals generate electrical charges when heated and piezoelectric crystals generate electrical charges when tightened, compressed or pressed.
    [0031] In a non-limiting realization, specific particles of
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    16/25 Appropriate piezoelectric crystals may include, but are not necessarily limited to, ZnO, berlinite (AlPO4), lithium tantalate (LiTaO3), gallium orthophosphate (GaPO4), BaTiO3, SrTiO3, PbZrTiO3, KNbO3, LiNbO3, LiNbO3, LiN , sodium tungstate, Ba2NaNb5O5, Pb2KNb5O15, potassium sodium tartrate, tourmaline, topaz and their mixtures. The total pyroelectric coefficient of ZnO is -9.4 C / m 2 K. ZnO and these other crystals are generally not soluble in water.
    [0032] In a non-limiting explanation, when the aqueous carrier fluid mixed with very small piezoelectric crystals, such as nano-sized ZnO, is used in conditions of high temperature and / or pressure, the pyroelectric crystals are heated and / or pressed and high surface loads are generated. These surface charges allow the crystal particles to associate, bond, connect, or otherwise relate the fine solids together to fix them together and also to the surrounding substrate surfaces. The association or relationship of fine solids is thought to be very roughly analogous to the crosslinking of polymer molecules by crosslinkers, in a non-limiting image.
    [0033] In a non-limiting embodiment, the nano-sized solid particles and powders useful herein include, but are not necessarily limited to, alkaline earth metal oxides, or alkaline earth metal hydroxides, or mixtures thereof. In a non-limiting embodiment, the alkaline earth metal in these additives may include, but is not necessarily limited to, magnesium, calcium, barium, strontium, combinations thereof and the like. In a non-limiting embodiment, MgO can be obtained in high purity of at least 95% by weight, where the balance can be impurities such as Mg (OH) 2, Dog, Ca (OH) 2, SiO2, Al2O3, and the like.
    [0034] In an alternative embodiment, nano-sized particulate additives may have a second attraction or function utility
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    17/25 retention that can further improve which materials can be removed from or exchanged in the base fluid to be reused; that is, after adding nanoparticles on the particulate substrate, another second or alternative functional particle can be attracted to and uniquely retained by the nanoparticle coating. Non-limiting examples are zeolites, activated carbon, nanofibers, carbon nanotubes, functionalized carbon nanotubes, graphene, graphene oxide, functionalized graphene or graphene oxide, functionalized clays, gold, silver, palladium, platinum metal particles and the like in size nano, metal doped zeolites, alkaline earth metal peroxides, and the like and their combinations. The second or alternative functional particle retained by solid particles of nano size may have a useful range for engineering reuse of the carrier carrier fluid to be filtered; such as selecting polymer and / or hydrocarbon removal, polymer and / or hydrocarbon alteration, biofilm prevention, assisting removal of organic particles, selecting cation removal, and the like.
    [0035] In another non-limiting embodiment, the average particle size of the additives in particles and agents is 1000 nm or less and alternative ranges between about 1 nanometer independently up to about 500 nanometers. In another non-limiting embodiment, the average particle size varies between about 4 nanometers independently up to about 500 nm, alternatively up to about 100 nanometers. In another non-restrictive version, the particles may have an average particle size of about 250 nm or less, in a different version about 100 nm or less, alternatively about 90 nm or less, and in another possible version about 50 nm or less, alternatively 40 nm or less. Within the present context, independently and alternatively they mean that any lower limit can be combined with any upper limit
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    18/25 for a particular type of track.
    [0036] The amount of nano-sized particles in the carrier fluid can vary from about 20 to about 500 pptg (about 2.4 to about 60 kg / 1000 liters). Alternatively, the lower limit of the proportion range can be about 50 pptg (about 6 kg / 1000 liters), while the upper limit of the particle proportion can independently be about 300 pptg (about 36 kg / 1000 liters).
    [0037] The present nano-sized particles can be added to a mineral oil or other hydrocarbon as the carrier fluid - a synergistic combination that also serves to initially coat, or at least partially coat, the nanoparticles for the sand particles or substrate, which are then placed or formed into a particle pack. In another non-limiting embodiment, the present nano-sized particles coated on substrate particles, beads or sand can be added to an aqueous fluid during a treatment. In a non-limiting embodiment, the substrate particles carrying the additives in comparatively smaller particles can be passed through fluid to be filtered in addition to or alternatively to the fluid passage over a particle pack or bed. For refilling substrate particles already in place, a variety of treatment fluids can be used with a variety of components. For example, to re-treat substrate particles in a bed, a light brine containing nanoparticles can be used. Optionally, additives such as surfactants, polymers, and the like can be used in the retreatment fluid.
    [0038] It has been found that nano-sized particles such as MgO can be used to remove contaminants such as clay and non-clay particles from liquids, that is, to remove, reduce or rid them of being present in the fluid, such as Like water. Again, al
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    19/25 some nanoparticles not only have comparatively high surface areas and their small sizes, but also have relatively high surface charges that allow them to associate, bind or connect other particles together, including other charged particles, but also other non- loaded. In a non-limiting embodiment, these associations or connections between the contaminating particles and the nano-sized particles are due to electrical attractions and other intermolecular forces or effects as noted earlier.
    [0039] Laboratory tests have shown that relatively small amounts of MgO nanoparticles can remove and separate dispersed clay particles from a fluid containing a surfactant. These are the same types of nanoparticles previously described with regard to fixing fines.
    [0040] The nanoparticles can be applied as a dry powder directly to and placed on and in a package of dry substrate particles. Alternatively, nanoparticles can be added and suspended in water to be placed on and in a wet or dry substrate package. In one embodiment, a mixture of a coating agent and nanoparticles at least partially covers the selected bed of sand or other porous media (substrate particles). If sand or gravel is at least partially coated with the coating agent and the nanoparticles, then contaminants and impurities can be removed from the fluid, for example, used fracture fluid that has had reduced or broken viscosity, sludge cleaning fluid. perforation of recovered nano- and / or microemulsion, washing fluid / cement spacer recovered, and thus contaminants and impurities can be eliminated or reduced by purifying the recovered treatment fluid.
    [0041] The amount of nano-sized particles in the material
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    20/25 package or ceramic bed or sand can be from about 1 pound of nanoparticles to about 200 pounds to 5000 pounds of sand. It will be appreciated that any other unit of weight can be used, for example, from about 1 gram of nanoparticles to about 200 grams to 5000 grams of sand. In an alternative embodiment, the nanoparticles are present in an amount of about 1 part by weight of nanoparticles to about 1000 independently to about 2000 parts of ceramic or sand package material.
    [0042] The present nano-sized particles can be added to water, a glycol, alcohol, polyol, olefin, vegetable oil, fish oil, or mineral oil, or mixtures of these, such as the carrier fluid, a combination that also serves to coat initially, or at least partially coat, the nanoparticles for ceramic beads or sand. In another non-limiting embodiment, the present nano-sized particles coated on ceramic particles or sand can be added to an aqueous fluid during a treatment. [0043] Particles of sand, ceramic, glass or other substrate in the optional package or bed can have an average particle size of about 10 mesh to about 325 mesh (about 2000 microns to about 45 microns), in a non-limiting realization. Alternatively, the substrate particles can vary in size from about 20 mesh independently to about 200 mesh (from about 850 microns independently to about 75 microns). The substrate particle size range can be wide, such as from about 40 mesh to about 200 mesh (from about 425 microns to about 250 microns), or the particle size range can be relatively narrow, such as as from about 20 mes to about 40 mesh (from about 850 microns to about 425 microns).
    [0044] Laboratory tests have shown that nanometer MgO particles and monopropylene glycol (PG) coated on a package
    Petition 870190094064, of 9/19/2019, p. 26/38
    21/25 20/40 mesh sand (850/425 microns) can successfully remove contaminants from waste water.
    [0045] Although the present processes and structures are sometimes described here typically as having use in waste water fluids, such as those for paper processing, the compositions and processes are also expected to be useful in oil field recovery, for example example, formation water produced, exhausted drilling muds, metalworking, agricultural operations, mining operations, environmental remediation operations, dumping operations, cleaning operations, manufacturing operations and the like.
    [0046] The regeneration, recovery, or recharge of substrate particles carrying nanoparticles, whether or not they are structured in substrate beds or sand packages, involves a one-step and optionally two-step acid treatment. One objective is to remove substantially the nanoparticles or other particulate additives, including the fine solids or contaminants on them, that is, associated with the substrate particles or the sand through the action of the nanoparticles. By removing substantially at least 50% of the nanoparticles and / or the fine / contaminating solids, in a non-limiting embodiment, alternatively at least 75% of the nanoparticles and / or the fine / contaminating solids, and in another non-restrictive version by least 95% of nanoparticles and / or fines / contaminants. Of course, removal of all (100%) nanoparticles and / or fines / contaminants may be desirable last, but this may not be practical due to difficulties in ensuring that all nanoparticles and / or fine solids / contaminants are contacted with acids. It will be appreciated that removing covers removal of nanoparticles and the fine solids / contaminants by dissolving them, as well as other chemical compounds and / or
    Petition 870190094064, of 9/19/2019, p. 27/38
    22/25 new physical demarcation processes.
    [0047] The particle pack is contacted with a first acid, which can be an inorganic acid, an organic acid, or mixtures thereof - except that hydrofluoric acid (HF) is not used. Optionally, the particle pack is subsequently contacted with a second acid that includes HF, but optionally can include any other inorganic or organic acids, even the same as those used in the first contact. HF is introduced, injected or pumped into the second bed of particles to dissolve clays and quartz and to prevent the formation of CaF2 and MgF2 precipitates.
    [0048] Suitable inorganic acids for refilling particle packs include, but are not necessarily limited to, hydrochloric acid, phosphorous acid, phosphonic acid, sulfuric acid, sulfonic acid and mixtures thereof. Suitable organic acids for refilling particle packs include, but are not necessarily limited to, acetic acid, formic acid, glutaric acid, succinic acid, and adipic acid, oxalic acid (ethanedioic acid), malonic acid (propanedioic acid), pyelic acid (heptanedioic acid), and mixtures thereof. The mixture of dicarboxylic acids, glutaric acid, succinic acid and adipic acid is known as HTO (high temperature organic) acid. Further details on HTO acid can be found in US patent 6,805,198.
    [0049] It will be appreciated that when contacting particle packets with the first acid and optional second acid therein needs to be contacted for a period of time longer than merely briefly so that the acids have time to contact and dissolve the nanoparticles and / or the particulates fine (for example, fine or contaminants). However, an exact time period for contacting any particular particle pack will vary depending on a wide variety of interdependent factors, and thus such periods are difficult to predict. For example, the nature of the particle package, including the nature
    Petition 870190094064, of 9/19/2019, p. 28/38
    23/25 of the substrate particles (for example, sand, gravel, ceramic beads, glass beads, etc.), the nature of the nanoparticles, the nature of the fine solids (for example, contaminants, etc.), the amount of the solids fine (for example, how much the particle pack is loaded, or how closed or full or saturated the particle pack is with the fine solids), the size of the particle pack, the mechanism for acid release, temperatures and pressures involved in refilling particle packets, etc., all affect soaking time. However, to provide some idea of typical soaking times for the entire acid treatment, the particle pack can contact the fluid from about 15 minutes to about 3 hours, in another non-limiting realization of about 0.5 hours about 1 hour. The soaking time for the first acid ranges from about 5 minutes to about 1 hour, and the soaking time for the second acid ranges from about 10 minutes to about 2 hours.
    [0050] How much acid is needed can be roughly estimated. For first-stage acid, the amount of nanoparticles used for pretreatment is known and the expected amount of fine solids (eg, carbonate particles) from the formation based on core analyzes can be estimated. For second-stage acid, based on the HF resistance used, one to three pore volumes (pore volume of the substrate package) of the acid are necessary or useful.
    [0051] In a non-limiting embodiment, the concentration of the acid in the first acid treatment can be about 10% or less, alternatively about 5% or less. The amount of HF in the second acid treatment is low, for example, about 2% or less, alternatively about 1% or less. However, as noted, other aci
    Petition 870190094064, of 9/19/2019, p. 29/38
    24/25 dos may also be present together with HF in the second acid treatment and these other non-HF acids may be present in an amount of about 10% or less.
    [0052] In the previous specification, it will be evident that various modifications and changes can be made without departing from the broader scope of the invention as shown in the attached claims. Likewise, the specification is to be seen in an illustrative rather than restrictive sense. For example, combinations of substrate particles, particulate additives, nanoparticles, coating agents, fluids being filtered, acid treatment conditions, refill conditions, acids, and other components and conditions falling within claimed but not specifically identified parameters or experienced in a particular process or composition, are anticipated to be within the scope of this invention. Also, when a fluid is being filtered to separate fine solids from a fluid, in particular one containing a surfactant, it is not necessary that the separation be complete (100% removal of fine solids) for the process to be considered a success, although removal as much of the fine fluid solids as possible is certainly a goal.
    [0053] The present invention may suitably comprise, consist or consist essentially of the elements shown and an element not shown can be practiced in the absence. For example, the process for filtering a fluid can consist of or consists essentially of water, at least one surfactant and fine solids, and / or the process can consist of or consists essentially of fluid contact with substrate particles carrying over the same additives in comparatively smaller particles, so removing at least a portion of the fine solids from it to yield a filtered fluid containing the surfactant, where particulate additives are present in an effective amount to remove at least one
    Petition 870190094064, of 9/19/2019, p. 30/38
    25/25 portion of the fine solids.
    [0054] The words comprising and understanding as used by all claims are to be interpreted as including but not limited to.
    权利要求:
    Claims (10)
    [1]
    1. Process for the filtration of a fluid comprising water, at least one surfactant and fine solids, the process characterized by the fact that it comprises:
    contacting the fluid with substrate particles coated with comparatively smaller particle additives on them, thus removing at least a portion of the fine solids from it to yield a filtered fluid containing the surfactant, where particulate additives are present in an amount of about from 1 part by weight of particulate additives to 200 to 5000 parts by weight of substrate particles to remove at least a portion of the fine solids from the fluid, with particulate additives:
    have an average particle size of 1000 nm or less, and are selected from the group consisting of alkaline earth metal oxides, alkaline earth metal hydroxides, alkali metal oxides, alkali metal hydroxides, transition metal oxides, metal hydroxides transition, post-transition metal oxides, post-transition metal hydroxides, piezoelectric crystals, pyroelectric crystals, and mixtures thereof; and reuse the filtered fluid containing the surfactant in an operation selected from the group consisting of:
    introducing the filtered fluid down the well into a well as a spacer or flushing fluid in front of the introduction of cement for casing cementation in the well;
    adding an acid to the fluid and introducing the filtered fluid down the well into a well to contact an underground formation as an acidulating matrix fluid;
    adding an acid to the fluid and introducing the filtered fluid down the well into a well to contact a carbonate reservoir
    Petition 870190094064, of 9/19/2019, p. 32/38
    [2]
    2/3 underground;
    adding an acid to the fluid and introducing the filtered fluid down the well into a well before, during or after drilling an underground formation to open the holes near the well;
    not necessarily in any order: dilution of the fluid, addition of a polymer to the fluid, and introduction of filtered fluid down the well into a well for slickwater fracture of an underground formation;
    introducing the filtered fluid down the well into a well as a pre-wash and / or as a post wash in front of and / or behind, respectively, introduction of a gelled fluid - crosslinked polymer and / or a VES gelled fluid; and their combinations.
    2. Process according to claim 1, characterized by the fact that the surfactant is a viscoelastic surfactant and the fluid is gelled with the viscoelastic surfactant in an effective amount to gel the aqueous fluid and the process further comprises breaking the fluid gel gelled before or simultaneously with the contact of the fluid with the substrate particles.
    [3]
    3. Process according to claim 1, characterized by the fact that the surfactant is an emulsifier and the fluid is a reservoir and / or nano- and / or micro-emulsion cleaning fluid.
    [4]
    4. Process according to claim 1, characterized by the fact that the surfactant is a detergent and the fluid is a reservoir and / or well cleaning fluid.
    [5]
    5. Process according to claim 4, characterized by the fact that:
    the alkaline earth metal is selected from the group consisting of magnesium, calcium, strontium, and barium, the alkali metal is selected from the group consisting of lithium,
    Petition 870190094064, of 9/19/2019, p. 33/38
    3/3 sodium, potassium, the transition metal is selected from the group consisting of titanium and zinc, and the post-transition metal is aluminum and its mixtures.
    [6]
    6. Process according to claim 1, characterized by the fact that the substrate particles are selected from the group consisting of sand, gravel, ceramic beads, glass beads and their combinations.
    [7]
    Process according to claim 1, characterized in that it further comprises at least partial coating of the substrate particles with a coating agent comprising a carrier fluid selected from the group consisting of water, brine, alcohol, glycol, polyol, solvents, vegetable oil, mineral oil and their combinations and the particulate additive.
    [8]
    Process according to claim 1, characterized in that the average particle size of the substrate particles varies from about 10 mesh to about 325 mesh (about 2000 microns to about 45 microns).
    [9]
    Process according to claim 1, characterized by the fact that the second functional particulate is included on the substrate particles to remove contaminants from the recovered treatment fluid.
    [10]
    10. Process according to claim 9, characterized by the fact that the second functional particulate is selected from the group consisting of zeolites, activated carbon, nanofibers, carbon nanotubes, functionalized carbon nanotubes, graphene, graphene oxide, functionalized graphene or graphene oxide, functionalized clays, gold, silver, palladium, platinum and similar nano-sized metal particles, metal doped zeolites, alkaline earth metal peroxides and combinations thereof.
    类似技术:
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    BR112012017732B1|2019-12-17|process for filtration of a fluid comprising water, at least one surfactant and fine solids
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    同族专利:
    公开号 | 公开日
    WO2011084776A2|2011-07-14|
    CA2781564C|2014-07-29|
    EP2516335A4|2015-06-03|
    NZ600575A|2013-08-30|
    US8499832B2|2013-08-06|
    CA2781564A1|2011-07-14|
    AU2010339708B2|2014-09-04|
    AU2010339708A1|2012-07-05|
    WO2011084776A3|2011-11-17|
    MX2012006572A|2012-06-28|
    US20110108270A1|2011-05-12|
    BR112012017732A2|2016-09-13|
    EP2516335A2|2012-10-31|
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    法律状态:
    2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2018-12-18| B06T| Formal requirements before examination|
    2019-07-02| B07A| Technical examination (opinion): publication of technical examination (opinion)|
    2019-10-22| B09A| Decision: intention to grant|
    2019-12-17| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 21/12/2010, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US28876109P| true| 2009-12-21|2009-12-21|
    US12/971,557|US8499832B2|2004-05-13|2010-12-17|Re-use of surfactant-containing fluids|
    PCT/US2010/061469|WO2011084776A2|2009-12-21|2010-12-21|Re-use of surfactant-containing fluids|
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