WO2019005290A1 - Composition aqueuse de clarificateur d'eau stabilisée à basse température et procédés d'utilisation - Google Patents

Composition aqueuse de clarificateur d'eau stabilisée à basse température et procédés d'utilisation Download PDF

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Publication number
WO2019005290A1
WO2019005290A1 PCT/US2018/030766 US2018030766W WO2019005290A1 WO 2019005290 A1 WO2019005290 A1 WO 2019005290A1 US 2018030766 W US2018030766 W US 2018030766W WO 2019005290 A1 WO2019005290 A1 WO 2019005290A1
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water
oil
composition
aqueous
emulsion
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PCT/US2018/030766
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English (en)
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Troy E. KNIGHT
Kaylie L. Young
Despina N. LOUFAKIS
Stephen M. Hoyles
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Dow Global Technologies Llc
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G33/00—Dewatering or demulsification of hydrocarbon oils
    • C10G33/04—Dewatering or demulsification of hydrocarbon oils with chemical means
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • B01D17/02—Separation of non-miscible liquids
    • B01D17/04—Breaking emulsions
    • B01D17/047—Breaking emulsions with separation aids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/80—Additives

Definitions

  • the present invention relates to a freeze protected aqueous water clarifier composition and method for demulsifying and clarifying oil-water emulsions and dispersions derived from petroleum production and refining operations using said aqueous water clarifier composition.
  • a dispersion is a mixture in which one phase is dispersed in another, continuous phase, of a different composition or phase.
  • An emulsion is a dispersion comprising two immiscible liquids, one of which is dispersed as droplets (internal phase) in the other
  • emulsions are dispersions, but not all dispersions are emulsions.
  • Stable emulsions are those which are unable to resolve themselves into their constituent phases without some form of mechanical or chemical treatment.
  • hydrocarbons including, but not limited to, crude oil, gas and their derivative products
  • hydrocarbons including, but not limited to, crude oil, gas and their derivative products
  • mixtures and dispersions of oil and water.
  • Such mixtures typically also contain other compounds, including but not limited to, waxes, asphaltenes, various salts, suspended materials, biological surface active material from the ground, added surface active corrosion/scale inhibiting reagents, etc., which may vary from location to location.
  • synthetic and natural surfactants produced either in-situ or added in enhanced oil recovery techniques such as akali- surfactant (AS) and alkali- surfactant-polymer (ASP) floods, can cause phase separation issues.
  • AS alkali- surfactant
  • ASP alkali- surfactant-polymer
  • breaking implies that the emulsifying films around the droplets of water or oil are "broken" so that coalescing may occur and result in separation of the oil and water phases over time, for example, by gravitational settling.
  • demulsifiers describe the class of agents which break or separate an emulsion, whether normal or reverse, into its constituent phases.
  • Clarifiers describe compounds which are applied to break emulsions and separate the oil phase from the water, thereby, making the water “clearer.”
  • a large quantity of water may be pumped down into the ground via one or more injector wells to push oil in the underground formation toward the producing well and out of the ground.
  • formation water is produced from the well in combination with the oil.
  • SAGD steam assisted gravity drainage
  • demulsifiers such as polyalkylene glycols (PAGs), block copolymers of poly(ethylene oxide) (PEO) and poly(propylene oxide) (PPO), and alkylphenol resin alkoxylates are generally used.
  • PAGs polyalkylene glycols
  • PEO poly(ethylene oxide)
  • PPO poly(propylene oxide)
  • alkylphenol resin alkoxylates are generally used.
  • water clarifiers are also added to the crude emulsion stream.
  • the produced water fraction may contain as little as 100 parts per million (ppm) oil entrained in the water phase.
  • ppm parts per million
  • a "reverse” i.e., oil in water, emulsion is formed.
  • This emulsion appears anywhere from brown to black, depending on the amount of impurities present.
  • Such produced water may be generated in huge quantities (i.e., up to millions of gallons per day), and is either reinjected into the formation, or disposed of into the ocean.
  • Clarification of such demulsified oilfield water typically involves use of acrylate polymers, cationic polymers, cationic poly electrolytes, and water- soluble amphiphilic polymers to flocculate suspended oily and particulate materials and, thereby, obtain clear(er) water.
  • the prior art includes many patents and general literature relating to demulsification and clarification of oil- water dispersions and emulsions produced by petroleum industry operations.
  • US Patent Application Publication US 2007/0244248 discloses the use of a polymer containing aromatic and oleophilic groups for demulsifying oil-water emulsions.
  • USP 5,100,582 discloses a very specific composition of tetrapolymer containing random combinations of acrylic acid, methacrylic acid, methyl methacrylate and butyl acrylate for use as demulsifying agent for water-in-crude oil.
  • USP 6,025,426 and USP 5,330,650 each teach the use of hydrophilic cationic copolymers of acrylamide having high molecular weight as water clarification aids.
  • USP 4,582,628 discloses the use of vinyl-type polymers, derived from hydrophilic and hydrophobic vinyl monomers, for demulsifying petroleum industry emulsions of oil and water.
  • Low molecular weight, water soluble, cationic polymers of dimethylaminoethyl acrylate methyl chloride and benzyl chloride quaternary salt are disclosed in USP 5,643,460 for breaking oil in water emulsions resulting from oilfield operations.
  • USP 5,472,617 provides a method for demulsifying a crude oil and water emulsion which involves adding demulsifiers made from (meth)acrylates of oxyalkylates copolymerized with hydrophilic monomers.
  • Chinese Patent Application Publication CN1883740 discloses the use of polymers derived from hydrophobic (meth)acrylate ester monomers and hydrophilic (meth)acrylic acid monomers, and having molecular weights of 5,000 to 100,000 g/mol, for demulsifying crude oil and water emulsions.
  • US Patent Publication US 2011 0031163 discloses hydrophobically modified, surfactant modified, and lightly crosslinked anionic acrylate copolymers for separating oil and water dispersions or emulsions generated in connection with oilfield operations.
  • the present invention provides such a stabilized aqueous water clarifier composition and a method for use thereof for separating oil and water phases of an oil-water dispersion or emulsion derived from petroleum industry operations, wherein the aqueous water clarifier composition is stable between -40°C to 60°C.
  • the aqueous water clarifier composition is provided to the oil-water emulsion in an amount to result in a demulsifying effective.
  • the aqueous water clarifier composition comprises i) a hydrophobically modified alkylene oxide urethane copolymer, preferably a hydrophobically modified ethoxylated urethane (HEUR); ii) a diol, preferably ethylene glycol, propylene glycol, or mixtures thereof; iii) a glycol ether having the structure:
  • R 2 -0-CH 2 CH 2 -OH wherein R and R 1 are independently H, or a Ci to C5 linear or branched alkyl group and R 2 is R 3 -(OCH2CH2) n - wherein R 3 is a H or a linear or branched Ci to C3 alkyl group and n is equal to 1 or 2, preferably ethyleneglycol monoethylether, ethyleneglycol monopropylether, ethyleneglycol monobutylether, ethyleneglycol monopentylether, or mixtures thereof; iv) optionally a viscosifier, preferably xanthan gum, wellan gum, schleroglucan, and/or guar gum; and v) water.
  • R and R 1 are independently H, or a Ci to C5 linear or branched alkyl group and R 2 is R 3 -(OCH2CH2) n - wherein R 3 is a H or a linear or branched Ci to C3 alky
  • the present invention provides a method for inhibiting and mitigating the formation of oil-water emulsions generated during petroleum industry operations from oil and aqueous precursors which become mixed during the operations.
  • This method for inhibiting and mitigating the formation of oil- water emulsions comprises providing a demulsifying effective amount, preferably 1 to 10,000 ppm, of the aforesaid aqueous water clarifier composition to the oil precursor, the aqueous precursor, or both, prior to, during or after mixing of the precursors.
  • the oil-water dispersion or emulsion may be an oil in water dispersion or emulsion, or a water in oil dispersion or emulsion.
  • FIG. 1 is a plot of viscosity versus shear rate for Examples 8, 18, and 19.
  • FIG. 2 is a photograph of the results of a water clarification test for examples with and without a water clarifier composition of the present invention.
  • Polymer Science, second edition, 1971, is a relatively large molecule made up of the reaction products of smaller chemical repeat units.
  • Polymers may have structures that are linear, branched, star shaped, looped, hyperbranched, crosslinked, or a combination thereof; polymers may have a single type of repeat unit ("homopolymers") or they may have more than one type of repeat unit (“copolymers”).
  • Copolymers may have the various types of repeat units arranged randomly, in sequence, in blocks, in other arrangements, or in any mixture or combination thereof.
  • Chemicals that react with each other to form the repeat units of a polymer are known herein as "monomers," and a polymer is said herein to be made of, or comprise, “polymerized units” of the monomers that reacted to form the repeat units.
  • the chemical reaction or reactions in which monomers react to become polymerized units of a polymer, whether a homopolymer or any type of copolymer, are known herein as “polymerizing” or “polymerization.”
  • Polymer molecular weights can be measured by standard methods such as, for example, size exclusion chromatography (also called gel permeation chromatography) or intrinsic viscosity.
  • production operations includes, but not is limited to, activities and processes for exploration, production, refining and chemical processing of hydrocarbons including, but not limited to, crude oil, gas and their derivatives.
  • exploration often involves the initial drilling of wells wherein drilling fluid, or drilling mud, which is typically a mixture of liquid and gaseous fluids and solids, is used as lubricant and heat sink. Suitable dispersants are helpful to stabilize such mud to a homogenous composition.
  • Production operations include, but are not limited to, pumping large quantities of water into the ground, as described above, which commensurately generates large quantities of "formation water,” an oil in water dispersion or emulsion.
  • Oil refining processes include but are not limited to, the removal of inorganic solids and salts (referred to as "desalting") from produced oil. Desalting operations produce oil in water mixtures which require clarification and/or demulsifying prior to discharge or reuse.
  • chemical processing in the petroleum industry includes many various activities such as, for example, without limitation, production of ethylene by fractionation which involves water quench operations. The quench operations of ethylene manufacturing generate quench waters containing heavy, middle and light hydrocarbons and, therefore, require demulsifying and/or clarification. Persons of ordinary skill in the art will readily recognize the many various operations performed in the petroleum industry to which the present invention is reasonably applicable and the invention is intended to include all such applications.
  • oil-water emulsion includes dispersions even where a stable emulsion does not exist and also includes water in oil emulsions and oil in water emulsions, as well as multiple emulsions, such as water in oil in water.
  • Oil is the continuous, or external, phase in water in oil emulsions.
  • the continuous, or external, phase is water.
  • Endpoints of ranges are considered to be definite and are recognized to incorporate within their tolerance other values within the knowledge of persons of ordinary skill in the art, including, but not limited to, those which are insignificantly different from the respective endpoint as related to this invention (in other words, endpoints are to be construed to incorporate values "about” or “close” or “near” to each respective endpoint).
  • the range and ratio limits, recited herein, are combinable. For example, if ranges of 1-20 and 5-15 are recited for a particular parameter, it is understood that ranges of 1-5, 1-15, 5- 20, or 15-20 are also contemplated and encompassed thereby.
  • aqueous water clarifier compositions of the present invention is defined herein to mean the composition does not form a gel or precipitate due to temperature, be it at a low-temperature, a high temperature, or cycling between a low-temperature and a high temperature.
  • low temperatures are -40°C or higher and high temperatures are 60°C and lower.
  • the present invention provides an aqueous water clarifying composition, a method to make said clarifying composition, and for use thereof to separate oil and water phases of an oil-water dispersion or emulsion derived from petroleum industry operations.
  • the aqueous water clarifying composition comprises a hydrophobically modified alkylene oxide urethane copolymer, i.e., copolymers including both alkylene oxide and urethane groups.
  • the copolymers preferably have a Mw of 1,000 to 500,000 Daltons but more preferably 10,000 to 100,000 Daltons.
  • the copolymers are preferably non-ionic and may be branched or linear.
  • the copolymers preferably include at least 40 wt%, 50 wt%, 85 wt%, 90 wt% and in some embodiments even 95 wt% of alkylene oxide groups along with urethane groups preferably serving as linking groups between blocks of alkylene oxide or as terminal groups.
  • alkylene oxide is used interchangeable with the term
  • oxyalkylene and both collectively refer to units having the structure -(O-A)- wherein O-A represents the monomeric residue of the polymerization reaction product of a C2-4 alkylene oxide. Examples include but are not limited to: oxy ethylene with the structure -(OCH2CH2)- ; oxypropylene with the structure -(OCH(CH3)CH2)-; oxytrimethylene with the structure - (OCH2CH2CH2)-; and oxybutylene with the general structure -(OC4H8)-. Polymers containing these units are often referred to as "poly oxy alky lenes.” The poly oxyalkylene units can be homopolymeric or copolymeric. Examples of homopolymers of
  • polyoxyalkylenes include, but are not limited to polyoxyethylene, which contains units of oxyethylene; polyoxy propylene, which contains units of oxypropylene;
  • polyoxytrimethylene which contains units of oxytrimethylene
  • polyoxybutylene which contains units of oxybutylene.
  • polyoxy butylene include a homopolymer containing units of 1,2-oxybutylene, - OCH(C2Hs)CH2)-; and polytetrahydrofuran, a homopolymer containing units of 1,4-oxybutylene, - (OCH2CH2CH2CH2)-.
  • the polyoxyalkylene segments can be copolymeric, containing two or more different oxyalkylene units.
  • the different oxyalkylene units can be arranged randomly to form a random polyoxyalkylene; or can be arranged in blocks to form a block polyoxyalkylene.
  • Block polyoxyalkylene polymers have two or more neighboring polymer blocks, wherein each of the neighboring polymer blocks contain different oxyalkylene units, and each polymer block contains at least two of the same oxyalkylene units.
  • Oxyethylene is the preferred oxyalkylene segment.
  • the subject copolymer preferably includes a plurality of oxyalkylene segments or blocks having a Mw of from 200 to 10,000 and more preferably 2,000 to 10,000.
  • the oxyalkylene segments are preferably linked by reaction with a multi- functional isocyanate (forming a urethane).
  • the multi-functional isocyanates can be aliphatic, cycloaliphatic, or aromatic; and can be used singly or in admixture of two or more, including mixtures of isomers.
  • organic polyisocyanates examples include 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-l,6- diisocyanato hexane, 1,10-decamethylene diisocyanate, 4,4'-methylenebis
  • Preferred species of copolymers include so-called "HEUR" materials (i.e.
  • hydrophobically modified ethoxylated urethane conventionally used as rheology modifiers in water-based fluids including cosmetics, paints, detergents, personal care formulations.
  • HEUR materials are described in: US2014/0011967, US2013/015819, US2012/0130000, US2009/0318595, US7741402, and US4155892 - the entire subject of which is incorporated herein by reference.
  • HEUR materials are typically built up from water-soluble poly (oxyethylene) segments joined by urethane groups. Hydrophobic end groups may be incorporated by reacting hydrophobic alcohols, amines, or acids with the diisocyanate groups, the resulting hydrophobic group effectively including the hydrophobic residue of the diisocyanate.
  • hydrophobic monoisocyanates may be reacted with terminal poly(oxy ethylene) chains.
  • the diisocyanates used to link the water-soluble segments serve as internal hydrophobic groups, if the diisocyanate molecule is large enough and hydrophobic enough, or internal hydrophobes may be efficiently built up by reacting the diisocyanates with hydrophobic active hydrogen compounds, such as diols or diamines. Excess diisocyanate may also be reacted with water to build up hydrophobic blocks.
  • the hydrophobic ally modified alkylene oxide urethane copolymer is present in an amount equal to or greater than 2 weight percent, preferably equal to or greater than 4, and more preferably equal to or greater than 6 weight percent, based on the total weight of the aqueous water clarifier composition.
  • the aqueous water clarifier composition comprises the hydrophobically modified alkylene oxide urethane copolymer in an amount equal to or less than 20 weight percent, preferably equal to or less than 15, and more preferably equal to or less than 10 weight percent, based on the total weight of the aqueous water clarifier composition.
  • the aqueous water clarifier composition further comprises one or more alcohol.
  • Suitable alcohols may be selected from the group consisting of glycols, glycol ethers, methanol, ethanol and combinations thereof.
  • the alcohol is represented by the following formula:
  • R 2 -0-CH 2 CH 2 -OH wherein R and R 1 are independently H, or a Ci to Cs linear or branched alkyl group and R 2 is H, a Ci to Cs linear or branched alkyl group or R 3 -(OCH2CH2) n - wherein R 3 is a H or a linear or branched Ci to Cs alkyl group and n is equal to 1 or 2, with the proviso that if R 1 and/or R is a Ci to Cs alkyl group, R 2 is H or a Ci to C3 linear or branched alkyl group.
  • the glycol ether has the structure: R 1 R
  • R 2 -0-CH 2 CH 2 -OH wherein R and R 1 are independently H, or a Ci to Cs linear or branched alkyl group and R 2 is R 3 -(OCH2CH2) n - wherein R 3 is a H or a linear or branched Ci to C3 alkyl group and n is equal to 1 or 2.
  • the alcohol is selected from methanol, ethanol, propanol, isopropanol, diethyleneglycol monobutyl ether, ethyleneglycol monobutyl ether, diethylene glycol monoethyl ether, ethyleneglycol monobutylether, ethyleneglycol monopropylether, dipropyleneglycol monomethyl ether, dipropyleneglycol monobutyl ether, propylene glycol monomethyl ether, propyleneglycol monopropyl ether, propyleneglycol monobutyl ether, butyl acetate, propylene glycol, ethylene glycol, and combinations thereof.
  • the aqueous water clarifier composition comprises a diol, preferably ethylene glycol, propylene glycol, or a mixture thereof and a glycol ether, preferably ethyleneglycol monomethylether, ethyleneglycol monoethylether, ethyleneglycol monopropylether, ethyleneglycol monobutylether, ethyleneglycol monopentylether, or mixtures thereof.
  • the aqueous water clarifier composition comprises each one or more alcohol in an amount equal to or greater than 1 weight percent, preferably equal to or greater than 7.5, and more preferably equal to or greater than 15 weight percent, based on the total weight of the aqueous water clarifier composition.
  • the aqueous water clarifier composition comprises each one or more alcohol in an amount equal to or less than 50 weight percent, preferably equal to or less than 40, and more preferably equal to or less than 30 weight percent, based on the total weight of the aqueous water clarifier composition.
  • the aqueous water clarifier composition may further comprises a viscosifier.
  • Suitable viscosifiers include galactomannans such as guar, derivatized guars such as hydroxypropyl guar, carboxymethyl guar, carboxymethylhydroxypropyl guar,
  • hydrophobically modified galactomannans xanthan gum, hydroxyethylcellulose, and polymers, copolymers and terpolymers containing acrylamide monomer, and the like.
  • suitable viscosifiers include: polysaccharides, such as, for example, guar gums, high-molecular weight polysaccharides composed of mannose and galactose sugars, including guar derivatives such as hydroxypropyl guar (HPG), carboxymethyl guar (CMG), and carboxymethylhydroxypropyl guar (CMHPG), and other polysaccharides such as xanthan, diutan, and scleroglucan; cellulose derivatives such as hydroxyethyl cellulose (HEC), hydroxypropyl cellulose (HPC),
  • polysaccharides such as, for example, guar gums, high-molecular weight polysaccharides composed of mannose and galactose sugars, including guar derivatives such as hydroxypropyl guar (HPG), carboxymethyl guar (CMG), and carboxymethylhydroxypropyl guar (CMHPG), and other polysaccharides such as xanthan
  • CHEC carboxymethylhydroxypropyl cellulose
  • synthetic polymers such as, but not limited to, acrylic and methacrylic acid, ester and amide polymers and copolymers, polyalkylene oxides such as polymers and copolymers of ethylene glycol, propylene glycol or oxide, and the like.
  • the polymers are preferably water soluble.
  • associative polymers for which viscosity properties are enhanced by suitable surfactants and hydrophobically modified polymers can be used, such as cases where a charged polymer in the presence of a surfactant having a charge that is opposite to that of the charged polymer, the surfactant being capable of forming an ion-pair association with the polymer resulting in a hydrophobically modified polymer having a plurality of hydrophobic groups, as described published application US 2004209780.
  • the viscosifier is xanthan gum, wellan gum, schleroglucan and/or guar gum.
  • the viscosifier is present in an amount equal to or greater than lOOppm, preferably equal to or greater than 250ppm, and more preferably equal to or greater than 500ppm weight percent, based on the total weight of the aqueous water clarifier composition.
  • the aqueous water clarifier composition comprises the viscosifier in an amount equal to or less than 1 weight percent, preferably equal to or less than 0.1 weight percent, and more preferably equal to or less than 750ppm, based on the total weight of the aqueous water clarifier composition.
  • the aqueous water clarifier composition of the present invention comprises water.
  • the amount of water will make up the balance of the weight of the aqueous water clarifier composition such that the weight percents for all the components, i.e., the hydrophobically modified alkylene oxide urethane copolymer, one or more alcohol, optionally a viscosifier, any additional components, and water will add up to a total of 100 weight percent.
  • the present invention also provides for a method to make the aqueous water clarifier composition of the present invention.
  • the hydrophobically modified alkylene oxide urethane copolymer, one or more alcohol, optionally the viscosifier, and the water may be added together in any order or sequence and each component may be added in its entire amount at once or a partial amount at two or more times.
  • the hydrophobically modified alkylene oxide urethane copolymer is solubilized in part, or all, of the water with all, or part, of the glycol ether prior to adding the bulk of the diol (i.e., greater than 85 wt% of the diol).
  • the viscosifier may be added at any time before or after the addition of the diol.
  • the present invention also provides a method for inhibiting and mitigating the formation of oil-water emulsions generated during petroleum industry operations from oil (organic) and water (aqueous) precursors which become mixed during said operations and otherwise form oil-water dispersions and emulsions.
  • This method for inhibiting and mitigating the formation of oil-water emulsions comprises providing the above-described aqueous water clarifier composition to the oil precursor, the aqueous precursor, or both, prior to, during or after mixing of the precursors.
  • the use of the aqueous water clarifier composition in accordance with the present invention may reduce the viscosity of the resulting mixture of oil and water and, thus, better flow characteristics may be achieved which may facilitate further processing and handling.
  • aqueous water clarifier composition is provided to the oil- water emulsion is not critical and many delivery methods are well known and understood by persons of ordinary skill in the relevant art.
  • reverse emulsion breaker compounds which are typically lower molecular weight, high charge materials that break reverse emulsions so that the flocculants can function better, is common in petroleum industry operations.
  • Examples of such reverse emulsion breaker compounds are, without limitation, poly amines, poly amine quats, tannins, and metal salts (A1-, Fe-based chlorides, hydroxides, etc.).
  • the method of the present invention may further comprise use of the above-described aqueous water clarifier compositions along with such reverse emulsion breaker compounds.
  • Blends and formulations of the aqueous water clarifier composition with other components such as, without limitation, additional antifreeze agents, solvents, biocides, neutralizing agents, flow aids, and the like, may be formed and used in accordance with the method of the present invention.
  • Such blends and formulations may be prepared as an emulsion or aqueous solution or otherwise.
  • HEUR is a hydrophobically modified ethoxylated urethane available as
  • EG is ethylene glycol
  • PG is propylene glycol
  • EGPE is ethyleneglycol monopropylether available as Propyl CELLOSOLVETM from The Dow Chemical Company;
  • EGBE is ethyleneglycol monobutylether available as Butyl CELLOSOLVE from The Dow Chemical Company;
  • EGHE is ethyleneglycol monohexylether available as Hexyl CELLOSOLVE from The Dow Chemical Company;
  • MTG methoxytriglycol available
  • PGBE propyleneglycol monobutylether available as DOWANOLTM PnB from The Dow Chemical Company;
  • DEGHE is diethylene glycol monohexyl ether available as Hexyl CARBITOLTM L from The Dow Chemical Company;
  • Xanthan gum is xanthan gum.
  • Table 1 shows formulations at different HEUR loading levels. Examples 2 to 6 demonstrate acceptable flow and phase stability.
  • Examples 7 to 10 are allowed to remain at -40°C for 4 days. It can be seen that Examples 7 and 8 showed viscous flow while Examples 9 and 10 flowed easily when inverted. Pour point results showed very low values for Examples 9 and 10.
  • xanthan gum is added at various levels to the composition of Example 8. As can be seen in Table 3, xanthan gum dosages equal to or greater than 500ppm yielded nearly homogeneous or homogeneous formulations for 1 week at -40 °C. Examples 14 to 17 all remained phase stable and flowable for 4 weeks at -40°C. Table 3
  • Examples 18 and 19 are compositions corresponding to the compositions of
  • the one cycle of the "low/high” temperature cycling consists of cycling from -40°C for 20 hours, to room temperature for 4 hours, to 60°C for 20 hours, back to room temperature for 4 hours, back to -40°C for 20 hours, and back to room temperature.
  • "Low/room temperature” temperature cycling consists of cycling from - 40°C for 20 hours, to room temperature for 4 hours and then repeated for a total of four cycles.
  • the viscosity profiles for the two sets of formulations is measured using the TA rheometer and is shown in FIG. 1.
  • Example 23 is a blank (i.e., no clarifier added) and Example 24 is the results using the composition of Example 16.
  • An artificial emulsion is prepared in the lab using aged crude oil. Then, 8 oz. (185 mL) prescription bottles are filled with emulsion to the 100 mL mark and are dosed with 50ppm actives of Example 16. One bottle was left blank to serve as the control. Both bottles are hand-shaken for 50 times and are allowed to stand in front of a light source to observe performance. The results are shown in FIG. 2. The test showed that the bottle that is dosed with a clarifier composition of the present invention resulted in good oil- water separation with the resulting water clearer than the blank.

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  • Oil, Petroleum & Natural Gas (AREA)
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  • General Chemical & Material Sciences (AREA)
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Abstract

L'invention concerne une composition aqueuse de clarificateur d'eau qui est stable à basses températures, un procédé de fabrication et un procédé d'utilisation. Ladite composition aqueuse de clarificateur d'eau comprend : i) un copolymère d'uréthane d'oxyde d'alkylène à modification hydrophobe ; ii) un diol ; iii) un éther de glycol ; et iv) éventuellement un améliorant de viscosité. Selon la présente invention, les compositions aqueuses de clarificateur d'eau sont utiles pour désémulsionner et clarifier des dispersions huile-eau et des émulsions issues d'opérations de l'industrie pétrolière.
PCT/US2018/030766 2017-06-30 2018-05-03 Composition aqueuse de clarificateur d'eau stabilisée à basse température et procédés d'utilisation WO2019005290A1 (fr)

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