WO2015050759A2 - Libération contrôlée de tensioactifs pour une récupération améliorée de pétrole - Google Patents

Libération contrôlée de tensioactifs pour une récupération améliorée de pétrole Download PDF

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WO2015050759A2
WO2015050759A2 PCT/US2014/057169 US2014057169W WO2015050759A2 WO 2015050759 A2 WO2015050759 A2 WO 2015050759A2 US 2014057169 W US2014057169 W US 2014057169W WO 2015050759 A2 WO2015050759 A2 WO 2015050759A2
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sulfonate
surfactant
salt
sparingly soluble
polymer
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PCT/US2014/057169
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English (en)
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WO2015050759A3 (fr
Inventor
Yun Chea Chang
Mazen Y. Kanj
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Saudi Arabian Oil Company
Aramco Services Company
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Priority claimed from US14/043,403 external-priority patent/US9580639B2/en
Application filed by Saudi Arabian Oil Company, Aramco Services Company filed Critical Saudi Arabian Oil Company
Publication of WO2015050759A2 publication Critical patent/WO2015050759A2/fr
Publication of WO2015050759A3 publication Critical patent/WO2015050759A3/fr
Priority to SA516370745A priority Critical patent/SA516370745B1/ar
Priority to SA517390640A priority patent/SA517390640B1/ar
Priority to SA517390642A priority patent/SA517390642B1/ar

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
    • C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
    • C09K8/588—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
    • C09K2208/10—Nanoparticle-containing well treatment fluids

Definitions

  • the field of invention relates to compositions, delivery systems, and methods suitable for the enhanced oil recovery process.
  • Surfactants are used in enhanced oil recovery (EOR) processes.
  • EOR enhanced oil recovery
  • the presence of a surfactant at the water/oil interface facilitates oil recovery.
  • One embodiment of the invention is a composition for the controlled release of surfactants in oil recovery operation, the composition being made of an aqueous sulfonate solution and a metal salt selected from aluminium nitrate nonahydrate, calcium chloride dehydrate, magnesium chloride hexahydrate, cobalt chloride hexahydrate, and other metal salts, wherein the mean diameter of the formed sparingly soluble sulfonate surfactant-metal salt particle is between 20 nm and 100 nm and solubility of the sparingly soluble sulfonate surfactant-metal salt particle is less than 100 ppm at room temperature.
  • the sparingly soluble sulfonate surfactant-metal salt particle additionally contains hydrolyzed polyacrylamide.
  • Another embodiment of the invention is a hydrocarbon recovery composition
  • a hydrocarbon recovery composition comprising a composition which comprises an aqueous sulfonate solution and a metal salt selected from aluminium nitrate nonahydrate, calcium chloride dehydrate, magnesium chloride hexahydrate, cobalt chloride hexahydrate, and other metal salts, wherein the mean diameter of the formed sparingly soluble sulfonate surfactant-metal salt particle is between 20 nm and 100 nm and solubility of the sparingly soluble sulfonate surfactant-metal salt particle is less than 100 ppm at room temperature.
  • the sparingly soluble sulfonate surfactant-metal salt particle additionally contains hydrolyzed polyacrylamide
  • Another embodiment of the invention is a delivery system for controlling the release of surfactants in hydrocarbon recovery operation, the delivery system comprising an aqueous sulfonate solution and a salt selected from aluminium nitrate nonahydrate, calcium chloride dehydrate, magnesium chloride hexahydrate, cobalt chloride hexahydrate, and other metal salts, wherein the mean diameter of the formed sparingly soluble sulfonate surfactant- metal salt particle is between 20 nm and 100 nm and solubility of the sparingly soluble sulfonate surfactant -metal salt particle less than 100 ppm at room temperature; in an amount operable such that the sulfonate in the aqueous solution reduces surface tension of the hydrocarbon so that oil recovery is increased.
  • the sparingly soluble sulfonate surfactant-metal salt particle further contains hydrolyzed polyacrylamide.
  • Another embodiment of the invention is a method of delivering a controlled release of surfactants composition, the method including the following the steps, such as: (1) delivering an aqueous solution into a reservoir, the aqueous solution containing an aqueous sulfonate solution; and a metal salt selected from aluminium nitrate nonahydrate, calcium chloride dehydrate, magnesium chloride hexahydrate, cobalt chloride hexahydrate, and other metal salts; wherein the mean diameter of the formed sparingly soluble sulfonate surfactant- metal salt particle is between 20 nm and 100 nm and solubility of the sparingly soluble sulfonate surfactant-metal salt particle is less than 100 ppm at room temperature; and (2) delivering water to the reservoir.
  • Another embodiment of the invention is a method of treating a hydrocarbon containing formation by (a) providing a hydrocarbon recover ⁇ ' composition to at least a portion of the hydrocarbon containing formation, wherein the hydrocarbon recovery composition comprises (1) an aqueous sulfonate solution and (2) a metal salt selected from aluminium nitrate nonahydrate, calcium chloride dehydrate, magnesium chloride hexahydrate, cobalt chloride hexahydrate, and other metal salts; wherein the mean diameter of the sparingly soluble sulfonate surfactant-metal salt particle is between 20 nm and 100 nm and solubility of the sparingly soluble sulfonate surfactant-metal salt particle is less than 100 ppm at room temperature; and (b) allowing the hydrocarbon recover ⁇ ' composition to interact with hydrocarbons in the hydrocarbon containing formation.
  • the hydrocarbon recovery composition comprises (1) an aqueous sulfonate solution and (2) a metal salt selected from aluminium nitrate nonahydrate
  • a method of producing a sparingly soluble sulfonate surfactant-metal salt particle includes the steps of introducing an aqueous solution containing a metal ion salt into a reactor.
  • the method includes introducing an aqueous solution containing a sulfonate surfactant and a polymer into the reactor.
  • the method includes operating the reactor such that the sulfonate surfactant-metal salt particle forms from the interaction of the metal ion from the salt, the sulfonate surfactant and the polymer.
  • the sulfonate surfactant-metal salt particle has an average particle size diameter in a range of from about 50 nm to about 450 nm and is sparingly soluble in water at room temperature.
  • a sparingly soluble sulfonate surfactant-metal salt particle includes a metal ion salt of an alkyf aryl sulfonate, a metal ion salt of a petroleum sulfonate and a hydrophobicaSly modified hydrophilic polymer.
  • the sulfonate surfactant-metal salt particle has an average particle size diameter in a range of from about 50 nm to about 450 nm and is sparingly soluble in water at room temperature.
  • Anionic surfactants can form salts some cations in situ. Salt formation is considered problematic and undesirable during enhanced oil recovery (EOR) since the formation of surfactant salts with ions present in the water or the ro e results in the immediate loss of surfactants for extracting hydrocarbons.
  • EOR enhanced oil recovery
  • surfactant-metal salts can be engineered and used in such ways as to contribute to the EOR process for the long-term.
  • the sparingly soluble surfactant-metal salt particles or capsules should be small - 200 nm or less. This permits the surfactant-metal salt particles to travel into the formation and through the pores in the reservoir.
  • the surfactant-metal salt particle size can be manipulated by controlling the nucleation rate for the precipitation of the particles. Another way to manipulate the particle size is to use a mechanical milling device to grind down larger particles.
  • nano- sized particles have to be dispersibie within in the reservoir environment conditions, that is, up to 100 °C and with 25 wt.% salinity of aqueous solution.
  • active ingredients are often delivered to a targeted area in a controlled release fashion such that one dose of active ingredient can sustain efficacy for a longer period.
  • surfactants will be delivered in a controlled manner and released at the oil/water interface.
  • the delivered salt particle is akin to micro reservoirs of surfactant that feed the surfactant molecules to the oil/water interface at a constant concentration and a constant rate. As a result, residual oil at the treatment site is continually solubilized.
  • Anionic surfactants such as sulfonates, are converted into surfactant-metal salt particles.
  • the surfactant has a negative charge which reacts with the positively charged cations.
  • some of the resulting surfactant salts are partially or sparingly soluble in water.
  • the sparingly soluble surfactant-metal salts being only slightly soluble in water, supply surfactant at a limited and controlled rate given the surfactant concentration in the water. This provides a continuous, low level of surfactant concentration at the oil/water interface of the treatment site for extended periods.
  • the sparingly soluble surfactant-metal salt nanoparticles can supply a constant flux of surfactant molecules into the surfactant solution. Because of this sustained supply of fresh surfactant molecules, more residual oil may be recovered over a period of time.
  • the invention provides colloidal surfactant salts that maintain a constant free surfactant concentration in the surfactant solution. Because of this constant and sustained supply of fresh surfactant molecules more residual oil may be recovered.
  • Coupled elements, components or steps may be present, utilized or combined with other elements, components or steps not expressly referenced.
  • the verb "couple” and its conjugated forms means to complete any- type of required junction, including electrical, mechanical or fluid, to form a singular object from two or more previously non-joined objects. If a first device couples to a second device, the connection can occur either directly or through a common connector. "Operable” and its various forms means fit for its proper functioning and able to be used for its intended use.
  • compositions and deliver ⁇ ' systems disclosed provide a means to slowly release sulfonate surfactant in an aqueous solution, maintain the local sulfonate surfactant concentration at a constant level, and sustain the release of the sulfonate surfactant over a long period.
  • the rock in a reservoir is porous with a wide pore size distribution. Pores can be as small as 1 micron and as large as 20 micron.
  • a particle is a discrete entity of solid matter in a dispersed state with a diameter at or less than about 50 micrometers (50 ⁇ ). Larger size particles could be trapped by the pores.
  • the sparingly soluble sulfonate-metal salt particles can traverse through pores of this size.
  • An embodiment of the sparingly soluble sulfonate-metal salt particles has an average particle size diameter in a range of from about 50 nm to about 200 nm.
  • Anionic surfactant salts thai are precipitated by different cations have different solution solubility, which affects the surfactant salt particle size and the amount of sulfonate surfactant in the aqueous solution.
  • the free surfactant concentration in the formed surfactant solution can be regulated by the choice of the surfactant salt to introduce into the aqueous solution.
  • Sparingly soluble surfactant-metal salt particles can be made smaller than 200 nm, smaller than 100 nm, or smaller than 50 nm.
  • the sulfonate-metal salt particles are sparingly soluble.
  • a saturated solution of a sparingly soluble salt in water may be considered to exist in a dynamic equilibrium of two opposing reactions.
  • the dissolution of the solid salt and the crystallization of the salt are the two opposing reactions.
  • the rates of the two reactions are equal there is dynamic equilibrium.
  • the sulfonate-metal salt has a solubility of 100 ppm in water, and 1.0 weight percent of sulfonate-metal salt is added in 1 liter of water, the sulfonate surfactant concentration in the aqueous solution is held constant at 100 ppm.
  • Sulfonate-metal salt introduced into water releases sulfonate surfactant until the sulfonate surfactant in the aqueous solution achieves a concentration of 100 ppm, when a dynamic equilibrium forms between the sulfonate solution and the sulfonate-metal salt.
  • An embodiment of the sparingly soluble sulfonate-metal salt particles has a solubility in a range of from about 50 parts -per-million (ppm) to about 300 ppm in water at room temperature.
  • An embodiment of the sparingly soluble sulfonate-metal salt particles has a solubility in a range of from about 50 ppm to about 200 ppm in water at room temperature.
  • An embodiment of the sparingly soluble sulfonate-metal salt particles has a solubility in a range of from about 50 ppm to about 100 ppm in water at room temperature.
  • the replenishment of the sulfonate surfactant into the aqueous solution is driven by thermodynamic equilibrium between the solid, sparingly soluble surfactant-metal salt and the soluble surfactant in the aqueous solution.
  • the transport of the sulfonate surfactant from the surfactant-metal salt into the surfactant solution depends on the concentration of free surfactant already present in the solution, the equilibrium between the sparingly soluble surfactant-metal salt particles, and the rate of adsorption of free surfactant by present hy drocarbons. For example, if the sulfonate surfactant in solution is consumed upon contacting oil within a day, then another 100 ppm of sulfonate surfactant is replenished into the solution from the solid surfactant salt particles.
  • the 100 ppm free surfactant concentration is maintained in the aqueous sulfonate solution by the presence of the sparingly soluble sulfonate-metal salt particles.
  • the sparingly soluble sulfonate-metal salt particles contain sufficient amount of sulfonate surfactant to allow for sustained release from several hours to several days
  • the aqueous solution in which the sparingly soluble sulfonate-metal salt particles is dispersed can range from de-ionized water to saline water, with salinity as high as 25 weight percent.
  • the concentration of the sulfonate surfactant in the solution is dependent on the sparing solubility of the sulfonate-metal salt.
  • a dispersion consists of a fine insoluble or only slightly soluble particles distributed throughout a continuous medium.
  • a "dispersion” is a two-phase system where one phase consists of finely divided particles (often in the colloidal size range) distributed throughout a bulk substance, the salt particles being the disperse or internal phase and the bulk substance the continuous or external phase.
  • a dispersion is usually polydisperse - the dispersed salt particles usually have different sizes and shapes.
  • a solid-in-liquid colloidal dispersion (loosely called solutions) can be precipitated. In the case of the sparingly soluble surfactant salts, the surfactant salts precipitate out of the solution. Larger particles will gradually coalesce and settle out.
  • the sparingly soluble surfactant -metal salt particle includes a. metal ion salt of an anionic surfactant and a polymer.
  • Useful metal ions include aluminum, calcium, magnesium, cobalt, zinc, barium, copper nitrate, and strontium.
  • Useful anionic surfactants include alkyi sulfonates, alkyi aryl sulfonates, including dodecyl benzene sulfonate, alkyi aryf ether phosphates, alkyi ether phosphates, alky ether sulfates, and alkyi sulfates, and petroleum sulfonates.
  • Useful polymers include partially hydroiyzed polyacrylamide, xanthan gum and polyvinyl pyrroiidone, hydrophobicallv modified hydrophilic polymers, including polymers made from monomers of dimethylaminoethyl methacrylate and cetyldimethylammoniumeihyl methacrylate halide, polyvinyl acetate, polyvinyl alcohol and gelatins.
  • An embodiment of the sparingly soluble surfactant-metal salt particle includes the metal ion salt of an alkyi aryl sulfonate, the metal ion salt of a petroleum sulfonate and a hydrophobicallv modified hydrophilic polymer and has an average particle size diameter in a range of from about 50 nm to about 450 nm.
  • An embodiment of the sparingly soluble surfactant-metal salt particle is where the petroleum sulfonate includes sulfonated benzenoid, cyeloaliphatie, paraffmic hydrocarbons, and combinations thereof.
  • about 0.1 to about 2.0 weight percent of polymer is mixed with about 0.05 to about 5 weight percent of a metal ion salt at a temperature between about 0 °C and about 120 °C.
  • useful polymers include partially ydroiyzcd poSyaerylamide, xanthan gum and polyvinyl pyrroiidone.
  • Examples of useful metal ion salts include aluminum nitrate nonahydrate, caicium chloride dihydraie, magnesium chloride hexahvdrate, cobalt chloride hexahydrate, zinc chloride, barium chloride dihydraie, copper nitrate, and strontium chloride hexahvdrate.
  • anionic surfactant To the polymer/salt mixture about 0.05 to about 5 weight percent of anionic surfactant is then added with vigorous stirring at temperatures about 0 °C and about 90 °C.
  • useful anionic surfactants include alkyl sulfonates, alkyl aryl sulfonates, alkyl aryl ether phosphates, alkyl ether phosphates, alky ether sulfates, and alkyl sulfates.
  • An additional example of a useful metal ion salt includes copper nitrate hemi(pentahydrate).
  • useful polymers include polyvinyl acetate, polyvinyl alcohol and gelatins.
  • Another useful polymer is a hydrophobically modified hydrophilic polymer.
  • An example of a commercially-available product that contains a hydrophobically modified hydrophilic polymer is HPT-lTM from Halliburton Energy Services.
  • HPT-lTM is a commercially-available product that contains a hydrophobically modified hydrophilic polymer from Halliburton Energy Services.
  • Alkyl sulfonates are primary and secondary paraffin sulfonates (PS and SAS) and a-olefin sulfonates (AOS).
  • Alkyl aryl sulfonates include alkyl benzene sulfonates such as dodecyl benzene sulfonate, which is a linear alkyl benzene (LAB) sulfonate surfactant.
  • LAB linear alkyl benzene
  • the alkyl sulfonates and the alkyl aryl sulfonates do not include any other heteroatoms except for the sulfonate functional group.
  • a useful anionic surfactant is a sodium sulfonate that is prepared by treating a petroleum fraction, such as a heavy naphtha, lube oil, white oil or a vacuum distillation cut containing C3 -40 PNAs, with sulfur trioxide (SO 3 ).
  • the resulting "petroleum sulfonate" is a mixture thai can comprise sulfonated benzenoid (both alkyl aryl and aryl), cvcloaliphaiic and paraffinic (alkyl) hydrocarbons in various ratios to one another depending on the nature of the source petroleum fraction.
  • Another benefit is that the produced petroleum sulfonate is both water and hydrocarbon soluble.
  • An example of a commercially-available product that contains petroleum sulfonate is PETRO ' NATE® EOR- 2095 sodium sulfonate from Chemtura.
  • the size of the sparingly soluble surfactant-metal salt particle can be controlled by the addition rates of anionic surfactant and the metal salt while in aqueous solution. Since the oil reservoir pore sizes vary, a distribution of different particle sizes can be used accordingly to help oil recovery throughout a hydrocarbon-bearing formation.
  • the sparingly soluble surfactant-metal salt particles can be polydisperse.
  • Process variables including temperature, flow rate of introduced reactants relative to the reactor volume, concentration of components, stirring rate in a batch reactor can all have an effect on controlling the particle size of the sparingly soluble surfactant-metal salt particle such that the average particle size diameter of about 50 nm to about 450 nm is achieved.
  • the attributes of the introduced aqueous solution of the metal ion salt affects the particle size of the sulfonated surfactant salt particle.
  • An embodiment of the method of producing a sparingly soluble surfactant-metal salt particle includes where the metal ion salt concentration is in a range of from about 0.1 to about 20 wt % of t e aqueous solution containing the metal ion salt. Where the reactor has a fixed volume, an embodiment of the method includes where the aqueous solution containing the metal ion salt has a residence time in a range of from about 0.33 minutes to about 3 minutes in the reactor.
  • the attributes of the introduced aqueous solution containing the sulfonate surfactant and the polymer affects the particle size of the sulfonated surfactant salt particle.
  • An embodiment of the method of producing a sparingly soluble surfactant-metal salt particle includes where the sulfonate surfactant is selected from the group consisting of an alkyl sulfonate, an alkyl aryl sulfonate, and combinations thereof.
  • An embodiment of the method includes where the alkyl aryl sulfonate is dodecyl benzene sulfonate.
  • An embodiment of the method includes where the sulfonate surfactant comprises a mixture of a petroleum sulfonate and dodecyl benzene sulfonate.
  • An embodiment of the method includes where the polymer is selected from the group consisting of polyacrylamide, polyvinyl acetate, polyvinyl alcohol, xanthan gum, gelatins, a hydrophobically modified hydrophilic polymer, and combinations thereof.
  • An embodiment of the method includes where the sulfonated surfactant salt particle comprises the metal ion salt of dodecyl benzene sulfonate, the metal ion salt of sulfonated petroleum and a hydrophobically modified hydrophilic polymer.
  • An embodiment of the method includes where the sulfonate surfactant concentration is in a range of from about 0.1 to about 20 wt, % of the aqueous solution containing the sulfonate surfactant and the polymer.
  • An embodiment of the method includes where the polymer concentration is in a range of from about 0.1 to about 20 wt. % of the aqueous solution containing the sulfonate surfactant and the polymer.
  • an embodiment of the method includes where the solution containing the sulfonate surfactant and the polymer are introduced into the reactor such that the sulfonate surfactant and the polymer have a residence time in a range of from about 0.17 minutes to about 1.5 minutes in the reactor.
  • An embodiment of the method of producing a sparingly soluble surfactant-metal salt particle includes where the solution containing the sulfonate surfactant and the polymer is a non-aqueous solution.
  • An embodiment of the method of producing a sparingly soluble surfactant-metal salt particle includes where the reactor is operated such that a temperature is maintained in a range of from about 0 °C to about 95 °C during sparingly soluble surfactant-metal salt particle formation.
  • An embodiment of the method includes where the reactor is a batch-type mixing reactor and the reactor is maintained at a mixing rate of 10 to 5,000 RPM during sulfonate surfactant salt particle formation.
  • An embodiment of the method includes where the reactor is operated such that the sulfonated surfactant salt particle has an average particle size diameter in a range of from about 50 nm to about 200 nm.
  • a metal ion salt at temperatures about 0 °C and about 90 C C is added to about 0,05 to about 5 weight percent of alkyi sulfonate with vigorous stirring.
  • An embodiment of the method of treating a hydrocarbon containing formation includes introducing a slug of solution containing nano particles of surfactant salts, polymer and water into the reservoir. The slug is then followed by a. water flood. The rates of the floods are adjusted such that an optimum amount of oil is recovered.
  • an aqueous dispersion consisting 0.05 to 5 weight percent of polymer, and 0.05 to 5 weight percent of the anionic surfactant salt particles with mean particle size less than 200 nm, is injected into an oil containing reservoir.
  • the injected dispersion is then maintained in the reservoir for 1 hour to 1 ,000 hours. After the shut in period, the dispersion slug is followed by water flooding.
  • the particle size is measured by Zetasizer, such as for example, one made by Malvern Instniment.
  • Zetasizer such as for example, one made by Malvern Instniment.
  • the number averaged particle size of the anionic surfactant salt particles is determined from the sample.
  • the resulting salt dispersion is centrifuged and filtered.
  • the supernatant sulfonate concentration in the supernatant is measured by the Total Carbon Analyzer.
  • This example demonstrates that small particle size aluminum sulfonate salt can be prepared.
  • Two ml of 0.3% partially hydrolyzed polyacrylamide was mixed with two ml. of 1% aluminum nitrate nonahydrate at 0 °C.
  • Nineteen mL of 0.1 wt. % (1000 ppm) PETRONATE ⁇ EOR-2095 was then added with vigorous stirring.
  • the resulting precipitate particle size was measured by the Zetasizer and number averaged particle size was determined to be 109 nm.
  • This example demonstrates that small particle size calcium sulfonate salt can be prepared.
  • This example is similar to Example 1 , except that 1% calcium chloride dehydrate was used instead of aluminum nitrate nonahydrate. The resulting precipitate particle size was 73 nm.
  • This example demonstrates that small particle size magnesium sulfonate salt can be prepared.
  • This example is similar to Example ! , except that 1% magnesium chloride hexahydrate was used instead of aluminum nitrate nonahydrate. The resulting precipitate particle size was 62 nm.
  • Example 4
  • This example demonstrates that small particle size cobalt sulfonate salt can be prepared.
  • This example is similar to Example 1. except that 1% cobalt chloride hexahydrate was used instead of aluminum nitrate nonahydrate. The resulting precipitate particle size was 87 nm.
  • This example demonstrates that the free sulfonate concentration in the supernatant can be modulated by the presence of sulfonate salt.
  • This example is similar to Example 1, except that no partially hydrolyzed polyacrylamide solution was added. The resulting salt dispersion was centrifuged and filtered. The supernatant sulfonate concentration in the supernatant was measured by the Total Carbon Analyzer. It was found that the supernatant contained 63 parts per million of sulfonate. In other words, initial surfactant concentration of 1,000 ppm was reduced to a constant free sulfonate concentration in the supernatant of 63 ppm.
  • This example demonstrates that the free sulfonate concentration in the supernatant can be modulated by the presence of sulfonate salt.
  • This example is similar to Example 5, except that calcium chloride dihydrate, instead of aluminum nitrate nonahydrate, was used. The resulting salt dispersion was centrifuged and filtered. The supernatant sulfonate concentration in the supernatant was measured by the Total Carbon Analyzer. It was found that the supernatant contained 83 parts per million of sulfonate. In other words, initial surfactant concentration of 1,000 ppm was reduced to a constant free sulfonate concentration in the supernatant of 83 ppm.
  • This example demonstrates that the free sulfonate concentration in the supernatant can be modulated by the presence of sulfonate salt.
  • This example is similar to Example 5, except that magnesium chloride hexahydrate, instead of aluminum nitrate nonahydrate, was used. The resulting salt dispersion was centrifuged and filtered. The supernatant sulfonate concentration in the supernatant was measured by the Total Carbon Analyzer. It was found that the supernatant contained 300 parts per million of sulfonate. In other words, initial surfactant concentration of 1,000 ppm was reduced to a constant free sulfonate concentration in the supernatant of 300 ppm.
  • This example demonstrates that the free sulfonate concentration in the supernatant can be modulated by the presence of sulfonate salt.
  • This example is similar to Example 5, except that cobalt chloride hexahydrate, instead of aluminum nitrate nonahydrate, was used. The resulting salt dispersion was centrifuged and filtered. The supernatant sulfonate concentration in the supernatant was measured by the Total Carbon Analyzer. It was found that the supernatant contained 106 parts per million of sulfonate. In other words, initial surfactant concentration of 1,000 ppm was reduced to a constant free sulfonate concentration in the supernatant of 106 ppm.
  • Example 9 demonstrates that the particle size of the cobalt sulfonate salt can be controlled by the anionic sulfonate surfactant and by cobalt salt fluid introduction flow rates.
  • a reactor containing 30 niL of water was stirred vigorously at room temperature.
  • a 30 mL of 1 wt. % cobalt chloride hexahydrate aqueous solution was pumped into the reactor at a rate of about 10 mL/min.
  • a 60 niE non-aqueous solution containing 0.5 wt. % PETRONATE® EOR-2095 and 5 wt. % HPT-1TM was simultaneously pumped into the reactor at a rate of about 20 mL/min.
  • the resulting average particle size diameter for the described run was determined to be about 232 nm.
  • Table 1 summarizes the average cobalt sulfonate surfactant salt particle size as a function of three different introduction feed flow- rates of the cobalt salt solution and the petroleum sulfonate surfactant solution.
  • the cobalt sulfonate surfactant salt particle sizes were measured by a Field Flow Fractionation instrument (Model AF2000; Postnova; Germany).
  • Example 10 demonstrates that the particle size of the zinc sulfonate salt can be controlled by the anionic surfactant and the zinc salt fluid introduction flow rates.
  • a reactor containing 30 niL of water was stirred vigorously at room temperature.
  • a 30 niL of 1 wt. % zinc chloride aqueous solution was pumped into the reactor at a rate of about 10 mL/min.
  • a 60 ml. non-aqueous solution containing 0.5 wt. % PETRO ATE® EOR- 2095 and 5 wt. % HPT-1 was simultaneously pumped into the reactor at a rate of about 20 mL/min.
  • the resulting average particle size diameter for the described run was determined to be about 170 nm.
  • Table 2 summarizes the average zinc sulfonate surfactant salt particle size as a function of three different introduction feed flow rates of the zinc salt solution and the petroleum sulfonate surfactant solution.
  • the zinc sulfonate surfactant salt particle sizes were measured using the Field Flow Fractionation of Example 9.
  • Table 2 Zinc ion and petroleum sulfonate solution flow rates, residence times and zinc sulfonate surfactant salt particle size for three given sets of feed flow rates.
  • Example 1 1 Zinc ion and petroleum sulfonate solution flow rates, residence times and zinc sulfonate surfactant salt particle size for three given sets of feed flow rates.
  • Example 1 1 Zinc ion and petroleum sulfonate solution flow rates, residence times and zinc sulfonate surfactant salt particle size for three given sets of feed flow rates.
  • Example 1 1 demonstrates that the particle size of the aluminum sulfonate salt can be controlled by the anionic surfactant and the aluminum salt fluid introduction flow rates,
  • a reactor containing 30 mL of water was stirred vigorously at room temperature.
  • a 30 mL of 1 wt. % aluminum nitrate nonahydrate aqueous solution was pumped into the reactor at a rate of about 10 mL/min.
  • a 60 mL non-aqueous solution containing 0.5 wt. % PETRONATE ⁇ EOR-2095 and 5 wt. % HPT-1 was simultaneously pumped into the reactor at a rate of about 20 mL/min.
  • the resulting average particle size diameter for the described run was determined to be about 430 nm.
  • Table 3 summarizes the average aluminum sulfonate surfactant salt particle size as a function of three different introduction feed flow rates of the aluminum salt solution and the petroleum sulfonate surfactant solution.
  • the aluminum sulfonate surfactant salt particle sizes were measured using the Field Flow Fractionation of Example 9.
  • Table 3 Aluminum ion and petroleum sulfonate solution flow rates, residence times and average aluminum sulfonate surfactant salt particle size for three given sets of feed flow rates.
  • Example 12 demonstrates that the particle size of the copper sulfonate salt can be controlled by the anionic surfactant and the copper salt fluid introduction flow rates.
  • a reactor containing 30 mL of water was stirred vigorously at room temperature.
  • a 30 mL of 1 wt. % copper nitrate hemi(pentahydraie) aqueous solution was pumped into the reactor at a rate of about 30 mL/min.
  • a 60 ml, non-aqueous solution containing 0.5 wt. % PETRONATE® EOR-2095 and 5 wt, % HPT-1TM was simultaneously pumped into the reactor at a rate of about 20 mL/min.
  • the resulting average particle size diameter for the described run was determined to be about 366 nm.
  • Table 4 summarizes the average copper sulfonate surfactant salt particle size as a function of three different introduction feed flow rates of the copper salt solution and the petroleum sulfonate surfactant solution. The copper sulfonate surfactant salt particle sizes were measured using the Field Flow Fractionation of Example 9.
  • Table 4 Copper ion and petroleum sulfonate solution flow rates, residence times and copper sulfonate surfactant salt particle size for three given sets of feed flow rates.

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Abstract

Cette invention concerne une particule de sulfonate-sel métallique peu soluble qui contient le sel d'ion métallique d'un alkylarylsulfonate, le sel d'ion métallique d'un sulfonate de pétrole et un polymère hydrophile à modification hydrophobe, ladite particule ayant un diamètre de particule moyen dans une plage d'environ 50 à environ 450 nm et étant peu soluble dans l'eau à température ambiante. Cette invention concerne en outre un procédé de production de ladite particule de sulfonate-sel métallique peu soluble comprenant les étapes d'introduction d'une solution aqueuse contenant un sel d'ion métallique dans un réacteur, d'introduction d'une solution aqueuse contenant un tensioactif de type sulfonate et un polymère dans le réacteur, et de mise en marche du réacteur pour que la particule de sulfonate-sel métallique peu soluble se forme à partir de l'interaction de l'ion métallique du sel, du tensioactif de type sulfonate et du polymère.
PCT/US2014/057169 2013-10-01 2014-09-24 Libération contrôlée de tensioactifs pour une récupération améliorée de pétrole WO2015050759A2 (fr)

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SA516370745A SA516370745B1 (ar) 2013-10-01 2016-03-16 إطلاق مقنن لمواد خافضة للتوتر السطحي للاستخلاص المعزز للنفط
SA517390640A SA517390640B1 (ar) 2013-10-01 2016-03-16 إطلاق مقنن لمواد خافضة للتوتر السطحي للاستخلاص المعزز للنفط
SA517390642A SA517390642B1 (ar) 2013-10-01 2016-03-16 إطلاق مقنن لمواد خافضة للتوتر السطحي للاستخلاص المعزز للنفط

Applications Claiming Priority (2)

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US14/043,403 US9580639B2 (en) 2011-07-18 2013-10-01 Controlled release of surfactants for enhanced oil recovery
US14/043,403 2013-10-01

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WO2015050759A2 true WO2015050759A2 (fr) 2015-04-09
WO2015050759A3 WO2015050759A3 (fr) 2015-06-25

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US4319636A (en) * 1980-02-19 1982-03-16 Texaco Inc. Surfactant waterflood oil recovery process
US6790813B2 (en) * 2002-11-21 2004-09-14 Chevron Oronite Company Llc Oil compositions for improved fuel economy
US8946132B2 (en) * 2011-07-18 2015-02-03 Saudi Arabian Oil Company Controlled release of surfactants for enhanced oil recovery

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SA517390640B1 (ar) 2021-02-24
SA516370745B1 (ar) 2018-02-12
WO2015050759A3 (fr) 2015-06-25
SA517390642B1 (ar) 2020-12-31

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