WO2010047705A1 - Acides gras saponifiés comme modificateurs de viscosité pour fluides gélifiés par des tensioactifs viscoélastiques - Google Patents

Acides gras saponifiés comme modificateurs de viscosité pour fluides gélifiés par des tensioactifs viscoélastiques Download PDF

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WO2010047705A1
WO2010047705A1 PCT/US2008/080856 US2008080856W WO2010047705A1 WO 2010047705 A1 WO2010047705 A1 WO 2010047705A1 US 2008080856 W US2008080856 W US 2008080856W WO 2010047705 A1 WO2010047705 A1 WO 2010047705A1
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fluid
ves
viscosity
ammonium
gelled
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PCT/US2008/080856
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James B. Crews
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Baker Hughes Incorporated
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Publication of WO2010047705A1 publication Critical patent/WO2010047705A1/fr

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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
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/602—Compositions for stimulating production by acting on the underground formation containing 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
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/62—Compositions for forming crevices or fractures
    • C09K8/66—Compositions based on water or polar solvents
    • C09K8/68—Compositions based on water or polar solvents containing organic compounds
    • 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
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/62—Compositions for forming crevices or fractures
    • C09K8/70—Compositions for forming crevices or fractures characterised by their form or by the form of their components, e.g. foams
    • 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
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/80—Compositions for reinforcing fractures, e.g. compositions of proppants used to keep the fractures open
    • 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
    • C09K2208/26—Gel breakers other than bacteria or enzymes
    • 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
    • C09K2208/30—Viscoelastic surfactants [VES]

Definitions

  • the present invention relates to gelled treatment fluids used during hydrocarbon recovery operations, and more particularly relates, in one embodiment, to methods of "breaking" or reducing the viscosity of aqueous treatment fluids containing viscoelastic surfactant gelling agents used during hydrocarbon recovery operations, as well as to increasing the viscosity of these fluids.
  • Hydraulic fracturing is a method of using pump rate and hydraulic pressure to fracture or crack a subterranean formation. Once the crack or cracks are made, high permeability proppant, relative to the formation permeability, is pumped into the fracture to prop open the crack. When the applied pump rates and pressures are reduced or removed from the formation, the crack or fracture cannot close or heal completely because the high permeability proppant keeps the crack open.
  • the propped crack or fracture provides a high permeability path connecting the producing wellbore to a larger formation area to enhance the production of hydrocarbons.
  • fracturing fluids are aqueous based liquids that have either been gelled or foamed.
  • a polymeric gelling agent such as a solvatable polysaccharide, for example guar and derivatized guar polysaccharides.
  • the thickened or gelled fluid helps keep the proppants within the fluid.
  • Gelling can be accomplished or improved by the use of crosslinking agents or crosslinkers that promote crosslink- ing of the polymers together, thereby Increasing the viscosity of the fluid.
  • One of the more common crosslinked polymeric fluids is borate crossli ⁇ ked guar.
  • the recovery of fracturing fluids may be accomplished by reducing the viscosity of the fluid to a low value so that it may flow naturally from the formation under the influence of formation fluids.
  • Crosslinked gels generally require viscosity breakers to be injected to reduce the viscosity or "break" the gel. Enzymes, oxidizers, and acids are known polymer viscosity breakers.
  • Enzymes are effective within a pH range, typically a 2.0 to 10.0 range, with increasing activity as the pH is lowered towards neutral from a pH of 10.0.
  • Most conventional borate crosslinked fracturing fluids and breakers are designed from a fixed high crossli ⁇ ked fluid pH value at ambient temperature and/or reservoir temperature. Optimizing the pH for a borate crosslinked gel is important to achieve proper crosslink stability and controlled enzyme breaker activity.
  • aqueous drilling and treating fluids may be gelled or have their viscosity increased by the use of non-polymeric viscoelastic surfactants (VES).
  • VES non-polymeric viscoelastic surfactants
  • These VES materials are in many cases advantageous over the use of polymer gelling agents in that they are comprised of low molecular weight surfactants rather than high molecular weight polymers.
  • the VES materials may leave less gel residue within the pores of oil producing formations, leave no "filter cake” (dehydrated polymer) on the formation face, leave a minimal amount of residual surfactant coating the proppant, and inherently do not create microgels or "fish-eye”-type polymeric masses.
  • VES gelled fluids have relied on "external” or “reservoir” conditions for viscosity reduction (breaking) and VES fluid removal (clean-up) during hydrocarbon production. Additionally, over the past decade it has been found that reservoir brine dilution has only a minor, if any, breaking effect on VES gel within the reservoir.
  • VES fluid viscosity reduction gel breaking or thinning
  • results have showed many instances where VES fluid in portions of the reservoir are not broken or are incompletely broken resulting in residual formation damage (hydrocarbon production impairment).
  • VES breaking and clean-up takes a long time, such as several days up to possibly months
  • post-treatment clean-up fluids i.e. use of external VES breaking solutions
  • VES-gelled fluids are not comprised of polysaccharide polymers that are easily degraded by use of enzymes or oxidizers, but are comprised of surfactants that associate and form viscous rod- or worm-shaped micelle structures. Conventional enzymes and oxidizers have not been found to act and degrade the surfactant molecules or the viscous micelle structures they form.
  • a method for affecting the viscosity of aqueous fluids gelled with a viscoelastic surfactant comprising introducing into an aqueous fluid gelled with at least one viscoelastic surfactant a composition in an amount effective to increase or decrease the viscosity of the gelled aqueous fluid, where the composition comprises a soap reaction product of a fatty acid with an alkaline compound that may be an alkali metal halide salt, an alkaline earth metal halide salt, and/or an ammonium salt.
  • the reaction of the fatty acid with the alkaline compound is conducted in the presence of a water soluble base including, but not necessarily limited to, alkali metal bases, ammonia, ammonium hydroxide, methylamine, trimethylamine, ethylmethylamine, ethanolamine, triethanolamine, urea, choline, and mixtures thereof.
  • the fatty acid may be those found in plant oils and animal oils.
  • the alkali metal halide salt and alkaline earth metal halide salt may have a cation including, but not necessarily limited to, Na + , K + , Li + , Cs + , Ca + , Mg + , Ba + , Sr + , and/or NH 4 + .
  • the ammonium salt may be ammonium bromide, ammonium iodide, ammonium bicarbonate and/or ammonium nitrate.
  • an aqueous fluid that includes water; at least one viscoelastic surfactant (VES) in an amount effective to increase (gel) the viscosity of the aqueous fluid and a composition in an amount effective to affect the viscosity of the gelled aqueous fluid (increase or decrease viscosity), where the composition comprises at least one soap reaction product of a fatty acid with an alkaline compound that may be an alkali metal halide salt, an alkaline earth metal halide salt, and/or an ammonium salt.
  • VES viscoelastic surfactant
  • reaction of the fatty acid with the alkaline compound is conducted in the presence of a water soluble base including, but not necessarily limited to, alkali metal bases, ammonia, ammonium hydroxide, methylamine, trimethylamine, ethylmethylamine, ethanolamine, triethan ⁇ iamine, urea, choline, and mixtures thereof.
  • a water soluble base including, but not necessarily limited to, alkali metal bases, ammonia, ammonium hydroxide, methylamine, trimethylamine, ethylmethylamine, ethanolamine, triethan ⁇ iamine, urea, choline, and mixtures thereof.
  • FIG. 1 is a graph showing the effect of using various types of hydroxides within WG-3L gelled fluid at 150T (66 0 C);
  • FIG. 2 is a graph showing the effects of using varying amounts of vegetable oil (corn oil) within WG-3L gelled fluid at 150 0 F (66 0 C);
  • FIG. 3 is a graph of showing the effects of using various different types of vegetable oil from those of FIG. 2 within WG-3L gelled fluid at 15O 0 F (66°C);
  • FIG. 4 is a graph showing the effects of using various common hydroxides within WG-3L gelled fluid that contains 0.4% bv corn oil;
  • FIG. 5 is a graph showing the effects of using two common hydroxides within WG-3L gelled fluid that contains 0.6% bv canola oil
  • FIG. 6 is a graph showing the effects of using two hydroxyl compounds within WG-3L gelled fluid that contains 0.2% bv canola oil at 18O 0 F (82°C);
  • FlG. 7 is a graph showing the effects of using various amounts of Bertolli Extra Virgin type olive oil within WG-3L gelled fluid and when CaOH is then added with olive oil;
  • FIG. 8 is a graph showing the effects of using readily water soluble components such as NaOH and CaCI 2 to saponify canola oil at 15O 0 F (66°C).
  • aqueous fluids gelled with viscoelastic surfactants are typically used in wellbore completions, such as hydraulic fracturing, without the use of an internal breaker system, and generally rely on external downhole conditions for the VES-gelled fluid to break, such as dilution with reservoir brine and more importantly gel breaking through interaction with reservoir hydrocar- bons during production of such reservoir fluids to the surface.
  • external downhole conditions has provided many instances where unbroken or poorly broken VES fluid remains within the hydrocarbon section of the reservoir after a VES fluid treatment and has impaired hydrocarbon production.
  • a new method has been discovered to affect the viscosity of aqueous fluids gelled with viscoelastic surfactants ⁇ i.e. surfactants that develop viscosity in aqueous brines by formation of rod- or worm-shaped micelle structures).
  • the improvement will allow relatively very quick breaks, such as within 1 to 2 hours, compared to the current technology of using bacteria to break VES which takes at least 12 or more hours, and more typically 4 to 7 days.
  • the viscosity- affecting components discussed herein may be added to the gel and put into solution during a VES-gel treatment and the alteration of the fatty acid or the saponification may occur during mixing and pumping of the fluid downhole.
  • the method may also be used where most of the saponification occurs within the reservoir shortly after the treatment is over.
  • the viscosity-affecting components may increase or decrease the viscosity of the gelled aqueous fluids. In the case of decreasing the viscosity of the aqueous gelled fluid, it is not necessary for the gel to be completely “broken" (e.g. to the approximate viscosity of water) or for all of the gel to be eliminated for the method or additive to be considered successful.
  • the components may be pre-formed and added later separately, if needed, as an external breaker solution to remove VES gelled fluids already placed downhole.
  • SPE paper 71658 addresses how polymeric based frac pack fluids are designed in light of near-wellbore and fracture cooldown by the injection of the cooler fluids that are pumped ahead of the frac pack treat- ment and when required fluid efficiency is low, and is incorporated herein by reference.
  • the co-surfactant or saponification or soap reaction product may be formed within the fluid in situ using one or more fatty acids and one or more metal bases and/or one or more alkali metal halide salts or alkaline earth metal halide salts.
  • Being able to form co-surfactants in situ is a novel and unique, however, either above ground prior to a job, during the treatment, or after the treatment. It is expected that the introduction of the altered fatty acids after the treatment would be primarily for the VES breaking application.
  • Suitable naturally-occurring fatty acids include, but are not necessarily limited to, plant oils: e.g. corn oil, safflower oil, canola oil, olive oil, peanut oil, sunflower oil, soybean oil, almond oil, and the like; and animal oils: e.g. fish oils, mammal oils, including fats. Fats are oils that are in a solid form at ambient temperature. Preferably the natural fatty acids are in glyceride form.
  • the natural fatty acids may also be in the free fatty acid form.
  • the oil composition may be made up of various triglycerides (TG), diglycerides (DG), and/or monoglycerides (MG). Additionally, the use of oils that are higher in polyunsaturated fatty acids PUFA) and/or monounsaturated fatty acids (MUFA) than saturated fatty acids (SFA) are of utility, and in many non-restrictive cases preferred.
  • the alteration of fatty acids by an alkali or alkaline earth metal base and/or alkali or alkaline earth metal salt may improve the viscosity of a VES-gelled fluid over 100%.
  • the alteration or modification may be designed to completely reduce the VES viscosity of the fluid.
  • the use of this chemical technology is simple and economical to use.
  • up to 50% less VES gelling agent i.e. surfactant
  • a relatively small amount of altered fatty acid is needed for enhancing the VES fluid viscosity.
  • the VES fluid viscosity breaks back to water, or water viscosity.
  • two or more times the amount of altered fatty acids are typically required to decrease and completely break the VES fluid viscosity, as compared with the relatively smaller amounts needed to enhance the VES fluid viscosity.
  • the amount needed for either application is dependant on several factors, which include VES concentration, fluid temperature, mix water salinity, type and amount base saponifying agents used, and the like.
  • the amount of fatty acid soap that is formed to enhance the VES fluid viscosity is a relatively small amount and appears to readily associate with the larger amount of viscoelastic surfactants present in the fluid; thereby the soap readily stays soluble or dispersed within the viscosity enhanced fluid.
  • the amount of soap compounds typically about two or more times the amount of soap compounds ⁇ i.e. amount of saponified fatty acids formed) are required, with total amount of soap needed depending on the types and amounts of soaps formed, fluid temperature, VES concentration, mix water salinity, and the like.
  • soaps formed by divalent ions have more breaking activity than monovalent forms: that is, "hard soaps” more readily degrade VES viscosity than "soft soaps".
  • Hard soaps are defined herein to include, but are not necessarily limited to, calcium, magnesium and the like soaps.
  • Soft soaps are defined herein to include, but not necessarily be limited to, sodium, potassium, triethanolamine, and the like soaps.
  • Hard soaps are known to be much less soluble in water than soft soaps and can, at high enough concentrations, in certain VES fluids and under certain conditions potentially precipitate and scale.
  • a ratio of soft to hard soap may be of utility: that is, the ratio of soft soap to hard soap may be optimized where the soft soaps aids the solubility and dispersibility of the hard soaps formed, with the ratio of them controllable to limit a potential phase separation or precipitating of hard soap from the broken VES fluid.
  • one or more hard soap "solubilizers" besides the viscoelastic surfactant and soft soaps described herein may be used. There are several common hard soap solubilizers and chemistries that may be of utility for this invention.
  • a non-limiting example is BASF products JORDAPON ® Cl and ACI, which are sodium and ammonium cocoyl isethionate surfactants commonly used in the personal care industry, which have a Lime Soap Dispersion Index of about 17 parts sodium or ammonium cocoyl isethionate to 100 parts calcium oleate, can be used to solubilize or disperse hard soaps generated by this invention, with ammonium cocoyl isethionate being the most preferred.
  • Other suitable hard soap solubilizers or dispersants include, but are not necessarily limited to, sodium laureth-13 carboxylate, ammonium laureth-13 carboxylate. Different alkali metal forms of these solubilizers, such as the potassium and lithium forms, may also be useful. In other non-limiting examples alky! glucosides, alkyl glycols, and the like solubilizers or dispersants may be utilized.
  • Controlled viscosity reduction rates may be achieved from 75 ⁇ F to about 280 0 F (about 24°C to about 138°C), in one non-limiting embodiment.
  • these gel-breaking products work by rearrangement of the VES micelle type or structure from rod-shaped or worm-shaped elongated structures to more spherical structures.
  • the compositions herein will reduce the viscosity of the gelled aqueous fluid either directly, or by disaggregation or rearrangement of the VES micellar structure.
  • Disaggregating may be understood in one non-limiting embodiment when the micelles are not closely associated physically, that is no longer aggregated together, as contrasted with rearrangement which may be understood as a different physical arrangement or aggregation that has reduced viscosity.
  • the use of the disclosed breaker system is ideal for controlled viscosity reduction of VES based fracturing fluids.
  • the breaking system may also be used for breaking gravel pack and loss circulation pill fluids composed of VES. This VES breaking method is a significant improvement in that it gives breaking rates for VES based fluids that the industry is accustomed to with conventional polymer based fracturing fluids, such as borate crosslinked guar.
  • the products of interaction of fatty acids with saponifying agents listed herein may be used to improve or increase the viscosity of the VES-gelled fluids in such a way that the effective amount of VES needed may be reduced, yet give the same or increased viscosity or gelling power.
  • the ability of the VES-gelled fluid to transport sand, proppant or other particulates may also be improved. While it is expected that the effect of the use of metal bases together with fatty acids will either increase VES-gelled fluid viscosity or decrease the viscosity, it is not expected that in most cases both would occur simultaneously. It may be possible in some non-limiting embodiments that first an increase in viscosity and then a decrease in viscosity may occur. It has been discovered that in at least one instance both effects may occur sequentially (please see Example 5 and FIG. 5).
  • U.S. Pat. No. 6,506,710 to Hoey, et al. concerns viscoelastic surfactants and compositions thereof for underground use, such as in stimulation fluids, drilling muds, fracturing fluids, and in applications such as permeability modification, gravel packing, cementing and the like; similar uses to those herein.
  • This document teaches limits on the amount of free fatty acids that should be present in the compositions to enhance the product's performance vs. temperature. Free fatty acid contents are listed, that is the inventors therein list a range of how much fatty acid may be used or included within the final product composition. However, there is no teaching about how the chemistry of these fatty acids is functioning, other than that some optimum amount of free fatty acid improves product yield and viscosity at temperatures up to 80 0 C.
  • compositions such as those of the 710 patent include about 1.0 to about 2.0 bw free fatty acids. These fatty acids may be used, and alternatively and possibly more importantly the addition of certain specific types and amounts of plant oils into VES-gelled fluid, may be altered by adding an alkali ⁇ e.g. Na 1 K, Cs, etc.) and/or alkaline earth metal (e.g. Ca, Mg, Ba, etc.) base (e.g.
  • anions of the salts exchange with those of the base(s) in an effective or advantageous way, although the inventor does not want to be limited to any particular explanation.
  • inorganic bases organic bases, or bases with salts may be employed to optimize the soap compounds that are formed upon saponification.
  • suitable bases include, but are not limited to various valences of hydroxides and oxides of Fe, Mn, Cu, Zn, Zr, Mo 1 V, Co 1 Al, Sn and the like; and alkaline organic base ions such as: diethanol- ami ⁇ e, triethanolamine, choline, and the like. It has also been discovered that halide salts of these alkali metals and alkaline earth metals also give useful soap reaction products, as do ammonium salts.
  • Suitable alkali metal halide salts include, but are not limited to, halide salts of Na 1 K, Li, and/or Cs, including chloride and bromide salts.
  • Suitable alkaline earth metal halide salts include, but are not limited to, halide salts of Ca, Mg, Ba, and/or Sr 1 including chloride and bromide salts.
  • Suitable ammonium salts include, but are not necessarily limited to, ammonium bromide, ammonium chloride, ammonium bicarbonate and/or ammonium nitrate.
  • the type of "soap" compounds that are produced may be controlled, along with their amount, to alter the VES gel micelles in useful ways.
  • the methods and compositions herein involve base-altered fatty acid, more specifically, fatty acids within or introduced into a VES-gelled fluid may be selectively altered by controlled saponification to yield various types and amounts of soap compounds.
  • These compounds may be formed during product use, in one non-limiting embodiment, during the mixing and pumping of a fluid into a well.
  • These compounds or products may be used to substantially improve fluid viscosity or to break down the rod-shaped or worm- shaped VES micelles to regular, spherically-shaped, non-viscous micelles in a brine medium, such as a fluid used in a hydrocarbon recovery operation.
  • VES gelling agent typically more expensive than the soap compounds.
  • VES gelling agent may be used to save money and reduce VES fluid costs to the operator and to make VES technology more affordable.
  • the application of "breaking" the VES fluid viscosity i.e. using the soap compounds to reduce the VES viscosity, should improve VES gel clean-up from a reservoir after a treatment or operation.
  • the breaking mechanism herein involves certain types and amounts of saponified fatty acid compounds that will interfere with the VES surfactant's association and cause the VES rod/worm- shaped micelles to become more unstable over time.
  • the use of this internal breaker sys- tern by itself or in combination with external downhole breaking conditions should help assure and improve hydrocarbon production compared to many prior meth- ods that use only external mechanisms to break the VES fluid for effective and complete VES fluid clean-up after a treatment.
  • the methods and compositions herein may be for flowback of a fracturing fluid, or additionally for clean-up of VES diverter fluids during wellbore or matrix acidizing. It is expected that the chemical technology described herein will help resolve clean-up problems.
  • fatty acids and, more importantly, the addition of specific types and amounts of plant and related oils into a VES gelled fluid, and then altering them through adding an alkali and/or alkaline earth metal base and/or organic base "saponifies" the fatty acids into soap.
  • the addition and presence of salts may also influence the saponification reactions and type or types of soap that are generated over time.
  • Suitable alkali metals include, but are not necessarily limited to sodium, potassium, cesium, and combinations thereof.
  • Suitable alkaline earth metals include, but are not necessarily limited to calcium, magnesium, barium, and combinations thereof.
  • these metals may be introduced in the form of bases, particularly hydroxides, such as NaOH, MgOH 1 CaOH 1 etc.
  • the metals may be also introduced by the addition of salts, such as KCI, NH 4 CI, NaBr, MgCI ⁇ , CaCI 2 , CaBr 2 , etc. That is, a blend of two or more bases, organic bases, or bases with salts may be used to give custom soap compounds that achieve viscosity increase, decrease, or both sequentially, or control the saponification rate.
  • the type of "soap" compounds that are produced may be controlled, along with their amounts and their water solubility, dispersibility, and association with one another.
  • a blend of two or more oils may be used to give custom soap compounds that achieve the same effective results.
  • two or more specific bases, or specific bases and salts, and two or more specific plant or other oils may be combined to achieve the same or better results as compared to using one. That is, the custom soap compounds may be generated in a variety of ways and give the methods and fluids even greater functionality compared to other VES breaking mechanisms prior to this point in time.
  • VES product when added to a brine mix water (such as 3% by weight KCI water) may cause the water to become alkaline (such as if ammonia is present in the VES product) that the addition of salts of alkali metals (such as calcium chloride) with a vegetable oil (such as canola oil) can induce saponification of the vegetable oil and create VES-breaking calcium-based soap compounds during heating.
  • alkali, alkaline, and transition metals may saponify oils (such as plant oils) into VES-affecting or VES-breaking soap compounds over time at certain fluid temperatures, such as 150 0 F (66 0 C).
  • a VES breaking composition may be made from a readily water soluble alkali metal base (such as NaOH 1 KOH, etc.) and a readily water soluble alkaline earth metal salt (such as CaCl2, MgC ⁇ , etc.), and thus promote a composition in the VES fluid where VES-breaking soap compounds are formed or generated over time, such as calcium soap molecules.
  • This unique composition may be utilized for primarily breaking VES fluids, that is, alkali metal, alkaline earth metal or transition metal soap compounds formed in sufficient concentration to alter the elongated VES micelle to rearrange it into a structure such as non-viscous spherical micelles, in one non-limiting embodiment.
  • the composition may also be used to produce trace amounts of alkali, alkaline earth and transition metal soap molecules that in trace or relatively small amounts may enhance VES viscosity - that is, positively influence the VES elongated micelles in trace or small amounts where the VES micelles have better integrity and possible viscosity.
  • salts such as CaCI 2
  • alkali bases such as KOH
  • the rate of VES viscosity break may be controlled by the type and amount of: 1) VES used; 2) plant, fish, or animal oil used; 3) alkali, alkaline earth and/or transition metal salt used; 4) fluid temperature; and 5) time at the fluid temperature.
  • This VES composition principally utilizes saponification type monovalent bases and multivalent salts that are readily water soluble, rather than slowly or slightly soluble solid particles in brine fluids. Being readily and entirely water soluble allows the monovalent bases and multivalent salts to go wherever the VES fluid goes, without concern for possible filtering out of any solid particle on or slightly within a porous media, such as the reservoir formation face during VES fluid leak-off under hydraulic pressure during a gravel pack or frac-pack treatment.
  • Suitable water soluble bases useful herein include, but are not limited to, alkali metal bases (such as NaOH, KOH 1 LiOH, and the like), ammonia, ammonium hydroxide (NH4OH), and organic bases such as methylamine, trimethylamine, ethylmethylamine, ethanolamine, triethanolamine, urea, choline, and the like, and mixtures thereof.
  • alkali metal bases such as NaOH, KOH 1 LiOH, and the like
  • ammonia ammonium hydroxide (NH4OH)
  • organic bases such as methylamine, trimethylamine, ethylmethylamine, ethanolamine, triethanolamine, urea, choline, and the like, and mixtures thereof.
  • the components listed are readily water soluble, and will therefore travel with the VES fluid into a porous media such as a sandstone formation, and in such a porous media can still saponify the plant oils distributed as microemulsions within the VES fluid, thus generating VES breaking compounds in the porous media, an advantage over the multivalent bases.
  • the VES fluid containing a plant oil (such as olive oil) with a monovalent base (such as KOH) may also contain in part a relatively small amount of multivalent salts, or may rely totally and entirely on the multivalent salts present within the reservoir (e.g.
  • the stoichiometric ratio of the base (such as NaOH) and salt (such as CaCl 2 ) to fatty acids (such as canola oil) may be important. Using less base and salt and not fully saponifying the fatty acids may have some utility. One non- restrictive example would be to change the reaction rate, that is, the rate of saponification, i.e. how much fatty acid soap is present in fluid overtime.
  • Changing the rate may be needed at elevated temperatures (in one non-limiting instance, above about 180 0 F (82 0 C)), and this may be one method of controlling rate, e.g. slowing it down.
  • the type and amount of base and salt may control the rate of saponification.
  • Combinations of bases and salts and also the type and amount of fatty acids may also be used to control rate of saponification.
  • Each oil has a different fatty acid composition, that is, different types and amounts of the various fatty acids ⁇ i.e.
  • oils in particular, but most oils also include diglycerides, monoglycerides, and free fatty acids; and the fatty acids within oils also vary in length of carbon chain, amount of double carbon bonds, placement of double bonds, and the like), and further each oil may also have different types and amounts of natural impurities (non-fatty acid constituents) that may influence rate of saponification.
  • a stoichiometric excess amount of metal base and salt relative to the fatty acid functionality would probably be used.
  • the presence and use of salts with bases may influence the initial portion of saponification products generated and may continue to influence the type and amount of specific soap compounds formed over time.
  • the fluid pH can be optimized to influence the type of base present with various types of salts present in the VES fluid over time.
  • the reaction of salts of alkali metal halide salts and/or alkaline earth metal halide salts with fatty acids may include a high pH material like sodium hydroxide, ammonium hydroxide, etc., for the salt to then be able to saponify with the fatty acid.
  • fatty acids such as from vegetable oils
  • a high pH material like sodium hydroxide, ammonium hydroxide, etc.
  • Ethanolamines such as triethanol- amine (TEA) may also be used as agents to raise the pH of the reaction system. Ethanolamines may also be agents that directly saponify fatty acids alone.
  • chelants including but not necessarily limited to, aminocarboxylic acids, iminodisuccinates, polyaspartates, gluconates, and the like may influence the saponification products generated.
  • use of chelants may influence the metal-base species that may be present or generated along with the type of salts present over time, including as the VES fluid temperature shifts, e.g. during initial fluid heat-up as the fluid is pumped downhole or upon reaching final temperature within the reservoir.
  • chelants that may be of utility, such as K 5 DTPA versus NHaEDTA 1 to vary the rate of alkaline earth metal-base disassociation and the type and amount of cation exchange as a method or mechanism to optimize rate and type of saponification.
  • Another non-limiting example would be the use of one or more polymer to influence the interaction of the viscoelastic surfactant and types of soaps formed.
  • Other agents besides salts, pH buffers, polymers, solubilizers, scale inhibitors, and chelants may be found to be of utility to optimize or further alter the saponification chemistry, the soaps generated, and their association with the viscoelastic surfactant and with one another.
  • compositions and methods herein would be suitable within a temperature range of about 75 to about 280 0 F (about 24 to about 138"C) 1 and in another non-restrictive version between a lower limit of about 90 0 F (32°C) to an optional upper limit of about 23O 0 F (110 0 C).
  • gel-breaking and viscosity-enhancing embodiment herein it is difficult to specify in advance with accuracy the amount of the various viscosity-affecting components that should be added to a particular aqueous fluid gelled with viscoelastic surfactants to sufficiently or fully break the gel, in general.
  • the amount of soap reaction product that may be effective in the methods and fluids herein may range from about 50 to about 20,000 ppm, based on the total amount of the fluid.
  • the amount of soap reaction product may range from an alternative lower limit of about 500 ppm to a non-restrictive upper limit of about 12,000 ppm.
  • the fluid will be exposed and heated to, whether the VES fluid viscosity increases or decreases is dependant on the amount or proportion of fatty acid soap compounds formed. For instance, as a non-limiting generality, at relatively low concentrations viscosity enhancement occurs, while at relatively higher concentrations viscosity decrease occurs.
  • the amount is dependant on the given temperature.
  • VES and the aqueous fluid are blended for a period of time sufficient to form a gelled or viscosified solution.
  • the VES that is useful may be any of the VES systems that are familiar to those in the well service industry, and may include, but are not limited to, amines, amine salts, quaternary ammonium salts, amidoamine oxides, amine oxides, mixtures thereof and the like.
  • Viscoelastic surfactants improve the fracturing (frac) fluid performance through the use of a polymer-free system.
  • the viscoelastic surfactants suitable for use herein include, but are not necessarily limited to, non-ionic, cationic, amphoteric, and zwitterionic surfactants.
  • zwitterionic/amphoteric surfactants include, but are not necessarily limited to, dihydroxyl alkyl glycinate, alkyl ampho acetate or propionate, alkyl betaine, alkyl amidopropyl betaine and alkylimino mono- or di- propionates derived from certain waxes, fats and oils.
  • Quaternary amine surfac- tants are typically cationic, and the betaines are typically zwitterionic.
  • the thickening agent may be used in conjunction with an inorganic water-soluble salt or organic additive such as phthalic acid, salicylic acid or their salts.
  • non-ionic fluids are inherently less damaging to the producing formations than cationic fluid types, and are more efficacious per pound than anionic gelling agents.
  • Amine oxide viscoelastic surfactants have the potential to offer more gelling power per pound, making it less expensive than other fluids of this type.
  • the amine oxide gelling agents RN * (R') 2 O " may have the following structure (I):
  • R is an alkyl or alkylamido group averaging from about 8 to 24 carbon atoms and R' are independently alkyl groups averaging from about 1 to 6 carbon atoms.
  • R is an alkyl or alkylamido group averaging from about 8 to 16 carbon atoms and R' are independently alkyl groups averaging from about 2 to 3 carbon atoms.
  • the amidoamine oxide gelling agent is Akzo Nobel's AROMOX APA-T formulation, which should be understood as a dipropylamine oxide since both R 1 groups are propyl.
  • Suitable materials include CLEARFRACTM, which may also comprise greater than 10% of a glycol.
  • VES is an amine oxide.
  • APA-T is sold by Baker Oil Tools as SURFRAQTM VES.
  • SURFRAQ is a VES liquid product that is 50-65% APA-T and from about 25-40% propylene glycol. These viscoelastic surfactants are capable of gelling aqueous solutions to form a gelled base fluid.
  • the additives herein may be used to prepare a VES fluid system, sold by Baker Oil Tools as DIAMOND FRAQTM. DIAMOND FRAQTM with its assured breaking technology overcomes reliance on external reservoir conditions in order to break, as compared with products such as CLEARFRACTM.
  • the method and compositions herein also cover commonly known materials as AROMOX APA-T manufactured by Akzo Nobel and other known viscoelastic surfactant gelling agents common to stimulation treatment of subterranean formations.
  • the amount of VES included in the fracturing fluid depends on at least two factors. One involves generating enough viscosity to control the rate of fluid leak off into the pores of the fracture, and the second involves creating a viscosity high enough to keep the proppa ⁇ t particles suspended therein during the fluid injecting step, in the non-limiting case of a fracturing fluid.
  • the VES is added to the aqueous fluid in concentra- tions ranging from about 0.5 to 25% by volume, alternatively up to about 12 vol % of the total aqueous fluid (from about 5 to 120 gallons per thousand gallons (gptg))-
  • the range for the present methods and compositions is from about 1.0 to about 6.0% by volume VES product.
  • the amount of VES ranges from 2 to about 10 volume %.
  • the viscosity-affecting compositions herein may be used to reduce or increase the viscosity of a VES-gelled aqueous fluid regardless of how the VES-gelled fluid is ultimately utilized.
  • the vis- cosity breaking or improving compositions could be used in all VES applications including, but not limited to, VES-gelled friction reducers, VES viscosifiers for loss circulation pills, fracturing fluids, gravel pack fluids, viscosifiers used as diverters in acidizing (including foam diverters), VES viscosifiers used to clean up drilling mud filter cake, remedial clean-up of fluids after a VES treatment (post- VES treatment), in regular or foamed fluid forms ⁇ i.e.
  • a value of the methods and compositions herein is that a fracturing or other fluid may be designed to have enhanced breaking characteristics. That is, fluid breaking is no longer dependant on external reservoir conditions for vis- cosity break: the rate of viscosity reduction, if essentially complete break is achieved, occurs more completely throughout the reservoir interval. Importantly, better clean-up of the VES fluid from the fracture and wellbore may be achieved thereby. Better clean-up of the VES directly influences the success of the fracture treatment, which is an enhancement of the well's hydrocarbon productivity. Previous VES fluid clean-up limitations and failures may now be overcome or improved by the use of this clean-up technology.
  • an aqueous fracturing fluid is first prepared by blending a VES into an aqueous fluid.
  • the aqueous fluid could be, for example, water, brine, aqueous-based foams or water-alcohol mixtures. Any suitable mixing apparatus may be used for this procedure.
  • the VES and the aqueous fluid are blended for a period of time sufficient to form a gelled or viscosified solution.
  • the viscosity-affecting compositions may be added separately.
  • Propping agents are typically added to the base fluid after the addi- tion of the VES.
  • Propping agents include, but are not limited to, for instance, quartz sand grains, glass and ceramic beads, bauxite grains, walnut shell fragments, aluminum pellets, nylon pellets, and the like.
  • the propping agents are normally used in concentrations between about 1 to 14 pounds per gallon (120- 1700 kg/m 3 ) of fracturing fluid composition, but higher or lower concentrations may be used as the fracture design required.
  • the base fluid may also contain other conventional additives common to the well service industry such as water wetting surfactants, non-emulsifiers and the like.
  • the base fluid may also contain other non-conventional additives which may contribute to the viscosity affecting action of the VES fluid, and which are added for that purpose.
  • Any or all of the above saponification products may be provided in an extended release form such as encapsulation by polymer or otherwise, peptization with binder compounds, absorbed or some other method of layering on a microscopic particle or porous substrate, and/or a combination thereof.
  • the plant, fish and/or animal oils may be micro and/or macro encapsulated to permit slow or timed release thereof.
  • the coating material may slowly dissolve or be removed by any conventional mechanism, or the coating could have very small holes or perforations therein for the soap or saponification products within to diffuse through slowly.
  • a mixture of fish gelatin and gum arabic encapsulation coating available from ISP Hallcrest may be used to encapsulate plant, fish and other oils.
  • polymer encapsulation coatings such as used in fertilizer technology available from Scotts Company, specifically POLY-S ® product coating technology, or polymer encapsulation coating technology from Fritz Industries could possibly be adapted to the oxide and/or hydroxide bases used in the methods and compositions herein.
  • the saponification products could also be absorbed onto zeolites, such as Zeolite A, Zeolite 13X, Zeolite DB-2 (available from PQ Corporation, Valley Forge, Pennsylvania) or Zeolites Na-SKS5, Na-SKS6, Na-SKS7, Na-SKS9, Na-SKSIO, and Na-SKS13, (available from Hoechst Aktie ⁇ ippo, now an affiliate of Aventis SA), and other porous solid substrates such as MICROSPONGETM (available from Advanced Polymer Systems, Redwood, California) or placed within microscopic particles such as carbon nanotubes or buckmi ⁇ ster fullerenes.
  • zeolites such as Zeolite A, Zeolite 13X, Zeolite DB-2 (available from PQ Corporation, Valley Forge, Pennsylvania) or Zeolites Na-SKS5, Na-SKS6, Na-SKS7, Na-SKS9, Na-SKSIO, and Na-SKS13, (available from Hoechst Aktie ⁇
  • the "soaps" or component reactants may be both absorbed into and onto porous or other substrates and then encapsulated or coated, as described above.
  • the fracturing fluid may pumped at a rate sufficient to initiate and propagate a fracture in the formation and to place propping agents into the fracture.
  • a typical fracturing treatment would be conducted by mixing a 20.0 to 60.0 gallon/1000 gal water (volume/volume - the same values may be used with any SI volume unit, e.g.
  • the method is practiced in the absence of gel-forming polymers and/or gels or aqueous fluid having their viscosities enhanced by polymers.
  • the method herein may be practiced where there are no other viscosity decreasing agents in the gelled aqueous fluid besides the soap reaction products.
  • polymers may also be added to the VES-gelled fluid for fluid loss control purposes.
  • polymers may also be added to the VES-gelled fluid for fluid loss control purposes.
  • Types of polymers that may serve as fluid loss control agents include, but are not necessarily limited to, various starches, polyvinyl acetates, polylactic acid, guar and other polysaccharides, gelatins, and the like.
  • Viscosity reduction may be visually detected. Shaking the samples and comparing the elasticity of gel and rate of air bubbles rising out of the fluid may be used to estimate the amount of viscosity reduction observed. Measurements to acquire quantitative viscosity reduction of each sample were obtained using a Brookfield PVS rheometer. Tests were performed at 15O 0 F (66°C) with 300 psi (2.1 MPa) pressure and 40 sec '1 shear, except for Examples 6 and 7 which were run at 18O 0 F (82°C).
  • FIG. 1 Shown in FIG. 1 is a graph of the effect of using various types of hydroxides within WG-3L gelled fluid at 150 0 F (66 0 C).
  • a viscosity increase was observed with the addition of NaOH and CaOH.
  • the viscosity increase may be due to NaOH and CaOH base-mediated saponification of fatty acids from WG-3L product, and these particular saponified fatty acids appear to act as viscosity enhancing co-surfactants at the concentrations generated and conditions tested.
  • Gelling agent WG-3L typically has 1.0 to 2.0% bw free fatty acids within the final product composition. In a 4.0% bv WG-3L gelled fluid the free fatty acid content typically ranges from 0.04 to 0.08% bv (0.4 to 0.8 gptg).
  • EXAMPLE 2 EXAMPLE 2
  • FIG. 2 Shown in FIG. 2 are the test results showing the effect of using varying amounts of vegetable oil within WG-3L fluid at 150 0 F (66 0 C). Tests show that up to approximately 0.6% bv corn oil has minor to no gelled effect on VES fluid viscosity, but at higher corn oil concentrations VES micelle structure and viscosity is proportionally degraded by the oil alone.
  • EXAMPLE 3 Shown in FIG. 3 are test results showing effect of using various types of vegetable oil within WG-3L gelled fluid at 150° F (66°C). The data shows that up to approximately 0.6% bv corn or canola oils have little effect on VES fluid viscosity. However, 0.6% bv safflower (which is the relatively higher oleic-type) and olive oil (Bertolli Extra Light type) both measurably reduce VES gel viscosity and micelle structure.
  • FIG. 4 Shown in FIG. 4 are the effects of using various common hydroxides within WG-3L gelled fluid that contains 0.4% bv corn oil.
  • the substantial increase in viscosity by addition of NaOH may be due to NaOH-mediated saponification of the added corn oil fatty acids and the free fatty acids contained in the WG-3L product.
  • the decrease and eventual complete break in VES gel viscosity by CaOH addition may be due to the type and amount of CaOH base-mediated saponification that occurs over time at 150 0 F (66°C) with corn oil fatty acids.
  • Test results showing the effects of using two common hydroxides within WG-3L gelled fluid that contains 0.6% bv canola oil are shown in FIG. 5.
  • the addition of NaOH appears to show NaOH-mediated saponification of canola oil enhances viscosity, but not quite as much as NaOH-mediated saponification of corn oil, as seen in FIG. 4.
  • the initial viscosity increase followed by rapid and complete viscosity reduction by CaOH addition may be due to the type and amount of CaOH base-mediated saponification that occurs over time at 150 0 F (66"C) with canola oil fatty acids. So far the only base found to work in decreasing VES micelle viscosity is CaOH, but it is expected that others may be found.
  • Test results showing the effects of using highly water soluble metal- base and salt within WG-3L gelled fluid that contains 0.4% canola oil are shown in FIG. 8.
  • the metal-base selected was NaOH and the salt was CaCI 2 .
  • the data shows that canola oil alone at 0.4% had no negative or positive influence on the VES fluid viscosity.
  • With the addition of 20 pptg CaCt the VES fluid containing canola oil had slightly enhanced fluid viscosity.
  • alkali metal halide salt may react to a relatively small degree with a fatty acid to form a soap reaction product that affects the viscosity of an aqueous fluid gelled with a VES that has an alkaline compound like ammonia present in the product.
  • the soap com- pounds appear to act as co-surfactants: they interact, associate, and become part of the VES elongated micelle, and when present in the VES micelle in low concentrations (for a given temperature) they enhance the VES surfactants in producing more robust worm-like micelle structures, although the inventor does not want to be limited by any particular theory.
  • Example 6 shows that a small amount of canola oil (0.2% bv) does not change or decrease the VES viscosity at 180 0 F (82°C).
  • the reheal viscosity phenomenon shows that the amount of CaOH- based soap compounds formed at one temperature and which yielded complete VES gel break at an elevated temperature is not enough to break or rearrange the micelles at a cooler temper, such as 75°F (24°C).
  • This reheal viscosity also shows that the (e.g. CaOH-based) soap compounds do appear to act as co-surfactants at cooler temperatures, but at the elevated test temperature the same compounds act as VES gel breakers, causing complete viscosity reduction.
  • whether a VES fluid has increased viscosity or decreased viscosity depends at least in part on the amount of soap compound (CaOH-based, in one non-limiting embodiment) for a given temperature.
  • an inventive test fluid has been heated until it was completely broken in viscosity, and then the fluid was maintained at that test temperature an additional 2 hours at the broken viscosity (viscosity of water). Upon cooling down the fluid completely rehealed in viscosity and showed a very floppy gel character. The same fluid was put back on the rheometer and approximately as the fluid reached the former test temperature, the fluid viscosity was reduced back to water - that is, a fully broken gel). [0084] It has also been demonstrated in part, as shown in FIG. 8, that readily water soluble compounds may be used for viscosity enhancement or viscosity breaking, depending on the amount of each component added.
  • compositions and methods are provided for breaking and/or increasing the viscosity of aqueous treatment fluids gelled with viscoelastic surfactants (VESs).
  • VESs viscoelastic surfactants
  • Compositions and methods have been described for increasing and/or breaking VES-surfactant fluids where the additive is in a phase internal to the VES-surfactant fluid. Further, compositions and methods have been demon- strated for breaking VES-gelled fluids where contact with reservoir fluids as an external breaking mechanism is not required. Compositions and methods have also been shown for increasing the viscosity of and/or breaking VES-surfactant substrates fluids relatively quickly. Additionally, methods and VES fluid compositions are provided for breaking and/or increasing the viscosity of aqueous fluids gelled with viscoelastic surfactants using readily available materials at relatively inexpensive concentrations.

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Abstract

La présente invention concerne des fluides rendus visqueux avec des tensioactifs viscoélastiques (VES) et dont la viscosité peut être altérée (augmentée ou réduite) par l’action indirecte ou directe d’une composition qui contient au moins un acide gras qui a été altéré, modifié ou mis à réagir avec un sel d’halogénure de métal alcalin, un sel d’halogénure de métal alcalino-terreux, et/ou un sel d’ammonium et une base soluble dans l’eau. La composition contenant le produit de saponification obtenu servirait de co-tensioactif avec le VES pour augmenter la viscosité et/ou éventuellement par désagrégation, ou altérerait la structure micellaire de fluide gélifié par le VES. Par exemple, mais non exclusivement, la viscosité d’une saumure liquide gélifiée avec un tensioactif à base d’oxydes d’amine est rompue avec une composition contenant des acides gras à l’état naturel dans de l’huile de colza mis à réagir avec une base soluble dans l’eau telle que NaOH, KOH, NH4OH, et similaires et avec un sel d’halogénure alcalin tel que CaCI2, MgCI2, NaCI, NH4CI et similaires.
PCT/US2008/080856 2008-10-23 2008-10-23 Acides gras saponifiés comme modificateurs de viscosité pour fluides gélifiés par des tensioactifs viscoélastiques WO2010047705A1 (fr)

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EP2592128A1 (fr) * 2011-11-11 2013-05-15 Baker Hughes Incorporated Saponification induite par des particules métalliques d'acides gras comme rupteurs pour fluides gélifiés par tensioactifs viscoélastiques
US10053646B2 (en) 2015-03-24 2018-08-21 Corbion Biotech, Inc. Microalgal compositions and uses thereof

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WO2006124826A1 (fr) * 2005-05-13 2006-11-23 Baker Hughes Incorporated Deployage d'additif pour des fluides a base de tensioactif viscoelastique

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US20060211775A1 (en) * 2005-03-16 2006-09-21 Baker Hughes Incorporated Saponified fatty acids as breakers for viscoelastic surfactant-gelled fluids
WO2006102042A1 (fr) * 2005-03-16 2006-09-28 Baker Hughes Incorporated Acides gras saponifies convenant comme rupteurs pour fluides gelifies par tensioactifs viscoelastiques
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2592128A1 (fr) * 2011-11-11 2013-05-15 Baker Hughes Incorporated Saponification induite par des particules métalliques d'acides gras comme rupteurs pour fluides gélifiés par tensioactifs viscoélastiques
US10053646B2 (en) 2015-03-24 2018-08-21 Corbion Biotech, Inc. Microalgal compositions and uses thereof

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