WO2019155184A1 - Fluides et procédés - Google Patents

Fluides et procédés Download PDF

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Publication number
WO2019155184A1
WO2019155184A1 PCT/GB2019/050203 GB2019050203W WO2019155184A1 WO 2019155184 A1 WO2019155184 A1 WO 2019155184A1 GB 2019050203 W GB2019050203 W GB 2019050203W WO 2019155184 A1 WO2019155184 A1 WO 2019155184A1
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WIPO (PCT)
Prior art keywords
additive
slurry
imbibition
composition
diverting agent
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PCT/GB2019/050203
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English (en)
Inventor
Xiyuan Chen
Christopher George BURKE
Jeffrey Carl Dawson
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Independence Oilfield Chemicals Llc
Appledene Limited
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Application filed by Independence Oilfield Chemicals Llc, Appledene Limited filed Critical Independence Oilfield Chemicals Llc
Publication of WO2019155184A1 publication Critical patent/WO2019155184A1/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
    • C09K8/62—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
    • C09K8/66—Compositions based on water or polar solvents
    • C09K8/68—Compositions based on water or polar solvents containing organic compounds
    • C09K8/685—Compositions based on water or polar solvents containing organic compounds containing cross-linking agents
    • 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
    • C09K8/84—Compositions based on water or polar solvents
    • C09K8/86—Compositions based on water or polar solvents containing organic compounds
    • C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular 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
    • C09K8/84—Compositions based on water or polar solvents
    • C09K8/86—Compositions based on water or polar solvents containing organic compounds
    • C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
    • C09K8/885—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • C09K8/84—Compositions based on water or polar solvents
    • C09K8/86—Compositions based on water or polar solvents containing organic compounds
    • C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
    • C09K8/887—Compositions based on water or polar solvents containing organic compounds macromolecular compounds containing cross-linking agents
    • 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
    • C09K8/84—Compositions based on water or polar solvents
    • C09K8/86—Compositions based on water or polar solvents containing organic compounds
    • C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
    • C09K8/90—Compositions based on water or polar solvents containing organic compounds macromolecular compounds of natural origin, e.g. polysaccharides, cellulose

Definitions

  • This invention relates to fluids and methods using same. Particularly, although not exclusively, the invention relates to a method of treating a subterranean formation, a slurry and/or treatment fluid for use in the method and a method of making such a fluid. Preferred embodiments relate to use of a slurry and/or treatment fluid to facilitate fracturing of a subterranean formation.
  • Hydraulic fracturing is a process needed to produce oil and gas from unconventional reservoirs such as coal beds, tight sandstones and shales.
  • a fracturing fluid is injected at rates and pressures necessary to cause formation failure by inducing fractures or cracks in the formation. These cracks originate through perforations at the well-bore and radiate out into the formation.
  • a perforation is produced by a projectile fired from a perforating tool to create a hole through a well-bore steel casing and cement casing and into the formation, a distance 6 to 18 inches from the casing.
  • propping agent or proppant is added to the pumped fluid.
  • most proppant comprises small-sized sand such as 0.25 pounds of 100 mesh sand per gallon of water.
  • the amount of, for example, sand is systematically increased and, at some point, the size of the sand may be increased to, for example, 40/70 or 30/50 mesh.
  • the purpose of the sand is to form a sand pack in the fracture which is orders of magnitude more permeable than the formation strata. The sand pack is then able to maintain a conductive pathway from the reservoir to the wellbore for the recovery of the reservoir fluids.
  • perforations in the casing are eroded.
  • a perforation tunnel between the casing and the fracture is packed with proppant to produce a permeable pathway into the well-bore.
  • Sand concentrations will normally range from 200,000 lb to 500,000 lb per fracturing stage and the water can range from 2,000 to 7,000 barrels of water.
  • Diverting agents may be used during a fracturing process.
  • the first step is to stop sand or proppant addition. Once all the sand or proppant in the wellbore has cleared a perforated region of a well-bore, its injection rate may be reduced to 6 to 10 bbl/min and a diverting agent may be added in 300 to 1000 lb slugs, normally at concentrations of about 3 Ib/gal of fluid. Once the diverting agent clears surface pumping equipment and enters a well head, the rate can be increased to about 20 bbl/min, but again reduced to 6 to 10 bbl/min as the diverting agent reaches the perforations.
  • a diverting agent should have an ability to block fluid flow at a concentration that can be operationally managed.
  • a diverting agent suitably possesses some method of blocking fluid flow once a sand pack is established, such as the agent being malleable or deformable.
  • the agent being malleable or deformable.
  • pressure sometimes influenced by temperature, will cause the product to pack and deform to block any further fluid flow, this then terminating the permeability in the flow channel.
  • a diverting agent is easy removal to allow continued recovery of oil and gas from previously fractured portions of the well, in addition to the newly fractured portions, to enhance ultimate recovery of oil and gas from the reservoir. This may involve self-degradation of the diverting agent. Alternatively, a mixture of diverting agent and a degrading composition may be used, with the requirement that the degrading substance becomes part of the diverting pack.
  • PLA polylactic acid
  • the particles of PLA are expected to decompose to lactic acid oligomers within hours or days, this being relatively easily accomplished in reservoirs above 200°F.
  • cooler reservoirs there is a problem that the rate of decomposition is too slow to be practical.
  • a method of treating a subterranean formation penetrated by a well-bore comprising the step of introducing a slurry or treatment fluid into the subterranean formation via the well-bore to plug a region of the well-bore, wherein said slurry or treatment fluid includes a diverting agent and an additive (herein referred to as an “imbibition additive”), wherein the diverting agent and imbibition additive interact such that the imbibition additive causes swelling of the diverting agent and/or increases the susceptibility of the diverting agent to degradation in use.
  • imbibition additive an additive
  • Said imbibition additive is preferably an organic liquid at standard temperature and pressure (STP) (i.e. at 0°C and 1 atm).
  • Said imbibition additive may have a boiling point of greater than 120°C, for example greater than 150°C. The boiling point may be less than 300°C.
  • Said imbibition additive may have a melting point of at least -100°C for example at least -60°C.
  • Said imbibition additive may have a molecular weight of at least 100 g/mol, preferably at least 120 g/mol.
  • the molecular weight may be less than 400 g/mol, for example less than 325 g/mol or less than 250 g/mol.
  • Said imbibition additive may include carbon, hydrogen and oxygen atoms only.
  • Said imbibition additive may include an ester moiety.
  • the ester may be an optionally- substituted alkyl (e.g. a C1 -6 or C1 -4 alkyl) or phenyl, ester.
  • Said ester may be an alkyl, benzyl or phenyl ester. Whilst said ester may include more than one ester moiety (e.g two ester moieties as found in a malonate), if preferably includes a single ester moiety.
  • Said imbibition additive may include a ketone moiety for example an alkyl, phenyl or benzyl carbonyl moiety. It preferably includes an alkylcarbonyl moiety. A preferred alkylcarbonyl moiety may be a C1 -4 alkylcarbonyl moiety, with a methylcarbonyl moiety being especially preferred. Said imbibition additive preferably includes a single ketone moiety of the type described.
  • a said ketone moiety and a carbonyl group of an ester moiety are preferably separated by no more than 3 atoms and, preferably are separated by a single atom, for example a single carbon-atom.
  • Said imbibition additive is preferably an acetoacetate. It may be an optionally- substituted, preferably unsubstituted, benzyl, phenyl or alkyl (especially a C1 -6 or C1 -4 alkyl) acetoacetate. Said imbibition additive may be selected from methyl, ethyl, propyl, butyl and phenyl acetoacetate. Preferably, said imbibition additive is selected from ethyl acetoacetate and butyl acetoacetate.
  • the amount of imbibition additive may be selected according to the amount of diverting agent (especially PLA) in said treatment fluid.
  • the ratio of the weight of diverting agent divided by the weight of imbibition additive may be in the range 100:1 to 5:1 , preferably in the range 80:1 to 10:1 , more preferably in the range 75:1 to 25:1 .
  • the imbibition additive may be incorporated into the treatment fluid at any stage in its preparation.
  • the imbibition additive permeates particles of diverting agent (e.g. PLA) and the particles become more malleable, thereby improving their ability to pack and function as a diverting agent. Furthermore, it is found that the imbibition additive increases the rate of degradation of the diverting agent (e.g. PLA) which may be particularly relevant to formations with temperatures below 200°F. Then, the use of the imbibition additive may facilitate well clean-up particularly in relatively low temperature wells.
  • diverting agent e.g. PLA
  • the method of the first aspect may comprise treating a subterranean formation wherein the temperature in a region plugged by the treatment fluid is less than 300°F, less than 250°F or less than 200°F.
  • the method may comprise the steps of:
  • step (ii) selecting a slurry prepared as described in step (i);
  • the method may comprise step (i) (a), step (i)(b), step (iii), step(iv) and step(v); or may comprise step (ii), step (iii), step(iv) and step(v).
  • the imbibition additive may be included in step(i) or step(iii) or in a separate step.
  • Said oil suitably comprises a hydrophobic liquid which is suitably inert.
  • Said hydrophobic liquid may be a hydrocarbon. It may be selected from paraffinic hydrocarbons, napthenic hydrocarbons, aromatic hydrocarbons, benzene, xylene, toluene, mineral oils, diesel oil, kerosenes, naphthas (including hydrotreated naphtha), petrolatums, branch-chain isoparaffinic solvents, branch-chain hydrocarbons, saturated, linear, and/or branched paraffin hydrocarbons and combinations thereof.
  • Said oil may be a natural, modified or synthetic oil; or a vegetable oil such as canola oil, soy oil, coconut oil, rapeseed oil and the like.
  • a preferred oil may be selected from diesel, kerosene, refined mineral oils, raffinates and hydro-treated naphtha.
  • a preferred oil is hydro-treated naphtha, preferably having a C - C 16 carbon chain. It may have a specific gravity of 0.79 to 0.85 and a flash point exceeding 200°F.
  • Said pre-composition may comprise 25 to 65 wt% of oil in total, for example a single type of oil which may be selected from those described.
  • Said pre-composition preferably comprises 30 to 60 wt% of oil in total, especially 35 to 55 wt% of oil in total.
  • Said pre-composition may include 20 to 65 wt% of said one or more organic polymers. It preferably includes 30 to 60 wt%, more preferably 35 to 55 wt% of organic polymers.
  • Said one or more organic polymers in said pre-composition may include a polyacrylamide.
  • Said pre-composition may include 10 to 40 wt%, preferably 15 to 35 wt%, more preferably 20 to 30 wt% of polyacrylamide polymers, especially a single polyacrylamide polymer.
  • said polyacrylamide is an ionic polyacrylamide.
  • Said ionic polyacrylamide may include 0.1 -50mol%, preferably 5-40mol%, more preferably 10-30mol% of ionic repeat units. The balance suitably comprises non-ionic acrylamide repeat units.
  • said polyacrylamide may be an anionic or cationic polyacrylamide, it is preferably an anionic polyacrylamide.
  • Said polyacrylamide may be partially hydrolysed acrylamide.
  • Said polyacrylamide preferably includes a repeat unit which includes an optionally substituted acrylamide, for example an alkylacrylamide (e.g. methacrylamide) or N,N- dialkylacrylamide (e.g. N,N-dimethylacrylamide).
  • an alkylacrylamide e.g. methacrylamide
  • N,N- dialkylacrylamide e.g. N,N-dimethylacrylamide
  • Said optionally-substituted acrylamide may be of formula I wherein each R 5 independently represents a hydrogen atom or an optionally-substituted (preferably unsubstituted) C 1-4 alkyl, preferably C 1-2 alkyl, more preferably a methyl group and wherein R 6 and R 7 independently represent a hydrogen atom or an optionally- substituted (preferably unsubstituted) C ⁇ o alkyl, preferably alkyl, preferably C W2 alkyl, preferably C H0 alkyl, such as a C 1-8 alkyl, preferably C 1-4 alkyl, preferably alkyl, more preferably a methyl group.
  • R 5 , R 6 and R 7 preferably represent hydrogen atoms.
  • the ratio of the number of other repeat units in said polyacrylamide divided by the number of repeat units of formula I may be less than 0.6, 0.5, 0.4, 0.3 or 0.2. Said ratio may be at least 0.0025, at least 0.005, at least 0.05 or at least 0.1 .
  • Said polyacrylamide may include (e.g. in combination with repeat unit of formula I) a repeat unit which includes an acrylate or sulfonate moiety, for example an acrylate or sulfonate salt, or a pyrrolidone moiety.
  • Polymers which include sulfonate salts may be preferred when the formulation is used with water which includes high levels of hardness ions, for example magnesium, calcium, strontium, barium or ferrous ions.
  • Said polyacrylamide may include a repeat unit of formula I in combination with: a repeat unit comprising a moiety of formula II
  • O* moiety is an O moiety or is covalently bonded to another atom or group; a repeat unit comprising a vinyl pyrrolidone moiety; or a repeat unit comprising a moiety of formula III
  • R 1 and R 2 are independently selected from a hydrogen atom and an optionally- substituted alkyl group.
  • An optionally-substituted alkyl group may define an electrically neutral hydrophobe.
  • An optionally-substituted alkyl group may incorporate an -S0 3 R 3 moiety wherein R 3 is selected from a hydrogen atom and a cationic moiety, for example an alkali metal cation, especially Na + .
  • Said optionally-substituted alkyl group may include 1 to 36, preferably 1 to 20, more preferably 1 to 10 carbon atoms.
  • Said repeat unit may be derived from and/or based on AMPS.
  • Said polyacrylamide may be derived from one or more of the following monomers:
  • Methacrylamidopropyltrimethylammonium chloride Acryloyloxyethyltrimethylammonium chloride , Dimethyldiallylammonium chloride;
  • Anionic monomers - Sodium Acrylate, Sodium 2-Acrylamido-2-methylpropane sulfonate;
  • Non-ionic Monomers - Acrylamide, Methacrylamide, N,N Dimethylacrylamide, Vinyl pyrolidonone.
  • Said polyacrylamide may include monovalent (e.g. NH 4 + . Li + , Na + , K + , Rb + or Cs + ), divalent (e.g. Be 2+ , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Fe 2+ , Cu 2+ or Zn 2+ ) or trivalent (e.g. Fe 3+ or Al 3+ ) cations. It preferably includes monovalent cations, with Na + being preferred.
  • Said polyacrylamide preferably includes acrylamide repeat units and acrylate, for example sodium acrylate, repeat units.
  • Said polyacrylamide may have a molecular weight of at least 200,000 Daltons, suitably at least 500,000 Daltons, preferably at least 1 ,000,000 Daltons.
  • the molecular weight may be less than 50,000,000 Daltons or less than 30,000,000 Daltons.
  • Molecular weight, described herein, may be measured by Measurement of Intrinsic Viscosity (see ISO 1628/1 -1984-1 1 -01); and using Intrinsic Viscosity/Molecular Weight Correlation via the Mark-Houwink Equation.
  • Said one or more organic polymers in said pre-composition may comprise one or more gums.
  • Said pre-composition may include 5 to 40 wt%, preferably 15 to 30 wt% of gums in total.
  • Said pre-composition may include one or more gums selected from a galactomannan (e.g. guar gum and locust bean gum) and xanthan gum.
  • Said pre-composition may include 5 to 30 wt%, preferably 15 to 25 wt% of guar gum.
  • Said pre-composition may include 1 to 10 wt% of one or more other gums. It preferably includes 2 to 7 wt%, more preferably 3 to 6 wt% of xanthan gum.
  • Said pre-composition may include one or more suspending agents for suspending solids in the oil.
  • Said pre-composition may include less than 5 wt% of suspending agents in total.
  • Said pre-composition may include 1 to 4 wt%, preferably 1 .7 to 3 wt%, more preferably 2 to 3 wt% of suspending agents in total.
  • a suspending agent (A) may be organophilic. It is preferably insoluble in said pre-composition. It is preferably a clay, for example an organophilic clay.
  • a said organophilic clay which associates with oily surfaces and rejects aqueous surfaces, may be the reaction product of purified smectite clay (such as hectorite, bentonite, attapulgite, sepiolite, montmorillonate, etc.) and a quaternary ammonium salt. It includes coated clay (or lignite) such as clay coated with a fatty-acid quaternary amine. The coating imparts dispersability of the clay in the oil.
  • Exemplary organophilic clays include those disclosed in U.S. Patent Publication No. 2007019771 1 and U.S. Patent Publication No. 20100305008, herein incorporated by reference.
  • organo bentonites such as BENTONE® clays of Elementis Specialties, Inc. and Claytone SF, a product of Southern Clay Products. Further, such organophilic clays may be ion exchanged clays; see, for instance, U.S. Patent Publication No. 20010056149, herein incorporated by reference.
  • Said pre-composition may include at least 0.5 wt%, preferably at least 1 .0 wt%, more preferably at least 1 .5 wt% of organophilic clay. It may include less than 3 wt% or less than 2.5 wt% of organophilic clay.
  • Said pre-composition may include a suspending agent (B) which may comprise a solvent, for example a solvent arranged to activate organophilic clay.
  • Said solvent is preferably oxygenated. It may be selected from a monohydric or polyhydric alcohol (e.g. a 6 alcohol or glycol or glycerol), a glycol ether and an organic carbonate, for example an alkylene carbonate such as propylene carbonate or glycerol carbonate.
  • Said pre-composition may include at least 0.1 wt% of suspending agent (B); it may include less than 5 wt% of suspending agent (B). It preferably includes 0.1 to 1 .5 wt%, for example 0.2 to 1 wt% of suspending agent (B).
  • Said pre-composition may include a suspending agent (C) which may be a surface active agent, for example a surfactant.
  • the pre-composition may include less than 0.5 wt%, for examples less than 0.1 wt% of suspending agent (C).
  • said pre-composition comprises:
  • Step (i)(b) may comprise contacting 1 to 10 parts by volume (pbv) of said precomposition with 1000 parts of water.
  • 2 to 7 pbv, preferably 3 to 5 pbv of said pre-composition may be contacted with 1000 pbv water.
  • step (i)(b) over 500 gallons or over 1000 gallons of a mixture comprising said pre-composition and water is made.
  • step (i)(b) the mixture is preferably agitated to facilitate wetting and dispersion of any solids.
  • Said diverting agent is suitably in a particulate form, at least at the beginning of step (i)(b) of the method.
  • Said diverting agent may be arranged to produce acid, for example after decomposition.
  • Diverting agent may comprise, preferably consist essentially of, a polyester.
  • Diverting agent may be selected from polyesters obtained by polymerization of hydroxycarboxylic acids, such as the aliphatic polyester of lactic acid, referred to as polylactic acid; glycolic acid, referred to as polyglycolic acid; 3-hydroxbutyric acid, referred to as polyhydroxybutyrate; 2-hydroxyvaleric acid, referred to as polyhydroxyvalerate; epsilon caprolactone, referred to as polyepsilon caprolactone or polyprolactone; the polyesters obtained by esterification of hydroxylaminoacids such as serine, threonine and tyrosine; and the copolymers obtained by mixtures of the monomers listed above.
  • R1 , R2, R3, R4 is either H, linear alkyl, such as CH3, CH2CH3 (CH2)nCH3, branched alkyl, aryl, alkylaryl, a functional alkyl group (bearing carboxylic acid groups, amino groups, hydroxyl groups, thiol groups, or others) or a functional aryl group (bearing carboxylic acid groups, amino groups, hydroxyl groups, thiol groups, or others); x is an integer between 1 and 1 1 ; y is an integer between 0 and 10; and z is an integer between 2 and 50,000.
  • linear alkyl such as CH3, CH2CH3 (CH2)nCH3, branched alkyl, aryl, alkylaryl
  • a functional alkyl group bearing carboxylic acid groups, amino groups, hydroxyl groups, thiol groups, or others
  • a functional aryl group bearing carboxylic acid groups, amino groups, hydroxyl groups, thiol groups,
  • polyesters like those described herein can hydrolyze and degrade to yield hydroxycarboxylic acids.
  • polyesters include those made by the polymerization of polycarboxylic monomers with polyhydric monomers such as oxalic acid or citric acid polymerized with ethylene glycol or glycerol, so that on hydrolysis, an acid is produced that increases the fluid acidity.
  • a preferred diverting agent is a polymer of lactic acid, suitably a polylactic acid (PLA), polylactate or polylactide.
  • Lactic acid is a chiral molecule and has two optical isomers. These are D-lactic acid and L-lactic acid.
  • the poly(L-lactic acid) and poly(D-lactic acid) forms are generally crystalline in nature.
  • Polymerization of a mixture of the L- and D-lactic acids to poly(DL-lactic acid) results in a polymer that is more amorphous in nature.
  • the polymers described herein are essentially linear. The degree of polymerization of the linear polylactic acid can vary from a few units (2-10 units) (oligomers) to several thousands (e.g. 2000-5000).
  • Said diverting agent is preferably polylactic acid (PLA).
  • the method may comprise contacting said diverting agent with the pre-composition after the pre-composition has been contacted with water in step (i)(b).
  • Said method of step (i)(b) may comprise contacting solid diverting agent with a fluid to define a slurry which includes 1 to 20 lb of diverting agent per US gallon of fluid, suitably an aqueous fluid produced by contact of said pre-composition with water.
  • a slurry is defined which includes 3 to 10 lb, more preferably 5 to 9 lb, especially 6.5 to 8.5 lb, of diverting agent per US gallon of fluid, as described.
  • said method of step (i)(b) may comprise contacting solid diverting agent with fluid to define a slurry which includes 0.12 to 2.38 kg (preferably 0.36 to 1 .19 kg, more preferably 0.59 to 1 .07 kg, especially 0.77 to 1 .01 kg) of diverting agent per litre of fluid as described.
  • the method may comprise preparing a treatment fluid which includes 0.003 to 0.066 kg (preferably 0.005 to 0.033 kg, especially 0.008 to 0.0290 kg) of imbibition additive per litre of fluid as described.
  • Said slurry may include a cross-linker for cross-linking polymer(s) included the slurry.
  • Said slurry may include a viscosifying agent (which may be defined at least in part by said organic polymers) which is suitably arranged to suspend particulates in the slurry.
  • the viscosifying agent may comprise any crosslinked polymer.
  • the viscosifying agent may be a metal-crosslinked polymer.
  • Suitable polymers for making a metal-crosslinked polymer viscosifier include, for example, polysaccharides such as substituted galactomannans, such as guar gums, high-molecular weight polysaccharides composed of mannose and galactose sugars, or guar derivatives such as hydroxypropyl guar (HPG), carboxymethylhydroxypropyl guar (CMHPG) and carboxymethyl guar (CMG), hydrophobically modified guars, guar- containing compounds, and synthetic polymers.
  • polysaccharides such as substituted galactomannans, such as guar gums, high-molecular weight polysaccharides composed of mannose and galactose sugars, or guar derivatives such as hydroxypropyl guar (HPG), carboxymethylhydroxypropyl guar (CMHPG) and carboxymethyl guar (CMG), hydrophobically modified guars, guar- containing compounds, and synthetic
  • Crosslinking agents based on boron, titanium, zirconium or aluminum complexes are typically used to increase the effective molecular weight of the polymer and make the viscosifying agent better suited for use in high-temperature wells, for example for carrying solids (e.g. proppant or other diverting agents) in the treatment of subterranean formations.
  • polymers effective as viscosifying agents include polyvinyl polymers, polymethacrylamides, cellulose ethers, lignosulfonates, and ammonium, alkali metal, and alkaline earth salts thereof. More specific examples of other typical water soluble polymers are acrylic acid-acrylamide copolymers, acrylic acid-methacrylamide copolymers, polyacrylamides, partially hydrolyzed polyacrylamides, partially hydrolyzed polymethacrylamides, polyvinyl alcohol, polyalkyleneoxides, other galactomannans, heteropolysaccharides obtained by the fermentation of starch-derived sugar and ammonium and alkali metal salts thereof.
  • Cellulose derivatives such as hydroxyethylcellulose (HEC) or hydroxypropylcellulose (HPC), carboxymethylhydroxyethylcellulose (CMHEC) and carboxymethycellulose (CMC), may be used, with or without crosslinkers, as may xanthan, diutan, and scleroglucan.
  • HEC hydroxyethylcellulose
  • HPC hydroxypropylcellulose
  • CMC carboxymethylhydroxyethylcellulose
  • CMC carboxymethycellulose
  • Said slurry and/or treatment fluid may be arranged to define a sealing composition which is introduced into the subterranean formation in step (iv) of the method.
  • the method preferably comprises allowing the slurry and/or treatment fluid to form a degradable seal in the subterranean formation.
  • the slurry and/or treatment fluid is arranged to degrade over time.
  • said slurry could be introduced into the formation without dilution, it is preferred that the slurry is contacted with an aqueous formulation, thereby to prepare a said treatment fluid which is suitably introduced into the formation.
  • the aqueous formulation with which the slurry is contacted may be an injection fluid or may be another source of water which may be fresh water or produced water.
  • Said treatment fluid introduced into the subterranean formation in step (iii) may include:
  • imbibition additive especially an acetoacetate
  • Said treatment fluid may include:
  • treatment fluid may include less than 2 wt% or less than 1 wt% of other ingredients.
  • the sum of the wt% of diverting agent, especially PLA, imbibition additive and water is at least 97 wt%, at least 98 wt% or at least 99 wt%.
  • the sum of the wt% of ingredients described herein as being in said pre-composition is less than 1 wt%, preferably less than 0.1 wt%.
  • the wt% of polyacrylamide(s) is less than 1 wt%, more preferably, less than 0.5 wt %, especially less than 0.1 wt%.
  • the wt% of guar is less than 1 wt%, more preferably less than 0.5 wt%, especially less than 0.1 wt%.
  • the method of the first aspect suitably comprises a method of hydraulic stimulation of the subterranean formation.
  • the method may comprise introducing fluid, for example said treatment fluid into a first fracture in the formation, suitably so the fluid, for example said treatment fluid containing diverting agent at least partially hydraulically isolates the first fracture.
  • a stimulation fluid e.g. a fracturing fluid
  • the resulting diverting agent seal produced by fluid introduced into the first fracture
  • the method may comprise introducing fluid, for example treatment fluid into at least 2, preferably at least 3 or at least 4 fractures. After said introduction, at least 2 or at least 3 other fractures may be created and/or expanded.
  • fluid for example treatment fluid, introduced into the formation
  • the proppant may have a size of at least 140 US mesh; it may have a size of less than 5 US mesh.
  • the proppant may be selected from sand, bauxite, and man-made intermediate or high strength materials.
  • a said treatment fluid introduced into the formation includes at least 2.9wt%, for example at least 5wt%, of proppants. Higher percentages of proppants may be used as a treatment progresses.
  • the fluid, for example treatment fluid introduced in step (iv) is preferably pumped to refracture producing wells, but can be part of an initial fracturing treatment before a well is placed into production to get better distribution of proppant along the entire interval.
  • the injection rate of fluid into the formations is preferably in the range to 6 to 10 bbl/min.
  • the number of open perforations is determined from the injection pressure. Once the number of perforations is determined, a portion of the open perforations will be taking a majority of the fracturing fluid. This can be 5 to 50% of the perforation, but more often is 10 to 60% and most often is 20 to 30%.
  • the imbibition additive is suitably a solvent as described herein.
  • the use of the imbibition additive may be particularly beneficial when the formation temperature is less than 200°F (93°C).
  • the imbibition additive e.g. solvent
  • post treatment of the diverter pack in the well-bore with an oxidizing agents like sodium or ammonium persulfate at concentrations ranging from 2.0 to 20 lb per 1000 gallons (ppt) oxidizer can easily degrade the outer skin of the diverting agent. This removes the more malleable portions of the particles, so the particles in the pack can be released from the pack by fluid flow from the fracture flow and eventually recovered on the surface.
  • the invention extends to a method of fracturing a subterranean formation, the method comprising:
  • a slurry or treatment fluid as described in the first aspect may be as described in step (i) and/or is a treatment fluid which is introduced in step (iv) of the first aspect.
  • the slurry and/or treatment fluid may include any feature of the slurry and/or treatment fluid of the first aspect.
  • Said slurry and/or treatment fluid may be a combination of the pre-composition, water, diverting agent and imbibition additive as described in the first aspect.
  • a process for preparing a slurry or treatment fluid for treating a subterranean formation comprising the steps of:
  • Said imbibition additive may be added in step(a), step(b) or in a separate step.
  • the process of the third aspect may include any feature of the method described in the first aspect.
  • MaxPureTM PD210_- a petroleum hydro-treated middle distillate with CAS number being 64742-46-7.
  • ClaytoneTM SF_- an organophilic clay used as the oil-carrier suspending agent.
  • LutensolTM TDA9 a surfactant to assist polymer hydration once the slurry is added to water.
  • Guar 40-45 - a guar gum grade that will provide a Fann 35 viscosity of 40 cP at 51 1 sec 1 in 3 minutes after mixing a 0.48 wt% concentration in water in a Waring blender shearing at 2000 rpm for 2 minutes.
  • the grade also provides 45 cP at the same shear rate after 60 minutes.
  • FlojetTMDRP 3015 an ultra-fine grind high molecular weight 30% anionic polyacrylamide.
  • VisLink200TM- a borate based cross-linker from Innospec Oilfield ServicesTM.
  • aqueous, high density slurry formulations comprising a high concentration of diverting agent particulate, for example multisized polylactic acid (PLA).
  • a precomposition is prepared.
  • This may comprise an oil-based slurry comprising suspending polymers and suspending agents.
  • the oil-based slurry may comprise polyacrylamide, guar gum and xanthan gum, as suspending polymers together with suspending agents.
  • the slurry also includes a solvent (e.g. an ester of acetoacetate) which the PLA particles imbibe.
  • the slurry may optionally be diluted with water. Thereafter, the fluid may be introduced into a subterranean formation so as to block perforations in the formation and allow other parts of the formation to be fractured.
  • the pre-composition in the form of an oil-based slurry may include any oil commonly used to create oilfield oil-based slurries. It may include diesel, kerosene, refined mineral oils, raffinates and hydro-treated naphtha.
  • a preferred oil is hydro-treated naphtha having a C - C 16 carbon chain and a specific gravity of 0.79 to 0.85 and a flash point exceeding 200°F.
  • the pre-composition may include 35 to 65 wt% of oil in total. It preferably includes 40 to 60 wt% or, more preferably, 45 to 55 wt% of oil in total, wherein the oil(s) may be selected from those stated.
  • the pre-composition may include one or more suspending agents which are suitably arranged to facilitate suspension of diverting agent particulates (e.g. PLA) when provided in the aqueous formulation.
  • suspending agents e.g. PLA
  • the pre-composition comprises three suspending agents - an organophilic clay, an activating solvent and a surfactant.
  • the organophilic clay can be any organophilic clay that provides suspension to the particulates in the aqueous slurry formulation. Suitable clays include BentoneTM 150 and BentoneTM 155 from ElementisTM or ClaytoneTM EM, ClaytoneTM AF and ClaytoneTM SFTM.
  • the activating solvent can be any oxygenated solvent that can activate the organophilic clays and may include C1 to C6 alcohols, glycol ethers and organic carbonates.
  • the surfactant can be any non-ionic surfactant having a hydrophobic group with 6 to 24, for example 9 to 16 carbon atoms, and a degree of ethoxylation ranging from 6 to 18, for example 6 to 12.
  • the HLB of the surfactant may range from 11 to 15.
  • the concentration of the organophilic clay in the pre-composition may be in the range from 1 wt% to 3wt%, preferably 1.25 wt% to 2.75 wt% and, especially, 1.50 wt% to 2.00 wt%.
  • the total amount of activating solvent in the pre-composition may be in the range 0.0 wt% to 1 .0 wt%, preferably in the range 0.25 wt% to 0.75 wt% and, especially in the range 0.3 wt% to 0.5 wt%.
  • the total amount of surfactant in the pre-composition may be in the range 0 wt% to 1 wt%, preferably in the range 0 wt% to 0.5 wt% and, especially, in the range 0 wt% to 0.2 wt%.
  • the suspending polymers in the pre-composition may comprise a mixture which comprises one or more of a galactomannan (e.g guar gum), xanthan gum and polyacrylamide.
  • the polyacrylamide is high molecular weight exceeding 10 MM g/mole in number average molecular weight, preferably 12 MM g/mole and most preferred exceeding 15 MM g/mole molecular weight.
  • a preferred polymer is also useful as a hydraulic fracturing friction reducer and may be composed of 10% to 40% (mole percent) of anionic acrylate to enhance polymer expansion and viscosity in water.
  • the size distribution may be small with a mean size of 150 pm.
  • the concentration in the slurry can range from 10wt% to 40wt% and more preferred from 15wt% to 35wt% and most preferred from 20wt% to 30wt%.
  • the xanthan gum may be any type useful as a rheology modifier and exhibiting high yield stresses.
  • the gum can be acylated or non-acylated.
  • the concentration can range from 0wt% to 10wt% and more preferred from 2wt% to 8wt% and most preferred from 4wt% to 6wt%.
  • the galactomannan may be selected from guar gum and locust bean gum.
  • the guar gum can be any fracturing grade guar gum. Guar gum is normally graded by its 3 minute and 60 minute hydration viscosity using 0.48wt% polymer in 500 ml of 2wt% KCI water sheared at 2,000 rpm for 2 minutes in a WaringTM blender and poured into a FannTM 35 viscometer cup with an R1 B1 rotor/bob assembly to be sheared at 51 1 sec 1 .
  • a guar gum having a viscosity of 36 cP in 3 minutes and 42 cP in 60 minutes is graded as a 3642 grade guar. In preferred embodiments, the higher the grade the better the suspension so that Grade 3642 works well, but Grade 4045 works better and 4552 works best as a suspending polymer.
  • a specific example of a pre-composition which may be used in preparing the slurry formulation is as follows. Note that the order of materials presented in the table represents the order of addition used in preparing the pre-composition, but the guar gum, xanthan gum and polyacrylamide polymers can be added in any order.
  • An aqueous, high-density slurry formulation can be made using the pre-composition either in a manufacturing plant, at a well-site or at any place conducive to mixing large volumes of aqueous slurries, whichever is convenient based on slurry volumes or well-site operational logistics.
  • the pre-composition is added to any fresh water having a Total Dissolved Solids (TDS) of under 4,000 ppm and hardness under 1000 ppm.
  • TDS Total Dissolved Solids
  • the amount of water is selected to deliver a desired amount of diverting agent to perforations in a subterranean formation.
  • the pre-composition can be added to the water in either a continuous manner to a flowing stream of water or in a batch-wise manner with good agitation to assist hydration of polymers in the pre-composition.
  • An advantage of the pre-composition is its ability to disperse in the water prior to hydration to prevent lumping or“fish-eyes”.
  • Typical loadings can range from 1 to 6 gallons pre-composition per 1000 gallon of water (i.e. gallons per thousand or gpt). More preferred is 1 .5 to 5.0 gpt and most preferred is 2.0 to 4.0 gpt.
  • the diverting agent can be added to the polymer solution. It is preferred to keep the minimum concentration of diverting agent greater than or equal to 3 Ib/gal. In this case, for 1000 gal of polymer solution, at least 4,200 lb of diverter is necessary.
  • Any diverting agent can be used that is immiscible with water and will either slowly degrade or can be removed later with a degrading fluid. Later removal may involve the addition of a strongly oxidizing agent to flush the well-bore after a fracturing treatment such as after the plug drill out process if a“plug and perf” process was used for zonal isolation but before well-cleanup.
  • a strongly oxidizing agent to flush the well-bore after a fracturing treatment such as after the plug drill out process if a“plug and perf” process was used for zonal isolation but before well-cleanup.
  • a preferred chemical diverting agent is sized polylactic acid. A typical size distribution of a preferred PLA is shown in the Table 1 .
  • the additional solvent is included in the aqueous slurry formulation and arranged to permeate the PLA particles.
  • the additional solvent may be an ester of acetoacetate, such as methyl, ethyl, propyl, butyl and phenyl acetoacetate. The most preferred are ethyl and butyl acetoacetate.
  • the ester of acetoacetate may be added to the slurry formulation (or a precursors) before, during or after addition of the PLA.
  • aqueous slurry formulation can also include one or more biocides to extend its life.
  • Biocide may be added at any time during slurry preparation.
  • biocide may be added to water added to the pre-composition; to the mixture prepared just before addition of the diverting agent; or it may be added after addition of the diverting agent.
  • Typical biocides include tetrakis (hydroxymethyl) phosphonium sulfate, methyl or chloro isothiazolone, glutaraldehyde, quaternary ammonium-based surfactants such as didecyldimethyl ammonium chloride and mixtures of glutaraldehyde and didecyldimethylammonium chloride.
  • Common mixtures can be 12wt% glutaraldehyde 3wt% didecyldimethylammonium chloride.
  • the slurry formulation can be pumped alone as a treating fluid itself or diluted with injection (or other aqueous) fluid, with the proviso that the diverting agent concentration preferably remains greater than or equal to 3.0 lbs of diverter per gallon of fluid. If diluted, this water can be fresh water, flow-back water from other previously fractured wells or produced water with the water quality, expressed as ppm of Total Dissolved Solids (TDS), to not exceed 100,000 ppm.
  • TDS Total Dissolved Solids
  • the amount of slurry formulation required depends on the expected number of perforations taking fluid. In general 3 to 5 lbs diverting again may be used per perforation.
  • Treating fluid including the slurry formulation is suitably injected at a pump rate between 6 and 10 bbl/min until the slurry slug clears the well head.
  • the rate can then increase to 20 bbl/min until the slug reaches the perforation.
  • the slurry rate is then dropped to less than 10 bbl/min with a pressure of placement below that needed to fracture the well.
  • 7.5 lb of PLA is added to 1 .0 gallons of the pre-composition and additional water added to form an aqueous based diverter slurry (ABDS). It has been found, in preferred embodiments, that the maximum amount of PLA should be no greater than 7.5 lb PLA per gallon of pre-composition
  • the table below shows, for a range of pump rates, the volume of ABDS and additional water needed to make a fluid which is injected into a well.
  • the slurry formulation may include about 0.7wt% of butyl acetoacetate.
  • the balance of wt% is mostly water. It may be possible to reduce the amount of PLA in the ABDS to be equivalent to 3 lb PLA per gallon of ABDS. In this case, the PLA concentration would be 4.2 lb PLA to ? a gallon of the pre-composition used to make the ABDS. In this case, for each pump rate, the ABDS could be used as the treating fluid without the need for additional water.
  • the slurry formulation described, including the acetoacetate may be particularly useful for treating reservoirs with temperatures below 200°F.
  • the polylactic acid particulates degrade too slowly and the temperature is too low to induce the needed malleability to seal the perforations.
  • the acetoacetate will permeate the particles to make them more malleable, and, furthermore, assists in the particle degradation to allow improved well clean-up.
  • the efficiency of imbibition of the acetoacetate can be improved by increasing the salinity of the water used in the slurry formulation. Salinity can be increased by the addition of sodium chloride. .
  • the slurry formulation can readily be prepared and used at suitable concentrations. It is found to provide an improved seal and be more easily cleaned up compared to an equivalent slurry formulation to that described (except that it does not include an ester of acetoacetate such as t-butyl acetoacetate.

Abstract

La présente invention concerne un procédé de traitement d'une formation souterraine pénétrée par un puits de forage qui comprend l'étape consistant à introduire une suspension ou un fluide de traitement dans la formation souterraine par l'intermédiaire du puits de forage pour boucher une région du puits de forage, ladite suspension ou ledit fluide de traitement comprenant un agent de déviation d'agent de déviation qui est, de façon appropriée, un acide polylactique (PLA) et un additif (ici appelé "additif d'imbibition") qui est, de façon appropriée, un acétoacétate. L'agent de déviation et l'additif d'imbibition interagissent de telle sorte que l'additif d'imbibition provoque le gonflement de l'agent de déviation et/ou augmente la sensibilité de l'agent de déviation à la dégradation lors de l'utilisation.
PCT/GB2019/050203 2018-02-07 2019-01-24 Fluides et procédés WO2019155184A1 (fr)

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CN111274528A (zh) * 2020-03-02 2020-06-12 中国石油大学(北京) 储层裂缝渗吸质量预测方法及系统
CN115216283A (zh) * 2022-08-13 2022-10-21 大庆信辰油田技术服务有限公司 一种暂堵转向剂及其制备方法

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WO2014065975A1 (fr) * 2012-10-26 2014-05-01 Halliburton Energy Services, Inc. Matériaux d'entretien de puits de forage et procédés pour les préparer et les utiliser
WO2016201445A1 (fr) * 2015-06-12 2016-12-15 Univar Usa, Inc. Transport amélioré d'agent de soutènement pour la fracturation hydraulique

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US5067566A (en) * 1991-01-14 1991-11-26 Bj Services Company Low temperature degradation of galactomannans
US20010056149A1 (en) 1999-04-28 2001-12-27 Southern Clay Products, Inc. Process for treating smectite clays to facilitate exfoliation
US20050037928A1 (en) * 2003-01-31 2005-02-17 Qi Qu Method of using viscoelastic vesicular fluids to enhance productivity of formations
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CN111274528A (zh) * 2020-03-02 2020-06-12 中国石油大学(北京) 储层裂缝渗吸质量预测方法及系统
CN111274528B (zh) * 2020-03-02 2021-09-17 中国石油大学(北京) 储层裂缝渗吸质量预测方法及系统
CN115216283A (zh) * 2022-08-13 2022-10-21 大庆信辰油田技术服务有限公司 一种暂堵转向剂及其制备方法
CN115216283B (zh) * 2022-08-13 2024-01-16 大庆信辰油田技术服务有限公司 一种暂堵转向剂及其制备方法

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