WO2014060686A1 - Drilling fluid containing graphene - Google Patents

Drilling fluid containing graphene Download PDF

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Publication number
WO2014060686A1
WO2014060686A1 PCT/FR2013/052421 FR2013052421W WO2014060686A1 WO 2014060686 A1 WO2014060686 A1 WO 2014060686A1 FR 2013052421 W FR2013052421 W FR 2013052421W WO 2014060686 A1 WO2014060686 A1 WO 2014060686A1
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WIPO (PCT)
Prior art keywords
graphene
drilling fluid
oil
masterbatch
drilling
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Application number
PCT/FR2013/052421
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French (fr)
Inventor
Julien Beausoleil
Serge Bordere
Patrick Delprat
Patrice Gaillard
Alexander Korzhenko
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Arkema France
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Publication of WO2014060686A1 publication Critical patent/WO2014060686A1/en

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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
    • C09K8/02—Well-drilling compositions
    • C09K8/03—Specific additives for general use in well-drilling compositions
    • C09K8/032—Inorganic additives
    • 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
    • C09K8/02—Well-drilling compositions
    • C09K8/04—Aqueous well-drilling compositions
    • C09K8/26—Oil-in-water emulsions
    • 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
    • C09K8/02—Well-drilling compositions
    • C09K8/32—Non-aqueous well-drilling compositions, e.g. oil-based

Definitions

  • the present invention relates to a water-based or organic-based drilling fluid for drilling in subterranean formations containing graphene and at least one weighting agent and optionally a surfactant and / or a thickening agent other than graphene. It also relates to a process for preparing this fluid, from a masterbatch based on graphene and oil, and the use of this fluid for drilling in underground rock formations.
  • Drilling fluids also known as drilling muds, are complex fluids used for drilling oil wells. They are injected, usually continuously, via the drill string into the borehole. Their multiple functions include, for example, the transport of rock cuttings to the surface, the maintenance in the borehole of sufficient hydrostatic pressure to prevent the collapse of the crossed rock formation, or the lubrication and cooling of the rock formation. drill head.
  • oil-based sludge usually inverse emulsions of brine in oil phase
  • water-based sludge water-based sludge.
  • Maintaining a hydrostatic pressure sufficient to compensate for the lateral pressure of the rock formation traversed by the wellbore requires the gradual increase in the density of the drilling fluid as drilling progresses to the deep zones.
  • This increase in density is obtained by addition of agents weighting agents), that is to say finely ground solid materials, of high density and insoluble in the drilling fluid.
  • agents weighting agents that is to say finely ground solid materials, of high density and insoluble in the drilling fluid.
  • the decantation of the weighting agent for example during the temporary stop of the injection of sludge, can have disastrous consequences such as a plugging of the well or a local decrease in the hydrostatic pressure of the column. of fluid resulting in the collapse of the well.
  • Maintaining suspension of the weighting agent is typically provided by thickening or viscosifying agents, conventionally chosen from clays, organophilic or not, and organic polymers soluble in the drilling fluid.
  • thickening or viscosifying agents conventionally chosen from clays, organophilic or not, and organic polymers soluble in the drilling fluid.
  • the organic polymers undergo degradation due to the high temperatures that prevail at these depths and become partially or totally ineffective.
  • the Applicant has proposed to use carbon nanotubes to keep the weighting agents in suspension in the drilling muds.
  • carbon nanotubes Although they have good viscosifying properties over a wide temperature range, carbon nanotubes are expensive to manufacture and are not always available in sufficient quantities for application in the drilling of subterranean formations.
  • graphene used in relatively small amounts, is an excellent thickening agent which both has excellent heat stability and makes it possible to keep in suspension large quantities of very light-weighting agent. dense, such as barite or calcite, even under conditions of high temperature and high pressure, without giving the drilling fluid excessive viscosity.
  • the interest of the drilling fluids of the present invention containing graphene resides in particular in their particular viscoelastic behavior characterized by a high yield value or yield stress. associated with a relatively moderate viscosity.
  • the yield point determined according to the Herschel-Bulkley model (Hemphill T., Campos W., and Pilehvari A.: "Yield-power Law Model More Accurately Predicts Mud Rheology", Oil & Gas Journal 91, No. 34 August 23, 1993), pages 45 - 50), is the shear stress, below which the behavior of the fluid is substantially that of a solid (infinite viscosity) and beyond which the fluid has a thixotropic behavior.
  • Herschel-Bulkley provides information on the ability of the fluid to hold particles of a dense solid in suspension in a viscoplastic fluid. The higher this threshold, the more the fluid opposes the sedimentation of the particles in suspension. Graphene gives drilling fluids, aqueous or oily, a flow threshold significantly higher than organic polymers present in equivalent amounts.
  • Graphene thus advantageously replaces, in part or in full, the thickeners of organic polymer type, clays, fatty acids or carbon nanotubes, used in drilling fluids, especially under conditions of high pressure and high temperature.
  • the present invention therefore relates to a drilling fluid in underground rock formations, comprising
  • It also relates to a drilling method in underground rock formations using such drilling fluids, wherein the graphene content of the drilling fluid is optionally increased as the depth of drilling, the drilling temperature and / or the drilling pressure.
  • the subject of the invention is also a process for manufacturing this drilling fluid, comprising the dilution of a masterbatch free of organic polymer, comprising graphene and at least one oil, in an aqueous and / or organic liquid base comprising at least one weighting agent in particulate form and optionally at least one surfactant and / or at least one thickening agent other than graphene.
  • It also relates to a masterbatch in the form of granules, suitable for the implementation of this method, comprising graphene and at least one oil, said masterbatch being free of organic polymer.
  • the liquid base used in the drilling fluids of the present invention can in principle be any base conventionally used in drilling fluids. It may be for example a particularly advantageous aqueous base for economic and ecological reasons.
  • aqueous bases contain in a known manner water-soluble salts intended mainly to increase the density of the base.
  • Preferred salts include halides and formates of sodium, potassium, calcium, zinc, cesium, and combinations thereof.
  • Particularly preferred salts are calcium chloride, calcium bromide, potassium formate, cesium / potassium formate and combinations thereof.
  • These aqueous bases may also contain small fractions of organic solvents that are miscible with water and / or immiscible with water.
  • These aqueous bases may optionally be in the form of oil-in-water emulsions.
  • the liquid base is then either an oil or a water-in-oil emulsion containing preferably at most 50% by weight, in particular at most 20% by weight of water.
  • the drilling fluid further contains at least one surfactant capable of stabilizing the oil-in-water emulsion. emulsion.
  • Surfactants capable of stabilizing an inverse emulsion generally have a hydro-lipophilic balance (HLB) of less than 7.
  • the amount of surfactant sufficient to stabilize the water-in-oil emulsion depends, of course, on the respective proportions of the aqueous and oily but is generally between 1% and 5% by weight.
  • the surfactant (s) are preferably chosen from nonionic and anionic surfactants.
  • US2006-0046937 discloses surfactants suitable for use in the formulation of drilling muds of the present invention.
  • surfactants capable of stabilizing an oil-in-water emulsion generally have a hydro-lipophilic balance (HLB) greater than 7.
  • the oil used in the drilling fluids of the present invention i.e. the oil constituting the liquid base or the oil forming the continuous phase of the water-in-oil emulsion or discontinuous phase an oil-in-water emulsion, is defined as a medium, liquid at room temperature (25 ° C) and atmospheric pressure, immiscible with water (formation of 2 phases visible to the naked eye at ambient temperature and atmospheric pressure) .
  • This liquid medium has in particular a solubility in water, measured according to the method OECD TG 105, less than or equal to 1 mg / l.
  • This liquid medium may be more or less viscous; in particular, it has a dynamic viscosity at ambient temperature between 0.1cp and 500cp and preferably between 0.3 and 300cp.
  • oils which are generally miscible with one another.
  • These oils can be polar or, better, apolar.
  • a mineral oil preferably a fluorinated oil, a diesel oil or a synthetic oil, more preferably a mineral oil.
  • it may be a paraffin oil such as those sold by Shell under the brand Sarapar ® or one marketed by Total under the trade name ® EDC 99-DW or EDC ® 95-11; this oil has a viscosity of 3.5 cps.
  • a refined paraffinic oil having a content of polycyclic aromatic compounds of less than 3% by weight may be used.
  • oils of this type include:
  • oils are especially marketed by Shell under the trade name Catenex ® SNR by Exxon Mobil under the trade name Flexon 683 TOTAL under the trade name Plaxolene MS or H & R under the name European Vivatec 500.
  • the oils may comprise from 40 to 97% by weight, preferably from 45 to 95% by weight and, more preferably, from 70 to 95% by weight, based on the weight of the masterbatch.
  • any particulate solid having a density greater than that of the liquid base preferably with a density of at least 2 g / cm 3 and, for drilling at great depth. preferably a density greater than 3 g / cm 3 or even 4 g / cm 3 .
  • These weighting agents are known and are chosen for example from barite (BaSO 4 ), calcite (CaCO 3 ), dolomite (CaCO 3 .MgCO 3 ), hematite (Fe 2 O 3 ), magnetite (Fe 3 0 4 ), ilmenite (FeTiO 3 ) and siderite (FeC0 3 ).
  • the weighting agent used in a particularly preferred manner is barite.
  • the amount of weighting agent depends essentially on the density that it is desired to impart to the drilling fluid. This density, and therefore the amount of weighting agent used, generally increases gradually with the depth of the wellbore.
  • the drilling fluids of the present invention are preferably for deep drilling and therefore have a relatively high density, preferably an overall density of at least 1.5, preferably greater than 2.5.
  • the upper limit of the weighting agent content is essentially determined by the viscosity problems caused by too high a solids content.
  • the weighting agent is used in the drilling fluids of the present invention in a concentration of between 10 and 70% by weight, based on the total weight of the drilling fluid. The percentage of weighting agent is very variable depending on the desired density.
  • the drilling fluid according to the invention also contains graphene.
  • graphene is used to designate a plane graph sheet, isolated and individualized, but also, by extension, an assembly comprising between one and a few tens of sheets and having a flat structure or more or less wavy.
  • FLG Few Layer Graphene or slightly stacked graphene
  • NGP Nanosized Graphene Plates or graphene plates of nanometric dimension
  • CNS Carbon NanoSheets or nano-graphene sheets
  • GNRs Graphene NanoRibbons or nano-graphene ribbons
  • carbon nanotubes and nanofibers which consist respectively of the winding of one or more sheets of graphene in a coaxial manner and of the turbostratic stacking of these sheets. It is furthermore preferred that the graphene used according to the invention is not subjected to an additional step of chemical oxidation or functionalization.
  • the graphene used according to the invention is advantageously obtained by chemical vapor deposition or CVD. It is then typically in the form of particles having a thickness of less than 50 nm, preferably less than 15 nm, more preferably less than 5 nm, and less than one micron side dimensions, preferably less than 10 to 1000 nm, preferably 50 to 600 nm, and more preferably 100 to 400 nm.
  • Each of these particles generally contains from 1 to 50 sheets, preferably from 1 to 20 sheets, more preferably from 1 to 10 sheets, or even from 1 to 5 sheets, which are capable of being disconnected from each other in the form of independent leaflets, for example during an ultrasound treatment.
  • the process for the manufacture of graphene by CVD generally comprises the decomposition of a gaseous source of carbon, in particular a hydrocarbon, such as ethylene, methane or acetylene, under a flow of inert gas such as argon or nitrogen, the dilution ratio of the hydrocarbon in the inert gas being for example about 1: 5.
  • This decomposition is carried out at a temperature of 900 to 1000 ° C., preferably from 960 to 1000 ° C., generally at atmospheric pressure, over a catalyst in the form of a powder.
  • The can in particular be a metal catalyst supported or not on an inert substrate.
  • the catalyst may be for example cobalt optionally mixed with iron and supported on magnesia, in a molar ratio of cobalt to magnesia generally less than 10%.
  • the catalyst is usually prepared by impregnating the support with alcoholic or glycol solutions of cobalt salts and optionally iron, followed by evaporation of the solvent and a calcination step.
  • Another CVD method for obtaining graphene according to this invention comprises the following steps:
  • an active catalyst for the synthesis of graphene comprising a mixed oxide of formula AFe 2 O 4 where A is at least one element mixed valence metal having at least two valencies, one of which is equal to +2, in particular chosen from cobalt, copper or nickel, the catalyst being of spinel structure,
  • step b) heating said catalyst in the reactor at a temperature between 500 and 1500 ° C, preferably between 500 and 800 ° C, or even between 610 and 800 ° C, c) contacting a gaseous carbon source with the catalyst of step b), optionally in a fluidized bed, and catalytic decomposition thereof at a temperature of 500 to 800 ° C, preferably of 610 to 800 ° C , the gas source being selected from alcohols C 1 -C 1 2 and hydrocarbons C 1 -C 1 2, such as alkanes or alkenes, preferably ethylene, which may be mixed with a flow of a reducing agent such as hydrogen and optionally an inert gas,
  • the amount of graphene used in the drilling fluids of the present invention depends, inter alia, on the amount and density of the weighting agent used, the drilling depth, the nature of the liquid base, and the absence or presence of other thickening agents in the drilling fluid.
  • This amount is preferably between 0.1 and 3% by weight, based on the total weight of the drilling fluid.
  • graphene is the only thickening agent, i.e. the drilling fluid is essentially free of other known thickeners such as organic polymers, fatty acids, clays or thickening systems based on surfactants and electrolytes and carbon nanotubes.
  • the concentration of graphene in the drilling fluid is then relatively high, preferably between 1 and 3% by weight, and in particular between 1.5 and 3% by weight, relative to the total weight of the drilling fluid.
  • Graphene is also useful for enhancing the effect of conventional thickening systems, for example thickening systems based on polymers or carbon nanotubes (or CNTs).
  • the drilling fluids of the present invention thus further contain one or more organic polymers soluble in the aqueous phase and / or in the oily phase of the liquid base and / or CNTs.
  • the concentration of graphene is then preferably between 0.1 and 1% by weight, relative to the total weight of the drilling fluid.
  • the CNTs possibly used in this embodiment are, in particular, multi-wall nanotubes comprising, for example, from 5 to 15 sheets and preferably having a mean diameter of between 10 and 30 nm, or even between 10 and 15 nm, an average length of 0.1 to 10 ⁇ and a specific surface area of between 200 and 250 m 2 / g.
  • These nanotubes can also be prepared by CVD.
  • crude (non-functionalized but optionally purified and / or milled) NTCs will preferably be used for oil-based or inverse-emulsion drilling fluids.
  • nanotubes functionalized with ionic organic groups For water-based drilling fluids, use will preferably be made of nanotubes functionalized with ionic organic groups.
  • Such crude carbon nanotubes are especially commercially available from Arkema under the trade name Graphistrength® ® C100.
  • organic thickening polymers are chosen from those conventionally used in drilling fluids, and examples that may be mentioned include guar gum, hydroxypropylguar, carboxymethylguar, hydroxypropylcellulose, hydroxyethylcellulose and xanthan. starch, polyacrylates, poly (diallyldimethylammonium chloride).
  • graphene be introduced in a form easy to handle for the manufacturers of drilling muds, which avoids its dispersion in the environment and therefore does not require the use of systems. complex hoods, filters, depressed premises, and other systems limiting its dispersion.
  • the Applicant has developed a masterbatch in solid form, free of organic polymer, said masterbatch comprising (and preferably consisting of) graphene and at least one oil as described above, which also makes the subject of this invention.
  • This masterbatch further ensures easy dispersion of graphene into the liquid base of the drilling fluid.
  • the amount of graphene in the masterbatch is generally 5 to 30% by weight, preferably 10 to 20% by weight based on the weight of the masterbatch.
  • a preferred method of manufacturing the drilling fluid according to the invention thus comprises the dilution of a masterbatch free of organic polymer, comprising (and preferably consisting of) graphene and at least one oil, in an aqueous liquid base and or organic comprising at least one weighting agent in particulate form and optionally at least one surfactant and / or at least one thickening agent other than graphene.
  • the masterbatch used in this process may comprise any oil chosen from:
  • R5COOR6 synthetic oils of formula R5COOR6 in which R5 represents an aryl group or the residue of a higher linear or branched fatty acid containing from 7 to 30 carbon atoms and R6 represents a hydrocarbon chain, branched or otherwise, optionally hydroxylated, containing from 3 to 30 carbon atoms, such as for example PurCellin® (cetostearyl alcohol octanoate) oil, isononyl isononanoate, C12-C15 alcohol benzoate, isostearyl benzoate, isopropyl myristate, octanoates, decanoates or ricinoleates of alcohols or polyalcohols;
  • PurCellin® cetostearyl alcohol octanoate
  • isononyl isononanoate C12-C15 alcohol benzoate
  • isostearyl benzoate isopropyl myristate, octanoates, decanoates or
  • silicone oils such as polydimethylsiloxanes, liquid at room temperature; polydimethylsiloxanes comprising alkyl or alkoxy groups, pendent and / or at the end of the silicone chain, groups having from 2 to 24 carbon atoms; phenyl silicones such as phenyl trimethicones, phenyl dimethicones, phenyl trimethylsiloxy diphenylsiloxanes, diphenyl dimethicones and diphenyl methyldiphenyl trisiloxanes;
  • oils of mineral origin such as linear or branched hydrocarbons, such as paraffin oils and its derivatives, optionally refined, petroleum jelly, polydecenes, hydrogenated polyisobutene such as Parleam®, squalane;
  • alkyl cycloalkanes and (alkyl) cycloalkenes in which the alkyl chain is linear or branched, saturated or unsaturated, having from 1 to
  • Carbon atoms such as cyclohexane, dioctylcyclohexane, 2,4-dimethyl-3-cyclohexene and dipentene;
  • aromatic hydrocarbons such as benzene, toluene, p-cymene, naphthalene, anthracene;
  • fluorinated oils such as perfluoroalkanes in C8 to
  • the oil contained in the masterbatch may be the same as, or different from, the formulation of the drilling fluid to which it is added.
  • the masterbatch according to the invention may alternatively comprise more viscous oils, often called greases.
  • fats examples include:
  • specialty fats such as semisynthetic fats, bentone-based greases, optionally containing fluorinated compounds, lithium / calcium soap fats and greases containing copper, in particular those available from the company TOTAL under the trade names MARSON SY 00 and SY 2, SPECIS CU, CALORIS 23 and MS23, STATERMIC XHT and NR, TIFORA PG, BIOMULTIS SEP 2, MULTIS COMPLEX HV2; and
  • This masterbatch can be prepared using a compounding device.
  • Compounding devices are well known to those skilled in the art. They are conventionally used in the plastics industry for the melt blending of thermoplastic polymers and additives to produce composites. These devices generally comprise feed means, in particular at least one hopper for pulverulent materials (here, graphene) and / or at least one injection pump for liquid materials (here, the oil); high shear mixing means, for example a co-rotating or counter-rotating twin-screw extruder (for example a DSM micro-extruder) or a co-kneader, usually comprising a worm disposed in a sheath (tube ) heated; an outlet head which gives shape to the outgoing material; and cooling means, in air or with the aid of a water circuit, of the material.
  • feed means in particular at least one hopper for pulverulent materials (here, graphene) and / or at least one injection pump for liquid materials (here, the oil); high shear mixing means, for example a co-rotating or counter-
  • co-kneaders examples include the BUSS MDK 46 co-kneaders and those of the BUSS MKS or MX series sold by the company BUSS AG, all of which consist of a screw shaft provided with fins. , disposed in a heating sleeve possibly consisting of several parts and whose inner wall is provided with kneading teeth adapted to cooperate with the fins for produce shearing of the kneaded material.
  • the shaft is rotated and provided with oscillation movement in the axial direction by a motor.
  • These co-kneaders may be equipped with a granule manufacturing system, adapted for example to their outlet orifice, which may consist of an extrusion screw.
  • the co-kneaders that can be used according to the invention preferably have an L / D screw ratio ranging from 7 to 22, for example from 10 to 20.
  • the compounding step is generally carried out at a close temperature (for example ⁇ 5 ° C.) of the ambient temperature (25 ° C.).
  • the masterbatch according to the invention obtained for example according to the method described above, can be diluted in an aqueous and / or organic liquid base comprising at least one weighting agent in particulate form and optionally at least one surfactant and / or at least one thickening agent other than graphene, for producing the drilling fluid according to the invention.
  • the masterbatch is incorporated directly into the final formulation of the drilling fluid. It is preferred, however, that the weighting agent be added to the liquid base after introduction of the masterbatch therein.
  • the masterbatch and the liquid base are subjected to a mechanical treatment, preferably before mixing with the weighting agent.
  • This treatment may be of any kind, provided that it makes it possible to obtain a homogeneous dispersion of graphene in the liquid base.
  • This treatment advantageously comprises an ultrasonic treatment or a shear of the dispersion mixture with using a rotor-stator system or using a blade mixer.
  • Such a rotor-stator system generally comprises a rotor controlled by a motor and provided with fluid guide systems perpendicular to the axis of the rotor, such as blades or blades arranged substantially radially or a flat disc provided with peripheral teeth, said rotor being optionally provided with a ring gear, and a stator arranged concentrically with respect to the rotor, and at a short distance outside thereof, said stator being equipped on at least a portion of its circumference; openings, for example in a grid or defining between them one or more rows of teeth, which are adapted to the passage of fluid sucked into the rotor and ejected by the guide systems to said openings.
  • One or more of the aforementioned teeth may be provided with sharp edges. The fluid is thus subjected to high shear, both in the gap between the rotor and the stator and through the openings in the stator.
  • rotor-stator system An example of a rotor-stator system is in particular marketed by SILVERSON under the trade name Silverson L4RT. Another type of rotor-stator system is marketed by the company IKA-WERKE under the trade name Ultra-Turrax. Other rotor-stator systems still consist of colloid mills, deflocculating turbines and high-shear mixers of the rotor-stator type, such as the apparatus marketed by the company IKA-WERKE or the company ADMIX.
  • the speed of the rotor is set to at least 1000 rpm and preferably at least 3000 rpm or even at least 5,000 rpm, for example. example for 5 to 15 minutes.
  • the width of the gap between the rotor and the stator is less than 1 mm and preferably less than 200 ⁇ m, more preferably less than 100 ⁇ m and better still less than 50 ⁇ m. less than 40 ym.
  • the rotor-stator system used according to the invention advantageously confers a shear of 1,000 to 10 9 s -1 .
  • the latter is particularly suitable for deep drilling, i.e. under high temperature and high pressure conditions.
  • the drilling temperature is therefore greater than or equal to 200 ° C, in particular greater than 250 ° C.
  • High-temperature and high-pressure drilling is, however, only a preferred embodiment of the process of the invention and the drilling fluids of the present invention, due to their high flow threshold associated with a relatively low viscosity, also prove very useful even at low or medium depth.
  • the drilling fluids of the present invention may be used throughout the duration of the drilling by gradually increasing the graphene content as the drilling depth, the drilling temperature and / or or drilling pressure.
  • Such a method is distinguished by a great simplicity due to the possibility of continuous recycling of drilling fluid that can be reused after removal of cuttings and addition of additional amounts of weighting agent and graphene.
  • the drilling fluid preferably does not contain any thickening agent other than graphene and possibly CNTs.
  • the drilling method of the present invention comprises the progressive replacement of one or more thickening agents present in the fluid, chosen for example from clays (bentonite, montmorillonite, attapulgite, organophilic clays) or polymers. graphene, and possibly
  • NTC NTC
  • thickeners such as organic polymers and / or thickening clays, and introducing graphene, and possibly CNTs, only from a certain depth when the thermal degradation of the organic polymers or the excessive content of solids provided by the clays begins to pose the problems described in the introduction.
  • graphene can be introduced into the drilling fluid in the form of a masterbatch as described above but not necessarily containing a weighting agent.
  • the pH of the resulting solution was adjusted to a value of 6 by adding, dropwise and stirring, ammonia (NH 4 OH).
  • the molar ratio between iron nitrate and cobalt nitrate in the aqueous solution was substantially of the order of 2.
  • This aqueous solution was placed in a Pyrex crystallizer at a temperature of 80 ° C. for a period of substantially order of 12 hours, so as to form a substantially dehydrated homogeneous gel.
  • the homogeneous gel thus obtained was heated to a temperature of about 200 ° C, so as to decompose the citric acid.
  • the expansion of the homogeneous gel was then observed to foam which was allowed to develop for about 30 minutes until stabilization.
  • This foam was then crushed gently to form a powder which was heated at a temperature of 400 ° C
  • This powder had a single oxide phase having a spinel type structure with a crystalline domain size of between 14 nm and 20 nm (determined by X-ray diffraction) and a specific surface area of 7 m 2 / g. 2- Graphene synthesis
  • Graphene synthesis was performed in a horizontal quartz reactor. 20 mg of the catalyst powder obtained above was placed in an alumina crucible which was placed in the center of a horizontal quartz tubular reactor with an inside diameter of about 18 mm. The catalyst powder was heated under a gaseous flow of hydrogen (3 ⁇ 4 53 cm 3 / min) and argon (Ar 160 cm 3 / min) to a temperature of 650 ° C. temperature gradient of 630 ° C / h. When the temperature reached 650 ° C, ethylene (C 2 H 4 , 32 cm 3 / min) was introduced into the gas mixture and the gas flow and the temperature were maintained for one hour. After 1 h, the heating and gaseous flows of ethylene and hydrogen were stopped. The powder obtained was cooled to a temperature of 300 ° C. under argon. The amount of product recovered at the end of the reaction was 220 mg. b) Preparation of a masterbatch
  • a quantity by weight of mineral oil (EDC 99 DW of TOTAL) identical to that of graphene is introduced into the injection pump of the first zone of the apparatus, before the first restriction ring.
  • the mixing is carried out at room temperature.
  • solid rods are obtained which are cut, without the use of a water jet, to obtain a masterbatch in the form of solid granules containing 15% by weight of graphene and 85% by weight of oil. .

Abstract

The invention relates to a drilling fluid having an organic or aqueous base, intended for drilling in underground formations, containing graphene and at least one weighting agent and, optionally, a surfactant and/or a thickening agent other than graphene. The invention also relates to a method for producing said fluid from a masterbatch based on graphene and oil, as well as to the use thereof for drilling in underground rock formations.

Description

Fluide de forage contenant du graphène  Drilling fluid containing graphene
OBJET DE L'INVENTION OBJECT OF THE INVENTION
La présente invention concerne un fluide de forage à base aqueuse ou organique, destiné au forage dans des formations souterraines, contenant du graphène et au moins un agent alourdissant ainsi qu'éventuellement un tensioactif et/ou un agent épaississant autre que le graphène. Elle concerne également un procédé de préparation de ce fluide, à partir d'un mélange-maître à base de graphène et d'huile, ainsi que l'utilisation de ce fluide pour le forage dans des formations rocheuses souterraines.  The present invention relates to a water-based or organic-based drilling fluid for drilling in subterranean formations containing graphene and at least one weighting agent and optionally a surfactant and / or a thickening agent other than graphene. It also relates to a process for preparing this fluid, from a masterbatch based on graphene and oil, and the use of this fluid for drilling in underground rock formations.
ARRIERE-PLAN DE L'INVENTION BACKGROUND OF THE INVENTION
Les fluides de forage, également appelés boues de forage, sont des fluides complexes utilisés pour le forage des puits pétroliers. Ils sont injectés, généralement en continu, via le train de tiges dans le trou de forage. Leurs fonctions multiples comprennent par exemple le transport des déblais rocheux jusqu'à la surface, le maintien dans le trou de forage d'une pression hydrostatique suffisante pour prévenir l'effondrement de la formation rocheuse traversée, ou encore la lubrification et le refroidissement de la tête de forage. Il y a principalement deux familles de boues de forage : les boues à base d'huile (généralement des émulsions inverses de saumure dans une phase d'huile) et les boues à base d'eau.  Drilling fluids, also known as drilling muds, are complex fluids used for drilling oil wells. They are injected, usually continuously, via the drill string into the borehole. Their multiple functions include, for example, the transport of rock cuttings to the surface, the maintenance in the borehole of sufficient hydrostatic pressure to prevent the collapse of the crossed rock formation, or the lubrication and cooling of the rock formation. drill head. There are two main families of drilling muds: oil-based sludge (usually inverse emulsions of brine in oil phase) and water-based sludge.
Le maintien d'une pression hydrostatique suffisante pour compenser la pression latérale de la formation rocheuse traversée par le puits de forage, nécessite l'augmentation progressive de la densité du fluide de forage au fur et à mesure que le forage avance vers les zones profondes. Cette augmentation de la densité est obtenue par addition d'agents alourdissants (en anglais weighting agents) , c'est-à-dire de matériaux solides finement broyés, de densité importante et insolubles dans le fluide de forage. Plus la profondeur des puits de forage est importante, plus la quantité et/ou la densité de l'agent alourdissant utilisé augmentent, et plus le système de maintien en suspension de l'agent alourdissant dans le fluide de forage doit être efficace. Maintaining a hydrostatic pressure sufficient to compensate for the lateral pressure of the rock formation traversed by the wellbore requires the gradual increase in the density of the drilling fluid as drilling progresses to the deep zones. This increase in density is obtained by addition of agents weighting agents), that is to say finely ground solid materials, of high density and insoluble in the drilling fluid. The greater the depth of the wellbore, the greater the quantity and / or density of the weighting agent used, and the more the system for keeping the agent weighing in the drilling fluid in suspension must be effective.
En effet, la décantation de l'agent alourdissant, par exemple lors de l'arrêt provisoire de l'injection de boue, peut avoir des conséquences désastreuses telles qu'un bouchage du puits ou encore une diminution locale de la pression hydrostatique de la colonne de fluide aboutissant à l'effondrement du puits.  Indeed, the decantation of the weighting agent, for example during the temporary stop of the injection of sludge, can have disastrous consequences such as a plugging of the well or a local decrease in the hydrostatic pressure of the column. of fluid resulting in the collapse of the well.
Le maintien en suspension de l'agent alourdissant est typiquement assuré par des agents épaississants ou viscosifiants , choisis classiquement parmi les argiles, organophiles ou non, et les polymères organiques solubles dans le fluide de forage. Or, au-delà d'une certaine profondeur de forage, lorsque le système de maintien en suspension de l'agent alourdissant doit être particulièrement efficace, les polymères organiques subissent une dégradation due aux températures élevées qui régnent à ces profondeurs et deviennent partiellement ou totalement inefficaces.  Maintaining suspension of the weighting agent is typically provided by thickening or viscosifying agents, conventionally chosen from clays, organophilic or not, and organic polymers soluble in the drilling fluid. However, beyond a certain depth of drilling, when the suspension of the weighting agent suspension system must be particularly effective, the organic polymers undergo degradation due to the high temperatures that prevail at these depths and become partially or totally ineffective.
Le problème de la dégradation thermique des polymères organiques ne peut pas être résolu par leur remplacement par des argiles. En effet, les argiles utilisées classiquement en tant qu'agents épaississants (bentonite, montmorillonite, attapulgite, argiles organophiles) résistent, certes, à des températures nettement plus élevées que les polymères organiques, mais pour le forage à grande profondeur la quantité d'argile nécessaire pour maintenir en suspension des quantités importantes d'agent alourdissant très dense est considérable. Les boues de forage présentent alors une teneur en solides excessivement élevée qui pose des problèmes de maintien en circulation des boues dus à une viscosité excessive . The problem of thermal degradation of organic polymers can not be solved by replacing them with clays. Indeed, clays conventionally used as thickening agents (bentonite, montmorillonite, attapulgite, organophilic clays) resist, certainly, at significantly higher temperatures than organic polymers, but for deep drilling the amount of clay necessary to maintain in suspension large amounts of very dense weighting agent is considerable. Drilling muds then have a grade in excessively high solids which poses problems of sludge maintenance due to excessive viscosity.
Ainsi, les systèmes utilisés actuellement, qu'ils soient à base de polymères ou d'argiles, ne permettent malheureusement pas d'assurer un maintien en suspension de l'agent alourdissant au-delà d'une température d'environ 250°C.  Thus, the systems currently used, whether based on polymers or clays, unfortunately do not allow to maintain suspension of the weighting agent beyond a temperature of about 250 ° C.
Pour surmonter ce problème, la Demanderesse a proposé d'utiliser des nanotubes de carbone pour maintenir en suspension les agents alourdissants dans les boues de forage.  To overcome this problem, the Applicant has proposed to use carbon nanotubes to keep the weighting agents in suspension in the drilling muds.
Bien qu' ils présentent de bonnes propriétés viscosifiantes dans une large gamme de températures, les nanotubes de carbone sont toutefois coûteux à fabriquer et ne sont pas toujours disponibles dans des quantités suffisantes pour une application dans le forage de formations souterraines .  Although they have good viscosifying properties over a wide temperature range, carbon nanotubes are expensive to manufacture and are not always available in sufficient quantities for application in the drilling of subterranean formations.
Il subsiste donc le besoin de disposer d'autres agents de suspension qui présentent les mêmes propriétés avantageuses que les nanotubes de carbone.  There is therefore still a need for other suspending agents which have the same advantageous properties as carbon nanotubes.
Or, il est apparu à la Demanderesse que le graphène, utilisé en des quantités relativement faibles, constitue un excellent agent épaississant qui, à la fois, présente une excellente stabilité à chaud et permet de maintenir en suspension des quantités importantes d'agent alourdissant très dense, tel que la baryte ou la calcite, y compris dans des conditions de haute température et haute pression, sans pour autant conférer au fluide de forage une viscosité excessive .  However, it has been found by the Applicant that graphene, used in relatively small amounts, is an excellent thickening agent which both has excellent heat stability and makes it possible to keep in suspension large quantities of very light-weighting agent. dense, such as barite or calcite, even under conditions of high temperature and high pressure, without giving the drilling fluid excessive viscosity.
L' intérêt des fluides de forage de la présente invention contenant du graphène réside en particulier dans leur comportement viscoélastique particulier caractérisé par un seuil d'écoulement (yield value ou yield stress) élevé associé à une viscosité relativement modérée. Le seuil d'écoulement, déterminé selon le modèle de Herschel-Bulkley (Hemphill T., Campos W., et Pilehvari A. : « Yield-power Law Model More Accurately Predicts Mud Rheology », Oil & Gas Journal 91, n° 34 August 23, 1993), pages 45 - 50), est la contrainte de cisaillement (shear stress) en deçà de laquelle le comportement du fluide est sensiblement celui d'un solide (viscosité infinie) et au-delà de laquelle le fluide présente un comportement thixotrope. The interest of the drilling fluids of the present invention containing graphene resides in particular in their particular viscoelastic behavior characterized by a high yield value or yield stress. associated with a relatively moderate viscosity. The yield point, determined according to the Herschel-Bulkley model (Hemphill T., Campos W., and Pilehvari A.: "Yield-power Law Model More Accurately Predicts Mud Rheology", Oil & Gas Journal 91, No. 34 August 23, 1993), pages 45 - 50), is the shear stress, below which the behavior of the fluid is substantially that of a solid (infinite viscosity) and beyond which the fluid has a thixotropic behavior.
La valeur du seuil d'écoulement, dans le modèle de The value of the flow threshold, in the model of
Herschel-Bulkley, renseigne sur la capacité du fluide à maintenir en suspension des particules d'un solide dense dans un fluide viscoplastique au repos. Plus ce seuil est élevé, plus le fluide s'oppose à la sédimentation des particules en suspension. Le graphène confère aux fluides de forage, à base aqueuse ou huileuse, un seuil d'écoulement considérablement plus élevé que ne le font des polymères organiques présents en des quantités équivalentes . Herschel-Bulkley, provides information on the ability of the fluid to hold particles of a dense solid in suspension in a viscoplastic fluid. The higher this threshold, the more the fluid opposes the sedimentation of the particles in suspension. Graphene gives drilling fluids, aqueous or oily, a flow threshold significantly higher than organic polymers present in equivalent amounts.
Par ailleurs, il est thermiquement stable à des températures allant jusqu'à 325°C, voire au-delà.  Moreover, it is thermally stable at temperatures up to 325 ° C, or even beyond.
Enfin, en particulier lorsqu' il est obtenu par dépôt chimique en phase vapeur (ou CVD) , le graphène peut être produit en grande quantité dans des conditions économiquement favorables .  Finally, particularly when it is obtained by chemical vapor deposition (or CVD), graphene can be produced in large quantities under economically favorable conditions.
L'utilisation de graphène en des teneurs très faibles, de préférence inférieures à 3 % en poids, ne présente pas les problèmes de viscosité excessive décrits ci-dessus pour les argiles épaississantes, ce qui permet un pompage plus aisé et un meilleur écoulement des fluides les contenant.  The use of graphene at very low levels, preferably less than 3% by weight, does not exhibit the excessive viscosity problems described above for thickening clays, which allows for easier pumping and better flow of fluids. containing them.
Le graphène remplace ainsi avantageusement, en partie ou en totalité, les agents épaississants de type polymères organiques, argiles, acides gras ou nanotubes de carbone, utilisés dans des fluides de forage, en particulier dans des conditions de haute pression et haute température. Graphene thus advantageously replaces, in part or in full, the thickeners of organic polymer type, clays, fatty acids or carbon nanotubes, used in drilling fluids, especially under conditions of high pressure and high temperature.
RESUME DE L'INVENTION SUMMARY OF THE INVENTION
La présente invention a par conséquent pour objet un fluide de forage dans des formations rocheuses souterraines, comprenant  The present invention therefore relates to a drilling fluid in underground rock formations, comprising
(a) une base liquide aqueuse et/ou organique,  (a) an aqueous and / or organic liquid base,
(b) au moins un agent alourdissant, sous forme particulaire, ayant une masse volumique au moins égale à 2 g/cm3, de préférence au moins égale à 4 g/cm3, en suspension dans ladite base liquide, et (b) at least one weighting agent, in particulate form, having a density of at least 2 g / cm 3 , preferably at least 4 g / cm 3 , suspended in said liquid base, and
(c) du graphène .  (c) graphene.
Elle a également pour objet un procédé de forage dans des formations rocheuses souterraines utilisant de tels fluides de forage, dans lequel la teneur en graphène du fluide de forage est éventuellement augmentée au fur et à mesure de l'augmentation de la profondeur de forage, de la température de forage et/ou de la pression de forage.  It also relates to a drilling method in underground rock formations using such drilling fluids, wherein the graphene content of the drilling fluid is optionally increased as the depth of drilling, the drilling temperature and / or the drilling pressure.
L'invention a encore pour objet un procédé de fabrication de ce fluide de forage, comprenant la dilution d'un mélange-maître exempt de polymère organique, comprenant du graphène et au moins une huile, dans une base liquide aqueuse et/ou organique comprenant au moins un agent alourdissant sous forme particulaire et éventuellement au moins un agent tensioactif et/ou au moins un agent épaississant autre que le graphène.  The subject of the invention is also a process for manufacturing this drilling fluid, comprising the dilution of a masterbatch free of organic polymer, comprising graphene and at least one oil, in an aqueous and / or organic liquid base comprising at least one weighting agent in particulate form and optionally at least one surfactant and / or at least one thickening agent other than graphene.
Elle a encore pour objet un mélange-maître sous forme de granulés, adapté à la mise en œuvre de ce procédé, comprenant du graphène et au moins une huile, ledit mélange-maître étant exempt de polymère organique.  It also relates to a masterbatch in the form of granules, suitable for the implementation of this method, comprising graphene and at least one oil, said masterbatch being free of organic polymer.
Elle a également pour objet un procédé de préparation de ce mélange-maître, comprenant les étapes consistant à : (a) introduire puis malaxer le graphène et ladite au moins une huile, dans un dispositif de compoundage, pour obtenir un composite, It also relates to a process for preparing this masterbatch, comprising the steps of: (a) introducing and kneading graphene and said at least one oil, in a compounding device, to obtain a composite,
(b) extruder puis refroidir ledit composite de façon à obtenir un mélange-maître sous forme solide,  (b) extruding and then cooling said composite to obtain a masterbatch in solid form,
(c) mettre en forme ledit mélange-maître pour obtenir des granulés.  (c) shaping said masterbatch to obtain granules.
DESCRIPTION DETAILLEE DETAILED DESCRIPTION
La base liquide utilisée dans les fluides de forage de la présente invention peut en principe être n' importe quelle base utilisée classiquement dans des fluides de forage. Il peut s'agir par exemple d'une base aqueuse particulièrement avantageuse pour des raisons économiques et écologiques. Ces bases aqueuses contiennent de manière connue des sels hydrosolubles destinés principalement à augmenter la densité de la base. Les sels préférés comprennent des halogénures et formates de sodium, de potassium, de calcium, de zinc, de césium et des combinaisons de ceux-ci. On peut citer comme sels particulièrement préférés, le chlorure de calcium, le bromure de calcium, le formate de potassium, le formate de césium/potassium et des combinaisons de ceux-ci. Ces bases aqueuses peuvent contenir en outre de faibles fractions de solvants organiques miscibles à l'eau et/ou non miscibles à l'eau. Ces bases aqueuses peuvent éventuellement se présenter sous la forme d'émulsions huile-dans-eau.  The liquid base used in the drilling fluids of the present invention can in principle be any base conventionally used in drilling fluids. It may be for example a particularly advantageous aqueous base for economic and ecological reasons. These aqueous bases contain in a known manner water-soluble salts intended mainly to increase the density of the base. Preferred salts include halides and formates of sodium, potassium, calcium, zinc, cesium, and combinations thereof. Particularly preferred salts are calcium chloride, calcium bromide, potassium formate, cesium / potassium formate and combinations thereof. These aqueous bases may also contain small fractions of organic solvents that are miscible with water and / or immiscible with water. These aqueous bases may optionally be in the form of oil-in-water emulsions.
Dans certains cas, il peut toutefois être intéressant, voire nécessaire, de limiter la teneur en eau des fluides de forage, par exemple lorsque le puits traverse des formations rocheuses contenant une fraction importante de composants hydrosolubles ou hydro-dispersibles susceptibles d'être emportés par le fluide. La base liquide est alors soit une huile, soit une émulsion eau-dans-huile contenant de préférence au plus 50% en poids, en particulier au plus 20% en poids d'eau. In some cases, however, it may be advantageous, even necessary, to limit the water content of the drilling fluids, for example when the well passes through rock formations containing a large fraction of water-soluble or water-dispersible components that may be washed away. the fluid. The liquid base is then either an oil or a water-in-oil emulsion containing preferably at most 50% by weight, in particular at most 20% by weight of water.
Lorsque la base aqueuse est une telle émulsion eau-dans- huile, également appelée émulsion inverse, ou que la base aqueuse est une émulsion huile-dans-eau, le fluide de forage contient en outre au moins un agent tensioactif capable de stabiliser l' émulsion .  When the aqueous base is such a water-in-oil emulsion, also called inverse emulsion, or the aqueous base is an oil-in-water emulsion, the drilling fluid further contains at least one surfactant capable of stabilizing the oil-in-water emulsion. emulsion.
Les agents tensioactifs capables de stabiliser une émulsion inverse ont généralement une balance hydro-lipophile (HLB) inférieure à 7. La quantité d'agent tensioactif suffisante pour stabiliser l' émulsion eau-dans-huile dépend bien entendu des proportions respectives des phases aqueuse et huileuse mais est généralement comprise entre 1% et 5 % en poids. Le ou les agents tensioactifs sont de préférence choisis parmi les agents tensioactifs non-ioniques et anioniques. Le document US2006-0046937 décrit des agents tensio-actifs susceptibles d'être utilisés dans la formulation des boues de forage de la présente invention. De leur côté, les agents tensioactifs capables de stabiliser une émulsion huile-dans-eau ont généralement une balance hydro- lipophile (HLB) supérieure à 7.  Surfactants capable of stabilizing an inverse emulsion generally have a hydro-lipophilic balance (HLB) of less than 7. The amount of surfactant sufficient to stabilize the water-in-oil emulsion depends, of course, on the respective proportions of the aqueous and oily but is generally between 1% and 5% by weight. The surfactant (s) are preferably chosen from nonionic and anionic surfactants. US2006-0046937 discloses surfactants suitable for use in the formulation of drilling muds of the present invention. On the other hand, surfactants capable of stabilizing an oil-in-water emulsion generally have a hydro-lipophilic balance (HLB) greater than 7.
L'huile utilisée dans les fluides de forage de la présente invention, c'est-à-dire l'huile constituant la base liquide ou bien l'huile formant la phase continue de 1' émulsion eau-dans-huile ou la phase discontinue d'une émulsion huile-dans-eau, est définie comme un milieu, liquide à température ambiante (25°C) et pression atmosphérique, non miscible à l'eau (formation de 2 phases visibles à l'œil nu à température ambiante et pression atmosphérique) . Ce milieu liquide présente notamment une solubilité dans l'eau, mesurée selon la méthode OECD TG 105, inférieure ou égale à 1 mg/1. Ce milieu liquide peut être plus ou moins visqueux ; en particulier, il présente une viscosité dynamique à température ambiante comprise entre 0,lcp et 500cp et de préférence entre 0,3 et 300cp. The oil used in the drilling fluids of the present invention, i.e. the oil constituting the liquid base or the oil forming the continuous phase of the water-in-oil emulsion or discontinuous phase an oil-in-water emulsion, is defined as a medium, liquid at room temperature (25 ° C) and atmospheric pressure, immiscible with water (formation of 2 phases visible to the naked eye at ambient temperature and atmospheric pressure) . This liquid medium has in particular a solubility in water, measured according to the method OECD TG 105, less than or equal to 1 mg / l. This liquid medium may be more or less viscous; in particular, it has a dynamic viscosity at ambient temperature between 0.1cp and 500cp and preferably between 0.3 and 300cp.
Selon l'invention, on peut utiliser une ou plusieurs huiles généralement miscibles entre elles. Ces huiles peuvent être polaires ou, mieux, apolaires.  According to the invention, it is possible to use one or more oils which are generally miscible with one another. These oils can be polar or, better, apolar.
On préfère utiliser une huile minérale, une huile fluorée, une huile diesel ou une huile synthétique, plus préférentiellement une huile minérale. Avantageusement, il peut s'agir d'une huile de paraffine telle que celles commercialisées par Shell sous la marque Sarapar® ou celle commercialisée par TOTAL sous la dénomination commerciale EDC® 99-DW ou EDC® 95-11 ; cette huile présente une viscosité de 3,5 cps . En variante, on peut utiliser une huile paraffinique raffinée, ayant une teneur en composés aromatiques polycycliques inférieure à 3% en poidsIt is preferred to use a mineral oil, a fluorinated oil, a diesel oil or a synthetic oil, more preferably a mineral oil. Advantageously, it may be a paraffin oil such as those sold by Shell under the brand Sarapar ® or one marketed by Total under the trade name ® EDC 99-DW or EDC ® 95-11; this oil has a viscosity of 3.5 cps. Alternatively, a refined paraffinic oil having a content of polycyclic aromatic compounds of less than 3% by weight may be used.
(déterminée par extraction au DMSO selon la méthode IP 346) et une température de transition vitreuse inférieure à -45°C, par exemple de -58°C ± 3°C (telle que déterminée selon la norme ASTM E 1356) . Des huiles raffinées de ce type sont notamment : (determined by DMSO extraction according to IP 346) and a glass transition temperature below -45 ° C, for example -58 ° C ± 3 ° C (as determined according to ASTM E 1356). Refined oils of this type include:
- les MES, produites par extraction au solvant de distillats lourds de pétrole ou par traitement de ces distillats avec de l'hydrogène en présence de catalyseur (hydrotraitement) ,  - MES produced by solvent extraction of petroleum heavy distillates or by treatment of these distillates with hydrogen in the presence of a catalyst (hydrotreatment),
- les TDAE, qui sont des extraits aromatiques traités de distillats traités.  - TDAE, which are aromatic extracts treated with treated distillates.
Des exemples de telles huiles sont notamment commercialisés par SHELL sous la dénomination commerciale Catenex® SNR, par EXXON MOBIL sous la dénomination commerciale Flexon 683, par TOTAL sous la dénomination commerciale Plaxolene MS ou par H&R European sous la dénomination Vivatec 500. Les huiles peuvent représenter de 40 à 97% en poids, de préférence de 45 à 95% en poids et, mieux, de 70 à 95% en poids, par rapport au poids du mélange-maître. Examples of such oils are especially marketed by Shell under the trade name Catenex ® SNR by Exxon Mobil under the trade name Flexon 683 TOTAL under the trade name Plaxolene MS or H & R under the name European Vivatec 500. The oils may comprise from 40 to 97% by weight, preferably from 45 to 95% by weight and, more preferably, from 70 to 95% by weight, based on the weight of the masterbatch.
On peut utiliser en tant qu'agent alourdissant en principe n' importe quel solide particulaire ayant une densité supérieure à celle de la base liquide, de préférence une masse volumique au moins égale à 2 g/cm3 et, pour les forages à grande profondeur, de préférence une masse volumique supérieure à 3 g/cm3, voire à 4 g/cm3. Ces agents alourdissants sont connus et sont choisis par exemple parmi la baryte (BaS04) , la calcite (CaC03) , la dolomite (CaC03.MgC03) , l'hématite (Fe203) , la magnétite (Fe304) , l'ilménite (FeTi03) et la sidérite (FeC03) . L'agent alourdissant utilisé de manière particulièrement préférée est la baryte. It is possible to use, as weighing agent in principle, any particulate solid having a density greater than that of the liquid base, preferably with a density of at least 2 g / cm 3 and, for drilling at great depth. preferably a density greater than 3 g / cm 3 or even 4 g / cm 3 . These weighting agents are known and are chosen for example from barite (BaSO 4 ), calcite (CaCO 3 ), dolomite (CaCO 3 .MgCO 3 ), hematite (Fe 2 O 3 ), magnetite (Fe 3 0 4 ), ilmenite (FeTiO 3 ) and siderite (FeC0 3 ). The weighting agent used in a particularly preferred manner is barite.
La quantité d'agent alourdissant dépend essentiellement de la densité que l'on souhaite conférer au fluide de forage. Cette densité, et donc la quantité d'agent alourdissant utilisée, augmente en général progressivement avec la profondeur du puits de forage. Les fluides de forage de la présente invention sont de préférence destinés au forage à grande profondeur et ont par conséquent une densité relativement élevée, de préférence une densité globale au moins égale à 1,5, de préférence supérieure à 2,5. La limite supérieure de la teneur en agent alourdissant est déterminée essentiellement par les problèmes de viscosité qu'entraîne une teneur trop élevée en solides. De façon générale, l'agent alourdissant est utilisé dans les fluides de forage de la présente invention en une concentration comprise entre 10 et 70 % en poids, par rapport au poids total du fluide de forage. Le pourcentage d'agent alourdissant est très variable en fonction de la densité recherchée. Pour maintenir l'agent alourdissant en suspension, le fluide de forage selon l'invention renferme en outre du graphène . Dans cette description, le terme « graphène » est utilisé pour désigner un feuillet de graphite plan, isolé et individualisé, mais aussi, par extension, un assemblage comprenant entre un et quelques dizaines de feuillets et présentant une structure plane ou plus ou moins ondulée. Cette définition englobe ainsi les FLG (Few Layer Graphène ou graphène faiblement empilé) , les NGP (Nanosized Graphène Plates ou plaques de graphène de dimension nanométrique) , lesThe amount of weighting agent depends essentially on the density that it is desired to impart to the drilling fluid. This density, and therefore the amount of weighting agent used, generally increases gradually with the depth of the wellbore. The drilling fluids of the present invention are preferably for deep drilling and therefore have a relatively high density, preferably an overall density of at least 1.5, preferably greater than 2.5. The upper limit of the weighting agent content is essentially determined by the viscosity problems caused by too high a solids content. In general, the weighting agent is used in the drilling fluids of the present invention in a concentration of between 10 and 70% by weight, based on the total weight of the drilling fluid. The percentage of weighting agent is very variable depending on the desired density. To maintain the weighting agent in suspension, the drilling fluid according to the invention also contains graphene. In this description, the term "graphene" is used to designate a plane graph sheet, isolated and individualized, but also, by extension, an assembly comprising between one and a few tens of sheets and having a flat structure or more or less wavy. This definition thus includes FLG (Few Layer Graphene or slightly stacked graphene), NGP (Nanosized Graphene Plates or graphene plates of nanometric dimension),
CNS (Carbon NanoSheets ou nano-feuilles de graphène) , les GNR (Graphène NanoRibbons ou nano-rubans de graphène) . Elle exclut en revanche les nanotubes et nanofibres de carbone, qui sont respectivement constitués de l'enroulement d'un ou plusieurs feuillets de graphène de manière coaxiale et de l'empilement turbostratique de ces feuillets. On préfère par ailleurs que le graphène utilisé selon l'invention ne soit pas soumis à une étape supplémentaire d'oxydation chimique ou de fonctionnalisation . CNS (Carbon NanoSheets or nano-graphene sheets), GNRs (Graphene NanoRibbons or nano-graphene ribbons). On the other hand, it excludes carbon nanotubes and nanofibers, which consist respectively of the winding of one or more sheets of graphene in a coaxial manner and of the turbostratic stacking of these sheets. It is furthermore preferred that the graphene used according to the invention is not subjected to an additional step of chemical oxidation or functionalization.
Le graphène utilisé selon l'invention est avantageusement obtenu par dépôt chimique en phase vapeur ou CVD. Il se présente alors, de façon caractéristique, sous forme de particules d'une épaisseur de moins de 50 nm, de préférence de moins de 15 nm, plus préférentiellement de moins de 5 nm, et de dimensions latérales inférieures au micron, de préférence de 10 à 1000 nm, préférentiellement de 50 à 600 nm, et plus préférentiellement de 100 à 400 nm. Chacune de ces particules renferme en général de 1 à 50 feuillets, de préférence de 1 à 20 feuillets, plus préférentiellement de 1 à 10 feuillets, voire de 1 à 5 feuillets, qui sont susceptibles d'être désolidarisés les uns des autres sous la forme de feuillets indépendants, par exemple lors d'un traitement par ultrasons. Le procédé de fabrication du graphène par CVD comprend en général la décomposition d'une source gazeuse de carbone, en particulier un hydrocarbure, tel que de l'éthylène, du méthane ou de l'acétylène, sous flux de gaz inerte tel que de l'argon ou de l'azote, le taux de dilution de l'hydrocarbure dans le gaz inerte étant par exemple d'environ 1:5. Cette décomposition est effectuée à une température de 900 à 1000°C, de préférence de 960 à 1000°C, généralement à pression atmosphérique, sur un catalyseur sous forme de poudre. Le peut notamment être un catalyseur métallique supporté ou non sur un substrat inerte. Il peut s'agir par exemple de cobalt éventuellement mélangé à du fer et supporté sur de la magnésie, dans un rapport molaire du cobalt à la magnésie généralement inférieur à 10%. Le catalyseur est habituellement préparé par imprégnation du support à l'aide de solutions alcooliques ou glycoliques de sels de cobalt et éventuellement de fer, suivie d'une évaporation du solvant et d'une étape de calcination. The graphene used according to the invention is advantageously obtained by chemical vapor deposition or CVD. It is then typically in the form of particles having a thickness of less than 50 nm, preferably less than 15 nm, more preferably less than 5 nm, and less than one micron side dimensions, preferably less than 10 to 1000 nm, preferably 50 to 600 nm, and more preferably 100 to 400 nm. Each of these particles generally contains from 1 to 50 sheets, preferably from 1 to 20 sheets, more preferably from 1 to 10 sheets, or even from 1 to 5 sheets, which are capable of being disconnected from each other in the form of independent leaflets, for example during an ultrasound treatment. The process for the manufacture of graphene by CVD generally comprises the decomposition of a gaseous source of carbon, in particular a hydrocarbon, such as ethylene, methane or acetylene, under a flow of inert gas such as argon or nitrogen, the dilution ratio of the hydrocarbon in the inert gas being for example about 1: 5. This decomposition is carried out at a temperature of 900 to 1000 ° C., preferably from 960 to 1000 ° C., generally at atmospheric pressure, over a catalyst in the form of a powder. The can in particular be a metal catalyst supported or not on an inert substrate. It may be for example cobalt optionally mixed with iron and supported on magnesia, in a molar ratio of cobalt to magnesia generally less than 10%. The catalyst is usually prepared by impregnating the support with alcoholic or glycol solutions of cobalt salts and optionally iron, followed by evaporation of the solvent and a calcination step.
Un autre procédé de CVD pour l'obtention de graphène selon cette invention comprend les étapes suivantes :  Another CVD method for obtaining graphene according to this invention comprises the following steps:
a) l'introduction dans un réacteur de synthèse, et éventuellement la mise en lit fluidisé dans ledit réacteur, d'un catalyseur actif pour la synthèse de graphène, comprenant un oxyde mixte de formule AFe2Û4 où A est au moins un élément métallique à valence mixte présentant au moins deux valences dont l'une est égale à +2, en particulier choisi parmi le cobalt, le cuivre ou le nickel, le catalyseur étant de structure spinelle, a) the introduction into a synthesis reactor, and optionally the fluidized bed in said reactor, of an active catalyst for the synthesis of graphene, comprising a mixed oxide of formula AFe 2 O 4 where A is at least one element mixed valence metal having at least two valencies, one of which is equal to +2, in particular chosen from cobalt, copper or nickel, the catalyst being of spinel structure,
b) le chauffage dudit catalyseur dans le réacteur, à une température comprise entre 500 et 1500°C, de préférence entre 500 et 800°C, voire entre 610 et 800°C, c) la mise en contact d'une source gazeuse de carbone avec le catalyseur de l'étape b) , éventuellement en lit fluidisé, et sa décomposition catalytique à une température de 500 à 800°C, de préférence de 610 à 800°C, la source gazeuse étant choisie parmi les alcools en C1-C12 et les hydrocarbures en C1-C12, tels que les alcanes ou les alcènes, de préférence l'éthylène, qui peut être mélangé à un flux d'un agent réducteur comme l'hydrogène et éventuellement à un gaz inerte, b) heating said catalyst in the reactor at a temperature between 500 and 1500 ° C, preferably between 500 and 800 ° C, or even between 610 and 800 ° C, c) contacting a gaseous carbon source with the catalyst of step b), optionally in a fluidized bed, and catalytic decomposition thereof at a temperature of 500 to 800 ° C, preferably of 610 to 800 ° C , the gas source being selected from alcohols C 1 -C 1 2 and hydrocarbons C 1 -C 1 2, such as alkanes or alkenes, preferably ethylene, which may be mixed with a flow of a reducing agent such as hydrogen and optionally an inert gas,
d) la récupération du graphène produit en c) en sortie du réacteur.  d) the recovery of graphene produced in c) at the outlet of the reactor.
La quantité de graphène utilisée dans les fluides de forage de la présente invention dépend, entre autres, de la quantité et de la densité de l'agent alourdissant utilisé, de la profondeur de forage, de la nature de la base liquide, et de l'absence ou de la présence d'autres agents épaississants dans le fluide de forage.  The amount of graphene used in the drilling fluids of the present invention depends, inter alia, on the amount and density of the weighting agent used, the drilling depth, the nature of the liquid base, and the absence or presence of other thickening agents in the drilling fluid.
Cette quantité est de préférence comprise entre 0,1 et 3 % en poids, rapporté au poids total du fluide de forage.  This amount is preferably between 0.1 and 3% by weight, based on the total weight of the drilling fluid.
Dans un mode de réalisation particulier de la présente invention, le graphène constitue le seul agent épaississant, c'est-à-dire le fluide de forage est essentiellement exempt d'autres agents épaississants connus tels que les polymères organiques, les acides gras, les argiles ou les systèmes épaississants à base d'agents tensioactifs et d' électrolytes et les nanotubes de carbone. La concentration du graphène dans le fluide de forage est alors relativement élevée, de préférence comprise entre 1 et 3 % en poids, et en particulier entre 1,5 et 3 % en poids, par rapport au poids total du fluide de forage.  In a particular embodiment of the present invention, graphene is the only thickening agent, i.e. the drilling fluid is essentially free of other known thickeners such as organic polymers, fatty acids, clays or thickening systems based on surfactants and electrolytes and carbon nanotubes. The concentration of graphene in the drilling fluid is then relatively high, preferably between 1 and 3% by weight, and in particular between 1.5 and 3% by weight, relative to the total weight of the drilling fluid.
Le graphène est également utile pour renforcer l'effet de systèmes épaississants classiques, par exemple des systèmes épaississants à base de polymères ou de nanotubes de carbone (ou NTC) . Dans un autre mode de réalisation de la présente invention, les fluides de forage de la présente invention contiennent ainsi en outre un ou plusieurs polymères organiques solubles dans la phase aqueuse et/ou dans la phase huileuse de la base liquide et/ou des NTC. La concentration de graphène est alors de préférence comprise entre 0,1 et 1 % en poids, par rapport au poids total du fluide de forage. Graphene is also useful for enhancing the effect of conventional thickening systems, for example thickening systems based on polymers or carbon nanotubes (or CNTs). In another embodiment of the present invention, the drilling fluids of the present invention thus further contain one or more organic polymers soluble in the aqueous phase and / or in the oily phase of the liquid base and / or CNTs. The concentration of graphene is then preferably between 0.1 and 1% by weight, relative to the total weight of the drilling fluid.
Les NTC éventuellement utilisés dans ce mode de réalisation sont en particulier des nanotubes multi-parois comprenant par exemple de 5 à 15 feuillets et ayant de préférence un diamètre moyen compris entre 10 et 30 nm, voire entre 10 et 15 nm, une longueur moyenne de 0,1 à 10 μιη et une surface spécifique comprise entre 200 et 250 m2/g. Ces nanotubes peuvent également être préparés par CVD. Dans la présente invention, on utilisera de préférence des NTC bruts (non fonctionnalisés mais éventuellement purifiés et/ou broyés) pour des fluides de forage à base d'huile ou à base d'émulsion inverse. Pour des fluides de forage à base d'eau, on utilisera de préférence des nanotubes fonctionnalisés par des groupements organiques ioniques. De tels nanotubes de carbone bruts sont notamment disponibles sur le marché auprès de la société ARKEMA sous la dénomination commerciale Graphistrength® C100. The CNTs possibly used in this embodiment are, in particular, multi-wall nanotubes comprising, for example, from 5 to 15 sheets and preferably having a mean diameter of between 10 and 30 nm, or even between 10 and 15 nm, an average length of 0.1 to 10 μιη and a specific surface area of between 200 and 250 m 2 / g. These nanotubes can also be prepared by CVD. In the present invention, crude (non-functionalized but optionally purified and / or milled) NTCs will preferably be used for oil-based or inverse-emulsion drilling fluids. For water-based drilling fluids, use will preferably be made of nanotubes functionalized with ionic organic groups. Such crude carbon nanotubes are especially commercially available from Arkema under the trade name Graphistrength® ® C100.
Ces polymères organiques épaississants sont choisis parmi ceux utilisés classiquement dans les fluides de forage, et l'on peut citer à titre d'exemples la gomme de guar, 1 ' hydroxypropylguar, le carboxyméthylguar, 1' hydroxypropylcellulose, l' hydroxyéthylcellulose, le xanthane, l'amidon, les polyacrylates , le poly (chlorure de diallyldiméthylammonium) . Pour fabriquer le fluide de forage selon l'invention, on préfère que le graphène soit introduit sous une forme aisée à manipuler pour les fabricants des boues de forage, qui évite sa dispersion dans l'environnement et ne nécessite donc pas l'utilisation de systèmes complexes de hottes, filtres, mises en dépression des locaux, et autres systèmes limitant sa dispersion. Pour ce faire, la Demanderesse a mis au point un mélange-maître sous forme solide, exempt de polymère organique, ledit mélange-maître comprenant (et de préférence constitué par) du graphène et au moins une huile telle que décrite précédemment, qui fait également l'objet de cette invention. Ce mélange-maître assure en outre une dispersion facile du graphène dans la base liquide du fluide de forage. La quantité de graphène dans le mélange-maître représente généralement de 5 à 30% en poids, de préférence de 10 à 20% en poids par rapport au poids du mélange-maître. These organic thickening polymers are chosen from those conventionally used in drilling fluids, and examples that may be mentioned include guar gum, hydroxypropylguar, carboxymethylguar, hydroxypropylcellulose, hydroxyethylcellulose and xanthan. starch, polyacrylates, poly (diallyldimethylammonium chloride). To manufacture the drilling fluid according to the invention, it is preferred that graphene be introduced in a form easy to handle for the manufacturers of drilling muds, which avoids its dispersion in the environment and therefore does not require the use of systems. complex hoods, filters, depressed premises, and other systems limiting its dispersion. To do this, the Applicant has developed a masterbatch in solid form, free of organic polymer, said masterbatch comprising (and preferably consisting of) graphene and at least one oil as described above, which also makes the subject of this invention. This masterbatch further ensures easy dispersion of graphene into the liquid base of the drilling fluid. The amount of graphene in the masterbatch is generally 5 to 30% by weight, preferably 10 to 20% by weight based on the weight of the masterbatch.
Un procédé de fabrication préféré du fluide de forage selon l'invention comprend donc la dilution d'un mélange- maître exempt de polymère organique, comprenant (et de préférence constitué par) du graphène et au moins une huile, dans une base liquide aqueuse et/ou organique comprenant au moins un agent alourdissant sous forme particulaire et éventuellement au moins un agent tensioactif et/ou au moins un agent épaississant autre que le graphène.  A preferred method of manufacturing the drilling fluid according to the invention thus comprises the dilution of a masterbatch free of organic polymer, comprising (and preferably consisting of) graphene and at least one oil, in an aqueous liquid base and or organic comprising at least one weighting agent in particulate form and optionally at least one surfactant and / or at least one thickening agent other than graphene.
Le mélange-maître mis en œuvre dans ce procédé peut comprendre une huile quelconque choisie parmi :  The masterbatch used in this process may comprise any oil chosen from:
les huiles végétales à forte teneur (par exemple au moins 50% en poids) en triglycérides constitués d'esters d'acides gras et de glycérol, dont les acides gras peuvent avoir des longueurs de chaînes variées, ces dernières pouvant être linéaires ou ramifiées, saturées ou insaturées ; ces huiles sont notamment les huiles de germe de blé, de maïs, de tournesol, de lin, de karité, de ricin, d'amandes douces, de macadamia, d'abricot, de soja, de coton, de luzerne, de pavot, de potimarron, de sésame, de courge, d'avocat, de noisette, de pépins de raisin ou de cassis, d'onagre, de millet, d'orge, de quinoa, d'olive, de seigle, de carthame, de bancoulier, de passiflore, de rosier muscat ; ou encore les triglycérides des acides caprylique /caprique ; vegetable oils with a high content (for example at least 50% by weight) of triglycerides consisting of esters of fatty acids and of glycerol, the fatty acids of which may have various chain lengths, the latter possibly being linear or branched, saturated or unsaturated; these oils include wheat germ, corn, sunflower, flax, shea, castor oil, sweet almonds, macadamia, apricot, soya, cotton, alfalfa, poppy, pumpkin, sesame, squash, avocado, hazelnut, grape seed or blackcurrant, evening primrose, millet, barley, quinoa, olive, rye, safflower, bancoulier, passionflower, muscat rose; or the triglycerides of caprylic / capric acids;
les huiles de synthèse de formule R5COOR6 dans laquelle R5 représente un groupe aryle ou le reste d'un acide gras supérieur, linéaire ou ramifié, comportant de 7 à 30 atomes de carbone et R6 représente une chaîne hydrocarbonée, ramifiée ou non, éventuellement hydroxylée, contenant de 3 à 30 atomes de carbone, comme par exemple l'huile de PurCellin® (octanoate de l'alcool cétostéarylique) , 1 ' isononanoate d'isononyle, le benzoate d'alcools en C12 à C15, le benzoate d ' isostéaryle, le myristate d ' isopropyle, des octanoates, décanoates ou ricinoléates d'alcools ou de polyalcools ;  synthetic oils of formula R5COOR6 in which R5 represents an aryl group or the residue of a higher linear or branched fatty acid containing from 7 to 30 carbon atoms and R6 represents a hydrocarbon chain, branched or otherwise, optionally hydroxylated, containing from 3 to 30 carbon atoms, such as for example PurCellin® (cetostearyl alcohol octanoate) oil, isononyl isononanoate, C12-C15 alcohol benzoate, isostearyl benzoate, isopropyl myristate, octanoates, decanoates or ricinoleates of alcohols or polyalcohols;
les éthers de synthèse comme l'éther de pétrole ;  synthetic ethers such as petroleum ether;
les alcools gras, linéaires ou ramifiés, saturés ou insaturés, en C6 à C26 comme l'alcool oléique ou l'octyl dodécanol ;  linear or branched, saturated or unsaturated C6 to C26 fatty alcohols such as oleic alcohol or octyl dodecanol;
éventuellement, les huiles siliconées telles que les polydiméthylsiloxanes , liquides à température ambiante ; les polydiméthylsiloxanes comportant des groupements alkyle ou alcoxy, pendants et/ou en bout de chaîne siliconée, groupements ayant de 2 à 24 atomes de carbone ; les silicones phénylées comme les phényl triméthicones , les phényl diméthicones , les phényl triméthylsiloxy diphénylsiloxanes , les diphényl diméthicones et les diphényl méthyldiphényl trisiloxanes ;  optionally, silicone oils such as polydimethylsiloxanes, liquid at room temperature; polydimethylsiloxanes comprising alkyl or alkoxy groups, pendent and / or at the end of the silicone chain, groups having from 2 to 24 carbon atoms; phenyl silicones such as phenyl trimethicones, phenyl dimethicones, phenyl trimethylsiloxy diphenylsiloxanes, diphenyl dimethicones and diphenyl methyldiphenyl trisiloxanes;
les huiles d'origine minérale comme les hydrocarbures linéaires ou ramifiés, tels que les huiles de paraffine et de ses dérivés, éventuellement raffinées, la vaseline, les polydécènes, le polyisobutène hydrogéné tel que le Parleam®, le squalane ; oils of mineral origin, such as linear or branched hydrocarbons, such as paraffin oils and its derivatives, optionally refined, petroleum jelly, polydecenes, hydrogenated polyisobutene such as Parleam®, squalane;
les hydrocarbures cycliques comme les cyclic hydrocarbons such as
(alkyl) cycloalcanes et les (alkyl) cycloalcènes dont la chaîne alkyle est linéaire ou ramifiée, saturée ou non, ayant de 1 à(alkyl) cycloalkanes and (alkyl) cycloalkenes in which the alkyl chain is linear or branched, saturated or unsaturated, having from 1 to
30 atomes de carbone, tels que le cyclohexane, le dioctylcyclohexane, le 2 , 4-diméthyl-3-cyclohexène et le dipentène ; Carbon atoms, such as cyclohexane, dioctylcyclohexane, 2,4-dimethyl-3-cyclohexene and dipentene;
les hydrocarbures aromatiques comme le benzène, le toluène, le p-cymène, le naphtalène, 1 ' anthracène ;  aromatic hydrocarbons such as benzene, toluene, p-cymene, naphthalene, anthracene;
les huiles fluorées comme les perfluoralcanes en C8 à fluorinated oils such as perfluoroalkanes in C8 to
C24 ; C24;
les huiles fluorosiliconées ;  fluorosilicone oils;
et leurs mélanges.  and their mixtures.
L'huile contenue dans le mélange-maître peut être identique à celle contenue dans la formulation du fluide de forage à laquelle elle est ajoutée, ou elle peut être différente de celle-ci.  The oil contained in the masterbatch may be the same as, or different from, the formulation of the drilling fluid to which it is added.
Le mélange-maître selon l'invention peut en variante comprendre des huiles plus visqueuses, appelées souvent graisses .  The masterbatch according to the invention may alternatively comprise more viscous oils, often called greases.
Des exemples de graisses sont notamment :  Examples of fats include:
- les graisses industrielles, telles que celles au sulfonate de calcium complexe, disponibles notamment dans la gamme CERAN ou sous la référence AXA GRl auprès de la société industrial greases, such as those with complex calcium sulphonate, available in particular in the CERAN range or under the reference AXA GRl from the company
TOTAL ; TOTAL;
- les graisses de spécialité, telles que les graisses semi-synthétiques, les graisses à base de bentone, renfermant éventuellement des composés fluorés, les graisses à savon lithium / calcium et les graisses renfermant du cuivre, en particulier celles disponibles auprès de la société TOTAL sous les dénominations commerciales MARSON SY 00 et SY 2, SPECIS CU, CALORIS 23 et MS23, STATERMIC XHT et NR, TIFORA PG, BIOMULTIS SEP 2, MULTIS COMPLEX HV2 ; et specialty fats, such as semisynthetic fats, bentone-based greases, optionally containing fluorinated compounds, lithium / calcium soap fats and greases containing copper, in particular those available from the company TOTAL under the trade names MARSON SY 00 and SY 2, SPECIS CU, CALORIS 23 and MS23, STATERMIC XHT and NR, TIFORA PG, BIOMULTIS SEP 2, MULTIS COMPLEX HV2; and
- leurs mélanges.  - their mixtures.
Ce mélange-maître peut être préparé en utilisant un dispositif de compoundage.  This masterbatch can be prepared using a compounding device.
Les dispositifs de compoundage sont bien connus de l'homme du métier. Ils sont classiquement utilisés dans l'industrie des matières plastiques pour le mélange à l'état fondu de polymères thermoplastiques et d'additifs en vue de produire des composites. Ces dispositifs comprennent généralement des moyens d'alimentation, notamment au moins une trémie pour les matériaux pulvérulents (ici, le graphène) et/ou au moins une pompe d'injection pour les matériaux liquides (ici, l'huile) ; des moyens de malaxage à fort cisaillement, par exemple une extrudeuse à double vis co- rotative ou contre-rotative (par exemple une micro-extrudeuse de DSM) ou un co-malaxeur, comprenant habituellement une vis sans fin disposée dans un fourreau (tube) chauffé ; une tête de sortie qui donne sa forme au matériau sortant ; et des moyens de refroidissement, sous air ou à l'aide d'un circuit d'eau, du matériau. Celui-ci se trouve généralement sous forme de jonc sortant en continu du dispositif et qui peut être découpé ou mis sous forme de granulés, après refroidissement. D'autres formes peuvent toutefois être obtenues en adaptant une filière de la forme voulue sur la tête de sortie.  Compounding devices are well known to those skilled in the art. They are conventionally used in the plastics industry for the melt blending of thermoplastic polymers and additives to produce composites. These devices generally comprise feed means, in particular at least one hopper for pulverulent materials (here, graphene) and / or at least one injection pump for liquid materials (here, the oil); high shear mixing means, for example a co-rotating or counter-rotating twin-screw extruder (for example a DSM micro-extruder) or a co-kneader, usually comprising a worm disposed in a sheath (tube ) heated; an outlet head which gives shape to the outgoing material; and cooling means, in air or with the aid of a water circuit, of the material. This is generally in the form of rod outgoing continuous device and can be cut or granulated after cooling. Other forms can however be obtained by fitting a die of the desired shape on the output head.
Des exemples de co-malaxeurs utilisables selon l'invention sont les co-malaxeurs BUSS MDK 46 et ceux de la série BUSS MKS ou MX, commercialisés par la société BUSS AG, qui sont tous constitués d'un arbre à vis pourvu d'ailettes, disposé dans un fourreau chauffant éventuellement constitué de plusieurs parties et dont la paroi interne est pourvue de dents de malaxage adaptées à coopérer avec les ailettes pour produire un cisaillement de la matière malaxée. L'arbre est entraîné en rotation, et pourvu d'un mouvement d'oscillation dans la direction axiale, par un moteur. Ces co-malaxeurs peuvent être équipés d'un système de fabrication de granulés, adaptés par exemple à leur orifice de sortie, qui peut être constitué d'une vis d'extrusion. Examples of co-kneaders that can be used according to the invention are the BUSS MDK 46 co-kneaders and those of the BUSS MKS or MX series sold by the company BUSS AG, all of which consist of a screw shaft provided with fins. , disposed in a heating sleeve possibly consisting of several parts and whose inner wall is provided with kneading teeth adapted to cooperate with the fins for produce shearing of the kneaded material. The shaft is rotated and provided with oscillation movement in the axial direction by a motor. These co-kneaders may be equipped with a granule manufacturing system, adapted for example to their outlet orifice, which may consist of an extrusion screw.
Les co-malaxeurs utilisables selon l'invention ont de préférence un rapport de vis L/D allant de 7 à 22, par exemple de 10 à 20.  The co-kneaders that can be used according to the invention preferably have an L / D screw ratio ranging from 7 to 22, for example from 10 to 20.
L'étape de compoundage est généralement mise en œuvre à température proche (par exemple ± 5°C) de la température ambiante (25 °C) .  The compounding step is generally carried out at a close temperature (for example ± 5 ° C.) of the ambient temperature (25 ° C.).
Comme indiqué précédemment, le mélange-maître selon l'invention, obtenu par exemple selon le procédé décrit ci- dessus, peut être dilué dans une base liquide aqueuse et/ou organique comprenant au moins un agent alourdissant sous forme particulaire et éventuellement au moins un agent tensioactif et/ou au moins un agent épaississant autre que le graphène, en vue de la fabrication du fluide de forage selon l'invention. Selon une forme d'exécution de l'invention, le mélange maître est incorporé directement dans la formulation finale du fluide de forage. On préfère toutefois que l'agent alourdissant soit ajouté à la base liquide après introduction du mélange-maître dans celle-ci.  As indicated above, the masterbatch according to the invention, obtained for example according to the method described above, can be diluted in an aqueous and / or organic liquid base comprising at least one weighting agent in particulate form and optionally at least one surfactant and / or at least one thickening agent other than graphene, for producing the drilling fluid according to the invention. According to one embodiment of the invention, the masterbatch is incorporated directly into the final formulation of the drilling fluid. It is preferred, however, that the weighting agent be added to the liquid base after introduction of the masterbatch therein.
Dans ce dernier cas, on préfère en outre selon l'invention que le mélange-maître et la base liquide soient soumis à un traitement mécanique, de préférence avant mélange avec l'agent alourdissant. Ce traitement peut être de nature quelconque, pour autant qu'il permette d'obtenir une dispersion homogène du graphène dans la base liquide. Ce traitement comprend avantageusement un traitement aux ultrasons ou un cisaillement de la dispersion mélange à l'aide d'un système rotor-stator ou à l'aide d'un mélangeur à pales . In the latter case, it is furthermore preferred according to the invention that the masterbatch and the liquid base are subjected to a mechanical treatment, preferably before mixing with the weighting agent. This treatment may be of any kind, provided that it makes it possible to obtain a homogeneous dispersion of graphene in the liquid base. This treatment advantageously comprises an ultrasonic treatment or a shear of the dispersion mixture with using a rotor-stator system or using a blade mixer.
Un tel système rotor-stator comprend généralement un rotor commandé par un moteur et pourvu de systèmes de guidage de fluide, perpendiculaires à l'axe du rotor, tels que des lames ou pales disposées sensiblement radialement ou un disque plat pourvu de dents périphériques, ledit rotor étant éventuellement pourvu d'une couronne dentée, et un stator disposé de façon concentrique par rapport au rotor, et à une faible distance à l'extérieur de celui-ci, ledit stator étant équipé sur au moins une portion de sa circonférence d'ouvertures, ménagées par exemple dans une grille ou définissant entre elles une ou plusieurs rangées de dents, qui sont adaptées au passage du fluide aspiré dans le rotor et éjecté par les systèmes de guidage vers lesdites ouvertures. Une ou plusieurs des dents précitées peuvent être pourvues d'arêtes vives. Le fluide est ainsi soumis à un cisaillement important, à la fois dans l'entrefer entre le rotor et le stator et au travers des ouvertures ménagées dans le stator.  Such a rotor-stator system generally comprises a rotor controlled by a motor and provided with fluid guide systems perpendicular to the axis of the rotor, such as blades or blades arranged substantially radially or a flat disc provided with peripheral teeth, said rotor being optionally provided with a ring gear, and a stator arranged concentrically with respect to the rotor, and at a short distance outside thereof, said stator being equipped on at least a portion of its circumference; openings, for example in a grid or defining between them one or more rows of teeth, which are adapted to the passage of fluid sucked into the rotor and ejected by the guide systems to said openings. One or more of the aforementioned teeth may be provided with sharp edges. The fluid is thus subjected to high shear, both in the gap between the rotor and the stator and through the openings in the stator.
Un exemple de système de rotor-stator est notamment commercialisé par la société SILVERSON sous la dénomination commerciale Silverson L4RT. Un autre type de système rotor- stator est commercialisé par la société IKA-WERKE sous la dénomination commerciale Ultra-Turrax . D' autres systèmes rotor-stator encore sont constitués des moulins colloïdaux, des turbines défloculeuses et des mélangeurs à fort cisaillement de type rotor-stator, tels que les appareils commercialisés par la société IKA-WERKE ou par la société ADMIX.  An example of a rotor-stator system is in particular marketed by SILVERSON under the trade name Silverson L4RT. Another type of rotor-stator system is marketed by the company IKA-WERKE under the trade name Ultra-Turrax. Other rotor-stator systems still consist of colloid mills, deflocculating turbines and high-shear mixers of the rotor-stator type, such as the apparatus marketed by the company IKA-WERKE or the company ADMIX.
On préfère selon l'invention que la vitesse du rotor soit réglée à au moins 1.000 tours/min et de préférence à au moins 3000 tours/min voire à au moins 5.000 tours/min, par exemple pendant 5 à 15 minutes. En outre, on préfère que la largeur de l'entrefer entre le rotor et le stator soit de moins de 1 mm et de préférence de moins de 200 ym, plus préférentiellement de moins de 100 ym et, mieux, de moins de 50 ym voire de moins de 40 ym. Par ailleurs, le système rotor-stator utilisé selon l'invention confère avantageusement un cisaillement de 1.000 à 109 s-1. It is preferred according to the invention that the speed of the rotor is set to at least 1000 rpm and preferably at least 3000 rpm or even at least 5,000 rpm, for example. example for 5 to 15 minutes. In addition, it is preferred that the width of the gap between the rotor and the stator is less than 1 mm and preferably less than 200 μm, more preferably less than 100 μm and better still less than 50 μm. less than 40 ym. Furthermore, the rotor-stator system used according to the invention advantageously confers a shear of 1,000 to 10 9 s -1 .
Grâce à l'excellente résistance thermique du graphène utilisé dans les fluides de forage de la présente invention, ce dernier est particulièrement approprié pour le forage à grande profondeur, c'est-à-dire dans des conditions de haute température et de haute pression.  Due to the excellent heat resistance of graphene used in the drilling fluids of the present invention, the latter is particularly suitable for deep drilling, i.e. under high temperature and high pressure conditions.
Dans un mode de réalisation préféré du procédé de forage de la présente invention, la température de forage est par conséquent supérieure ou égale à 200°C, en particulier supérieure à 250°C.  In a preferred embodiment of the drilling method of the present invention, the drilling temperature is therefore greater than or equal to 200 ° C, in particular greater than 250 ° C.
Le forage à haute température et haute pression n'est toutefois qu'un mode de réalisation préféré du procédé de l'invention et les fluides de forage de la présente invention, grâce à leur seuil d'écoulement élevé associé à une viscosité relativement faible, s'avèrent également très utiles même à profondeur faible ou moyenne.  High-temperature and high-pressure drilling is, however, only a preferred embodiment of the process of the invention and the drilling fluids of the present invention, due to their high flow threshold associated with a relatively low viscosity, also prove very useful even at low or medium depth.
Il est ainsi possible d'utiliser les fluides de forage de la présente invention pendant toute la durée du forage en augmentant progressivement la teneur en graphène au fur et à mesure de l'augmentation de la profondeur de forage, de la température de forage et/ou de la pression de forage. Un tel procédé se distingue par une grande simplicité due à la possibilité de recyclage continu du fluide de forage qui peut être réutilisé après élimination des déblais et addition de quantités supplémentaires d'agent alourdissant et de graphène . Dans un mode de réalisation particulier du procédé de forage de la présente invention, le fluide de forage ne contient de préférence pas d'agent épaississant autre que le graphène et éventuellement des NTC. It is thus possible to use the drilling fluids of the present invention throughout the duration of the drilling by gradually increasing the graphene content as the drilling depth, the drilling temperature and / or or drilling pressure. Such a method is distinguished by a great simplicity due to the possibility of continuous recycling of drilling fluid that can be reused after removal of cuttings and addition of additional amounts of weighting agent and graphene. In a particular embodiment of the drilling method of the present invention, the drilling fluid preferably does not contain any thickening agent other than graphene and possibly CNTs.
Dans un autre mode de réalisation, le procédé de forage de la présente invention comprend le remplacement progressif d'un ou plusieurs agents épaississants présents dans le fluide, choisis par exemple parmi les argiles (bentonite, montmorillonite, attapulgite, argiles organophiles ) ou les polymères organiques, par le graphène, et éventuellement des In another embodiment, the drilling method of the present invention comprises the progressive replacement of one or more thickening agents present in the fluid, chosen for example from clays (bentonite, montmorillonite, attapulgite, organophilic clays) or polymers. graphene, and possibly
NTC, au fur et à mesure de l'augmentation de la profondeur de forage, de la température de forage et/ou de la pression de forage. Il peut en effet être intéressant, principalement pour des raisons de coût de production des fluides de forage, d'utiliser en début de forage des agents épaississants connus et peu coûteux tels que les polymères organiques et/ou des argiles épaississantes, et de n'introduire le graphène, et éventuellement les NTC, qu'à partir d'une certaine profondeur lorsque la dégradation thermique des polymères organiques ou la teneur excessive en matières solides apportées par les argiles commence à poser les problèmes décrits en introduction . NTC, as the drilling depth, drilling temperature, and / or drilling pressure increases. It may indeed be interesting, mainly for reasons of production cost of the drilling fluids, to use at the start of drilling known and inexpensive thickeners such as organic polymers and / or thickening clays, and introducing graphene, and possibly CNTs, only from a certain depth when the thermal degradation of the organic polymers or the excessive content of solids provided by the clays begins to pose the problems described in the introduction.
Dans tous les cas, le graphène peut être introduit dans le fluide de forage sous la forme d'un mélange-maître tel que décrit précédemment mais ne contenant pas nécessairement d'agent alourdissant.  In all cases, graphene can be introduced into the drilling fluid in the form of a masterbatch as described above but not necessarily containing a weighting agent.
L'invention sera mieux comprise à la lumière de l'exemple suivant, donné à des fins d'illustration seulement et qui n'a pas pour but de limiter la portée de l'invention telle que définie par les revendications annexées.  The invention will be better understood in the light of the following example, given for purposes of illustration only and which is not intended to limit the scope of the invention as defined by the appended claims.
EXEMPLE a) Fabrication du graphène par CVD EXAMPLE a) Graphene manufacture by CVD
On a fabriqué du graphène selon le procédé décrit ci- dessous . 1- Préparation d'un catalyseur CoFe∑04 pour la synthèse de graphène . Graphene was made according to the method described below. 1- Preparation of a CoFe Σ 0 4 catalyst for the synthesis of graphene
Dans un bêcher de 250 mL, on a préparé 37,5 ml d'une solution aqueuse d'acide citrique à une concentration de 0,4 M, à laquelle on a ajouté 1,1 g de nitrate de cobalt (Co(N03)2), 6H20) et 3,1 g de nitrate de fer (Fe(N03)3), 9H20) .In a 250 ml beaker, 37.5 ml of an aqueous solution of citric acid at a concentration of 0.4 M was prepared, to which 1.1 g of cobalt nitrate (Co (NO 3) 2 ), 6H 2 O) and 3.1 g of iron nitrate (Fe (NO 3 ) 3 ), 9H 2 O).
On a ajusté le pH de la solution obtenue à une valeur de 6 par addition, goutte-à-goutte et sous agitation, d'ammoniaque (NH4OH) . Le rapport molaire entre le nitrate de fer et le nitrate de cobalt dans la solution aqueuse était sensiblement de l'ordre de 2. On a placé cette solution aqueuse dans un cristallisoir en pyrex à une température de 80°C pendant une durée sensiblement de l'ordre de 12 h, de façon à former un gel homogène sensiblement déshydraté. The pH of the resulting solution was adjusted to a value of 6 by adding, dropwise and stirring, ammonia (NH 4 OH). The molar ratio between iron nitrate and cobalt nitrate in the aqueous solution was substantially of the order of 2. This aqueous solution was placed in a Pyrex crystallizer at a temperature of 80 ° C. for a period of substantially order of 12 hours, so as to form a substantially dehydrated homogeneous gel.
On a chauffé le gel homogène ainsi obtenu à une température de l'ordre de 200 °C, de façon à décomposer l'acide citrique. On a observé alors l'expansion du gel homogène en une mousse que l'on a laissé se développer pendant environ 30 min jusqu'à stabilisation. On a broyé ensuite délicatement cette mousse de façon à former une poudre que l'on a chauffée à une température de 400 °C pendant The homogeneous gel thus obtained was heated to a temperature of about 200 ° C, so as to decompose the citric acid. The expansion of the homogeneous gel was then observed to foam which was allowed to develop for about 30 minutes until stabilization. This foam was then crushed gently to form a powder which was heated at a temperature of 400 ° C
4 heures à l'air atmosphérique. On a obtenu ainsi une poudre cristalline de ferrite de cobalt. 4 hours to atmospheric air. A crystalline powder of cobalt ferrite was thus obtained.
Cette poudre présentait une unique phase d'oxyde possédant une structure de type spinelle avec une taille de domaine cristallin comprise entre 14 nm et 20 nm (déterminée par diffraction des rayons X) et une surface spécifique de 7 m2/g. 2- Synthèse du graphène This powder had a single oxide phase having a spinel type structure with a crystalline domain size of between 14 nm and 20 nm (determined by X-ray diffraction) and a specific surface area of 7 m 2 / g. 2- Graphene synthesis
On a réalisé une synthèse de graphène dans un réacteur en quartz horizontal. On a placé 20 mg de la poudre de catalyseur obtenue ci-dessus dans un creuset en alumine que l'on a placé au centre d'un réacteur tubulaire horizontal à quartz de diamètre intérieur de l'ordre de 18 mm. On a chauffé la poudre de catalyseur, sous un flux gazeux formé d'hydrogène (¾, 53 cm3/min) et d'argon (Ar, 160 cm3/min) , jusqu'à la température de 650°C selon un gradient de température de 630°C/h. Lorsque la température a atteint 650°C, on a introduit de l'éthylène (C2H4, 32 cm3/min) dans le mélange gazeux et on a maintenu le flux gazeux et la température pendant une durée d'une heure. Après 1 h, on a arrêté le chauffage et les flux gazeux d' éthylène et d'hydrogène. La poudre obtenue a été refroidie jusqu'à la température de 300 °C sous argon. La quantité de produit récupéré en fin de réaction a été de 220 mg. b) Préparation d'un mélange-maître Graphene synthesis was performed in a horizontal quartz reactor. 20 mg of the catalyst powder obtained above was placed in an alumina crucible which was placed in the center of a horizontal quartz tubular reactor with an inside diameter of about 18 mm. The catalyst powder was heated under a gaseous flow of hydrogen (¾ 53 cm 3 / min) and argon (Ar 160 cm 3 / min) to a temperature of 650 ° C. temperature gradient of 630 ° C / h. When the temperature reached 650 ° C, ethylene (C 2 H 4 , 32 cm 3 / min) was introduced into the gas mixture and the gas flow and the temperature were maintained for one hour. After 1 h, the heating and gaseous flows of ethylene and hydrogen were stopped. The powder obtained was cooled to a temperature of 300 ° C. under argon. The amount of product recovered at the end of the reaction was 220 mg. b) Preparation of a masterbatch
On introduit, dans le puits d'alimentation de zone 1 d'un co-malaxeur BUSS MDK 46 (L/D = 11), du graphène obtenu comme décrit ci-dessus. Une quantité pondérale d'huile minérale (EDC 99 DW de TOTAL) identique à celle de graphène est introduite dans la pompe d'injection de la première zone de l'appareil, avant la première bague de restriction. Le malaxage est effectué à température ambiante. En sortie du co-malaxeur, on obtient des joncs solides qui sont découpés, sans utilisation de jet d'eau, pour obtenir un mélange-maître sous forme de granulés solides renfermant 15% en poids de graphène et 85% en poids d'huile. c) Fabrication d'un fluide de forage Le mélange-maître préparé comme décrit ci-dessus est imprégné de la même huile minérale que celle utilisée pour sa préparation, à raison de 1 partie en poids de mélange-maître pour 2 parties en poids d'huile, pendant au moins 8 heures. La suspension est ensuite rediluée dans la même huile pour atteindre un taux de graphène de 1% en poids. Cette suspension est alors soumise à un traitement mécanique dans un système rotor-stator (Silverson® L4RT de SILVERSON) pendant 10 minutes pour obtenir une dispersion de graphène stable, c'est-à-dire ne présentant pas de sédimentation apparente après 24 heures. Un agent alourdissant comme la baryte est ensuite introduit dans cette dispersion pour obtenir un fluide de forage. A graphene obtained as described above is introduced into the zone 1 feed well of a BUSS MDK 46 (L / D = 11) co-kneader. A quantity by weight of mineral oil (EDC 99 DW of TOTAL) identical to that of graphene is introduced into the injection pump of the first zone of the apparatus, before the first restriction ring. The mixing is carried out at room temperature. At the outlet of the co-kneader, solid rods are obtained which are cut, without the use of a water jet, to obtain a masterbatch in the form of solid granules containing 15% by weight of graphene and 85% by weight of oil. . (c) Manufacture of a drilling fluid The masterbatch prepared as described above is impregnated with the same mineral oil as that used for its preparation, at a proportion of 1 part by weight of masterbatch to 2 parts by weight of oil, for at least 8 hours. The suspension is then rediluted in the same oil to reach a graphene content of 1% by weight. This suspension is then subjected to mechanical treatment in a rotor-stator system (Silverson L4RT Silverson ®) for 10 minutes to obtain a stable graphene dispersion, that is to say having no apparent sedimentation after 24 hours. A weighting agent such as barite is then introduced into this dispersion to obtain a drilling fluid.

Claims

REVENDICATIONS
1. Fluide de forage dans des formations rocheuses souterraines, comprenant 1. Drilling fluid in underground rock formations, including
(a) une base liquide aqueuse et/ou organique,  (a) an aqueous and / or organic liquid base,
(b) au moins un agent alourdissant, sous forme particulaire , ayant une masse volumique au moins égale à 2 g/cm3, de préférence au moins égale à 4 g/cm3, en suspension dans ladite base liquide, et (b) at least one weighting agent, in particulate form, having a density of at least 2 g / cm 3 , preferably at least 4 g / cm 3 , suspended in said liquid base, and
(c) du graphène .  (c) graphene.
2. Fluide de forage selon la revendication 1, caractérisé par le fait que la base liquide est une base à phase continue huileuse telle qu'une huile ou une émulsion eau-dans-huile contenant au plus 50% en poids, de préférence au plus 20% en poids d'eau.  2. Drilling fluid according to claim 1, characterized in that the liquid base is an oily continuous phase base such as an oil or a water-in-oil emulsion containing at most 50% by weight, preferably at most 20% by weight of water.
3. Fluide de forage selon la revendication 1, caractérisé par le fait que la base liquide est une base à phase continue aqueuse, notamment une émulsion huile-dans- eau .  3. Drilling fluid according to claim 1, characterized in that the liquid base is an aqueous continuous phase base, in particular an oil-in-water emulsion.
4. Fluide de forage selon l'une quelconque des revendications 1 à 3, caractérisé par le fait qu'il contient de 0,1 à 3 % en poids de graphène.  4. Drilling fluid according to any one of claims 1 to 3, characterized in that it contains from 0.1 to 3% by weight of graphene.
5. Fluide de forage selon l'une quelconque des revendications 1 à 4, caractérisé en ce que le graphène est obtenu suivant un procédé de dépôt chimique en phase vapeur.  5. Drilling fluid according to any one of claims 1 to 4, characterized in that the graphene is obtained by a chemical vapor deposition process.
6. Fluide de forage selon la revendication 5, caractérisé en ce que le graphène se présente sous forme de particules d'une épaisseur de moins de 50 nm, de préférence de moins de 15 nm, plus préférentiellement de moins de 5 nm, et de dimensions latérales de 10 nm à moins de 1000 nm, préférentiellement de 50 à 600 nm, et plus préférentiellement de 100 à 400 nm et en ce que chacune des particules de graphène renferme de 1 à 50 feuillets, de préférence de 1 à 20 feuillets, plus préférentiellement de 1 à 10 feuillets, voire de 1 à 5 feuillets. 6. Drilling fluid according to claim 5, characterized in that the graphene is in the form of particles having a thickness of less than 50 nm, preferably less than 15 nm, more preferably less than 5 nm, and lateral dimensions from 10 nm to less than 1000 nm, preferably from 50 to 600 nm, and more preferably from 100 to 400 nm and in that each of the graphene particles contains from 1 to 50 sheets, preferably from 1 to 50 20 leaflets, more preferably from 1 to 10 leaflets, or even from 1 to 5 leaflets.
7. Fluide de forage selon l'une quelconque des revendications 1 à 6, caractérisé par le fait que la phase huileuse contient une huile minérale, une huile fluorée, une huile diesel ou une huile synthétique, de préférence une huile minérale.  7. Drilling fluid according to any one of claims 1 to 6, characterized in that the oily phase contains a mineral oil, a fluorinated oil, a diesel oil or a synthetic oil, preferably a mineral oil.
8. Fluide de forage selon l'une quelconque des revendications 1 à 7, caractérisé par le fait que l'agent alourdissant est choisi parmi la baryte (BaSC^) la calcite 8. Drilling fluid according to any one of claims 1 to 7, characterized in that the weighting agent is selected from baryta (BaSC ^) calcite
(CaC03) , la dolomite (CaC03.MgC03) , l'hématite (Fe203) , la magnétite (Fe304) , l'ilménite (FeTi03) et la sidérite (FeC03) , et leur mélanges, de préférence la baryte. (CaCO 3 ), dolomite (CaCO 3 .MgCO 3 ), hematite (Fe 2 O 3 ), magnetite (Fe 3 O 4 ), ilmenite (FeTiO 3 ) and siderite (FeCO 3 ), and mixtures thereof, preferably barite.
9. Fluide de forage selon l'une quelconque des revendications 1 à 7, caractérisé en ce qu'il contient en outre au moins un agent épaississant autre que le graphène, choisi parmi les polymères organiques solubles dans la phase aqueuse et/ou dans la phase huileuse de la base liquide et/ou des nanotubes de carbone.  9. Drilling fluid according to any one of claims 1 to 7, characterized in that it further contains at least one thickening agent other than graphene, selected from organic polymers soluble in the aqueous phase and / or in the oily phase of the liquid base and / or carbon nanotubes.
10. Fluide de forage selon l'une quelconque des revendications 1 à 8, caractérisé en ce qu'il est exempt de polymères organiques solubles dans la phase aqueuse et/ou dans la phase huileuse de la base liquide.  10. Drilling fluid according to any one of claims 1 to 8, characterized in that it is free of organic polymers soluble in the aqueous phase and / or in the oily phase of the liquid base.
11. Procédé de fabrication du fluide de forage selon l'une quelconque des revendications 1 à 10, caractérisé en ce qu'il comprend la dilution d'un mélange-maître exempt de polymère organique, comprenant du graphène et au moins une huile, dans une base liquide aqueuse et/ou organique comprenant au moins un agent alourdissant sous forme particulaire et éventuellement au moins un agent tensioactif et/ou au moins un agent épaississant autre que le graphène.  11. A method of manufacturing the drilling fluid according to any one of claims 1 to 10, characterized in that it comprises the dilution of a masterbatch free of organic polymer, comprising graphene and at least one oil, in an aqueous and / or organic liquid base comprising at least one weighting agent in particulate form and optionally at least one surfactant and / or at least one thickening agent other than graphene.
12. Mélange-maître sous forme de granulés, adapté à la mise en œuvre du procédé selon la revendication 11, comprenant du graphène et au moins une huile, ledit mélange- maître étant exempt de polymère organique. 12. Masterbatch in the form of granules, suitable for carrying out the process according to Claim 11, comprising graphene and at least one oil, said masterbatch being free of organic polymer.
13. Mélange-maître selon la revendication 12, caractérisé en ce qu'il renferme de 5 à 30% en poids, de préférence de 10 à 20% en poids, de graphène, par rapport au poids du mélange-maître.  13. Masterbatch according to claim 12, characterized in that it contains from 5 to 30% by weight, preferably from 10 to 20% by weight, of graphene, relative to the weight of the masterbatch.
14. Procédé de préparation du mélange-maître selon l'une des revendications 12 et 13, comprenant les étapes consistant à :  14. Process for the preparation of the masterbatch according to one of claims 12 and 13, comprising the steps of:
(a) introduire puis malaxer le graphène et ladite au moins une huile, dans un dispositif de compoundage, pour obtenir un composite,  (a) introducing and kneading graphene and said at least one oil, in a compounding device, to obtain a composite,
(b) extruder puis refroidir ledit composite de façon à obtenir un mélange-maître sous forme solide,  (b) extruding and then cooling said composite to obtain a masterbatch in solid form,
(c) mettre en forme ledit mélange-maître pour obtenir des granulés.  (c) shaping said masterbatch to obtain granules.
15. Procédé de forage dans des formations rocheuses souterraines utilisant un fluide de forage selon l'une quelconque des revendications 1 à 10.  15. A method of drilling in underground rock formations using a drilling fluid according to any one of claims 1 to 10.
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