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  • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
  • C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/24—Homopolymers or copolymers of amides or imides
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  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L39/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions of derivatives of such polymers
  • C08L39/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L39/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions of derivatives of such polymers
  • C08L39/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
  • C08L39/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
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  • 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
  • C09K8/035—Organic additives
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  • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
  • C09K8/60—Compositions for stimulating production by acting on the underground formation
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
  • C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/234—Macromolecular compounds
  • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
  • C10L1/2364—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing amide and/or imide groups
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/234—Macromolecular compounds
  • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
  • C10L1/2381—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds polyamides; polyamide-esters; polyurethane, polyureas
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/234—Macromolecular compounds
  • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
  • C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
  • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
  • C10L3/10—Working-up natural gas or synthetic natural gas
  • C10L3/107—Limiting or prohibiting hydrate formation
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  • C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
  • C09K2208/22—Hydrates inhibition by using well treatment fluids containing inhibitors of hydrate formers
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  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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  • C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
  • C09K2208/24—Bacteria or enzyme containing gel breakers
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  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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  • C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
  • C09K2208/26—Gel breakers other than bacteria or enzymes
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
  • C10L1/1852—Ethers; Acetals; Ketals; Orthoesters
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L2250/00—Structural features of fuel components or fuel compositions, either in solid, liquid or gaseous state
  • C10L2250/04—Additive or component is a polymer
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
  • C10L2290/14—Injection, e.g. in a reactor or a fuel stream during fuel production
  • C10L2290/141—Injection, e.g. in a reactor or a fuel stream during fuel production of additive or catalyst

Definitions

• the present invention relates to the field of hydrocarbon extraction and more particularly the field of additives used to facilitate the extraction and transport of said hydrocarbons to the surface.
• the present invention particularly relates to a method for inhibiting the formation of gas hydrates which are commonly known to disrupt the flow of hydrocarbons in the extraction and transport lines of said hydrocarbons.
• hydrocarbons mainly oil, gas, condensate and others
• hydrocarbons mainly oil, gas, condensate and others
• Fluids extracted or fluids produced, or production fluids
• fluids including oil, gas, condensate, water and mixtures thereof.
• petroleum is meant in the sense of the present invention crude oil, that is to say unrefined, from a deposit.
• gas means raw natural gas, that is to say untreated gas, directly extracted from a deposit, such as, for example, hydrocarbons, such as methane, ethane, propane, butane, hydrogen sulphide, carbon dioxide and other gaseous compounds under operating conditions, and mixtures thereof.
• hydrocarbons such as methane, ethane, propane, butane, hydrogen sulphide, carbon dioxide and other gaseous compounds under operating conditions, and mixtures thereof.
• the composition of the extracted natural gas varies considerably according to the wells.
• the gas may include gaseous hydrocarbons, water and other gases.
• condensates are understood to mean hydrocarbons having an intermediate density.
• the condensates generally comprise hydrocarbon mixtures which are liquid under the operating conditions.
• these production fluids usually comprise an aqueous phase in greater or lesser amount.
• the origin of this aqueous phase can be endogenous and / or exogenous to the underground reservoir containing the hydrocarbons, the exogenous aqueous phase generally coming from a water injection, also called injection water.
• injection water also called injection water.
• the fluid transport pipes produced are often placed on the seabed, at increasingly greater depths, where the seawater temperature is often less than 15 ° C. , more often less than 10 ° C, even close to or equal to 4 ° C.
• clathrates also called hydrate crystals, gas hydrates or more simply hydrates.
• clathrates are solid crystals (similar to those of water in the form of ice) formed by water molecules, also called “recipient”, around one or more molecules of gas, also called “guests” Such as methane, ethane, propane, butane, carbon dioxide or hydrogen sulphide.
• crystals are most often induced by a lowering of the temperature of production fluids that come out hot geological reservoirs that contain them and that enter a cold zone. These crystals can grow more or less rapidly and agglomerate and can cause clogging or clogging of production lines, hydrocarbon transport lines (oil, condensate, gas), valves, valves and other elements that may be clogged totally. or at least partially.
• a second approach is to maintain the temperature of the pipe at a temperature above the formation temperature and / or agglomeration of hydrates at a given pressure.
• a third approach, frequently used, is to add an additive called "thermodynamic hydrate inhibitor" or "THI" in the English language, usually an alcohol or alcohol derivative, for example methanol, or glycol, in product fluids containing the guest water / gas mixture (s).
• THI thermodynamic hydrate inhibitor
• alcohol or alcohol derivative for example methanol, or glycol
• This fourth solution is to add a low dosage additive, called LDHI ("Low Dosage Hydrate Inhibitor" in English) in fluids products including the water / guest gas mixture (s).
• LDHI Low Dosage Hydrate Inhibitor
• This additive is also called anti-hydrate and is introduced at a low dosage, generally between 1% and 4% by weight, relative to the weight of water, it being understood that higher or lower amounts are of course possible.
• Two types of anti-hydrate additives are currently known, anti-caking agents and kinetic anti-hydrates.
• the anti-caking agents are not inhibitors of the formation of hydrate crystals, but have the property of dispersing them, which consequently prevents said hydrate crystals from agglomerating with each other.
• the hydrate crystals thus dispersed can no longer clog the transport lines of oil and gas production fluids, thus increasing production, particularly oil and gas extraction.
• the anti-caking agents retain their effectiveness even at low temperatures. They make it possible in particular to avoid the problems of clogging the ducts at temperatures generally 15 ° C. below the minimum temperature at which the hydrate crystals are formed, for a given pressure.
• the kinetic anti-hydrates act on the germination and growth of hydrate crystals, by delaying the formation of crystals by several hours or even several days.
• kinetic antihydrates work hard with strong sub-coolings. Indeed, at temperatures of more than 10 ° C below the minimum temperature at which the hydrate crystals are formed for a given pressure (SC ⁇ 10 ° C), the effectiveness of the anti-caking agents is reduced.
• Another object of the present invention is to provide a kinetic hydrate inhibitor which is effective under the usual conditions of use, that is to say for a dosage of between 0.1% and 10% by weight. weight, based on the total weight of the aqueous phase in a production fluid.
• Another objective is to propose a kinetic hydrate inhibitor which is not very toxic for the environment, but also inexpensive and easy to produce.
• compositions comprising mixtures of specific polymers make it possible to satisfy the abovementioned objectives and in particular to behave as kinetic anti-hydrates with relatively long induction times, and in particular longer than those observed with the known kinetic anti-hydrates of the prior art, and this for relatively important sub-coolings.
• These polymer compositions are also environmentally friendly and easy to prepare with reasonable production costs.
• the present invention relates to a composition
• a composition comprising:
• the polymer whose repeating unit comprises at least one amide function is a polymer whose amide functions are connected to the polymer chain.
• the nitrogen atoms of the amide functions may be substituted, and are preferably substituted, more preferably mono-substituted, more preferably disubstituted.
• the Nitrogen atoms of the pendant amide functions are disubstituted, the two substituents can form a ring so as to form a lactam with the amide chain.
• the substituents of the nitrogen atoms of the pendant amide functions may also comprise one or more nitrogen atom (s), preferably a nitrogen atom.
• This or these nitrogen atom (s) which substitute the nitrogen atoms of the pendant amide functions may also have reacted with one or more alkylating agent (s), so as to form an ammonium cation, the anion which can be chosen from all the anions known to those skilled in the art, and in particular from halides (for example chloride, bromide), sulphonates (for example methanesulfonate, para-toluenesulfonate), sulphates (for example methyl sulfate, ethyl sulfate), carbonates (eg methyl carbonate), and others.
• halides for example chloride, bromide
• sulphonates for example methanesulfonate, para-toluenesulfonate
• sulphates for example methyl sulfate
• the polymer whose repeating unit comprises at least one amide function is preferably a polymer obtained by polymerization of one or more monomers chosen from (meth) acrylamides substituted or not, the monomers vinyl with lactam groups, in particular vinylpyrrolidones, vinylcaprolactams.
• non-limiting examples are vinylpyrrolidone (VP), vinylcaprolactam (VCap), acrylamide, methacrylamide, N-alkylacrylamide, N-alkylmethacrylamide and ⁇ , ⁇ -dialkylacrylamide.
• the polymer whose repeating unit comprises at least one amide function may of course be a homopolymer, a co-polymer or a terpolymer.
• the term "co-polymer” in this invention means a polymer resulting from the polymerization of two different monomers.
• the term "terpolymer” in the present invention is understood to mean a polymer resulting from the polymerization of three different monomers.
• co-polymers and ter-polymers that may be used in the context of the present invention may be co-polymers, and terpolymers, blocks or grafts, random, periodic or random, preferably of low molecular weight.
• low molecular weight is meant a mass of between 1000 and 5000 atomic mass units (uma) and preferably between 1500 and 4000 uma.
• the monomers that can be used to form the co-polymers and other ter-polymers explained above can be of any type and are advantageously chosen from functionalized and vinyl-unsaturated monomers, such as, for example, and, but not limited to, those selected from acrylic acid, substituted alkyl acrylates, ⁇ , ⁇ -dialkylaminoalkyl acrylates and their corresponding quaternary alkyl chlorides, hydroxyalkyl acrylates, methacrylic acid, substituted alkyl methacrylates, ⁇ , ⁇ -dialkylaminoalkyl methacrylates and their corresponding quaternary alkyl chlorides, hydroxyalkyl methacrylates, and the like, as well as mixtures of two or more of them in all proportions.
• functionalized and vinyl-unsaturated monomers such as, for example, and, but not limited to, those selected from acrylic acid, substituted alkyl acrylates, ⁇ , ⁇ -dialkylaminoalkyl acrylates and their
• alkyl or “alkyl” represents, unless otherwise indicated, a saturated hydrocarbon radical, linear or branched having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, more preferably from 1 to 4 carbon atoms.
• Still other monomers may enter into the formation of the abovementioned co-polymers and ter-polymers, and among these may be mentioned, without being limiting, the monomers containing at least one hydroxyl function and / or at least one a functional group convertible to hydroxyl function.
• Such monomers are in particular described in detail in WO20101 17660. Among these monomers, mention may be made especially of vinyl acetate.
• the monomers used for the preparation of the polymer whose repeating unit comprises at least one amide function (polymer a) of the composition of the present invention) are chosen from the monomers of vinylcaprolactam type (VCap) and vinylpyrrolidone type (VP).
• copolymers and ter-polymers resulting from the copolymerization of at least one vinyl monomer containing amide groups and / or cyclic amides (lactams) with a monomer containing a hydroxyl function and / or a functional group convertible to the hydroxyl function refers to the copolymers resulting, for example, from the polymerization of the monomers of the vinylpyrrolidone (VP), vinylcaprolactam (VCap) and acrylamide type with monomers containing a hydroxyl function and / or a functional group convertible to the hydroxyl function and in particular the monomers thus described in detail in WO20101 17660.
• VP vinylpyrrolidone
• VCap vinylcaprolactam
• the copolymers of this type according to the invention are obtained by polymerization of vinylcaprolactams (VCap) and / or vinylpyrrolidones (VP) with vinyl acetate and more preferably by polymerization of vinylcaprolactams (VCap) with vinyl acetate.
• VCap vinylcaprolactams
• VP vinylpyrrolidones
• the VCapA / P mass ratio is between 95/5 and 50. / 50, preferably between 75/25 and 50/50 and even more preferably between 60/40 and 50/50.
• the polymer a) of the composition of the present invention is a polyvinylcaprolactam / polyvinylpyrrolidone copolymer (1/1) (in mol), such as for example the product sold by BASF under the Luvicap 55W ® name .
• the copolymer a) of the composition according to the present invention is a VCap / VOH polymer obtained by polymerization of N-vinyl-2-caprolactam and vinyl acetate in a suitable solvent. known to those skilled in the art (butylglycol for example) followed by hydrolysis of the polymer in an alkaline medium.
• the mass ratio VCap / VOH in the final polymer is between 50/50 and 95/5, preferably between 60/40 and 85/15 and even more preferably between 65/35 and 75/25.
• the total amount of the copolymer or copolymers a) present in the composition of the invention is preferably between 1% and 50% by weight, more preferably between 5% and 40% by weight, and better still between 10% and 50% by weight. % and 30% by weight, relative to the total weight of the composition.
• the polyetheramine b) of the composition of the present invention advantageously has at least two secondary and / or tertiary amine functions.
• this polyetheramine has two terminal amine functional groups, the two functions being secondary or tertiary amine functions, it is most preferably the two terminal amine functions are both secondary amine functions.
• the polyetheramine b) of the composition according to the invention has a molecular weight (Mw) greater than 100 g. mol "1 , more preferably greater than 200 g mol -1 .
• This polyetheramine b) may for example be represented by formula (I) below:
• R 1 and R 2 which are identical or different, represent a saturated or unsaturated, linear or branched hydrocarbon-based chain containing from 1 to 24 carbon atoms, preferably from 1 to 12 carbon atoms, more preferably from 1 to 6 carbon atoms; , and quite preferably R 1 and R 2, which are identical or different, represent a saturated linear or branched hydrocarbon chain containing from 3 to 6 carbon atoms, inclusive limits,
• R3 represents the hydrogen atom, the methyl radical or the ethyl radical
• n represents an integer between 1 and 50 inclusive.
• radicals R3 may be identical or different, so that the polyetheramine of formula (I) may comprise alternating sequences, in blocks or random, of ethylene chains. oxy, propyleneoxy and / or butyleneoxy, preferably ethyleneoxy and / or propyleneoxy chains.
• the polyetheramine b) present in the composition according to the present invention corresponds to the formula (I) in which R 1, R 2 and R 3 are as defined above and n represents an integer between 1 and 40, preferably between 1 and 30, more preferably between 1 and 20, most preferably between 1 and 10 inclusive, and typically between 4 and 8 inclusive.
• polyether amines are for example those marketed by Huntsman under the generic name Jeffamine ®, and described for example in the document available on the website of Huntsman to http: // www .huntsman.com / portal / page / portal / performance products / Media% 20Library / globai / files / jeffamine polyetheramines.pdf.
• the total amount of the polyetheramine (s) present (s) in the composition of the invention is generally between 0.5% and 40% by weight, preferably between 1% and 30% by weight. and more preferably between 5% and 20% by weight, relative to the total weight of the composition.
• composition according to the present invention may optionally comprise one or more organic solvents.
• organic solvents that can be used are advantageously chosen from alkyl alcohols containing from 1 to 4 carbon atoms. carbon, glycol ethers and their mixtures.
• the organic solvent used is a glycol or a glycol mixture, and most preferably the organic solvent is butyl glycol.
• the total amount of organic solvent (s) present in the composition of the invention is generally between 30% and 90%, preferably between 50% and 90%, and more preferably between 60% and 90%. % and 85% by weight, relative to the total weight of the composition.
• composition according to the present invention can be easily prepared for example by mixing the various components, according to any means well known to those skilled in the art, in any order, according to the compatibilities and miscibility of the components between them.
• the compositions can thus be prepared by mixing by means of a stirrer, at ambient temperature and at atmospheric pressure.
• composition according to the invention allows the formation and / or agglomeration of hydrate crystals to be delayed for several hours or even several days, in particular for subunits. -coolings above 10 ° C. It has further been observed that the composition useful in the context of the present invention often results in a longer induction time than the compositions or products currently available commercially.
• composition according to the present invention thus allows to work at lower temperatures than current temperatures while increasing the extraction efficiency and in particular the production yield of oil and / or gas .
• this composition is effective at low concentrations, for example at dosages of between 0.1% and 10% by weight, preferably between 0.2% and 7% by weight, preferably still between 0.2% and 5% by weight and better still between 1% and 4% by weight, relative to the total weight of the aqueous phase in a production fluid, and very particularly between 0.2% and 4%, typically between 0.2% and 3%, in particular between 1% and 3% by weight.
• the composition according to the present invention is also inexpensive, easy to produce and low in toxicity.
• the present invention relates to a method for retarding or even preventing the formation and / or agglomeration of gas hydrates, comprising a step of adding a composition as defined herein. above in a mixture of composition capable of forming hydrates, as described previously in this text, and in particular in a production fluid comprising an aqueous phase and one or more gases.
• the total content of the aqueous phase, present in the production fluid is generally between 10% and 90% by weight, relative to the total weight of the production fluid, that is to say relative to the total weight of the fluids (aqueous phase and hydrocarbons).
• the treatment of fluid with a very high content in aqueous phase or containing less than 10% of aqueous phase, or even less than 1% of aqueous phase would not be outside the scope of the invention.
• the total content of the aqueous phase defined above corresponds to the total proportion of aqueous phase initially present in the production fluid, that is to say in the initial mixture (aqueous phase and other extraction liquids).
• crude oils such as hydrocarbons, condensates, .
• the aqueous phase of the production fluid further comprises one or more dissolved gases capable of forming gas hydrates with water at a given temperature and pressure.
• gases present in the aqueous phase of the production fluid are so-called "guest" gases, as defined above, and generally comprise methane, ethane, propane, butane, carbon dioxide, hydrogen sulphide, and their mixtures.
• composition according to the invention is added in an amount of between 0.1% and 10% by weight, preferably between 0.2% and 7% by weight, more preferably between 0.2% and 5% by weight. and more preferably between 1% and 4% by weight, relative to the total weight of the aqueous phase in a production fluid, and more particularly between 0.2% and 4%, typically between 0.2% and 3%, in especially between 1% and 3% by weight.
• the composition may be introduced into the production fluid continuously, discontinuously, regularly or not, or temporarily, in one or more times.
• the introduction of the composition is generally carried out upstream of the zone at risk of presence of hydrates, whether on the surface, at the wellhead or downhole.
• the fluid treated with the composition according to the invention is a drilling mud or a completion fluid.
• the composition is introduced into the drilling mud or into the completion fluid, before or during the injection of the drilling mud or the completion fluid.
• the present invention also relates to the use of a composition as defined above for retarding or even preventing the formation and / or agglomeration of hydrates, and preferably in a process of extraction of oil and / or gas and / or condensates.
• an aqueous phase comprising a solution of NaCl at 1 ⁇ L -1 .
• the tests were carried out at a pressure of 135 bar (13.5 MPa) pressure value which is characteristic of the operating conditions where there is a risk of hydrate formation.
• the equilibrium temperature of this mixture at 135 bar (13.5 MPa) is about 19.5 ° C.
• the gas hydrates form when the temperature becomes lower than or equal to 19.5 ° C.
• the tests are carried out in a mechanically stirred cell and temperature controlled by a double jacket.
• the cell is cylindrical in shape with an internal volume of approximately 292.6 cm 3 (149 mm high and 50 mm in diameter). It is made of steel resistant to 200 bar (20 MPa) and protected by valve.
• the operating pressure is provided by a Haskel AG-30 gas booster. The cell is instrumented to be able to follow continuously the internal pressure, the stirring torque and the temperature.
• the assembly is then heated and maintained at 30 ° C for 24 hours to erase the thermal history of the mixture and then lowered at a rate of 0.2 ° C / min to the temperature corresponding to the sub-cooling target (here 9.5 ° C and 4.5 ° C for respective sub-cooling of 10 ° C and 15 ° C).
• the kinetic efficiency of the anti-hydrate compositions is measured at different sub-cooling (10 ° C and 15 ° C) but also at different dosages.
• the dosage corresponds here to the amount (weight) of anti-hydrate composition introduced into the aqueous phase relative to the weight of the water.
• the kinetic performance of the anti-hydrate compositions is determined by measuring the delay time in the formation of hydrate crystals. This time, also called induction time, is expressed in hours or days. In other words, the longer the induction time, the better the anti-hydrate.
• this time is measured from the moment when the temperature in the cell reaches the target temperature of the test corresponding to the sub-cooling studied (9.5 ° C. and 4.5 ° C. for sub-cooling). 10 and 15 ° C) and the pressure in the cell is stabilized.
• the end point for measuring the induction time corresponds to the beginning of hydrate formation. It is marked on the pressure curve as a function of time by the point where the pressure begins to fall in the cell (pressure drop corresponding to the gas consumption to form solid hydrates) and confirmed by an increase in the torque of the agitator (viscosification of the solid loading medium) and possibly a very slight exothermic peak on the temperature curve.
• composition A according to the invention and the comparative compositions B, C, D and E were prepared by mixing the various components whose amounts are expressed in Table 1 below.
• VCap polyvinylcaprolactam homopolymer sold by the company BASF
• the kinetic efficiency of the anti-hydrate compositions is evaluated for respective dosages of 1% and 3% by weight for each of the compositions A (invention), B, C, D and E (comparative).
• Each of the compositions to be tested is introduced into the aqueous phase and the experiment is conducted as described above.
• the kinetic performance of these compositions, characterized by the induction time, was measured twice, and the average of these measurements is expressed in Table 2 below.
• compositions of the present invention are more efficient than the comparative compositions. Indeed, in the composition according to the present invention or when the vinylcaprolactam / vinylpyrrolidone copolymer is mixed with a secondary diamine (composition A), it takes 105 hours to see the appearance of gas hydrates (for a dosage of 1% by weight) and 120 hours (for a dosage of 3% by weight).
• composition C comprising only the solvent and the same secondary diamine only delays by 10 hours the appearance of the hydrates, for a dosage of 1% by weight, and 15 hours for a dosage of 3% by weight.
• Composition B comprising only the solvent and the same copolymer only allows their formation to be delayed by 86 hours (for a dosage of 1% by weight) and 90 hours (for a dosage of 3% by weight).
• composition A is much more efficient than the known compositions of the prior art, for example the composition E according to US6180699, which does not delay the formation of hydrate. than 50 hours (for a dosage of 1% by weight) and 60 hours (for a dosage of 3% by weight).
• compositions A (invention) and B, C, D and E (comparative) are evaluated, according to the protocol described above, at the doses of 1% and 3% by weight of each of compositions A (invention), and B, C, D and E (comparative).
• composition D delays the formation of gas hydrates by only 8 hours, while the composition according to the invention (composition A) delays this formation by 26 hours.
• composition B the vinylcaprolactam / vinylpyrrolidone copolymer alone (composition B), as well as the secondary diamine alone (composition C), are poor kinetic anti-hydrates with strong sub-cooling, since they found that they do not delay. little or no hydrate formation in these temperature conditions.
• composition A With a dosage of 3% by weight of composition A, the formation of gas hydrates is delayed by 90 hours, for a sub-cooling of 15 ° C.
• composition according to the present invention results in a longer induction time for larger sub-coolings (15 ° C) than observed with the compositions of the prior art. It is thus possible to work at lower temperatures than current temperatures while increasing the production yield of oil and / or gas.
• the kinetic efficiency of the anti-hydrate compositions is measured at different sub-cooling (10 ° C. and 11 ° C.).
• the dosage corresponds here to the amount (weight) of the antihydrate composition introduced into the aqueous phase relative to the weight of the water.
• the induction time is measured from the moment when the temperature in the cell reaches the temperature of 9.5 ° C. for a sub-cooling of 10 ° C. and the pressure in the cell is stabilized. In the absence of training after a certain time, the test is continued by lowering the temperature in the cell to reach 8.5 ° C for a sub-cooling of 1 1 ° C. Once the pressure in the cell stabilized at 8.5 ° C, the induction time at 8.5 ° C is measured. The end point for measuring the induction time corresponds to the beginning of hydrate formation.
• composition F according to the invention was prepared by mixing the various components whose amounts are expressed in Table 4 below.
• the test composition is introduced into the aqueous phase and the experiment is conducted as described above.
• composition F the composition of the present invention is more efficient than the comparative composition B which is eliminated for the sub-cooling of 10 ° C.
• composition F was continued for a greater sub-cooling, now 1 1 ° C, according to the protocol described above, at a dose of 1% by weight.
• composition according to the present invention makes it possible to work at temperatures lower than the current temperatures and corresponding to sub-cooling values encountered during from production.
• the objective of the thermal stability injection test is to determine whether the anti-hydrate composition can be injected into the line transporting the water / gas / condensate fluids, when they are still hot, without causing deposition or clogging.
• the test consists of two parts.
• the anti-hydrate composition F is stored in a closed bottle in a climatic chamber for 24 hours at 90 ° C. without noting the slightest change in appearance.
• An aqueous solution of 30 g of sodium chloride (NaCl) per liter is prepared and heated to 90 ° C on a hot plate. In a few seconds, the composition F is injected with a syringe into the aqueous solution so as to have a concentration of 1% by weight. We do not note the appearance of any deposit or gel or suspension for 1 hour.
• the objective of the emulsion test is to determine whether the anti-hydrate composition can be injected into the line transporting the water / gas / condensate fluids, without causing problems in the downstream installations related to the presence of emulsion. stable.
• an aqueous solution of 30 g of NaCl per liter and of white spirit in equal proportion is poured. This operation is repeated in two other bottles.
• the mixtures are completed by the addition of 2% by weight of formulation A or F respectively for the second and third vials.
• the three flasks are shaken vigorously until a visually homogeneous emulsion is obtained.
• the vials are observed after 19 seconds, 43 seconds and 1 minute and 2 seconds.
• the emulsion has almost completely disappeared as early as 19 seconds.
• the vial containing composition A and the vial containing composition F the emulsion is still stable at 43 seconds.
• no emulsion is stable, there is a separation of the two phases.
• the purpose of the dehydration test is to determine whether the antihydrate composition can be separated from the water which contains it, by evaporation of the water. Indeed, it may be useful to separate the anti-hydrate additive, once the fluids are out of the thermally favorable zone hydrates, before rejecting the water produced during the exploitation of the field, so as to limit the environmental impact or on the rock receiving the produced water.
• [0106] was prepared 200 ml of a 0.5% aqueous solution by weight of formulation F and 1 gL "1 NaCl.
• the solution is placed in a container in narrow and wide glass, so as to have a large area contact between the solution and the glass
• the open container is placed in an oven at 130 ° C until there is only 2 mL of liquid left, no deposit on the walls excepted a few spots containing crystals of NaCl and resulting from the evaporation of a few drops of water sprayed on the walls during filling.Also the aqueous solution remains clear.Thus the antihydrate composition F can be separated from the water without risking deposit in the facilities.

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