EP1676896A1 - Process for transporting hydrates suspended in plant effluents using a non-polluting additiv - Google Patents

Process for transporting hydrates suspended in plant effluents using a non-polluting additiv Download PDF

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Publication number
EP1676896A1
EP1676896A1 EP20050292604 EP05292604A EP1676896A1 EP 1676896 A1 EP1676896 A1 EP 1676896A1 EP 20050292604 EP20050292604 EP 20050292604 EP 05292604 A EP05292604 A EP 05292604A EP 1676896 A1 EP1676896 A1 EP 1676896A1
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EP
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Prior art keywords
fluid
component
weight
gas
carbon atoms
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EP20050292604
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German (de)
French (fr)
Inventor
Anne Sequin
Christine Dalmazzone
Annie Audibert-Hayet
Vincent Pauchard
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IFP Energies Nouvelles IFPEN
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IFP Energies Nouvelles IFPEN
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Classifications

    • 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
    • C10L3/108—Production of gas hydrates
    • 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
    • C10L3/003—Additives for gaseous fuels
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17D—PIPE-LINE SYSTEMS; PIPE-LINES
    • F17D1/00—Pipe-line systems
    • F17D1/08—Pipe-line systems for liquids or viscous products
    • F17D1/16—Facilitating the conveyance of liquids or effecting the conveyance of viscous products by modification of their viscosity
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S585/00—Chemistry of hydrocarbon compounds
    • Y10S585/949—Miscellaneous considerations
    • Y10S585/95—Prevention or removal of corrosion or solid deposits
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T137/00—Fluid handling
    • Y10T137/0318—Processes
    • Y10T137/0391—Affecting flow by the addition of material or energy

Definitions

  • the invention relates to a method for transporting hydrates of natural gas, petroleum gas or other gases in suspension in a fluid comprising water, one of said gases and a liquid hydrocarbon.
  • composition comprising at least one ester, associated with a nonionic co-surfactant agent of the carboxylic acid polymerized type (dimer and / or trimer).
  • the gases that form hydrates may in particular comprise at least one hydrocarbon selected from methane, ethane, ethylene, propane, propene, n-butane and isobutane, and optionally H 2 S and / or CO 2 .
  • hydrates are formed when the water is in the presence of gas, either in the free state, or in the dissolved state in a liquid phase, such as a liquid hydrocarbon, and when the temperature reached by the mixture, in particular water, gas and possibly liquid hydrocarbons, such as oil, becomes lower than the thermodynamic temperature of hydrate stability, this temperature being given for a known gas composition and when their pressure is set.
  • gas either in the free state, or in the dissolved state in a liquid phase, such as a liquid hydrocarbon
  • hydrates can be feared, especially in the oil and gas industry, for which the conditions of hydrate formation can be met.
  • a way envisaged, particularly in production at sea is to reduce or even remove, the treatments applied to the crude or the gas to be transported from the deposit to the coast and in particular to leave all or part of the water in the fluid to be transported.
  • These treatments at sea are generally carried out on a platform located on the surface near the reservoir, so that the effluent, initially hot, can be treated before the thermodynamic conditions of hydrate stability are reached because of cooling of the effluent with seawater.
  • hydrate corks can lead to a cessation of production and thus cause significant financial losses.
  • the return to service of the facility, especially if it is production or transportation at sea can be long, because the decomposition of hydrates formed is very difficult to achieve. Indeed, when the production of an underwater field of natural gas or oil and gas containing water reaches the surface of the seabed and is then transported to the bottom of the sea, it happens, by lowering the temperature of the effluent produced, the thermodynamic conditions are met for hydrates to form, agglomerate and block the transfer lines.
  • the temperature at the bottom of the sea can be, for example, 3 or 4 ° C.
  • Insulation of the transport pipes has also been recommended, so as to prevent the temperature of the transported fluid from reaching the hydrate formation temperature under the operating conditions. Such a technique is also very expensive.
  • nonionic or anionic surfactant compounds have been tested for their effect of retarding the formation of hydrates in a fluid containing a gas, in particular a hydrocarbon, and water.
  • a gas in particular a hydrocarbon, and water.
  • Kuliev et al Surfactants Studied as Hydrate Formation Inhibitors. Gazovoe Delo No. 10 1972, 17-19, reported in Chemical Abstracts 80, 1974, 98122r.
  • Amphiphilic compounds obtained by reaction of at least one succinic derivative chosen from the group formed by polyalkenyl succinic acids and anhydrides on at least one polyethylene glycol monoether have also been proposed to reduce the tendency of gas hydrates to agglomerate. natural gas, petroleum gas or other gases (EP-A-582507).
  • the invention provides a method for transporting hydrates in suspension within a fluid comprising at least water, a gas and a liquid hydrocarbon under conditions where hydrates can be formed from water and water.
  • gas characterized in that said fluid incorporates an additive comprising at least one composition comprising at least one ester, associated with a nonionic co-surfactant of the carboxylic acid polymerized type (dimer and / or trimer).
  • the mixture used in the invention combines at least one component A consisting of at least one ester formed between at least one monocarboxylic acid, linear or branched, and at least one alcohol (monoalcohol or polyol), linear or branched, and at least one component B consisting of at least one polymerized fatty acid.
  • the ester can be obtained by esterification, transesterification or interesterification.
  • Component A consists more particularly of at least one ester formed between at least one monocarboxylic acid, linear or branched, containing from 8 to 24 carbon atoms, more especially from 14 to 18 carbon atoms, and at least one alcohol, linear or branched containing from 2 to 200 carbon atoms and more especially from 6 to 30 carbon atoms.
  • the polyols may be esterified in whole or in part according to the fatty acid / alcohol stoichiometry used during the esterification reaction, the nature of the fatty acids being that described above.
  • hydrophilic / lipophilic balance (HLB) of the ester is generally between 2 and 12, and preferably between 3 and 8.
  • the preferred ester according to the invention is an ester or a mixture of sorbitol esters, of sorbitan or of its derivatives and more particularly the mixture designated by sorbitan monooleate.
  • Component B present in the mixture used in the invention is derived from a dimerization reaction of unsaturated monocarboxylic fatty acids containing, for example, from 8 to 18 carbon atoms.
  • the reaction product provides a mixture of compounds containing from 16 to 80 carbon atoms and consisting of a mixture of higher monomers, dimers, trimers and oligomers, and more particularly dimers (from 16 to 36 carbon atoms).
  • Dimers can be represented by the formula: the sum q + r can take a value of 4 to 14.
  • trimers can be represented by the formula: the sum q + r can take a value of 4 to 14.
  • Component B preferably is a mixture of monounsaturated fatty acid dimers of 16 carbon atoms (palmitic acid) and monounsaturated fatty acid of 18 carbon atoms (oleic acid).
  • the mixture used in the fluid of the invention will comprise from 10 to 95% by weight, preferably from 30 to 90% by weight and even more preferably from 50 to 80%, by weight of constituent A.
  • co-surfactant (component B) then represents from 5 to 90% by weight, of preferably from 10 to 70% by weight and even more preferably from 20 to 50% by weight of the mixture
  • the solvent content in the final mixture will be between 20 and 80% by weight and preferably between 30 and 70% by weight.
  • these compositions are added to the fluid to be treated at concentrations generally ranging from 0.1 to 5% by weight, preferably from 0.2 to 3% by weight. in mass, with respect to the liquid hydrocarbon.
  • the apparatus has a loop of 10 meters consisting of tubes of internal diameter equal to 7.7 mm; a 2-liter reactor comprising an inlet and an outlet for the gas, a suction and a discharge for the mixture: condensate, water and additive initially introduced.
  • the reactor makes it possible to put the loop under pressure.
  • Tubes of diameter similar to those of the loop ensure the flow of fluids from the loop to the reactor, and vice versa, via a gear pump placed between the two.
  • a sapphire cell integrated in the circuit allows a visualization of the circulating liquid, and therefore hydrates, if they have formed.
  • the fluids water, oil, additive
  • the installation is then brought to a pressure of 7 MPa.
  • Homogenization of the liquids is ensured by their circulation in the loop and the reactor, then only in the loop.
  • pressure drop and flow rate it imposes a rapid decrease in temperature from 17 to 4 ° C (temperature below the formation temperature of the hydrates), it is then maintained at this value.
  • the duration of the tests can vary from a few minutes to several hours: a powerful additive makes it possible to maintain the circulation of the suspension of hydrates with a loss of load and a stable flow.
  • the gas used comprises in volume 98% of methane and 2% of ethane.
  • the experiment is conducted under a pressure of 7 MPa, kept constant by gas supply, with a liquid flow rate of 110 kg / hour. Under these conditions, the formation of a plug in the coil is observed a few minutes after the start of hydrate formation (at a temperature of about 10.8 ° C.): the hydrates form a block and the circulation of the fluid becomes impossible.
  • the procedure is as in Comparative Example 1, with the same fluid, the same gas, at the same pressure and with the same flow rate, but the circulating fluid is added 1% by weight relative to the volume of condensate.
  • a mixture according to the invention containing 70% by weight of sorbitan monooleate and 30% by weight of C16-C18 fatty acid dimer.
  • an increase in the loss of charge during the formation of hydrates is observed, followed by its decrease and its stabilization during more than 24 hours at a temperature of 4 ° C.
  • a descent into temperature at 0 ° C does not affect the circulation of the suspension, the remaining hydrates dispersed in the fluids.
  • the classification "WGK” is given according to the "Administrative Regulation on the Classification of Substances Hazardous to Waters into Water Hazard Classes” (Verwaltungsvorschrift wassergefährdende Stoffe - VwVwS) of 17 May 1999.
  • the "WGK” classification of a mixture can be determined , according to Annex 4 of the new "VwVwS” regulations, by a calculation rule from the "WGK” classification of each component of the mixture or on the basis of eco-toxicological test results determined on the mixture.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Water Supply & Treatment (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Method for transporting hydrates in suspension within a fluid comprising water, a gas and a liquid hydrocarbon (where hydrates can be formed starting from water and gas), comprises incorporating the fluid mixture containing component A of formed esters enters to a 8-24C monocarboxylic acid and 2-200C alcohol, and component B of non-ionic surface-active agents such as monocarboxylic polymerized unsaturated fatty acids.

Description

L'invention concerne un procédé pour transporter des hydrates de gaz naturel, de gaz de pétrole ou d'autres gaz en suspension au sein d'un fluide comprenant de l'eau, un desdits gaz et un hydrocarbure liquide.The invention relates to a method for transporting hydrates of natural gas, petroleum gas or other gases in suspension in a fluid comprising water, one of said gases and a liquid hydrocarbon.

Elle concerne plus particulièrement un procédé dans lequel on met en jeu une composition comprenant au moins un ester, associé à un agent co-tensioactif non-ionique du type acide carboxylique polymérisé (dimère et/ou trimère).It relates more particularly to a process in which there is involved a composition comprising at least one ester, associated with a nonionic co-surfactant agent of the carboxylic acid polymerized type (dimer and / or trimer).

Les gaz qui forment des hydrates peuvent notamment comprendre au moins un hydrocarbure choisi parmi le méthane, l'éthane, l'éthylène, le propane, le propène, le n-butane et l'isobutane, et éventuellement de l'H2S et/ou du CO2.The gases that form hydrates may in particular comprise at least one hydrocarbon selected from methane, ethane, ethylene, propane, propene, n-butane and isobutane, and optionally H 2 S and / or CO 2 .

Ces hydrates se forment lorsque l'eau se trouve en présence de gaz, soit à l'état libre, soit à l'état dissout dans une phase liquide, telle qu'un hydrocarbure liquide, et lorsque la température atteinte par le mélange notamment d'eau, de gaz et éventuellement d'hydrocarbures liquides, tels que de l'huile, devient inférieure à la température thermodynamique de stabilité des hydrates, cette température étant donnée pour une composition des gaz connue et lorsque leur pression est fixée.These hydrates are formed when the water is in the presence of gas, either in the free state, or in the dissolved state in a liquid phase, such as a liquid hydrocarbon, and when the temperature reached by the mixture, in particular water, gas and possibly liquid hydrocarbons, such as oil, becomes lower than the thermodynamic temperature of hydrate stability, this temperature being given for a known gas composition and when their pressure is set.

La formation d'hydrates peut être redoutée, notamment dans l'industrie pétrolière et gazière, pour lesquelles les conditions de formation d'hydrates peuvent être réunies. En effet, pour diminuer le coût de production du pétrole brut et du gaz, tant au point de vue des investissements qu'au point de vue de l'exploitation, une voie envisagée, notamment en production en mer, est de réduire, voire de supprimer, les traitements appliqués au brut ou au gaz à transporter du gisement à la côte et notamment de laisser toute ou partie de l'eau dans le fluide à transporter. Ces traitements en mer s'effectuent en général sur une plate-forme située en surface à proximité du gisement, de manière que l'effluent, initialement chaud, puisse être traité avant que les conditions thermodynamiques de stabilité des hydrates ne soient atteintes du fait du refroidissement de l'effluent avec l'eau de mer.The formation of hydrates can be feared, especially in the oil and gas industry, for which the conditions of hydrate formation can be met. In fact, in order to reduce the cost of production of crude oil and gas, both from the point of view of investment and from the point of view of exploitation, a way envisaged, particularly in production at sea, is to reduce or even remove, the treatments applied to the crude or the gas to be transported from the deposit to the coast and in particular to leave all or part of the water in the fluid to be transported. These treatments at sea are generally carried out on a platform located on the surface near the reservoir, so that the effluent, initially hot, can be treated before the thermodynamic conditions of hydrate stability are reached because of cooling of the effluent with seawater.

Cependant, comme cela arrive pratiquement lorsque les conditions thermodynamiques requises pour former des hydrates sont réunies, l'agglomération des hydrates entraîne le blocage des conduites de transport par création de bouchons qui empêchent tout passage de pétrole brut ou de gaz.However, as this happens almost when the thermodynamic conditions required to form hydrates are met, the agglomeration of hydrates causes the blockage of the transport pipes by creating plugs that prevent any passage of crude oil or gas.

La formation de bouchons d'hydrates peut entraîner un arrêt de la production et provoquer ainsi des pertes financières importantes. De plus, la remise en service de l'installation, surtout s'il s'agit de production ou de transport en mer, peut être longue, car la décomposition des hydrates formés est très difficile à réaliser. En effet, lorsque la production d'un gisement sous-marin de gaz naturel ou de pétrole et de gaz comportant de l'eau atteint la surface du sol marin et est ensuite transportée au fond de la mer, il arrive, par l'abaissement de la température de l'effluent produit, que les conditions thermodynamiques soient réunies pour que des hydrates se forment, s'agglomèrent et bloquent les conduites de transfert. La température au fond de la mer peut être, par exemple, de 3 ou 4 °C.The formation of hydrate corks can lead to a cessation of production and thus cause significant financial losses. In addition, the return to service of the facility, especially if it is production or transportation at sea, can be long, because the decomposition of hydrates formed is very difficult to achieve. Indeed, when the production of an underwater field of natural gas or oil and gas containing water reaches the surface of the seabed and is then transported to the bottom of the sea, it happens, by lowering the temperature of the effluent produced, the thermodynamic conditions are met for hydrates to form, agglomerate and block the transfer lines. The temperature at the bottom of the sea can be, for example, 3 or 4 ° C.

Des conditions favorables à la formation d'hydrates peuvent aussi être réunies de la même façon à terre, pour des conduites pas (ou pas assez profondément) enfouies dans le sol terrestre, lorsque par exemple la température de l'air ambiant est froide.Favorable conditions for the formation of hydrates can also be met in the same way on land, for pipes not (or not deep enough) buried in the earth's soil, when for example the temperature of the ambient air is cold.

Pour éviter ces inconvénients, on a cherché, dans l'art antérieur, à utiliser des produits qui, ajoutés au fluide, pourraient agir comme inhibiteurs en abaissant la température thermodynamique de stabilité des hydrates. Ce sont notamment des alcools, tels que le méthanol, ou des glycols, tels que le mono-, le di- ou le triéthylène glycol. Cette solution est très onéreuse car la quantité d'inhibiteurs à ajouter peut atteindre 10 à 40 % de la teneur en eau ; de plus, ces alcools induisent une pollution des effluents car ces inhibiteurs sont difficiles à récupérer.To avoid these drawbacks, it has been sought, in the prior art, to use products which, added to the fluid, could act as inhibitors by lowering the thermodynamic temperature of hydrate stability. These include alcohols, such as methanol, or glycols, such as mono-, di- or triethylene glycol. This solution is very expensive because the amount of inhibitors to be added can reach 10 to 40% of the water content; in addition, these alcohols induce effluent pollution because these inhibitors are difficult to recover.

On a également préconisé l'isolation des conduites de transport, de manière à éviter que la température du fluide transporté n'atteigne la température de formation des hydrates dans les conditions opératoires. Une telle technique est, elle aussi, très coûteuse.Insulation of the transport pipes has also been recommended, so as to prevent the temperature of the transported fluid from reaching the hydrate formation temperature under the operating conditions. Such a technique is also very expensive.

Par ailleurs, divers composés tensioactifs non-ioniques ou anioniques ont été testés pour leur effet de retardement de la formation d'hydrates au sein d'un fluide renfermant un gaz, notamment un hydrocarbure, et de l'eau. On peut citer par exemple l'article de Kuliev et al : « Surfactants Studied as Hydrate Formation Inhibitors . » Gazovoe Delo n° 10 1972, 17-19, rapporté dans Chemical Abstracts 80, 1974, 98122r.In addition, various nonionic or anionic surfactant compounds have been tested for their effect of retarding the formation of hydrates in a fluid containing a gas, in particular a hydrocarbon, and water. For example, the article by Kuliev et al: Surfactants Studied as Hydrate Formation Inhibitors. Gazovoe Delo No. 10 1972, 17-19, reported in Chemical Abstracts 80, 1974, 98122r.

On a encore décrit l'utilisation d'additifs capables de modifier le mécanisme de formation des hydrates, puisque, au lieu de s'agglomérer rapidement les uns aux autres et de former des bouchons, les hydrates formés se dispersent dans le fluide sans s'agglomérer et sans obstruer les conduites. On peut citer à cet égard la demande de brevet EP-A-323 774 au nom de la demanderesse, qui décrit l'utilisation de composés amphiphiles non-ioniques choisis parmi les esters de polyols et d'acides carboxyliques, substitués ou non-substitués, et les composés à fonction imide ; la demande de brevet EP-A-323 775, également au nom de la demanderesse, qui décrit notamment l'utilisation de composés appartenant à la famille des diéthanolamides d'acides gras ou de dérivés d'acides gras ; le brevet US-A-4 856 593 qui décrit l'utilisation de composés tensioactifs tels que des phosphonates organiques, des esters phosphates, des acides phosphoniques, leurs sels et leurs esters, des polyphosphates inorganiques et leurs esters ainsi que des polyacrylamides et des polyacrylates ; et la demande de brevet EP-A-457 375, qui décrit l'utilisation de composés tensioactifs anioniques, tels que les acides alkylarylsulfoniques et leurs sels de métaux alcalins.The use of additives capable of modifying the mechanism of formation of hydrates has also been described since, instead of rapidly agglomerating with one another and forming plugs, the hydrates formed are dispersed in the fluid without being formed. agglomerate and without obstructing the pipes. In this regard, mention may be made of the patent application EP-A-323 774 in the name of the applicant, which describes the use of nonionic amphiphilic compounds chosen from esters of polyols and of carboxylic acids, substituted or unsubstituted and imide functional compounds; the patent application EP-A-323,775, also in the name of the applicant, which describes in particular the use of compounds belonging to the family of diethanolamides of fatty acids or of fatty acid derivatives; US-A-4,856,593 which discloses the use of surface active compounds such as organic phosphonates, phosphate esters, phosphonic acids, their salts and esters, inorganic polyphosphates and their esters as well as polyacrylamides and polyacrylates ; and EP-A-457,375, which describes the use of anionic surfactant compounds, such as alkylarylsulfonic acids and their alkali metal salts.

Des composés amphiphiles obtenus par réaction d'au moins un dérivé succinique choisi dans le groupe formé par les acides et les anhydrides polyalkényl succiniques sur au moins un monoéther de polyéthylène glycol ont également été proposés pour réduire la tendance à l'agglomération des hydrates de gaz naturel, de gaz de pétrole ou d'autres gaz (demande de brevet EP-A-582507).Amphiphilic compounds obtained by reaction of at least one succinic derivative chosen from the group formed by polyalkenyl succinic acids and anhydrides on at least one polyethylene glycol monoether have also been proposed to reduce the tendency of gas hydrates to agglomerate. natural gas, petroleum gas or other gases (EP-A-582507).

On a maintenant découvert que, pour transporter des hydrates en suspension au sein d'un fluide comprenant de l'eau, du gaz et un hydrocarbure liquide, il était particulièrement avantageux d'utiliser comme additif un ou plusieurs compositions comprenant au moins un ester, associé à un agent co-tensioactif non-ionique du type acide carboxylique polymérisé (dimère et/ou trimère).It has now been discovered that in order to transport hydrates in suspension in a fluid comprising water, gas and a liquid hydrocarbon, it was particularly advantageous to use as additive one or more compositions comprising at least one ester, combined with a nonionic co-surfactant agent of the polymerized carboxylic acid type (dimer and / or trimer).

Ainsi, l'invention propose un procédé pour transporter des hydrates en suspension au sein d'un fluide comprenant au moins de l'eau, un gaz et un hydrocarbure liquide dans des conditions où des hydrates peuvent se former à partir d'eau et de gaz, caractérisé en ce qu'on incorpore audit fluide un additif comprenant au moins une composition comprenant au moins un ester, associé à un agent co-tensioactif non-ionique du type acide carboxylique polymérisé (dimère et/ou trimère).Thus, the invention provides a method for transporting hydrates in suspension within a fluid comprising at least water, a gas and a liquid hydrocarbon under conditions where hydrates can be formed from water and water. gas, characterized in that said fluid incorporates an additive comprising at least one composition comprising at least one ester, associated with a nonionic co-surfactant of the carboxylic acid polymerized type (dimer and / or trimer).

Le mélange utilisé dans l'invention associe au moins un constituant A consistant en au moins un ester formé entre au moins un acide monocarboxylique, linéaire ou ramifié, et au moins un alcool (monoalcool ou polyol), linéaire ou ramifié, et au moins un constituant B consistant en au moins un acide gras polymérisé.The mixture used in the invention combines at least one component A consisting of at least one ester formed between at least one monocarboxylic acid, linear or branched, and at least one alcohol (monoalcohol or polyol), linear or branched, and at least one component B consisting of at least one polymerized fatty acid.

L'ester peut être obtenu par estérification, transestérification ou interestérification.The ester can be obtained by esterification, transesterification or interesterification.

Le constituant A consiste plus particulièrement en au moins un ester formé entre au moins un acide monocarboxylique, linéaire ou ramifié, contenant de 8 à 24 atomes de carbone, plus spécialement de 14 à 18 atomes de carbone, et au moins un alcool, linéaire ou ramifié contenant de 2 à 200 atomes de carbone et plus spécialement de 6 à 30 atomes de carbone.Component A consists more particularly of at least one ester formed between at least one monocarboxylic acid, linear or branched, containing from 8 to 24 carbon atoms, more especially from 14 to 18 carbon atoms, and at least one alcohol, linear or branched containing from 2 to 200 carbon atoms and more especially from 6 to 30 carbon atoms.

L'acide peut être par exemple un acide monocarboxylique linéaire ou ramifié, saturé ou insaturé, ou hydroxylé, répondant par exemple à l'une des formules suivantes dans lesquelles n = 7 :

        CH3-(CH2)n-COOH     (acide octanoïque)

        CH3-CH(CH3)-(CH2)n-COOH     (acide undécénoïque)

        CH3-CH2-CH(CH3)-(CH2)n-COOH     (acide laurique)

        CH3-(CH2)n-CH=CH-(CH2)n-COOH     (acide oléique)

        CH3-(CH2)n-2-CH(OH)-CH2-CH=CH-(CH2)n-COOH     (acide ricinoléique)

        CH3-(CH2)n-1-(CH=CH-CH2-CH=CH)-(CH2)n-COOH     (acides arachidique et gadoléique)

        CH3-(CH2)n-(CH=CH-CH=CH-CH=CH)-(CH2)n-COOH     (acide érucique)

The acid may be, for example, a linear or branched, saturated or unsaturated or hydroxylated monocarboxylic acid, corresponding, for example, to one of the following formulas in which n = 7:

CH 3 - (CH 2 ) n -COOH (octanoic acid)

CH 3 -CH (CH 3 ) - (CH 2 ) n -COOH (undecenoic acid)

CH 3 -CH 2 -CH (CH 3 ) - (CH 2 ) n -COOH (lauric acid)

CH 3 - (CH 2 ) n -CH = CH- (CH 2 ) n -COOH (oleic acid)

CH 3 - (CH 2 ) n-2 -CH (OH) -CH 2 -CH = CH- (CH 2 ) n -COOH (ricinoleic acid)

CH 3 - (CH 2 ) n-1 - (CH = CH-CH 2 -CH = CH) - (CH 2 ) n -COOH (arachidic and gadoleic acids)

CH 3 - (CH 2 ) n - (CH = CH-CH = CH-CH = CH) - (CH 2 ) n -COOH (erucic acid)

L'alcool peut être :

  • ● un monoalcool :
    • primaire : R-CH2-OH
    • secondaire : (R-)2 CH-OH
    • tertiaire (R-)3 C-OH
      avec R = CxHy, x = 1 à 21 et y = 2x+1
  • ● un alcool polyhydroxylé, en particulier :
    • ■ un diol, tel que par exemple :
      • l'éthylèneglycol et ses polymères :

                HO-(CH2-CH2)-OH

        HOCH2-CH2-O(CH2-CH2-O)m-CH2-CH2OH avec m = 1 à 100
      • le propylène glycol : CH3-CHOH-CH2-OH
      • le néopentylglycol : HOCH2-C(CH3)(CH3)-CH2OH
    • ■ un triol, tel que par exemple :
      • le glycérol : CH2OH-CHOH-CH2OH
      • le triméthylolpropane : CH2OH-C(CH2OH)(CH2OH)-CH2CH3
    • ■ un tétraalcool, tel que par exemple :
      • le pentaérhytritol : (CH2OH)4C
    • ■ un hexol, tel que par exemple :
      • le sorbitol : CH2OH-CHOH-CHOH-CHOH-CHOH-CH2OH et son anhydride cyclique, le sorbitan, ou encore un dérivé de sorbitan.
    • ■ un polyglycérol :

              CH2OH-CHOH-CH2-(O-CH2-CHOH-CH2)p-O-CH2-CHOH-CH2OH

      avec p = 1 à 8.
Alcohol can be:
  • ● a monoalcohol:
    • primary: R-CH 2 -OH
    • secondary: (R-) 2 CH-OH
    • tertiary (R-) 3 C-OH
      with R = C x H y , x = 1 to 21 and y = 2x + 1
  • ● a polyhydroxy alcohol, in particular:
    • ■ a diol, such as for example:
      • ethylene glycol and its polymers:

        HO- (CH 2 -CH 2 ) -OH

        HOCH 2 -CH 2 -O (CH 2 -CH 2 -O) m -CH 2 -CH 2 OH with m = 1 to 100
      • propylene glycol: CH 3 -CHOH-CH 2 -OH
      • neopentyl glycol: HOCH 2 -C (CH 3 ) (CH 3 ) -CH 2 OH
    • ■ a triol, such as for example:
      • glycerol: CH 2 OH-CHOH-CH 2 OH
      • trimethylolpropane: CH 2 OH-C (CH 2 OH) (CH 2 OH) -CH 2 CH 3
    • A tetrahydric alcohol, such as for example:
      • pentaerythritol: (CH 2 OH) 4 C
    • ■ a hexol, such as for example:
      • sorbitol: CH 2 OH-CHOH-CHOH-CHOH-CHOH-CH 2 OH and its cyclic anhydride, sorbitan, or a sorbitan derivative.
    • ■ a polyglycerol:

      CH 2 OH-CHOH-CH 2 - (O-CH 2 -CHOH-CH 2 ) p -O-CH 2 -CHOH-CH 2 OH

      with p = 1 to 8.

Les polyols peuvent être estérifiés de manière totale ou partielle selon la stoechiométrie acide gras/alcool utilisée lors de la réaction d'estérification, la nature des acides gras étant celle décrite ci dessus.The polyols may be esterified in whole or in part according to the fatty acid / alcohol stoichiometry used during the esterification reaction, the nature of the fatty acids being that described above.

Plus spécialement, l'Équilibre Hydrophile / Lipophile (HLB) de l'ester est en général compris entre 2 et 12, et de préférence entre 3 et 8.More specifically, the hydrophilic / lipophilic balance (HLB) of the ester is generally between 2 and 12, and preferably between 3 and 8.

L'ester préféré selon l'invention est un ester ou un mélange d'esters de sorbitol, de sorbitan ou de ses dérivés et plus particulièrement le mélange désigné par monooléate de sorbitan.The preferred ester according to the invention is an ester or a mixture of sorbitol esters, of sorbitan or of its derivatives and more particularly the mixture designated by sorbitan monooleate.

Le constituant B présent dans le mélange utilisé dans l'invention est issu d'une réaction de dimérisation d'acides gras monocarboxyliques insaturés renfermant par exemple de 8 à 18 atomes de carbone. Le produit de réaction fournit un mélange de composés contenant de 16 à 80 atomes de carbone et constitué d'un mélange de monomères, dimères, trimères et oligomères supérieurs, et plus particulièrement de dimères (de 16 à 36 atomes de carbone).Component B present in the mixture used in the invention is derived from a dimerization reaction of unsaturated monocarboxylic fatty acids containing, for example, from 8 to 18 carbon atoms. The reaction product provides a mixture of compounds containing from 16 to 80 carbon atoms and consisting of a mixture of higher monomers, dimers, trimers and oligomers, and more particularly dimers (from 16 to 36 carbon atoms).

Les dimères peuvent être représentés par la formule :

Figure imgb0001
la somme q + r pouvant prendre une valeur de 4 à 14.Dimers can be represented by the formula:
Figure imgb0001
 the sum q + r can take a value of 4 to 14.

Les trimères peuvent être représentés par la formule :

Figure imgb0002
la somme q + r pouvant prendre une valeur de 4 à 14.The trimers can be represented by the formula:
Figure imgb0002
 the sum q + r can take a value of 4 to 14.

Le constituant B considéré de préférence est un mélange de dimères d'acide gras mono-insaturé de16 atomes de carbone (acide palmitique) et d'acide gras mono-insaturé de 18 atomes de carbone (acide oléique).Component B preferably is a mixture of monounsaturated fatty acid dimers of 16 carbon atoms (palmitic acid) and monounsaturated fatty acid of 18 carbon atoms (oleic acid).

De préférence, le mélange utilisé dans le fluide de l'invention comprendra de 10 à 95 % en poids, de préférence de 30 à 90 % en poids et de manière encore plus préférée de 50 à 80 %, en poids de constituant A. Le co-tensioactif (constituant B) représente alors de 5 à 90 % en poids, de préférence de 10 à 70 % en poids et de manière encore plus préférée de 20 à 50 %, en poids du mélangePreferably, the mixture used in the fluid of the invention will comprise from 10 to 95% by weight, preferably from 30 to 90% by weight and even more preferably from 50 to 80%, by weight of constituent A. co-surfactant (component B) then represents from 5 to 90% by weight, of preferably from 10 to 70% by weight and even more preferably from 20 to 50% by weight of the mixture

La teneur en solvant dans le mélange final sera comprise entre 20 et 80 % en masse et de préférence entre 30 et 70 % en masse.The solvent content in the final mixture will be between 20 and 80% by weight and preferably between 30 and 70% by weight.

Dans leur utilisation comme additifs pour réduire la tendance à l'agglomération des hydrates, ces compositions sont ajoutées dans le fluide à traiter à des concentrations allant en général de 0,1 à 5 % en masse, de préférence de 0,2 à 3 % en masse, par rapport à l'hydrocarbure liquide.In their use as additives for reducing the tendency of hydrates to agglomerate, these compositions are added to the fluid to be treated at concentrations generally ranging from 0.1 to 5% by weight, preferably from 0.2 to 3% by weight. in mass, with respect to the liquid hydrocarbon.

Pour tester l'efficacité des produits utilisés dans le procédé de l'invention, on a simulé le transport de fluides formant des hydrates, tels que des effluents pétroliers et on a procédé à des essais de formation d'hydrates à partir de gaz, de condensat et d'eau, à l'aide de l'appareillage décrit ci-après.To test the efficiency of the products used in the process of the invention, the transport of hydrate-forming fluids, such as petroleum effluents, was simulated and hydrate formation tests were carried out using gas, condensate and water, using the apparatus described below.

L'appareillage comporte une boucle de 10 mètres constituée de tubes de diamètre intérieur égal à 7,7 mm ; un réacteur de 2 litres comprenant une entrée et une sortie pour le gaz, une aspiration et un refoulement pour le mélange : condensat, eau et additif initialement introduit. Le réacteur permet de mettre la boucle sous pression.The apparatus has a loop of 10 meters consisting of tubes of internal diameter equal to 7.7 mm; a 2-liter reactor comprising an inlet and an outlet for the gas, a suction and a discharge for the mixture: condensate, water and additive initially introduced. The reactor makes it possible to put the loop under pressure.

Des tubes de diamètre analogue à ceux de la boucle assurent la circulation des fluides de la boucle au réacteur, et inversement, par l'intermédiaire d'une pompe à engrenages placée entre les deux. Une cellule saphir intégrée dans le circuit permet une visualisation du liquide en circulation, et donc des hydrates, s'ils se sont formés.Tubes of diameter similar to those of the loop ensure the flow of fluids from the loop to the reactor, and vice versa, via a gear pump placed between the two. A sapphire cell integrated in the circuit allows a visualization of the circulating liquid, and therefore hydrates, if they have formed.

Pour déterminer l'efficacité des additifs selon l'invention, on introduit les fluides (eau, huile, additif) dans le réacteur ; l'installation est ensuite portée sous une pression de 7 MPa. L'homogénéisation des liquides est assurée par leur circulation dans la boucle et le réacteur, puis uniquement dans la boucle. En suivant les variations de perte de charge et de débit, on impose une rapide diminution de la température, de 17 à 4 °C (température inférieure à la température de formation des hydrates), celle-ci est ensuite maintenue à cette valeur.To determine the effectiveness of the additives according to the invention, the fluids (water, oil, additive) are introduced into the reactor; the installation is then brought to a pressure of 7 MPa. Homogenization of the liquids is ensured by their circulation in the loop and the reactor, then only in the loop. By following the variations in pressure drop and flow rate, it imposes a rapid decrease in temperature from 17 to 4 ° C (temperature below the formation temperature of the hydrates), it is then maintained at this value.

La durée des tests peut varier de quelques minutes à plusieurs heures : un additif performant permet de maintenir la circulation de la suspension d'hydrates avec une perte de charge et un débit stable.The duration of the tests can vary from a few minutes to several hours: a powerful additive makes it possible to maintain the circulation of the suspension of hydrates with a loss of load and a stable flow.

Les exemples suivants illustrent l'invention mais ne doivent en aucune manière être considérés comme limitatifs.The following examples illustrate the invention but should in no way be considered as limiting.

EXEMPLE 1 (comparatif)EXAMPLE 1 (comparative)

Dans cet exemple, on opère avec un fluide composé en volume de 10 % d'eau et de 90 % de condensat.In this example, one operates with a fluid composed in volume of 10% water and 90% condensate.

La composition pondérale du condensat est :

  • ● pour les molécules ayant moins de 11 atomes de carbone :
    • 20 % de paraffines et d'isoparaffines, 48 % de naphtènes, 10 % d'aromatiques ; et
  • ● pour les molécules ayant au moins 11 atomes de carbone :
    • 22 % d'un mélange de paraffines, d'isoparaffines, de naphtènes et d'aromatiques.
The weight composition of the condensate is:
  • ● for molecules with less than 11 carbon atoms:
    • 20% paraffins and isoparaffins, 48% naphthenes, 10% aromatics; and
  • ● for molecules with at least 11 carbon atoms:
    • 22% of a mixture of paraffins, isoparaffins, naphthenes and aromatics.

Le gaz utilisé comprend en volume 98 % de méthane et 2 % d'éthane. L'expérimentation est conduite sous une pression de 7 MPa, maintenue constante par apport de gaz, avec un débit liquide de 110 kg/heure. Dans ces conditions, on observe la formation d'un bouchon dans le serpentin, quelques minutes après le début de la formation des hydrates (à une température d'environ 10,8 °C) : les hydrates forment un bloc et la circulation du fluide devient impossible.The gas used comprises in volume 98% of methane and 2% of ethane. The experiment is conducted under a pressure of 7 MPa, kept constant by gas supply, with a liquid flow rate of 110 kg / hour. Under these conditions, the formation of a plug in the coil is observed a few minutes after the start of hydrate formation (at a temperature of about 10.8 ° C.): the hydrates form a block and the circulation of the fluid becomes impossible.

EXEMPLE 2EXAMPLE 2

Dans cet exemple, on opère comme dans l'Exemple 1 comparatif, avec le même fluide, le même gaz, à la même pression et avec le même débit, mais on ajoute au fluide en circulation 1 % en masse par rapport au volume de condensat, un mélange selon l'invention ontenant 70% en poids de monooléate de sorbitan et de 30% en poids de dimère d'acide gras en C16-C18. Dans ces conditions, on observe une augmentation de la perte de charge lors de la formation des hydrates (à une température d'environ 10 °C), suivie de sa diminution et de sa stabilisation pendant plus de 24 heures à une température de 4 °C. Une descente en température à 0 °C n'affecte pas la circulation de la suspension, les hydrates restant dispersés dans les fluides.In this example, the procedure is as in Comparative Example 1, with the same fluid, the same gas, at the same pressure and with the same flow rate, but the circulating fluid is added 1% by weight relative to the volume of condensate. a mixture according to the invention containing 70% by weight of sorbitan monooleate and 30% by weight of C16-C18 fatty acid dimer. Under these conditions, an increase in the loss of charge during the formation of hydrates (at a temperature of approximately 10 ° C.) is observed, followed by its decrease and its stabilization during more than 24 hours at a temperature of 4 ° C. A descent into temperature at 0 ° C does not affect the circulation of the suspension, the remaining hydrates dispersed in the fluids.

EXEMPLE 3: Toxicité et biodégradabilité du mélange selon l'invention ("Water Hazard Classes" "WGK") EXAMPLE 3 Toxicity and biodegradability of the mixture according to the invention ("Water Hazard Classes""WGK")

La classification « WGK » est donnée selon l'"Administrative Regulation on the Classification of Substances Hazardous to Waters into Water Hazard Classes" (Verwaltungsvorschrift wassergefährdende Stoffe - VwVwS) du 17 mai 1999. La classification "WGK" d'un mélange peut être déterminée, selon l'Annexe 4 des nouvelles réglementations "VwVwS", par une règle de calcul a partir de la classification "WGK" de chaque constituant du mélange ou sur la base de résultats de tests éco-toxicologiques déterminés sur le mélange.The classification "WGK" is given according to the "Administrative Regulation on the Classification of Substances Hazardous to Waters into Water Hazard Classes" (Verwaltungsvorschrift wassergefährdende Stoffe - VwVwS) of 17 May 1999. The "WGK" classification of a mixture can be determined , according to Annex 4 of the new "VwVwS" regulations, by a calculation rule from the "WGK" classification of each component of the mixture or on the basis of eco-toxicological test results determined on the mixture.

On a effectué des tests sur les constituants A et B du mélange décrit dans l'Exemple 2, utilisé selon l'invention.

  1. 1) Toxicité orale aiguë sur le rat OECD 401 : la dose létale LD 50 est de 15 900 mg/l.
  2. 2) WGK= 1.
  3. 3) Toxicité aiguë OECD 203 :
    • LC50 (24 h) : pas de toxicité aiguë
    • LC50 (48 h) : pas de toxicité aiguë
    • LC50 (72 h) : pas de toxicité aiguë
    • LC50 (96 h) : pas de toxicité aiguë
  4. 4) Biodégradation OECD 301 D (28 j.) : biodégradabilité facile - 83,3 %.
Assays A and B of the mixture described in Example 2 used according to the invention were tested.
  1. 1) Acute Oral Toxicity to the Rat OECD 401: The lethal LD 50 dose is 15 900 mg / l.
  2. 2) WGK = 1.
  3. 3) Acute toxicity OECD 203:
    • LC50 (24 h): no acute toxicity
    • LC50 (48 h): no acute toxicity
    • LC50 (72 h): no acute toxicity
    • LC50 (96 h): no acute toxicity
  4. 4) Biodegradation OECD 301 D (28 days): easy biodegradability - 83.3%.

Claims (14)

Procédé pour transporter des hydrates en suspension au sein d'un fluide comprenant de l'eau, un gaz et un hydrocarbure liquide, dans des conditions où des hydrates peuvent se former à partir d'eau et du gaz, caractérisé en ce qu'on incorpore audit fluide un mélange comprenant lui-même: - au moins constituant A choisi parmi les esters formés entre au moins un acide monocarboxylique, linéaire ou ramifié, contenant de 8 à 24 atomes de carbone et au moins un alcool, linéaire ou ramifié, contenant de 2 à 200 atomes de carbone ; - et au moins un constituant B consistant en au moins un agent co-tensioactif non-ionique choisi parmi les acides gras monocarboxyliques insaturés polymérisés. A method for transporting hydrates in suspension in a fluid comprising water, a gas and a liquid hydrocarbon under conditions where hydrates can be formed from water and gas, characterized in that incorporates in said fluid a mixture comprising itself: at least one constituent A chosen from esters formed between at least one monocarboxylic acid, linear or branched, containing from 8 to 24 carbon atoms and at least one alcohol, linear or branched, containing from 2 to 200 carbon atoms; and at least one constituent B consisting of at least one non-ionic co-surfactant agent chosen from polymerized unsaturated monocarboxylic fatty acids. Fluide selon la revendication 1 caractérisé en ce que ledit constituant A est formé entre au moins un acide monocarboxylique, linéaire ou ramifié, contenant de 14 à 18 atomes de carbone et au moins un alcool, linéaire ou ramifié, contenant de 6 à 30 atomes de carbone.Fluid according to Claim 1, characterized in that the said constituent A is formed between at least one linear or branched monocarboxylic acid containing from 14 to 18 carbon atoms and at least one linear or branched alcohol containing from 6 to 30 carbon atoms. carbon. Fluide selon la revendication 1 ou 2 caractérisé en ce que le HLB (équilibre hydrophile-lipophile) dudit constituant A est en général compris entre 2 et 12.Fluid according to claim 1 or 2, characterized in that the HLB (hydrophilic-lipophilic balance) of said component A is generally between 2 and 12. Fluide selon la revendication 1 à 3 caractérisé en ce que ledit constituant B comprend au moins un acide gras monocarboxylique insaturé de 8 à 18 atomes de carbone dimérisé et/ou au moins au moins un acide gras monocarboxylique insaturé de 8 à 18 atomes de carbone trimérisé.Fluid according to claim 1 to 3 characterized in that said component B comprises at least one dimerized unsaturated monocarboxylic fatty acid of 8 to 18 carbon atoms and / or at least one unsaturated monocarboxylic fatty acid of 8 to 18 carbon atoms trimerised . Fluide selon l'une des revendications 1 à 4 caractérisé en ce que ledit mélange comprend de 10 à 95 % en poids de constituant A et de 5 à 90 % en poids de constituant B.Fluid according to one of claims 1 to 4 characterized in that said mixture comprises from 10 to 95% by weight of component A and from 5 to 90% by weight of component B. Fluide selon la revendication 5 caractérisé en ce que ledit mélange comprend de 30 à 90 % en poids de constituant A et de10 à 70 % en poids de constituant B.Fluid according to claim 5 characterized in that said mixture comprises from 30 to 90% by weight of component A and from 10 to 70% by weight of component B. Fluide selon la revendication 5 caractérisé en ce que ledit mélange comprend de 50 à 80 % en poids de constituant A et de 20 à 50 % en poids de constituant B.Fluid according to claim 5 characterized in that said mixture comprises from 50 to 80% by weight of component A and from 20 to 50% by weight of component B. Fluide selon l'une des revendications 1 à 7 caractérisé en ce que ledit constituant A est le monooléate de sorbitan et en ce que ledit constituant B est un dimère d'acides gras mono-insaturés en C16-C18.Fluid according to one of claims 1 to 7 characterized in that said component A is sorbitan monooleate and in that said component B is a dimer of monounsaturated C 16 -C 18 fatty acids. Fluide selon l'une des revendications 1 à 8 caractérisé en ce que ladite phase aqueuse est de l'eau douce, de l'eau salée, consistant en eau de mer ou en saumure.Fluid according to one of claims 1 to 8 characterized in that said aqueous phase is fresh water, salt water, consisting of seawater or brine. Procédé selon l'une des revendications 1 à 9 caractérisé en ce que ladite composition est incorporée audit fluide à une concentration de 0,1 à 5 % en masse par rapport à l'hydrocarbure liquide présent.Process according to one of Claims 1 to 9, characterized in that the said composition is incorporated in the said fluid at a concentration of 0.1 to 5% by weight relative to the liquid hydrocarbon present. Procédé selon la revendication 10, caractérisé en ce que ladite concentration est de 0,2 à 3 % en masse par rapport à l'hydrocarbure liquide présent.Process according to Claim 10, characterized in that the said concentration is 0.2 to 3% by weight relative to the liquid hydrocarbon present. Procédé selon l'une des revendications 1 à 11, caractérisé en ce que, dans ledit fluide, ledit gaz comprend au moins un hydrocarbure choisi parmi le méthane, l'éthane, l'éthylène, le propane, le propène, le n-butane, l'isobutane, et éventuellement de l'H2S et/ou du CO2.Process according to one of Claims 1 to 11, characterized in that , in said fluid, said gas comprises at least one hydrocarbon chosen from methane, ethane, ethylene, propane, propene and n-butane. , isobutane, and optionally H2S and / or CO2. Procédé selon l'une des revendications 1 à 12 caractérisé en ce que ledit fluide comprend du gaz naturel.Method according to one of claims 1 to 12 characterized in that said fluid comprises natural gas. Procédé selon l'une des revendications 1 à 13 caractérisé en ce que ledit fluide comprend du gaz de pétrole et au moins un hydrocarbure liquide.Process according to one of Claims 1 to 13, characterized in that the said fluid comprises petroleum gas and at least one liquid hydrocarbon.
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US7851413B2 (en) 2010-12-14
NO20055895L (en) 2006-06-14

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