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EP0807678B1 - Process for inhibiting or retarding the formation of hydrates in a production effluent - Google Patents

Process for inhibiting or retarding the formation of hydrates in a production effluent Download PDF

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Publication number
EP0807678B1
EP0807678B1 EP97401004A EP97401004A EP0807678B1 EP 0807678 B1 EP0807678 B1 EP 0807678B1 EP 97401004 A EP97401004 A EP 97401004A EP 97401004 A EP97401004 A EP 97401004A EP 0807678 B1 EP0807678 B1 EP 0807678B1
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EP
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Prior art keywords
monomers
methyl
group
hydrogen atom
general formula
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EP97401004A
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German (de)
French (fr)
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EP0807678A1 (en
Inventor
Anne Sinquin
Marie Velly
Jean-Pierre Durand
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IFP Energies Nouvelles IFPEN
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IFP Energies Nouvelles IFPEN
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    • 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

Definitions

  • the invention relates to a method for inhibiting or retarding the formation, growth and / or agglomeration of hydrates of natural gas, petroleum gas or other gases by using at least one additive.
  • the gases that form hydrates may in particular comprise at least one hydrocarbon selected from methane, ethane, ethylene, propane, propene, n-butane and iso-butane, and optionally H 2 S and / or CO 2 .
  • hydrates are formed when the water is in the presence of gas, either in the state free, either in the dissolved state in a liquid phase, such as a liquid hydrocarbon, and when the temperature reached by the mixture including water, gas and liquid hydrocarbons, such as oil, becomes lower than the thermodynamic temperature of formation of hydrates, this temperature being given for a known gas composition and when their pressure is fixed.
  • thermodynamics required to form hydrates are met, agglomeration hydrates causes the blocking of the transport pipes by creating plugs which prevent any passage of crude oil or gas.
  • hydrate corks can lead to a cessation of production and thus cause significant financial losses.
  • the return to service of the installation especially in the case of production or transport at sea, can be long, because the decomposition of the hydrates formed is very difficult to achieve.
  • the temperature at the bottom of the sea can be, for example, 3 or 4 ° C.
  • Conditions favorable for the formation of hydrates can also be combined with the same way on land, for pipes not (or not deep enough) buried in the terrestrial soil, when for example the temperature of the ambient air is cold.
  • Amphiphilic compounds obtained by reaction of at least one derivative succinic selected from the group consisting of acids and anhydrides polyalkenylsuccinic acids on at least one polyethylene glycol monoether have also been proposed to reduce the tendency to agglomerate gas hydrates natural gas, petroleum gas or other gases (EP-A-582507).
  • water-soluble polymers that can be neutral or positively charged homopolymers or copolymers, or polyampholytes and which are derived from one or more nitrogenous monomers, allow, at low concentrations, to inhibit or delay formation, growth and / or agglomeration of hydrates of natural gas, petroleum gas or other gases, with an efficiency very much higher than the compounds previously described.
  • the invention provides a method for inhibiting or delaying formation, growth and / or agglomeration of hydrates within a fluid comprising water and a gas, under conditions where hydrates can form (from the water and of gas), characterized in that at least one homopolymer or water-soluble copolymer generally defined as deriving from at least a nitrogenous monomer selected from neutral monomers, cationic monomers positively charged) and the amphoteric monomers (i.e. times a positive charge and a negative charge) defined below.
  • neutral monomers illustrating these formulas include dimethylaminoethyl acrylate and dimethylaminoethyl methacrylate.
  • cationic monomers examples include methacrylate-ethyl-trimethyl ammonium, methacrylamido-N-propyl-trimethyl chloride ammonium and diallyl dimethyl ammonium chloride.
  • amphoteric monomers mention may be made of methosulphonate of ethyl trimethylammonium acrylate.
  • Cationic monomers, amphoteric monomers and monomers neutrals from [A] to [K] defined in the foregoing description may be included in homopolymers or copolymers, in all proportions, that is to say ranging, for each, from 0 to 100 mol%.
  • the invention also proposes the use of copolymers as additives resulting from the combination of at least one of the monomers described above (monomer cationic, amphoteric monomer and / or neutral monomer of [A] to [K]), with at least an anionic (or negatively charged) monomer and / or at least one neutral monomer other than those already described above.
  • the anionic monomers considered are more particularly monomers containing carboxylate groups or sulphonate groups and more precisely monomers acrylate, methacrylate, itaconate, 2-acrylamido-2-methylpropane sulfonate, 2-methacryloyloxy ethane sulfonate, 3-acrylamido-3-methyl butanoate, styrene sulfonate, styrene carboxylate, vinyl sulfonate, anhydride maleic or maleic acid.
  • cationic monomers amphoteric monomers and / or the neutral monomers of [A] to [K] described above, also one or more other neutral nitrogen-containing monomers such as acrylamide, alkyl-type monomers acrylamide or vinyl acetamide.
  • the proportions of cationic monomers, in amphoteric monomers, in monomers neutral from [A] to [K], in monomers anionic and / or additional neutral monomers may vary, for each monomers, for example from 1 to 99%, more particularly from 10 to 70% by weight. mol.
  • Cationic monomers, amphoteric monomers and monomers Neutrals of [C] to [K] described above may still be associated with one or more other N-vinyl lactam neutral nitrogenous monomers, in particular N-vinyl-2-pyrrolidone, N-vinyl- ⁇ -valerolactam and N-vinyl- ⁇ -caprolactam.
  • the proportions of cationic monomers, in amphoteric monomers, in neutral monomers of [C] to [K] and in the monomers additional neutrals may vary, for each of the monomers, for example from 1 to 99%, and more particularly from 10 to 70 mol%.
  • homopolymers and copolymers in relation to the nature of the monomers that can enter their homopolymers and copolymers considered in the invention may consist of neutral, cationic (co) polymers or polyampholytes (these latter containing both positively charged monomers and negatively charged monomers).
  • the polymers described in the invention may be linear or branched. Their mass can vary from 3000 to several millions.
  • the homo and copolymers as described above can be added to the fluid to be treated alone or as mixtures of two or more of them.
  • copolymers may be copolymers which differ from each other for example by the nature of the patterns of at least one type and / or composition different in at least one pattern and / or by their molecular weight.
  • Homo or copolymers, as well as their mixtures in all proportions may be added to the fluid to be treated at concentrations generally ranging from 0.05 to 5% by weight, preferably 0.1 to 2% by weight, based on water.
  • the homo or copolymers recommended as additives in the invention may be mixed with one or more alcohols (monoalcohols or polyols) containing for example from 1 to 6 carbon atoms, more particularly the mono-, the di- or tri-ethylene glycol, ethanol or methanol, the latter being the preferred alcohol.
  • This alcohol or these alcohols is (are) added in general in proportions ranging from 0.5 to 20% by weight, preferably 1 to 10% by weight, relative to the water present in the fluid to be treated.
  • the homo or copolymer (s) considered in the invention can then be dissolved beforehand in a hydro-alcoholic medium and then added in the medium to be treated, so as to obtain final concentrations of homo or copolymers generally ranging from 0.05 to 3% by weight, preferably from 0.1 to 1% by weight. mass with respect to the water present in the fluid to be treated.
  • the water-soluble homo or copolymers considered in the invention can be used either in pure water medium, for example in water of condensation, or in saline medium, for example in production water.
  • the device used consists of 16 mm diameter tubes, in which are 8 ml of a 20% by weight aqueous solution of THF containing optionally the additive to be tested. Each tube is filled with a glass ball of one diameter of 8 mm, to ensure proper mixing of the solution.
  • the tubes are placed on a rotary shaker, which rotates at 20 rpm. The latter is placed in a refrigerated chamber at 2 ° C.
  • This test is to determine the lag time before the training hydrates. This latency corresponds to the interval measured between the moment when the tubes are introduced into the refrigerated chamber and the moment when the hydrate formation (appearance of a disorder).
  • Each series of tests is conducted in the presence of a reference mixture not containing no additive, and the lag times provided for an additive correspond to an average of the times measured over 16 tests.
  • the solutions of pure water / THF have an average latency of 35 minutes.
  • Example 1 The experimental procedure of Example 1 is repeated replacing pure water with a mixture of pure water and 5% of methanol by mass and lowering the temperature of the refrigerated chamber at -1 ° C.
  • Example 1 The experimental procedure of Example 1 is repeated replacing pure water With a solution of NaCl 3.5% by weight, the temperature of the refrigerated chamber is lowered to 0 ° C. Under these conditions, the average latency of the solutions NaCl / THF in the absence of additive is 42 minutes.
  • DMAC diallyl dimethyl ammonium chloride
  • AMPDAPS poly [3- (2-acrylamido-2-methyl-propyl-dimethyl-ammonio) -1-propane sulfonate]
  • a terpolymer containing 60 mol% of acrylamide type units, 25 mol% of acrylamido-methyl-propane units sulfonate (AMPS) and 15 mol% of methacrylamido-N-propyl-trimethyl chloride units ammonium (MAPTAC) or 0.3% by weight of a copolymer NVP / AMPDAPS (60/40 mol) inhibit the formation of THF hydrates during a period longer than 6 hours.
  • the apparatus includes a loop of 6 meters consisting of tubes of diameter 7.7 mm, a 2-liter reactor with an inlet and an outlet for gas, suction and discharge for the water and additive mixture initially introduced.
  • the reactor makes it possible to put the loop under pressure.
  • Diameter tubes analogous to those of the loop ensure the circulation of the fluid from the loop to the reactor, and conversely, via a gear pump placed between the two.
  • a sapphire cell integrated in the circuit allows a visualization of the liquid in circulation and therefore hydrates if they formed.
  • the fluid is introduced (water and additive) in the reactor.
  • the installation is then brought under a pressure of 7 MPa.
  • the solution is homogenized by its circulation in the loop and the reactor, then the loop is isolated from the reactor.
  • the pressure is kept constant by adding methane, and a gradual reduction of the temperature (0.5 ° C / min) of 17 ° C to 5 ° C, which corresponds to the chosen experimental temperature.
  • the principle of these tests is to determine, on the one hand, the temperature of formation of methane hydrates in the loop, and secondly the lag time preceding their formation.
  • the latency time corresponds to the measured time between beginning of the test (fluid circulation at 17 ° C) and detection of hydrate formation (exothermic, high gas consumption).
  • the duration of the tests may vary from a few minutes to several hours: a powerful additive inhibits the formation of hydrates, or keeps them dispersed in fluids for several hours.
  • the methane hydrates are form at a temperature of 10.0 ° C. and after an induction time of 30.degree. minutes.
  • the formation of hydrates leads to an immediate blockage of the circulation of the fluid + hydrate mixture in the loop.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)
  • Gas Separation By Absorption (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

L'invention concerne un procédé pour inhiber ou retarder la formation, la croissance ou/et l'agglomération des hydrates de gaz naturel, de gaz de pétrole ou d'autres gaz, par utilisation d'au moins un additif. 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'iso-butane, et éventuellement de l'H2S et/ou du CO2.The invention relates to a method for inhibiting or retarding the formation, growth and / or agglomeration of hydrates of natural gas, petroleum gas or other gases by using at least one additive. The gases that form hydrates may in particular comprise at least one hydrocarbon selected from methane, ethane, ethylene, propane, propene, n-butane and iso-butane, 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 dissous 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 formation 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 state free, either in the dissolved state in a liquid phase, such as a liquid hydrocarbon, and when the temperature reached by the mixture including water, gas and liquid hydrocarbons, such as oil, becomes lower than the thermodynamic temperature of formation of hydrates, this temperature being given for a known gas composition and when their pressure is fixed.

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 une 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 formation 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 industry oil and gas, for which hydrate formation conditions may be to be united. In fact, to reduce the cost of production of crude oil and gas, from the point of view of investment and from the point of view of exploitation, one envisaged, particularly in offshore production, is to reduce or even eliminate applied to the crude or 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 sea treatments are generally carried out on a platform located on the surface at near the deposit, so that the initially hot effluent can be treated before the thermodynamic conditions of hydrate formation are affected by the 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 entraíne le blocage des conduites de transport par création de bouchons qui empêchent tout passage de pétrole brut ou de gaz.However, as it happens practically, when the conditions thermodynamics required to form hydrates are met, agglomeration hydrates causes the blocking of the transport pipes by creating plugs which prevent any passage of crude oil or gas.

La formation de bouchons d'hydrates peut entraíner 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 installation, especially in the case of production or transport at sea, can be long, because the decomposition of the hydrates formed is very difficult to achieve. Indeed, when the production of an underwater natural gas or oil and gas deposit with water reaches the surface of the sea floor and is then transported to the bottom of the sea, it happens, by lowering the temperature of the effluent produced, that 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.Conditions favorable for the formation of hydrates can also be combined with the same way on land, for pipes not (or not deep enough) buried in the terrestrial 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 formation des hydrates. Ce sont notamment des alcools, tels que le méthanol, ou des glycols, tels que le mono-, le di- ou le tri-éthylèneglycol. Cette solution est très onéreuse car la quantité d'inhibiteurs à ajouter peut atteindre 10 à 40% de la teneur en eau et ces inhibiteurs sont difficiles à récupérer complètement.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 formation of hydrates. These include alcohols, such as methanol, or glycols, such as mono-, di- or tri-ethylene glycol. This solution is very expensive because the amount of inhibitors to add can reach 10 to 40% of the water content and these inhibitors are difficult to recover completely.

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.It has also been advocated for the insulation of the transport pipes, so as to prevent the temperature of the transported fluid from reaching the formation temperature hydrates under the operating conditions. Such a technique is also very expensive.

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-323774 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-323775, 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-4956593 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 homopolyacrylamides et des copolymères-acrylamide-acrylates ; et la demande de brevet EP-A-457375, 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 the formation of hydrates, since instead of rapidly others and to form plugs, the hydrates formed are dispersed in the fluid without to agglomerate and without obstructing the pipes. In this respect, the following EP-A-323774 in the name of the applicant, which describes the use of compounds nonionic amphiphiles chosen from esters of polyols and of acids carboxylic acids, substituted or unsubstituted, and imide-functional compounds; the Patent Application EP-A-323775, also in the name of the applicant, which describes especially the use of compounds belonging to the family of diethanolamides fatty acids or fatty acid derivatives; US-A-4956593 which describes the use of surface-active compounds such as organic phosphonates, esters phosphates, phosphonic acids, their salts and esters, polyphosphates inorganic and their esters, as well as homopolyacrylamides and copolymers-acrylamide-acrylates ; and the patent application EP-A-457375, which describes the use of anionic surfactant compounds, such as alkylarylsulphonic acids and their salts of alkali metals.

Des composés amphiphiles obtenus par réaction d'au moins un dérivé succinique choisi dans le groupe formé par les acides et les anhydrides polyalkénylsucciniques sur au moins un monoéther de polyéthylèneglycol 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 derivative succinic selected from the group consisting of acids and anhydrides polyalkenylsuccinic acids on at least one polyethylene glycol monoether have have also been proposed to reduce the tendency to agglomerate gas hydrates natural gas, petroleum gas or other gases (EP-A-582507).

Par ailleurs, on a également préconisé l'utilisation d'additifs capables d'inhiber ou de retarder la formation et/ou la croissance des hydrates. On peut citer à cet égard la demande de brevet EP-A-536950, qui décrit l'utilisation de dérivés de la tyrosine, la demande internationale WO-A-9325798, qui décrit l'utilisation de composés homopolymères et copolymères de la N-vinyl-2-pyrrolidone et leurs mélanges, la demande internationale WO-A-9412761 et le brevet US-A-5432292 qui décrivent l'utilisation de la poly(N-vinyl-2-pyrrolidone), de l'hydroxyéthyl cellulose et de leurs mélanges ou d'un terpolymère à base de N-vinyl-2-pyrrolidone, N-vinyl-ε-caprolactame et de diméthylaminoéthyl méthacrylate commercialisé sous le nom de GAFFIX VC-713. La demande internationale WO-A-9519408 décrit plus généralement l'utilisation de polymères aliphatiques contenant des N-hétérocycles carbonylés dans des formulations complexes. Il en est de même de la demande internationale WO-A-9532356, qui décrit notamment l'utilisation de terpolymère à base de N-vinyl-2-pyrrolidone, d'acrylamido méthyl propane sulfonate et d'acrylamide. Enfin, les demandes internationales WO-A-9517579 et WO-A-9604462 décrivent l'utilisation de dérivés ammonium, sulfonium et phosphonium alkylés soit seuls soit mélangés à un inhibiteur de corrosion.In addition, the use of additives capable of inhibiting or delaying the formation and / or growth of hydrates. In this respect, we can mention patent application EP-A-536950, which describes the use of tyrosine derivatives, the International Application WO-A-9325798, which describes the use of compounds homopolymers and copolymers of N-vinyl-2-pyrrolidone and mixtures thereof, the International Application WO-A-9412761 and US-A-5432292 which describe the use of poly (N-vinyl-2-pyrrolidone), hydroxyethyl cellulose and their mixtures or a terpolymer based on N-vinyl-2-pyrrolidone, N-vinyl-ε-caprolactam and dimethylaminoethyl methacrylate sold under the name of GAFFIX VC-713. International Application WO-A-9519408 describes more generally the use of aliphatic polymers containing N-heterocycles carbonylated in complex formulations. The same is true of the demand WO-A-9532356, which describes in particular the use of terpolymer base of N-vinyl-2-pyrrolidone, acrylamido methyl propane sulphonate and acrylamide. Finally, international applications WO-A-9517579 and WO-A-9604462 describe the use of alkylated ammonium, sulphonium and phosphonium derivatives either only be mixed with a corrosion inhibitor.

On a maintenant découvert que certains polymères hydrosolubles qui peuvent être des homopolymères ou des copolymères neutres ou chargés positivement, ou encore des polyampholytes et qui dérivent d'un ou de plusieurs monomères azotés, permettent, à de faibles concentrations, d'inhiber ou de retarder la formation, la croissance et/ou l'agglomération des hydrates de gaz naturel, de gaz de pétrole ou d'autres gaz, avec une efficacité très nettement supérieure aux composés précédemment décrits.It has now been discovered that certain water-soluble polymers that can be neutral or positively charged homopolymers or copolymers, or polyampholytes and which are derived from one or more nitrogenous monomers, allow, at low concentrations, to inhibit or delay formation, growth and / or agglomeration of hydrates of natural gas, petroleum gas or other gases, with an efficiency very much higher than the compounds previously described.

Ainsi, l'invention propose un procédé pour inhiber ou retarder la formation, la croissance et/ou l'agglomération des hydrates au sein d'un fluide comprenant de l'eau et un gaz, dans des conditions où des hydrates peuvent se former (à partir de l'eau et du gaz), caractérisé en ce qu'on incorpore audit fluide au moins un homopolymère ou copolymère hydrosoluble défini d'une manière générale comme dérivant d'au moins un monomère azoté choisi parmi les monomères neutres, les monomères cationiques (ou chargés positivement) et les monomères amphotères (c'est-à-dire comportant à la fois une charge positive et une charge négative) définis ci-après.Thus, the invention provides a method for inhibiting or delaying formation, growth and / or agglomeration of hydrates within a fluid comprising water and a gas, under conditions where hydrates can form (from the water and of gas), characterized in that at least one homopolymer or water-soluble copolymer generally defined as deriving from at least a nitrogenous monomer selected from neutral monomers, cationic monomers positively charged) and the amphoteric monomers (i.e. times a positive charge and a negative charge) defined below.

Les monomères neutres sont choisis parmi :

  • les monomères [A] possédant au moins une fonction amine tertiaire et éventuellement au moins une foncion amide sur une chaíne latérale et répondant à la formule générale [1] :
    Figure 00040001
dans laquelle R' est un atome d'hydrogène ou un groupement méthyle, R" est choisi parmi les groupements divalents -COO-, -CO-NH-, -CO-NH-CO-NH- ou -C6H4-, R1 est choisi parmi les groupements divalents suivants -(CH2)n-, avec 1 ≤ n ≤ 3, -C(CH3)2-, -C(CH3)2-(CH2)2- ou -CH2-CH(OH)CH2-, R2 est un atome d'hydrogène ou un radical méthyle, éthyle ou iso-propyle, R3 est un atome d'hydrogène ou un radical méthyle ou éthyle ;
  • les monomères [B] possédant au moins une fonction amide sur une chaíne latérale et répondant à la formule générale [2] :
    Figure 00050001
    dans laquelle R' est un atome d'hydrogène ou un groupement méthyle et R4 un groupement -C(CH3)2-CH2-CO-CH3 ou -CH2OH ;
  • les monomères [C] possédant un radical azoté aromatique pendant et répondant à la formule générale [3] :
    Figure 00050002
    dans laquelle R' est un atome d'hydrogène ou un groupement méthyle ;
  • les monomères [D] possédant une fonction succinimide sur une chaíne latérale et répondant à la formule générale [4] :
    Figure 00060001
    dans laquelle R' est un atome d'hydrogène ou un groupement méthyle ;
  • et les monomères [E], répondant à la formule générale [5] : (CH2=CH-(CH2))2-N-R5 dans laquelle, R5 est une chaíne alkyle CnH2n+1, avec 1 ≤ n ≤ 10, ou un groupement hydroxyle ou un groupement -(CH2)2-CO-NH2.
The neutral monomers are chosen from:
  • the monomers [A] possessing at least one tertiary amine function and optionally at least one amide functional group on a side chain and corresponding to the general formula [1]:
    Figure 00040001
in which R 'is a hydrogen atom or a methyl group, R "is chosen from the divalent groups -COO-, -CO-NH-, -CO-NH-CO-NH- or -C 6 H 4 -, R 1 is chosen from the following divalent groups - (CH 2 ) n -, with 1 ≤ n ≤ 3, -C (CH 3 ) 2 -, -C (CH 3 ) 2 - (CH 2 ) 2 - or -CH 2 -CH (OH) CH 2 -, R 2 is a hydrogen atom or a methyl, ethyl or iso-propyl radical, R 3 is a hydrogen atom or a methyl or ethyl radical;
  • monomers [B] possessing at least one amide function on a side chain and corresponding to the general formula [2]:
    Figure 00050001
    in which R 'is a hydrogen atom or a methyl group and R 4 a -C (CH 3 ) 2 -CH 2 -CO-CH 3 or -CH 2 OH group;
  • monomers [C] possessing an aromatic nitrogen radical during and corresponding to the general formula [3]:
    Figure 00050002
    wherein R 'is a hydrogen atom or a methyl group;
  • monomers [D] possessing a succinimide function on a side chain and corresponding to the general formula [4]:
    Figure 00060001
    wherein R 'is a hydrogen atom or a methyl group;
  • and the monomers [E], corresponding to the general formula [5]: (CH 2 = CH- (CH 2 )) 2 -NR 5 wherein, R 5 is a C n H 2n + 1 alkyl chain, with 1 ≤ n ≤ 10, or a hydroxyl group or a - (CH 2 ) 2 -CO-NH 2 group .

Comme exemples de monomères neutres illustrant ces formules, on peut citer le diméthyl-amino-éthyl acrylate et le diméthyl-amino-éthyl méthacrylate.Examples of neutral monomers illustrating these formulas include dimethylaminoethyl acrylate and dimethylaminoethyl methacrylate.

Les monomères cationiques considérés plus particulièrement dans la définition des polymères de l'invention sont ceux qui comportent des groupements ammonium quaternaire. Il peut s'agir de monomères dérivant de la quaternisation par chlorométhylation, sulfométhylation, sulfoéthylation ou chlorobenzylation des monomères de type [A], [C] ou [E] décrits ci-dessus. Ces monomères cationiques [F], [G] et [H] répondent respectivement aux formules générales [6], [7] et [8] ci-après :

  • les monomères [F], à la formule générale [6] :
    Figure 00070001
dans laquelle R' est un atome d'hydrogène ou un groupement méthyle, R" est choisi parmi les groupements divalents -COO-, -CO-NH-, -CO-NH-CO-NH- ou -C6H4-, R1 est choisi parmi les groupements divalents suivants -(CH2)n-, avec 1 ≤ n ≤ 3, -C(CH3)2-, -C(CH3)2-(CH2)2- ou -CH2-CH(OH)CH2-, R2 est un atome d'hydrogène, ou un radical méthyle, éthyle ou iso-propyle, R3 est un atome d'hydrogène ou un radical méthyle ou éthyle, R6 est choisi parmi les groupements méthyle, éthyle ou benzyle et X est un ion chlorure ou un ion CH3OSO3-;
  • les monomères [G], à la formule générale [7]:
    Figure 00070002
    dans laquelle R' est un atome d'hydrogène ou un groupement méthyle, R7 un groupement -C(CH3)2-CO-CH3, -CH2OH, méthyle, éthyle ou benzyle et X est un ion chlorure ou un ion CH3OSO3-;
  • et les monomères [H], à la formule générale [8] : (CH2=CH-(CH2))2-N+-R5R6 X- dans laquelle, R5 est une chaíne alkyle CnH2n+1, avec 1 ≤ n ≤ 10, un groupement hydroxyle ou un groupement (CH2)2-CO-NH2, R6 est choisi parmi les groupements méthyle, éthyle ou benzyle et X est un ion chlorure ou un ion CH3OSO3 -.
The cationic monomers considered more particularly in the definition of the polymers of the invention are those which comprise quaternary ammonium groups. They may be monomers deriving from the quaternization by chloromethylation, sulfomethylation, sulfoethylation or chlorobenzylation of the [A], [C] or [E] type monomers described above. These cationic monomers [F], [G] and [H] respectively correspond to the general formulas [6], [7] and [8] below:
  • the monomers [F], with the general formula [6]:
    Figure 00070001
in which R 'is a hydrogen atom or a methyl group, R "is chosen from the divalent groups -COO-, -CO-NH-, -CO-NH-CO-NH- or -C 6 H 4 -, R 1 is chosen from the following divalent groups - (CH 2 ) n -, with 1 ≤ n ≤ 3, -C (CH 3 ) 2 -, -C (CH 3 ) 2 - (CH 2 ) 2 - or -CH 2 -CH (OH) CH 2 -, R 2 is a hydrogen atom, or a methyl, ethyl or iso-propyl radical, R 3 is a hydrogen atom or a methyl or ethyl radical, R 6 is chosen from the methyl, ethyl or benzyl groups and X is a chloride ion or a CH 3 OSO 3 - ion;
  • the monomers [G], with the general formula [7]:
    Figure 00070002
    in which R 'is a hydrogen atom or a methyl group, R 7 a -C (CH 3 ) 2 -CO-CH 3 , -CH 2 OH, methyl, ethyl or benzyl group and X is a chloride ion or a ion CH 3 OSO 3 -;
  • and the monomers [H], with the general formula [8]: (CH 2 = CH- (CH 2 )) 2 -N + -R 5 R 6 X - in which, R 5 is a C n H 2n + 1 alkyl chain, with 1 ≤ n ≤ 10, a hydroxyl group or a (CH 2 ) 2 -CO-NH 2 group , R 6 is chosen from methyl and ethyl groups; or benzyl and X is a chloride ion or a CH 3 OSO 3 - ion.

Comme exemples de monomères cationiques, on peut citer le chlorure de méthacrylate-éthyl-triméthyl ammonium, le chlorure de méthacrylamido-N-propyl-triméthyl ammonium et le chlorure de diallyl-diméthyl ammonium.Examples of cationic monomers that may be mentioned include methacrylate-ethyl-trimethyl ammonium, methacrylamido-N-propyl-trimethyl chloride ammonium and diallyl dimethyl ammonium chloride.

Les monomères amphotères [I], [J] et [K] (comportant à la fois une charge positive et une charge négative) considérés dans la définition des polymères de l'invention répondent aux formules générales suivantes :

  • les monomères [I], à la formule générale [9] :
    Figure 00090001
    dans laquelle R', R8 et R9 sont soit des atomes d'hydrogène soit des groupements méthyle, R10 est choisi parmi les groupements divalents -COO- ou -CO-NH-, R11 et R12 sont choisis parmi les groupements divalents suivants -(CH2)n-, avec 1 ≤ n ≤ 3, -C(CH3)2- ou -C(CH3)2-(CH2)2- et G- est un groupement chargé négativement de type carboxylate ou sulfonate ;
  • les monomères [J], à la formule générale [10] :
    Figure 00090002
    dans laquelle R13 est un atome d'hydrogène ou un groupement méthyle, R14 est choisi parmi les groupements divalents -(CH2)n-, avec 1 ≤ n ≤ 4, ou -CH2-C6H4- et G- est un groupement chargé négativement de type carboxylate ou sulfonate ;
  • et les monomères [K], à la formule générale [11] :
    Figure 00100001
    dans laquelle R' est un atome d'hydrogène ou un groupement méthyle, R15 est un groupement divalent de type -(CH2)n-, avec 1 ≤ n ≤ 4, et G- est un groupement chargé négativement de type carboxylate ou sulfonate.
The amphoteric monomers [I], [J] and [K] (comprising both a positive charge and a negative charge) considered in the definition of the polymers of the invention correspond to the following general formulas:
  • the monomers [I], with the general formula [9]:
    Figure 00090001
    in which R ', R 8 and R 9 are either hydrogen atoms or methyl groups, R 10 is chosen from the divalent groups -COO- or -CO-NH-, R 11 and R 12 are chosen from groups following divalents - (CH 2 ) n -, with 1 ≤ n ≤ 3, -C (CH 3 ) 2 - or -C (CH 3 ) 2 - (CH 2 ) 2 - and G - is a negatively charged group of type carboxylate or sulfonate;
  • the monomers [J], with the general formula [10]:
    Figure 00090002
    in which R 13 is a hydrogen atom or a methyl group, R 14 is chosen from divalent groups - (CH 2 ) n -, with 1 ≤ n ≤ 4, or -CH 2 -C 6 H 4 - and G - is a negatively charged group of carboxylate or sulfonate type;
  • and the monomers [K], with the general formula [11]:
    Figure 00100001
    in which R 'is a hydrogen atom or a methyl group, R 15 is a divalent group of type - (CH 2 ) n -, with 1 ≤ n ≤ 4, and G - is a negatively charged group of carboxylate type or sulfonate.

Comme exemple de monomères amphotères, on peut citer le méthosulfonate d'acrylate d'éthyl-triméthyl ammonium. As an example of amphoteric monomers, mention may be made of methosulphonate of ethyl trimethylammonium acrylate.

Les monomères cationiques, les monomères amphotères et les monomères neutres de [A] à [K] définis dans la description qui précède peuvent être inclus dans les homopolymères ou copolymères, en toutes proportions, c'est-à-dire allant, pour chacun, de 0 à 100% molaire.Cationic monomers, amphoteric monomers and monomers neutrals from [A] to [K] defined in the foregoing description may be included in homopolymers or copolymers, in all proportions, that is to say ranging, for each, from 0 to 100 mol%.

L'invention propose également la mise en jeu comme additifs, de copolymères résultant de l'association d'au moins un des monomères décrits ci-dessus (monomère cationique, monomère amphotère et/ou monomère neutre de [A] à [K]), avec au moins un monomère anionique (ou chargé négativement) et/ou au moins un monomère neutre autre que ceux déjà décrits plus haut.The invention also proposes the use of copolymers as additives resulting from the combination of at least one of the monomers described above (monomer cationic, amphoteric monomer and / or neutral monomer of [A] to [K]), with at least an anionic (or negatively charged) monomer and / or at least one neutral monomer other than those already described above.

Les monomères anioniques considérés sont plus particulièrement des monomères contenant des groupements carboxylate ou des groupements sulfonate et plus précisément des monomères acrylate, méthacrylate, itaconate, 2-acrylamido-2-méthyl-propane sulfonate, 2-méthacryloyloxy éthane sulfonate, 3-acrylamido-3-méthyl butanoate, styrène sulfonate, styrène carboxylate, vinyl sulfonate, anhydride maléique ou acide maléique.The anionic monomers considered are more particularly monomers containing carboxylate groups or sulphonate groups and more precisely monomers acrylate, methacrylate, itaconate, 2-acrylamido-2-methylpropane sulfonate, 2-methacryloyloxy ethane sulfonate, 3-acrylamido-3-methyl butanoate, styrene sulfonate, styrene carboxylate, vinyl sulfonate, anhydride maleic or maleic acid.

Peuvent être associés aux monomères cationiques, aux monomères amphotères et/ou aux monomères neutres de [A] à [K] décrits ci dessus, également un ou plusieurs autres monomères azotés neutres tels que des monomères de type acrylamide, alkyl acrylamide ou vinyl acétamide.May be associated with cationic monomers, amphoteric monomers and / or the neutral monomers of [A] to [K] described above, also one or more other neutral nitrogen-containing monomers such as acrylamide, alkyl-type monomers acrylamide or vinyl acetamide.

Dans ces copolymères, les proportions en monomères cationiques, en monomères amphotères, en monomères neutres de [A] à [K], en monomères anioniques et/ou en les monomères neutres additionnels peuvent varier, pour chacun des monomères, par exemple de 1 à 99 %, plus particulièrement de 10 à 70 % en moles.In these copolymers, the proportions of cationic monomers, in amphoteric monomers, in monomers neutral from [A] to [K], in monomers anionic and / or additional neutral monomers may vary, for each monomers, for example from 1 to 99%, more particularly from 10 to 70% by weight. mol.

Les monomères cationiques, les monomères amphotères et les monomères neutres de [C] à [K] décrits ci-dessus peuvent encore être associés à un ou plusieurs autres monomères azotés neutres de type N-vinyl lactame, en particulier la N-vinyl-2-pyrrolidone, le N-vinyl-δ-valérolactame et le N-vinyl-ε-caprolactame. Cationic monomers, amphoteric monomers and monomers Neutrals of [C] to [K] described above may still be associated with one or more other N-vinyl lactam neutral nitrogenous monomers, in particular N-vinyl-2-pyrrolidone, N-vinyl-δ-valerolactam and N-vinyl-ε-caprolactam.

Dans ces copolymères, les proportions en monomères cationiques, en monomères amphotères, en monomères neutres de [C] à [K] et en les monomères neutres additionnels peuvent varier, pour chacun des monomères, par exemple de 1 à 99 %, et plus particulièrement de 10 à 70 % en moles.In these copolymers, the proportions of cationic monomers, in amphoteric monomers, in neutral monomers of [C] to [K] and in the monomers additional neutrals may vary, for each of the monomers, for example from 1 to 99%, and more particularly from 10 to 70 mol%.

Compte tenu de la définition des homopolymères et des copolymères donnée plus haut, en relation avec la nature des monomères qui peuvent entrer dans leur constitution, les homopolymères et les copolymères considérés dans l'invention peuvent consister en des (co)polymères neutres, cationiques ou en des polyampholytes (ces derniers contenant à la fois des monomères chargés positivement et des monomères chargés négativement).Given the definition of homopolymers and copolymers given above, in relation to the nature of the monomers that can enter their homopolymers and copolymers considered in the invention may consist of neutral, cationic (co) polymers or polyampholytes (these latter containing both positively charged monomers and negatively charged monomers).

Les polymères décrits dans l'invention peuvent être linéaires ou ramifiés. Leur masse peut varier de 3000 à plusieurs millions.The polymers described in the invention may be linear or branched. Their mass can vary from 3000 to several millions.

Dans le procédé de l'invention, les homo et copolymères tels que décrits ci-dessus peuvent être ajoutés dans le fluide à traiter seuls ou sous forme de mélanges de deux ou plusieurs d'entre eux. Lorsque plusieurs copolymères sont utilisés en mélange, il peut s'agir de copolymères qui différent entre eux par exemple par la nature des motifs d'au moins un type et/ou par une composition différente en au moins un motif et/ou par leur masse moléculaire.In the process of the invention, the homo and copolymers as described above can be added to the fluid to be treated alone or as mixtures of two or more of them. When several copolymers are used in a mixture, it may be copolymers which differ from each other for example by the nature of the patterns of at least one type and / or composition different in at least one pattern and / or by their molecular weight.

Les homo ou copolymères, ainsi que leurs mélanges en toutes proportions peuvent être ajoutés dans le fluide à traiter à des concentrations allant en général de 0,05 à 5% en masse, de préférence de 0,1 à 2% en masse, par rapport à l'eau.Homo or copolymers, as well as their mixtures in all proportions may be added to the fluid to be treated at concentrations generally ranging from 0.05 to 5% by weight, preferably 0.1 to 2% by weight, based on water.

Par ailleurs, les homo ou copolymères préconisés comme additifs dans l'invention peuvent être mélangés à un ou plusieurs alcools (monoalcools ou polyols) renfermant par exemple de 1 à 6 atomes de carbone, plus particulièrement le mono-, le di- ou le tri-éthylèneglycol, l'éthanol ou le méthanol, ce dernier étant l'alcool préféré. Cet alcool (ou ces alcools) est (sont) ajouté(s) en général en des proportions allant de 0,5 à 20% en masse, de préférence de 1 à 10% en masse, par rapport à l'eau présente dans le fluide à traiter. Le (ou les) homo ou copolymère(s) considérés dans l'invention peuvent être alors préalablement dissous en milieu hydro-alcoolique et ensuite ajoutés au milieu à traiter, de façon à obtenir des concentrations finales en homo ou copolymères allant en général de 0,05 à 3% en masse, de préférence de 0,1 à 1% en masse par rapport à l'eau présente dans le fluide à traiter.Moreover, the homo or copolymers recommended as additives in the invention may be mixed with one or more alcohols (monoalcohols or polyols) containing for example from 1 to 6 carbon atoms, more particularly the mono-, the di- or tri-ethylene glycol, ethanol or methanol, the latter being the preferred alcohol. This alcohol (or these alcohols) is (are) added in general in proportions ranging from 0.5 to 20% by weight, preferably 1 to 10% by weight, relative to the water present in the fluid to be treated. The homo or copolymer (s) considered in the invention can then be dissolved beforehand in a hydro-alcoholic medium and then added in the medium to be treated, so as to obtain final concentrations of homo or copolymers generally ranging from 0.05 to 3% by weight, preferably from 0.1 to 1% by weight. mass with respect to the water present in the fluid to be treated.

La présence dans le milieu d'additif(s) cinétique(s) tels que les polymères préconisés dans l'invention et d'alcool(s) tels que par exemple le méthanol, permet, par leurs actions conjuguées, d'obtenir des retards à la formation des hydrates extrêmement satisfaisants et ce, d'une part, en diminuant les quantités d'additifs utilisés (alcool et polymères) et, d'autre part, - et surtout - en permettant d'opérer dans une gamme de températures beaucoup plus basses.The presence in the medium of kinetic additive (s) such as polymers in the invention and alcohol (s) such as for example methanol, allows, by their combined actions, to obtain delays in the formation of hydrates extremely satisfying, on the one hand, by reducing the quantities of additives used (alcohol and polymers) and, on the other hand, - and above all - by making it possible to operate in a much lower temperature range.

Les homo ou copolymères hydrosolubles considérés dans l'invention peuvent être utilisés soit en milieu eau pure, par exemple dans de l'eau de condensation, soit en milieu salin, par exemple dans de l'eau de production.The water-soluble homo or copolymers considered in the invention can be used either in pure water medium, for example in water of condensation, or in saline medium, for example in production water.

L'invention sera mieux comprise à la lecture des expérimentations suivantes, nullement limitatives. Les exemples 4 à 9 sont donnés à titre comparatif et ne font pas partie de l'invention.The invention will be better understood on reading the following experiments, in no way limiting. Examples 4 to 9 are given for comparative purposes and do not part of the invention.

Exemple 1Example 1

La procédure expérimentale de sélection des additifs est menée sur des hydrates de tétrahydrofuranne (THF). Une solution eau pure/THF (80/20 en masse) forme des hydrates sous pression atmosphérique à 4°C (voir : "Kinetic Inhibitors of Natural Gas Hydrates", Sloan, E.D. et al.; 1994).The experimental procedure for the selection of additives is carried out on hydrates of tetrahydrofuran (THF). A solution of pure water / THF (80/20 by weight) forms hydrates at atmospheric pressure at 4 ° C (see: "Kinetic Inhibitors of Natural Gas Hydrates ", Sloan, E.D. et al., 1994).

Le dispositif utilisé est constitué de tubes de diamètre 16 mm, dans lesquels sont introduits 8 ml d'une solution aqueuse à 20% en masse de THF contenant éventuellement l'additif à tester. On introduit dans chaque tube une bille en verre d'un diamètre de 8 mm, afin d'assurer un brassage correct de la solution. Les tubes sont placés sur un agitateur rotatif, qui tourne à 20 tours/min.. Ce dernier est placé dans une enceinte réfrigérée à 2°C.The device used consists of 16 mm diameter tubes, in which are 8 ml of a 20% by weight aqueous solution of THF containing optionally the additive to be tested. Each tube is filled with a glass ball of one diameter of 8 mm, to ensure proper mixing of the solution. The tubes are placed on a rotary shaker, which rotates at 20 rpm. The latter is placed in a refrigerated chamber at 2 ° C.

Le principe de ce test est de déterminer le temps de latence précédant la formation des hydrates. Ce temps de latence correspond à l'intervalle mesuré entre le moment où les tubes sont introduits dans l'enceinte réfrigérée et le moment où on observe la formation des hydrates (apparition d'un trouble).The principle of this test is to determine the lag time before the training hydrates. This latency corresponds to the interval measured between the moment when the tubes are introduced into the refrigerated chamber and the moment when the hydrate formation (appearance of a disorder).

Chaque série de tests est menée en présence d'un mélange de référence ne contenant pas d'additif, et les temps de latence fournis pour un additif correspondent à une moyenne des temps mesurés sur 16 essais.Each series of tests is conducted in the presence of a reference mixture not containing no additive, and the lag times provided for an additive correspond to an average of the times measured over 16 tests.

Dans les conditions opératoires décrites ci-dessus, les solutions eau pure/THF ont un temps de latence moyen de 35 minutes.Under the operating conditions described above, the solutions of pure water / THF have an average latency of 35 minutes.

Dans les conditions opératoires mises en oeuvre, l'addition de 0,5% en masse d'un copolymère contenant 10% en mole de motifs diméthyl-amino-éthyl méthacrylate (MADAME) et 90% en mole de motifs acrylamide (AA) multiplie le temps de latence par approximativement 4,5, l'addition de 0,5% en masse d'un poly(chlorure de méthacrylate-éthyl-triméthyl ammonium) (MAC) conduit quant à lui à un temps d'induction qui est en moyenne plus de 7 fois supérieur à celui de l'eau pure. L'addition de 0,3% en masse d'un copolymère contenant 55% en mole de motifs acrylamide (AA) et 45% en mole de motifs chlorure de diallyl-diméthyl ammonium (DADMAC) permet de multiplier par plus 5 le temps de latence.Under the operating conditions used, the addition of 0.5% by weight of a copolymer containing 10 mol% of dimethylaminoethyl methacrylate units (MADAME) and 90% in mole of acrylamide units (AA) multiplies the latency by approximately 4.5, the addition of 0.5% by weight of a poly (chlorine methacrylate-ethyl-trimethylammonium) (MAC) leads to a of induction which is on average more than 7 times higher than that of pure water. The bill 0.3% by weight of a copolymer containing 55% by mole of acrylamide (AA) units and 45 mol% of diallyl dimethyl ammonium chloride units (DADMAC) to multiply the latency by plus 5.

Enfin, l'addition de 0,5% en masse de poly(méthosulfate d'acrylate-éthyl-triméthyl ammonium) ou l'addition de 0,3% en masse d'un copolymère contenant 50% en mole de motifs de N-vinyl-2-pyrrolidone (NVP) et 50% en mole de motifs chlorure de méthacrylate-éthyl-triméthyl ammonium (MAC) ou encore d'un copolymère contenant 32% en mole de motifs [3-(2-acrylamido-2-méthyl-propyl-diméthyl-ammonio)-1-propane sulfonate] (AMPDAPS) et 68% en mole de motifs acrylamide (AA) inhibe la formation des hydrates de THF pendant une période supérieure à 6 heures.Finally, the addition of 0.5% by weight of poly (acrylate-ethyl-trimethyl methosulphate) ammonium) or the addition of 0.3% by weight of a copolymer containing 50% in mole of N-vinyl-2-pyrrolidone (NVP) units and 50 mol% of chloride units of methacrylate-ethyl-trimethylammonium (MAC) or a copolymer containing 32% by mole of [3- (2-acrylamido-2-methyl-propyl-dimethyl-ammonio) -1-propane sulfonate] (AMPDAPS) and 68 mol% of acrylamide units (AA) inhibits the formation of THF hydrates for a period greater than 6 hours.

De même, l'addition d'un mélange de type DADMAC + AA/MADAME (70/30 en moles) dans un rapport 60/40 en masse, à une concentration de 0,3% en masse par rapport à l'eau inhibe également la formation des hydrates de THF pendant une période supérieure à 6 heures. Similarly, the addition of a mixture of DADMAC + AA / MADAME type (70/30 in moles) in a 60/40 ratio by mass, at a concentration of 0.3% by weight compared to water also inhibits the formation of THF hydrates during a period greater than 6 hours.

Exemple 2Example 2

La procédure expérimentale de l'exemple 1 est répétée en remplaçant l'eau pure par un mélange eau pure + 5% de méthanol en masse et en abaissant la température de l'enceinte réfrigérée à -1°C.The experimental procedure of Example 1 is repeated replacing pure water with a mixture of pure water and 5% of methanol by mass and lowering the temperature of the refrigerated chamber at -1 ° C.

Dans ces conditions, le temps de latence moyen des solutions eau pure + 5% de méthanol/THF en l'absence d'additif est de 29 minutes.Under these conditions, the average latency of pure water solutions + 5% methanol / THF in the absence of additive is 29 minutes.

L'addition de 0,15% en masse par rapport à l'eau, d'un copolymère contenant 50% en mole de motifs diméthyl-amino-éthyl acrylate (ADAME) et 50% en mole de motifs acide acrylique (Ac Acrylique) dans le milieu eau + 5% de méthanol multiplie le temps de latence par plus de 5.The addition of 0.15% by weight, with respect to the water, of a copolymer containing 50 mol% of dimethylaminoethyl acrylate (ADAME) units and 50 mol% of acrylic acid (Ac Acrylic) units in the water medium + 5% methanol multiplies the latency by more than 5.

Exemple 3Example 3

La procédure expérimentale de l'exemple 1 est répétée en remplaçant l'eau pure par une solution de NaCl 3,5% en masse, la température de l'enceinte réfrigérée est abaissée à 0°C. Dans ces conditions, le temps de latence moyen des solutions NaCl/THF en l'absence d'additif est de 42 minutes.The experimental procedure of Example 1 is repeated replacing pure water With a solution of NaCl 3.5% by weight, the temperature of the refrigerated chamber is lowered to 0 ° C. Under these conditions, the average latency of the solutions NaCl / THF in the absence of additive is 42 minutes.

L'addition de 0,5% en masse d'un poly(chlorure de diallyl-diméthyl ammonium) (DADMAC) permet de multiplier par environ 5 le temps de latence. L'addition de 0,5% en masse d'un poly[3-(2-acrylamido-2-méthyl-propyl-diméthyl-ammonio)-1-propane sulfonate] (AMPDAPS) permet de multiplier par environ 6 le temps de latence. Enfin, l'addition de 0,5% en masse d'un terpolymère contenant 50% en mole de motifs acrylamide (AA), 35% de mole de motifs chlorure de méthacrylamido-N-propyl-triméthyl ammonium (MAPTAC) et 15% de mole de motifs acrylate de sodium conduit à un temps de latence moyen plus de 7 fois supérieur à celui obtenu sans additif.The addition of 0.5% by weight of a poly (diallyl dimethyl ammonium chloride) (DADMAC) allows you to multiply the latency by about 5. The addition of 0.5% by weight of a poly [3- (2-acrylamido-2-methyl-propyl-dimethyl-ammonio) -1-propane sulfonate] (AMPDAPS) allows to multiply by about 6 the time of latency. Finally, the addition of 0.5% by weight of a terpolymer containing 50 mol% of acrylamide (AA) units, 35% of moles of methacrylamido-N-propyl-trimethyl chloride units ammonium (MAPTAC) and 15% mole of sodium acrylate units leads to an average latency more than 7 times higher than that obtained without additive.

L'addition de 0,3% en masse d'un terpolymère contenant 60% en mole de motifs de type acrylamide, 25% en mole de motifs acrylamido-méthyl-propane sulfonate (AMPS) et 15% en mole de motifs chlorure de méthacrylamido-N-propyl-triméthyl ammonium (MAPTAC) ou de 0,3% en masse d'un copolymère NVP/AMPDAPS (60/40 en moles) inhibent la formation des hydrates de THF pendant une période supérieure à 6 heures.The addition of 0.3% by weight of a terpolymer containing 60 mol% of acrylamide type units, 25 mol% of acrylamido-methyl-propane units sulfonate (AMPS) and 15 mol% of methacrylamido-N-propyl-trimethyl chloride units ammonium (MAPTAC) or 0.3% by weight of a copolymer NVP / AMPDAPS (60/40 mol) inhibit the formation of THF hydrates during a period longer than 6 hours.

Exemples 4, 5, 6, 7, 8 et 9 (comparatifs)Examples 4, 5, 6, 7, 8 and 9 (comparative)

Différents additifs sortant du cadre de l'invention ont été testés à titre de comparaison dans les conditions précédemment décrites (exemples 1, 2 et 3) :

  • Ex. 4 : Polyvinylpyrrolidone (poids moléculaire 10 000 ; 0,5% en masse)
  • Ex. 5 : Polyacrylamide (0,5% en masse)
  • Ex. 6 : Copolymère acrylamide/acrylate de sodium (0,5% en masse)
  • Ex. 7 : Chlorure de tétrabutyl ammonium (0,5% en masse)
  • Ex. 8 : HE-300 (terpolymère N-vinyl-2-pyrrolidone / acrylamido-méthyl-propane-sulfonate / acrylamide : 0,3% en masse)
  • Ex. 9 : GAFFIX VC - 713 (N - vinyl - 2 - pyrrolidone / N-vinyl-ε-caprolactame /diméthylaminoéthyl méthacrylate ; 0,3% en masse)
    • Various additives outside the scope of the invention were tested for comparison under the conditions previously described (Examples 1, 2 and 3):
  • Ex. 4: Polyvinylpyrrolidone (molecular weight 10,000, 0.5% by weight)
  • Ex. 5: Polyacrylamide (0.5% by weight)
  • Ex. 6: Acrylamide / sodium acrylate copolymer (0.5% by weight)
  • Ex. 7: Tetrabutyl ammonium chloride (0.5% by weight)
  • Ex. 8 : HE-300 (terpolymer N-vinyl-2-pyrrolidone / acrylamido-methyl-propane-sulfonate / acrylamide: 0.3% by weight)
  • Ex. 9: GAFFIX VC-713 (N-vinyl-2-pyrrolidone / N-vinyl-ε-caprolactam / dimethylaminoethyl methacrylate, 0.3% by weight)

    • Dans les conditions de tests mises en oeuvre, ces additifs présentent des temps d'induction précédant la formation des hydrates nettement plus courts que les substances mentionnées dans l'invention, comme le montrent les résultats rassemblés dans le tableau ci-dessous. Additif (% molaire des motifs) Concentration (% en masse) Conditions opératoires Temps de latence (min) Ex. 1 : - sans additif / eau pure/THF à 2°C 35 - MADAME/AA (10/90) 0,5 " " 155 - MAC 0,5 " " 270 - ADQUAT 0,5 " " >360 - DADMAC/AA (45/55) 0,3 " " 180 - PVP/MAC (50/50) 0,3 " " >360 - AMPDAPS/AA (32/68) 0,3 " " >360 - DADMAC + AA/MADAME (70/30)
    [40/60 en masse]     0,3 " " >360     Ex. 2 : - sans additif / eau + 5% MeOH/THF à -1°C 29 - ADAME/ Ac. Acrylique (50/50) 0,15 " " 148 Ex.3 : - sans additif / NaCl 3,5%/THF à 0°C 42 - DADMAC 0,5 " " 220 - AMPDAPS 0,5 " " 248 - MAPTAC/AA/Ac.acrylique (50/35/15) 0,5 " " 302 - AA/AMPS/MAPTAC (60/25/15) 0,5 NaCl 3,5%/THF à 0°C >360 - PVP/AMPDAPS (60/40) 0,3 NaCl 3,5%/THF à 0°C >360 Ex. 4 : 0,5 eau pure/THF à 2°C 45 Ex. 5 : 0,5 " " 100 Ex. 6 : 0,5 " " 71 Ex. 7 : 0,5 " " 48 Ex. 8 : 0,3 " " 150 Ex. 9 : 0,3 NaCl 3,5%/THF à 0°C 204     Under the test conditions used, these additives have induction times preceding the formation of hydrates significantly shorter than the substances mentioned in the invention, as shown by the results summarized in the table below. Additive (% molar of the patterns) Concentration (% by mass) Operating conditions Latency time (min) Ex. 1: - additives free / pure water / THF at 2 ° C 35 - MADAME / AA (10/90) 0.5 "" 155 - MAC 0.5 "" 270 - ADQUAT 0.5 "" > 360 - DADMAC / AA (45/55) 0.3 "" 180 - PVP / MAC (50/50) 0.3 "" > 360 - AMPDAPS / AA (32/68) 0.3 "" > 360 - DADMAC + AA / MADAME (70/30)
    [40/60 en masse]     0.3 "" > 360     Ex. 2: - additives free / water + 5% MeOH / THF at -1 ° C 29 - ADAME / Ac. Acrylic (50/50) 0.15 "" 148 Ex.3: - additives free / 3.5% NaCl / THF at 0 ° C 42 - DADMAC 0.5 "" 220 - AMPDAPS 0.5 "" 248 - MAPTAC / AA / Acrylic Acid (50/35/15) 0.5 "" 302 - AA / AMPS / MAPTAC (60/25/15) 0.5 3.5% NaCl / THF at 0 ° C > 360 - PVP / AMPDAPS (60/40) 0.3 3.5% NaCl / THF at 0 ° C > 360 Ex. 4: 0.5 pure water / THF at 2 ° C 45 Ex. 5: 0.5 "" 100 Ex. 6: 0.5 "" 71 Ex. 7: 0.5 "" 48 Ex. 8: 0.3 "" 150 Ex. 9: 0.3 3.5% NaCl / THF at 0 ° C 204

    Exemple 10:Example 10

    Pour tester l'efficacité des produits utilisés dans le procédé de l'invention, en présence d'hydrates de méthane, on a procédé à des essais de formation d'hydrates à partir de gaz et d'eau, à l'aide de l'appareillage décrit ci-après.To test the effectiveness of the products used in the process of the invention, the presence of methane hydrates, hydrate formation tests were carried out at from gas and water, using the apparatus described below.

    L'appareillage comporte une boucle de 6 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 eau et additif initialement introduit. Le réacteur permet de mettre la boucle sous pression. Des tubes de diamètre analogue à ceux de la boucle assurent la circulation du fluide 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 si ils se sont formés.The apparatus includes a loop of 6 meters consisting of tubes of diameter 7.7 mm, a 2-liter reactor with an inlet and an outlet for gas, suction and discharge for the water and additive mixture initially introduced. The reactor makes it possible to put the loop under pressure. Diameter tubes analogous to those of the loop ensure the circulation of the fluid from the loop to the reactor, and conversely, via a gear pump placed between the two. A sapphire cell integrated in the circuit allows a visualization of the liquid in circulation and therefore hydrates if they formed.

    Pour déterminer l'efficacité des additifs selon l'invention, on introduit le fluide (eau et additif) dans le réacteur. L'installation est ensuite portée sous une pression de 7 MPa. La solution est homogénéisée par sa circulation dans la boucle et le réacteur, puis la boucle est isolée du réacteur. La pression est maintenue constante par apport de méthane, et on impose une diminution progressive de la température (0,5°C/min) de 17°C à 5°C, qui correspond à la température expérimentale choisie.In order to determine the effectiveness of the additives according to the invention, the fluid is introduced (water and additive) in the reactor. The installation is then brought under a pressure of 7 MPa. The solution is homogenized by its circulation in the loop and the reactor, then the loop is isolated from the reactor. The pressure is kept constant by adding methane, and a gradual reduction of the temperature (0.5 ° C / min) of 17 ° C to 5 ° C, which corresponds to the chosen experimental temperature.

    Le principe de ces essais est de déterminer, d'une part la température de formation des hydrates de méthane dans la boucle, et d'autre part le temps de latence précédant leur formation. Le temps de latence, correspond au temps mesuré entre le début du test (circulation du fluide à 17°C) et la détection de la formation des hydrates (exothermie, forte consommation en gaz). La durée des tests peut varier de quelques minutes à plusieurs heures : un additif performant inhibe la formation des hydrates, ou les maintient dispersés dans les fluides pendant plusieurs heures.The principle of these tests is to determine, on the one hand, the temperature of formation of methane hydrates in the loop, and secondly the lag time preceding their formation. The latency time corresponds to the measured time between beginning of the test (fluid circulation at 17 ° C) and detection of hydrate formation (exothermic, high gas consumption). The duration of the tests may vary from a few minutes to several hours: a powerful additive inhibits the formation of hydrates, or keeps them dispersed in fluids for several hours.

    En l'absence d'additif (milieu : eau désionisée), les hydrates de méthane se forment à une température voisine de 10,0°C et après un temps d'induction de 30 minutes. La formation des hydrates conduit à un blocage immédiat de la circulation du mélange fluide + hydrates dans la boucle. In the absence of additive (medium: deionized water), the methane hydrates are form at a temperature of 10.0 ° C. and after an induction time of 30.degree. minutes. The formation of hydrates leads to an immediate blockage of the circulation of the fluid + hydrate mixture in the loop.

    L'addition de 0,3% en poids du terpolymère AA/AMPS/MAPTAC (60/25/15) inhibe totalement la formation des hydrates de méthane dans les conditions de pression et de température imposées pour ce test même après 24 heures de circulation.The addition of 0.3% by weight of the AA / AMPS / MAPTAC terpolymer (60/25/15) completely inhibits the formation of methane hydrates under pressure conditions and temperature imposed for this test even after 24 hours of circulation.

    Claims (12)

    1. A process for inhibiting or retarding hydrate formation, growth and/or agglomeration in a fluid comprising water and a gas such as a natural gas, petroleum gas or other gas, under conditions in which hydrates can form (from the water and gas), characterized in that it comprises incorporating into the fluid at least one hydrosoluble homopolymer or copolymer derived from at least one nitrogen-containing monomer selected from:
      cationic monomers selected from:
      monomers [F], having general formula [6]:
      Figure 00350001
      where R' is a hydrogen atom or a methyl group, R" is selected from divalent groups -COO-, -CO-NH-, -CO-NH-CO-NH- or C6H4-, R1 is selected from the following divalent groups: -(CH2)n-, where 1 ≤ n ≤ 3, -C(CH3)2-, -C(CH3)2-(CH2)2- or CH2-CH(OH)CH2-, R2 is a hydrogen atom or a methyl, ethyl or isopropyl radical, R3 is a hydrogen atom or a methyl or ethyl radical, R6 is selected from methyl, ethyl or benzyl groups and X is a chloride ion or a CH3OSO3 - ion;
      monomers [G], having general formula [7]:
      Figure 00360001
      where R' is a hydrogen atom or a methyl group, R7 is a -C(CH3)2-CO-CH3 group, -CH2OH group; a methyl, ethyl or benzyl group, and X is a chloride ion or a CH3OSO3 - ion;
      and monomers [H], having general formula [8]: (CH2=CH-(CH2))2-N+-R5R6 X-   [8] where R5 is a CnH2n+1 alkyl chain, where 1 ≤ n ≤ 10, a hydroxy group or a (CH2)2-CO-NH2 group, R6 is selected from methyl, ethyl or benzyl groups and X is a chloride ion or a CH3OSO3 - ion;
      amphoteric monomers selected from:
      monomers [I], having general formula [9]:
      Figure 00370001
      where R', R8 and R9 are either hydrogen atoms or methyl groups, R10 is selected from the following divalent groups: -COO- or -CO-NH-, R11 and R12 are selected from the following divalent groups: -(CH2)n, where 1 ≤ n ≤ 3, -C(CH3)2- or - C(CH3)2-(CH2)2- and G- is a negatively charged carboxylate or sulphonate type group;
      monomers [J], having general formula [10]:
      Figure 00370002
      where R13 is a hydrogen atom or a methyl group, R14 is selected from the divalent groups -(CH2)n-, where 1 ≤ n ≤ 4, or -CH2-C6H4- and G- is a negatively charged carboxylate or sulphonate type group;
      and monomers [K], having general formula [11]:
      Figure 00380001
      where R' is a hydrogen atom or a methyl group, R15 is a divalent -(CH2)n type group, where 1 ≤ n ≤ 4, and G- is a negatively charged carboxylate or sulphonate type group.
      and neutral monomers selected from:
      monomers [A] containing at least one tertiary amine moiety and optionally at least one amide moiety on a side chain and having general formula [1]:
      Figure 00390001
      where R' is a hydrogen atom or a methyl group, R" is selected from divalent groups -COO-, -CO-NH-, -CO-NH-CO-NH- or C6H4-, R1 is selected from the following divalent groups: -(CH2)n-, where 1 ≤ n ≤ 3, -C(CH3)2-, -C(CH3)2-(CH2)2 and CH2-CH(OH)CH2-, R2 is a hydrogen atom or a methyl, ethyl or isopropyl radical, R3 is a hydrogen atom or a methyl or ethyl radical;
      monomers [B] having general formula [2]:
      Figure 00390002
      where R' is a hydrogen atom or a methyl group and R4 is a -C(CH3)2-CH2-CO-CH3 or CH2OH group;
      monomers [C] having general formula [3]:
      Figure 00400001
      where R' is a hydrogen atom or a methyl group;
      monomers [D] having general formula [4]:
      Figure 00400002
      where R' is a hydrogen atom or a methyl group;
      and monomers [E] having general formula [5]: (CH2=CH-(CH2))2-N-R5   [5] where R5 is a CnH2n+1 chain, where 1 ≤ n ≤ 10, or a hydroxy group or a (CH2)2-CO-NH2 group.
    2. A process according to claim 1 characterized in that at least one copolymer derived from at least one monomer selected from monomers [A] to [K] and at least one anionic monomer selected from monomers containing carboxylate or sulphonate groups is used.
    3. A process according to claim 2 characterized in that said anionic monomer is selected from acrylate, methacrylate, itaconate, 2-acrylamido-2-methyl-propane sulphonate, 2-methacryloyloxy ethane sulphonate, 3-acrylamido-3-methyl butanoate, styrene sulphonate, styrene carboxylate, vinyl sulphonate, maleic anhydride or maleic acid monomers.
    4. A process according to claim 1 characterized in that at least one copolymer derived from at least one monomer selected from monomers [A] to [K] and at least one neutral monomer selected from acrylamide, alkyl acrylamide or vinyl acetamide type monomers is used.
    5. A process according to any one of claims 1 to 4 characterized in that at least one copolymer derived from at least one monomer selected from monomers [C] to [K] and at least one N-vinyl lactame type monomer selected from N-vinyl-2-pyrrolidone, N-vinyl-δ-valerolactame and N-vinyl-ε-caprolactame, is used, in proportions of 1 mole % to 99 mole %.
    6. A process according to any one of claims 1 to 5 characterized in that said polymer has a molecular mass of 3000 to several million.
    7. A process according to any one of claims 1 to 6 characterized in that said polymer is added to the fluid to be treated at a concentration of 0.05% to 5% by weight with respect to the water.
    8. A process according to any one of claims 1 to 7 characterized in that said polymer is added to the fluid to be treated jointly with at least one alcohol containing 1 to 6 carbon atoms.
    9. A process according to claim 8 characterized in that said alcohol is selected from mono-, di- and tri-ethyleneglycol, ethanol and methanol.
    10. A process according to any one of claims 8 and 9 characterized in that said alcohol is added in a proportion of 0.5% to 20% by weight with respect to the water present in the fluid to be treated.
    11. A process according to any one of claims 1 to 10 characterized in that said polymer is first dissolved in a hydro-alcoholic medium then added to the medium to be treated to obtain a final polymer concentration of 0.05% to 3% by weight with respect to the water present in the fluid to be treated.
    12. A process according to any one of claims 1 to 11 characterized in that said hydrosoluble polymer is used in a pure water medium or in a saline medium.
    EP97401004A 1996-05-15 1997-05-05 Process for inhibiting or retarding the formation of hydrates in a production effluent Expired - Lifetime EP0807678B1 (en)

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