EP0807678A1 - 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 PDFInfo
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- EP0807678A1 EP0807678A1 EP97401004A EP97401004A EP0807678A1 EP 0807678 A1 EP0807678 A1 EP 0807678A1 EP 97401004 A EP97401004 A EP 97401004A EP 97401004 A EP97401004 A EP 97401004A EP 0807678 A1 EP0807678 A1 EP 0807678A1
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- 0 *C(c1ccccc1C=C)=C Chemical compound *C(c1ccccc1C=C)=C 0.000 description 2
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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 delaying the formation, growth or / and agglomeration of hydrates of natural gas, petroleum gas or other gases, by using at least one additive.
- the gases which form hydrates can in particular comprise at least one hydrocarbon chosen 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 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 d water, gas and possibly liquid hydrocarbons, such as oil, becomes lower than the thermodynamic temperature of hydrate formation, this temperature being given for a known composition of gases and when their pressure is fixed.
- Hydrate formation can be feared, especially in the oil and gas industry, for which hydrate formation conditions can be met. Indeed, to reduce the cost of producing crude oil and gas, both from the point of view of investments and from the point of view of exploitation, one way envisaged, in particular in production at sea, is to reduce, even remove, the treatments applied to the crude oil or to 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 deposit, so that the effluent, initially hot, can be treated before the thermodynamic conditions for hydrate formation are reached due to the effluent cooling with seawater.
- hydrate plugs can cause production to stop and thus cause significant financial losses.
- the return to service of the installation especially if it is a question 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 to the formation of hydrates can also be met in the same way on the ground, for pipes which are not (or not deep enough) buried in the ground, when for example the temperature of the ambient air is cold.
- patent application EP-A-323774 in the name of the applicant, which describes the use of nonionic amphiphilic compounds chosen from polyol esters of substituted or unsubstituted carboxylic acids , and the imide functional compounds
- 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 derivatives of fatty acids
- US-A-4956593 which describes the use of surfactant compounds such as organic phosphonates, esters phosphates, phosphonic acids, their salts and esters, inorganic polyphosphates and their esters, as well as homopolyacrylamides and copolymers-acrylamide-acrylates
- patent application EP-A-457375 which describes the use of anionic surfactants, such as alkylarylsulfonic acids and their alkali metal salts.
- Amphiphilic compounds obtained by reaction of at least one succinic derivative chosen from the group formed by polyalkenylsuccinic acids and anhydrides on at least one polyethylene glycol monoether have also been proposed to reduce the tendency for agglomeration of natural gas hydrates, petroleum gas or other gases (patent application EP-A-582507).
- International application WO-A-9519408 more generally describes the use of aliphatic polymers containing carbonylated N-heterocycles in complex formulations.
- international applications WO-A-9517579 and WO-A-9604462 describe the use of ammonium, sulfonium and phosphonium derivatives alkylated either alone or mixed with a corrosion inhibitor.
- water-soluble polymers which may be neutral or positively charged homopolymers or copolymers, or else polyampholytes and which derive from one or more nitrogenous monomers, allow, at low concentrations, to inhibit or retard the formation, growth and / or agglomeration of hydrates of natural gas, petroleum gas or other gases, with an efficiency clearly superior to the compounds described above.
- neutral monomers illustrating these formulas mention may be made of dimethyl-amino-ethyl acrylate and of dimethyl-amino-ethyl methacrylate.
- cationic monomers mention may be made of methacrylate-ethyl-trimethyl ammonium chloride, methacrylamido-N-propyltrimethyl ammonium chloride and diallyl-dimethyl ammonium chloride.
- amphoteric monomers mention may be made of ethyl trimethyl ammonium acrylate methosulfonate.
- the cationic monomers, the amphoteric monomers and the neutral monomers from [A] to [E] defined in the preceding description may be included in the homopolymers or copolymers, in any proportions, that is to say ranging, for each, from 0 to 100 mol%.
- the invention also proposes the use as additives, of copolymers resulting from the combination of at least one of the monomers described above (cationic monomer, amphoteric monomer and / or neutral monomer from [A] to [E]) , with at least one 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 sulfonate groups and more precisely acrylate, methacrylate, itaconate, 2-acrylamido-2-methyl-propane sulfonate, 2-methacryloyloxy ethane sulfonate, 3-acrylamido-3 monomers. -methyl butanoate, styrene sulfonate, styrene carboxylate, vinyl sulfonate, maleic anhydride or maleic acid.
- the proportions of cationic monomers, amphoteric monomers, neutral monomers from [A] to [E], anionic monomers and / or additional neutral monomers can vary, for each of the monomers, for example from 1 to 99%, more particularly from 10 to 70% by moles.
- the cationic monomers, the amphoteric monomers and the neutral monomers from [C] to [E] described above can also be combined with one or more other neutral nitrogenous monomers of the N-vinyl lactam type, in particular N-vinyl-2. -pyrrolidone, N-vinyl- ⁇ -valerolactam and N-vinyl- ⁇ -caprolactam.
- the proportions of cationic monomers, amphoteric monomers, neutral monomers from [C] to [E] and additional neutral monomers can vary, for each of the monomers, for example from 1 to 99%, and more particularly from 10 to 70% by moles.
- the homopolymers and copolymers considered in the invention may consist of neutral, cationic (co) polymers or into polyampholytes (the latter containing both positively charged monomers and negatively charged monomers).
- the polymers described in the invention can be linear or branched. Their mass can vary from 3000 to several million.
- the homo and copolymers as described above can be added to the fluid to be treated alone or in the form of mixtures of two or more of them.
- copolymers may be copolymers which differ from one another, for example by the nature of the units of at least one type and / or by a different composition in at least one unit and / or by their mass molecular.
- the homo or copolymers, as well as their mixtures in all proportions, can be added to the fluid to be treated at concentrations generally ranging from 0.05 to 5% by mass, preferably from 0.1 to 2% by mass, relative at the water.
- the homo or copolymers recommended as additives in the invention can be mixed with one or more alcohols (monoalcohols or polyols) containing, for example, from 1 to 6 carbon atoms, more particularly mono-, di- or tri -ethylene glycol, ethanol or methanol, the latter being the preferred alcohol.
- This alcohol or these alcohols) is (are) added (s) in general in proportions ranging from 0.5 to 20% by mass, preferably from 1 to 10% by mass, relative to the water present in the fluid to be treated.
- the homo (s) or copolymer (s) considered in the invention can then be dissolved beforehand in a hydro-alcoholic medium and then added to the medium to be treated, so as to obtain final concentrations of homo or copolymers generally ranging from 0.05 to 3% by mass, preferably from 0.1 to 1% by mass relative to the water present in the fluid to be treated.
- the water-soluble homopolymers or copolymers considered in the invention can be used either in pure water medium, for example in condensing water, or in saline medium, for example in production water.
- the device used consists of tubes with a diameter of 16 mm, into which are introduced 8 ml of an aqueous solution at 20% by mass of THF optionally containing the additive to be tested. A glass ball with a diameter of 8 mm is introduced into each tube, in order to ensure correct mixing of the solution.
- the tubes are placed on a rotary agitator, which rotates at 20 rpm. The latter is placed in a refrigerated enclosure at 2 ° C.
- This latency time corresponds to the interval measured between the moment when the tubes are introduced into the refrigerated enclosure and the moment when the formation of hydrates is observed (appearance of a cloudiness).
- Each series of tests is carried out in the presence of a reference mixture containing no additive, and the latency times provided for an additive correspond to an average of the times measured over 16 tests.
- the pure water / THF solutions have an average latency time of 35 minutes.
- Example 1 The experimental procedure of Example 1 is repeated, replacing the pure water with a mixture of pure water + 5% methanol by mass and lowering the temperature of the refrigerated enclosure to -1 ° C.
- the average latency time of pure water solutions + 5% methanol / THF in the absence of an additive is 29 minutes.
- Example 1 The experimental procedure of Example 1 is repeated, replacing the pure water with a 3.5% by mass NaCl solution. the temperature of the refrigerated chamber is lowered to 0 ° C. Under these conditions, the average latency time of the NaCl / THF solutions 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% by mole of acrylamide-type units, 25% by mole of acrylamido-methyl-propane sulfonate units (AMPS) and 15% by mole of methacrylamido chloride units -N-propyltrimethyl ammonium (MAPTAC) or 0.3% by mass of a PVP / AMPDAPS copolymer (60/40 in moles) inhibit the formation of THF hydrates for a period greater than 6 hours.
- the apparatus comprises a 6-meter loop made up of tubes with an 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 water and additive mixture initially introduced. .
- the reactor puts the loop under pressure. Tubes of diameter similar to those of the loop ensure the circulation of the fluid from the loop to the reactor, and vice versa, by means of a gear pump placed between the two.
- a sapphire cell integrated into the circuit allows visualization of the circulating liquid and therefore of the hydrates if they have formed.
- the fluid water and additive
- 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 decrease in temperature (0.5 ° C / min) from 17 ° C to 5 ° C is imposed, 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 on the other hand the lag time preceding their formation.
- the latency time corresponds to the time measured between the start of the test (circulation of the fluid at 17 ° C) and the detection of the formation of hydrates (exotherm, high gas consumption).
- the duration of the tests can vary from a few minutes to several hours: a high-performance additive inhibits the formation of hydrates, or keeps them dispersed in the fluids for several hours.
- methane hydrates are formed at a temperature in the region of 10.0 ° C and after an induction time of 30 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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- 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)
Abstract
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 delaying the formation, growth or / and agglomeration of hydrates of natural gas, petroleum gas or other gases, by using at least one additive. The gases which form hydrates can in particular comprise at least one hydrocarbon chosen 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 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 d water, gas and possibly liquid hydrocarbons, such as oil, becomes lower than the thermodynamic temperature of hydrate formation, this temperature being given for a known composition of gases 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.Hydrate formation can be feared, especially in the oil and gas industry, for which hydrate formation conditions can be met. Indeed, to reduce the cost of producing crude oil and gas, both from the point of view of investments and from the point of view of exploitation, one way envisaged, in particular in production at sea, is to reduce, even remove, the treatments applied to the crude oil or to 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 deposit, so that the effluent, initially hot, can be treated before the thermodynamic conditions for hydrate formation are reached due to the effluent cooling 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 practically happens, when the thermodynamic conditions required to form hydrates are met, the agglomeration of hydrates causes the transport pipes to be blocked by creating plugs which 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'agît 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 plugs can cause production to stop and thus cause significant financial losses. In addition, the return to service of the installation, especially if it is a question of production or transport at sea, can be long, because the decomposition of the hydrates formed is very difficult to achieve. When the production of an underwater deposit of natural gas or oil and gas comprising 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 so that hydrates form, agglomerate and block the transfer pipes. 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 to the formation of hydrates can also be met in the same way on the ground, for pipes which are not (or not deep enough) buried in the ground, 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, attempts have been made in the prior art to use products which, added to the fluid, could act as inhibitors by lowering the thermodynamic temperature for the formation of hydrates. These are in particular 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 be added 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 recommended to insulate the transport lines, 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.
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 hydrate formation mechanism has also been described, since, instead of rapidly agglomerating each other and forming plugs, the hydrates formed disperse in the fluid without agglomerate and without obstructing the pipes. Mention may be made in this regard: patent application EP-A-323774 in the name of the applicant, which describes the use of nonionic amphiphilic compounds chosen from polyol esters of substituted or unsubstituted carboxylic acids , and the imide functional compounds; 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 derivatives of fatty acids; US-A-4956593 which describes the use of surfactant compounds such as organic phosphonates, esters phosphates, phosphonic acids, their salts and esters, inorganic polyphosphates and their esters, as well as homopolyacrylamides and copolymers-acrylamide-acrylates; and patent application EP-A-457375, which describes the use of anionic surfactants, 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 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 succinic derivative chosen from the group formed by polyalkenylsuccinic acids and anhydrides on at least one polyethylene glycol monoether have also been proposed to reduce the tendency for agglomeration of natural gas hydrates, petroleum gas or other gases (patent application 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.Furthermore, the use of additives capable of inhibiting or delaying the formation and / or growth of hydrates has also been recommended. In this regard, mention may be made of patent application EP-A-536950, which describes the use of tyrosine derivatives, international application WO-A-9325798, which describes the use of homopolymer and copolymer compounds of N- vinyl-2-pyrrolidone and their mixtures, international application WO-A-9412761 and patent US-A-5432292 which describe the use of poly (N-vinyl-2-pyrrolidone), hydroxyethyl cellulose and mixtures thereof or of 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 more generally describes the use of aliphatic polymers containing carbonylated N-heterocycles in complex formulations. The same applies to international application WO-A-9532356, which describes in particular the use of terpolymer based on N-vinyl-2-pyrrolidone, of acrylamide methyl propane sulfonate and of acrylamide. Finally, international applications WO-A-9517579 and WO-A-9604462 describe the use of ammonium, sulfonium and phosphonium derivatives alkylated either alone or 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 which may be neutral or positively charged homopolymers or copolymers, or else polyampholytes and which derive from one or more nitrogenous monomers, allow, at low concentrations, to inhibit or retard the formation, growth and / or agglomeration of hydrates of natural gas, petroleum gas or other gases, with an efficiency clearly superior to the compounds described above.
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 cationiques (ou chargés positivement), les monomères amphotères (c'est-à-dire comportant à la fois une charge positive et une charge négative) et les monomères neutres choisis parmi :
- les monomères [A] possédant au moins une fonction amine tertiaire et éventuellement au moins une foncion amide sur une chaîne latérale et répondant à la formule générale [1] :
- les monomères [B] possédant au moins une fonction amide sur une chaîne latérale et répondant à la formule générale [2] :
- les monomères [C] possédant un radical azoté aromatique pendant et répondant à la formule générale [3] :
- les monomères [D] possédant une fonction succinimide sur une chaîne latérale et répondant à la formule générale [4] :
- et les monomères [E], répondant à la formule générale [5] :
(CH2=CH-(CH2))2-N-R5 [5]
dans laquelle, R5 est une chaîne alkyle CnH2n+1, avec 1 ≤ n ≤ 10, ou un groupement hydroxyle ou un groupement -(CH2)2-CO-NH2.
- the monomers [A] having at least one tertiary amine function and optionally at least one amide function on a side chain and corresponding to the general formula [1]:
- the monomers [B] having at least one amide function on a side chain and corresponding to the general formula [2]:
- the monomers [C] having a pendant aromatic nitrogen radical and corresponding to the general formula [3]:
- the monomers [D] having a succinimide function on a side chain and corresponding to the general formula [4]:
- and the monomers [E], corresponding to the general formula [5]:
(CH 2 = CH- (CH 2 )) 2 -NR 5 [5]
in which, R 5 is an alkyl chain C n H 2n + 1 , with 1 ≤ n ≤ 10, or a hydroxyl group or a group - (CH 2 ) 2 -CO-NH 2 .
Comme exemples de monomères neutres illustrant ces formules, on peut citer le diméthyl-amino-éthyl acrylate et le diméthyl-amino-éthyl méthacrylate.As examples of neutral monomers illustrating these formulas, mention may be made of dimethyl-amino-ethyl acrylate and of dimethyl-amino-ethyl 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] :
- les monomères [G], à la formule générale [7] :
- et les monomères [H], à la formule générale [8] :
(CH2=CH-(CH2))2-N+-R5R6 X- [8]
dans laquelle, R5 est une chaîne 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 monomers [F], to the general formula [6]:
- the monomers [G], to the general formula [7]:
- and the monomers [H], to the general formula [8]:
(CH 2 = CH- (CH 2 )) 2 -N + -R 5 R 6 X - [8]
in which, R 5 is an alkyl chain C n H 2n + 1 , with 1 ≤ n ≤ 10, a hydroxyl group or a group (CH 2 ) 2 -CO-NH 2 , 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-propyltriméthyl ammonium et le chlorure de diallyl-diméthyl ammonium.As examples of cationic monomers, mention may be made of methacrylate-ethyl-trimethyl ammonium chloride, methacrylamido-N-propyltrimethyl ammonium chloride 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] :
- les monomères [J], à la formule générale [10] :
- et les monomères [K], à la formule générale [11] :
- the monomers [I], to the general formula [9]:
- the monomers [J], to the general formula [10]:
- and the monomers [K], to the general formula [11]:
Comme exemple de monomères amphotères, on peut citer le méthosulfonate d'acrylate d'éthyl-triméthyl ammoniumAs an example of amphoteric monomers, mention may be made of ethyl trimethyl ammonium acrylate methosulfonate.
Les monomères cationiques, les monomères amphotères et les monomères neutres de [A] à [E] 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.The cationic monomers, the amphoteric monomers and the neutral monomers from [A] to [E] defined in the preceding description may be included in the homopolymers or copolymers, in any 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 [E]), 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 as additives, of copolymers resulting from the combination of at least one of the monomers described above (cationic monomer, amphoteric monomer and / or neutral monomer from [A] to [E]) , with at least one 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 sulfonate groups and more precisely acrylate, methacrylate, itaconate, 2-acrylamido-2-methyl-propane sulfonate, 2-methacryloyloxy ethane sulfonate, 3-acrylamido-3 monomers. -methyl butanoate, styrene sulfonate, styrene carboxylate, vinyl sulfonate, maleic anhydride or maleic acid.
Peuvent être associés aux monomères cationiques, aux monomères amphotères et/ou aux monomères neutres de [A] à [E] décrits ci dessus, également un ou plusieurs autres monomères azotés neutres tels que des monomères de type acrylamide, alkyl acrylamide ou vinyl acétamide.Can be associated with cationic monomers, amphoteric monomers and / or neutral monomers from [A] to [E] described above, also one or more other neutral nitrogenous monomers such as monomers of the acrylamide, alkyl acrylamide or vinyl acetamide type.
Dans ces copolymères, les proportions en monomères cationiques, en monomères amphotères, en monomères neutres de [A] à [E], 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, amphoteric monomers, neutral monomers from [A] to [E], anionic monomers and / or additional neutral monomers can vary, for each of the monomers, for example from 1 to 99%, more particularly from 10 to 70% by moles.
Les monomères cationiques, les monomères amphotères et les monomères neutres de [C] à [E] 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.The cationic monomers, the amphoteric monomers and the neutral monomers from [C] to [E] described above can also be combined with one or more other neutral nitrogenous monomers of the N-vinyl lactam type, 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 [E] 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, amphoteric monomers, neutral monomers from [C] to [E] and additional neutral monomers can vary, for each of the monomers, for example from 1 to 99%, and more particularly from 10 to 70% by moles.
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 which can enter into their constitution, the homopolymers and copolymers considered in the invention may consist of neutral, cationic (co) polymers or into polyampholytes (the 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 can be linear or branched. Their mass can vary from 3000 to several million.
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 in the form of mixtures of two or more of them. When several copolymers are used in admixture, they may be copolymers which differ from one another, for example by the nature of the units of at least one type and / or by a different composition in at least one unit and / or by their mass molecular.
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.The homo or copolymers, as well as their mixtures in all proportions, can be added to the fluid to be treated at concentrations generally ranging from 0.05 to 5% by mass, preferably from 0.1 to 2% by mass, relative at the 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.Furthermore, the homo or copolymers recommended as additives in the invention can be mixed with one or more alcohols (monoalcohols or polyols) containing, for example, from 1 to 6 carbon atoms, more particularly mono-, di- or tri -ethylene glycol, ethanol or methanol, the latter being the preferred alcohol. This alcohol (or these alcohols) is (are) added (s) in general in proportions ranging from 0.5 to 20% by mass, preferably from 1 to 10% by mass, relative to the water present in the fluid to be treated. The homo (s) or copolymer (s) considered in the invention can then be dissolved beforehand in a hydro-alcoholic medium and then added to the medium to be treated, so as to obtain final concentrations of homo or copolymers generally ranging from 0.05 to 3% by mass, preferably from 0.1 to 1% by mass relative 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 the polymers recommended in the invention and of alcohol (s) such as for example methanol, makes it possible, by their combined actions, to obtain delays on the formation of extremely satisfactory hydrates, 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 range of temperatures much lower.
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 homopolymers or copolymers considered in the invention can be used either in pure water medium, for example in condensing water, 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, which are in no way limitative. Examples 4 to 9 are given by way of comparison and do not form part of the invention.
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 tetrahydrofuran hydrates (THF). A pure water / THF solution (80/20 by mass) forms hydrates under 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 tubes with a diameter of 16 mm, into which are introduced 8 ml of an aqueous solution at 20% by mass of THF optionally containing the additive to be tested. A glass ball with a diameter of 8 mm is introduced into each tube, in order to ensure correct mixing of the solution. The tubes are placed on a rotary agitator, which rotates at 20 rpm. The latter is placed in a refrigerated enclosure 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 latency time preceding the formation of hydrates. This latency time corresponds to the interval measured between the moment when the tubes are introduced into the refrigerated enclosure and the moment when the formation of hydrates is observed (appearance of a cloudiness).
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 carried out in the presence of a reference mixture containing no additive, and the latency 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 pure water / THF solutions have an average latency time 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 mass of a copolymer containing 10% by mole of dimethyl-amino-ethyl methacrylate units (MADAME) and 90% by mole of acrylamide (AA) units the latency time by approximately 4.5, the addition of 0.5% by mass of a poly (methacrylate-ethyl-trimethyl ammonium chloride) (MAC) leads to an induction time which is average more than 7 times that of pure water. The addition of 0.3% by mass of a copolymer containing 55% by mole of acrylamide (AA) units and 45% by mole of diallyl-dimethyl ammonium chloride (DADMAC) units makes it possible to multiply the time by more than 5 latency.
Enfin, l'addition de 0,5% en masse de poly(méthosulfate d'acrylate-éthyltriméthyl 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-propyldiméthyl-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-ethyltrimethyl ammonium methosulfate) or the addition of 0.3% by weight of a copolymer containing 50% by mole of N-vinyl- units. 2-pyrrolidone (NVP) and 50% by mole of methacrylate-ethyl-trimethyl ammonium chloride (MAC) units or of a copolymer containing 32% by mole of [3- (2-acrylamido-2-methyl-propyldimethyl) units -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 mass relative to water inhibits also the formation of THF hydrates for a period longer than 6 hours.
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 the pure water with a mixture of pure water + 5% methanol by mass and lowering the temperature of the refrigerated enclosure to -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 time of pure water solutions + 5% methanol / THF in the absence of an 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 mass relative to water, of a copolymer containing 50% by mole of dimethyl-amino-ethyl acrylate units (ADAME) and 50% by mole of acrylic acid units (Ac Acrylic) in the water medium + 5% methanol multiplies the lag time by more than 5.
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 NaC1/THF en l'absence d'additif est de 42 minutes.The experimental procedure of Example 1 is repeated, replacing the pure water with a 3.5% by mass NaCl solution. the temperature of the refrigerated chamber is lowered to 0 ° C. Under these conditions, the average latency time of the NaCl / THF solutions 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 mass of a poly (diallyl-dimethyl ammonium chloride) (DADMAC) makes it possible to multiply the latency time by approximately 5. The addition of 0.5% by mass of a poly [3- (2-acrylamido-2-methyl-propyl-dimethyl-ammonio) -1-propane sulfonate] (AMPDAPS) makes it possible to multiply by 6 latency. Finally, the addition of 0.5% by mass of a terpolymer containing 50% by mole of acrylamide units (AA), 35% by mole of methacrylamido-N-propyl-trimethyl ammonium chloride units (MAPTAC) and 15% of mole of sodium acrylate units leads to an average latency more than 7 times greater 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-propyltriméthyl ammonium (MAPTAC) ou de 0,3% en masse d'un copolymère PVP/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 mass of a terpolymer containing 60% by mole of acrylamide-type units, 25% by mole of acrylamido-methyl-propane sulfonate units (AMPS) and 15% by mole of methacrylamido chloride units -N-propyltrimethyl ammonium (MAPTAC) or 0.3% by mass of a PVP / AMPDAPS copolymer (60/40 in moles) inhibit the formation of THF hydrates for a period greater than 6 hours.
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)
- Ex. 4: Polyvinylpyrrolidone (molecular weight 10,000; 0.5% by mass)
- Ex. 5: Polyacrylamide (0.5% by mass)
- Ex. 6: Acrylamide / sodium acrylate copolymer (0.5% by mass)
- Ex. 7: Tetrabutyl ammonium chloride (0.5% by mass)
- Ex. 8 : HE-300 (N-vinyl-2-pyrrolidone / acrylamido-methyl-propane-sulfonate / acrylamide terpolymer: 0.3% by mass)
- Ex. 9: GAFFIX VC - 713 (N - vinyl - 2 - pyrrolidone / N-vinyl-ε-caprolactam / dimethylaminoethyl methacrylate; 0.3% by mass)
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.
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, in the presence of methane hydrates, hydrate formation tests were carried out from gas and water, using l '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 comprises a 6-meter loop made up of tubes with an 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 water and additive mixture initially introduced. . The reactor puts the loop under pressure. Tubes of diameter similar to those of the loop ensure the circulation of the fluid from the loop to the reactor, and vice versa, by means of a gear pump placed between the two. A sapphire cell integrated into the circuit allows visualization of the circulating liquid and therefore of the hydrates if they have 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.To determine the effectiveness of the additives according to the invention, the fluid (water and additive) is introduced into 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 decrease in temperature (0.5 ° C / min) from 17 ° C to 5 ° C is imposed, 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 on the other hand the lag time preceding their formation. The latency time corresponds to the time measured between the start of the test (circulation of the fluid at 17 ° C) and the detection of the formation of hydrates (exotherm, high gas consumption). The duration of the tests can vary from a few minutes to several hours: a high-performance additive inhibits the formation of hydrates, or keeps them dispersed in the 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 an additive (medium: deionized water), methane hydrates are formed at a temperature in the region of 10.0 ° C and after an induction time of 30 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 the pressure and temperature conditions imposed for this test even after 24 hours of circulation .
Claims (15)
(CH2=CH-(CH2))2-N-R5 [5]
dans laquelle, R5 est une chaîne alkyle CnH2n+1, avec 1 ≤ n ≤ 10, ou un groupement hydroxyle ou un groupement (CH2)2-CO-NH2.
(CH 2 = CH- (CH 2 )) 2 -NR 5 [5]
in which, R 5 is an alkyl chain C n H 2n + 1 , with 1 ≤ n ≤ 10, or a hydroxyl group or a group (CH 2 ) 2 -CO-NH 2 .
(CH2=CH-(CH2))2-N+-R5R6 X- [8]
dans laquelle, R5 est une chaîne 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 -.
(CH 2 = CH- (CH 2 )) 2 -N + -R 5 R 6 X - [8]
in which, R 5 is an alkyl chain C n H 2n + 1 , with 1 ≤ n ≤ 10, a hydroxyl group or a group (CH 2 ) 2 -CO-NH 2 , R 6 is chosen from methyl and ethyl groups or benzyl and X is a chloride ion or a CH 3 OSO 3 - ion.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9606200 | 1996-05-15 | ||
| FR9606200A FR2748773B1 (en) | 1996-05-15 | 1996-05-15 | PROCESS FOR INHIBITING OR DELAYING THE FORMATION OR AGGLOMERATION OF HYDRATES IN A PRODUCTION EFFLUENT |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0807678A1 true EP0807678A1 (en) | 1997-11-19 |
| EP0807678B1 EP0807678B1 (en) | 2005-09-07 |
Family
ID=9492257
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP97401004A Expired - Lifetime EP0807678B1 (en) | 1996-05-15 | 1997-05-05 | Process for inhibiting or retarding the formation of hydrates in a production effluent |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US5981816A (en) |
| EP (1) | EP0807678B1 (en) |
| CN (1) | CN1072709C (en) |
| AR (1) | AR007156A1 (en) |
| BR (1) | BR9703143A (en) |
| CA (1) | CA2206918C (en) |
| FR (1) | FR2748773B1 (en) |
| MX (1) | MX9703503A (en) |
| NO (1) | NO321773B1 (en) |
| RU (1) | RU2167846C2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2767067A1 (en) * | 1997-08-05 | 1999-02-12 | Inst Francais Du Petrole | Inhibition of formation, growth and agglomeration of hydrates in natural gas and petroleum |
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| CA2231453A1 (en) * | 1995-06-02 | 1996-12-05 | Yoshikazu Fujii | Clathrate hydrate inhibitor and method of inhibiting the formation of clathrate hydrates using it |
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| AU732692B2 (en) * | 1997-09-09 | 2001-04-26 | Shell Internationale Research Maatschappij B.V. | Method and compound for inhibiting the plugging of conduits by gas hydrates |
| US6194622B1 (en) * | 1998-06-10 | 2001-02-27 | Exxonmobil Upstream Research Company | Method for inhibiting hydrate formation |
| FR2792997B1 (en) | 1999-04-29 | 2001-06-29 | Inst Francais Du Petrole | FORMULATION OF ADDITIVES FOR IMPROVING THE TRANSPORT OF PETROLEUM EFFLUENTS LIKELY TO CONTAIN HYDRATES AND METHOD USING THIS FORMULATION |
| US6222083B1 (en) | 1999-10-01 | 2001-04-24 | Exxonmobil Upstream Research Company | Method for inhibiting hydrate formation |
| DE10134224B4 (en) | 2001-07-13 | 2012-12-20 | Clariant Produkte (Deutschland) Gmbh | Additives for inhibiting gas hydrate formation |
| US6978837B2 (en) * | 2003-11-13 | 2005-12-27 | Yemington Charles R | Production of natural gas from hydrates |
| US20060094913A1 (en) * | 2004-11-04 | 2006-05-04 | Spratt Paul A | Ion pair amphiphiles as hydrate inhibitors |
| DE102006057856A1 (en) * | 2006-12-08 | 2008-06-19 | Evonik Oxeno Gmbh | Production of alkyl tertiary butyl ether and a hydrocarbon stream containing 1-butene and a small amount of isobutene comprises using a catalyst volume in a side reactor corresponding a catalyst volume in a reactive distillation column |
| WO2009114674A1 (en) * | 2008-03-12 | 2009-09-17 | University Of Wyoming | Dual function gas hydrate inhibitors |
| US8921478B2 (en) | 2008-10-17 | 2014-12-30 | Nalco Company | Method of controlling gas hydrates in fluid systems |
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| US8618025B2 (en) | 2010-12-16 | 2013-12-31 | Nalco Company | Composition and method for reducing hydrate agglomeration |
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| US9663666B2 (en) * | 2015-01-22 | 2017-05-30 | Baker Hughes Incorporated | Use of hydroxyacid to reduce the localized corrosion potential of low dose hydrate inhibitors |
| RU2601649C1 (en) * | 2015-10-19 | 2016-11-10 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Российский государственный университет нефти и газа (национальный исследовательский университет) имени И.М. Губкина" | Method of inhibiting formation of hydrates in hydrocarbon-containing raw material |
| RU2601355C1 (en) * | 2015-10-19 | 2016-11-10 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Российский государственный университет нефти и газа (национальный исследовательский университет) имени И.М. Губкина" | Composition for inhibiting formation of hydrates in hydrocarbon-containing raw material |
| CN105669894A (en) * | 2016-01-12 | 2016-06-15 | 常州大学 | Method for preparing CH4 hydrate inhibitor and application thereof |
| CN111393570B (en) * | 2020-04-30 | 2022-05-24 | 中海石油(中国)有限公司 | Hyperbranched polyvinylpyrrolidone natural gas hydrate inhibitor with inner salt structure and preparation method and application thereof |
| CN112961255B (en) * | 2021-02-23 | 2022-07-19 | 中国石油大学(华东) | Environment-friendly natural gas hydrate decomposition inhibitor and preparation method and application thereof |
| CN115197367A (en) * | 2022-07-20 | 2022-10-18 | 西南石油大学 | Ternary hydrate inhibitor based on vinyl pyrrolidone and preparation method thereof |
| US20240026049A1 (en) * | 2022-07-21 | 2024-01-25 | Envision Biomedical LLC | Dual-phase zwitterionic monomers |
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- 1996-05-15 FR FR9606200A patent/FR2748773B1/en not_active Expired - Fee Related
-
1997
- 1997-05-05 EP EP97401004A patent/EP0807678B1/en not_active Expired - Lifetime
- 1997-05-13 BR BR9703143A patent/BR9703143A/en not_active IP Right Cessation
- 1997-05-13 MX MX9703503A patent/MX9703503A/en active IP Right Grant
- 1997-05-14 CA CA002206918A patent/CA2206918C/en not_active Expired - Fee Related
- 1997-05-14 NO NO19972225A patent/NO321773B1/en not_active IP Right Cessation
- 1997-05-14 RU RU97107763/04A patent/RU2167846C2/en not_active IP Right Cessation
- 1997-05-15 CN CN97113227A patent/CN1072709C/en not_active Expired - Fee Related
- 1997-05-15 AR ARP970102050A patent/AR007156A1/en unknown
- 1997-05-15 US US08/857,048 patent/US5981816A/en not_active Expired - Lifetime
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| EP0323774A1 (en) * | 1987-12-30 | 1989-07-12 | Institut Francais Du Petrole | Process to delay the formation and/or to reduce the tendency to agglomerate of hydrates |
| EP0323775A1 (en) * | 1987-12-30 | 1989-07-12 | Institut Français du Pétrole | Process to delay the formation and/or to reduce the tendency to agglomerate of hydrates |
| WO1994012761A1 (en) * | 1992-11-20 | 1994-06-09 | Colorado School Of Mines | Method for controlling clathrate hydrates in fluid systems |
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| FR2767067A1 (en) * | 1997-08-05 | 1999-02-12 | Inst Francais Du Petrole | Inhibition of formation, growth and agglomeration of hydrates in natural gas and petroleum |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2748773A1 (en) | 1997-11-21 |
| NO321773B1 (en) | 2006-07-03 |
| US5981816A (en) | 1999-11-09 |
| NO972225L (en) | 1997-11-17 |
| NO972225D0 (en) | 1997-05-14 |
| MX9703503A (en) | 1998-04-30 |
| AR007156A1 (en) | 1999-10-13 |
| EP0807678B1 (en) | 2005-09-07 |
| CA2206918A1 (en) | 1997-11-15 |
| CN1172848A (en) | 1998-02-11 |
| RU2167846C2 (en) | 2001-05-27 |
| CA2206918C (en) | 2008-02-19 |
| FR2748773B1 (en) | 1998-06-26 |
| BR9703143A (en) | 1998-09-08 |
| CN1072709C (en) | 2001-10-10 |
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