EP0946688A1 - Additives to inhibit the formation of gas hydrate - Google Patents

Additives to inhibit the formation of gas hydrate

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Publication number
EP0946688A1
EP0946688A1 EP97950130A EP97950130A EP0946688A1 EP 0946688 A1 EP0946688 A1 EP 0946688A1 EP 97950130 A EP97950130 A EP 97950130A EP 97950130 A EP97950130 A EP 97950130A EP 0946688 A1 EP0946688 A1 EP 0946688A1
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EP
European Patent Office
Prior art keywords
monomers
polymers
mol
gas
gas hydrate
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP97950130A
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German (de)
French (fr)
Inventor
Peter Klug
Michael Feustel
Volker Frenz
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Clariant Produkte Deutschland GmbH
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Clariant GmbH
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
    • C09K2208/22—Hydrates inhibition by using well treatment fluids containing inhibitors of hydrate formers

Definitions

  • Gas hydrates are crystalline inclusion compounds of gas molecules in water that form under certain temperature and pressure conditions (low temperature and high pressure).
  • the water molecules form cage structures around the corresponding gas molecules.
  • the lattice structure formed from the water molecules alone is thermodynamically unstable, the lattice is only stabilized by the inclusion of gas molecules and an ice-like connection is formed which, depending on the pressure and gas composition, also exists above the freezing point of water (up to over 25 ° C) can.
  • An overview of the subject of gas hydrates can be found in Sloan, Clathrate Hydrates of Natural Gases, M. Dekker, New York, 1990.
  • the gas hydrates that form from water and the natural gas components methane, ethane, propane, isobutane, n-butane, nitrogen, carbon dioxide and hydrogen sulfide are of particular importance.
  • the existence of these gas hydrates is a major problem, particularly in today's natural gas production, especially when wet gas or multi-phase mixtures of water, gas and alkane mixtures are exposed to low temperatures under high pressure.
  • gas hydrate formation can also lead to problems when drilling to open up new gas or oil deposits with the appropriate pressure and temperature conditions.
  • the formation of gas hydrate in gas pipelines or in the transport of multi-phase mixtures can be suppressed by using larger amounts (double-digit percentages in relation to the water phase) of lower alcohols, such as methanol, glycol or diethylene glycol.
  • lower alcohols such as methanol, glycol or diethylene glycol.
  • the addition of these additives causes the thermodynamic limit of gas hydrate formation to be shifted to lower temperatures and higher pressures (thermodynamic inhibition).
  • the addition of these thermodynamic inhibitors causes greater safety problems (flash point and toxicity of the alcohols), logistical problems (large storage tanks, recycling of these solvents) and correspondingly high costs, especially in offshore production.
  • thermodynamic inhibitors Today, attempts are therefore being made to replace thermodynamic inhibitors by adding additives (use amount ⁇ 2%) in the temperature and pressure ranges in which gas hydrates can form, which either delay gas hydrate formation over time (threshold hydrate inhibitors, kinetic inhibition) or make the gas hydrate agglomerates small and pumpable so that they can be transported through the pipeline (so-called agglomerate inhibitors or anti-agglomerates).
  • thermodynamic inhibitors In addition to the known thermodynamic inhibitors, a large number of monomeric and polymeric classes of substances which represent kinetic or agglomerate inhibitors have been described in the patent literature as gas hydrate inhibitors.
  • EP-A-309210 discloses i.a. Sodium polyacrylates, sodium polymethacrylates and polyacrylamides.
  • WO 95/32356 describes polymers for use as gas hydrate inhibitors which contain monomers with a cyclic or acyclic amide group; Polymers with cyclic amide groups can additionally contain ionic groups, preferably anionic groups.
  • strongly polar zwitterionic polymers which contain both anionic and cationic groups are also particularly suitable. These can effectively prevent the formation of gas hydrates in low doses and, in contrast to the polyacrylates and polymethacrylates listed in EP-A-309210, are insensitive to saline water phases.
  • the invention thus relates to the use of polymers which are composed of one or different anionic monomers and one or different cationic monomers and, if appropriate, also of nonionic monomers, as additives for preventing the formation, growth and / or agglomeration of gas hydrate crystals in a mixture of water and petroleum / natural gas components in the production or transportation of petroleum and / or natural gas.
  • These zwitterionic polymers contain, in different proportions, both monomers with anionic polarity and also cationic polarity, as well as optionally also nonionic monomers.
  • the polymerization is preferably carried out as solution polymerization in water or as precipitation polymerization, as described in DE-A-4034642.
  • Polymers whose anionic building blocks are monomers with at least one polymerizable double bond and with carbon, sulfonic and / or phosphonic acid groups are particularly suitable.
  • Suitable anionic monomers for the purposes of the invention are all anionic molecules with one or more polymerizable double bonds, e.g. Vinyl sulfonate, methyl lyl sulfonate, sodium 2-acrylamido-2-methyl-1-propane sulfonate (AMPS), styrene sulfonic acid, acrylic acid, methacrylic acid (or its salts), vinyl phosphonate, acrylic acid and sodium 2-acrylamido-2-methyl- are preferred 1-propane sulfonate (AMPS).
  • AMPS 2-acrylamido-2-methyl-1-propane sulfonate
  • Maleic anhydride is also to be regarded as an anionic monomer in the context of the invention, since after polymerization it can easily be converted into anionic polymer building blocks by saponification or formation of half-esters or half-amides. Of these monomer units, one or more are independently present in the polymer in concentrations of 1-99, preferably 10-90 mol%.
  • quaternary ammonium salts with polymerizable double bonds such as dimethyldiallylammonium chloride (DADMAC), dibutyldiallylammonium chloride (DADBAC), diallylpiperidinium bromide, triethylallylammonium bromide, allyltrimethylammonium bromide and analogous derivatives of, for example, trimethyl acid and methacrylate ammonium ethyl acrylate (chloride or methosulfate), trimethylammonium ethyl methacrylate, N- (3-trimethylammonium propyl) acrylamide or N- (3-trimethyl!
  • DADMAC dimethyldiallylammonium chloride
  • DADBAC dibutyldiallylammonium chloride
  • diallylpiperidinium bromide triethylallylammonium bromide
  • allyltrimethylammonium bromide and analogous derivatives of, for example, trimethyl acid and methacrylate
  • ammonium propyl) methacrylamide (MAPTAC).
  • vinyl monomers which contain amine functions or can release them after modification, for example diallylamine, triallylamine or vinylformamide. These monomer units are present in the polymer at 1-99, preferably at 10-90 mol%.
  • these polymers may also contain nonionic groups;
  • vinyl monomers such as acrylic acid esters and amides, vinyl acetate, ⁇ -olefins, allypolyglycols or allyl-alkylpolyglycols, vinyl ethers such as isobutyl vinyl ether or methyl vinyl ether and N-alkyl acetamides are suitable for this.
  • monomers with a cyclic or acyclic amide grouping such as e.g. Vinyl pyrrolidone, vinyl caprolactam, vinyl N-methylacetamide (VIMA) and acrylamide.
  • the molecular weight of these polymers can be varied within a wide range; the polymers have molecular weights of about 1000 to> 10 7 , preferably molecular weights of about 10,000 to about 1,000,000.
  • the products can in principle be used as an anhydrous pure substance, but advantageously they are generally used as aqueous solutions in order to ensure convenient metering at low viscosity.
  • the polymers can be used alone or in combination with other known gas hydrate inhibitors. Typical use concentrations based on 100% active substance are 0.01-2% by weight, especially concentrations between 0.02-1% by weight (200-10000 ppm). Mixtures of the abovementioned polymers with polymers containing amide groups, such as polyvinylpyrrolidone, polyvinylcaprolactam, polyacrylolylpyrrolidine and with polymers made from vinylpyrrolidone and vinylcaprolactam (for example VC 713, product from International Specialty Products) and with alkylpolyglycosides, hydroxyethyl cellulose, carboxymethyl ammonium compounds and with unsubstituted ammonium cellulose as well as (quartary methyl ammonium compounds) as well as (quartary methyl ammonium compounds) and also esterquats) and amine oxides.
  • polymers containing amide groups such as polyvinylpyrrolidone, polyvinylcaprolactam, polyacrylo
  • Example 2 As can be shown in the test examples below, the formation of gas hydrate without an inhibitor sets in quickly under the test conditions and leads to a sharp increase in torque, so that the formation of large hydrate agglomerates can be concluded.
  • the zwitterionic polymers are effective over a wide molecular weight range of approximately 10000-1000000 (Examples 2-5).
  • AMPS / DADMAC polymers with a higher DADMAC content also behave similarly (Example 6).
  • Example 7 shows that polymers with other cationic constituents (MAPTAC) and nonionic component are also effective at a gas / water ratio of 6: 4 and a dosage of 1000 ppm.
  • MATAC polymers with other cationic constituents
  • nonionic component are also effective at a gas / water ratio of 6: 4 and a dosage of 1000 ppm.
  • the formation of gas hydrates can be observed compared to an uninhibited test, but these form smaller agglomerates, which cause a significantly lower torque.
  • the product acts as an agglomerate inhibitor.
  • test products were dissolved in 176 ml of deionized water in a steel stirred autoclave with temperature control and torque transducer at a volume ratio of gas and water phase of 6: 4 and a gas pressure of 47-51 bar was applied. From an initial temperature of 10 ° C., the mixture was cooled to 4 ° C. in the course of 6 hours, then to 2 ° C. in the course of 4 hours, stirred at 2 ° C. for 7 hours and heated to 10 ° C. again in the course of 4 hours. A decrease in pressure according to the thermal expansion of the gas is first observed.
  • the measured pressure decreases, an increase in the measured torque being observed; further growth and increasing agglomeration of these hydrate nuclei quickly leads to a further increase in the measured torque without an inhibitor.
  • the reaction mixture is warmed up, the gas hydrates decompose again, so that the starting state is reached again at the end of the experiment.
  • the K value given in the examples means the intrinsic viscosity of the polymer solution and represents a measure of the average molecular weight.

Abstract

The present invention relates to the use of polymers, comprising one or more different anionic monomers, one or more different cationic monomers and possibly non-ionic monomers as additives to prevent the formation, growth and/or agglomeration of gas hydrate crystals in a mixture of water and crude petrolium/ natural gas constituents during the extraction or transport of crude petroleum and/or natural gas.

Description

Beschreibungdescription
Additive zur Inhibierung der GashydratbildungAdditives to inhibit gas hydrate formation
Gashydrate sind kristalline Einschlußverbindungen von Gasmolekülen in Wasser, die sich unter bestimmten Temperatur- und Druckverhältnissen (niedrige Temperatur und hoher Druck) bilden. Hierbei bilden die Wassermoleküle Käfigstrukturen um die entsprechenden Gasmoleküle aus. Das aus den Wassermolekülen gebildete Gittergerüst alleine ist thermodynamisch instabil, erst durch die Einbindung von Gasmolekülen wird das Gitter stabilisiert und es entsteht eine eisähnliche Verbindung, die in Abhängigkeit von Druck und Gaszusammensetzung auch über den Gefrierpunkt von Wasser (bis über 25 °C) hinaus existieren kann. Ein Überblick über das Thema Gashydrate ist in Sloan, Clathrate Hydrates of Natural Gases, M. Dekker, New York, 1990 zu finden.Gas hydrates are crystalline inclusion compounds of gas molecules in water that form under certain temperature and pressure conditions (low temperature and high pressure). The water molecules form cage structures around the corresponding gas molecules. The lattice structure formed from the water molecules alone is thermodynamically unstable, the lattice is only stabilized by the inclusion of gas molecules and an ice-like connection is formed which, depending on the pressure and gas composition, also exists above the freezing point of water (up to over 25 ° C) can. An overview of the subject of gas hydrates can be found in Sloan, Clathrate Hydrates of Natural Gases, M. Dekker, New York, 1990.
In der Erdöl- und Erdgasindustrie sind insbesondere die Gashydrate von großer Bedeutung, die sich aus Wasser und den Erdgasbestandteilen Methan, Ethan, Propan, Isobutan, n-Butan, Stickstoff, Kohlendioxid und Schwefelwasserstoff bilden. Insbesondere in der heutigen Erdgasförderung stellt die Existenz dieser Gashydrate ein großes Problem dar, besonders dann, wenn Naßgas oder Mehrphasengemische aus Wasser, Gas und Alkangemischen unter hohem Druck niedrigen Temperaturen ausgesetzt werden. Hier führt die Bildung der Gashydrate aufgrund ihrer Unlöslichkeit und kristallinen Struktur zu Blockierung verschiedenster Fördereinrichtungen, wie Pipelines, Ventilen oder Produktionseinrichtungen, in denen über längere Strecken bei niedrigeren Temperaturen Naßgas oder Mehrphasengemische transportiert werden, wie dies speziell in kälteren Regionen der Erde oder auf dem Meeresboden vorkommt.In the petroleum and natural gas industry, the gas hydrates that form from water and the natural gas components methane, ethane, propane, isobutane, n-butane, nitrogen, carbon dioxide and hydrogen sulfide are of particular importance. The existence of these gas hydrates is a major problem, particularly in today's natural gas production, especially when wet gas or multi-phase mixtures of water, gas and alkane mixtures are exposed to low temperatures under high pressure. Here, the formation of gas hydrates due to their insolubility and crystalline structure leads to blocking of a wide variety of conveying devices, such as pipelines, valves or production facilities, in which wet gas or multi-phase mixtures are transported over long distances at lower temperatures, as is especially the case in colder regions of the world or on the seabed occurs.
Außerdem kann die Gashydratbildung auch beim Bohren zur Erschließung neuer Gas- oder Erdöllagerstätten bei entsprechenden Druck- und Temperaturverhältnissen zu Problemen führen. Um solche Probleme zu vermeiden, kann die Gashydratbildung in Gaspipelines oder beim Transport von Mehrphasengemischen durch Einsatz von größeren Mengen (zweistellige Prozentbeträge bezüglich der Wasserphase) an niederen Alkoholen, wie Methanol, Glykol, oder Diethylenglykol unterdrückt werden. Der Zusatz dieser Additive bewirkt, daß die thermodynamische Grenze der Gashydratbildung nach niedrigeren Temperaturen und höheren Drücken verlagert wird (thermodynamische Inhibierung). Durch den Zusatz dieser thermodynamischen Inhibitoren werden allerdings größere Sicherheitsprobleme (Flammpunkt und Toxizität der Alkohole), logistische Probleme (große Lagertanks, Recycling dieser Lösungsmittel) und dementsprechend hohe Kosten, speziell in der offshore-Förderung, verursacht.In addition, gas hydrate formation can also lead to problems when drilling to open up new gas or oil deposits with the appropriate pressure and temperature conditions. In order to avoid such problems, the formation of gas hydrate in gas pipelines or in the transport of multi-phase mixtures can be suppressed by using larger amounts (double-digit percentages in relation to the water phase) of lower alcohols, such as methanol, glycol or diethylene glycol. The addition of these additives causes the thermodynamic limit of gas hydrate formation to be shifted to lower temperatures and higher pressures (thermodynamic inhibition). The addition of these thermodynamic inhibitors, however, causes greater safety problems (flash point and toxicity of the alcohols), logistical problems (large storage tanks, recycling of these solvents) and correspondingly high costs, especially in offshore production.
Heute versucht man deshalb, thermodynamische Inhibitoren zu ersetzen, indem man in den Temperatur- und Druckbereichen, in denen sich Gashydrate bilden können, Additive (Einsatzmenge < 2 %) zusetzt, die die Gashydratbildung entweder zeitlich hinauszögern (threshold hydrate inhibitors, kinetische Inhibierung) oder die Gashydratagglomerate klein und pumpbar gestalten, so daß diese durch die Pipeline transportiert werden können (sog. Agglomerat-Inhibitoren oder Anti-Agglomerates).Today, attempts are therefore being made to replace thermodynamic inhibitors by adding additives (use amount <2%) in the temperature and pressure ranges in which gas hydrates can form, which either delay gas hydrate formation over time (threshold hydrate inhibitors, kinetic inhibition) or make the gas hydrate agglomerates small and pumpable so that they can be transported through the pipeline (so-called agglomerate inhibitors or anti-agglomerates).
Als Gashydratinhibitoren wurden in der Patentliteratur neben den bekannten thermodynamischen Inhibitoren eine Vielzahl monomerer als auch polymerer Substanzklassen beschrieben, die kinetische oder Agglomeratinhibitoren darstellen.In addition to the known thermodynamic inhibitors, a large number of monomeric and polymeric classes of substances which represent kinetic or agglomerate inhibitors have been described in the patent literature as gas hydrate inhibitors.
Die EP-A-309210 offenbart zu diesem Zwecke u.a. Natriumpolyacrylate, Natriumpolymethacrylate sowie Polyacrylamide.For this purpose, EP-A-309210 discloses i.a. Sodium polyacrylates, sodium polymethacrylates and polyacrylamides.
Besondere Wirksamkeit zeigen, wie in US 5420370, WO 93/25798, WO 94/24413, US 5432292 und WO 95/19408 beschrieben, vorwiegend nichtionische Polymere und Copolymere von vinylischen Monomeren mit cyclischer Amidstruktur, besonders von Vinylpyrrolidon und Vinylcaprolactam. In WO 95/32356 werden Polymere zur Verwendung als Gashydratinhibitoren beschrieben, die Monomere mit einer cyclischen oder acyclischen Amidgruppierung enthalten; dabei können Polymere mit cyclischen Amidgruppierungen zusätzlich ionische Gruppen, bevorzugt anionische Gruppen enthalten.Particularly effective, as described in US 5420370, WO 93/25798, WO 94/24413, US 5432292 and WO 95/19408, are predominantly nonionic polymers and copolymers of vinyl monomers with a cyclic amide structure, in particular of vinyl pyrrolidone and vinyl caprolactam. WO 95/32356 describes polymers for use as gas hydrate inhibitors which contain monomers with a cyclic or acyclic amide group; Polymers with cyclic amide groups can additionally contain ionic groups, preferably anionic groups.
Viele von diesen Additiven sind allerdings bisher nicht wirksam genug oder nicht in ausreichender Menge oder nur zu hohen Preisen erhältlich; andererseits sind einige Additive, speziell Polyacrylate wegen ihrer Salzwasserunverträglichkeit nur unter nichtsalinen Einsatzbedingungen wirksam.However, many of these additives have so far not been effective enough or are not available in sufficient quantities or only at high prices; on the other hand, some additives, especially polyacrylates, are only effective under non-saline conditions because of their salt water intolerance.
Aufgabe der vorliegenden Erfindung war es also, neue effektive Additive zu finden, die die Bildung von Gashydraten verlangsamen (kinetische Inhibitoren) bzw. die Gashydratkristalle klein und pumpbar halten (Anti-Agglomerates), um die zur Zeit noch verwendeten thermodynamischen Inhibitoren (Methanol und Glykole), die beträchtliche Sicherheitsprobleme und Logistikprobleme verursachen, ersetzen zu können.It was therefore the object of the present invention to find new effective additives which slow the formation of gas hydrates (kinetic inhibitors) or keep the gas hydrate crystals small and pumpable (anti-agglomerates) in order to use the thermodynamic inhibitors (methanol and glycols) which are still used at present ), which can cause considerable security and logistics problems.
Wie nun überraschenderweise gefunden wurde, sind neben den oben angeführten nichtionischen Polymeren zur Gashydratinhibierung auch stark polare zwitterionische Polymere, die sowohl anionische als auch kationische Gruppen enthalten, besonders geeignet. Diese können in niedriger Dosierung die Bildung von Gashydraten effektiv unterbinden und sind im Gegensatz zu den in EP-A- 309210 aufgeführten Polyacrylaten und Polymethacrylaten gegenüber salinen Wasserphasen unempfindlich.As has now surprisingly been found, in addition to the nonionic polymers mentioned above for inhibiting gas hydrate, strongly polar zwitterionic polymers which contain both anionic and cationic groups are also particularly suitable. These can effectively prevent the formation of gas hydrates in low doses and, in contrast to the polyacrylates and polymethacrylates listed in EP-A-309210, are insensitive to saline water phases.
Gegenstand der Erfindung ist somit die Verwendung von Polymeren, die aus einem oder verschiedenen anionischen Monomeren und aus einem oder verschiedenen kationischen Monomeren sowie gegebenenfalls auch aus nichtionischen Monomeren aufgebaut sind, als Additive zur Verhinderung der Bildung, des Wachstums und/oder der Agglomeration von Gashydratkristallen in einer Mischung aus Wasser und Erdöl-/Erdgasbestandteilen bei der Förderung oder dem Transport von Erdöl und/oder Erdgas. Diese zwitterionischen Polymere enthalten, in unterschiedlichen Anteilen, sowohl Monomere mit anionischer Polarität, als auch kationischer Polarität, sowie zusätzlich gegebenenfalls auch nichtionische Monomere. Sie können u.a. durch radikalische Polymerisation nach den Verfahren der Lösungspolymerisation, Substanzpolymerisation, Emulsionspolymerisation, inversen Emulsionspolymerisation, Fällungspolymerisation oder Gelpolymerisation aus den Monomeren erzeugt werden. Vorzugsweise wird die Polymerisation als Lösungspolymerisation in Wasser oder als Fällungspolymerisation durchgeführt, wie dies in DE-A-4034642 beschrieben ist.The invention thus relates to the use of polymers which are composed of one or different anionic monomers and one or different cationic monomers and, if appropriate, also of nonionic monomers, as additives for preventing the formation, growth and / or agglomeration of gas hydrate crystals in a mixture of water and petroleum / natural gas components in the production or transportation of petroleum and / or natural gas. These zwitterionic polymers contain, in different proportions, both monomers with anionic polarity and also cationic polarity, as well as optionally also nonionic monomers. They can be produced from the monomers, inter alia, by radical polymerization using the methods of solution polymerization, bulk polymerization, emulsion polymerization, inverse emulsion polymerization, precipitation polymerization or gel polymerization. The polymerization is preferably carried out as solution polymerization in water or as precipitation polymerization, as described in DE-A-4034642.
Besonders geeignet sind Polymere, deren anionische Bausteine Monomere mit mindestens einer polymerisationsfähigen Doppelbindung und mit Carbon-, Sulfon- und/oder Phosphonsäuregruppen darstellen.Polymers whose anionic building blocks are monomers with at least one polymerizable double bond and with carbon, sulfonic and / or phosphonic acid groups are particularly suitable.
Als anionische Monomere im Sinne der Erfindung sind alle anionischen Moleküle mit einer oder mehreren polymerisationsfähigen Doppelbindungen geeignet, z.B. Vinylsulfonat, Methai lylsulfonat, Natrium-2-acrylamido-2-methyl-1 -propansulfonat (AMPS), Styrolsulfonsäure, Acrylsäure, Methacrylsäure (bzw. deren Salze), Vinylphosphonat, bevorzugt sind Acrylsäure und Natrium-2-acrylamido-2-methyl- 1 -propansulfonat (AMPS). Als anionisches Monomer im Sinne der Erfindung ist auch Maleinsäureanhydrid anzusehen, da sich dieses nach Polymerisation leicht durch Verseifung oder Bildung von Halbestern oder Halbamiden in anionische Polymerbausteine überführen läßt. Von diesen Monomereinheiten sind im Polymer eine oder mehrere unabhängig voneinander in Konzentrationen von 1-99, bevorzugt zu 10-90 Mol-% vertreten.Suitable anionic monomers for the purposes of the invention are all anionic molecules with one or more polymerizable double bonds, e.g. Vinyl sulfonate, methyl lyl sulfonate, sodium 2-acrylamido-2-methyl-1-propane sulfonate (AMPS), styrene sulfonic acid, acrylic acid, methacrylic acid (or its salts), vinyl phosphonate, acrylic acid and sodium 2-acrylamido-2-methyl- are preferred 1-propane sulfonate (AMPS). Maleic anhydride is also to be regarded as an anionic monomer in the context of the invention, since after polymerization it can easily be converted into anionic polymer building blocks by saponification or formation of half-esters or half-amides. Of these monomer units, one or more are independently present in the polymer in concentrations of 1-99, preferably 10-90 mol%.
Als kationische Monomere im Sinne der Erfindung sind alle kationischen Moleküle mit einer oder mehreren polymerisationsfähigen Doppelbindungen geeignet. Bevorzugt sind quartäre Ammoniumsalze mit polymerisationsfähigen Doppelbindungen wie Dimethyldiallylammoniumchlorid (DADMAC), Dibutyldiallylammoniumchlorid (DADBAC), Diallylpiperidiniumbromid, Triethylallylammoniumbromid, Allyltrimethylammoniumbromid sowie analoge Derivate von Acrylsäure und Methacrylsäure wie z.B. Trimethylammonium- ethylacrylat (Chlorid oder Methosulfat), Trimethylammonium-ethylmethacrylat, N- (3-Trimethylammoniumpropyl)-acrylamid oder N-(3-Trimethy!ammoniumpropyl)- methacrylamid (MAPTAC). Weiterhin sind auch vinylische Monomere geeignet, die Aminfunktionen enthalten oder nach Modifizierung freisetzen können, z.B. Diallylamin, Triallylamin oder Vinylformamid. Diese Monomereinheiten sind im Polymer zu 1-99, bevorzugt zu 10-90 Mol-% vertreten.All cationic molecules with one or more polymerizable double bonds are suitable as cationic monomers for the purposes of the invention. Preferred are quaternary ammonium salts with polymerizable double bonds such as dimethyldiallylammonium chloride (DADMAC), dibutyldiallylammonium chloride (DADBAC), diallylpiperidinium bromide, triethylallylammonium bromide, allyltrimethylammonium bromide and analogous derivatives of, for example, trimethyl acid and methacrylate ammonium ethyl acrylate (chloride or methosulfate), trimethylammonium ethyl methacrylate, N- (3-trimethylammonium propyl) acrylamide or N- (3-trimethyl! ammonium propyl) methacrylamide (MAPTAC). Also suitable are vinyl monomers which contain amine functions or can release them after modification, for example diallylamine, triallylamine or vinylformamide. These monomer units are present in the polymer at 1-99, preferably at 10-90 mol%.
Zusätzlich zu den oben aufgeführten ionischen Monomeren können in diesen Polymeren auch nichtionische Gruppen enthalten sein; es eignen sich hierzu prinzipiell alle vinylischen Monomeren, wie Acrylsäureester und -amide, Vinylacetat, α-Olefine, Allypolyglykole oder Allyl-alkylpolyglykole, Vinylether wie Isobutylvinylether oder Methylvinylether und N-Alkylacetamide. Bevorzugt sind neben Vinylacetat Monomere mit einer cyclischen oder acyclischen Amidgruppierung wie z.B. Vinylpyrrolidon, Vinylcaprolactam, Vinyl-N-methylacetamid (VIMA) und Acrylamid.In addition to the ionic monomers listed above, these polymers may also contain nonionic groups; In principle, all vinyl monomers such as acrylic acid esters and amides, vinyl acetate, α-olefins, allypolyglycols or allyl-alkylpolyglycols, vinyl ethers such as isobutyl vinyl ether or methyl vinyl ether and N-alkyl acetamides are suitable for this. In addition to vinyl acetate, monomers with a cyclic or acyclic amide grouping such as e.g. Vinyl pyrrolidone, vinyl caprolactam, vinyl N-methylacetamide (VIMA) and acrylamide.
Das Molekulargewicht dieser Polymeren kann in weiten Bereichen variiert werden; die Polymere weisen Molekulargewichte von ca. 1000 bis > 107, bevorzugt Molekulargewichte von ca. 10000 bis ca. 1000000 auf.The molecular weight of these polymers can be varied within a wide range; the polymers have molecular weights of about 1000 to> 10 7 , preferably molecular weights of about 10,000 to about 1,000,000.
Die Produkte können prinzipiell als wasserfreie Reinsubstanz eingesetzt werden, vorteilhafterweise setzt man sie aber im allgemeinen als wäßrige Lösungen ein, um eine bequeme Dosierung bei niedriger Viskosität zu gewährleisten.The products can in principle be used as an anhydrous pure substance, but advantageously they are generally used as aqueous solutions in order to ensure convenient metering at low viscosity.
Besondere Wirksamkeit zeigen einerseits, wie den angeführten Beispielen entnommen werden kann, Polymere auf Basis Natrium-2-acrylamido-2-methyl-1 -propansulfonat (AMPS) und Diallyldimethylammoniumchlorid (DADMAC). Diese können, wie in DE-A-4034642 beschrieben, bei höheren Molekulargewichten (Beispiel 2) auch als Bohrspülmittel Verwendung finden. Die Wirksamkeit bei der Gashydratbekämpfung ist hierbei allerdings über einen weiten Molekulargewichtsbereich von ca. 10000-1000000 gegeben. Ebenfalls besonders geeignet sind Polymere aus Natrium-2-acrylamido-2- methyl-1 -propansulfonat (AMPS) und N-(3-Trimethylammoniumpropyl)- methacrylamid (MAPTAC) mit Acrylamid (Beispiel 7). Wie bei den vorgenannten Polymeren beobachtet man bei höherer Konzentration (1000 ppm) vollständige Inhibierung der Gashydratbildung, bei schärferen Meßbedingungen (geringere Konzentration oder höheres Gas-Wasser-Verhältnis) eine deutliche Verringerung der Hydratagglomeration.Polymers based on sodium 2-acrylamido-2-methyl-1-propanesulfonate (AMPS) and diallyldimethylammonium chloride (DADMAC), on the one hand, show particular effectiveness, as can be seen from the examples given. As described in DE-A-4034642, these can also be used as drilling fluids at higher molecular weights (example 2). The effectiveness in combating gas hydrate is, however, given over a wide molecular weight range of approx. 10000-1000000. Polymers of sodium 2-acrylamido-2-methyl-1-propanesulfonate (AMPS) and N- (3-trimethylammoniumpropyl) methacrylamide (MAPTAC) with acrylamide (example 7) are also particularly suitable. As with the abovementioned polymers, complete inhibition of gas hydrate formation is observed at a higher concentration (1000 ppm), and a clear reduction in hydrate agglomeration is observed under more severe measuring conditions (lower concentration or higher gas / water ratio).
Die Polymere können alleine oder in Kombination mit anderen bekannten Gashydratinhibitoren eingesetzt werden. Typische Einsatzkonzentrationen bezogen auf 100 % Wirksubstanz sind 0,01-2 Gew.-%, speziell Konzentrationen zwischen 0,02-1 Gew.-% (200-10000 ppm). Besonders geeignet sind auch Mischungen der vorstehend genannten Polymere mit Amidgruppen enthaltenden Polymeren wie Polyvinylpyrrolidon, Polyvinylcaprolactam, Polyacrylolylpyrrolidin sowie mit Polymeren aus Vinylpyrrolidon und Vinylcaprolactam (z.B. VC 713, Produkt von International Specialty Products) sowie mit Alkylpolyglykosiden, Hydroxyethylcellulose, Carboxymethylcellulose sowie mit quartären Ammoniumverbindungen (unsubstituiert sowie Esterquats) und Aminoxiden.The polymers can be used alone or in combination with other known gas hydrate inhibitors. Typical use concentrations based on 100% active substance are 0.01-2% by weight, especially concentrations between 0.02-1% by weight (200-10000 ppm). Mixtures of the abovementioned polymers with polymers containing amide groups, such as polyvinylpyrrolidone, polyvinylcaprolactam, polyacrylolylpyrrolidine and with polymers made from vinylpyrrolidone and vinylcaprolactam (for example VC 713, product from International Specialty Products) and with alkylpolyglycosides, hydroxyethyl cellulose, carboxymethyl ammonium compounds and with unsubstituted ammonium cellulose as well as (quartary methyl ammonium compounds) as well as (quartary methyl ammonium compounds) and also esterquats) and amine oxides.
Die Wirksamkeit der Polymere wurde durch Autoklavenversuche mit Wasser-Gasgemischen untersucht.The effectiveness of the polymers was investigated by autoclave tests with water-gas mixtures.
Hierzu wird E-Wasser im Autoklaven mit ca. 50 bar eines Erdgases, das Struktur-Il-Hydrate bildet (vorwiegend Methan, Gehalt an n-Propan > 1 %) beaufschlagt und unter Rühren mit einem Temperaturprogramm (siehe unten) abgekühlt, wobei der Druckverlauf Keimbildung und Wachstum der Gashydrate beschreibt und das erzeugte Drehmoment, das ein Maß für die Hydratagglomerisation darstellt, über einen Drehmomentaufnehmer gemessen wird.For this purpose, approx. 50 bar of natural gas, which forms structure II hydrates (predominantly methane, content of n-propane> 1%), is applied to the electric water in the autoclave and cooled with a temperature program (see below), with the Pressure profile describes nucleation and growth of the gas hydrates and the torque generated, which is a measure of the hydrate agglomeration, is measured via a torque transducer.
Wie in den unten angeführten Versuchsbeispielen gezeigt werden kann, setzt die Gashydratbildung ohne Inhibitor unter den Versuchsbedingungen schnell ein und führt zu einer starken Drehmomentzunahme, so daß auf die Bildung großer Hydratagglomerate geschlossen werden kann. Dagegen führt der Zusatz von geringen Mengen (bei Beispiel 2: 900 ppm = 0,09 %) der Polymere über die gesamte Versuchsdauer zu einer völligen Inhibierung der Gashydratbildung; bei noch geringerer Einsatzkonzentration (450 ppm im Beispiel 2) wird trotz deutlicher Druckabnahme (d.h. Bildung von Hydratkeimen) zumindest eine deutliche Drehmomentverminderung beobachtet, was für eine Wirkung der Polymere als Agglomerisationsinhibitoren bei niedriger Dosierung spricht. Die zwitterionischen Polymere sind über einen weiten Molekulargewichtsbereich von ca. 10000-1000000 (Beispiele 2-5) wirksam. Auch AMPS/DADMAC-Polymere mit höherem DADMAC-Anteil verhalten sich ähnlich (Beispiel 6). Beispiel 7 zeigt, daß auch Polymere mit anderen kationischen Bestandteilen (MAPTAC) und nichtionischer Komponente bei einem Gas-Wasser-Verhältnis von 6 : 4 und einer Dosierung von 1000 ppm wirksam sind. Unter verschärften Versuchsbedingungen (höheres Gas-Wasser-Verhältnis von 8 : 2, d.h. geringerer Druckabfall bei der Gashydratbildung) ist im Vergleich zu einem uninhibierten Versuch zwar die Bildung von Gashydraten zu beobachten, diese bilden aber kleinere Agglomerate, die ein bedeutend geringeres Drehmoment verursachen. Auch hier wirkt das Produkt als Agglomerat-Inhibitor.As can be shown in the test examples below, the formation of gas hydrate without an inhibitor sets in quickly under the test conditions and leads to a sharp increase in torque, so that the formation of large hydrate agglomerates can be concluded. In contrast, the addition of small amounts (in Example 2: 900 ppm = 0.09%) of the polymers leads to a complete inhibition of gas hydrate formation over the entire duration of the experiment; at an even lower use concentration (450 ppm in Example 2), despite a significant decrease in pressure (ie formation of hydrate nuclei), at least a significant reduction in torque is observed, which speaks for an effect of the polymers as agglomeration inhibitors at low dosage. The zwitterionic polymers are effective over a wide molecular weight range of approximately 10000-1000000 (Examples 2-5). AMPS / DADMAC polymers with a higher DADMAC content also behave similarly (Example 6). Example 7 shows that polymers with other cationic constituents (MAPTAC) and nonionic component are also effective at a gas / water ratio of 6: 4 and a dosage of 1000 ppm. Under stricter test conditions (higher gas-water ratio of 8: 2, ie lower pressure drop during gas hydrate formation), the formation of gas hydrates can be observed compared to an uninhibited test, but these form smaller agglomerates, which cause a significantly lower torque. Here too the product acts as an agglomerate inhibitor.
Beispiele:Examples:
Die Apparatur zur Messsung der Gashydratinhibierung wird in D. Lippmann, Dissertation, Techn. Universität Clausthal, 1995 beschrieben.The apparatus for measuring gas hydrate inhibition is described in D. Lippmann, dissertation, Technical University Clausthal, 1995.
Die Versuchsprodukte wurden in einem Stahl-Rührautoklaven mit Temperatursteuerung und Drehmomentaufnehmer bei einem Volumenverhältnis von Gas- und Wasserphase von 6 : 4 in 176 ml E-Wasser gelöst und ein Gasdruck von 47-51 bar aufgedrückt. Von einer Anfangstemperatur von 10 °C wurde innerhalb 6 h auf 4 °C, dann innerhalb 4 h auf 2 °C gekühlt, 7 h bei 2 °C gerührt und innerhalb 4 h wieder auf 10 °C aufgeheizt. Dabei wird zunächst eine Druckabnahme gemäß der thermischen Ausdehnung des Gases beobachtet. Tritt die Bildung von Gashydratkeimen auf, so verringert sich der gemessene Druck, wobei ein Anstieg des gemessenen Drehmomentes zu beobachten ist; weiteres Wachstum und zunehmende Agglomerisation dieser Hydratkeime führt ohne Inhibitor schnell zu einem weiteren Anstieg des gemessenen Drehmomentes. Beim Aufwärmen des Reaktionsgemisches zerfallen die Gashydrate wieder, so daß am Ende des Versuchs wieder der Ausgangszustand erreicht wird. Der in den Beispielen angegebene K-Wert bedeutet die Eigenviskosität der Polymerlösung und stellt ein Maß für das mittlere Molekulargewicht dar.The test products were dissolved in 176 ml of deionized water in a steel stirred autoclave with temperature control and torque transducer at a volume ratio of gas and water phase of 6: 4 and a gas pressure of 47-51 bar was applied. From an initial temperature of 10 ° C., the mixture was cooled to 4 ° C. in the course of 6 hours, then to 2 ° C. in the course of 4 hours, stirred at 2 ° C. for 7 hours and heated to 10 ° C. again in the course of 4 hours. A decrease in pressure according to the thermal expansion of the gas is first observed. If the formation of gas hydrate nuclei occurs, the measured pressure decreases, an increase in the measured torque being observed; further growth and increasing agglomeration of these hydrate nuclei quickly leads to a further increase in the measured torque without an inhibitor. When the reaction mixture is warmed up, the gas hydrates decompose again, so that the starting state is reached again at the end of the experiment. The K value given in the examples means the intrinsic viscosity of the polymer solution and represents a measure of the average molecular weight.
Beispiel 1 :Example 1 :
Referenzversuch ohne InhibitorReference experiment without inhibitor
Beispiel 2:Example 2:
Copolymer Natrium-2-acrylamido-2-methyl-1 -propansulfonat (AMPS)/Diallyldimethylammoniumchlorid (DADMAC) 76 : 24; K-Wert (0,5 % in Wasser) = 150Copolymer sodium 2-acrylamido-2-methyl-1-propanesulfonate (AMPS) / diallyldimethylammonium chloride (DADMAC) 76:24; K value (0.5% in water) = 150
Beispiel 3:Example 3:
Copolymer Natrium-2-acrylamido-2-methyl-1 -propansulfonat (AMPS)/DiaIlyldimethylammoniumchlorid (DADMAC) 76 : 24; K-Wert (0,5 % in Wasser) = 125Copolymer sodium 2-acrylamido-2-methyl-1-propane sulfonate (AMPS) / dialdehyde dimethyl ammonium chloride (DADMAC) 76:24; K value (0.5% in water) = 125
Beispiel 4:Example 4:
Copolymer Natrium-2-acrylamido-2-methyl-1 -propansulfonat (AMPS)/Diallyldimethylammoniumchlorid (DADMAC) 76 : 24; K-Wert (0,5 % in Wasser) = 93Copolymer sodium 2-acrylamido-2-methyl-1-propanesulfonate (AMPS) / diallyldimethylammonium chloride (DADMAC) 76:24; K value (0.5% in water) = 93
Beispiel 5:Example 5:
Copolymer Natrium-2-acrylamido-2-methyl-1 -propansulfonat (AMPS)/Diallyldimethylammoniumchlorid (DADMAC) 76 : 24; K-Wert (0,5 % in Wasser) = 41Copolymer sodium 2-acrylamido-2-methyl-1-propanesulfonate (AMPS) / diallyldimethylammonium chloride (DADMAC) 76:24; K value (0.5% in water) = 41
Beispiel 6:Example 6:
Copolymer Natrium-2-acrylamido-2-methyl-1 -propansulfonatCopolymer sodium 2-acrylamido-2-methyl-1-propane sulfonate
(AMPS)/Diallyldimethylammoniumchlorid (DADMAC) 24 : 76, K-Wert (0,5 % in Wasser) = 86(AMPS) / diallyldimethylammonium chloride (DADMAC) 24:76, K value (0.5% in Water) = 86
Beispiel 7:Example 7:
Copolymer N-(3-Trimethylammoniumpropyl)-methacrylamid (MAPTAC)/Natrium-2-acrylamido-2-methyl-1 -propansulfonat (AMPS)/Acrylamid ca. 20 : 65 : 15, K-Wert 0,5 % in Wasser = 150Copolymer N- (3-trimethylammoniumpropyl) methacrylamide (MAPTAC) / sodium 2-acrylamido-2-methyl-1-propane sulfonate (AMPS) / acrylamide approx. 20:65:15, K value 0.5% in water 150
Beispiel 8: ohne Inhibitor, Gas-Wasser-Verhältnis 8 : 2Example 8: without inhibitor, gas-water ratio 8: 2
Tabelle 1 : Ergebnisse der Beispiele 1 bis 8Table 1: Results of Examples 1 to 8
Gas-Wasser-Verhältnis 8 : 2 Gas-water ratio 8: 2

Claims

Patentansprüche: Claims:
1. Verwendung von Polymeren, die aus einem oder verschiedenen anionischen Monomeren und aus einem oder verschiedenen kationischen Monomeren sowie gegebenenfalls auch aus nichtionischen Monomeren aufgebaut sind, als Additive zur Verhinderung der Bildung, des Wachstums und/oder der Agglomeration von Gashydratkristallen in einer Mischung aus Wasser und Erdöl-/Erdgasbestandteilen bei der Förderung oder dem Transport von Erdöl und/oder Erdgas.1. Use of polymers which are composed of one or different anionic monomers and of one or different cationic monomers and optionally also of nonionic monomers as additives for preventing the formation, growth and / or agglomeration of gas hydrate crystals in a mixture of water and petroleum / natural gas components in the production or transportation of petroleum and / or natural gas.
2. Verwendung der Polymeren nach Anspruch 1 , deren anionische Bausteine Monomere mit mindestens einer polymerisationsfähigen Doppelbindung und mit Carbon-, Sulfon- und/oder Phosphonsäuregruppen darstellen.2. Use of the polymers according to claim 1, whose anionic building blocks are monomers with at least one polymerizable double bond and with carbon, sulfonic and / or phosphonic acid groups.
3. Verwendung der Polymeren nach Anspruch 1 oder 2, deren anionische Bausteine die Monomeren Vinylsulfonat, Methallylsulfonat, Natrium-2-acrylamido-2- methyl-1 -propansulfonat (AMPS), Acrylsäure, Methacrylsäure oder Vinylphosphonat oder Mischungen davon in Anteilen von 1-99, bevorzugt 10-90 Mol-% darstellen.3. Use of the polymers according to claim 1 or 2, the anionic building blocks of the monomers vinyl sulfonate, methallyl sulfonate, sodium 2-acrylamido-2-methyl-1-propane sulfonate (AMPS), acrylic acid, methacrylic acid or vinyl phosphonate or mixtures thereof in proportions of 1- 99, preferably 10-90 mol%.
4. Verwendung der Polymeren nach mindestens einem der Ansprüche 1 bis 3, deren anionische Bausteine die Monomeren Natrium-2-acrylamido-2-methyl-1- propansulfonat (AMPS) und/oder Acrylsäure in Anteilen von 10-90 Mol-% darstellen.4. Use of the polymers according to at least one of claims 1 to 3, the anionic building blocks of which are the monomers sodium 2-acrylamido-2-methyl-1-propanesulfonate (AMPS) and / or acrylic acid in proportions of 10-90 mol%.
5. Verwendung der Polymeren nach Anspruch 1 , deren kationische Bausteine quartäre Ammoniumsalze mit einem polymerisationsfähigen Rest am N-Atom in Anteilen von 1-99, bevorzugt von 10-90 Mol-% darstellen.5. Use of the polymers according to claim 1, the cationic building blocks of which represent quaternary ammonium salts with a polymerizable radical on the N atom in proportions of 1-99, preferably 10-90 mol%.
6. Verwendung der Polymeren nach Anspruch 1 oder 5, deren kationische Bausteine die Monomeren Dimethyldiallylammoniumchlorid (DADMAC), Trimethylammonium-ethylacrylat und/oder N-(3-Trimethylammoniumpropyl)- methacrylamid (MAPTAC) in Anteilen von 10-90 Mol-% darstellen. 6. Use of the polymers according to claim 1 or 5, the cationic building blocks of which are the monomers dimethyldiallylammonium chloride (DADMAC), trimethylammonium ethyl acrylate and / or N- (3-trimethylammonium propyl) methacrylamide (MAPTAC) in proportions of 10-90 mol%.
7. Verwendung der Polymeren nach mindestens einem der Ansprüche 1 bis 6, wobei die Polymere außer aus kationischen und anionischen Monomeren auch aus nichtionischen Monomeren mit vinylischer Doppelbindung in Anteilen von 1-99, bevorzugt 10-90 Mol-% aufgebaut sind.7. Use of the polymers according to at least one of claims 1 to 6, the polymers being composed not only of cationic and anionic monomers but also of nonionic monomers having a vinyl double bond in proportions of 1-99, preferably 10-90 mol%.
8. Verwendung der Polymeren nach Anspruch 7, deren nichtionische Bausteine acyclische und/oder cyclische Monomere mit einer Amidbindung darstellen.8. Use of the polymers according to claim 7, the nonionic building blocks of which are acyclic and / or cyclic monomers with an amide bond.
9. Verwendung eines Polymers auf Basis von 80 bis 20 Mol-% Natrium-2-acrylamido-2-methyl-1 -propansulfonat (AMPS) und von 20 bis 80 Mol-% Dimethyldiallyammoniumchlorid (DADMAC) als Gashydratinhibitor gemäß Anspruch 1.9. Use of a polymer based on 80 to 20 mol% of sodium 2-acrylamido-2-methyl-1-propanesulfonate (AMPS) and from 20 to 80 mol% of dimethyldiallyammonium chloride (DADMAC) as a gas hydrate inhibitor according to claim 1.
10. Verwendung eines Polymers auf Basis von Natrium-2-acrylamido-2-methyl-1- propansulfonat (AMPS), N-(3-Trimethylammoniumpropyl)-methacrylamid (MAPTAC) und Acrylamid als Gashydratinhibitor gemäß Anspruch 1.10. Use of a polymer based on sodium 2-acrylamido-2-methyl-1-propanesulfonate (AMPS), N- (3-trimethylammonium propyl) methacrylamide (MAPTAC) and acrylamide as gas hydrate inhibitor according to claim 1.
11. Verwendung der Polymere nach mindestens einem der Ansprüche 1 bis 10 in Kombination mit weiteren als Gashydratinhibitoren wirksamen Substanzen, vorzugsweise quartären Ammoniumsalzen, Esterquats, Aminoxiden, Alkylpolyglukosiden, Polyvinylpyrollidon, Polyvinylcaprolactam und dessen Copolymere mit anderen Monomeren.11. Use of the polymers according to at least one of claims 1 to 10 in combination with other substances effective as gas hydrate inhibitors, preferably quaternary ammonium salts, ester quats, amine oxides, alkyl polyglucosides, polyvinyl pyrollidone, polyvinyl caprolactam and its copolymers with other monomers.
12. Verfahren zur Verhinderung der Bildung, des Wachstums und/oder der Agglomeration von Gashydratkristallen in einer Mischung aus Wasser und Erdöl- /Erdgasbestandteilen bei der Förderung oder dem Transport von Erdöl und/oder Erdgas, dadurch gekennzeichnet, daß Polymere, die aus einem oder verschiedenen anionischen Monomeren und aus einem oder verschiedenen kationischen Monomeren sowie gegebenenfalls auch aus nichtionischen Monomeren aufgebaut sind, in einer Konzentration, bezogen auf 100% Wirksubstanz, von 0,01 bis 2 Gew.- %, zu dieser Mischung zugegeben oder in die Förderstelle eingebracht werden. 12. A method for preventing the formation, growth and / or agglomeration of gas hydrate crystals in a mixture of water and petroleum / natural gas constituents in the production or transportation of petroleum and / or natural gas, characterized in that polymers consisting of or various anionic monomers and from one or different cationic monomers and optionally also from nonionic monomers, in a concentration, based on 100% active substance, of 0.01 to 2% by weight, are added to this mixture or introduced into the feed station .
EP97950130A 1996-11-18 1997-11-06 Additives to inhibit the formation of gas hydrate Withdrawn EP0946688A1 (en)

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