NO327578B1 - Use of a water-soluble polymer as an additive for inhibiting gas hydrate formation. - Google Patents
Use of a water-soluble polymer as an additive for inhibiting gas hydrate formation. Download PDFInfo
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- NO327578B1 NO327578B1 NO20063743A NO20063743A NO327578B1 NO 327578 B1 NO327578 B1 NO 327578B1 NO 20063743 A NO20063743 A NO 20063743A NO 20063743 A NO20063743 A NO 20063743A NO 327578 B1 NO327578 B1 NO 327578B1
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- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 11
- 239000000654 additive Substances 0.000 title claims abstract description 9
- 229920003169 water-soluble polymer Polymers 0.000 title claims abstract description 9
- 230000000996 additive effect Effects 0.000 title claims description 6
- 230000002401 inhibitory effect Effects 0.000 title claims description 5
- NMJORVOYSJLJGU-UHFFFAOYSA-N methane clathrate Chemical compound C.C.C.C.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O NMJORVOYSJLJGU-UHFFFAOYSA-N 0.000 title description 5
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- 150000004677 hydrates Chemical class 0.000 claims abstract description 11
- 238000005553 drilling Methods 0.000 claims abstract description 8
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 8
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 8
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 5
- 229920000642 polymer Polymers 0.000 claims description 45
- 150000001768 cations Chemical class 0.000 claims description 8
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 8
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- -1 quaternary ammonium cations Chemical class 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000005462 imide group Chemical group 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 abstract 1
- 125000000962 organic group Chemical group 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 11
- 239000003112 inhibitor Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 4
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 4
- 230000002528 anti-freeze Effects 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical class OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000003973 alkyl amines Chemical class 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 description 2
- KZSNJWFQEVHDMF-BYPYZUCNSA-N L-valine Chemical compound CC(C)[C@H](N)C(O)=O KZSNJWFQEVHDMF-BYPYZUCNSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007942 carboxylates Chemical group 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- BMFVGAAISNGQNM-UHFFFAOYSA-N isopentylamine Chemical compound CC(C)CCN BMFVGAAISNGQNM-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- CRSOQBOWXPBRES-UHFFFAOYSA-N neopentane Chemical compound CC(C)(C)C CRSOQBOWXPBRES-UHFFFAOYSA-N 0.000 description 2
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 1
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- BUIXEGYUDCDLCD-UHFFFAOYSA-N 3-(2-methylpropoxy)propan-1-ol Chemical compound CC(C)COCCCO BUIXEGYUDCDLCD-UHFFFAOYSA-N 0.000 description 1
- MXRGSJAOLKBZLU-UHFFFAOYSA-N 3-ethenylazepan-2-one Chemical compound C=CC1CCCCNC1=O MXRGSJAOLKBZLU-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004201 L-cysteine Substances 0.000 description 1
- 235000013878 L-cysteine Nutrition 0.000 description 1
- 229920000805 Polyaspartic acid Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229920006322 acrylamide copolymer Polymers 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 229940024606 amino acid Drugs 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000007798 antifreeze agent Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- NISGSNTVMOOSJQ-UHFFFAOYSA-N cyclopentanamine Chemical compound NC1CCCC1 NISGSNTVMOOSJQ-UHFFFAOYSA-N 0.000 description 1
- 239000000412 dendrimer Substances 0.000 description 1
- 229920000736 dendritic polymer Polymers 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- MKRTXPORKIRPDG-UHFFFAOYSA-N diphenylphosphoryl azide Chemical compound C=1C=CC=CC=1P(=O)(N=[N+]=[N-])C1=CC=CC=C1 MKRTXPORKIRPDG-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229920000587 hyperbranched polymer Polymers 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 229920001308 poly(aminoacid) Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 108010064470 polyaspartate Proteins 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- NTKBNCABAMQDIG-UHFFFAOYSA-N trimethylene glycol-monobutyl ether Natural products CCCCOCCCO NTKBNCABAMQDIG-UHFFFAOYSA-N 0.000 description 1
- 229960004295 valine Drugs 0.000 description 1
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/028—Polyamidoamines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1092—Polysuccinimides
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Oppfinnelsen vedrører anvendelse av vannløselige polymerer som inneholder én eller flere strukturelle enheter av formel I, hvor R1 og R2 er H eller en organisk gruppe med 1-12 karbonatomer, X er en fordelergruppe eller en binding, som additiver for å inhibere dannelsen av gasshydrater i forbindelse med hydrokarbonproduksjon og -transport, inkludert produksjons-, bore-, kompletterings-, og fraktureringsoperasjoner. Formel IThe invention relates to the use of water-soluble polymers containing one or more structural units of formula I, wherein R 1 and R 2 are H or an organic group having 1-12 carbon atoms, X is a distribution group or a bond, as additives to inhibit the formation of gas hydrates in in connection with hydrocarbon production and transport, including production, drilling, completion and fracturing operations. Formula I
Description
Område for oppfinnelsen Field of the invention
Den foreliggende oppfinnelsen vedrører anvendelser av vannløselig polymer som en additiv for å inhibere dannelse av gasshydrater, for eksempel i rørledninger for produksjon av olje og naturgass og for å transportere dem, og i boring, komplettering og frak-tureringsoperasj oner. The present invention relates to applications of water-soluble polymer as an additive to inhibit the formation of gas hydrates, for example in pipelines for the production of oil and natural gas and to transport them, and in drilling, completion and fracturing operations.
Bakgrunnsteknikk Background technology
Gasshydrater er klatrater (inklusjonsforbindelser) av små molkyler i et gitter av vann-molekyler. Innen petroleumsindustrien vil naturgass og petroleumsfluider inneholde en rekke av disse små molekylene, som kan danne gasshydrater. De inkluderer hydrokarboner, så som metan, etan, propan, isobutan så vel som nitrogen, karbondioksid og hy-drogensulfid. Større hydrokarboner, så som n-butan, neopentan, etylen, cyklopentan, cykloheksan og benzen er også hydratdannende komponenter. Når disse hydratdannende komponentene er til stede med vann ved eleverte trykk og reduserte temperaturer, har blandingen en tendens til å danne gasshydratkrystaller. For eksempel danner etan ved et trykk på 1 MPa hydrater bare ved en temperatur på under 4 grader C, hvormed ved 3 MPa kan gasshydrater bare dannes under 14 grader C. Disse temperaturene og trykkene er typiske driftsmiljøer hvor petroleumsfluider produseres og transporteres, eller i borings-, kompletterings-, eller fraktureringsoperasjoner i olje og gassindustrien. Gas hydrates are clathrates (inclusion compounds) of small molecules in a lattice of water molecules. Within the petroleum industry, natural gas and petroleum fluids will contain a number of these small molecules, which can form gas hydrates. They include hydrocarbons such as methane, ethane, propane, isobutane as well as nitrogen, carbon dioxide and hydrogen sulfide. Larger hydrocarbons such as n-butane, neopentane, ethylene, cyclopentane, cyclohexane and benzene are also hydrate-forming components. When these hydrate-forming components are present with water at elevated pressures and reduced temperatures, the mixture tends to form gas hydrate crystals. For example, ethane at a pressure of 1 MPa forms hydrates only at a temperature below 4 degrees C, whereby at 3 MPa gas hydrates can only form below 14 degrees C. These temperatures and pressures are typical operating environments where petroleum fluids are produced and transported, or in drilling -, completion or fracturing operations in the oil and gas industry.
Dersom gasshydrater tillates å bli dannet på innsiden av en rørledning anvendt for å transportere naturgass og/eller andre petroleumsfluider, kan de til slutt blokkere rørled-ningen. Hydratblokkering kan føre til en nedstengning av produksjonen og gi vesentlige økonomisk tap. Olje- og gassindustrien anvender forskjellige midler for å forhindre dannelsen av hydratblokkeringer i rørledninger. Disse inkluderer oppvarming av rørled-ninger, trykkreduksjon, fjerning av vann og tilsetting av termodynamiske inhibitorer (anti-frysmidler), så som metanol og etylenglykoler, som reduserer smeltepunktet. Hver av disse fremgangsmåtene er kostbare å implementere og opprettholde. Den mest vanli-ge fremgangsmåten anvendt i dag er å tilsette anti-frysmidler. Imidlertid må disse anti-frysemidlene tilsettes ved høye konsentrasjoner, typisk 10-40 vektprosent av vannet til stede, for å kunne være effektive. Gjenvinning av anti-frysmidler er vanligvis også på-krevd og er en kostbar prosedyre. If gas hydrates are allowed to form inside a pipeline used to transport natural gas and/or other petroleum fluids, they can eventually block the pipeline. Hydrate blocking can lead to a shutdown of production and cause significant economic losses. The oil and gas industry uses various means to prevent the formation of hydrate blockages in pipelines. These include heating of pipelines, pressure reduction, removal of water and addition of thermodynamic inhibitors (anti-freeze agents), such as methanol and ethylene glycols, which lower the melting point. Each of these practices is expensive to implement and maintain. The most common method used today is to add antifreeze. However, these antifreezes must be added at high concentrations, typically 10-40% by weight of the water present, to be effective. Recovery of antifreeze is usually also required and is an expensive procedure.
Et alternativ til fremgangsmåtene ovenfor er å kontrollere gasshydratdannelsesprosessen ved bruk av nukleasjons- og krystallvektinhibitorer. Disse kjemikalietypene er svært kjente og anvendes i andre industrielle prosesser. Fordelen med å benytte disse kjemika-liene for å kontrollere gasshydratdannelse er at de kan anvendes ved konsentrasjoner på 0,01 til 3 %, som er mye lavere enn for anti-frysmidler. An alternative to the above methods is to control the gas hydrate formation process using nucleation and crystal weight inhibitors. These chemical types are very well known and are used in other industrial processes. The advantage of using these chemicals to control gas hydrate formation is that they can be used at concentrations of 0.01 to 3%, which is much lower than for antifreezes.
Eksempler inkluderer en fremgangsmåte for å tilsette polyvinylpyrolidon eller en kopolymer av vinylpyrolidon og .alfa.-olefiner (se internasjonalt patent lagt åpent nr. W093/25798), en fremgangsmåte for å tilsette en kopolymer av vinylpyrolidon, vinyl-kaprolaktam og dimetylaminoetyl-metakrylat (se internasjonalt patent lagt åpent nr. W094/12761), en fremgangsmåte for å tilsette en polymer eller kopolymer som inneholder pyrolidonkarbonyl-aspartatgrupper (se US patent 6232273), en fremgangsmåte for å tilsette en blanding av kvartinært ammoniumsalt og en polyaminosyre eller salt derav som har strukturelle enheter avledet fra minst én aminosyre, minst 50 % av hvilke enheter har minst to karboksylsyregrupper, spesielt polyasparaginsyre (internasjonalt patent lagt åpent nr. WO96/29502). Examples include a process for adding polyvinylpyrrolidone or a copolymer of vinylpyrrolidone and .alpha.-olefins (see International Patent Laid Open No. WO93/25798), a process for adding a copolymer of vinylpyrrolidone, vinylcaprolactam and dimethylaminoethyl methacrylate ( see International Patent Laid Open No. WO94/12761), a process for adding a polymer or copolymer containing pyrrolidone carbonyl aspartate groups (see US Patent 6232273), a process for adding a mixture of quaternary ammonium salt and a polyamino acid or salt thereof which have structural units derived from at least one amino acid, at least 50% of which units have at least two carboxylic acid groups, especially polyaspartic acid (International Patent Laid Open No. WO96/29502).
Således er det behov for alternative billige fremgangsmåter for å forhindre hydratblokkeringer i olje- og gassboring og -produksjon. En ytterligere fordel vil være dersom hydratinhibitoren er biodegraderbare. Thus, there is a need for alternative inexpensive methods to prevent hydrate blockages in oil and gas drilling and production. A further advantage would be if the hydrate inhibitor is biodegradable.
Det er et formål med denne oppfinnelsen å tilveiebringe en additiv og en fremgangsmåte for å kontrollere gasshydratdannelse ved anvendelse av nevnte additiver tilsatt ved lave konsentrasjoner til en strøm av minst noen lette hydrokarboner og vann. It is an object of this invention to provide an additive and a method for controlling gas hydrate formation using said additives added at low concentrations to a stream of at least some light hydrocarbons and water.
Oppsummering av oppfinnelsen Summary of the invention
Sammenfatningsvis er oppfinnelsen slik som gjort rede for i de vedføyde krav. In summary, the invention is as explained in the appended claims.
Detaljert beskrivelse av oppfinnelsen Detailed description of the invention
Foreliggende oppfinnelse vedrører anvendelse av vannløselig polymer som en additiv for inhibering av dannelsen av gasshydrater i forbindelse med hydrokarbonproduksjon og -transport, inkludert produksjons-, bore-, kompletterings- og fraktureringsoperasjoner, hvori den vannløselige polymeren inkluderer én eller flere strukturelle elementer av formel III, hvori hver R3 og R4 uavhengig er H eller Ci-5-alkyl. The present invention relates to the use of water-soluble polymer as an additive for inhibiting the formation of gas hydrates in connection with hydrocarbon production and transport, including production, drilling, completion and fracturing operations, in which the water-soluble polymer includes one or more structural elements of formula III, wherein each R 3 and R 4 is independently H or C 1-5 alkyl.
I en annen utførelse inneholder polymerene 5-100 mol% av strukturelle elementer til formel III. In another embodiment, the polymers contain 5-100 mol% of structural elements of formula III.
I en foretrukket utførelse av oppfinnelsen har polymerene innholdende de strukturelle enhetene til formel III, vil R3 være isobutyl eller isopropyl og R4 er H. In a preferred embodiment of the invention, the polymers have the structural units of formula III, R3 will be isobutyl or isopropyl and R4 is H.
I en annen foretrukket utførelse av oppfinnelsen inneholder polymerene noen strukturelle enheter av formel III, hvor R3 er metyl og R4 er H, og noen av de strukturelle elementene til formel III med R3 som isobutyl eller isopropyl, og R4 er H. In another preferred embodiment of the invention, the polymers contain some structural units of formula III, where R3 is methyl and R4 is H, and some of the structural elements of formula III with R3 as isobutyl or isopropyl, and R4 is H.
Noen av de strukturelle enhetene i polymerene som inneholder strukturelle enheter av formel III kan ha formel IV. Some of the structural units in the polymers containing structural units of formula III may have formula IV.
hvori R5 er H+ eller en kation som inkluderer metallkationer og kvartenære ammoniumkationer. wherein R5 is H+ or a cation including metal cations and quaternary ammonium cations.
I en annen foretrukket utførelse av oppfinnelsen inneholder polymerene noen strukturelle enheter av formel III som har noen alkylgrupper R3 eller R4 som inneholder en amin-gruppe som inneholder dimetylamingrupper. In another preferred embodiment of the invention, the polymers contain some structural units of formula III which have some alkyl groups R3 or R4 containing an amine group containing dimethylamine groups.
I en annen utførelse av oppfinnelsen inkluderer polymerene én eller flere strukturelle elementer av formel V In another embodiment of the invention, the polymers include one or more structural elements of formula V
hvori hver R5 og R7 er uavhengig H eller Ci-5-alkyler; og hvori noen av alkylgruppene representert av R6 og R7 kan bære en hydroksy-, amino-, karboksylsyre-, eller karboksy-latsubstituent. wherein each R 5 and R 7 is independently H or C 1-5 alkyl; and wherein any of the alkyl groups represented by R6 and R7 may carry a hydroxyl, amino, carboxylic acid, or carboxylate substituent.
I en foretrukket utførelse av oppfinnelsen har polymerene som inneholder de strukturelle enhetene av formel V en R$ som er isobutyl eller isopropyl og R7 er H. In a preferred embodiment of the invention, the polymers containing the structural units of formula V have an R$ which is isobutyl or isopropyl and R7 is H.
I en annen foretrukket utførelse av oppfinnelsen inneholder polymerene noen strukturelle enheter av formel V, hvor R3 er metyl og R4 er H, og noen av de strukturelle elementene av formel V hvor R3 er isobutyl elle isopropyl og R4 er H. In another preferred embodiment of the invention, the polymers contain some structural units of formula V, where R3 is methyl and R4 is H, and some of the structural elements of formula V where R3 is isobutyl or isopropyl and R4 is H.
Noen av de strukturelle enhetene i polymerene som inneholder strukturelle enheter av formel III har formel IV. Some of the structural units in the polymers containing structural units of formula III have formula IV.
Noen av de strukturelle enhetene i polymerene som inneholder strukturelle enheter av formel V kan ha formel VI. Some of the structural units in the polymers containing structural units of formula V may have formula VI.
hvori noen av de strukturelle enhetene i polymeren har formel VI hvori Rg er H+ eller et kation som inkluderer metallkationer og kvartinære ammoniumkationer. wherein some of the structural units of the polymer have the formula VI wherein Rg is H+ or a cation which includes metal cations and quaternary ammonium cations.
I en utførelse av oppfinnelsen inneholder polymerene 2 eller flere forskjellige strukturelle enheter av formel I. Fordelingen av enhetene i polymeren kan være tilfeldig eller en eksakt sekvens eller alternering. In one embodiment of the invention, the polymers contain 2 or more different structural units of formula I. The distribution of the units in the polymer can be random or an exact sequence or alternation.
I en utførelse av oppfinnelsen kan to eller flere polymerer som inneholder én eller flere strukturelle enheter av formel I brukes. Fordelingen av enhetene i polymerene kan være tilfeldig eller en eksakt sekvens eller alternering. In one embodiment of the invention, two or more polymers containing one or more structural units of formula I can be used. The distribution of the units in the polymers can be random or an exact sequence or alternation.
I en utførelse av oppfinnelsen er polymeren eller polymerene krysslenkede eller forgre-nede. In one embodiment of the invention, the polymer or polymers are cross-linked or branched.
I en utførelse av oppfinnelsen er de strukturelle elementene som i formel I laget ved å reagere polysuccinimid eller kopolymerer derav med én eller flere aminer eller diami-ner. Eksempler på alkylaminer som kan reagere med polysuccinimid og polymerer derav for å danne det ønskede produktet inkluderer metylamin, dimetylamin, etylamin, dietylamin, n-propylamin, iso-propylamin, iso-butylamin, n-butylamin, t-butylamin, n-pentylamin, iso-pentylamin og cyklopentylamin, 3-(dimetylamin)propylamin og 2-(dimetylamin)etylamin. Ikke alle de cykliske imidgruppene kan reagere med nevnte alkylaminer. I slike tilfeller kan de gjenværende imidgruppene forsåpes (hydrolyseres) for å danne karboksylsyre eller karboksylatgrupper. In one embodiment of the invention, the structural elements as in formula I are made by reacting polysuccinimide or copolymers thereof with one or more amines or diamines. Examples of alkylamines which can react with polysuccinimide and polymers thereof to form the desired product include methylamine, dimethylamine, ethylamine, diethylamine, n-propylamine, iso-propylamine, iso-butylamine, n-butylamine, t-butylamine, n-pentylamine, isopentylamine and cyclopentylamine, 3-(dimethylamine)propylamine and 2-(dimethylamine)ethylamine. Not all of the cyclic imide groups can react with said alkylamines. In such cases, the remaining imide groups can be saponified (hydrolyzed) to form carboxylic acid or carboxylate groups.
Polymerene i oppfinnelsen kan brukes sammen med en synergist (ytelsesforhøyende kjemikalie). Eksempler på synergister inkluderer polymerer og kopolymerer av N-vinylkaprolaktam, N-vinyl-pyrrolidon og alkylerte vinylpyrolidoner, alkyl- og dialky-lakrylamidpolymerer og kopolymerer, hyperforgrenede polymerer eller dendrimerer inkludert polyesteramider, polymerer og kopolymerer av maleinanhydrid, som har reagert med alkylaminer for å danne imid eller amidgrupper, polysakkarider og derivater av slike inkludert sukker og stivelse, polyoksyalkylendiaminer, små alkoholer, små glykoletere eller ketoner, amfifile molekyler med molekylvekt på mindre enn 1000 Dalton, proteiner, peptider eller polyaminosyrer. The polymers of the invention can be used together with a synergist (performance enhancing chemical). Examples of synergists include polymers and copolymers of N-vinyl caprolactam, N-vinyl pyrrolidone and alkylated vinyl pyrrolidones, alkyl and dialkyl acrylamide polymers and copolymers, hyperbranched polymers or dendrimers including polyester amides, polymers and copolymers of maleic anhydride, which have reacted with alkylamines to forming imide or amide groups, polysaccharides and derivatives thereof including sugars and starches, polyoxyalkylenediamines, lower alcohols, lower glycol ethers or ketones, amphiphilic molecules of molecular weight less than 1000 Daltons, proteins, peptides or polyamino acids.
Foretrukne små glykoletere inkluderer n-butyoksyetanol, iso-butyksoetanol, n-butoksypropanol eller iso-butoksypropanol. Disse kan være løsningsmiddelet for klatrathydratinhibitorene i denne oppfinnelsen. Preferred small glycol ethers include n-butyoxyethanol, iso-butyxoethanol, n-butoxypropanol or iso-butoxypropanol. These may be the solvent for the clathrate hydrate inhibitors of this invention.
Foretrukne amfifile molekyler inkluderer kvartenære ammoniumoverflateaktive stoffer. Preferred amphiphilic molecules include quaternary ammonium surfactants.
Polymerene ved oppfinnelsen kan også anvendes som avleiringsinhibitorer og/eller korrosjonsinhibitorer. Dvs. at i noen tilfeller kan det være unødvendig å anvende et annet molekyl som avleirings- eller korrosjonsinhibitorer dersom klatrathydratinhibitorene ved denne oppfinnelsen kan gjøre jobben. The polymers of the invention can also be used as deposit inhibitors and/or corrosion inhibitors. That is that in some cases it may be unnecessary to use another molecule as scale or corrosion inhibitors if the clathrate hydrate inhibitors of this invention can do the job.
Eksempel 1 Example 1
9,7 g (0,1 mol) polysuccinimid og 40 ml dimetylformamid ble puttet inn i en 100 ml flaske utstyrt med en rører. Når polymeren ble oppløst, ble 7,2 g (0,12 mol) isopropylamin tilsatt dråpevis ved romtemperatur over en periode på 30 minutter. Etter tilsettingen ble forbindelsene rørt i ytterligere 2 timer ved romtemperatur, og den resulterende reaksjonsblandingen ble helt inn i overskuddsdietyleter for å felle ut den ringåpnede polymeren. Polymeren ble vasket med dietyleter og tørket i vakuum. Således ble det oppnådd en kinetisk hydratinhibitorprøve (1). 9.7 g (0.1 mol) of polysuccinimide and 40 ml of dimethylformamide were placed in a 100 ml flask equipped with a stirrer. When the polymer was dissolved, 7.2 g (0.12 mol) of isopropylamine was added dropwise at room temperature over a period of 30 minutes. After the addition, the compounds were stirred for an additional 2 hours at room temperature, and the resulting reaction mixture was poured into excess diethyl ether to precipitate the ring-opened polymer. The polymer was washed with diethyl ether and dried in vacuo. Thus, a kinetic hydrate inhibitor sample (1) was obtained.
Eksempel 2 Example 2
9,7 g (0,1 mol) polysuccinimid og 100 ml dimetylformamid ble puttet inn i en 250 ml flaske utstyrt med en rører. Når polymeren hadde blitt løst opp, ble 3,6 g (0,06 mol) isopropylamin oppløst i 30 ml av 2,0 molar metylamin i tetrahydrofuran tilsatt dråpevis ved romtemperatur over en periode på 30 minutter. Etter tilsettingen ble forbindelsene rørt i ytterligere to timer ved romtemperatur, og den resulterende reaksjonsblandingen ble helt inn i overskuddsdietyleter for å felle ut den ringåpnede polymeren. Polymeren ble vasket med dietyleter og tørket i vakuum. Således ble det oppnådd en kinetisk hyd-ratinhibitorprøve (2). 9.7 g (0.1 mol) of polysuccinimide and 100 ml of dimethylformamide were placed in a 250 ml flask equipped with a stirrer. Once the polymer had been dissolved, 3.6 g (0.06 mole) of isopropylamine dissolved in 30 ml of 2.0 molar methylamine in tetrahydrofuran was added dropwise at room temperature over a period of 30 minutes. After the addition, the compounds were stirred for an additional two hours at room temperature, and the resulting reaction mixture was poured into excess diethyl ether to precipitate the ring-opened polymer. The polymer was washed with diethyl ether and dried in vacuo. Thus, a kinetic hydrate inhibitor sample (2) was obtained.
Eksempel 3 Example 3
L-valin (0,1 mol) og L-cysteinsyre (0,1 mol) ble reagert med difenylfosforylasid i DMF (100 ml) ved 0°C med røring. Løsningen ble varmet til romtemperatur og rørt i 3 dager. Løsningen ble helt inn i overskuddsdiemetylformamid for å danne en utfelling som ble filtrert av og tørket. Således ble det oppnådd en kinetisk hydratinhibitorprøve (3). L-valine (0.1 mol) and L-cysteine acid (0.1 mol) were reacted with diphenylphosphoryl azide in DMF (100 mL) at 0°C with stirring. The solution was warmed to room temperature and stirred for 3 days. The solution was poured into excess dimethylformamide to form a precipitate which was filtered off and dried. Thus, a kinetic hydrate inhibitor sample (3) was obtained.
Eksemplene 1-3 er alle innenfor kravene i oppfinnelsen. Examples 1-3 are all within the requirements of the invention.
Claims (14)
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| NO20063743A NO327578B1 (en) | 2006-08-22 | 2006-08-22 | Use of a water-soluble polymer as an additive for inhibiting gas hydrate formation. |
| PCT/NO2007/000290 WO2008023989A1 (en) | 2006-08-22 | 2007-08-20 | Additives for inhibiting gas hydrate formation |
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| US6232273B1 (en) * | 1995-06-02 | 2001-05-15 | Nippon Shokubai Co., Ltd. | Clathrate hydrate inhibitor and method of inhibiting the formation of clathrate hydrates using it |
| JP2003336084A (en) * | 2002-05-23 | 2003-11-28 | Mitsubishi Rayon Co Ltd | Gas hydrate production controlling agent and method for controlling production of gas hydrate using the same |
| US6867262B1 (en) * | 1999-07-28 | 2005-03-15 | Basf Aktiengesellschaft | Grafted polymers as gas hydrate inhibitors |
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| US6825313B2 (en) * | 2002-05-07 | 2004-11-30 | Aquero Company | Copolymers of amino acids and methods of their production |
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| US6232273B1 (en) * | 1995-06-02 | 2001-05-15 | Nippon Shokubai Co., Ltd. | Clathrate hydrate inhibitor and method of inhibiting the formation of clathrate hydrates using it |
| US6867262B1 (en) * | 1999-07-28 | 2005-03-15 | Basf Aktiengesellschaft | Grafted polymers as gas hydrate inhibitors |
| JP2003336084A (en) * | 2002-05-23 | 2003-11-28 | Mitsubishi Rayon Co Ltd | Gas hydrate production controlling agent and method for controlling production of gas hydrate using the same |
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