NO166652B - PROCEDURE FOR CORROSION-INHIBITIVE TREATMENT OF METAL SURFACES. - Google Patents
PROCEDURE FOR CORROSION-INHIBITIVE TREATMENT OF METAL SURFACES. Download PDFInfo
- Publication number
- NO166652B NO166652B NO822904A NO822904A NO166652B NO 166652 B NO166652 B NO 166652B NO 822904 A NO822904 A NO 822904A NO 822904 A NO822904 A NO 822904A NO 166652 B NO166652 B NO 166652B
- Authority
- NO
- Norway
- Prior art keywords
- mixture
- corrosion
- weight
- petroleum
- epoxy resin
- Prior art date
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- 238000000034 method Methods 0.000 title claims description 23
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- PXKYONMGPHGXON-UHFFFAOYSA-N bis[(3-methyloxiran-2-yl)methyl] 2,3-dihydroxybutanedioate Chemical compound CC1OC1COC(=O)C(O)C(O)C(=O)OCC1C(C)O1 PXKYONMGPHGXON-UHFFFAOYSA-N 0.000 description 1
- UUGMXLZAGKJQPR-UHFFFAOYSA-N bis[(3-methyloxiran-2-yl)methyl] cyclohex-3-ene-1,2-dicarboxylate Chemical compound CC1OC1COC(=O)C1C(C(=O)OCC2C(O2)C)C=CCC1 UUGMXLZAGKJQPR-UHFFFAOYSA-N 0.000 description 1
- LAVPNNCPEKYKLQ-UHFFFAOYSA-N bis[(3-pentyloxiran-2-yl)methyl] oxalate Chemical compound CCCCCC1OC1COC(=O)C(=O)OCC1C(CCCCC)O1 LAVPNNCPEKYKLQ-UHFFFAOYSA-N 0.000 description 1
- QDDXFSVAOIFGQF-UHFFFAOYSA-N bis[(3-propan-2-yloxiran-2-yl)methyl] cyclohex-2-ene-1,4-dicarboxylate Chemical compound CC(C)C1OC1COC(=O)C1C=CC(C(=O)OCC2C(O2)C(C)C)CC1 QDDXFSVAOIFGQF-UHFFFAOYSA-N 0.000 description 1
- MRCWOUFSKOQILC-UHFFFAOYSA-N bis[(3-propyloxiran-2-yl)methyl] heptanedioate Chemical compound CCCC1OC1COC(=O)CCCCCC(=O)OCC1C(CCC)O1 MRCWOUFSKOQILC-UHFFFAOYSA-N 0.000 description 1
- XQISOOUWIGPXJO-UHFFFAOYSA-N bis[2-(3-butyloxiran-2-yl)ethyl] octanedioate Chemical compound CCCCC1OC1CCOC(=O)CCCCCCC(=O)OCCC1C(CCCC)O1 XQISOOUWIGPXJO-UHFFFAOYSA-N 0.000 description 1
- NGYVJDSFFQDWGX-UHFFFAOYSA-N bis[2-(3-ethyloxiran-2-yl)ethyl] benzene-1,2-dicarboxylate Chemical compound CCC1OC1CCOC(=O)C1=CC=CC=C1C(=O)OCCC1C(CC)O1 NGYVJDSFFQDWGX-UHFFFAOYSA-N 0.000 description 1
- BBNVHWBKQSNBME-UHFFFAOYSA-N bis[2-(3-methyloxiran-2-yl)ethyl] butanedioate Chemical compound CC1OC1CCOC(=O)CCC(=O)OCCC1C(C)O1 BBNVHWBKQSNBME-UHFFFAOYSA-N 0.000 description 1
- QNUNZFSSCCNKID-UHFFFAOYSA-N bis[2-(oxiran-2-yl)ethyl] pentanedioate Chemical compound C1OC1CCOC(=O)CCCC(=O)OCCC1CO1 QNUNZFSSCCNKID-UHFFFAOYSA-N 0.000 description 1
- PQONADZBGFSRFY-UHFFFAOYSA-N bis[3-(3-heptyloxiran-2-yl)propyl] benzene-1,4-dicarboxylate Chemical compound CCCCCCCC1OC1CCCOC(=O)C1=CC=C(C(=O)OCCCC2C(O2)CCCCCCC)C=C1 PQONADZBGFSRFY-UHFFFAOYSA-N 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N iso-butene Natural products CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- KSTBCRYHGOWRJG-UHFFFAOYSA-N n'-heptadecylpropane-1,3-diamine Chemical compound CCCCCCCCCCCCCCCCCNCCCN KSTBCRYHGOWRJG-UHFFFAOYSA-N 0.000 description 1
- UKNVXIMLHBKVAE-UHFFFAOYSA-N n'-hexadecylpropane-1,3-diamine Chemical compound CCCCCCCCCCCCCCCCNCCCN UKNVXIMLHBKVAE-UHFFFAOYSA-N 0.000 description 1
- RXFYAPDCERSOCN-UHFFFAOYSA-N n'-nonadecylpropane-1,3-diamine Chemical compound CCCCCCCCCCCCCCCCCCCNCCCN RXFYAPDCERSOCN-UHFFFAOYSA-N 0.000 description 1
- ITSJEKLZWRBYSX-UHFFFAOYSA-N n'-octadec-1-enylpropane-1,3-diamine Chemical compound CCCCCCCCCCCCCCCCC=CNCCCN ITSJEKLZWRBYSX-UHFFFAOYSA-N 0.000 description 1
- DXYUWQFEDOQSQY-UHFFFAOYSA-N n'-octadecylpropane-1,3-diamine Chemical compound CCCCCCCCCCCCCCCCCCNCCCN DXYUWQFEDOQSQY-UHFFFAOYSA-N 0.000 description 1
- HQMKMXCUDDEEPW-UHFFFAOYSA-N n'-pentadecylpropane-1,3-diamine Chemical compound CCCCCCCCCCCCCCCNCCCN HQMKMXCUDDEEPW-UHFFFAOYSA-N 0.000 description 1
- OWKYZAGJTTTXOK-UHFFFAOYSA-N n'-propylpropane-1,3-diamine Chemical compound CCCNCCCN OWKYZAGJTTTXOK-UHFFFAOYSA-N 0.000 description 1
- SSSZZOVUXFLWCQ-UHFFFAOYSA-N n'-tetradecylpropane-1,3-diamine Chemical compound CCCCCCCCCCCCCCNCCCN SSSZZOVUXFLWCQ-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- LNMIAOWRCMCSKL-UHFFFAOYSA-N octyl 2,14-dioxatricyclo[11.1.0.01,3]tetradecane-4-carboxylate Chemical compound C(CCCCCCC)OC(=O)C1C2C3(C(CCCCCCCC1)O3)O2 LNMIAOWRCMCSKL-UHFFFAOYSA-N 0.000 description 1
- KMAMDXMQIUOTAC-UHFFFAOYSA-N octyl 2,8-dioxatricyclo[5.1.0.01,3]octane-4-carboxylate Chemical compound C(CCCCCCC)OC(=O)C1C2C3(C(CC1)O3)O2 KMAMDXMQIUOTAC-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- FDLLNMKUVWDHKU-UHFFFAOYSA-N pentyl 1,4-dioxaspiro[2.2]pentane-2-carboxylate Chemical compound C(CCCC)OC(C1C2(CO2)O1)=O FDLLNMKUVWDHKU-UHFFFAOYSA-N 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 150000008442 polyphenolic compounds Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 150000005691 triesters Chemical class 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical class NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 1
- VSRBKQFNFZQRBM-UHFFFAOYSA-N tuaminoheptane Chemical compound CCCCCC(C)N VSRBKQFNFZQRBM-UHFFFAOYSA-N 0.000 description 1
- 229960003986 tuaminoheptane Drugs 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Classifications
-
- 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
- C09K8/54—Compositions for in situ inhibition of corrosion in boreholes or wells
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Wood Science & Technology (AREA)
- Epoxy Resins (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Description
Oppfinnelsen angår en fremgangsmåte til korrosjonshemmende behandling av metalloverflater av boreutstyr i en brønn til utvinning av naturlige fluider fra et underjordisk, reservoar, hvor metalloverflaten bringes i berøring med en blanding som omfatter en epoksyharpiks i en mengde på 2-5 0 vektprosent, et hydrokarbonfortynningsmiddel og eventuelt et polyamin og/eller en alkohol, under betingelser som bevirker dannelse av en film på overflaten. The invention relates to a method for anti-corrosion treatment of metal surfaces of drilling equipment in a well for extracting natural fluids from an underground reservoir, where the metal surface is brought into contact with a mixture comprising an epoxy resin in an amount of 2-50% by weight, a hydrocarbon diluent and optionally a polyamine and/or an alcohol, under conditions which cause the formation of a film on the surface.
Problemet med korrosjon av metalloverflater i berøring med luft og vann er velkjent. Korrosjon og gropdannelse akselereres i omgivelser hvor metalloverflåtene er i berøring med kjemikalier, f.eks. hydrogensulfid, karbondioksid og organiske syrer og vann med en høy elektrolyttkonsentrasjon. Slike omgivelser er typiske for de forhold som råder nede i olje- og gassbrønner, hvor korrosjon av metallrør, pumper og annet utstyr utgjør et alvorlig problem som krever overvåking av brønnene, hyppig vedlikehold og kostbar utskifting av deler. 01jeutvinningsoperasjoner i oljefelter på store havdyp byr på korrosjonsproblemer i sin mest ekstreme form. Metalloverflåtene nede i brønnen er i berøring med store mengder korroderende kjemikalier, f.eks. oppløste sure gasser som foreligger i den utvunnede olje, og dessuten er metalloverflåtene utsatt for temperaturer på 12Q°C eller høyere og trykk på 20 MPa eller høyere. De ekstreme temperatur- og trykkforhold bidrar til å akselerere korrosjonen og forsterke problemene med å anvende og opprettholde kjemisk beskyttelse av utstyret. I offshore-oljebrønner utsetter sekundærutvinningsoperasjoner som innbefatter vannflømming av de underjordiske formasjoner, utstyret nede i brønnen for meget korrosivt sjøvann inneholdende opp-løst oksygen. The problem of corrosion of metal surfaces in contact with air and water is well known. Corrosion and pitting are accelerated in environments where the metal surfaces are in contact with chemicals, e.g. hydrogen sulphide, carbon dioxide and organic acids and water with a high electrolyte concentration. Such environments are typical of the conditions prevailing in oil and gas wells, where corrosion of metal pipes, pumps and other equipment is a serious problem that requires monitoring of the wells, frequent maintenance and expensive replacement of parts. 01je extraction operations in oil fields at great ocean depths present corrosion problems in their most extreme form. The metal surfaces down in the well are in contact with large quantities of corrosive chemicals, e.g. dissolved acid gases present in the extracted oil, and furthermore the metal surfaces are exposed to temperatures of 12Q°C or higher and pressures of 20 MPa or higher. The extreme temperature and pressure conditions help to accelerate corrosion and exacerbate the problems of applying and maintaining chemical protection of the equipment. In offshore oil wells, secondary extraction operations that include waterflooding of the underground formations expose the equipment down in the well to highly corrosive seawater containing dissolved oxygen.
Vanlige korrosjonshemmende midler er ofte ikke virksomme i det hele tatt under slike ekstreme forhold, eller de reduserer korrosjonen bare for en kort periode og må deretter tilføres på nytt, ofte med sto<p>e omkostninger og besvær der-som brønnen ikke er lett tilgjengelig, eller byr på vanskelig-heter med hensyn til transport og anvendelse av store mengder kjemikalier, slik tilfellet er for en offshore-brønn. Common corrosion inhibitors are often not effective at all under such extreme conditions, or they only reduce corrosion for a short period and then have to be reapplied, often at great expense and difficulty where the well is not easily accessible , or presents difficulties with regard to the transport and application of large quantities of chemicals, as is the case for an offshore well.
Det er derfor en hensikt med oppfinnelsen å skaffe en fremgangsmåte til behandling av metalloverflater slik at der dannes en film som hindrer korrosjon av metallet, selv under ekstreme temperatur- og trykkforhold og i meget korrosive miljøer. It is therefore a purpose of the invention to provide a method for treating metal surfaces so that a film is formed which prevents corrosion of the metal, even under extreme temperature and pressure conditions and in highly corrosive environments.
Fremgangsmåte ifølge oppfinnelsen er karakterisert ved at der benyttes en blanding som i tillegg inneholder et petroleum- Method according to the invention is characterized in that a mixture is used which additionally contains a petroleum
sulfonat i en mengde på 1-80 vektprosent, regnet på vekten av blandingen, fortrinnsvis i et hydrokarbonfortynningsmiddel. sulfonate in an amount of 1-80 percent by weight, calculated on the weight of the mixture, preferably in a hydrocarbon diluent.
Egnede epoksyharpikser for bruk i den benyttede blanding omfatter alle epoksyharpikser som i gjennomsnitt har mer enn én tilstøtende epoksygruppe pr. molekyl. Epoksyharpiksen kan være mettet eller umettet, alifatisk, cykloalifatisk, aromatisk eller heterocyklisk og kan inneholde substituenter som ikke i vesentlig grad virker forstyrrende inn på herde-reaksjonen. De kan være monomere eller polymere. Suitable epoxy resins for use in the composition used include all epoxy resins having on average more than one adjacent epoxy group per molecule. The epoxy resin may be saturated or unsaturated, aliphatic, cycloaliphatic, aromatic or heterocyclic and may contain substituents which do not significantly interfere with the curing reaction. They can be monomeric or polymeric.
Egnede epoksyharpikser innbefatter glycidyletere fremstilt ved omsetting av epiklorhydrin med en hydroksylgruppeholdig forbindelse under alkaliske reaksjonsbetingelser. De epoksyhar-piksprodukter som fås når den hydroksylgruppeholdige forbindelse er bisfenol A, er representert ved formel I nedenfor, hvor n er lik eller større enn null, vanligvis 0-10, fortrinnsvis 0-2. Suitable epoxy resins include glycidyl ethers prepared by reacting epichlorohydrin with a hydroxyl group-containing compound under alkaline reaction conditions. The epoxy resin products obtained when the hydroxyl group-containing compound is bisphenol A are represented by formula I below, where n is equal to or greater than zero, usually 0-10, preferably 0-2.
Andre egnede epoksyharpikser kan fremstilles ved omsetting av epiklorhydrin med mononukleære di- og trihydroksy-fenolforbindelser, f.eks. resorcinol og floroglucinol, ut-valgte polynukleære polyhydroksyfenolforbindelser såsom bis (p-hydroksyf enyDmetan og 4 ,4 1 -dihydroksybif enyl eller alifatiske flerverdige alkoholer, f. eks. 1,4-butandiol og glycerol. Other suitable epoxy resins can be prepared by reacting epichlorohydrin with mononuclear di- and trihydroxy-phenolic compounds, e.g. resorcinol and phloroglucinol, selected polynuclear polyhydroxyphenol compounds such as bis(p-hydroxyphenylmethane and 4,4 1-dihydroxybiphenyl or aliphatic polyhydric alcohols, e.g. 1,4-butanediol and glycerol.
Epoksyharpikser som er egnet til bruk i oppfinnelsen, har molekylvekter som generelt ligger i området 50-10000, fortrinnsvis 200-1500. Den i handelen tilgjengelige EPONEpoxy resins which are suitable for use in the invention have molecular weights which are generally in the range 50-10000, preferably 200-1500. The commercially available EPON
828 -epoksyharpiks, et reaksjonsprodukt a<y> epiklorhydrin og 2,2-bis(4-hydroksyfenyl)propan (bisfenol A) med en molekylvekt på ca. 400, en epoksyd-ekyiyalent på 185-192 (ASTM D-1652) og en n-<y>erdi i- formelen I ovenfor på ca. 0,2 foretrekkes for tiden pga. den overlegne virkning av blandinger inneholdende EPON 828. 828 -epoxy resin, a reaction product a<y> epichlorohydrin and 2,2-bis(4-hydroxyphenyl)propane (bisphenol A) with a molecular weight of approx. 400, an epoxy ekyiyalent of 185-192 (ASTM D-1652) and an n-<y>erdi i- the formula I above of approx. 0.2 is currently preferred because the superior effect of mixtures containing EPON 828.
Andre epoksyholdige materialer som er egnet til bruk i den foreliggende oppfinnelse, omfatter de epoksyderte derivater av naturlige oljer såsom triestrene av glycerol med blandede, langkjedede, mettede og umettede syrer som inneholder f.eks. 16, 18 og 20 karbonatomer. Slike naturlige oljer er representert ved formel II: Other epoxy-containing materials suitable for use in the present invention include the epoxidized derivatives of natural oils such as the triesters of glycerol with mixed, long-chain, saturated and unsaturated acids containing e.g. 16, 18 and 20 carbon atoms. Such natural oils are represented by formula II:
hvor R betyr alkyl- og/eller alkenylgrupper inneholdende 15-19 karbonatomer, med det forbehold at epoksydasjonen av de nevnte oljer gir et polyepoksyd med mer enn én tilstøtende epoksygruppe pr. molekyl epoksydert olje. Soyaolje er et where R means alkyl and/or alkenyl groups containing 15-19 carbon atoms, with the proviso that the epoxidation of the mentioned oils gives a polyepoxide with more than one adjacent epoxy group per molecule epoxidized oil. Soybean oil is one
typisk triglycerid som kan omdannes til et polyepoksyd som er egnet til bruk i den foreliggende oppfinnelse. typically triglyceride which can be converted into a polyepoxide suitable for use in the present invention.
Andre polyepoksyder som er egnet til bruk i den foreliggende oppfinnelse, er avledet fra estere av polykarboksylsyrer, f.eks. maleinsyre, tereftalsyre, oksalsyre, ravsyre, azelainsyre, malonsyre, vinsyre, adipinsyre og lignende med umettede alkoholer som beskrevet ved formel III: Other polyepoxides suitable for use in the present invention are derived from esters of polycarboxylic acids, e.g. maleic acid, terephthalic acid, oxalic acid, succinic acid, azelaic acid, malonic acid, tartaric acid, adipic acid and the like with unsaturated alcohols as described by formula III:
hvor Q representerer en valensbinding eller de følgende grupper: 1,2-fenylen, 1,4-fenylen, metylen, dimetylen, tri-metylen, tetrametylen, pentametylen, heksametylen, heptame-tylen, vinylen, 1,2-cykloheksen, 1,4-cykloheksen, 1,2-eten-diol og lignende, og R' representerer alkenyl- og forgrenede alkenylgrupper med 4-14 karbonatomer. Representative epoksyderte estere avledet fra materialer beskrevet ved formel (III) innbefatter de følgende: di(2,3-epoksybutyl)tetra-hydroftalat, di (2,3-epoksyoktyl)oksalat, di (2,3-epoksyiso-butyl)adipat, di (3,4-epoksypentyl)succinat, di(4,5-epoksy-dodecyl)tereftalat, di(3,4-epoksyheksyl)ftalat, di ( 2,3-epoksy-butyl) tartrat, di (7,8-epoksytetradecyl)adipat, di(3,4-epoksy-butyl)glutarat, di(2,3-epoksyheksyl)pimelat, di(3,4-epoksy-oktyl)suberat, di (4,5-epoksydecyl)azelat, di (2,3-epoksy-isoheksyl)tetrahydrotereftalat og lignende. where Q represents a valence bond or the following groups: 1,2-phenylene, 1,4-phenylene, methylene, dimethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, vinylene, 1,2-cyclohexene, 1, 4-cyclohexene, 1,2-ethylenediol and the like, and R' represents alkenyl and branched alkenyl groups with 4-14 carbon atoms. Representative epoxidized esters derived from materials described by formula (III) include the following: di(2,3-epoxybutyl)tetrahydrophthalate, di(2,3-epoxyoctyl)oxalate, di(2,3-epoxyisobutyl)adipate, di (3,4-epoxypentyl)succinate, di(4,5-epoxy-dodecyl)terephthalate, di(3,4-epoxyhexyl)phthalate, di (2,3-epoxy-butyl) tartrate, di (7,8- epoxytetradecyl)adipate, di(3,4-epoxy-butyl)glutarate, di(2,3-epoxyhexyl)pimelate, di(3,4-epoxy-octyl)suberate, di (4,5-epoxydecyl)azelate, di ( 2,3-epoxyisohexyl)tetrahydroterephthalate and the like.
Foruten de ovennevnte forbindelser antas det at egnede polyepoksyder kan avledes fra estere fremstilt fra umettede alkoholer og umettede karboksylsyrer beskrevet ved formel IV: hvor R" er alkenyl- og cykloalkenylgrupper med 4-12 karbonatomer og R"' er alkenyl- og cykloalkenylgrupper med 4-12 karbonatomer. Representative epoksyderte estere innbefatter de følgende: 2,3-epoksypentyl-3,4-epoksybutyrat, 2,3-epoksy-butyl-3,4-epoksyheksanoat, 3,4-epoksyoktyl-2,3-epoksycyklo-heksankarboksylat, 2,3-epoksydodecyl-4,5-epoksyoktanoat, 2,3-epoksyisobutyl-4,5-epoksydodekanoat, 2,3-epoksycyklododecyl-3,4-epoksypentanoat, 3,4-epoksyoktyl-2,3-epoksycyklododekan-karboksylat og lignende. In addition to the above-mentioned compounds, it is believed that suitable polyepoxides can be derived from esters prepared from unsaturated alcohols and unsaturated carboxylic acids described by formula IV: where R" are alkenyl and cycloalkenyl groups with 4-12 carbon atoms and R"' are alkenyl and cycloalkenyl groups with 4- 12 carbon atoms. Representative epoxidized esters include the following: 2,3-epoxypentyl-3,4-epoxybutyrate, 2,3-epoxybutyl-3,4-epoxyhexanoate, 3,4-epoxyoctyl-2,3-epoxycyclohexanecarboxylate, 2,3 -epoxydodecyl-4,5-epoxyoctanoate, 2,3-epoxyisobutyl-4,5-epoxydodecanoate, 2,3-epoxycyclododecyl-3,4-epoxypentanoate, 3,4-epoxyoctyl-2,3-epoxycyclododecane carboxylate and the like.
Andre umettede materialer som kan epoksyderes for å gi harpikser som er egnet til bruk i den foreliggende fremgangsmåte, omfatter butadienbaserte polymerer, f.eks. butadien/- styrenkopolymerer, polyestere som er tilgjengelige som derivater av flerverdige alkoholer såsom etenglykol med umettede syreanhydrider, f.eks. maleinsyreanhydrid, og estere av umettede polykarboksylsyrer. Representative polyepoksyder avledet fra de sistnevnte omfatter de følgende: dimetyl-3,4,7,8-diepoksydekandioat, dibutyl-3,4,5,6-diepoksycyklo-heksan-1,2-dikarboksylat, dioktyl-3,4,7,8-diepoksyheksadekan-dioat, dietyl-5,6,9,10-diepoksytetradekandioat og lignende. Other unsaturated materials which can be epoxidized to give resins suitable for use in the present process include butadiene-based polymers, e.g. butadiene/styrene copolymers, polyesters available as derivatives of polyhydric alcohols such as ethylene glycol with unsaturated acid anhydrides, e.g. maleic anhydride, and esters of unsaturated polycarboxylic acids. Representative polyepoxides derived from the latter include the following: dimethyl 3,4,7,8-diepoxydecanedioate, dibutyl 3,4,5,6-diepoxycyclohexane-1,2-dicarboxylate, dioctyl-3,4,7, 8-diepoxyhexadecanedioate, diethyl 5,6,9,10-diepoxytetradecanedioate and the like.
Dimerer av diener såsom 4-yinylcykloheksen-l fra buta-dien og dicyklopentadien fra cyklopentadien kan omsettes. Dimers of dienes such as 4-ynylcyclohexene-1 from butadiene and dicyclopentadiene from cyclopentadiene can be reacted.
til epoksydIert<e> derivater som er egnet til bruk i fremgangsmåten. to epoxidized<e> derivatives which are suitable for use in the method.
Egnede petroleumsulfonater omfatter ammonium-, alkalimetall- og jordalkalimetall-petroleumsulfonater. Fremgangsmåter til fremstilling av petroleumsulfonater er kjent i faget og er beskrevet f.eks. i US-PS 3 135 693 og 2 884 445. Nøytralisering av de såkalte mahognysyrer (oljeoppløselige petroleumsulfon-syrer) med alkalimetallhydroksider,såsom litiumhydroksid, natriumhydroksid og kaliumhydroksid gir de tilsvarende alkalimetallpetroleuimsulfonater, som er en viktig bestanddel i den blanding som benyttes ifølge oppfinnelsen. I handelen tilgjengelige petroleumsulfonater, f.eks. slike som er tilgjengelige fra Witco Chemical Company og Stepan Chemical Company, kan også anvendes i den form de foreligger eller som av-oljede petroleumsulfonater. Petroleumsulfonatene i blandingen kan fås fra sulfonatiserbare hydrokarbonråmaterialer. Sulfonatiseringen kan utføres ved vanlige fremgangsmåter, f.eks. SO3/SO2: eller 20% oleum. Ekvivalentvektene av petroleum-sulf onat-komponentene varierer for alkalimetall- og ammonium-petroleumsulfonatenes vedkommende fra ca. 250 til ca. 700, fortrinnsvis 350-500 og helst 390-450. For jordalkalimetall-petroleumsulfonatene kan ekvivalentvekten ligge i området 900-1800, fortrinnsvis 1000-1600 og helst 1200-1500. Suitable petroleum sulfonates include ammonium, alkali metal, and alkaline earth metal petroleum sulfonates. Methods for the production of petroleum sulphonates are known in the art and are described, e.g. in US-PS 3 135 693 and 2 884 445. Neutralization of the so-called mahogany acids (oil-soluble petroleum sulphonic acids) with alkali metal hydroxides, such as lithium hydroxide, sodium hydroxide and potassium hydroxide, gives the corresponding alkali metal petroleum sulphonates, which are an important component in the mixture used according to the invention. Commercially available petroleum sulphonates, e.g. such as are available from Witco Chemical Company and Stepan Chemical Company, can also be used in their present form or as de-oiled petroleum sulfonates. The petroleum sulphonates in the mixture can be obtained from sulphonatizable hydrocarbon raw materials. The sulphonation can be carried out by usual methods, e.g. SO3/SO2: or 20% oleum. The equivalent weights of the petroleum sulphonate components vary for the alkali metal and ammonium petroleum sulphonates from approx. 250 to approx. 700, preferably 350-500 and preferably 390-450. For the alkaline earth metal petroleum sulphonates, the equivalent weight can lie in the range 900-1800, preferably 1000-1600 and preferably 1200-1500.
I en utførelsesform for oppfinnelsen omfatter den anvendte blanding videre et herdemiddel for epoksyharpiksen. Et hvilket som helst middel som er egnet til herding av epoksyharpikser, kan anvendes i sammensetningen og fremgangsmåten ifølge oppfinnelsen. Herdere for epoksyharpikser omfatter polyfunksjonelle aminer, syrer, anhydrider og aldehydharpikser. Herdere anvendes i en mengde som er virksom for herding av den mengde epoksyharpiks som anvendes. In one embodiment of the invention, the mixture used further comprises a curing agent for the epoxy resin. Any agent suitable for curing epoxy resins can be used in the composition and method according to the invention. Hardeners for epoxy resins include polyfunctional amines, acids, anhydrides and aldehyde resins. Hardeners are used in an amount that is effective for curing the amount of epoxy resin used.
Polyaminer som er egnet til bruk i denne utførelsesform/ omfatter forbindelser med mer enn én N-H-gruppe. Disse innbefatter alifatiiske, cykloalifatiske, aromatiske og heterocyk-liske aminer. Eksempler på herdere omfatter alifatiske polyaminer såsom etendiamin, dietentriamin, trietentetramin, tetraetenpentamin, 1,4-diaminobutan, 1,3-diaminobutan, heksa-metylendiamin,, 3-(n-propylamino) propylamin, N ,N1 -diety 1-1,3-propandiamin, heksapropenheptamin, penta(1-metylpropen) heksamin, tetrabutenpentamin, heksa(1,1-dimetyleten)-heptamin, di(1-metylbuten)triamin, pentaamylenheksamin, tri(l, 2,2-trimetyleten)tetramin, tetra(1,3-dimetylpropen)pentamin, penta (1, 5-dime/tylamylen) heksamin, 5-metyl-l, 9-nonandiamin, penta(1,2-dimetyl-l-isopropyleten)heksamin og N,N'-dibutyl-1,6-heksan:d!iamiiini- Polyamines suitable for use in this embodiment include compounds with more than one N-H group. These include aliphatic, cycloaliphatic, aromatic and heterocyclic amines. Examples of hardeners include aliphatic polyamines such as ethenediamine, diethenetriamine, triethenetetramine, tetraethenepentamine, 1,4-diaminobutane, 1,3-diaminobutane, hexa-methylenediamine,, 3-(n-propylamino) propylamine, N ,N1 -diethy 1-1, 3-propanediamine, hexapropeneheptamine, penta(1-methylpropene) hexamine, tetrabutenepentamine, hexa(1,1-dimethylethylene)heptamine, di(1-methylbutene)triamine, pentaamylenehexamine, tri(l,2,2-trimethylethylene)tetramine, tetra (1,3-dimethylpropene)pentamine, penta(1,5-dime/thylamylene)hexamine, 5-methyl-1,9-nonanediamine, penta(1,2-dimethyl-1-isopropylethylene)hexamine and N,N'- dibutyl-1,6-hexane:diamine-
En klasse polyamdner som er særlig egnet til bruk ved oppfinnelsen, er N-alkyl- og N-alkenyl-substituerte 1,3-diaminopropaner og blandinger derav. Eksempler på slike polyaminer innbefatter N-heksadecyl-1,3-diaminopropan, N-tetradecyl-1,3-diaminopropan, N-oktadecyl-1,3-diaminopropan, N-pentadecyl-1,3-diaminopropan, N-heptadecyl-1,3-diaminopropan, N-nonadecyl-1,3-diaminopropan og N-oktadecenyl-1,3-diaminopro-pan. Forskjellige i handelen tilgjengelige blandinger av N-alkylerte og N-alkenylerte diaminer kan anvendes i oppfinnelsen. Det for tiden foretrukkede polyamin er et i handelen tilgjengelig produkt solgt under handelsnavnet DUOMEEN T (Armour & Co.). Dette produkt er N-talg-1,3-diaminopropan hvor mesteparten av talg-substituentgruppene er alkyl og alkenyl med 16-18 karbonatomer hver, mens en mindre del av substituentgruppene har 14 karbonatomer hver. Det antas for tiden at virkningen av DUOMEEN i den anvendte blanding skyldes dets relativt høye molekylvekt, som gir et langkjedet "nett" som dekker metalloverflaten, dets flerverdighet og dets relativt høye kokepunkt, som tillater at det brukes i omgivelser med høy temperatur. Andre i handelen tilgjengelige materialer innbefatter N-kokos-1,3-diaminopropan, hvor mesteparten av kokos-substituentgruppene inneholder 12-14 karbonatomer (tilgjengelig i handelen under handelsnavnet DUOMEEN C), og N-soya-1,3-diaminopropan som inneholder C^-alkenylgrupper sammen med en mindre del <C>^g-alkylgrupper. A class of polyamides which are particularly suitable for use in the invention are N-alkyl- and N-alkenyl-substituted 1,3-diaminopropanes and mixtures thereof. Examples of such polyamines include N-hexadecyl-1,3-diaminopropane, N-tetradecyl-1,3-diaminopropane, N-octadecyl-1,3-diaminopropane, N-pentadecyl-1,3-diaminopropane, N-heptadecyl-1 ,3-diaminopropane, N-nonadecyl-1,3-diaminopropane and N-octadecenyl-1,3-diaminopropane. Various commercially available mixtures of N-alkylated and N-alkenylated diamines can be used in the invention. The currently preferred polyamine is a commercially available product sold under the trade name DUOMEEN T (Armour & Co.). This product is N-tallow-1,3-diaminopropane where most of the tallow substituent groups are alkyl and alkenyl with 16-18 carbon atoms each, while a smaller part of the substituent groups have 14 carbon atoms each. It is currently believed that the effect of DUOMEEN in the mixture used is due to its relatively high molecular weight, which provides a long-chain "net" covering the metal surface, its multivalency and its relatively high boiling point, which allows it to be used in high temperature environments. Other commercially available materials include N-coco-1,3-diaminopropane, where most of the coconut substituent groups contain 12-14 carbon atoms (available commercially under the trade name DUOMEEN C), and N-soy-1,3-diaminopropane, which contains C ^-alkenyl groups together with a smaller proportion of <C>^g-alkyl groups.
Ytterligere polyaminer som er egnet til bruk i fremgangsmåten, kan inneholde tre eller flere nitrogenatomer som vist ved de følgende eksempler: N-dodecyl-dietentriamin, N-tetradecyl-dietentriamin, N-tetradecyl-dipropentriamin", N-tetradecyltrieten-tetramin og de tilsvarende N-alkenyl-triaminer. Further polyamines which are suitable for use in the process may contain three or more nitrogen atoms as shown by the following examples: N-dodecyl-dietentriamine, N-tetradecyl-dietentriamine, N-tetradecyl-dipropenetriamine", N-tetradecyltrietene-tetramine and the corresponding N-alkenyl triamines.
Andre herdere som kan anvendes, innbefatter flerverdige nitrogenholdige forbindelser såsom aminosyrer, amino-alkoholer, aminonitriler og aminoketoner, karboksylsyrer og organiske anhydrider. Other hardeners which may be used include polyhydric nitrogen-containing compounds such as amino acids, amino alcohols, aminonitriles and aminoketones, carboxylic acids and organic anhydrides.
I en utførelsesform for oppfinnelsen benyttes en blanding som foruten det ovenfor beskrevne herdemiddel inneholder en alkohol. Alkoholer som er egnet til bruk i oppfinnelsen, omfatter alkanoler og polyoler som, inneholder minst én -0H-funksjonell gruppe med 1-15 karbonatomer såsom metanol, etanol, 1-propanol, 2-propanol, butanoler, pentanoler, heksanoler, heptanoler, oktanoler, l-pentadekanol og blandinger av alkanoler. Flerverdige alkoholer inneholdende 2-5 karbonatomer, f.eks. etenglykol, 1,3-propandiol, 2,3-butandiol, glycerol og pentaerytritol kan også anvendes. For tiden foretrekkes metanol, særlig i en korrosjonshemmende blanding som inneholder xylen som det aromatiske hydrokarbonfortynningsmiddel, EPON 828 som epoksyharpiksen, kalsiumpetroleumsulfonat som petroleumsulfonatet, og DUOMEEN T som polyaminet, både fordi DUOMEEN T er oppløselig i metanol ved værelsetemperatur og fordi det resulterende korrosjonshindrende system har god virkning. In one embodiment of the invention, a mixture is used which, in addition to the curing agent described above, contains an alcohol. Alcohols which are suitable for use in the invention include alkanols and polyols which contain at least one -OH functional group with 1-15 carbon atoms such as methanol, ethanol, 1-propanol, 2-propanol, butanols, pentanols, hexanols, heptanols, octanols , l-pentadecanol and mixtures of alkanols. Polyhydric alcohols containing 2-5 carbon atoms, e.g. ethylene glycol, 1,3-propanediol, 2,3-butanediol, glycerol and pentaerythritol can also be used. Currently, methanol is preferred, particularly in a corrosion inhibitor composition containing xylene as the aromatic hydrocarbon diluent, EPON 828 as the epoxy resin, calcium petroleum sulfonate as the petroleum sulfonate, and DUOMEEN T as the polyamine, both because DUOMEEN T is soluble in methanol at room temperature and because the resulting corrosion inhibitor system has good effect.
Et hydrokarbonfortynningsmiddel anvendes i blandingen ved fremgangsmåten ifølge oppfinnelsen. Eksempler på hydrokarbon-fortynningsmidler som er egnet til bruk i behandlingsmidlene, omfatter de isomere xylener, toluen, benzen, nafta, cyklo-heksylbenzen, brenselolje, dieselolje, tunge aromatiske oljer, Stoddart-oppløsningsmiddel, råolje og kondensat fra gassbrønner. For tiden er xylen det foretrukkede hydrokarbonfortynningsmiddel både fordi det er et virksomt oppløsningsmid-del for de andre foretrukkede bestanddeler og fordi den resulterende blanding har god korrosjonshemmende virkning. A hydrocarbon diluent is used in the mixture in the method according to the invention. Examples of hydrocarbon diluents suitable for use in the treatment agents include the isomeric xylenes, toluene, benzene, naphtha, cyclohexylbenzene, fuel oil, diesel oil, heavy aromatic oils, Stoddart solvent, crude oil and condensate from gas wells. Currently, xylene is the preferred hydrocarbon diluent both because it is an effective solvent for the other preferred ingredients and because the resulting mixture has good corrosion inhibitory action.
De høyere-kokende aromatiske hydrokarboner er særlig nyttige for dypere brønner med høyere temperaturer nede i brønnen og i olje- og gass-høytemperaturbrønner generelt. The higher-boiling aromatic hydrocarbons are particularly useful for deeper wells with higher downhole temperatures and in high-temperature oil and gas wells in general.
Som angitt nedenfor, er det i noen behandlingsmetoder fordelaktig å anvende et bærer- eller drivfluid til å tvinge en plugg av den korrosjonshemmende blanding ned i den brønn som skal behandles. Et hvilket som helst av de ovenfor angitte hydrokarboner som er angitt å være egnede fortyn-ningsmidler, kan anvendes. Av praktiske og økonomiske grunner er dieselolje, sjøvann eller kondensat fra den brønn som behandles, foretrukkede bærefluider. En inert gass såsom nitrogen kan anvendes som drivfluid. As indicated below, in some treatment methods it is advantageous to use a carrier or driving fluid to force a plug of the corrosion inhibitor mixture down into the well to be treated. Any of the above hydrocarbons indicated as suitable diluents may be used. For practical and economic reasons, diesel oil, seawater or condensate from the well being treated are preferred carrier fluids. An inert gas such as nitrogen can be used as the driving fluid.
Forskjellige azeotrope blandinger av alkohol og aromatiske hydrokarboner kan anvendes i den utførelsesform av oppfinnelsen som anvender alkoholholdige blandinger til i det minste delvis å gi fortynningsmiddel- og alkoholbestanddelene. Representative azeotrope blandinger omfatter (vektprosenttal-lene er angitt i parentes): metanol (39,1)/benzen (60,9), etanol (32)/benzen (68), 2-propanol (33,3)/benzen (66,7), 1-propanol (16,9)/benzen (83,1), isobutylalkohol (9,3)/benzen (90,7), 1-butanol (68)/p-xylen (32), 2-pentanol(28)/toluen (72) og heksanol (13)/p-xylen (87). Det antas videre at urene alkoholstrømmer såsom blandede butanoler som fås som et resultat av oksoteknologi som. anvender propen-matningsmaterial-er, kan anvendes i blandingene. Various azeotropic mixtures of alcohol and aromatic hydrocarbons can be used in the embodiment of the invention which uses alcoholic mixtures to at least partially provide the diluent and alcohol components. Representative azeotropic mixtures include (weight percentages are in parentheses): methanol (39.1)/benzene (60.9), ethanol (32)/benzene (68), 2-propanol (33.3)/benzene (66 .7), 1-propanol (16.9)/benzene (83.1), isobutyl alcohol (9.3)/benzene (90.7), 1-butanol (68)/p-xylene (32), 2- pentanol (28)/toluene (72) and hexanol (13)/p-xylene (87). It is further believed that impure alcohol streams such as mixed butanols obtained as a result of oxo technology which. using propene feed materials, can be used in the mixtures.
Bestanddelene i det korrosjonshindrende system kan blandes i en hvilken som helst rekkefølge. Blandingene fremstilles stort sett mindre enn 2 timer før de skal anvendes, med mindre man anvender et middel eller en fremgangsmåte som virker herde-retarderende. En utgangsoppløsning av epoksyharpiks (3 vektdeler) i et hydrokarbonfortynningsmiddel (1 volumdel) er meget godt egnet. The components of the anti-corrosion system can be mixed in any order. The mixtures are mostly prepared less than 2 hours before they are to be used, unless an agent or a method is used that has a hardening-retarding effect. A starting solution of epoxy resin (3 parts by weight) in a hydrocarbon diluent (1 part by volume) is very suitable.
I den utførelsesform for blandingen som omfatter epoksyharpiks , petroleumsulfonat og hydrokarbonfortynningsmiddel og ikke inneholder en herder eller alkohol, blir petroleum-sulf onatet enten i form av et av-oljet faststoff eller som en oppløsning i ikke-sulfonatisert olje tilsatt en oppløsning av epoksyharpiks (3 vektdeler) i et hydrokarbonfortynningsmiddel (1 volumdel). Vektprosent petroleumsulfonat i sluttblandingen varierer over det vide område 1,0-80, helst 5-50. In the embodiment of the mixture comprising epoxy resin, petroleum sulfonate and hydrocarbon diluent and not containing a hardener or alcohol, the petroleum sulfonate is either in the form of a de-oiled solid or as a solution in non-sulfonated oil added to a solution of epoxy resin (3 parts by weight) in a hydrocarbon diluent (1 part by volume). The percentage by weight of petroleum sulphonate in the final mixture varies over the wide range 1.0-80, preferably 5-50.
Vektprosent epoksyharpiks i sluttblandingen varierer over området 2-50. Resten av blandingen er hydrokarbonfortynningsmiddel i tilstrekkelig mengde til å holde blandingen i en stort sett fluid, pumpbar tilstand. The weight percentage of epoxy resin in the final mixture varies over the range 2-50. The remainder of the mixture is hydrocarbon diluent in an amount sufficient to maintain the mixture in a substantially fluid, pumpable state.
I den utførelsesform for oppfinnelsen som inneholder et polyamin, blir petroleumsulfonatet enten som et av-oljet faststoff eller som en oppløsning i ikke-sulfonatisert olje tilsatt en hydrokarbonoppløsning av epoksyharpiks og polyamin. Vektforholdet mellom polyamin og epoksyharpiks i sluttopp-løsningen skal være £ 1:500, fortrinnsvis £ 1:50 og helst 10:1 - 1:5. Vektprosent petroleumsulfonat i sluttoppløsningen varierer over området 1-80. Resten av blandingen er hydrokarbonfortynningsmiddel i tilstrekkelig mengde til å holde In the embodiment of the invention which contains a polyamine, the petroleum sulphonate either as a de-oiled solid or as a solution in non-sulphonated oil is added to a hydrocarbon solution of epoxy resin and polyamine. The weight ratio between polyamine and epoxy resin in the final solution should be £1:500, preferably £1:50 and preferably 10:1 - 1:5. The percentage by weight of petroleum sulphonate in the final solution varies over the range 1-80. The remainder of the mixture is hydrocarbon diluent in sufficient quantity to hold
blandingen i en stort sett fluid, pumpbar tilstand. the mixture in a largely fluid, pumpable state.
I den utførelsesform for oppfinnelsen som anvender en blanding inneholdende en alkohol, kan blandingen først fremstilles ved blanding av en første oppløsning av alkohol, hydrokarbonfortynningsmiddel og amin i f.eks. et forhold på ca. 1:1:1 (ml:ml:g) med en annen oppløsning av en epoksyharpiks i et hydrokarbon i et forhold på ca. 3:1 (g:ml). Vektforholdet mellom polyamin og epoksyharpiks i sluttoppløsningen skal være £ 1:500, fortrinnsvis £ 1:50 og helst 10:1 - 1:5. Petroleum-sulf onatet enten som et av-oljet faststoff eller som en oppløsning i ikke-sulfonatisert olje, tilsettes oppløsningen slik at vektprosent petroleumsulfonat i sluttblandingen varierer fortrinnsvis over området 1-70, helst 5-50. Vektprosent alkohol i sluttblandingen er £ 1, fortrinnsvis 5 - 80 og helst 8-60. Vektprosent epoksyharpiks i sluttblandingen varierer over det vide område 2-50, fortrinnsvis 5-40. Vektprosent polyamin i sluttblandingen varierer over området 0,01 - 96, fortrinnsvis 1-80, helst 5-60. Hydro-karbonf ortynningsmiddelet foreligger i en mengde som er tilstrekkelig til å holde blandingen i en stort sett fluid, pumpbar tilstand. In the embodiment of the invention that uses a mixture containing an alcohol, the mixture can first be prepared by mixing a first solution of alcohol, hydrocarbon diluent and amine in e.g. a ratio of approx. 1:1:1 (ml:ml:g) with another solution of an epoxy resin in a hydrocarbon in a ratio of approx. 3:1 (g:ml). The weight ratio of polyamine to epoxy resin in the final solution should be £1:500, preferably £1:50 and preferably 10:1 - 1:5. The petroleum sulphonate, either as a de-oiled solid or as a solution in non-sulphonated oil, is added to the solution so that the weight percentage of petroleum sulphonate in the final mixture varies preferably over the range 1-70, preferably 5-50. The weight percent alcohol in the final mixture is £1, preferably 5-80 and most preferably 8-60. The weight percentage of epoxy resin in the final mixture varies over the wide range 2-50, preferably 5-40. The percentage by weight of polyamine in the final mixture varies over the range 0.01-96, preferably 1-80, preferably 5-60. The hydrocarbon diluent is present in an amount sufficient to keep the mixture in a largely fluid, pumpable state.
Behandlinger med de korrosjonshemmende blandinger nede i brønnen kan utføres ved en rekke metoder avhengig av de spesielle kjemiske og fysiske egenskaper av den brønn som skal behandles. Ved behandling av metalloverflater nede i brønnen kan den korrosjonshemmende blanding anvendes som én oppløsning. Alternativt kan metalloverflåtene etter tur bringes i berøring med en oppløsning av herderen og et petroleumsulfonat og en oppløsning av epoksyharpiksen. I praksis kan harpiksoppløsnin-gen og petroleumsulfonatoppløsningen pumpes fra separate lagringstanker til en statisk mikser ved en T-forgrening like før blandingen pumpes ned i brønnen. De følgende behandlingsmetoder nede i brønnen kan anvendes for å påføre blandingen på metalloverflater av utstyr som anvendes til utvinning av naturlige fluider fra underjordiske reservoarer: Satsvis behandling. Blandingen av petroleumsulfonat, epoksyharpiks og hydrokarbonfortynningsmiddel feres inn i den ringformede åpning i en fQret brann mellom f6ringen og produksjonsrøret, fortrinnsvis i en oljebærer. Brønnen føres tilbake til produksjon, og de injiserte blandinger blir gradvis returnert med de produserte fluider, idet de på veien tjener til å belegge de metalloverflater de kommer i berøring med, med en korrosjonsbestandig film. Som et alternativ til denne metode kan en væskesøyle av behandlingsmiddelet plasseres i produk-sjonsrøret eller den ringformede åpning og tillates, å stå i et tidsrom som kan variere fra 10 min til 24 h før produksjonen gjenopptas, som regel minst 1 h. Treatments with the corrosion-inhibiting compounds down in the well can be carried out by a number of methods depending on the special chemical and physical properties of the well to be treated. When treating metal surfaces down in the well, the corrosion-inhibiting mixture can be used as one solution. Alternatively, the metal surfaces can in turn be brought into contact with a solution of the hardener and a petroleum sulphonate and a solution of the epoxy resin. In practice, the resin solution and the petroleum sulphonate solution can be pumped from separate storage tanks to a static mixer at a T-junction just before the mixture is pumped down the well. The following downhole treatment methods can be used to apply the mixture to metal surfaces of equipment used to extract natural fluids from underground reservoirs: Batch treatment. The mixture of petroleum sulphonate, epoxy resin and hydrocarbon diluent is fed into the annular opening in a controlled fire between the casing and the production pipe, preferably in an oil carrier. The well is returned to production, and the injected mixtures are gradually returned with the produced fluids, serving along the way to coat the metal surfaces they come into contact with with a corrosion-resistant film. As an alternative to this method, a liquid column of the treatment agent can be placed in the production tube or the annular opening and allowed to stand for a period of time that can vary from 10 min to 24 h before production is resumed, usually at least 1 h.
Utvidet satsvis behandling. Blandingen injiseres i den ringformede åpning av en fOret brønn, brønnen avstenges, og blandingen sirkuleres kontinuerlig sammen med brønnfluidene ned gjennom den ringformede åpning og opp gjennom produksjonsrøret i et tidsrom som kan variere innen vide grenser, men som vanligvis vil være 2-48 h. Ved slutten av den fastlagte periode blir brønnen ført tilbake til produksjon. Extended batch processing. The mixture is injected into the annular opening of a lined well, the well is shut off, and the mixture is continuously circulated together with the well fluids down through the annular opening and up through the production pipe for a period of time which can vary within wide limits, but which will usually be 2-48 h. At the end of the fixed period, the well is returned to production.
Pressbehandlin<g> ( Squeeze treatment). Blandingen injiseres i en fOret brønn som gjennomtrenger en underjordisk, formasjon, og tvinges inn i formasjonen mot formasjonstrykket med høytrykkspumper. Blandingen kan foreligge i en gelert eller dispergert polymermatriks basert f.eks. på polyakrylamider, biopolysakkarider eller celluloseetere. Etter at trykket er avlastet, blir behandlingsmiddelet langsomt tilbakeprodusert sammen med de utvunnede fluider, hvilket resulterer i påføring av en korrosjonsbestandig film på metalloverflater som kommer i berøring med behandlingsmiddelet etter hvert som det strømmer til overflaten. Denne metode er særlig egnet i gass- eller oljebrønner som står under høyt trykk. Squeeze treatment. The mixture is injected into a lined well that penetrates an underground formation, and is forced into the formation against the formation pressure with high-pressure pumps. The mixture can be present in a gelled or dispersed polymer matrix based e.g. on polyacrylamides, biopolysaccharides or cellulose ethers. After the pressure is relieved, the treatment agent is slowly re-produced along with the recovered fluids, resulting in the application of a corrosion-resistant film on metal surfaces that come into contact with the treatment agent as it flows to the surface. This method is particularly suitable in gas or oil wells that are under high pressure.
Spvdspissbehandl ing ( Spearhead treatment). En høykon-sentrert plugg av blandingen injiseres i produksjonsrøret i en fOret brønn og presses nedover i produksjonsrøret med nitrogen eller med en fluidsøyle av en saltlakeoppløsning, f.eks. en 2 vektprosents oppløsning av vandig kaliumklorid. Når trykket avlastes, blir den vandige saltlakesøyle eller nitrogen og den korrosjonshindrende blanding produsert opp gjennom produksjons-røret. Blandingen i form av en konsentrert plugg kommer i berøring med metallveggene i produksjonsrøret og etterlater en beskyttende film når den strømmer i en nedadgående og oppad-gående krets. Spearhead treatment. A highly concentrated plug of the mixture is injected into the production tubing in a lined well and forced down the production tubing with nitrogen or with a fluid column of a brine solution, e.g. a 2% by weight solution of aqueous potassium chloride. When the pressure is relieved, the aqueous brine column or nitrogen and the corrosion-inhibiting mixture are produced up through the production pipe. The mixture in the form of a concentrated plug contacts the metal walls of the production pipe and leaves a protective film as it flows in a downward and upward circuit.
Metalloverflater kan også beskyttes ved dypping eller sprøyting av overflatene med blandingene, hvoretter over-skytende fluid tillates å renne av fra de behandlede overflater ved omgivelsesforhold. På denne måte blir en beskyttende film dannet på metalloverflaten uten vanlig varmeherdingsbehandling eller utvidet lufttørkebehandling, selv om slike tørkebe-handlinger kan anvendes hvis det er ønskelig og forholdene tillater det. Fordelen ved å anvende et antikorrosjonssystem som ikke krever luft- eller varmetørking, er at systemet kan anvendes på metalloverflater som befinner seg flere hundre eller flere tusen fot under bakkenivået eller i et miljø som alltid er oversvømmet av saltlake eller andre fluider. Metal surfaces can also be protected by dipping or spraying the surfaces with the compositions, after which excess fluid is allowed to run off the treated surfaces at ambient conditions. In this way, a protective film is formed on the metal surface without the usual heat hardening treatment or extended air drying treatment, although such drying treatments can be used if desired and conditions permit. The advantage of using an anti-corrosion system that does not require air or heat drying is that the system can be used on metal surfaces that are several hundred or several thousand feet below ground level or in an environment that is always flooded with brine or other fluids.
Når blandingen påføres metall-produksjonsrøret av f.eks. en gass- eller oljebrønn, er det ikke nødvendig å for-belegge de behandlede metalloverflater med olje eller andre stoffer før blandingen anvendes, og de overflater som skal behandles, kan på forhånd ha et oljebelegg eller de kan være uten et slikt belegg. Det antas at fremgangsmåten vil være virksom for å hindre korrosjon i brønner som produserer så meget som 95% saltlake og 5% olje. When the mixture is applied to the metal production pipe of e.g. a gas or oil well, it is not necessary to pre-coat the treated metal surfaces with oil or other substances before the mixture is used, and the surfaces to be treated can have an oil coating in advance or they can be without such a coating. It is believed that the method will be effective in preventing corrosion in wells that produce as much as 95% brine and 5% oil.
Beskaffenheten av den film som dannes på denne måte, kan variere i henhold til den spesielle blanding som anvendes, og det miljø den anvendes i, men det er funnet at filmen generelt vil være et mykt, klebrig lag som fester seg til metalloverflaten. Det er ikke nødvendig at blandingen stivner til et hardt belegg, og det er funnet ved laboratorieforsøk at den påførte film er tilbøyelig til å opprettholde en klebrig eller fettaktig konsistens. The nature of the film thus formed may vary according to the particular composition used and the environment in which it is used, but it has been found that the film will generally be a soft, tacky layer which adheres to the metal surface. It is not necessary for the mixture to harden to a hard coating, and it has been found in laboratory tests that the applied film tends to maintain a sticky or greasy consistency.
Eksempel, i Example, i
En rekke korrosjonshemmende forsøk i laboratoriet ble utført i 1 l's Erlenmeyer-kolber utstyrt med magnetiske omrøringsstenger og under laboratoriebetingelser som var beregnet på å simulere korrosive olje/vann-miljøer som man støter på ved boreplasser i felten. En ladning på 50 ml råolje og 950 ml syntetisk saltlake ble anvendt i hvert forsøk. En langsom strøm av karbondioksid ble boblet gjennom oppløsningen i hvert forsøk for å holde blandingen nær metningspunktet med CO2 ved omgivelsesbetingelser. Etter at Erlenmeyer-kolben hadde fått tilført 950 ml syntetisk Nordsjø-vann (93,1 g CaCl2'2H20, 46,4 g MgCl2-6H20 og 781,1 g NaCl pr. 19 1 destillert H20) ble de korrosjonsinhiberende systemer tilført kolben og den angitte råolje deretter tilsatt. Korrosjonshastigheten og gropdannelse-indeksen ble bestemt ved et CORRATER-målesystem tilgjengelig fra Rohrback Instruments. En sonde av karbonstål ble hengt opp i den omrørte olje/vann-blanding, som ble holdt på ca. 49°C i hvert forsøk. A series of laboratory anti-corrosion tests were carried out in 1 L Erlenmeyer flasks equipped with magnetic stir bars and under laboratory conditions intended to simulate corrosive oil/water environments encountered at well sites in the field. A charge of 50 ml of crude oil and 950 ml of synthetic brine was used in each experiment. A slow stream of carbon dioxide was bubbled through the solution in each experiment to keep the mixture close to the saturation point with CO 2 at ambient conditions. After 950 ml of synthetic North Sea water (93.1 g CaCl2'2H20, 46.4 g MgCl2-6H20 and 781.1 g NaCl per 19 1 distilled H20) had been added to the Erlenmeyer flask, the corrosion-inhibiting systems were added to the flask and the specified crude oil then added. The corrosion rate and pitting index were determined by a CORRATER measurement system available from Rohrback Instruments. A carbon steel probe was suspended in the stirred oil/water mixture, which was held at approx. 49°C in each trial.
Eksempel 1 viser bruken av en trekomponentsblanding. En 0. 1 ml's porsjon av en blanding med et volumforhold på 50:50 av xylen og PHIL-AD-N smøreolje-tilsetningsstoff (inneholdende kalsium-petroleumsulfonat) ble blandet med en 0,1 ml's porsjon av en xylenoppløsning av EPON 828 epoksyharpiks. Epoksyharpiks-oppløsningen ble fremstilt ved blanding av 3 vektdeler EPON 828 med 1 volumdel xylen. Et sammenligningsforsøk ble utført med PHIL-AD-N i xylen (se forsøk 2 i tabell 1). Forsøk 3 er et ytterligere oppfinnelsesforsøk hvor en xylen/epoksyharpiks/- petroleumsulfonat-blanding ble eldet i 2 timer før prøvingen startet. Resultatene av disse forsøk er vist i tabell 1. Example 1 shows the use of a three-component mixture. A 0.1 ml portion of a 50:50 volume ratio mixture of xylene and PHIL-AD-N lubricating oil additive (containing calcium petroleum sulfonate) was mixed with a 0.1 ml portion of a xylene solution of EPON 828 epoxy resin. The epoxy resin solution was prepared by mixing 3 parts by weight of EPON 828 with 1 part by volume of xylene. A comparison experiment was performed with PHIL-AD-N in xylene (see experiment 2 in Table 1). Experiment 3 is a further invention experiment where a xylene/epoxy resin/petroleum sulphonate mixture was aged for 2 hours before the test started. The results of these experiments are shown in table 1.
Fra oppfinnelsesforsøkene 1 og 3 er det åpenbart at petroleumsulfonat/epoksyharpiks/xylen-systemet reduserer korrosjonshastigheten hurtigere enn petroleumsulfonat/xylensystemet. Det petroleumsulfonat som ble anvendt i disse forsøk, var kalsium-petroleumsulfonat fremstilt ved fremgangsmåten ifølge US-PS 3 135 693. Forsøk 3 tyder på at elding av petroleum-sulf onat/epoksyharpiks/xylen-systemet i 2 h øker den tid som er nødvendig for å redusere korrosjonshastigheten. From invention tests 1 and 3, it is obvious that the petroleum sulfonate/epoxy resin/xylene system reduces the corrosion rate faster than the petroleum sulfonate/xylene system. The petroleum sulfonate used in these experiments was calcium petroleum sulfonate prepared by the method according to US-PS 3,135,693. Experiment 3 indicates that aging the petroleum sulfonate/epoxy resin/xylene system for 2 h increases the time required to reduce the corrosion rate.
Eksempel 2 Example 2
Dette eksempel viser bruken av den utførelsesform for blandingen som inneholder et polyamin. Forsøket ble utført ved anvendelse av et CORRATOR-instrument som beskrevet i eksempel 1. En 0,2 ml's porsjon av en 1:1:1-blanding av PHIL-AD-N, xylen This example demonstrates the use of the embodiment of the composition containing a polyamine. The experiment was carried out using a CORRATOR instrument as described in Example 1. A 0.2 ml portion of a 1:1:1 mixture of PHIL-AD-N, xylene
og DUOMEEN T ble blandet med 0,05 ml av en 3:1 (vekt:vekt) and DUOMEEN T was mixed with 0.05 ml of a 3:1 (wt:wt)
EPON 828- og xylen-oppløsning for dannelse av behandlings-blandingen. Et sammenligningsforsøk (se forsøk 5 i tabell 2) ble utført med en behandlingsblanding inneholdende xylen, DUOMEEN T, EPON 828 og metanol, men ikke noe petroleumsulfonat. Resultatet av disse forsøk er vist i tabell 2. EPON 828 and xylene solution to form the treatment mixture. A comparison trial (see Trial 5 in Table 2) was conducted with a treatment mixture containing xylene, DUOMEEN T, EPON 828 and methanol, but no petroleum sulfonate. The results of these tests are shown in table 2.
Under henvisning til tabell 2 er det åpenbart at bruken av petroleumsulfonat istedenfor metanol i epoksyharpiks/xylen/- polyamin-systemet resulterte i en hurtigere reduksjon av korrosjonshastigheten. Det metanolholdige system er funnet å være en effektiv korrosjonsinhibitor. Det petroleumsulfonat som ble anvendt i forsøk 4, var kalsium-petroleumsulfonat fremstilt ved den fremgangsmåte som er beskrevet i US-PS 3 135 69.3. Forsøk 6 er et ytterligere oppfinnelsesforsøk som anvender et i handelen tilgjengelig natrium-petroleumsulfonat (WITCO TRS 10-410). I forsøk 6 ble en forsøks-utgangsoppløsning fremstilt ved blanding av 6 g xylen, 2 g WITCO TRS 10-410 og 2 g DUOMEEN T. En 0,2 ml's porsjon av denne oppløsning ble anvendt i forsøk 6 sammen med en 0,05 ml's porsjon av EPON 828 i xylen (3 vektdeler EPON 828 sammen med 1 vektdel xylen). Referring to Table 2, it is obvious that the use of petroleum sulphonate instead of methanol in the epoxy resin/xylene/polyamine system resulted in a faster reduction of the corrosion rate. The methanol-containing system has been found to be an effective corrosion inhibitor. The petroleum sulphonate used in experiment 4 was calcium petroleum sulphonate prepared by the method described in US-PS 3 135 69.3. Experiment 6 is a further inventive experiment using a commercially available sodium petroleum sulphonate (WITCO TRS 10-410). In experiment 6, an experimental starting solution was prepared by mixing 6 g of xylene, 2 g of WITCO TRS 10-410 and 2 g of DUOMEEN T. A 0.2 ml portion of this solution was used in experiment 6 together with a 0.05 ml portion of EPON 828 in xylene (3 parts by weight EPON 828 together with 1 part by weight xylene).
Eksempel 3 Example 3
Dette eksempel viser bruken av den utførelsesform for oppfinnelsen som inneholder en alkohol. Forsøkene ble utført ved anvendelse av et CORRATOR-instrument som beskrevet i eksempel 1. Forsøk 7 (se tabell 3) er et oppfinnelsesforsøk som omfatter tilsetning av kalsium-petroleumsulfonat (PHIL-AD-N-oljetilsetningsstoff) til EPON 828/DUOMEEN T/metanol/xylen-systemet. Forsøk 8 i tabell 3 er et sammenligningsforsøk som anvender EPON 828/DUOMEEN T/metanol/xylen-systemet. Forsøk 9 er et oppfinnelsesforsøk som anvender natrium-petroleumsulfonat (WITCO TRS 10-410) som petroleumsulfonatet. Den tilnærmede blanding av TRS 10-410 slik det mottas er 61 vektprosent natrium-petroleumsulfonat, 30-35 vektprosent ikke-sulfonatisert olje og 4-5 vektprosent vann. Den midlere ekvivalentvekt av natrium-petroleumsulfonatene varierer over området 410-430. This example shows the use of the embodiment of the invention which contains an alcohol. The tests were carried out using a CORRATOR instrument as described in example 1. Test 7 (see table 3) is an invention test which comprises the addition of calcium petroleum sulphonate (PHIL-AD-N oil additive) to EPON 828/DUOMEEN T/methanol /xylene system. Trial 8 in Table 3 is a comparative trial using the EPON 828/DUOMEEN T/methanol/xylene system. Experiment 9 is an invention experiment using sodium petroleum sulfonate (WITCO TRS 10-410) as the petroleum sulfonate. The approximate mixture of TRS 10-410 as received is 61 weight percent sodium petroleum sulfonate, 30-35 weight percent unsulfonated oil and 4-5 weight percent water. The average equivalent weight of the sodium petroleum sulphonates varies over the range 410-430.
I forsøk 9 ble TRS 10-410, slik det ble mottatt, blandet med like store volumer av xylen og metanol for å gi en blanding på 1:1:1 petroleumsulfonatoppløsning:xylen:metanol. Separate oppløsninger av amin og harpiks ble fremstilt som følger: DUOMEEN T-oppløsingen ble fremstilt ved blanding av DUOMEEN T, xylen og metanol i et forhold på 1:1:1 (g:ml:ml), og epoksy-harpiksoppløsningen ble fremstilt ved opplesning av 3 vektdeler EPON 828 i 1 vektdel xylen. Behandlingsblandingen (forsøk 9) ble deretter fremstilt ved blanding av 0,25 ml av petroleumsul-fonatblandingen med 0,02 ml av aminblandingen og 0,0 5 ml av harpiksblandingen. Resultatene fra korrosjonsforsøkene er angitt i tabell 3. In Run 9, TRS 10-410, as received, was mixed with equal volumes of xylene and methanol to give a mixture of 1:1:1 petroleum sulfonate solution:xylene:methanol. Separate solutions of amine and resin were prepared as follows: the DUOMEEN T solution was prepared by mixing DUOMEEN T, xylene and methanol in a ratio of 1:1:1 (g:ml:ml), and the epoxy resin solution was prepared by reading of 3 parts by weight EPON 828 in 1 part by weight xylene. The treatment mixture (Experiment 9) was then prepared by mixing 0.25 ml of the petroleum sulphonate mixture with 0.02 ml of the amine mixture and 0.05 ml of the resin mixture. The results from the corrosion tests are shown in table 3.
De i tabell 3 angitte resultater viser virkningen av blandingen med hensyn til hurtig reduksjon av korrosjonshastigheten til et meget lavt nivå. The results given in Table 3 show the effect of the mixture in rapidly reducing the corrosion rate to a very low level.
Claims (3)
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US29844481A | 1981-09-01 | 1981-09-01 |
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NO166652B true NO166652B (en) | 1991-05-13 |
NO166652C NO166652C (en) | 1991-08-21 |
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NO822904A NO166652C (en) | 1981-09-01 | 1982-08-27 | PROCEDURE FOR CORROSION-INHIBITIVE TREATMENT OF METAL SURFACES. |
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GB (1) | GB2105340B (en) |
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NO (1) | NO166652C (en) |
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1982
- 1982-07-05 CA CA000406579A patent/CA1176443A/en not_active Expired
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GB2105340B (en) | 1984-12-12 |
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GB2105340A (en) | 1983-03-23 |
CA1176443A (en) | 1984-10-23 |
MX162346A (en) | 1991-04-26 |
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