SE408917B - WAY TO PREVENT CORROSION OF METALS IN CONTACT WITH LIQUID SYSTEMS AND MEANS FOR PERFORMING THE PROCEDURE - Google Patents
WAY TO PREVENT CORROSION OF METALS IN CONTACT WITH LIQUID SYSTEMS AND MEANS FOR PERFORMING THE PROCEDUREInfo
- Publication number
- SE408917B SE408917B SE7712955A SE7712955A SE408917B SE 408917 B SE408917 B SE 408917B SE 7712955 A SE7712955 A SE 7712955A SE 7712955 A SE7712955 A SE 7712955A SE 408917 B SE408917 B SE 408917B
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- hydrogen
- carbon atoms
- alkylene
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- 238000005260 corrosion Methods 0.000 title claims description 17
- 230000007797 corrosion Effects 0.000 title claims description 17
- 238000000034 method Methods 0.000 title claims description 13
- 239000007788 liquid Substances 0.000 title claims description 7
- 229910052751 metal Inorganic materials 0.000 title claims description 5
- 239000002184 metal Substances 0.000 title claims description 5
- 150000002739 metals Chemical class 0.000 title claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 19
- -1 dodecyl Chemical group 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 150000001412 amines Chemical class 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- 125000001165 hydrophobic group Chemical group 0.000 claims description 9
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 5
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims 3
- 125000004429 atom Chemical group 0.000 claims 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- 239000003921 oil Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 230000002401 inhibitory effect Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- FXGZCYNJFWVBCS-UHFFFAOYSA-N 1-n-(3-octoxypropyl)propane-1,2-diamine Chemical compound CCCCCCCCOCCCNCC(C)N FXGZCYNJFWVBCS-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000005645 linoleyl group Chemical group 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- MEVOTDAVZZQWNV-UHFFFAOYSA-N 2-N-(3-dodecoxypropyl)propane-1,2-diamine Chemical compound C(CCCCCCCCCCC)OCCCNC(CN)C MEVOTDAVZZQWNV-UHFFFAOYSA-N 0.000 description 1
- RDCAZFAKCIEASQ-UHFFFAOYSA-N 3-octoxypropan-1-amine Chemical compound CCCCCCCCOCCCN RDCAZFAKCIEASQ-UHFFFAOYSA-N 0.000 description 1
- RFEIDPNPXDGTAJ-UHFFFAOYSA-N C(CCCCCCC)OCCCNC(CN)C Chemical compound C(CCCCCCC)OCCCNC(CN)C RFEIDPNPXDGTAJ-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000002519 antifouling agent Substances 0.000 description 1
- 239000007798 antifreeze agent Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 235000011148 calcium chloride Nutrition 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000002706 hydrostatic effect Effects 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010998 test method Methods 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
- C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
- C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
- C09K15/28—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing nitrogen, oxygen and sulfur
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/16—Sulfur-containing compounds
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Description
'2712955-9 2 för hydrostatisk provning, vatten-flödes operationer vid oljeutvinning, pipe-lines, raffinaderienheter och system för kemiska processer. '2712955-9 2 for hydrostatic testing, water-flow operations in oil extraction, pipelines, refinery units and chemical process systems.
Det har överraskande visat sig att sulfiter eller bisulfiter av eteraminer ger bättre korrosionsinhiberande effekt än sulfiter av mot- svarande aminer vilka ej innehåller etergrupper. Sulfiter eller bisul- fiter av eteraminer är också fördelaktiga genom att de kan formuleras såsom flytande produkter med väsentligt högre halt aktiv substans än sulfiter av fettaminer.It has surprisingly been found that sulphites or bisulphites of ether amines give a better corrosion-inhibiting effect than sulphites of corresponding amines which do not contain ether groups. Sulphites or bisulphites of ether amines are also advantageous in that they can be formulated as liquid products with a significantly higher content of active substance than sulphites of fatty amines.
Föreliggande uppfinning avser således ett sätt att inhíbera korro- sion av metaller i kontakt med vätskesystem varvid till systemen sättes en effektiv mängd av en sulfit eller bisulfit av en eteramin med den allmänna formeln X R - [ O-alkylen 1 - (CH ) - å - Y e a 2 m vari R är en organisk hydrofob grupp med minst 6 kolatomer, alkylen- gruppen är en etylen-, propylen- eller isopropylengrupp, a är ett tal mellan l och 5, m ett tal mellan 0 och H, X och Y oberoende av varandra är väte eller gruppen - (CH2)n - NH2 eller X är väte och Y gruppen - (CH2)n - NH - (CH2)n - NH2 vari n är ett tal mellan 2 och lO.The present invention thus relates to a method of inhibiting the corrosion of metals in contact with liquid systems, wherein an effective amount of a sulphite or bisulphite of an ether amine of the general formula XR - [O-alkylene 1 - (CH) - Y is 2 m wherein R is an organic hydrophobic group having at least 6 carbon atoms, the alkylene group is an ethylene, propylene or isopropylene group, a is a number between 1 and 5, m is a number between 0 and H, X and Y are independently of each other is hydrogen or the group - (CH 2) n - NH 2 or X is hydrogen and Y the group - (CH 2) n - NH - (CH 2) n - NH 2 wherein n is a number between 2 and 10.
Den organiska hydrofoba gruppen R är lämpligen en rak eller grenad alifatisk grupp med 6 till 22 kolatomer, företrädesvis 8 till 18 kol- atomer. Några exempel på lämpliga grupper är heptyl, oktyl, nonyl, decyl, dodecyl, hexadecyl, oktadecyl och omättade grupper såsom oleyl och lino- leyl. De organiska hydrofoba grupperna kan även utgöras av blandningar av naturligt förekommande grupper. _ I ovanstående formel är a företrädesvis ett tal mellan l och 2 och m är företrädesvis 0 då a är l och företrädesvis 2 till 3 då a;>Jn n är företrädesvis ett tal mellan 2 och 3. Det förstås emellertid att talet n ej hehöver vara detsamma då aminerna innehåller mer än en grupp - (CH2)n - NH2 eller gruppen - (CH2)n - NH - (CH2)n - NH2. Vidare förstås att amínen kan innehålla blandningar av etoxy- och propoxygrup- per. De föredragna eteramïnvrnu är oterdíuminnrnn.The organic hydrophobic group R is suitably a straight or branched aliphatic group having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms. Some examples of suitable groups are heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl, octadecyl and unsaturated groups such as oleyl and linoleyl. The organic hydrophobic groups may also be mixtures of naturally occurring groups. In the above formula, a is preferably a number between 1 and 2 and m is preferably 0 when a is 1 and preferably 2 to 3 when a;> Jn n is preferably a number between 2 and 3. It is understood, however, that the number n does not be the same when the amines contain more than one group - (CH2) n - NH2 or the group - (CH2) n - NH - (CH2) n - NH2. It is further understood that the amine may contain mixtures of ethoxy and propoxy groups. The preferred ether amines are the otterdiamines.
Exempel på lämpliga sulfiter och bísulfíter är de av }-oktoxypro- Pylämifl, êV N(5~dodekoxy propyl) propylrndiamín och av N(5-oktoxypropyl) propylendiamin.Examples of suitable sulfites and bisulfites are those of N-octoxypropylmethyl, N (5-dodecoxy propyl) propylenediamine and of N (5-octoxypropyl) propylenediamine.
Sulfiterna eller bísulfíterna av eteraminerna kan framställas genom att svaveldioxid eller svavelsyrlighet reageras med eteraminerna i vatten, alkoholer eller blandningar av dessa beroende på aminens kedjelängd, vid rumstemperatur eller svagt förhöjd temperatur. Då både bisulfit och sulfit bildas i en vattenhaltig lösning är produkten en blandning av 3 7712955-9 dessa om reaktionen genomföras i vattenhaltigt medium eller om reaktions- produkten senare utspädes med vatten; Saltet framställes företrädesvis genom att en ekvivalent av en amin får reagera med en ekvivalent eller mindre av S02 eller HZSOB med avseende på aminen, men vid di- eller polyaminer kan högre molära mängder av S02 användas så att fler än en av aminogrupperna reageras. Alkoholer- na som användes smnreaktionsmedium eller del därav kan vara lägre alko- holer såsom metanol, etanol, isopropylalkohol etc.The sulfites or bisulfites of the ether amines can be prepared by reacting sulfur dioxide or sulfuric acid with the ether amines in water, alcohols or mixtures thereof depending on the chain length of the amine, at room temperature or slightly elevated temperature. When both bisulfite and sulphite are formed in an aqueous solution, the product is a mixture of these if the reaction is carried out in aqueous medium or if the reaction product is later diluted with water; The salt is preferably prepared by reacting one equivalent of an amine with one equivalent or less of SO 2 or H 2 SO 3 with respect to the amine, but in the case of di- or polyamines, higher molar amounts of SO 2 may be used so that more than one of the amino groups is reacted. The alcohols used in the reaction medium or part thereof may be lower alcohols such as methanol, ethanol, isopropyl alcohol, etc.
Sulfiterna eller bisulfiterna kan insättas som kombinerade korro- sionsinhibitorer och kemiska avluftningsmedel i form av lösningar eller dispersioner i det inerta utspädningsmedel i vilket de framställes eller som koncentrat. En fördel med föreliggande produkter är att de kan for- muleras som flytande produkter med höga halter aktiv substans, upp till 65 viktprocent och mer.The sulfites or bisulfites can be used as combined corrosion inhibitors and chemical deaerators in the form of solutions or dispersions in the inert diluent in which they are prepared or as a concentrate. An advantage of the present products is that they can be formulated as liquid products with high levels of active substance, up to 65% by weight and more.
Föreliggande uppfinning avser även en förening för inhibering av korrosion av metaller i kontakt med vätskesystem vilken förening ut- göres av en sulfit eller bisulfit av en eteramin innehållande minst en organisk hydrofob grupp med 6 kolatomer eller mer.The present invention also relates to a compound for inhibiting corrosion of metals in contact with liquid systems, which compound is a sulphite or bisulphite of an etheramine containing at least one organic hydrophobic group having 6 carbon atoms or more.
Föreningarna enligt uppfinningen är sulfiter eller bisulfiter av eteramíner med den allmänna formeln X I _ - (cnzkn- N - Y R - [ O-alkylen Ja vari R är en organisk hydrofob grupp med minst 6 kolatomer, alkylen- gruppen är en etylen-, propylen- eller isopropylengrupp, a är ett*tal mellan l och 5, m ett tal mellan 0 och U, X och Y oberoende av varandra är väte eller gruppen - (CH2)n - NH2 eller X är väte och Y gruppen - (CH2)n - NH - (CH2)n--NH2 vari n.är ett tal mellan 2 och l0.The compounds of the invention are sulfites or bisulfites of etheramines of the general formula XI - (cnzkn- N - YR - [O-alkylene Ja wherein R is an organic hydrophobic group having at least 6 carbon atoms, the alkylene group is an ethylene-, propylene- or isopropylene group, a is a * number between 1 and 5, m a number between 0 and U, X and Y are independently hydrogen or the group - (CH 2) n - NH 2 or X is hydrogen and Y the group - (CH 2) n - NH - (CH 2) n - NH 2 wherein n is a number between 2 and 10.
Den organiska hydrofoba gruppen R är lämpligen en rak eller grenad alifatisk grupp med 6 till 22 kolatomer, företrädesvis 8 till 18 kol- atomer. Några exempel på lämpliga grupper är heptyl; oktyl, nonyl, decyl, dodecyl, hexadecyl, oktadecyl och omättade grupper såsom oleyl och lino- leyl. De organiska hydrofoba grupperna kan även vara blandningar av naturligt förekommande grupper.The organic hydrophobic group R is suitably a straight or branched aliphatic group having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms. Some examples of suitable groups are heptyl; octyl, nonyl, decyl, dodecyl, hexadecyl, octadecyl and unsaturated groups such as oleyl and linoleyl. The organic hydrophobic groups may also be mixtures of naturally occurring groups.
I ovanstående formel är a företrädesvis ett tal mellan 1 och 2 och m är företrädesvis 0 då a är 1 och företrädesvis 2 till 3 då a j>l. n är företrädesvis ett tal mellan 2 och 3. Det förstås emellertid att talet n ej behöver vara detsamma då aminen innehåller mer än en grupp _- (CH2)n- NH2 eller gruppen - (CH2)n - NH - (CH2)n - NH2. Vidare förstås att aminen kan innehålla blandningar av etoxy- och propoxy- grupper. De föredragna eteraminerna är eterdiaminerna. \7v129ss-9. I B Exempel på lämpliga sulfiter och bisulfiter är de av 3-oktoxy propylamin, av N(3-dodekoxy propyl) propylendiamin och av N(3-oktoxy propyl) propylendiamin. \ Den mängd av föreliggande föreningar som erfordras för att erhålla tillfredsställande skydd varierar inom vida gränser beroende på de spe- ciella systemen och deras korrosivitet. Föreningarna ger vanligen en väsentlig reduktion av såväl allmän korrosion som punktfrätning då de användes i koncentrationer av cirka l ppm räknat på den korrosiva vät- skans vikt. Den övre gränsen är inte kritisk utan sättes av ekonomiska skäl. Koncentrationer upp till och över 500 ppm kan användas men lämp- ligen användes koncentrationer inom intervallet l till 200 ppm.In the above formula, a is preferably a number between 1 and 2 and m is preferably 0 when a is 1 and preferably 2 to 3 when a j> 1. n is preferably a number between 2 and 3. However, it is understood that the number n need not be the same as the amine contains more than one group _- (CH2) n- NH2 or the group - (CH2) n - NH - (CH2) n - NH2. It is further understood that the amine may contain mixtures of ethoxy and propoxy groups. The preferred ether amines are the ether diamines. \ 7v129ss-9. I B Examples of suitable sulphites and bisulphites are those of 3-octoxy propylamine, of N (3-dodecoxy propyl) propylenediamine and of N (3-octoxy propyl) propylenediamine. The amount of the present compounds required to obtain satisfactory protection varies widely depending on the particular systems and their corrosivity. The compounds usually provide a significant reduction in both general corrosion and spot corrosion when used in concentrations of about 1 ppm based on the weight of the corrosive liquid. The upper limit is not critical but is set for economic reasons. Concentrations up to and above 500 ppm can be used, but suitably concentrations in the range 1 to 200 ppm are used.
Sulfiterna och bisulfiterna enligt föreliggande uppfinning är speciellt användbara inom de olika områdena inom oljeutvinning och petroleumindustri. De kan på i och för sig känt sätt sättas till korro- siva system inom primär, sekundär och tertiär oljeutvinning. De kan även inkapslas och så införas i oljekällorna varvid föreningarna långsamt frigöres då de vattenlösliga kapslarna upplöses. En annan teknik inom primär oljeutvinning där föreliggande föreningar kan användas är genom "squeezing". I detta fall injiceras' föreningarna under tryck i den producerande formationen, absorberas på mineralytorna och desorberas då vätskorna produceras. Föreningarna kan även på i och för sig känt sätt tillsättas vid vattenflödes operationer i sekundär oljeutvinning och tillsättas till pipe-lines, överföringsledningar,° raffinaderi- enheter etc.The sulfites and bisulfites of the present invention are particularly useful in the various fields of oil extraction and the petroleum industry. In a manner known per se, they can be added to corrosive systems in primary, secondary and tertiary oil extraction. They can also be encapsulated and thus introduced into the oil wells, whereby the compounds are slowly released when the water-soluble capsules are dissolved. Another technique in primary oil recovery where the present compounds can be used is by "squeezing". In this case, the compounds are injected under pressure into the producing formation, absorbed on the mineral surfaces and desorbed as the liquids are produced. The compounds can also be added in a manner known per se in water flow operations in secondary oil recovery and added to pipelines, transmission lines, refinery units, etc.
Sulfiterna och bisulfiterna enligt föreliggande uppfinning kan användas i kombination med andra inhibitorer och tillsammans med kata- lysatorer, såsom kobolt, vilka vanligen användes för sulfit som kemiskt avluftningsmedel. Föreningarna kan vidare användas tillsammans med tillsatser vilka normalt användes inom området såsom ytaktiva medel, frostskyddsmedel, "anti-fouling agents", kelatbíldare etc.The sulfites and bisulfites of the present invention can be used in combination with other inhibitors and in conjunction with catalysts, such as cobalt, which are commonly used for sulfite as a chemical deaerator. The compounds can further be used together with additives which are normally used in the field such as surfactants, antifreeze agents, anti-fouling agents, chelating agents, etc.
Uppfinníngen beskrives närmare i följande exempel vilka emellertid ej är avsedda begränsa densamma.The invention is described in more detail in the following examples which, however, are not intended to limit the same.
Exempel 1 20 gram N-(3-oktoxypropyl) propylendiamin löstes i 65 gram isopro- panol och 9,8 gram vatten. 5,2 gram S02 tillsattes. Temperaturen hölls under H00 C under reaktionen. Efter kylning bildades en klar lösning av reaktionsprodukten. 50 7112955-9 Exempel 2 En koncentrerad lösning framställdes genom att 60 gram N-(3-oktoxy- propyl) propylendíamin fick reagera med 15,6 gram S02 i ett utspädnings- medel av 20 gram etylenglykol och 5 gram vatten. Temperaturen hölls under 400 C under reaktionen. En klar stabil lösning erhölls.Example 1 20 grams of N- (3-octoxypropyl) propylenediamine was dissolved in 65 grams of isopropanol and 9.8 grams of water. 5.2 grams of SO 2 was added. The temperature was kept below H00 C during the reaction. After cooling, a clear solution of the reaction product formed. Example 2 A concentrated solution was prepared by reacting 60 grams of N- (3-octoxypropyl) propylenediamine with 15.6 grams of SO 2 in a diluent of 20 grams of ethylene glycol and 5 grams of water. The temperature was kept below 400 ° C during the reaction. A clear stable solution was obtained.
Exempel 3 20 gram N-(5-dekoxypropyl) propylendiamin löstes i 65 gram iso- propanol och 10 gram vatten.5 gram S02 tillsattes. Temperaturen hölls under N00 C vid reaktionen. Efter'kylning bildades en klar lösning av reaktionsprodukten.Example 3 20 grams of N- (5-decoxypropyl) propylenediamine was dissolved in 65 grams of isopropanol and 10 grams of water. 5 grams of SO 2 were added. The temperature was kept below N00 C during the reaction. After cooling, a clear solution of the reaction product formed.
Exempel N Korrosionstest Produkterna enligt exempel l och 3-samt två andra reaktionsproduk- ter av S02 och fettdiaminer, vilka ej innefattas inom föreliggande upp- finning, utvärderades. En polarisations resistans metod användes för kvantifiering av produkternas ínhiberande egenskaper.Example N Corrosion Test The products of Examples 1 and 3 and two other reaction products of SO 2 and fatty diamines, which are not included in the present invention, were evaluated. A polarization resistance method was used to quantify the inhibitory properties of the products.
Testmetod I en 1000 ml E-kolv hälldes 50 ml råolja och 950 ml saltvatten med följande sammansättning: komponent _Ã_ NaCl H,H Naflcdj o, 08 CaC12 0,05 MgCl2 _ 0,03 MgSOh 0,01 vatten 9H,U3 Blandningen omrördes kraftigt och koldioxid genombubblades under 30 minuter så att en blandning mättad på koldioxid och med en syrahalt av mindre än 0,5 ppm erhölls. En Magna Corrater utrustad med elek- troder av 1010 kolstål användes för mätningarna. Vid slutet av 30 minuters perioden nedfördes elektroderna i lösningen och inhibitorn tillsattes. Mätningar av den allmänna korrosionshastlgheten-(mil1s/ year) och punktfrätningsindex (PI) gjordes efter 5 minuter. Omrörnings- hastigheten och C02-genombubblingen mínskades starkt efter 30 minuter.Test method In a 1000 ml E-flask was poured 50 ml of crude oil and 950 ml of brine having the following composition: component _Ã_ NaCl H, H Na fl cdj o, 08 CaCl2 0.05 MgCl2 _ 0.03 MgSOh 0.01 water 9H, U3 and carbon dioxide was bubbled through for 30 minutes to obtain a mixture saturated with carbon dioxide and having an acid content of less than 0.5 ppm. A Magna Corrater equipped with 1010 carbon steel electrodes was used for the measurements. At the end of the 30 minute period, the electrodes were immersed in the solution and the inhibitor was added. Measurements of the general corrosion rate (mil1s / year) and point corrosion index (PI) were made after 5 minutes. The stirring speed and CO 2 bubbling were greatly reduced after 30 minutes.
En slutlig avläsning gjordes H5 minuter efter ínhibitortillsatsen.A final reading was made H5 minutes after the inhibitor addition.
Låga värden på korrosion och punktfrätning indikerar låg korrosion och låg tendens till punktfrätning. 'Low corrosion and spot corrosion values indicate low corrosion and low tendency to spot corrosion. '
Claims (3)
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SE7712955A SE408917B (en) | 1977-11-16 | 1977-11-16 | WAY TO PREVENT CORROSION OF METALS IN CONTACT WITH LIQUID SYSTEMS AND MEANS FOR PERFORMING THE PROCEDURE |
| NO783850A NO146708C (en) | 1977-11-16 | 1978-11-15 | PROCEDURE FOR AA PREVENTING CORROSION OF METALS IN CONTACT WITH A LIQUID SYSTEM |
| GB7844783A GB2011383B (en) | 1977-11-16 | 1978-11-16 | Sulphites and bisulphites of amines and their use for inhibiting corrosion |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SE7712955A SE408917B (en) | 1977-11-16 | 1977-11-16 | WAY TO PREVENT CORROSION OF METALS IN CONTACT WITH LIQUID SYSTEMS AND MEANS FOR PERFORMING THE PROCEDURE |
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| Publication Number | Publication Date |
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| SE7712955L SE7712955L (en) | 1979-05-17 |
| SE408917B true SE408917B (en) | 1979-07-16 |
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| SE7712955A SE408917B (en) | 1977-11-16 | 1977-11-16 | WAY TO PREVENT CORROSION OF METALS IN CONTACT WITH LIQUID SYSTEMS AND MEANS FOR PERFORMING THE PROCEDURE |
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| SE (1) | SE408917B (en) |
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