RU2166002C1 - Fatty amine/ethylene oxide/organophosphorus compound interaction product as inhibitor of hydrogen sulfide and carbon dioxide corrosion in mineralized aqueous media - Google Patents
Fatty amine/ethylene oxide/organophosphorus compound interaction product as inhibitor of hydrogen sulfide and carbon dioxide corrosion in mineralized aqueous media Download PDFInfo
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- RU2166002C1 RU2166002C1 RU2000108702A RU2000108702A RU2166002C1 RU 2166002 C1 RU2166002 C1 RU 2166002C1 RU 2000108702 A RU2000108702 A RU 2000108702A RU 2000108702 A RU2000108702 A RU 2000108702A RU 2166002 C1 RU2166002 C1 RU 2166002C1
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- inhibitor
- carbon dioxide
- hydrogen sulfide
- ethylene oxide
- aqueous media
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- 238000005260 corrosion Methods 0.000 title claims abstract description 14
- 230000007797 corrosion Effects 0.000 title claims abstract description 14
- 239000003112 inhibitor Substances 0.000 title claims abstract description 14
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 title claims abstract description 7
- 150000002903 organophosphorus compounds Chemical class 0.000 title claims abstract description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims description 20
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims description 10
- 150000001412 amines Chemical class 0.000 title claims description 10
- 239000001569 carbon dioxide Substances 0.000 title claims description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims description 10
- 229910000037 hydrogen sulfide Inorganic materials 0.000 title claims description 10
- 239000012736 aqueous medium Substances 0.000 title claims description 8
- 230000003993 interaction Effects 0.000 title abstract description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 235000014113 dietary fatty acids Nutrition 0.000 abstract 1
- 229930195729 fatty acid Natural products 0.000 abstract 1
- 239000000194 fatty acid Substances 0.000 abstract 1
- 150000004665 fatty acids Chemical class 0.000 abstract 1
- 230000001681 protective effect Effects 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000026731 phosphorylation Effects 0.000 description 1
- 238000006366 phosphorylation reaction Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 150000003139 primary aliphatic amines Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
Description
Изобретение относится к средствам защиты нефтепромыслового оборудования от сероводородной и углекислотной коррозии и может быть использовано в нефтедобывающей промышленности. The invention relates to the protection of oilfield equipment from hydrogen sulfide and carbon dioxide corrosion and can be used in the oil industry.
Известен ингибитор коррозии, включающий продукт взаимодействия первичных алифатических аминов, технического диметилфосфита и воды, взятых в мольном соотношении 1: (0,8 - 1,2): (0,8 - 1,2) (патент РФ N 2038421, МКИ C 23 F 11/00, 1995 г.). Однако данный ингибитор недостаточно эффективен в минерализованных водных средах, содержащих сероводород и углекислый газ. A known corrosion inhibitor, including the product of the interaction of primary aliphatic amines, technical dimethylphosphite and water, taken in a molar ratio of 1: (0.8 - 1.2): (0.8 - 1.2) (RF patent N 2038421, MKI C 23 F 11/00, 1995). However, this inhibitor is not effective enough in saline aqueous media containing hydrogen sulfide and carbon dioxide.
Известен состав для защиты нефтепромыслового оборудования от сероводородной и углекислотной коррозии, включающий амины и продукт обработки олефинов C5-C40 элементарной серой (патент РФ N 2061098, МКИ C 23 F 11/00, 1996 г.). Данный состав недостаточно эффективен.A known composition for the protection of oilfield equipment from hydrogen sulfide and carbon dioxide corrosion, including amines and the product of the processing of olefins C 5 -C 40 elemental sulfur (RF patent N 2061098, MKI C 23 F 11/00, 1996). This composition is not effective enough.
Наиболее близким к предлагаемому изобретению является ингибитор сероводородной и углекислотной коррозии, включающий талловое масло, смесь бис(алкилгексаоксиэтилен)фосфата, 2-этилендиаминометилфенола и/или 2,6-ди(этилендиаминометил)фенола и растворитель (патент РФ N 2141543, МКИ C 23 F 11/167, 1999 г. ). Известный ингибитор недостаточно эффективен в минерализованных водных средах. Closest to the proposed invention is an inhibitor of hydrogen sulfide and carbon dioxide corrosion, including tall oil, a mixture of bis (alkylhexaoxyethylene) phosphate, 2-ethylenediaminomethylphenol and / or 2,6-di (ethylenediaminomethyl) phenol and a solvent (RF patent N 2141543, MKI C 23 F 11/167, 1999). A known inhibitor is not effective enough in saline aqueous media.
В основу настоящего изобретения положена задача создания эффективного ингибитора сероводородной и углекислотной коррозии в минерализованных водных средах. The basis of the present invention is the creation of an effective inhibitor of hydrogen sulfide and carbon dioxide corrosion in mineralized aqueous media.
Поставленная задача решается продуктом взаимодействия 1 моли жирного амина, 10-30 молей окиси этилена и 2 молей фосфорорганического соединения в качестве ингибитора сероводородной и углекислотной коррозии в минерализованных водных средах. The problem is solved by the product of the interaction of 1 mole of a fatty amine, 10-30 moles of ethylene oxide and 2 moles of an organophosphorus compound as an inhibitor of hydrogen sulfide and carbon dioxide corrosion in mineralized aqueous media.
Продукт взаимодействия 1 моли жирного амина, 10-30 молей окиси этилена и 2 молей фосфорорганического соединения получают известным путем последовательного присоединения окиси этилена к амину с последующим фосфорилированием полученного продукта. The reaction product of 1 mole of a fatty amine, 10-30 moles of ethylene oxide and 2 moles of an organophosphorus compound is obtained by known sequentially adding ethylene oxide to an amine, followed by phosphorylation of the resulting product.
В качестве жирного амина используют синтетические жирные амины фракций C8 - C12, C10 - C16 по ТУ 113-03-0203796-018-92, или C17 - C20 по ТУ 6-02-740-79 или ТУ 6-02-795-87.As the fatty amine, synthetic fatty amines of the fractions C 8 - C 12 , C 10 - C 16 according to TU 113-03-0203796-018-92, or C 17 - C 20 according to TU 6-02-740-79 or
Окись этилена берут в соответствии с ГОСТ 7568-88. Ethylene oxide is taken in accordance with GOST 7568-88.
В качестве фосфорорганического соединения могут быть использованы, например, диметилфосфит (ДМФ) по ТУ 6-36-5763445-6-88, или P2O5 - фосфор (Y) оксид (2: 5) (фосфорный ангидрид) технический по ТУ 113-08-614-87, или фосфористая кислота (орто) по ТУ 6-09-4023-75, или кислота фосфорная (орто) по ГОСТ 6552-80, или кислота фосфорная экстракционная по ТУ 6-08-342-76.As an organophosphorus compound, for example, dimethyl phosphite (DMF) according to TU 6-36-5763445-6-88, or P 2 O 5 - phosphorus (Y) oxide (2: 5) (phosphoric anhydride) technical according to TU 113 can be used -08-614-87, or phosphorous acid (ortho) according to TU 6-09-4023-75, or phosphoric acid (ortho) according to GOST 6552-80, or extraction phosphoric acid according to TU 6-08-342-76.
Анализ известных технических решений показал, что в науке и технике нет объекта, аналогичного по предлагаемой совокупности признаков и наличию вышеуказанных свойств, что позволяет сделать вывод о соответствии изобретения критериям "новизна" и "изобретательский уровень". Analysis of the known technical solutions showed that in science and technology there is no object similar in the proposed combination of features and the presence of the above properties, which allows us to conclude that the invention meets the criteria of "novelty" and "inventive step".
Для доказательства соответствия заявляемого изобретения критерию "промышленная применимость" приводим конкретные примеры получения продукта. To prove the compliance of the claimed invention with the criterion of "industrial applicability" we give specific examples of the receipt of the product.
Пример N 1 (предлагаемый). Example No. 1 (proposed).
В реактор загружают 243 г первичных дистиллированных аминов C10 - C16 в присутствии катализатора (едкий натр 46%-ный) ~1 г. При температуре 110-125oC и непрерывном перемешивании добавляют окись этилена 754 г. При установлении постоянного давления в реакторе, что является признаком окончания реакции, массу охлаждают до 70-80oC, проводят анализ пробы на определение массовой доли полиэтиленгликолевых производных в пересчете на азот. Далее, при постоянном перемешивании в реактор загружают 163,2 г диметилфосфита, температура повышается до 130oC. Реакцию ведут 3 часа.Ethyl oxide 754 g was added to the reactor, 243 g of primary distilled amines C 10 - C 16 in the presence of a catalyst (sodium hydroxide 46%) ~ 1 g. At a temperature of 110-125 o C and continuous stirring , which is a sign of the end of the reaction, the mass is cooled to 70-80 o C, analyze the sample to determine the mass fraction of polyethylene glycol derivatives in terms of nitrogen. Further, with constant stirring, 163.2 g of dimethylphosphite was charged into the reactor, the temperature increased to 130 o C. The reaction was carried out for 3 hours.
Примеры N 2-20 выполняют аналогично примеру N 1, варьируя фракции аминов и фосфорорганического соединения (ФОС). Examples N 2-20 are performed analogously to
Пример N 21 (прототип). Example No. 21 (prototype).
Полученный ингибитор представляет собой жидкость коричневого цвета с плотностью 0,930-1,050 г/см3.The resulting inhibitor is a brown liquid with a density of 0.930-1.050 g / cm 3 .
Ингибитор коррозии испытывают в минерализованных водных средах, содержащих сероводород и углекислый газ. Общая минерализация водных сред составляет 21040,0 мг/л. A corrosion inhibitor is tested in mineralized aqueous media containing hydrogen sulfide and carbon dioxide. The total mineralization of aqueous media is 21040.0 mg / L.
Содержание CO2 = 5,5 - 15,5 мг/л, H2S = 186 - 237 мг/дм3, pH=5,5, плотность при 20oC = 1,140 г/см3, температура 22oC.The content of CO 2 = 5.5 - 15.5 mg / l, H 2 S = 186 - 237 mg / dm 3 , pH = 5.5, density at 20 o C = 1,140 g / cm 3 , temperature 22 o C.
Антикоррозионную активность полученных ингибиторов коррозии оценивают на модели сточной воды, близкой по содержанию H2S и CO2 к естественным условиям, и в реальных нефтепромысловых средах гравиметрическим методом. Испытания проводят в течение 6 часов на лабораторной установке типа "колесо" в закрытой системе со скоростью движения испытуемой среды 0,4 м/с, а также в герметично закрытых ячейках циркуляционного типа по ГОСТ 9.506.87. "Ингибиторы коррозии металлов в водно-нефтяных средах".The anticorrosive activity of the obtained corrosion inhibitors is evaluated on a model of wastewater that is close in its content to H 2 S and CO 2 to natural conditions, and in real oilfield environments by the gravimetric method. The tests are carried out for 6 hours on a laboratory setup of the wheel type in a closed system with a test medium moving speed of 0.4 m / s, as well as in hermetically closed circulation cells according to GOST 9.506.87. "Inhibitors of metal corrosion in water-oil environments."
Результаты испытаний представлены в таблице. The test results are presented in the table.
Данные, приведенные в таблице, подтверждают высокую эффективность предлагаемого ингибитора коррозии для высокоминерализованных сред, содержащих сероводород и углекислый газ. The data presented in the table confirm the high efficiency of the proposed corrosion inhibitor for highly mineralized environments containing hydrogen sulfide and carbon dioxide.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| RU2000108702A RU2166002C1 (en) | 2000-04-11 | 2000-04-11 | Fatty amine/ethylene oxide/organophosphorus compound interaction product as inhibitor of hydrogen sulfide and carbon dioxide corrosion in mineralized aqueous media |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| RU2000108702A RU2166002C1 (en) | 2000-04-11 | 2000-04-11 | Fatty amine/ethylene oxide/organophosphorus compound interaction product as inhibitor of hydrogen sulfide and carbon dioxide corrosion in mineralized aqueous media |
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| RU2166002C1 true RU2166002C1 (en) | 2001-04-27 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2214479C1 (en) * | 2002-10-02 | 2003-10-20 | Открытое акционерное общество "НАПОР" | Method of production of inhibitor for protection against hydrosulfide and carbon dioxide corrosion in mineralized aqueous media |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0286336A1 (en) * | 1987-04-02 | 1988-10-12 | Exxon Chemical Patents Inc. | Corrosion inhibitors |
| US5019343A (en) * | 1989-12-15 | 1991-05-28 | W. R. Grace & Co.-Conn. | Control of corrosion in aqueous systems using certain phosphonomethyl amines |
| RU2007502C1 (en) * | 1992-03-02 | 1994-02-15 | Нижнекамское производственное объединение "Нижнекамскнефтехим" | Salt deposition and corrosion inhibitor for carbon steel in salted water |
| RU2038421C1 (en) * | 1993-10-13 | 1995-06-27 | Акционерное общество "Напор" | Bactericide inhibitor of corrosion in mineralized hydrogen sulfide-containing aqueous media |
| RU2141543C1 (en) * | 1998-03-11 | 1999-11-20 | ОАО "Научно-исследовательский институт по нефтепромысловой химии" | Inhibitor of hydrogen-sulfide and/or carbonic acid corrosion |
-
2000
- 2000-04-11 RU RU2000108702A patent/RU2166002C1/en active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0286336A1 (en) * | 1987-04-02 | 1988-10-12 | Exxon Chemical Patents Inc. | Corrosion inhibitors |
| US5019343A (en) * | 1989-12-15 | 1991-05-28 | W. R. Grace & Co.-Conn. | Control of corrosion in aqueous systems using certain phosphonomethyl amines |
| RU2007502C1 (en) * | 1992-03-02 | 1994-02-15 | Нижнекамское производственное объединение "Нижнекамскнефтехим" | Salt deposition and corrosion inhibitor for carbon steel in salted water |
| RU2038421C1 (en) * | 1993-10-13 | 1995-06-27 | Акционерное общество "Напор" | Bactericide inhibitor of corrosion in mineralized hydrogen sulfide-containing aqueous media |
| RU2141543C1 (en) * | 1998-03-11 | 1999-11-20 | ОАО "Научно-исследовательский институт по нефтепромысловой химии" | Inhibitor of hydrogen-sulfide and/or carbonic acid corrosion |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2214479C1 (en) * | 2002-10-02 | 2003-10-20 | Открытое акционерное общество "НАПОР" | Method of production of inhibitor for protection against hydrosulfide and carbon dioxide corrosion in mineralized aqueous media |
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