RU2809103C1 - Hydrogen sulfide corrosion inhibitor of steel - Google Patents
Hydrogen sulfide corrosion inhibitor of steel Download PDFInfo
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- RU2809103C1 RU2809103C1 RU2023106350A RU2023106350A RU2809103C1 RU 2809103 C1 RU2809103 C1 RU 2809103C1 RU 2023106350 A RU2023106350 A RU 2023106350A RU 2023106350 A RU2023106350 A RU 2023106350A RU 2809103 C1 RU2809103 C1 RU 2809103C1
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- Prior art keywords
- corrosion
- steel
- hydrogen sulfide
- corrosion inhibitor
- solution
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- 238000005260 corrosion Methods 0.000 title claims abstract description 20
- 230000007797 corrosion Effects 0.000 title claims abstract description 20
- 239000003112 inhibitor Substances 0.000 title claims abstract description 8
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 6
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 6
- 229910000037 hydrogen sulfide Inorganic materials 0.000 title claims abstract description 6
- 239000010959 steel Substances 0.000 title claims abstract description 6
- -1 N-(1,3-dimethylimidazolidin-2-ylidene)-5-phenyl-1,3,4-thiadiazol-2-amine Chemical compound 0.000 claims abstract description 6
- 229910001209 Low-carbon steel Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 3
- 150000002391 heterocyclic compounds Chemical class 0.000 abstract description 2
- 150000002739 metals Chemical class 0.000 abstract description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 150000004867 thiadiazoles Chemical class 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 125000002636 imidazolinyl group Chemical group 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- FFSJPOPLSWBGQY-UHFFFAOYSA-N triazol-4-one Chemical class O=C1C=NN=N1 FFSJPOPLSWBGQY-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
Изобретение относится к использованию N-(1,3-диметилимидазолидин-2-илиден)-5-фенил-1,3,4-тиадиазол-2-амина как ингибитора коррозии малоуглеродистой стали в растворах соляной кислоты в присутствии сероводорода и применению его для защиты от коррозии газо- и нефтепромыслового оборудования, при травлении металлов и удалении окалины. The invention relates to the use of N-(1,3-dimethylimidazolidin-2-ylidene)-5-phenyl-1,3,4-thiadiazol-2-amine as a corrosion inhibitor of low-carbon steel in solutions of hydrochloric acid in the presence of hydrogen sulfide and its use for protection from corrosion of gas and oil field equipment, when etching metals and removing scale.
Исследованные соединения относятся к классу тиадиазолов, которые имеют в своем составе атомы N и S, а также ненасыщенные связи. Данные соединения проявляют защитные свойства по отношению к коррозии стали за счет избыточной электронной плотности, что способствует адсорбции соединения. Для повышения защитного действия в состав молекулы внесен имидазолиновый фрагмент, наличие которого приводит к росту защитного действия.The studied compounds belong to the class of thiadiazoles, which contain N and S atoms, as well as unsaturated bonds. These compounds exhibit protective properties against steel corrosion due to excess electron density, which promotes adsorption of the compound. To increase the protective effect, an imidazoline fragment was added to the molecule, the presence of which leads to an increase in the protective effect.
Различные производные тиадиазола изучают в качестве ингибиторов коррозии углеродистой стали (М. Lebrini, М. Lagrenee, Н. Vezin, L. Gengembre, F. Bentiss. Electrochemical and quantum chemical studies of new thiadiazole derivatives adsorption on mild steel in normal hydrochloric acid medium. Elsevier, 2005, p. 485-505), такие исследования являются перспективными в данной отрасли, так как данный класс веществ отвечает экологическим требованиям к современным ингибиторам коррозии (Tao Zh, Zhang Sh, Li W, Hou В Corrosion inhibition of mild steel in acidic solution by some oxo-triazole derivatives. Elsevier, 2009, p. 2588-2595).Various thiadiazole derivatives are being studied as corrosion inhibitors of carbon steel (M. Lebrini, M. Lagrenee, N. Vezin, L. Gengembre, F. Bentiss. Electrochemical and quantum chemical studies of new thiadiazole derivatives adsorption on mild steel in normal hydrochloric acid medium. Elsevier, 2005, p. 485-505), such research is promising in this industry, since this class of substances meets the environmental requirements for modern corrosion inhibitors (Tao Zh, Zhang Sh, Li W, Hou B Corrosion inhibition of mild steel in acidic solution by some oxo-triazole derivatives (Elsevier, 2009, pp. 2588-2595).
Целью изобретения является поиск новых гетероциклических соединений, которые снижают скорость коррозии малоуглеродистой стали при контакте с металлическим оборудованием и имеют доступные для масштабирования методики синтеза. Цель достигается тем, что содержание в 0,1 М растворе соляной кислоты в присутствии 250 мг/л сероводорода N-(1,3-диметилимидазолидин-2-илиден)-5-фенил-1,3,4-тиадиазол-2-амина (50 -200 мг/л) приводит к снижению скорости коррозии стали Ст3 (ГОСТ 380-2005) с 1,1 мм/год в неингибированном растворе до 0,2-0,1 мм/год в зависимости от концентрации.The purpose of the invention is to search for new heterocyclic compounds that reduce the rate of corrosion of low-carbon steel in contact with metal equipment and have synthesis methods available for scaling. The goal is achieved by the fact that the content of N-(1,3-dimethylimidazolidin-2-ylidene)-5-phenyl-1,3,4-thiadiazol-2-amine in a 0.1 M solution of hydrochloric acid in the presence of 250 mg/l hydrogen sulfide (50 -200 mg/l) leads to a decrease in the corrosion rate of St3 steel (GOST 380-2005) from 1.1 mm/year in an uninhibited solution to 0.2-0.1 mm/year depending on the concentration.
Пример 1. N-(1,3-диметилимидазолидин-2-илиден)-5-фенил-1,3,4-тиадиазол-2-амин К раствору N-[бис(метилсульфанил)метилиден]-5-фенил-1,3,4-тиадиазол-2-амина в ДМФА при непрерывном перемешивании добавляли раствор NN'-диметилэтилендиамина в ДМФА при комнатной температуре. Реакционную смесь выдерживали при 120°С в течение 8 часов. Затем смесь охлаждали и добавляли в ледяную воду. Полученное твердое вещество промывали водой, сушили и очищали колоночной хроматографией (элюент: петролейный эфир/этилацетат).Example 1. N-(1,3-dimethylimidazolidin-2-ylidene)-5-phenyl-1,3,4-thiadiazol-2-amine To a solution of N-[bis(methylsulfanyl)methylidene]-5-phenyl-1, 3,4-thiadiazol-2-amine in DMF, a solution of NN'-dimethylethylenediamine in DMF was added with continuous stirring at room temperature. The reaction mixture was kept at 120°C for 8 hours. The mixture was then cooled and added to ice water. The resulting solid was washed with water, dried and purified by column chromatography (eluent: petroleum ether/ethyl acetate).
Спектр ЯМР 1H, (400 МГц, CDCl3), d, м.д.: 7.81 (д, 6,6 Гц, 2Н), 7,36 (д, J=7,6 Гц, 2Н), 3,45 (с, 4Н), 2,85 (с, 6Н).NMR spectrum 1 H, (400 MHz, CDCl 3 ), d, ppm: 7.81 (d, 6.6 Hz, 2H), 7.36 (d, J=7.6 Hz, 2H), 3, 45 (s, 4H), 2.85 (s, 6H).
Спектр ЯМР 13С(101 МГц, CDCl3), d, м.д.: 172,00, 161,02, 159,12, 132,02, 129,52, 128,81, 126,93, 38,12, 34,60. 13 C NMR spectrum (101 MHz, CDCl 3 ), d, ppm: 172.00, 161.02, 159.12, 132.02, 129.52, 128.81, 126.93, 38.12 , 34.60.
Пример 2. Коррозионные испытания проводят в лабораторных условиях гравиметрическим (ГОСТ 9.506-87) методом в 0,1 М растворе соляной кислоты в воде в присутствии 250 мг/л H2S при стандартной температуре. Концентрацию сероводорода в растворе контролировали методом обратного йодометрического титрования. Скорость коррозии (П), степень торможения (γ) и ингибирующий эффект (Zгр) рассчитывали по формулам:Example 2. Corrosion tests are carried out in laboratory conditions by the gravimetric (GOST 9.506-87) method in a 0.1 M solution of hydrochloric acid in water in the presence of 250 mg/l H 2 S at standard temperature. The concentration of hydrogen sulfide in the solution was controlled by reverse iodometric titration. The corrosion rate (P), the degree of inhibition (γ) and the inhibitory effect (Z gr ) were calculated using the formulas:
где m0 - масса исходного образца, г; m - масса образца после коррозионных испытания и удаления продуктов коррозии, г; S - площадь поверхности образца, м2; τ - время испытания, ч; ρ - плотность Ст3, K0 и K - скорости коррозии стали соответственно в чистом растворе и с добавкой ингибитора, мм/год.where m 0 is the mass of the original sample, g; m is the mass of the sample after corrosion testing and removal of corrosion products, g; S is the surface area of the sample, m2 ; τ - test time, h; ρ is the density of St3, K 0 and K are the corrosion rates of steel, respectively, in a pure solution and with the addition of an inhibitor, mm/year.
Claims (3)
Publications (1)
| Publication Number | Publication Date |
|---|---|
| RU2809103C1 true RU2809103C1 (en) | 2023-12-06 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102285940A (en) * | 2011-07-15 | 2011-12-21 | 中国科学院海洋研究所 | Thiazoles compound and preparation and application thereof |
| RU2667265C1 (en) * | 2018-02-05 | 2018-09-18 | Общество с ограниченной ответственностью "ИФОТОП" | Application of n,n-dimethyl-para-anisidine as inhibitor of hydrogen sulfide corrosion and hydrogen enhancing |
| RU2776118C1 (en) * | 2021-07-12 | 2022-07-13 | Федеральное государственное автономное образовательное учреждение высшего образования "Пермский государственный национальный исследовательский университет" (ПГНИУ) | Inhibitor of hydrochloric acid corrosion of steel |
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102285940A (en) * | 2011-07-15 | 2011-12-21 | 中国科学院海洋研究所 | Thiazoles compound and preparation and application thereof |
| RU2667265C1 (en) * | 2018-02-05 | 2018-09-18 | Общество с ограниченной ответственностью "ИФОТОП" | Application of n,n-dimethyl-para-anisidine as inhibitor of hydrogen sulfide corrosion and hydrogen enhancing |
| RU2776118C1 (en) * | 2021-07-12 | 2022-07-13 | Федеральное государственное автономное образовательное учреждение высшего образования "Пермский государственный национальный исследовательский университет" (ПГНИУ) | Inhibitor of hydrochloric acid corrosion of steel |
Non-Patent Citations (1)
| Title |
|---|
| Tao Zh, Zhang Sh, Li W, Hou В Corrosion inhibition of mild steel in acidic solution by some oxo-triazole derivatives. Elsevier, 2009, p. 2588-2595. * |
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