RU2805531C1 - Steel corrosion inhibitor based on substituted imidazoline - Google Patents
Steel corrosion inhibitor based on substituted imidazoline Download PDFInfo
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- RU2805531C1 RU2805531C1 RU2023107034A RU2023107034A RU2805531C1 RU 2805531 C1 RU2805531 C1 RU 2805531C1 RU 2023107034 A RU2023107034 A RU 2023107034A RU 2023107034 A RU2023107034 A RU 2023107034A RU 2805531 C1 RU2805531 C1 RU 2805531C1
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- corrosion
- steel
- corrosion inhibitor
- mercaptophenyl
- dimethyl
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- 238000005260 corrosion Methods 0.000 title claims abstract description 22
- 230000007797 corrosion Effects 0.000 title claims abstract description 22
- 239000003112 inhibitor Substances 0.000 title claims abstract description 10
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 7
- 239000010959 steel Substances 0.000 title claims abstract description 7
- 150000002462 imidazolines Chemical class 0.000 title description 3
- -1 1,3-dimethyl-2-(4-mercaptophenyl)imidazolidine compound Chemical class 0.000 claims abstract description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 8
- 239000007864 aqueous solution Substances 0.000 abstract description 4
- 239000000243 solution Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 238000010306 acid treatment Methods 0.000 abstract description 2
- 238000002347 injection Methods 0.000 abstract description 2
- 239000007924 injection Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- NRLPPGBADQVXSJ-UHFFFAOYSA-N 4-sulfanylbenzaldehyde Chemical compound SC1=CC=C(C=O)C=C1 NRLPPGBADQVXSJ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- GUAWMXYQZKVRCW-UHFFFAOYSA-N n,2-dimethylaniline Chemical compound CNC1=CC=CC=C1C GUAWMXYQZKVRCW-UHFFFAOYSA-N 0.000 description 1
- KVKFRMCSXWQSNT-UHFFFAOYSA-N n,n'-dimethylethane-1,2-diamine Chemical compound CNCCNC KVKFRMCSXWQSNT-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229940083254 peripheral vasodilators imidazoline derivative Drugs 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 150000004867 thiadiazoles Chemical class 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Abstract
Description
Изобретение относится к средствам защиты металлов от коррозии, а именно к использованию 1,3-диметил-2-(4-меркаптофенил)имидазолидина как ингибитора коррозии малоуглеродистой стали в 15% водном растворе соляной кислоты, который может быть использован в нефтяной промышленности для кислотной обработки буровых скважин, а также для обработки призабойной зоны нефтяных и водонагнетательных скважин.The invention relates to means of protecting metals from corrosion, namely to the use of 1,3-dimethyl-2-(4-mercaptophenyl)imidazolidine as a corrosion inhibitor for low-carbon steel in a 15% aqueous solution of hydrochloric acid, which can be used in the oil industry for acid treatment drilling wells, as well as for treating the bottomhole zone of oil and water injection wells.
Исследованное соединение относится к классу замещенных имидазолинов, в составе которого N, S - атомы, а также ненасыщенные связи. В качестве ингибиторов кислотной коррозии стали применяют производные имидазолина, которые в своем составе также имеют атомы N или аминогруппы склонные к протонированию (RU 2 754 320 C1, RU 2754326 C1, RU 2754323 С1).The studied compound belongs to the class of substituted imidazolines, which contains N, S atoms, as well as unsaturated bonds. As inhibitors of acid corrosion of steel, imidazoline derivatives are used, which also contain N atoms or amino groups prone to protonation (RU 2 754 320 C1, RU 2754326 C1, RU 2754323 C1).
Различные производные тиадиазола изучают в качестве ингибиторов коррозии углеродистой стали (G Bereket, Е С Quantum chemical studies on some imidazole derivatives as corrosion inhibitors for iron in acidic medium. Elsevier, 2002, p.79-88), такие исследования являются перспективными в данной отрасли, так как данный класс веществ отвечает экологическим требованиям к современным ингибиторам коррозии (M.Ouakkiac, М. Galai, М. Cherkaoui. Imidazole derivatives as efficient and potential class of corrosion inhibitors for metals and alloys in aqueous electrolytes: A review. Elsevier, 2022). 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, а также расширение спектра возможных соединений, замедляющих коррозию стали. Полученный результат заключается в том, что 1,3-диметил-2-(4-меркаптофенил)имидазолидин подавляет коррозию малоуглеродистой стали Ст3 (ГОСТ 380-2005) в 15% водном растворе соляной кислоты, при концентрации 100 - 400 мг/л. Скорость коррозии в присутствии 1,3-диметил-2-(4-меркаптофенил)имидазолидина снижается с 13,5 мм/год в неингибированном растворе до 1,8 мм/год при 25°С при концентрации 400 мг/л.Various thiadiazole derivatives are being studied as corrosion inhibitors for carbon steel (G Bereket, E WITH Quantum chemical studies on some imidazole derivatives as corrosion inhibitors for iron in acidic medium. Elsevier, 2002, p.79-88), such research is promising in this industry, since this class of substances meets the environmental requirements for modern corrosion inhibitors (M. Ouakkiac, M. Galai, M. Cherkaoui. Imidazole derivatives as efficient and potential class of corrosion inhibitors for metals and alloys in aqueous electrolytes: A review (Elsevier, 2022). The purpose of the invention is to search for new heterocyclic compounds that reduce the corrosion rate of low-carbon steel in contact with metal equipment and have synthesis methods available for scaling, as well as expanding the range of possible compounds that slow down steel corrosion. The result obtained is that 1,3-dimethyl-2-(4-mercaptophenyl)imidazolidine suppresses corrosion of low-carbon steel St3 (GOST 380-2005) in a 15% aqueous solution of hydrochloric acid, at a concentration of 100 - 400 mg/l. The corrosion rate in the presence of 1,3-dimethyl-2-(4-mercaptophenyl)imidazolidine decreases from 13.5 mm/year in an uninhibited solution to 1.8 mm/year at 25°C at a concentration of 400 mg/l.
Пример 1. 1,3-диметил-2-(4-меркаптофенил)имидазолидинExample 1: 1,3-Dimethyl-2-(4-mercaptophenyl)imidazolidine
При кипячении 4-меркаптобензальдегида и N,N'-диметиланилина происходит циклизация с образованием соответствующего 1,3-диметил-2-(4-меркаптофенил)имидазолидина. Далее смесь N,N'-диметилэтилендиамина и 4-меркаптобензальдегида (1:1) кипятили в сухом толуоле в присутствии каталитического количества п-толуолсульфокислоты. Полученный продукт очищали перегонкой в вакууме.When 4-mercaptobenzaldehyde and N,N'-dimethylaniline are boiled, cyclization occurs to form the corresponding 1,3-dimethyl-2-(4-mercaptophenyl)imidazolidine. Next, a mixture of N,N'-dimethylethylenediamine and 4-mercaptobenzaldehyde (1:1) was boiled in dry toluene in the presence of a catalytic amount of p-toluenesulfonic acid. The resulting product was purified by vacuum distillation.
Спектр ЯМР 1Н (400 МГц, CDCl3), d, м.д.: 7.42 - 7.32(м, 2Н), 7.30 - 7.21 (м, 2Н), 3.41 - 3.36 (м, 2Н), 3.28 - 3.20 (м, 2Н), 2.57 - 2.46 (м, 6Н), 2.22 - 2.14 (м, 6Н). 1H NMR spectrum (400 MHz, CDCl 3 ), d, ppm: 7.42 - 7.32 (m, 2H), 7.30 - 7.21 (m, 2H), 3.41 - 3.36 (m, 2H), 3.28 - 3.20 ( m, 2H), 2.57 - 2.46 (m, 6H), 2.22 - 2.14 (m, 6H).
Спектр ЯМР 13С (101 МГц, CDCl3), d, м.д.: 138.83, 137.22, 129.65, 126.84, 92.30, 53.63, 39.72, 16.19. 13 C NMR spectrum (101 MHz, CDCl 3 ), d, ppm: 138.83, 137.22, 129.65, 126.84, 92.30, 53.63, 39.72, 16.19.
Пример 2. Коррозионные испытания проводят в лабораторных условиях гравиметрическим методом (ГОСТ 9.506-87) в 15% водном растворе соляной кислоты при стандартной температуре.Example 2. Corrosion tests are carried out in laboratory conditions using the gravimetric method (GOST 9.506-87) in a 15% aqueous solution of hydrochloric acid at standard temperature.
Скорость коррозии определяли гравиметрически, т.е. по убыли массы образцов Ст3 до и после выдержки в тестовых растворах в течение 24 часов при температуре 25°С. Скорость коррозии (П), степень торможения (γ) и ингибирующий эффект (Zгр) рассчитывали по формулам:The corrosion rate was determined gravimetrically, i.e. according to the weight loss of St3 samples before and after exposure to test solutions for 24 hours at a temperature of 25°C. 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; m - время испытания, ч; ρ - плотность Ст3, П0 и П - 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 ; m - test time, h; ρ is the density of St3, P 0 and P 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 |
|---|---|
| RU2805531C1 true RU2805531C1 (en) | 2023-10-18 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2330123C1 (en) * | 2006-11-29 | 2008-07-27 | Федеральное государственное образовательное учреждение высшего профессионального образования "Астраханский государственный технический университет" | Inhibitor for corrosion of metals in sulphuric, hydrochloric and orthophosphoric acid |
| WO2020046670A1 (en) * | 2018-08-31 | 2020-03-05 | Kao Corporation | Corrosion inhibitor compositions and methods of use in acid stimulation operations |
| RU2754326C1 (en) * | 2020-12-14 | 2021-09-01 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Башкирский государственный университет" | Method for producing bis-imidazolines and their derivatives based on pentaethylene hexamines for corrosion protection of oilfield equipment and pipelines |
| RU2754323C1 (en) * | 2020-12-14 | 2021-09-01 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Башкирский государственный университет" | Method for obtaining corrosion inhibitors based on bis-imidazolines for oilfield equipment and pipelines |
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2330123C1 (en) * | 2006-11-29 | 2008-07-27 | Федеральное государственное образовательное учреждение высшего профессионального образования "Астраханский государственный технический университет" | Inhibitor for corrosion of metals in sulphuric, hydrochloric and orthophosphoric acid |
| WO2020046670A1 (en) * | 2018-08-31 | 2020-03-05 | Kao Corporation | Corrosion inhibitor compositions and methods of use in acid stimulation operations |
| RU2754326C1 (en) * | 2020-12-14 | 2021-09-01 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Башкирский государственный университет" | Method for producing bis-imidazolines and their derivatives based on pentaethylene hexamines for corrosion protection of oilfield equipment and pipelines |
| RU2754323C1 (en) * | 2020-12-14 | 2021-09-01 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Башкирский государственный университет" | Method for obtaining corrosion inhibitors based on bis-imidazolines for oilfield equipment and pipelines |
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