CN105239076A - Dissymmetric bis-quaternary ammonium carbon dioxide corrosion inhibitor and preparation method thereof - Google Patents
Dissymmetric bis-quaternary ammonium carbon dioxide corrosion inhibitor and preparation method thereof Download PDFInfo
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- CN105239076A CN105239076A CN201510651459.2A CN201510651459A CN105239076A CN 105239076 A CN105239076 A CN 105239076A CN 201510651459 A CN201510651459 A CN 201510651459A CN 105239076 A CN105239076 A CN 105239076A
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Abstract
The invention relates to a dissymmetric bis-quaternary ammonium carbon dioxide corrosion inhibitor and a preparation method thereof, and belongs to the technical field of corrosion prevention for oil-gas gathering and transferring pipelines in offshore oil production. The corrosion inhibitor disclosed by the invention is composed of 40-60% of a dissymmetric bis-quaternary ammonium compound, and 40-60% of a low-molecular-weight alcohol solvent. The preparation method thereof comprises the following steps: adding a nitrogen heterocyclic ring compound and epoxy chloropropane with a molar ratio of 1.0: 1.05 in ethanol solution of a reactor, reacting for 3-5 hours under a condition of carrying out reflux at 85 DEG C, cooling to 55-65 DEG C, adding long-chain alkyl tertiary amine, continuing to react for 2-4 hours to obtain the dissymmetric bis-quaternary ammonium compound, then weighing the dissymmetric bis-quaternary ammonium compound and the low-molecular-weight alcohol solvent, and mutually mixing and uniformly stirring the dissymmetric bis-quaternary ammonium compound and the low-molecular-weight alcohol solvent to obtain the dissymmetric bis-quaternary ammonium carbon dioxide corrosion inhibitor. The corrosion inhibitor provided by the invention is capable of being used for corrosion prevention for oil-gas gathering and transferring pipelines in offshore oil production, high in compatibility with the medicaments of a demulsifier and the like, wide in adaptability, and capable of meeting the need of corrosion prevention under complex working conditions on site.
Description
Technical field
The present invention relates to a kind of asymmetric bi-quaternary ammonium salt class carbon dioxide corrosion inhibitor and preparation method thereof, belong to offshore oil production Oil-Gas Gathering Transferring Pipeline corrosion protection technology field.
Background technology
In the recovery process of at sea oil and gas, CO
2corrosion is the most general Corrosion Types run in oil-gas gathering and transportation process, has extremely strong corrodibility, CO
2the aqueous solution can cause metallic substance to corrode rapidly, makes pipe-line equipment generation early failure.Adding inhibiter is more effective corrosion protection steps.Inhibiter a kind of just can make metallic corrosion speed significantly reduced material when adding a small amount of in corrosive medium, and interpolation inhibiter has less investment, instant effect, the advantage such as convenient and easy, is the important means preventing metallic corrosion.
The investigation and application development of acidifying corrosion inhibitor for oil well is very fast in recent years, and inhibiter is various in style, as crude pyridine, 1901,1251,7461102,7707,7812, CT12 etc., these inhibiter can play a role under given conditions preferably.But along with the exploitation of deep-well, ultra deep well, cause temperature and pressure to improve further, and under identical pH value, due to CO
2total acidity higher than hydrochloric acid, therefore it is also more serious than hydrochloric acid to the corrosion of iron and steel, and it is even higher that its erosion rate can reach 7mm/a, therefore under the high temperature conditions operation time CO
2the problems demand of seriously corroded solves.
Current inhibiter employed both at home and abroad is all adsorption corrosion inhibitor substantially, as chain organic amine and derivative thereof, tetrahydroglyoxaline and salt thereof or imidazolidine derivatives quaternary ammonium salts, rosin Amine D derivative, generally believes that organic amine, organic amine salt, imidazolidine derivatives, quaternary ammonium salt corrosion mitigating effect are better.Conventional tetrahydroglyoxaline, amides inhibiter are usual water-soluble poor, even if carried out water-soluble transformation or optimization (as quaternized etc.), at the scene in use procedure, often be incompatible with oil-gas field chemical additives such as emulsion splitters, affect the result of use of the medicaments such as emulsion splitter, and be difficult to the corrosion mitigating effect at utmost playing self.
Bi-quaternary ammonium salt starts to be applied to the novel cats product of the class in metal slowly-releasing field in recent years, due in its molecular structure containing two hydrophobic groups and two hydrophilic groups, than traditional quaternary ammonium salt, there is low toxicity, preferably surfactivity and the good feature such as water-soluble.In recent years, bi-quaternary ammonium salt receives as the inhibiter of excellent property and pays close attention to widely, has broad application prospects, but research focuses mostly in the bi-quaternary ammonium salt of symmetrical configuration, less for the asymmetric bi-quaternary ammonium salt research containing heterocycle.
Chinese invention " a kind of composite corrosion inhibitor ", application number 201210208767.4 discloses a kind of composite corrosion inhibitor that carbonic acid gas, sulfide corrosion and salt, bacterium etc. can be suppressed to corrode, but still there is water-soluble poor problem, therefore, there is provided a kind of preparation method simple, and the preparation method of corrosion mitigating effect and water-soluble good asymmetric class bi-quaternary ammonium salt carbon dioxide corrosion inhibitor have important practical significance.
Summary of the invention
The object of this invention is to provide a kind of asymmetric bi-quaternary ammonium salt class carbon dioxide corrosion inhibitor and preparation method thereof, in the process used at the scene, under, wide adaptability, on-the-spot different working condition good from medicament compatiblenesies such as emulsion splitters, effect is good, corrosion inhibition is excellent, more can play good corrosion prevention effect in actual applications, the corrosion prevention needs under on-the-spot complex working conditions can be solved, can be used for the corrosion prevention of offshore oilfield Oil-Gas Gathering Transferring Pipeline.
For achieving the above object, the technical solution used in the present invention is as follows:
A kind of asymmetric bi-quaternary ammonium salt class carbon dioxide corrosion inhibitor, is made up of the component of following weight part: asymmetric organic diammonium compound 40 ~ 60%, low molecular alcoholic solvents 40 ~ 60%.
Described asymmetric bi-quaternary ammonium salt compounds has following general structure:
In n in formula, amount of carbon atom is 12,14,16 or 18.
Described low molecular alcoholic solvents is methyl alcohol or ethanol.
Present invention also offers a kind of preparation method of asymmetric bi-quaternary ammonium salt class carbon dioxide corrosion inhibitor, comprise the following steps:
(1) asymmetric organic diammonium compound is prepared: in the ethanolic soln of reactor, being sequentially added into mol ratio is 1.0:1.05 nitrogen-containing heterocycle compound and epoxy chloropropane, slow dropping epoxy chloropropane, under 85 DEG C of reflux conditionss, reacts 3 ~ 5 hours, be cooled to 55 ~ 65 DEG C, add long-chain alkyl tertiary amine, continue reaction 2 ~ 4 hours, obtain the homogeneous thick liquid of scarlet, be asymmetric organic diammonium compound, for subsequent use;
(2) take asymmetric organic diammonium compound and low molecular alcoholic solvents, asymmetric organic diammonium compound is mixed mutually with low molecular alcoholic solvents, stirs, namely obtain asymmetric bi-quaternary ammonium salt class carbon dioxide corrosion inhibitor.
Step (1) described nitrogen-containing heterocycle compound is pyridine or quinoline.
Step (1) described long-chain alkyl tertiary amine is Dodecyl Dimethyl Amine, dodecyldimethylamine base tertiary amine, hexadecyldimethyl benzyl ammonium tertiary amine or octadecyldimethyl tertiary amine.
The invention has the beneficial effects as follows:
1. the present invention adopts nitrogen-containing heterocycle compound and epoxy chloropropane open loop salify; carry out quaterisation again with long-chain alkyl tertiary amine and form asymmetric bi-quaternary ammonium salt compounds; containing multiple activated adsorption center such as nitrogen heterocyclic ring, two quaternary ammonium groups in molecule; the organic adsorption film formed has better provide protection to carbon steel, can be used for the gathering line of offshore oil production.
2. inhibiter provided by the invention has good water-soluble in high salinity oil-gas field production fluid, without the need to the dispersion of low mass molecule alcohol equal solvent with regard to solubilized.
3. inhibiter provided by the present invention can be used for the carbonated oil well of oil-gas field, gas well, surface gathering and transferring pipeline, and the corrosion prevention of water treatment system equipment installation.
Embodiment
Be described in further details the present invention below by example, these examples are only used for the present invention is described, do not limit the scope of the invention.
Embodiment 1
(1) in the ethanolic soln of reactor, being sequentially added into mol ratio is 1.0:1.05 quinoline and epoxy chloropropane, slow dropping epoxy chloropropane, under 85 DEG C of reflux conditionss, reacts 3 hours, be cooled to 55 DEG C, add dodecyldimethylamine base tertiary amine, continue reaction 2 hours, obtain the homogeneous thick liquid of scarlet, be asymmetric organic diammonium compound, for subsequent use;
(2) take asymmetric organic diammonium compound 45% and methyl alcohol 55%, mix mutually, stir, namely obtain asymmetric bi-quaternary ammonium salt class carbon dioxide corrosion inhibitor.
Embodiment 2
(1) in the ethanolic soln of reactor, being sequentially added into mol ratio is 1.0:1.05 quinoline and epoxy chloropropane, slow dropping epoxy chloropropane, under 85 DEG C of reflux conditionss, reacts 5 hours, be cooled to 65 DEG C, add hexadecyldimethyl benzyl ammonium tertiary amine, continue reaction 4 hours, obtain the homogeneous thick liquid of scarlet, be asymmetric organic diammonium compound, for subsequent use;
(2) take asymmetric organic diammonium compound 46% and ethanol 54%, mix mutually, stir, namely obtain asymmetric bi-quaternary ammonium salt class carbon dioxide corrosion inhibitor.
Embodiment 3
(1) in the ethanolic soln of reactor, being sequentially added into mol ratio is 1.0:1.05 quinoline and epoxy chloropropane, slow dropping epoxy chloropropane, under 85 DEG C of reflux conditionss, reacts 4 hours, be cooled to 60 DEG C, add octadecyldimethyl tertiary amine, continue reaction 3 hours, obtain the homogeneous thick liquid of scarlet, be asymmetric organic diammonium compound, for subsequent use;
(2) take asymmetric organic diammonium compound 43% and ethanol 57%, mix mutually, stir, namely obtain asymmetric bi-quaternary ammonium salt class carbon dioxide corrosion inhibitor.
Embodiment 4
(1) in the ethanolic soln of reactor, being sequentially added into mol ratio is 1.0:1.05 pyridine and epoxy chloropropane, slow dropping epoxy chloropropane, under 85 DEG C of reflux conditionss, reacts 3 hours, be cooled to 65 DEG C, add Dodecyl Dimethyl Amine, continue reaction 3 hours, obtain the homogeneous thick liquid of scarlet, be asymmetric organic diammonium compound, for subsequent use;
(2) take asymmetric organic diammonium compound 50% and methyl alcohol 50%, mix mutually, stir, namely obtain asymmetric bi-quaternary ammonium salt class carbon dioxide corrosion inhibitor.
Embodiment 5
(1) in the ethanolic soln of reactor, being sequentially added into mol ratio is 1.0:1.05 pyridine and epoxy chloropropane, slow dropping epoxy chloropropane, under 85 DEG C of reflux conditionss, reacts 5 hours, be cooled to 55 DEG C, add hexadecyldimethyl benzyl ammonium tertiary amine, continue reaction 3 hours, obtain the homogeneous thick liquid of scarlet, be asymmetric organic diammonium compound, for subsequent use;
(2) take asymmetric organic diammonium compound 60% and ethanol 40%, mix mutually, stir, namely obtain asymmetric bi-quaternary ammonium salt class carbon dioxide corrosion inhibitor.
In order to check the present invention's asymmetric bi-quaternary ammonium salt class carbon dioxide corrosion inhibitor at CO
2corrosion inhibition in environment, has carried out field experiment evaluation:
Table 1 erosion rate is tested
| Numbering | Inhibiter consumption (ppm) | Erosion rate (mm/a) |
| Embodiment 1 | 40 | 0.037 |
| Embodiment 2 | 40 | 0.042 |
| Embodiment 3 | 40 | 0.030 |
| Embodiment 4 | 40 | 0.035 |
| Embodiment 5 | 40 | 0.041 |
Claims (6)
1. an asymmetric bi-quaternary ammonium salt class carbon dioxide corrosion inhibitor, is characterized in that: be made up of the component of following weight part: asymmetric organic diammonium compound 40 ~ 60%, low molecular alcoholic solvents 40 ~ 60%.
2. a kind of asymmetric bi-quaternary ammonium salt class carbon dioxide corrosion inhibitor according to claim 1, is characterized in that: described asymmetric bi-quaternary ammonium salt compounds has following general structure:
In n in formula, amount of carbon atom is 12,14,16 or 18.
3. a kind of asymmetric bi-quaternary ammonium salt class carbon dioxide corrosion inhibitor according to claim 1, is characterized in that: described low molecular alcoholic solvents is methyl alcohol or ethanol.
4. a preparation method for asymmetric bi-quaternary ammonium salt class carbon dioxide corrosion inhibitor, is characterized in that: comprise the following steps:
(1) asymmetric organic diammonium compound is prepared: in the ethanolic soln of reactor, being sequentially added into mol ratio is 1.0:1.05 nitrogen-containing heterocycle compound and epoxy chloropropane, slow dropping epoxy chloropropane, under 85 DEG C of reflux conditionss, reacts 3 ~ 5 hours, be cooled to 55 ~ 65 DEG C, add long-chain alkyl tertiary amine, continue reaction 2 ~ 4 hours, obtain the homogeneous thick liquid of scarlet, be asymmetric organic diammonium compound, for subsequent use;
(2) take asymmetric organic diammonium compound and low molecular alcoholic solvents, asymmetric organic diammonium compound is mixed mutually with low molecular alcoholic solvents, stirs, namely obtain asymmetric bi-quaternary ammonium salt class carbon dioxide corrosion inhibitor.
5. the preparation method of a kind of asymmetric bi-quaternary ammonium salt class carbon dioxide corrosion inhibitor according to claim 4, is characterized in that: step (1) described nitrogen-containing heterocycle compound is pyridine or quinoline.
6. the preparation method of a kind of asymmetric bi-quaternary ammonium salt class carbon dioxide corrosion inhibitor according to claim 4, is characterized in that: step (1) described long-chain alkyl tertiary amine is Dodecyl Dimethyl Amine, dodecyldimethylamine base tertiary amine, hexadecyldimethyl benzyl ammonium tertiary amine or octadecyldimethyl tertiary amine.
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Cited By (6)
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| CN106147887A (en) * | 2016-07-14 | 2016-11-23 | 福建中源新能源股份有限公司 | The many phase corrosion inhibitors of a kind of methanol gasoline and the methanol gasoline of preparation thereof |
| CN108863967A (en) * | 2018-09-11 | 2018-11-23 | 四川格鑫拓科技有限公司 | A kind of triazine ring multi-quaternary ammonium salt antioxygen corrosion inhibiter and its preparation method and application |
| CN112410009A (en) * | 2020-11-23 | 2021-02-26 | 滨州市广友化工有限公司 | Gas well corrosion inhibitor for shale gas development and preparation method thereof |
| CN112680734A (en) * | 2020-12-09 | 2021-04-20 | 鞍钢集团矿业有限公司 | Corrosion inhibitor suitable for acidic medium and preparation method and application thereof |
| CN112778993A (en) * | 2020-11-09 | 2021-05-11 | 中海油(天津)油田化工有限公司 | Multi-quaternary ammonium salt corrosion inhibitor and preparation method thereof |
| CN114479008A (en) * | 2020-10-27 | 2022-05-13 | 中国石油化工股份有限公司 | Demulsifier and preparation method and application thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106147887A (en) * | 2016-07-14 | 2016-11-23 | 福建中源新能源股份有限公司 | The many phase corrosion inhibitors of a kind of methanol gasoline and the methanol gasoline of preparation thereof |
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| CN108863967A (en) * | 2018-09-11 | 2018-11-23 | 四川格鑫拓科技有限公司 | A kind of triazine ring multi-quaternary ammonium salt antioxygen corrosion inhibiter and its preparation method and application |
| CN114479008A (en) * | 2020-10-27 | 2022-05-13 | 中国石油化工股份有限公司 | Demulsifier and preparation method and application thereof |
| CN114479008B (en) * | 2020-10-27 | 2024-01-26 | 中国石油化工股份有限公司 | Demulsifier and preparation method and application thereof |
| CN112778993A (en) * | 2020-11-09 | 2021-05-11 | 中海油(天津)油田化工有限公司 | Multi-quaternary ammonium salt corrosion inhibitor and preparation method thereof |
| CN112778993B (en) * | 2020-11-09 | 2023-01-24 | 中海油(天津)油田化工有限公司 | Multi-quaternary ammonium salt corrosion inhibitor and preparation method thereof |
| CN112410009A (en) * | 2020-11-23 | 2021-02-26 | 滨州市广友化工有限公司 | Gas well corrosion inhibitor for shale gas development and preparation method thereof |
| CN112680734A (en) * | 2020-12-09 | 2021-04-20 | 鞍钢集团矿业有限公司 | Corrosion inhibitor suitable for acidic medium and preparation method and application thereof |
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