Quinoline quaternary ammonium salt corrosion inhibitor and preparation method thereof
By compounding quinoline quaternary ammonium salt corrosion inhibitors, a stable chemical adsorption film is formed, which solves the problem of poor solubility of existing corrosion inhibitors at high temperatures and achieves a highly efficient corrosion inhibition effect.
Patent Information
- Application Number
- CN202511664296.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-11-13
- Publication Date
- 2026-01-27
AI Technical Summary
Existing corrosion inhibitors have poor solubility under high temperature conditions, and their corrosion inhibition effect is difficult to meet the acidizing requirements of oil and gas fields.
Quinoline quaternary ammonium salt corrosion inhibitors are used, and a stable chemical adsorption film is formed by compounding propynyl alcohol, 2-hexyn-1-ol and N,N-dimethylpropynylamine. Combined with organophosphonic acid and surfactants, the corrosion inhibition effect is improved.
It significantly improves the corrosion inhibition effect at high temperatures, slows down the corrosion rate of metal materials, and makes the protective film structure more stable.
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Abstract
Description
Technical Field
[0001] This invention relates to the field of corrosion inhibitor technology, specifically to a quinoline quaternary ammonium salt corrosion inhibitor and its preparation method. Background Technology
[0002] Acidizing technology is one of the main measures for enhancing oil and gas production, boasting core advantages such as low cost and high returns. Its working principle is that acid injected into the formation erodes the rock surface, creating fractures and widening formation porosity, ultimately increasing permeability and achieving the goal of enhancing production and transforming low-permeability reservoirs. However, the acidizing process has significant drawbacks. Acids (hydrochloric acid, nitric acid, hydrofluoric acid, acetic acid, etc.) directly contact metal equipment after entering the formation, causing corrosion. This not only increases economic costs but can also threaten the lives of workers due to equipment damage. Therefore, adding corrosion inhibitors is the most effective and economical way to solve these problems. A small amount of corrosion inhibitor can effectively slow down the corrosion process. Currently commonly used oilfield corrosion inhibitors include imidazoline corrosion inhibitors, Mannich base corrosion inhibitors, quaternary ammonium salt corrosion inhibitors, other high-temperature corrosion inhibitors, and environmentally friendly corrosion inhibitors. With the deepening of oil and gas exploration and development, the number of high-temperature reservoir wells is increasing, placing higher demands on the high-temperature resistance of corrosion inhibitors.
[0003] Existing corrosion inhibitors exhibit poor solubility in acidic solutions, and their corrosion inhibition effects under high-temperature conditions are insufficient to meet practical requirements. Therefore, developing novel corrosion inhibitors with excellent corrosion inhibition performance at high temperatures has become a key research and development direction in the field of oil and gas field acidizing. Summary of the Invention
[0004] This invention proposes a quinoline quaternary ammonium salt corrosion inhibitor and its preparation method, which solves the problem of insufficient corrosion inhibition effect of corrosion inhibitors at high temperatures in related technologies.
[0005] The technical solution of the present invention is as follows: This invention proposes a quinoline quaternary ammonium salt corrosion inhibitor, comprising the following components in parts by weight: 28-32 parts of quinoline quaternary ammonium salt, 2-4 parts of thiourea, 8-10 parts of organophosphonic acid, 2-3 parts of alkynol, 2-5 parts of surfactant, and 22-46 parts of solvent; The alkynols are propynol, 2-hexyn-1-ol, and N,N-dimethylpropynylamine.
[0006] As a further technical solution, the mass ratio of propynyl alcohol, 2-hexyn-1-ol and N,N-dimethylpropynylamine is 2:1:0.15~0.65.
[0007] As a further technical solution, the mass ratio of propynyl alcohol, 2-hexyn-1-ol and N,N-dimethylpropynylamine is 2:1:0.3~0.45.
[0008] In this invention, the mass ratio of propynyl alcohol, 2-hexyn-1-ol and N,N-dimethylpropynylamine is 2:1:0.3~0.45. The synergistic effect of the three makes the protective film structure more stable and the corrosion inhibition effect of quinoline quaternary ammonium salt corrosion inhibitor is better.
[0009] As a further technical solution, organophosphonic acids include one or more of hydroxyethylidene diphosphonic acid, aminotrimethylphosphonic acid, ethylenediaminetetramethylidene phosphate, and 2-phosphonobutane-1,2,4-tricarboxylic acid.
[0010] As a further technical solution, the organophosphonic acid is hydroxyethylidene diphosphonic acid.
[0011] As a further technical solution, the surfactant includes one or more of hexadecyl pyridine bromide, polyhexaglycerol monostearate, and isooctyl glucoside.
[0012] As a further technical solution, the surface active agent is hexadecylpyridine bromide, polyglycerol monostearate, and isooctyl glucoside.
[0013] As a further technical solution, the mass ratio of hexadecylpyridine bromide, polyhexamethylene glycerol monostearate, and isooctyl glucoside is 1:2:1.4~2.4.
[0014] In the surfactant of this invention, when hexadecyl pyridine bromide, hexaglycerol monostearate, and isooctyl glucoside are used together, the strong adsorption of hexadecyl pyridine bromide, the steric stabilizing effect of hexaglycerol monostearate, and the HLB regulating ability of isooctyl glucoside synergistically improve the corrosion inhibition rate of quinoline quaternary ammonium salt corrosion inhibitor at high temperature. Moreover, the synergistic effect is optimal when the mass ratio of hexadecyl pyridine bromide, hexaglycerol monostearate, and isooctyl glucoside is 1:2:1.4~2.4.
[0015] As a further technical solution, the solvent includes one or more of water, ethanol, and ethylene glycol.
[0016] The present invention also proposes a method for preparing a quinoline quaternary ammonium salt corrosion inhibitor, which includes the following steps: mixing the components evenly to obtain the quinoline quaternary ammonium salt corrosion inhibitor.
[0017] The working principle and beneficial effects of this invention are as follows: In this invention, the combined use of propynyl alcohol, 2-hexyn-1-ol, and N,N-dimethylpropynylamine significantly improves the corrosion inhibition effect of quinoline quaternary ammonium salt corrosion inhibitors at high temperatures. Proynyl alcohol, 2-hexyn-1-ol, and N,N-dimethylpropynylamine all contain alkynyl groups, which can chemically react with the metal surface under high-temperature conditions to form a more stable chemisorption film. Proynyl alcohol also contains hydroxyl groups, which enhances the stability of adsorption. The long carbon chain structure of 2-hexyn-1-ol further optimizes the film's compactness and steric hindrance effect. The coordination effect of the nitrogen atom in N,N-dimethylpropynylamine further consolidates the stability of the protective film. The synergistic effect of these three components comprehensively improves the corrosion inhibition effect of quinoline quaternary ammonium salt corrosion inhibitors at high temperatures. Detailed Implementation
[0018] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.
[0019] In the following embodiments and comparative examples, Quinoline quaternary ammonium salt: Model number DR-1688, manufacturer: Wuhan Prof Biotechnology Co., Ltd. Thiourea: The manufacturer is Qingzhou Jinhui Chemical Plant; 2-Hexyne-1-ol: Manufacturer: Hubei Jiente Biotechnology Co., Ltd.; N,N-Dimethylpropyne: Model number JACS05656, manufacturer is JACS-Zhengzhou Jacks Chemical Products Co., Ltd.; Hydroxyethylidene diphosphonic acid: manufactured by Shandong Kason New Materials Co., Ltd.; Aminotrimethylphosphonic acid: manufactured by Shandong Kason New Materials Co., Ltd.; Hexadecylpyridine bromide: Manufacturer: Zhongshan Dixing Chemical Co., Ltd.; Hexaglycerol monostearate: model number shuer1254, manufacturer is Wuhan Shuer Biotechnology Co., Ltd.; Isooctyl glucoside: Model number APG08, manufacturer: Qingdao Tengyun Chemical Technology Co., Ltd.
[0020] Example 1 A quinoline quaternary ammonium salt corrosion inhibitor comprises the following components in parts by weight: 28 parts quinoline quaternary ammonium salt, 2 parts thiourea, 8 parts aminotrimethylphosphonic acid, 2 parts alkynol, 2 parts surfactant, and 22 parts solvent. The alkynols are propynol, 2-hexyn-1-ol and N,N-dimethylpropynylamine in a mass ratio of 2:1:0.15; The surfactant is a mixture of hexadecyl pyridine bromide and polyglycerol monostearate in a mass ratio of 1:2; The solvent is deionized water and ethanol in a mass ratio of 2:1; A method for preparing a quinoline quaternary ammonium salt corrosion inhibitor includes the following steps: mixing the above components evenly to obtain the quinoline quaternary ammonium salt corrosion inhibitor.
[0021] Example 2 A quinoline quaternary ammonium salt corrosion inhibitor comprises the following components in parts by weight: 32 parts quinoline quaternary ammonium salt, 4 parts thiourea, 10 parts hydroxyethylidene diphosphonic acid, 3 parts alkynol, 5 parts surfactant, and 46 parts solvent. The alkynols are propynol, 2-hexyn-1-ol and N,N-dimethylpropynylamine in a mass ratio of 2:1:0.65; The surfactant is a mixture of hexadecyl pyridine bromide and polyglycerol monostearate in a mass ratio of 1:2; The solvent is deionized water and ethylene glycol in a mass ratio of 2:1; A method for preparing a quinoline quaternary ammonium salt corrosion inhibitor includes the following steps: mixing the above components evenly to obtain the quinoline quaternary ammonium salt corrosion inhibitor.
[0022] Example 3 A quinoline quaternary ammonium salt corrosion inhibitor comprises the following components in parts by weight: 30 parts quinoline quaternary ammonium salt, 3 parts thiourea, 9 parts hydroxyethylidene diphosphonic acid, 2.5 parts alkynol, 3.5 parts surfactant, and 33 parts solvent; The alkynols are propynol, 2-hexyn-1-ol and N,N-dimethylpropynylamine in a mass ratio of 2:1:0.5; The surfactant is a mixture of hexadecyl pyridine bromide and polyglycerol monostearate in a mass ratio of 1:2; The solvent is deionized water and ethylene glycol in a mass ratio of 2:1; A method for preparing a quinoline quaternary ammonium salt corrosion inhibitor includes the following steps: mixing the above components evenly to obtain the quinoline quaternary ammonium salt corrosion inhibitor.
[0023] Example 4 The only difference between this embodiment and Example 3 is that the alkynol is propynol, 2-hexyn-1-ol and N,N-dimethylpropynylamine in a mass ratio of 2:1:0.45.
[0024] Example 5 The only difference between this embodiment and Example 3 is that the alkynols are propynol, 2-hexyn-1-ol and N,N-dimethylpropynylamine in a mass ratio of 2:1:0.3.
[0025] Example 6 The only difference between this embodiment and Example 3 is that the alkynol is propynol, 2-hexyn-1-ol and N,N-dimethylpropynylamine in a mass ratio of 2:1:0.15.
[0026] Example 7 The only difference between this embodiment and Example 4 is that the surfactant is a mixture of hexadecyl pyridine bromide and isooctyl glucoside in a mass ratio of 1:1.4.
[0027] Example 8 The only difference between this embodiment and Example 4 is that the surfactant is a mixture of polyglycerol monostearate and isooctyl glucoside in a mass ratio of 2:1.4.
[0028] Example 9 The only difference between this embodiment and Example 4 is that the surfactant is a mixture of hexadecyl pyridine bromide, polyglycerol monostearate, and isooctyl glucoside in a mass ratio of 1:2:1.4.
[0029] Example 10 The only difference between this embodiment and Example 4 is that the surfactant is hexadecyl pyridine bromide, polyglycerol monostearate, and isooctyl glucoside in a mass ratio of 1:2:2.4.
[0030] Comparative Example 1 The only difference between this comparative example and Example 3 is that the alkynol is propynol and N,N-dimethylpropynylamine in a mass ratio of 2:0.5.
[0031] Comparative Example 2 The only difference between this comparative example and Example 3 is that the alkynol is 2-hexyn-1-ol and N,N-dimethylpropyne in a mass ratio of 1:0.5.
[0032] Comparative Example 3 The only difference between this comparative example and Example 3 is that the alkynol is a mixture of propynol and 2-hexyn-1-ol in a mass ratio of 2:1.
[0033] The quinoline quaternary ammonium salt corrosion inhibitors prepared in Examples 1-10 and Comparative Examples 1-3 were tested according to the following method: According to the test method specified in SY / T 5273-2014 "Performance Inhibitors and Evaluation Methods for Oilfield Produced Water Treatment", the corrosive medium is a 20% hydrochloric acid solution by volume, the test piece is made of N80 steel, the test piece size is 76mm×13mm×1.5mm, and the test temperature is 350℃. The test results are shown in Table 1: Table 1 Performance test results of the quinoline quaternary ammonium salt corrosion inhibitors prepared in Examples 1-10 and Comparative Examples 1-3
[0034] 1. Compared with Comparative Examples 1-3, when using the quinoline quaternary ammonium salt corrosion inhibitor prepared in Examples 1-10, the corrosion rate of the test piece was lower than that of the quinoline quaternary ammonium salt corrosion inhibitor prepared in Comparative Examples 1-3. This indicates that the combined use of propynyl alcohol, 2-hexyn-1-ol and N,N-dimethylpropynylamine can slow down the corrosion rate of metallic materials, and the prepared quinoline quaternary ammonium salt corrosion inhibitor has excellent corrosion inhibition effect at high temperature.
[0035] 2. Compared with Examples 3-6, when the quinoline quaternary ammonium salt corrosion inhibitors prepared in Examples 4-5 were applied to the test pieces, the corrosion rate of the test pieces was significantly lower than that of the quinoline quaternary ammonium salt corrosion inhibitors prepared in Examples 3 and 6. This indicates that when the mass ratio of propynyl alcohol, 2-hexyn-1-ol and N,N-dimethylpropynylamine is limited to 2:1:0.3-0.45, the corrosion inhibition effect of the quinoline quaternary ammonium salt corrosion inhibitor is significantly improved.
[0036] 3. Compared with Examples 4 and 7-10, the uniform corrosion inhibition rate of the quinoline quaternary ammonium salt corrosion inhibitors prepared in Examples 9-10 is significantly higher than that in Examples 4 and 7-8. This indicates that using hexadecyl pyridine bromide, hexaglycerol monostearate, and isooctyl glucoside together can improve the corrosion inhibition rate of the quinoline quaternary ammonium salt corrosion inhibitor at high temperatures.
[0037] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.
Claims
1. A quinoline quaternary ammonium salt corrosion inhibitor, characterized in that, It includes the following components in parts by weight: 28-32 parts of quinoline quaternary ammonium salt, 2-4 parts of thiourea, 8-10 parts of organophosphonic acid, 2-3 parts of alkynol, 2-5 parts of surfactant, and 22-46 parts of solvent; The alkynols are propynol, 2-hexyn-1-ol, and N,N-dimethylpropynylamine.
2. The quinoline quaternary ammonium salt corrosion inhibitor according to claim 1, characterized in that, The mass ratio of propynyl alcohol, 2-hexyn-1-ol and N,N-dimethylpropynylamine is 2:1:0.15~0.
65.
3. The quinoline quaternary ammonium salt corrosion inhibitor according to claim 2, characterized in that, The mass ratio of propynyl alcohol, 2-hexyn-1-ol and N,N-dimethylpropynylamine is 2:1:0.3~0.
45.
4. The quinoline quaternary ammonium salt corrosion inhibitor according to claim 1, characterized in that, The organophosphonic acid includes one or more of hydroxyethylidene diphosphonic acid, aminotrimethylphosphonic acid, ethylenediaminetetramethylidene phosphate, and 2-phosphonobutane-1,2,4-tricarboxylic acid.
5. The quinoline quaternary ammonium salt corrosion inhibitor according to claim 4, characterized in that, The organophosphonic acid is hydroxyethylidene diphosphonic acid.
6. The quinoline quaternary ammonium salt corrosion inhibitor according to claim 1, characterized in that, The surfactant includes one or more of hexadecyl pyridine bromide, polyglycerol monostearate, and isooctyl glucoside.
7. The quinoline quaternary ammonium salt corrosion inhibitor according to claim 6, characterized in that, The surfactant is hexadecyl pyridine bromide, polyglycerol monostearate, and isooctyl glucoside.
8. The quinoline quaternary ammonium salt corrosion inhibitor according to claim 7, characterized in that, The mass ratio of hexadecyl pyridine bromide, polyhexamethylene glycerol monostearate, and isooctyl glucoside is 1:2:1.4~2.
4.
9. The quinoline quaternary ammonium salt corrosion inhibitor according to claim 1, characterized in that, The solvent includes one or more of water, ethanol, and ethylene glycol.
10. A method for preparing a quinoline quaternary ammonium salt corrosion inhibitor, used to prepare the quinoline quaternary ammonium salt corrosion inhibitor according to any one of claims 1 to 9, characterized in that, Includes the following steps: After the components are mixed evenly, a quinoline quaternary ammonium salt corrosion inhibitor is obtained.