CN107699900B - CO2 corrosion inhibitor for gathering and transportation pipelines of oil and gas fields and preparation method thereof - Google Patents
CO2 corrosion inhibitor for gathering and transportation pipelines of oil and gas fields and preparation method thereof Download PDFInfo
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- CN107699900B CN107699900B CN201710713356.3A CN201710713356A CN107699900B CN 107699900 B CN107699900 B CN 107699900B CN 201710713356 A CN201710713356 A CN 201710713356A CN 107699900 B CN107699900 B CN 107699900B
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
Abstract
The invention provides an oil-gas field setCO for pipeline2The corrosion inhibitor comprises the following components: 44-55 parts of imidazoline-benzoic acid derivative, 5-10 parts of thiourea, 10-18 parts of water, 5-8 parts of alkylphenol polyoxyethylene OP-10, 1-2 parts of triethanolamine, 2-5 parts of peregal O-25 and 7-28 parts of ethylene glycol monobutyl ether; wherein the imidazoline-benzoic acid derivative is synthesized by the reaction of imidazoline and benzoic acid. The invention provides CO for gathering and transporting pipelines of oil and gas fields2The corrosion inhibitor has good anti-corrosion effect on the gathering pipeline in harsh (such as high Cl < - > content, high salinity and high temperature) gathering pipeline corrosion environment.
Description
Technical Field
The invention relates to CO2A corrosion inhibitor and a preparation method thereof, in particular to CO for an oil-gas field gathering pipeline2A corrosion inhibitor and a preparation method thereof.
Background
Carbon dioxide is often present in oil gas as a component of natural gas or petroleum associated gas, and carbon dioxide is widely present in the oil gas development process through the carbon dioxide flooding oil extraction process. Carbon dioxide can form weak acid when meeting water, and has very strong corrosivity on carbon steel, so that important equipment such as oil-gas well pipe columns, gathering and transportation pipeline steel products and the like are seriously corroded comprehensively and locally, and huge economic loss and potential safety hazards are caused.
Control of CO2The corrosion method is more, and the adoption of a high-performance corrosion inhibitor is one of effective measures for preventing the corrosion of carbon dioxide. CO22The corrosion inhibitor is mainly imidazoline corrosion inhibitor, which has the characteristics of convenient use, no need of modifying equipment and pipeline, better corrosion prevention effect in acidic medium, and the like, and mature products have been developed at home at present, are applied to various oil and gas fields, and have certain effect. But the corrosion inhibition effect of the existing corrosion inhibitor product is limited for the harsh gathering pipeline corrosion environment (such as high Cl < - > content, high mineralization and high temperature). How to develop new corrosion inhibitors for these corrosive environments becomes a problem to be solved.
Disclosure of Invention
The invention provides CO for gathering and transporting pipelines of oil and gas fields2The corrosion inhibitor has specific composition and proportion, and can meet the corrosion inhibition requirement of a harsh gathering pipeline corrosion environment.
The invention also provides CO for the gathering and transportation pipeline of the oil and gas field2The corrosion inhibitor prepared by the method has good corrosion prevention effect on the gathering pipeline in a harsh gathering pipeline corrosion environment.
In the scheme of the application, the harsh gathering pipeline corrosion environment refers to a liquid environment inside the oil and gas field gathering pipeline with the Cl < - > content of 10-13 ten thousand mg/L, the mineralization degree of 18-22 ten thousand mg/L and the temperature of 40-60 ℃.
The invention provides CO for gathering and transporting pipelines of oil and gas fields2The corrosion inhibitor comprises the following components: 44-55 parts of imidazoline-benzoic acid derivative, 5-10 parts of thiourea, 10-18 parts of water, 5-8 parts of alkylphenol polyoxyethylene OP-10, 1-2 parts of triethanolamine, 2-5 parts of peregal O-25 and 7-28 parts of ethylene glycol monobutyl ether;
wherein the imidazoline-benzoic acid derivative is synthesized by the reaction of imidazoline and benzoic acid.
In one embodiment of the invention, the imidazoline is synthesized from oleic acid reacted with diethylenetriamine. Further, in one embodiment of the present invention, the imidazoline-benzoic acid derivative is prepared by mixing 40 to 50 parts by weight of imidazoline with 4 to 5 parts by weight of benzoic acid. Further, the imidazoline-benzoic acid derivative is prepared by mixing 40-50 parts by weight of imidazoline and 4-5 parts by weight of benzoic acid at 55-65 ℃.
In one embodiment of the invention, the imidazoline is synthesized by reacting oleic acid and diethylenetriamine in a molar ratio of 1: 1-4. Furthermore, the imidazoline is synthesized by the reaction of oleic acid and diethylenetriamine with the molar ratio of 1: 1-1.5.
In another embodiment of the invention, the imidazoline is synthesized by reacting oleic acid and diethylenetriamine in a molar ratio of 1:1-4 at a temperature of 130-160 ℃ and under normal pressure for 3-6 hours, and then at a temperature of 180-260 ℃ for 6-12 hours.
Furthermore, the imidazoline is synthesized by the reaction of oleic acid and diethylenetriamine with the molar ratio of 1:1-4 at the temperature of 140-.
The invention provides CO for gathering and transporting pipelines of oil and gas fields2The preparation method of the corrosion inhibitor comprises the step of mixing the components in the corrosion inhibitor. Further, the oil and gas field gathering and transportation pipeline uses CO2Preparation method of corrosion inhibitor and bagComprises the step of mixing the components of the corrosion inhibitor at 50-60 ℃.
The scheme of the invention has the following excellent effects:
1. CO of the invention2The preparation method of the corrosion inhibitor is simple, and the obtained CO for the gathering and transportation pipeline of the oil and gas field2The corrosion inhibitor has good corrosion prevention effect on the gathering pipeline in a harsher gathering pipeline corrosion environment (such as high Cl < - > content, high salinity and high temperature).
2. CO provided by the invention2The corrosion inhibitor is suitable for the oil field gathering and transportation environment at the temperature of 40-60 ℃, has excellent corrosion inhibition performance, has the corrosion rate of less than or equal to 0.076mm/a and the corrosion inhibition efficiency of more than or equal to 96 percent by adding 30ppm of the corrosion inhibitor, and is far higher than the requirement of more than or equal to 70 percent of the industrial standard.
Detailed Description
In the scheme of the application, benzoic acid is purchased from Shanghai chemical industry Co., Ltd, triethanolamine is purchased from Chisheng commercial Co., Ltd, peregal O-25 and alkylphenol polyoxyethylene OP-10 can be purchased from Jiangsu province sea safety petrochemical plant, and thiourea, oleic acid, diethylenetriamine and ethylene glycol monobutyl ether can be purchased from Jiangsu chemical industry technology Co., Ltd.
Example 1
1. CO for gathering and transporting pipeline of oil and gas field2Preparation of the corrosion inhibitor:
1) mixing oleic acid and diethylenetriamine at the molar ratio of 1:1 at the temperature of 140 ℃ and 160 ℃ and under normal pressure, reacting for 6 hours, and then reacting for 12 hours at the temperature of 240 ℃ and 260 ℃ to obtain imidazoline;
2) 50 parts by weight of imidazoline-benzoic acid derivative obtained in the step 1) and 5 parts by weight of benzoic acid are stirred uniformly and heated to 60 ℃ for reaction for 1 hour.
3) Fully dissolving 55 parts of imidazoline-benzoic acid derivative, 10 parts of thiourea, 10 parts of water, 8 parts of alkylphenol polyoxyethylene OP-10, 2 parts of triethanolamine, 5 parts of peregal O-25 and 10 parts of ethylene glycol monobutyl ether at 60 ℃, mixing and stirring uniformly to obtain the CO for the gathering and transportation pipeline of the oil and gas field2A corrosion inhibitor;
4) preparing a simulated liquid for simulating liquid in an oil-gas field gathering pipeline with the Cl < - > content of 10-13 ten thousand mg/L, the mineralization degree of 18-22 ten thousand mg/L and the temperature of 40 ℃:
the specific process is as follows: weighing 0.041g NaHCO3，0.4gNa2SO4，31.4CaCl2， 7.9gMgCl2·6H2O, 3.5g of KCl and 144.1g of NaCl are poured into a 1L volumetric flask, 800m of L of distilled water is added, stirring is carried out until all solids are dissolved uniformly, and then distilled water is used for fixing the volume to 1L, so that the oilfield simulation fluid is obtained.
5) Mixing the CO obtained in 2)2The corrosion inhibitor was added to the gathering line containing the simulant prepared in 3) at a concentration of 30ppm, and the corrosion rate of the gathering line was measured by the United states correst high temperature autoclave and weight loss coupon test method, and the results showed that 30ppm (concentration used in the following standard method) of CO prepared in this example was added2The corrosion inhibitor can realize that the corrosion rate of the steel sheet is less than or equal to 0.076mm/a, and the corrosion rate is reduced by 96 percent compared with the blank corrosion rate, namely the corrosion inhibition efficiency is more than or equal to 96 percent.
The detection method comprises the following steps: refer to standard SY/T5273-.
Example 2
1. CO for gathering and transporting pipeline of oil and gas field2Preparation of the corrosion inhibitor:
1) mixing oleic acid and diethylenetriamine in a molar ratio of 1:2 at the temperature of 140 ℃ and 160 ℃ and under normal pressure, reacting for 4 hours, and then reacting for 10 hours at the temperature of 200 ℃ and 240 ℃ to synthesize imidazoline;
2) stirring 40 parts by weight of imidazoline obtained in the step 1) and 4 parts by weight of benzoic acid uniformly, heating to 55 ℃, and reacting for 1 hour to form the imidazoline-benzoic acid derivative.
3) Fully dissolving and mixing 44 parts by weight of imidazoline-benzoic acid derivative obtained in the step 1), 5 parts by weight of thiourea, 15 parts by weight of water, 5 parts by weight of alkylphenol polyoxyethylene OP-10, 1 part by weight of triethanolamine, 2 parts by weight of peregal O-25 and 28 parts by weight of ethylene glycol monobutyl ether at the temperature of 50 ℃ to obtain CO for gathering and transportation pipelines of oil and gas fields2A corrosion inhibitor;
4) preparing a simulated liquid for simulating liquid in an oil-gas field gathering pipeline with the Cl < - > content of 10-13 ten thousand mg/L, the mineralization degree of 18-22 ten thousand mg/L and the temperature of 60 ℃:
the specific process is as follows: see example 1.
5) Mixing the CO obtained in 2)2The corrosion inhibitor was added to the gathering line containing the simulant prepared in 3) at a concentration of 30ppm, and the corrosion rate of the gathering line was measured by using a U.S. cotest high-temperature autoclave and a weightless coupon test method, and the results showed that 30ppm of CO prepared in this example was added2The corrosion inhibitor can realize that the corrosion rate of the steel sheet is less than or equal to 0.076mm/a, and the corrosion rate is reduced by 96 percent compared with the blank corrosion rate, namely the corrosion inhibition efficiency is more than or equal to 96 percent.
The detection method comprises the following steps: refer to standard SY/T5273-.
Example 3
1. CO for gathering and transporting pipeline of oil and gas field2Preparation of the corrosion inhibitor:
1) mixing oleic acid and diethylenetriamine in a molar ratio of 1:3 at the temperature of 140-;
2) stirring 40 weight parts of imidazoline obtained in the step 1) and 4.5 weight parts of benzoic acid uniformly, heating to 65 ℃, and reacting for 1 hour to form the imidazoline-benzoic acid derivative.
3) Mixing and stirring 44.5 parts by weight of imidazoline-benzoic acid derivative obtained in the step 1), 8 parts by weight of thiourea, 18 parts by weight of water, 7 parts by weight of alkylphenol polyoxyethylene OP-10, 1.5 parts by weight of triethanolamine, 3 parts by weight of peregal O-25 and 18 parts by weight of ethylene glycol monobutyl ether at 60 ℃ to obtain CO for gathering and transportation pipelines of oil and gas fields2A corrosion inhibitor;
4) preparing a simulated liquid for simulating liquid in an oil-gas field gathering pipeline with the Cl < - > content of 10-13 ten thousand mg/L, the mineralization degree of 18-22 ten thousand mg/L and the temperature of 50 ℃:
the specific process is as follows: see example 1.
5) Mixing the CO obtained in 2)2The corrosion inhibitor was added to the mold containing the formulation of 3) at a concentration of 30ppmIn the gathering and transportation pipeline of the simulated liquid, the corrosion rate of the gathering and transportation pipeline is detected by adopting a United states correst high-temperature autoclave and a weightless hanging piece test method, and the result shows that 30ppm of CO prepared in the embodiment is added2The corrosion inhibitor can realize that the corrosion rate of the steel sheet is less than or equal to 0.076mm/a, and the corrosion rate is reduced by 96 percent compared with the blank corrosion rate, namely the corrosion inhibition efficiency is more than or equal to 96 percent.
The detection method comprises the following steps: refer to standard SY/T5273-.
Example 4
1. CO for gathering and transporting pipeline of oil and gas field2Preparation of the corrosion inhibitor:
1) mixing oleic acid and diethylenetriamine in a molar ratio of 1:4 at the temperature of 130-;
2) stirring 48 weight parts of imidazoline obtained in the step 1) and 4.8 weight parts of benzoic acid uniformly, heating to 60 ℃, and reacting for 1 hour to form the imidazoline-benzoic acid derivative.
3) 52.8 parts by weight of imidazoline-benzoic acid derivative obtained in the step 1), 8 parts by weight of thiourea, 18 parts by weight of water, 7.2 parts by weight of alkylphenol polyoxyethylene OP-10, 1.5 parts by weight of triethanolamine, 5 parts by weight of peregal O-25 and 7.5 parts by weight of ethylene glycol monobutyl ether are mixed and stirred uniformly at 55 ℃, and then the CO for gathering and transportation pipelines of oil and gas fields is obtained2A corrosion inhibitor;
4) preparing a simulated liquid for simulating liquid in an oil-gas field gathering pipeline with the Cl < - > content of 10-13 ten thousand mg/L, the mineralization degree of 18-22 ten thousand mg/L and the temperature of 55 ℃:
the specific process is as follows: see example 1.
5) Mixing the CO obtained in 2)2The corrosion inhibitor was added to the gathering line containing the simulant prepared in 3) at a concentration of 30ppm, and the corrosion rate of the gathering line was measured by using a U.S. cotest high-temperature autoclave and a weightless coupon test method, and the results showed that 30ppm of CO prepared in this example was added2The corrosion inhibitor can realize that the corrosion rate of the steel sheet is less than or equal to 0.076mm/a, and the corrosion rate is reduced by 96 percent compared with the blank corrosion rate, namely the corrosion inhibition efficiency is more than or equal to 96 percent.
The detection method comprises the following steps: refer to standard SY/T5273-.
Example 5
1. CO for gathering and transporting pipeline of oil and gas field2Preparation of the corrosion inhibitor:
1) mixing oleic acid and diethylenetriamine in a molar ratio of 1:1.5 at the temperature of 140 ℃, (normal pressure) for reaction for 4 hours, and then reacting at the temperature of 180-;
2) stirring 40 parts by weight of imidazoline obtained in the step 1) and 4 parts by weight of benzoic acid uniformly, heating to 60 ℃, and reacting for 1 hour to form the imidazoline-benzoic acid derivative.
3) Mixing and stirring 44 parts by weight of imidazoline obtained in the step 1), 5 parts by weight of thiourea, 18 parts by weight of water, 7 parts by weight of alkylphenol polyoxyethylene OP-10, 1.5 parts by weight of triethanolamine, 2.5 parts by weight of peregal O-25 and 22 parts by weight of ethylene glycol monobutyl ether at 50 ℃ to obtain the CO for gathering and transportation pipelines of oil and gas fields2A corrosion inhibitor;
4) preparing a simulated liquid for simulating liquid in an oil-gas field gathering pipeline with the Cl < - > content of 10-13 ten thousand mg/L, the mineralization degree of 18-22 ten thousand mg/L and the temperature of 60 ℃:
the specific process is as follows: see example 1.
5) Mixing the CO obtained in 2)2The corrosion inhibitor was added to the gathering line containing the simulant prepared in 3) at a concentration of 30ppm, and the corrosion rate of the gathering line was measured by a test method using a cortest high-temperature autoclave and a weightless coupon, and the results showed that the CO prepared in this example was used2Corrosion inhibitor addition 30ppm of CO prepared in this example2The corrosion inhibitor can realize that the corrosion rate of the steel sheet is less than or equal to 0.076mm/a, and the corrosion rate is reduced by 96 percent compared with the blank corrosion rate, namely the corrosion inhibition efficiency is more than or equal to 96 percent.
The detection method comprises the following steps: refer to standard SY/T5273-.
Table 1 results of performance testing
Claims (5)
1. CO for gathering and transporting pipeline of oil and gas field2The corrosion inhibitor is characterized by comprising the following components: 44-55 parts of imidazoline-benzoic acid derivative, 5-10 parts of thiourea, 10-18 parts of water, 5-8 parts of alkylphenol polyoxyethylene OP-10, 1-2 parts of triethanolamine, 2-5 parts of peregal O-25 and 7-28 parts of ethylene glycol monobutyl ether;
wherein, the imidazoline is a synthetic product of oleic acid and diethylenetriamine with the molar ratio of 1:1-4, and the imidazoline-benzoic acid derivative is prepared by mixing 40-50 parts by weight of imidazoline and 4-5 parts by weight of benzoic acid at the temperature of 55-65 ℃;
the CO is2The preparation process of the corrosion inhibitor comprises the following steps: the components of the corrosion inhibitor are mixed at 50-60 ℃.
2. The CO for oil and gas field gathering pipelines of claim 12The corrosion inhibitor is characterized in that imidazoline is synthesized by reacting oleic acid and diethylenetriamine in a molar ratio of 1: 1-1.5.
3. The CO for oil and gas field gathering pipelines of claim 12The corrosion inhibitor is characterized in that imidazoline is synthesized by reacting oleic acid and diethylenetriamine with the molar ratio of 1:1-4 at the temperature of 130-160 ℃ and under normal pressure for 3-6 hours and then at the temperature of 180-260 ℃ for 6-12 hours.
4. The CO for oil and gas field gathering pipelines of claim 32The corrosion inhibitor is characterized in that imidazoline is synthesized by reacting oleic acid and diethylenetriamine with the molar ratio of 1:1-4 at the temperature of 140-160 ℃ and under normal pressure for 4-6 hours and then at the temperature of 180-260 ℃ for 6-12 hours.
5. The CO for oil and gas field gathering pipelines of any one of claims 1-42The preparation method of the corrosion inhibitor is characterized by comprising the step of mixing the components of the corrosion inhibitor at 50-60 ℃.
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| CN109183040A (en) * | 2018-07-18 | 2019-01-11 | 西安瑞杰油田物资实业开发有限公司 | A kind of petroleum pipeline sulfur resistive and the corrosion inhibiter of carbon dioxide and preparation method thereof |
| CN110241425A (en) * | 2019-07-26 | 2019-09-17 | 威海翔泽新材料科技有限公司 | A kind of high-sulfur corrosion inhibiter for oil-gas gathering and transportation process |
| CN112725804A (en) * | 2020-11-26 | 2021-04-30 | 天津大港油田滨港集团博弘石油化工有限公司 | High-efficiency corrosion inhibitor for resisting carbon dioxide corrosion and preparation method thereof |
| CN114806531A (en) * | 2021-01-29 | 2022-07-29 | 中国石油天然气股份有限公司 | High-flow-rate gathering and transportation corrosion inhibitor and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105132919A (en) * | 2015-09-17 | 2015-12-09 | 中国石油天然气股份有限公司 | Corrosion inhibitor for inhibiting CO2 corrosion in oil and gas fields and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105132919A (en) * | 2015-09-17 | 2015-12-09 | 中国石油天然气股份有限公司 | Corrosion inhibitor for inhibiting CO2 corrosion in oil and gas fields and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 在高CO2和Cl-环境中硫脲的缓蚀行为及其对复配缓蚀剂性能的影响;尹成先等;《腐蚀科学与防护技术》;20060930;第18卷(第5期);引言和第2.1部分 * |
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