CN116285925A - High-temperature corrosion inhibitor for high-concentration hydrochloric acid acidizing fluid and preparation method thereof - Google Patents

High-temperature corrosion inhibitor for high-concentration hydrochloric acid acidizing fluid and preparation method thereof Download PDF

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Publication number
CN116285925A
CN116285925A CN202310163204.6A CN202310163204A CN116285925A CN 116285925 A CN116285925 A CN 116285925A CN 202310163204 A CN202310163204 A CN 202310163204A CN 116285925 A CN116285925 A CN 116285925A
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hydrochloric acid
corrosion inhibitor
acidizing fluid
temperature corrosion
concentration hydrochloric
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李焕明
肖志军
程康康
张梁
范艳平
刘福仁
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Shandong Obiton Petroleum Technology Co ltd
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Shandong Obiton Petroleum Technology Co ltd
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/54Compositions for in situ inhibition of corrosion in boreholes or wells
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D215/00Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/04Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms
    • C07D215/10Quaternary compounds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60Compositions for stimulating production by acting on the underground formation
    • C09K8/62Compositions for forming crevices or fractures
    • C09K8/72Eroding chemicals, e.g. acids
    • C09K8/74Eroding chemicals, e.g. acids combined with additives added for specific purposes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2208/00Aspects relating to compositions of drilling or well treatment fluids
    • C09K2208/32Anticorrosion additives

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Abstract

The invention relates to the technical field of acidification corrosion inhibition for petroleum development, in particular to a high-temperature corrosion inhibitor for high-concentration hydrochloric acid acidizing fluid and a preparation method thereof. Comprises 20-30 parts of chloromethyl naphthalene quinoline quaternary ammonium salt mixture, 55-73 parts of solvent and 7-15 parts of surfactant; the quinoline quaternary ammonium salt mixture is prepared by sequentially adding glycol, quinoline and 1-chloromethyl naphthalene into a reaction vessel, starting stirring, heating to a reaction temperature, maintaining a certain reaction time, and then cooling to room temperature. The beneficial effects are as follows: the chloromethyl naphthalene quinoline quaternary ammonium salt in the high-temperature corrosion inhibitor has strong adsorption capacity, can have good corrosion inhibition effect at 150 ℃ in 28% hydrochloric acid liquid, has fewer components, is simple to prepare, does not contain extremely toxic substances, does not contain low-flash-point solvents, has small addition amount and low cost, and is beneficial to large-scale industrial production.

Description

High-temperature corrosion inhibitor for high-concentration hydrochloric acid acidizing fluid and preparation method thereof
Technical Field
The invention relates to the technical field of acidification corrosion inhibition for petroleum development, in particular to a high-temperature corrosion inhibitor for high-concentration hydrochloric acid acidizing fluid and a preparation method thereof.
Background
In the petroleum exploration and development process, acidizing operation is one of important means for improving the single well productivity of an oil and gas well. With the increasing depth of exploration and development, the bottom hole temperature is increased along with the increase, and especially under the condition of high acid liquor concentration (hydrochloric acid concentration 28%), the acid liquor can inevitably cause serious corrosion of a down-hole tubular column, and in order to reduce the acid liquor corrosion, a corrosion inhibitor is added into the acid liquor in the most common measure.
Along with the development of the oil and gas well in the middle and later stages, the well depth is continuously increased, and higher performance requirements are provided for corrosion inhibitors used in the acidizing operation of the oil and gas well. Much work has been done at home and abroad in developing and researching acidified inhibitors, but very few reports have been made on high performance inhibitors suitable for high temperature concentrated acids (hydrochloric acid concentration up to 28%). The conventional corrosion inhibitor product has the defects of low corrosion inhibition efficiency, poor compatibility, easiness in layering or precipitation, large addition amount, high price, extremely toxic alkynol substances and the like in the practical application process. Therefore, the research on the corrosion inhibitor for the high-temperature and high-concentration hydrochloric acid acidizing fluid has important significance for improving the acidizing effect, reducing the corrosion of equipment and pipelines and increasing the comprehensive economic benefit.
Disclosure of Invention
The invention aims at overcoming the defects in the prior art and provides a high-temperature corrosion inhibitor for high-concentration hydrochloric acid acidizing fluid and a preparation method thereof.
The invention relates to a high-temperature corrosion inhibitor for high-concentration hydrochloric acid acidizing fluid, which has the technical scheme that: the composite material is prepared from the following raw materials in parts by weight: 20-30 parts of chloromethyl naphthalene quinoline quaternary ammonium salt mixture, 55-73 parts of solvent and 7-15 parts of surfactant.
The preparation method of the high-temperature corrosion inhibitor for the high-concentration hydrochloric acid acidizing fluid comprises the following steps: sequentially adding a solvent, a surfactant and chloromethyl naphthalene quinoline quaternary ammonium salt mixture into a reactor, and stirring at room temperature for 1 hour to obtain a product.
Preferably, the preparation method of the chloromethyl naphthalene quinoline quaternary ammonium salt mixture comprises the following steps: sequentially adding ethylene glycol, quinoline and 1-chloromethyl naphthalene into a reaction vessel, starting stirring, heating to a reaction temperature, maintaining a certain reaction time, and then cooling to room temperature to obtain chloromethyl naphthalene quinoline quaternary ammonium salt mixture.
Preferably, the molar ratio of the quinoline to the 1-chloromethylnaphthalene to the ethylene glycol is 1:1.05:5.4.
preferably, the reaction temperature is 95℃and the reaction time is 10 hours.
Preferably, the solvent is water, and the surfactant is fatty alcohol polyoxyethylene ether.
Preferably, the fatty alcohol-polyoxyethylene ether is peregal O-15, peregal O-20 and combinations thereof.
The invention relates to an application of a high-temperature corrosion inhibitor for high-concentration hydrochloric acid acidizing fluid, which adopts the technical scheme that: the method is applied to high-concentration hydrochloric acid acidizing fluid.
Preferably, the high-concentration hydrochloric acid acidizing fluid comprises the following components in percentage by mass: 28% of hydrochloric acid, 4% of formic acid, 1.0-2.0% of high-temperature corrosion inhibitor and the balance of water.
Preferably, the temperature of the high-concentration hydrochloric acid acidizing fluid is less than or equal to 150 ℃, and formic acid is used as a high-temperature corrosion inhibitor auxiliary agent.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, high-flash-point glycol is used as a solvent in the synthesis of the chloromethyl naphthalene quinoline quaternary ammonium salt, so that the occurrence of flash and other risks in the production process is prevented, and the synthesized chloromethyl naphthalene quinoline quaternary ammonium salt mixture is always in a liquid state, so that the subsequent compounding of the corrosion inhibitor is facilitated;
compared with the conventional benzoquinoline chloride quaternary ammonium salt, the chloromethyl naphthalene quinoline quaternary ammonium salt prepared by the method has more benzene ring structures, the corrosion inhibitor molecules are easier to adsorb on the metal surface, the film forming capability of the corrosion inhibitor on the metal surface is improved, the desorption speed of the corrosion inhibitor from the metal surface under the conditions of high temperature and high concentration hydrochloric acid is reduced, and thus the corrosion inhibition efficiency is obviously improved;
the high-temperature corrosion inhibitor for the high-concentration hydrochloric acid acidizing fluid is formed by reacting quinoline and 1-chloromethyl naphthalene in glycol solution to generate chloromethyl naphthalene quinoline quaternary ammonium salt, wherein the reaction product does not need to be purified, and then fatty alcohol polyoxyethylene ether and water are compounded; the whole production process has the advantages of no three-waste pollution, less corrosion inhibitor component types, simple process, no extremely toxic substances, no low flash point solvent, low cost and the like;
the high-temperature corrosion inhibitor for the high-concentration hydrochloric acid acidizing fluid is suitable for stratum acidizing treatment at the well temperature of normal temperature to 150 ℃, and the concentration of hydrochloric acid in the acidizing fluid is 28%.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of illustration and explanation only and is not intended to limit the present invention.
Example 1
Firstly, the high-temperature corrosion inhibitor for the high-concentration hydrochloric acid acidizing fluid disclosed by the invention comprises the following components in percentage by mass (see table 1):
TABLE 1 high temperature Corrosion inhibitor Components of example 1
Figure SMS_1
The method specifically comprises the following steps:
(1) 111.7 parts of ethylene glycol, 43 parts of quinoline and 61.8 parts of 1-chloromethyl naphthalene are sequentially added into a reaction vessel and uniformly mixed;
(2) Placing the reaction vessel in an oil bath pot, and heating to 95 ℃;
(3) Keeping the reaction temperature at 95 ℃, and continuously stirring and reacting for 10 hours;
(4) Stopping heating and stirring, and cooling the reactant to room temperature to obtain chloromethyl naphthalene quinoline quaternary ammonium salt mixture;
(5) 60 parts of water, 13 parts of peregal O-15 and 27 parts of chloromethyl naphthalene quinoline quaternary ammonium salt mixture are sequentially added into a reactor, and stirring is continued for 1 hour at room temperature, so as to obtain the high-temperature corrosion inhibitor for the high-concentration hydrochloric acid acidizing fluid.
Example 2
Firstly, the preparation method of the high-temperature corrosion inhibitor for the high-concentration hydrochloric acid acidizing fluid comprises the following specific mass fractions (see table 2):
TABLE 2 high temperature Corrosion inhibitor Components of example 2
Figure SMS_2
The method specifically comprises the following steps:
(1) 111.7 parts of ethylene glycol, 43 parts of quinoline and 61.8 parts of 1-chloromethyl naphthalene are sequentially added into a reaction vessel and uniformly mixed;
(2) Placing the reaction vessel in an oil bath pot, and heating to 95 ℃;
(3) Keeping the reaction temperature at 95 ℃, and continuously stirring and reacting for 10 hours;
(4) Stopping heating and stirring, and cooling the reactant to room temperature to obtain chloromethyl naphthalene quinoline quaternary ammonium salt mixture;
(5) 65 parts of water, 10 parts of peregal O-20 and 25 parts of chloromethyl naphthalene quinoline quaternary ammonium salt mixture are sequentially added into a reactor, and stirring is continued for 1 hour at room temperature, so that the high-temperature corrosion inhibitor for high-concentration hydrochloric acid acidizing fluid is obtained.
Example 3
Firstly, the preparation method of the high-temperature corrosion inhibitor for the high-concentration hydrochloric acid acidizing fluid comprises the following specific mass fractions (see table 3):
TABLE 3 high temperature corrosion inhibitor component of example 3
Figure SMS_3
The method specifically comprises the following steps:
(1) 111.7 parts of ethylene glycol, 43 parts of quinoline and 61.8 parts of 1-chloromethyl naphthalene are sequentially added into a reaction vessel and uniformly mixed;
(2) Placing the reaction vessel in an oil bath pot, and heating to 95 ℃;
(3) Keeping the reaction temperature at 95 ℃, and continuously stirring and reacting for 10 hours;
(4) Stopping heating and stirring, and cooling the reactant to room temperature to obtain chloromethyl naphthalene quinoline quaternary ammonium salt mixture;
(5) 60 parts of water, 6 parts of peregal O-15, 6 parts of peregal O-20 and 28 parts of chloromethyl naphthalene quinoline quaternary ammonium salt mixture are sequentially added into a reactor, and stirring is continued for 1 hour at room temperature, so that the high-temperature corrosion inhibitor for high-concentration hydrochloric acid acidizing fluid is obtained.
Example 4
Firstly, the preparation method of the high-temperature corrosion inhibitor for the high-concentration hydrochloric acid acidizing fluid comprises the following specific mass fractions (see table 4):
TABLE 4 high temperature corrosion inhibitor component of example 4
Figure SMS_4
The method specifically comprises the following steps:
(1) 125.2 parts of ethylene glycol, 43 parts of quinoline and 61.8 parts of 1-chloromethyl naphthalene are sequentially added into a reaction vessel and uniformly mixed;
(2) Placing the reaction vessel in an oil bath pot, and heating to 95 ℃;
(3) Keeping the reaction temperature at 95 ℃, and continuously stirring and reacting for 10 hours;
(4) Stopping heating and stirring, and cooling the reactant to room temperature to obtain chloromethyl naphthalene quinoline quaternary ammonium salt mixture;
(5) 60 parts of water, 13 parts of peregal O-20 and 27 parts of chloromethyl naphthalene quinoline quaternary ammonium salt mixture are sequentially added into a reactor, and stirring is continued for 1 hour at room temperature, so that the high-temperature corrosion inhibitor for high-concentration hydrochloric acid acidizing fluid is obtained.
Performance tests are carried out on the high-temperature corrosion inhibitors in the embodiments 1-4, the high-temperature corrosion inhibitors in each embodiment keep good corrosion inhibition performance under the conditions of 150 ℃ and 28% hydrochloric acid concentration, and the high-concentration hydrochloric acid acidizing fluid comprises the following components in percentage by mass: 28% of hydrochloric acid, 4% of formic acid, 1.0-2.0% of high-temperature corrosion inhibitor and the balance of water. Wherein each high temperature corrosion inhibitorThe corrosion rate under the condition of 150 ℃ and 28% hydrochloric acid concentration is 40 g/(m) 2 H) formic acid as a high-temperature corrosion inhibitor auxiliary. The results of the high temperature corrosion inhibitor test of examples 1-4 are shown in Table 5.
TABLE 5 results of high temperature Corrosion inhibitor test of examples 1-4
Figure SMS_5
The above description is only a few preferred embodiments of the present invention, and any person skilled in the art may make modifications to the above described embodiments or make modifications to the same. Accordingly, the corresponding simple modifications or equivalent changes according to the technical scheme of the present invention fall within the scope of the claimed invention.

Claims (10)

1. A high-temperature corrosion inhibitor for high-concentration hydrochloric acid acidizing fluid is characterized in that: the composite material is prepared from the following raw materials in parts by weight: 20-30 parts of chloromethyl naphthalene quinoline quaternary ammonium salt mixture, 55-73 parts of solvent and 7-15 parts of surfactant.
2. The method for preparing the high-temperature corrosion inhibitor for the high-concentration hydrochloric acid acidizing fluid according to claim 1, which is characterized in that: the method comprises the following steps: sequentially adding a solvent, a surfactant and chloromethyl naphthalene quinoline quaternary ammonium salt mixture into a reactor, and stirring at room temperature for 1 hour to obtain a product.
3. The method for preparing the high-temperature corrosion inhibitor for the high-concentration hydrochloric acid acidizing fluid according to claim 1 or 2, which is characterized in that: the preparation method of the chloromethyl naphthalene quinoline quaternary ammonium salt mixture comprises the following steps: sequentially adding ethylene glycol, quinoline and 1-chloromethyl naphthalene into a reaction vessel, starting stirring, heating to a reaction temperature, maintaining a certain reaction time, and then cooling to room temperature to obtain chloromethyl naphthalene quinoline quaternary ammonium salt mixture.
4. The method for preparing the high-temperature corrosion inhibitor for the high-concentration hydrochloric acid acidizing fluid according to claim 3, which is characterized in that: the mol ratio of the quinoline to the 1-chloromethylnaphthalene to the glycol is 1:1.05:5.4.
5. the method for preparing the high-temperature corrosion inhibitor for the high-concentration hydrochloric acid acidizing fluid according to claim 4, which is characterized in that: the reaction temperature is 95 ℃, and the reaction time is 10 hours.
6. The method for preparing the high-temperature corrosion inhibitor for the high-concentration hydrochloric acid acidizing fluid according to claim 1 or 2, which is characterized in that: the solvent is water, and the surfactant is fatty alcohol polyoxyethylene ether.
7. The method for preparing the high-temperature corrosion inhibitor for the high-concentration hydrochloric acid acidizing fluid according to claim 6, which is characterized in that: the fatty alcohol polyoxyethylene ether is peregal O-15 and peregal O-20 and the combination thereof.
8. The use of the high temperature corrosion inhibitor for high concentration hydrochloric acid acidizing fluid as claimed in claim 7, characterized in that: the method is applied to high-concentration hydrochloric acid acidizing fluid.
9. The use of the high temperature corrosion inhibitor for high concentration hydrochloric acid acidizing fluid as claimed in claim 8, characterized in that: the high-concentration hydrochloric acid acidizing fluid comprises the following components in percentage by mass: 28% of hydrochloric acid, 4% of formic acid, 1.0-2.0% of high-temperature corrosion inhibitor and the balance of water.
10. The use of the high temperature corrosion inhibitor for high concentration hydrochloric acid acidizing fluid according to claim 9, characterized in that: the temperature of the high-concentration hydrochloric acid acidizing fluid is less than or equal to 150 ℃, and formic acid is used as a high-temperature corrosion inhibitor auxiliary agent.
CN202310163204.6A 2023-02-24 2023-02-24 High-temperature corrosion inhibitor for high-concentration hydrochloric acid acidizing fluid and preparation method thereof Pending CN116285925A (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1760320A (en) * 2005-10-18 2006-04-19 中国石油大学(华东) New typed high temperature acidified corrosion inhibitor and preparation method
CN107207954A (en) * 2014-12-22 2017-09-26 伦萨公司 Corrosion inhibitor composition for acidification
CN108410444A (en) * 2018-03-16 2018-08-17 中国石油大学(华东) A kind of acidification corrosion inhibitor and the preparation method and application thereof based on dimer indole derivative
CN112226220A (en) * 2020-09-29 2021-01-15 陈力群 High-temperature acidizing corrosion inhibitor and preparation method thereof
CN114634803A (en) * 2022-04-13 2022-06-17 西南石油大学 Ultrahigh-temperature-resistant acidizing corrosion inhibitor suitable for 180-200 ℃ and preparation method thereof
CN115449363A (en) * 2022-09-15 2022-12-09 西南石油大学 Preparation method of quaternary ammonium salt type high-temperature acidizing corrosion inhibitor

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1760320A (en) * 2005-10-18 2006-04-19 中国石油大学(华东) New typed high temperature acidified corrosion inhibitor and preparation method
CN107207954A (en) * 2014-12-22 2017-09-26 伦萨公司 Corrosion inhibitor composition for acidification
CN108410444A (en) * 2018-03-16 2018-08-17 中国石油大学(华东) A kind of acidification corrosion inhibitor and the preparation method and application thereof based on dimer indole derivative
CN112226220A (en) * 2020-09-29 2021-01-15 陈力群 High-temperature acidizing corrosion inhibitor and preparation method thereof
CN114634803A (en) * 2022-04-13 2022-06-17 西南石油大学 Ultrahigh-temperature-resistant acidizing corrosion inhibitor suitable for 180-200 ℃ and preparation method thereof
CN115449363A (en) * 2022-09-15 2022-12-09 西南石油大学 Preparation method of quaternary ammonium salt type high-temperature acidizing corrosion inhibitor

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