阅读说明：本技术 一种氧化还原响应型智能缓蚀剂、制备方法及其应用 (Oxidation-reduction response type intelligent corrosion inhibitor, preparation method and application thereof ) 是由 孙春同 赵西玉 韩庆建 孙霜青 孙永强 胡松青 孙方园 任平平 于 2019-10-15 设计创作，主要内容包括：本发明公开了一种氧化还原响应型智能缓蚀剂、制备方法及其应用,涉及油田金属智能防腐技术领域。其包括纳米容器和缓蚀药剂,纳米容器将缓蚀药剂包覆在其内部空间,纳米容器为含苯环和二硫键的中空介孔有机硅纳米容器,缓蚀药剂为2-巯基苯并噻唑。其制备方法包括：首先制备含苯环和二硫键的中空介孔有机硅纳米容器；然后将纳米容器分散在饱和2-巯基苯并噻唑的乙醇溶液中,进行缓蚀剂负载；离心清洗并真空干燥后即得。本发明智能缓蚀剂对氧化还原条件响应灵敏,制备方法简单,并且油田管道金属基材暴露在腐蚀环境中可实现缓蚀剂分子的主动和迅速释放。本发明在油井管道腐蚀防护和金属智能防腐涂层等领域具有广泛的应用前景。(The invention discloses an oxidation-reduction response type intelligent corrosion inhibitor, a preparation method and application thereof, and relates to the technical field of intelligent corrosion prevention of metal in oil fields. The corrosion inhibitor comprises a nano container and a corrosion inhibitor, wherein the corrosion inhibitor is coated in the inner space of the nano container, the nano container is a hollow mesoporous organic silicon nano container containing a benzene ring and a disulfide bond, and the corrosion inhibitor is 2-mercaptobenzothiazole. The preparation method comprises the following steps: firstly, preparing a hollow mesoporous organic silicon nano container containing benzene rings and disulfide bonds; then dispersing the nano container in an ethanol solution of saturated 2-mercaptobenzothiazole, and carrying out corrosion inhibitor loading; centrifugally cleaning and vacuum drying to obtain the product. The intelligent corrosion inhibitor disclosed by the invention is sensitive to response to redox conditions, the preparation method is simple, and active and rapid release of corrosion inhibitor molecules can be realized when the metal substrate of the oil field pipeline is exposed in a corrosive environment. The invention has wide application prospect in the fields of oil well pipeline corrosion protection, intelligent metal anti-corrosion coatings and the like.)

1. A redox response type intelligent corrosion inhibitor comprises a nano container and a corrosion inhibitor agent, and is characterized in that: the nano container is used for coating the corrosion inhibition medicament in the inner space of the nano container, the nano container is a hollow mesoporous organic silicon nano container containing a benzene ring and a disulfide bond, and the corrosion inhibition medicament is 2-mercaptobenzothiazole.

2. The intelligent oxidation-reduction-response corrosion inhibitor according to claim 1, wherein: the nano container is of a spherical structure.

3. The preparation method of the redox-responsive intelligent corrosion inhibitor according to claim 1 or 2, characterized by comprising the following steps in sequence:

s1, weighing ethyl orthosilicate as a precursor, adding the precursor into a mixed solution of ethanol, deionized water and ammonia water, and stirring at room temperature for reaction;

s2, dropwise adding the solution obtained in the step S1 into a solution containing deionized water and hexadecyl trimethyl ammonium bromide, and stirring at room temperature for reaction;

s3, adding ammonia water into the solution obtained in the step S2, dropwise adding a mixture of bis [3- (triethoxysilyl) propyl ] disulfide and bis (triethoxysilyl) benzene in a certain volume ratio, stirring at room temperature for reaction, and then centrifuging, cleaning and drying to obtain a product I;

s4, weighing a half of the first product, dispersing the first product in deionized water, adding a certain amount of hydrofluoric acid for etching, heating and stirring in an oil bath for reacting for a certain time, and then centrifuging, cleaning and drying to obtain a second product;

s5, dispersing the product II in a mixed solution of ethanol and hydrochloric acid, refluxing for 16h at 80 ℃, and then centrifuging, cleaning and drying to obtain a hollow mesoporous organosilicon nano container;

s6, dispersing the hollow mesoporous organic silicon nano container obtained in the step S5 in an ethanol solution containing 2-mercaptobenzothiazole, stirring for a certain time at room temperature, centrifuging to collect solids, and cleaning and drying by using deionized water to obtain the mesoporous organic silicon nano container.

4. The method for preparing the redox-responsive intelligent corrosion inhibitor according to claim 3, wherein the method comprises the following steps: the stirring reaction is carried out for 0.5h in the step S1, for 0.5h in the step S2 and for 6h in the step S3.

5. The method for preparing the redox-responsive intelligent corrosion inhibitor according to claim 3, wherein the method comprises the following steps: the steps S3, S4, and S5 are all cleaned with ethanol.

6. The method for preparing the redox-responsive intelligent corrosion inhibitor according to claim 3, wherein the method comprises the following steps: in the step S3, the volume ratio of bis [3- (triethoxysilyl) propyl ] disulfide to bis (triethoxysilyl) benzene is 1-4: 1 to 4.

7. The method for preparing the redox-responsive intelligent corrosion inhibitor according to claim 3, wherein the method comprises the following steps: in step S4, the amount of hydrofluoric acid used is 500-1000 μ L, the temperature of the oil bath is 50-70 ℃, and the reaction time is 1-2 h.

8. The method for preparing the redox-responsive intelligent corrosion inhibitor according to claim 3, wherein the method comprises the following steps: in the step S6, the concentration of the ethanol solution of the 2-mercaptobenzothiazole is 10-20 mg/mL, and the stirring time is 24-48 h.

9. Use of a redox-responsive smart corrosion inhibitor according to claim 1 or 2 in corrosion protection of oil well pipelines and smart corrosion protection coatings for metals.

Technical Field

The invention relates to the technical field of intelligent corrosion prevention of metal in oil fields, in particular to an oxidation-reduction response type intelligent corrosion inhibitor, a preparation method and application thereof.

Background

With continuous exploitation of most oil fields in China, many oil fields enter the middle and later stages of production exploitation, and in order to increase the yield of oil wells and improve the ultimate recovery rate, most oil fields adopt a water injection flooding oil extraction technology. However, when the water injection and oil displacement technology increases the yield of an oil well, serious corrosion problems can be caused, particularly, in an oil well with an injection and production (transportation) integrated alternative production mode, working conditions such as media, flow rate, temperature, dissolved oxygen, hydrogen sulfide, carbon dioxide, microorganisms and the like are different under the same shaft condition, the difference between injection and production (oil transportation) corrosion environments is very large, and the alternative corrosion environment brings serious corrosion to a ground gathering and transportation system and an underground pipe column, influences the normal production work of the oil field and brings great potential safety hazards. Therefore, in order to reduce the harm to oil extraction equipment and pipelines, a certain anticorrosion technology must be adopted, and the addition of the intelligent corrosion inhibitor is an effective measure with wide application range and low cost.

The corrosion inhibitor molecules are directly added into the water injection oil extraction system, which can cause the corrosion inhibitor to react with chemical components in the produced oil to lose activity, thereby failing to achieve the purpose of retarding and preventing the corrosion of the water injection oil extraction system. With the development of nanotechnology, intelligent corrosion inhibitors have attracted extensive attention. The intelligent corrosion inhibitor is characterized in that a nano material is adopted to coat the corrosion inhibitor in the inner space, and when a metal material is corroded, the corrosion inhibitor can cause stimulus response under the environmental change to release the corrosion inhibitor, so that the metal is slowed down and prevented from being corroded continuously.

Disclosure of Invention

One of the tasks of the invention is to provide an oxidation-reduction response type intelligent corrosion inhibitor, which can realize the high load capacity and the controlled release of oxidation-reduction response of the corrosion inhibitor, can effectively prevent and slow down the corrosion of oil field metals and has higher sensitivity.

The technical solution comprises:

an oxidation-reduction response type intelligent corrosion inhibitor comprises a nano container and a corrosion inhibitor, wherein the corrosion inhibitor is coated in the inner space of the nano container, the nano container is a hollow mesoporous organic silicon nano container containing a benzene ring and a disulfide bond, and the corrosion inhibitor is 2-mercaptobenzothiazole.

Further, the nano container is of a spherical structure.

The invention also provides a preparation method of the redox response type intelligent corrosion inhibitor, which sequentially comprises the following steps:

s1, weighing ethyl orthosilicate as a precursor, adding the precursor into a mixed solution of ethanol, deionized water and ammonia water, and stirring at room temperature for reaction;

s2, dropwise adding the solution obtained in the step S1 into a solution containing deionized water and hexadecyl trimethyl ammonium bromide, and stirring at room temperature for reaction;

s3, adding ammonia water into the solution obtained in the step S2, dropwise adding a mixture of bis [3- (triethoxysilyl) propyl ] disulfide and bis (triethoxysilyl) benzene in a certain volume ratio, stirring at room temperature for reaction, centrifuging, cleaning and drying to obtain a product I

S4, weighing a half of the product I, dispersing in deionized water, adding a certain amount of hydrofluoric acid for etching, heating and stirring in an oil bath for a certain time, centrifuging, cleaning and drying to obtain a product II

S5, dispersing the product II in a mixed solution of ethanol and hydrochloric acid, refluxing for 16h at 80 ℃, and then centrifuging, cleaning and drying to obtain a hollow mesoporous organosilicon nano container;

s6, dispersing the hollow mesoporous organic silicon nano container obtained in the step S5 in an ethanol solution containing 2-mercaptobenzothiazole, stirring for a certain time at room temperature, centrifuging to collect solids, and cleaning and drying by using deionized water to obtain the mesoporous organic silicon nano container.

Further, the reaction was stirred for 0.5h in step S1, for 0.5h in step S2, and for 6h in step S3.

Further, the steps S3, S4, and S5 are all cleaned with ethanol.

Further, in step S3, the volume ratio of bis [3- (triethoxysilyl) propyl ] disulfide to bis (triethoxysilyl) benzene is 1 to 4: 1 to 4.

More preferably, in step S4, the amount of hydrofluoric acid used is 500-1000 μ L, the temperature of the oil bath is 50-70 ℃, and the reaction time is 1-2 h.

Further preferably, in step S6, the concentration of the ethanol solution of 2-mercaptobenzothiazole is 10 to 20mg/mL, and the stirring time is 24 to 48 hours.

It is a further object of the present invention to provide the use of the above-described redox-responsive smart corrosion inhibitors.

The redox response type intelligent corrosion inhibitor is applied to corrosion protection of oil well pipelines and intelligent metal anticorrosive coatings.

Compared with the prior art, the invention has the following beneficial technical effects:

(1) the hollow mesoporous organosilicon nanometer container has a mesoporous shell frame containing benzene rings and disulfide bonds, high load and self-packaging of corrosion inhibitor molecules can be realized through interaction between the benzene rings and corrosion inhibitor molecules, and a nanometer valve is not required to be modified on the surface of the mesoporous shell to realize packaging of the corrosion inhibitor. Meanwhile, due to the existence of the disulfide bond, the quick response of the intelligent corrosion inhibitor under the redox condition can be realized, the interaction between the corrosion inhibitor molecules and the nano container is reduced, and the corrosion inhibitor molecules in the nano container are released. The redox response type release mechanism can realize quick response to metal corrosion, and once corrosion occurs, the intelligent corrosion inhibitor can respond, so that the metal is reduced and prevented from being continuously corroded.

(2) The nano container comprises the hollow mesoporous organic silicon material, high load on corrosion inhibitor molecules can be realized due to the existence of hollow cavities and mesoporous shell structures, and the self-packaging and redox stimulus response release of the corrosion inhibitor can be realized due to the benzene ring and the disulfide bond contained in the composition frame. The method has important guiding significance in the fields of intelligent metal corrosion prevention of oil field pipelines, intelligent metal corrosion prevention coatings and the like.

Drawings

The invention is further described below with reference to the accompanying drawings:

FIG. 1 is a diagram illustrating the structure and principle of the intelligent corrosion inhibitor of the present invention;

FIG. 2 is a thermogravimetric plot of the smart corrosion inhibitor of the present invention;

FIG. 3 is a graph of the release of the intelligent corrosion inhibitor of the present invention at different concentrations of the reducing agent versus time.

Detailed Description

The invention provides an oxidation-reduction response type intelligent corrosion inhibitor, a preparation method and application thereof, and in order to make the advantages and technical scheme of the invention clearer and clearer, the invention is described in detail with reference to specific embodiments.

The raw materials required by the invention can be purchased from commercial sources.

As shown in FIG. 1, the intelligent corrosion inhibitor of the invention has the following structure: a represents a hollow mesoporous organic silicon nano container containing a benzene ring and a disulfide bond, B represents adsorption corrosion inhibitor molecule 2-mercaptobenzothiazole, wherein B is positioned inside A, once corrosion occurs, the intelligent corrosion inhibitor can quickly respond, and therefore the effects of reducing and preventing continuous corrosion of metal are achieved.