阅读说明：本技术 一种水溶性硫化二聚体喹啉季铵盐缓蚀剂及其制备方法和应用 (Water-soluble vulcanized dimer quinoline quaternary ammonium salt corrosion inhibitor and preparation method and application thereof ) 是由 何金杯 吴婵 于 2020-06-19 设计创作，主要内容包括：本发明公开了一种水溶性硫化二聚体喹啉季铵盐缓蚀剂及其制备方法与应用。所述缓蚀剂为两分子二肼喹啉的硫化二聚体；所述缓蚀剂的制备方法为：将二肼喹啉和溶剂混合,升温到120-145℃,在KOH做促进剂的条件下缓慢滴加二硫化碳进行硫化反应,滴加完毕后,继续反应8-12h；降温并保持85-95℃,滴加氯化苄进行水溶性改性,反应8-12h,除去溶剂,萃取分离后得到硫化二聚体喹啉季铵盐缓蚀剂成品。本发明缓蚀剂的制备、提纯简单,使用时用量小、高温条件缓蚀性能强,特别是在硫化氢、二氧化碳开采过程中既有良好的耐高温性能又有非常好的缓蚀性能。(The invention discloses a water-soluble vulcanized dimer quinoline quaternary ammonium salt corrosion inhibitor and a preparation method and application thereof. The corrosion inhibitor is a vulcanized dimer of two molecules of dihydrazinoquinoline; the preparation method of the corrosion inhibitor comprises the following steps: mixing dihydrazinoquinoline with a solvent, heating to the temperature of 120-145 ℃, slowly dropwise adding carbon disulfide under the condition that KOH is used as an accelerator for carrying out a vulcanization reaction, and continuing the reaction for 8-12h after the dropwise addition is finished; cooling and keeping the temperature at 85-95 ℃, dropwise adding benzyl chloride for water-soluble modification, reacting for 8-12h, removing the solvent, and extracting and separating to obtain a finished product of the vulcanized dimer quinoline quaternary ammonium salt corrosion inhibitor. The corrosion inhibitor has the advantages of simple preparation and purification, small using amount during use, strong corrosion inhibition performance under high temperature conditions, and particularly good high temperature resistance and corrosion inhibition performance in the exploitation process of hydrogen sulfide and carbon dioxide.)

1. A water-soluble vulcanized dimer quinoline quaternary ammonium salt corrosion inhibitor is characterized in that the structural formula is as follows:

。

2. the preparation method of the vulcanized dimer quinoline quaternary ammonium salt corrosion inhibitor as claimed in claim 1, characterized by comprising the following steps:

s1, mixing dihydrazinoquinoline with a solvent, heating to 145 ℃ with temperature of 120-;

s2, cooling, and dropwise adding benzyl chloride at 85-95 ℃ to perform water-soluble modification, wherein the reaction lasts for 8-12 h;

and S3, removing the solvent, extracting and separating, and removing the extractant from the extract phase to obtain a finished product of the vulcanized dimer quinoline quaternary ammonium salt corrosion inhibitor.

3. The method for preparing the vulcanized dimer quinoline quaternary ammonium salt corrosion inhibitor according to claim 2, wherein the solvent in the step S1 is one or more of methanol, ethanol and isopropanol.

4. The method for preparing the vulcanized dimer quinoline quaternary ammonium salt corrosion inhibitor according to claim 2, wherein the mass ratio of the dihydrazinoquinoline to the solvent in the step S1 is 50: (20-50).

5. The method for preparing the vulcanized dimer quinoline quaternary ammonium salt corrosion inhibitor according to claim 2, wherein the accelerator in the step S1 is KOH, and the mass of the accelerator is 1-5% of that of dihydrazinoquinoline.

6. The method for preparing the vulcanized dimer quinoline quaternary ammonium salt corrosion inhibitor according to claim 2, wherein the molar ratio of dihydrazinoquinoline, carbon disulfide and benzyl chloride in the step S1 is 40: (20-25): (40-45).

7. The method for preparing the vulcanized dimer quinoline quaternary ammonium salt corrosion inhibitor according to claim 2, wherein in the step S3: the solvent removing step is to remove the solvent by a reduced pressure distillation method; the extractant used for extraction is one of diethyl ether, benzene and toluene.

8. The use of the cured dimer quinoline quaternary ammonium salt corrosion inhibitor of claim 1 in acidizing applications.

9. The application of the vulcanized dimer quinoline quaternary ammonium salt corrosion inhibitor as claimed in claim 8, wherein the corrosion inhibitor is added into the acid liquor according to a mass fraction of 0.1-2% in the acidification construction process.

10. The use of the corrosion inhibitor according to claim 9, wherein the acid solution has an acid concentration of 15-20 wt%.

[ technical field ] A method for producing a semiconductor device

The invention relates to the technical field of chemical synthesis, in particular to a water-soluble vulcanized dimer quinoline quaternary ammonium salt corrosion inhibitor and a preparation method and application thereof.

[ background of the invention ]

As more and more oil wells enter the later oil production stage, the oil well yield is lower and lower, and in order to increase the oil yield and improve the efficiency, the oil production method of acid fracturing is provided at the present stage. Oilfield acidification is a measure for Enhanced Oil Recovery (EOR), and is an effective technical measure for increasing the production of oil and gas wells and increasing the production of injection wells. The principle is that the permeability of stratum pores and cracks is recovered or improved through the dissolving and corrosion effects of acid liquor on rock cement or stratum pores, plugs in cracks and the like. Acidification can be divided into acid washing, matrix acidification and fracture acidification (also called acid fracturing) according to different processes. The acid washing is to inject a small amount of acid liquor into the shaft to remove acid-soluble particles, drill cuttings, scales and the like in the perforation of the shaft and dredge the perforation. Matrix acidizing is the injection of acid into the formation at a pressure below the fracture pressure of the rock, relying on the erosive effects of the acid to restore or increase the permeability of the formation in a larger area near the wellbore. Acid fracturing (acid fracturing) is to inject acid into a stratum under the pressure higher than the fracture pressure of rock to form cracks in the stratum, and the cracks with high conductivity are formed by uneven corrosion of acid liquor to the wall materials of the cracks. Acidizing construction an acidic aqueous solution (e.g., hydrochloric acid, hydrofluoric acid, organic acid) is injected into the formation using construction vehicles such as cement trucks, pump trucks, and the like. The injected acid liquor can dissolve stratum rock or cementing materials, so that the stratum permeability is increased, and the production of oil gas and the injection of displacement water are more convenient. In the acidification construction, in order to improve the acidification effect, a new process such as polymer thickening acid injection, organic retarding acid injection, variable viscosity acid acidification, viscoelastic surfactant acidification and the like can be adopted. In the process, the high-temperature acid liquor can severely corrode metal equipment, and an acidification corrosion inhibitor is added during acidification to inhibit the corrosion of the metal, reduce the use amount of the acid, improve the acidification effect and prolong the service life of the equipment.

Meanwhile, in the process of gathering and transporting hydrogen sulfide and carbon dioxide, the temperature of some blocks is very high, and in the process of mining, the mining temperature even reaches 350 ℃, so that a corrosion inhibitor with good corrosion inhibition performance at ultrahigh temperature is required.

However, the existing corrosion inhibitor has poor solubility in acid liquor when in use, cannot meet the requirement of corrosion inhibition capability level when in high-temperature acidification, and has large dosage and high cost; in addition, in the process of exploitation under a hydrogen sulfide and carbon dioxide system, no proper corrosion inhibitor which can resist the high temperature of 350 ℃ and has very good corrosion inhibition performance is available.

Therefore, a water-soluble corrosion inhibitor needs to be researched, which has the advantages of small using amount and strong corrosion inhibition performance under high temperature conditions when in use, and particularly has good high temperature resistance and very good corrosion inhibition performance in the exploitation process under a hydrogen sulfide and carbon dioxide system.

[ summary of the invention ]

The invention aims to overcome the defects of the prior art and provide a corrosion inhibitor which is low in dosage, resistant to high temperature and good in corrosion inhibition performance.

In order to achieve the purpose, the invention provides a water-soluble vulcanized dimer quinoline quaternary ammonium salt corrosion inhibitor, which is prepared by polymerizing two molecules of dihydrazinoquinoline by using carbon disulfide to form a vulcanized dimer, and then performing water-soluble salt formation modification, wherein the water-soluble vulcanized dimer quinoline quaternary ammonium salt corrosion inhibitor has the following specific structure:

the invention also aims to provide a preparation method of the water-soluble vulcanized dimer quinoline quaternary ammonium salt corrosion inhibitor, which comprises the following steps:

1. and (3) vulcanization: mixing dihydrazinoquinoline with a solvent, heating to the temperature of 120-145 ℃, dropwise adding carbon disulfide under the condition of an accelerator for a vulcanization reaction, and continuing the reaction for 8-12 hours after the dropwise addition is finished;

2. modification: cooling the reaction liquid, dropwise adding benzyl chloride at 85-95 ℃ for water-soluble modification, and reacting for 8-12 h;

3. removing impurities: removing the solvent from the reaction solution, extracting and separating, and removing the extractant from the extract phase to obtain the finished product of the vulcanized dimer quinoline quaternary ammonium salt corrosion inhibitor.

Further, the solvent in the step 1 is one or more of methanol, ethanol and isopropanol;

further, the mass ratio of dihydrazinoquinoline to the solvent in the step 1 is 50: (20-50);

further, the accelerator in the step 1 is KOH, and the mass of the accelerator is 1% of that of dihydrazinoquinoline;

further, the molar ratio of dihydrazinoquinoline to carbon disulfide to benzyl chloride in the step 1 is 40: (20-25): (40-45);

further, when the temperature exceeds 145 ℃ during the sulfurization reaction in the step 1, the reaction system needs to be cooled.

Further, the solvent removing step in the step 3 is to remove the solvent by a reduced pressure distillation method;

further, one of ether, benzene and toluene is selected as an extracting agent for extraction in the step 3.

The invention also aims to provide an application of the water-soluble vulcanized dimer quinoline quaternary ammonium salt corrosion inhibitor, which comprises the following steps: in the acidification construction, the corrosion inhibitor is added into the acid liquor according to the mass fraction of 0.1-2%, and the acidification corrosion inhibitor can be added into the acid liquor according to the mass fraction of 0.1-0.5% according to the performance of the main agent of the corrosion inhibitor, so that the corrosion inhibition effect can be achieved.

Further, the acid solution can be hydrochloric acid or earth acid, and the acid concentration of the acid solution can be in the range of 15-20 wt%.

The principle of the invention is as follows: the vulcanized dimer quinoline quaternary ammonium salt corrosion inhibitor is a compound containing a multi-element nitrogen-containing heterocyclic ring, and two molecules of quinoline derivatives are formed into a symmetrical dimer by using carbon disulfide, so that the vulcanized dimer quinoline quaternary ammonium salt corrosion inhibitor has stable performance at high temperature, is adsorbed on the surface of metal to form a more compact film, can generate intermolecular crosslinking polymerization in acid liquor at high temperature, and has good high-temperature corrosion resistance.

The invention has the beneficial effects that:

1) the corrosion inhibitor has good solubility in alcohol-water solution;

2) the corrosion inhibitor has good corrosion inhibition effect and strong corrosion inhibition performance under high-temperature acidification conditions;

3) the corrosion inhibitor has good high temperature resistance and corrosion inhibition performance in the exploitation process of hydrogen sulfide and carbon dioxide.

[ detailed description ] embodiments

In order to make the objects, technical solutions and advantageous effects of the present invention more apparent, the present invention is further described in detail with reference to the following detailed description. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.