Ionic liquid functionalized hexagonal boron nitride corrosion inhibitor as well as preparation method and application thereof
By grafting the ionic liquid onto the hexagonal boron nitride nanosheets, an ionic liquid functionalized hexagonal boron nitride corrosion inhibitor is constructed, which solves the problems of high cost and low corrosion inhibition efficiency of existing ionic liquid corrosion inhibitors, achieving higher corrosion inhibition efficiency and stability, and is suitable for large-scale industrial production.
Patent Information
- Application Number
- CN202411487357.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-10-24
- Publication Date
- 2025-02-25
AI Technical Summary
The existing ionic liquid corrosion inhibitors have problems such as high cost, low corrosion inhibition efficiency, poor dispersion and high volatility in oil well equipment, which limits their promotion and application in the field of corrosion inhibition of oil well equipment.
By grafting the ionic liquid onto the hexagonal boron nitride nanosheets, an ionic liquid functionalized hexagonal boron nitride corrosion inhibitor is constructed to form a composite corrosion inhibitor, which solves the above problems.
The stability of the corrosion inhibitor and its affinity with the metal surface are improved, its dispersion on the metal surface is significantly improved, and corrosion inhibition efficiency is reduced, and production costs and volatility are reduced.
Abstract
Description
Technical Field
[0001] The invention relates to the field of oil well equipment anticorrosion, and in particular to an ionic liquid functionalized hexagonal boron nitride corrosion inhibitor and a preparation method and application thereof. Background Art
[0002] Oil well acidification is an important measure to improve the economic benefits of oil field development. It is to inject acid solution into the formation through pressure equipment, use the acid solution to dissolve the rock, expand the permeability channel of the oil layer rock, dissolve the blockages in the seepage channel or create artificial cracks, so as to make the oil and gas channel unblocked. However, the process of injecting acid into the formation will cause serious corrosion to the surface pipeline and the wellbore pipe wall. In the process of oil and natural gas transmission containing a large amount of H2S, SO2, bacteria and pipeline condensate water, equipment such as gathering and transportation trunk roads, branch pipelines and gas distribution stations will also suffer from serious corrosion, and even cause safety accidents such as pipeline rupture, local perforation and equipment failure. Adding corrosion inhibitors is the most practical, cheapest and most effective way to protect oil and gas operating facilities. The corrosion inhibitors are adsorbed on the steel surface to form a protective film to prevent acid corrosion. At present, corrosion inhibitors containing carbonyl, aromatic aldehyde, acetylene alcohol, and nitrogen-containing heterocyclic compounds used in industry are generally biologically toxic and have poor environmental friendliness. In addition, the synthesis of corrosion inhibitors involves the use of toxic reagents, solvents, and catalysts. The discharge of these toxic reagents and solvents into the surrounding environment will bring ecological risks to soil and aquatic microorganisms and other organisms. At the same time, the synthesis of acidifying corrosion inhibitors such as imidazoles and Mannich bases requires high temperature conditions and a long time, which is costly and limits their application in industry.
[0003] In recent years, ionic liquids, as a new type of green solvent and "soft" functional material, have shown great potential in the application of corrosion inhibition of oil well equipment due to their excellent solubility, stability, wide liquid range, low vapor pressure and other characteristics. However, when used alone, ionic liquid corrosion inhibitors have poor stability to negative electrode materials due to their high viscosity and reduction potential, resulting in low fluidity and transmission efficiency, high cost of use, low corrosion inhibition efficiency, poor dispersibility and other problems, which limit their promotion and application in the field of corrosion inhibition of oil well equipment. Summary of the invention
[0004] Based on previous research and existing problems, the present invention proposes an ionic liquid functionalized hexagonal boron nitride corrosion inhibitor after further research and analysis. By grafting ionic liquid onto hexagonal boron nitride nanosheets, a new composite corrosion inhibitor is constructed to solve the problems of existing ionic liquid corrosion inhibitors such as high cost, low corrosion inhibition efficiency, poor dispersibility, and high volatility.
[0005] To achieve the above object, the present invention provides the following technical solutions:
[0006] An ionic liquid functionalized hexagonal boron nitride corrosion inhibitor comprises the following components by weight percentage:
[0007] Ionic liquid functionalized hexagonal boron nitride solution 25-40%
[0008] Dispersant 50-70%
[0009] Surfactant 5-25%.
[0010] Preferably, the ionic liquid functionalized hexagonal boron nitride solution comprises hexagonal boron nitride, ionic liquid and toluene solution, the mass ratio of hexagonal boron nitride to ionic liquid is 10:1-2:1, and the mass ratio of ionic liquid to toluene solution is 1:8-1:12;
[0011] Hexagonal boron nitride is a nanosheet with a diameter of 1-3 μm and a specific surface area of about 30 m 2 / g, purity 99.9%.
[0012] Preferably, the ionic liquid is one of 1-butyl-3-methyl-imidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-vinyl-3-ethylimidazolium bromide, and 1-allyl-3-methylimidazolium dicyandiamide.
[0013] Preferably, the dispersant is water.
[0014] Preferably, the surfactant is sodium dodecyl sulfate or sodium dodecyl sulfonate.
[0015] The present invention also proposes a method for preparing the ionic liquid functionalized hexagonal boron nitride corrosion inhibitor mentioned above, and the specific method steps are as follows:
[0016] S1. Prepare an ionic liquid functionalized hexagonal boron nitride solution: add hexagonal boron nitride, ionic liquid and toluene solution into a round-bottom flask, perform reflux reaction under oil bath heating, cool to room temperature after the reaction, and then filter and wash to obtain an ionic liquid functionalized hexagonal boron nitride solution;
[0017] S2. Add a dispersant and a surfactant to the ionic liquid functionalized hexagonal boron nitride solution to obtain an ionic liquid functionalized hexagonal boron nitride corrosion inhibitor.
[0018] Preferably, in S1, the reaction temperature of the oil bath heating is 80-100° C., and the reaction time is 12-20 h.
[0019] Preferably, in S1, a vacuum pump is used for reduced pressure filtration for 30 minutes.
[0020] Preferably, the washing agent is dichloromethane, and the toluene is removed by washing 3-5 times.
[0021] In addition, the present invention also proposes an application of an ionic liquid functionalized hexagonal boron nitride corrosion inhibitor, which is used for corrosion protection of oil field gathering and transportation pipelines.
[0022] Compared with the existing technology, the present invention provides an ionic liquid functionalized hexagonal boron nitride corrosion inhibitor and a preparation method and application thereof, which have the following beneficial effects:
[0023] (1) Hexagonal boron nitride (BN) itself has good chemical inertness and thermal stability, and can form a physical barrier on the metal surface, reducing the probability of corrosive media reaching the metal surface. After the ionic liquid (IL) molecules are grafted onto BN, they are tightly adsorbed on the metal surface. In addition to the electrostatic adsorption of IL anions and cations, IL and BN also have a π-π conjugated synergistic corrosion inhibition effect, forming a denser protective layer, increasing the stability of the corrosion inhibitor and its affinity with the metal surface, improving its dispersibility on the metal surface, and significantly improving the corrosion inhibition efficiency;
[0024] (2) BN-IL corrosion inhibitor has high thermochemical stability and is suitable for high temperature and harsh corrosion environments. Fixing IL on BN improves the dispersibility of IL, which can effectively reduce the volatility of IL and increase the durability of the corrosion inhibitor.
[0025] (3) The production conditions of BN-IL corrosion inhibitor are mild. The amount of ionic liquid used is effectively reduced through grafting modification, and the production cost is greatly reduced, making it suitable for large-scale industrial production and application. DETAILED DESCRIPTION
[0026] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative work are within the scope of protection of the present invention.
[0027] Example 1
[0028] 6 g of hexagonal boron nitride, 1 g of 1-butyl-3-methyl-imidazolium tetrafluoroborate ([Bmim][BF4]) ionic liquid and 10 g of toluene solution were added to a 50 ml round-bottom flask, and the reaction temperature was controlled to 90 ° C under oil bath heating conditions for reflux reaction. The reaction time was 16 hours. After the reaction was completed, it was cooled to room temperature 25 ° C, and a vacuum pump was used to reduce pressure and filter for 30 minutes. Then, dichloromethane was used as a detergent and washed 4 times to remove toluene, which was the hexagonal boron nitride solution functionalized with [Bmim][BF4] ionic liquid. Then, 12 g of water and 3 g of sodium dodecyl sulfate were added to obtain the hexagonal boron nitride corrosion inhibitor functionalized with [Bmim][BF4] ionic liquid.
[0029] Comparative Example 1
[0030] 6 g of hexagonal boron nitride was added with 12 g of water and 3 g of sodium dodecyl sulfate to obtain a hexagonal boron nitride corrosion inhibitor.
[0031] Comparative Example 2
[0032] 1-Butyl-3-methyl-imidazolium tetrafluoroborate ([Bmim][BF4]) ionic liquid is added with 12g of water and 3g of sodium dodecyl sulfate to obtain [Bmim][BF4] ionic liquid corrosion inhibitor.
[0033] Example 2
[0034] 6 g of hexagonal boron nitride, 1 g of 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIm][PF6]) ionic liquid and 8 g of toluene solution were added to a 50 ml round-bottom flask, and the reaction temperature was controlled to 90°C under oil bath heating conditions for reflux reaction for 12 h. After the reaction was completed, it was cooled to room temperature (25°C), and filtered under reduced pressure for 30 min using a vacuum pump. Then, dichloromethane was used as a detergent and washed three times to remove toluene, which was a hexagonal boron nitride solution functionalized with [BMIm][PF6] ionic liquid. Then, 14 g of water and 2 g of sodium dodecyl sulfate were added to obtain a hexagonal boron nitride corrosion inhibitor functionalized with [BMIm][PF6] ionic liquid.
[0035] Example 3
[0036] 6 g of hexagonal boron nitride, 1 g of 1-vinyl-3-ethylimidazolium bromide ([EMIm]Br) ionic liquid and 10 g of toluene solution were added to a 50 ml round-bottom flask, and the reaction temperature was controlled to 90°C under oil bath heating conditions for reflux reaction for 16 hours. After the reaction was completed, it was cooled to room temperature (25°C), and filtered under reduced pressure for 30 minutes using a vacuum pump. Then, dichloromethane was used as a detergent and washed 4 times to remove toluene, which was a hexagonal boron nitride solution functionalized with [EMIm]Br ionic liquid. Then, 10 g of water and 3 g of sodium dodecyl sulfate were added to obtain a hexagonal boron nitride corrosion inhibitor functionalized with [EMIm]Br ionic liquid.
[0037] Example 4
[0038] 2 g of hexagonal boron nitride, 1 g of 1-allyl-3-methylimidazolium dicyandiamide ([AMIM][DCA]) ionic liquid and 12 g of toluene solution were added to a 50 ml round-bottom flask, and the reaction temperature was controlled to 90°C under oil bath heating conditions for reflux reaction for 20 h. After the reaction was completed, the solution was cooled to room temperature (25°C), and filtered under reduced pressure for 30 min using a vacuum pump. Then, the solution was washed 5 times with dichloromethane as a detergent to remove toluene, thereby obtaining a hexagonal boron nitride solution functionalized with [BMIm][PF6] ionic liquid. Then, 5 g of water and 1 g of sodium dodecyl sulfate were added to obtain a hexagonal boron nitride corrosion inhibitor functionalized with [BMIm][PF6] ionic liquid.
[0039] Example 5
[0040] 2g of hexagonal boron nitride, 1g of 1-butyl-3-methyl-imidazolium tetrafluoroborate ([Bmim][BF4]) ionic liquid and 8g of toluene solution were added to a 50ml round-bottom flask, and the reaction temperature was controlled to 80°C under oil bath heating conditions for reflux reaction. The reaction time was 12h. After the reaction was completed, it was cooled to room temperature 25°C, and a vacuum pump was used to reduce pressure and filter for 30min. Then, dichloromethane was used as a detergent and washed 3 times to remove toluene, that is, the hexagonal boron nitride solution functionalized with [Bmim][BF4] ionic liquid was obtained. Then, 7g of water and 1g of sodium dodecyl sulfate were added to obtain the hexagonal boron nitride corrosion inhibitor functionalized with [Bmim][BF4] ionic liquid.
[0041] Example 6
[0042] 2 g of hexagonal boron nitride, 1 g of 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIm][PF6]) ionic liquid and 8 g of toluene solution were added to a 50 ml round-bottom flask, and the reaction temperature was controlled to 100 ° C under oil bath heating conditions for reflux reaction. The reaction time was 12 h. After the reaction was completed, it was cooled to room temperature 25 ° C, and a vacuum pump was used to reduce pressure and filter for 30 min. Then, dichloromethane was used as a detergent and washed 3 times to remove toluene, which was the hexagonal boron nitride solution functionalized with [BMIm][PF6] ionic liquid. Then, 7 g of water and 2 g of sodium dodecyl sulfate were added to obtain the hexagonal boron nitride corrosion inhibitor functionalized with [BMIm][PF6] ionic liquid.
[0043] Example 7
[0044] 10g of hexagonal boron nitride, 1g of 1-vinyl-3-ethylimidazolium bromide ([EMIm]Br) ionic liquid and 10g of toluene solution were added to a 50ml round-bottom flask, and the reaction temperature was controlled to be 100°C under oil bath heating conditions for reflux reaction. The reaction time was 20h. After the reaction was completed, it was cooled to room temperature 25°C, and a vacuum pump was used to reduce pressure and filter for 30min. Then, dichloromethane was used as a detergent and washed 5 times to remove toluene, which was the hexagonal boron nitride solution functionalized with [EMIm]Br ionic liquid. Then, 20g of water and 5g of sodium dodecyl sulfate were added to obtain the hexagonal boron nitride corrosion inhibitor functionalized with [EMIm]Br ionic liquid.
[0045] Example 8
[0046] 10g of hexagonal boron nitride, 1g of 1-allyl-3-methylimidazolium dicyandiamide ([AMIM][DCA]) ionic liquid and 12g of toluene solution were added to a 50ml round-bottom flask, and the reaction temperature was controlled to 90°C under oil bath heating conditions for reflux reaction for 16h. After the reaction was completed, it was cooled to room temperature 25°C, and filtered under reduced pressure for 30min using a vacuum pump. Then, dichloromethane was used as a detergent and washed 5 times to remove toluene, which was a hexagonal boron nitride solution functionalized with [AMIM][DCA] ionic liquid. Then, 20g of water and 6g of sodium dodecyl sulfate were added to obtain a hexagonal boron nitride corrosion inhibitor functionalized with [AMIM][DCA] ionic liquid.
[0047] Example 9
[0048] 10g of hexagonal boron nitride, 1g of 1-allyl-3-methylimidazolium dicyandiamide ([AMIM][DCA]) ionic liquid and 12g of toluene solution were added to a 50ml round-bottom flask, and the reaction temperature was controlled to be 100°C under oil bath heating conditions for reflux reaction for 20h. After the reaction was completed, it was cooled to room temperature of 25°C, and filtered under reduced pressure for 30min using a vacuum pump. Then, dichloromethane was used as a detergent and washed 4 times to remove toluene, which was the hexagonal boron nitride solution functionalized with [AMIM][DCA] ionic liquid. Then, 20g of water and 4g of sodium dodecyl sulfate were added to obtain the hexagonal boron nitride corrosion inhibitor functionalized with [AMIM][DCA] ionic liquid.
[0049] The corrosion rate test of acidizing corrosion inhibitor is carried out in accordance with the industry standard SY / T5405-1996SY / T "Test Methods and Evaluation Indicators for Acidizing Corrosion Inhibitors" for dynamic experiments:
[0050] (1) Steel sheet preparation: The steel sheet was polished with metallographic sandpaper, degreased with distilled water, anhydrous ethanol, and acetone in sequence, dried with filter paper, and dried in an oven for 2 h. The mass was accurately weighed with an analytical balance;
[0051] (2) The steel sheet is vertically suspended in a high temperature and high pressure dynamic corrosion tester and immersed in the experimental medium;
[0052] (3) After the experiment, the coupons were taken out, washed with distilled water, anhydrous ethanol, and acetone to remove oil, dried for 2 hours, and weighed;
[0053] (4) The evaluation experimental conditions are: working temperature of 100-140°C, working pressure of 16MPa, speed of 200r / min. The corrosive medium used is 15% hydrochloric acid, and the amount of corrosion inhibitor is 1-3%. The specific evaluation experimental conditions and results are shown in Table 1:
[0054] Table 1 Evaluation conditions and test results of corrosion rate of acidified corrosion inhibitor
[0055] sample Working temperature / ℃ Corrosion inhibitor dosage / % Corrosion inhibition efficiency Example 1 100 2 95.6 Comparative Example 1 100 1 78.5 Comparative Example 2 100 1 83.9 Example 2 100 1 93.5 Example 3 110 2 92.1 Example 4 110 3 92.8 Example 5 120 2 90.4 Example 6 120 3 92.9 Example 7 130 1 89.3 Example 8 130 2 89.9 Example 9 130 3 92.0
[0056] It can be seen from the data in the table that the corrosion inhibition efficiency of the ionic liquid functionalized hexagonal boron nitride corrosion inhibitor is significantly higher. Under the premise of the same corrosion inhibitor dosage, the corrosion inhibition efficiency will gradually decrease with the increase of temperature, but the change is not obvious. Under the conditions of 130°C and 1% corrosion inhibitor dosage, the corrosion inhibition efficiency can still reach 89.3%, and the thermal stability is good; at the same temperature, with the increase of the corrosion inhibitor dosage, the corrosion inhibition efficiency gradually increases. Under the conditions of 100°C and 2% corrosion inhibitor dosage, the corrosion inhibition efficiency can reach up to 95.6%; while the corrosion inhibition efficiencies of Comparative Examples 1 and 2 can only reach 78.5% and 83.9%. It shows that the ionic liquid functionalized hexagonal boron nitride corrosion inhibitor of the technical solution of the present invention is a corrosion inhibitor with good corrosion inhibition performance.
[0057] In summary, the ionic liquid functionalized hexagonal boron nitride corrosion inhibitor of the present invention is an inhibitor with excellent corrosion inhibition performance in acidic corrosive media, and can achieve a good corrosion inhibition effect at a relatively low dosage. The present invention fixes IL on BN, improves the dispersibility of IL, can effectively reduce the volatility of IL, and increases the thermal stability of the corrosion inhibitor. The production conditions are mild, the cost is reduced, and it is suitable for large-scale industrial production and application. The present invention has very important practical and research significance for the development of efficient, environmentally friendly, non-toxic new functionalized corrosion inhibitors.
[0058] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, it is still possible for a person skilled in the art to modify the technical solutions described in the aforementioned embodiments, or to replace some of the technical features therein with equivalents. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions claimed to be protected by the present invention.
Claims
1. An ionic liquid functionalized hexagonal boron nitride corrosion inhibitor, characterized in that: In terms of weight percentage, it includes the following components: Ionic liquid functionalized hexagonal boron nitride solution 25-40% Dispersant 50-70% Surfactant 5-25%.
2. The ionic liquid functionalized hexagonal boron nitride corrosion inhibitor according to claim 1, characterized in that: The ionic liquid functionalized hexagonal boron nitride solution comprises hexagonal boron nitride, ionic liquid and toluene solution, wherein the mass ratio of hexagonal boron nitride to the ionic liquid is 10:1-2:1, and the mass ratio of the ionic liquid to the toluene solution is 1:8-1:12; Hexagonal boron nitride is a nanosheet with a diameter of 1-3 μm and a specific surface area of about 30 m 2 / g, purity 99.9%.
3. The ionic liquid functionalized hexagonal boron nitride corrosion inhibitor according to claim 2, characterized in that: The ionic liquid is one of 1-butyl-3-methyl-imidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-vinyl-3-ethylimidazolium bromide, and 1-allyl-3-methylimidazolium dicyandiamide.
4. An ionic liquid functionalized hexagonal boron nitride corrosion inhibitor according to claim 2 or 3, characterized in that: The dispersant used is water.
5. An ionic liquid functionalized hexagonal boron nitride corrosion inhibitor according to claim 2 or 3, characterized in that: The surfactant is sodium dodecyl sulfate or sodium dodecyl sulfonate.
6. A method for preparing an ionic liquid functionalized hexagonal boron nitride corrosion inhibitor as claimed in any one of claims 2 to 5, characterized in that: The steps are as follows: S1. Prepare an ionic liquid functionalized hexagonal boron nitride solution: add hexagonal boron nitride, ionic liquid and toluene solution into a round-bottom flask, perform reflux reaction under oil bath heating, cool to room temperature after the reaction, and then filter and wash to obtain an ionic liquid functionalized hexagonal boron nitride solution; S2. Add a dispersant and a surfactant to the ionic liquid functionalized hexagonal boron nitride solution to obtain an ionic liquid functionalized hexagonal boron nitride corrosion inhibitor.
7. The method for preparing an ionic liquid functionalized hexagonal boron nitride corrosion inhibitor according to claim 5, characterized in that: In S1, the reaction temperature of the oil bath is 80-100°C, and the reaction time is 12-20h.
8. The method for preparing an ionic liquid functionalized hexagonal boron nitride corrosion inhibitor according to claim 7, characterized in that: In S1, the reduced pressure filtration was performed using a vacuum pump for 30 minutes.
9. The method for preparing an ionic liquid functionalized hexagonal boron nitride corrosion inhibitor according to claim 7, characterized in that: The washing agent is dichloromethane, and the toluene is removed by washing 3-5 times.
10. Use of the ionic liquid functionalized hexagonal boron nitride corrosion inhibitor according to any one of claims 1 to 5 or the ionic liquid functionalized hexagonal boron nitride corrosion inhibitor prepared by the method according to any one of claims 6 to 9, characterized in that: The corrosion inhibitor is used for the corrosion protection of oil field gathering and transportation pipelines.