Environment-friendly compound constructed by function-integrated molecules, intermediate, preparation method and application

Abstract

The invention relates to the technical field of ocean engineering anti-corrosion key materials, in particular to a function-integrated molecular-constructed environment-friendly compound, an intermediate, a preparation method and application. The compound is shown as a formula I. The compound has efficient and stable corrosion inhibition performance, has scale inhibition and sterilization characteristics, and is suitable for complex corrosive environments of oil and gas fields. According to the formula, the dependence of traditional chemical reagents is reduced, the production cost is reduced, an excellent effect is shown in an extreme corrosion environment, the service life of equipment is prolonged, and the production safety is improved. # imgabs1 # in # imgabs0 # formula

Description

Technical Field

[0001] The present invention relates to the technical field of key anti-corrosion materials for marine engineering, and more specifically to an environmentally friendly compound constructed with functional integrated molecules, an intermediate, a preparation method and an application thereof. Background Art

[0002] The corrosive conditions in oil and gas fields, characterized by high temperatures and high acidity, pose a major obstacle to the safe and reliable operation of equipment. In the process of oil extraction and oil and gas transportation in oil fields, equipment pipes and other materials mainly made of metal often encounter a series of problems. One of the main problems is the corrosion of pipelines and equipment, which can lead to significant economic losses, high costs, environmental pollution and waste of resources. With the continuous deepening of oil and gas exploration and development, these problems have become more and more common.

[0003] Corrosion inhibitors are widely considered to be one of the most effective strategies to reduce steel corrosion due to their economy, high efficiency and ease of use. Corrosion inhibitors are still the main anti-corrosion method used in oil fields at home and abroad. Traditional corrosion inhibitors have biological and environmental toxicity, and the problems caused by them are becoming increasingly prominent. In the past, corrosion inhibitors were mostly compound, such as compound fungicides, which have the effect of corrosion inhibition and sterilization, but often have many problems such as the use of hazardous chemicals, which further cause harm to the environment.

[0004] Therefore, the development of low-toxic, environmentally friendly green biological corrosion inhibitors has become a hot topic in current research. In order to reduce the use of chemicals, people are looking forward to synthesizing a corrosion inhibitor that integrates corrosion inhibition, sterilization, scale inhibition and other multifunctional functions, and finding more effective, more economical and more environmentally friendly anti-corrosion solutions, thereby improving the safety and production efficiency of oil and gas field equipment. Summary of the invention

[0005] The purpose of the present invention is to overcome the above-mentioned defects and deficiencies in the prior art and to provide an environmentally friendly compound with a functionally integrated molecular structure.

[0006] Another object of the present invention is to provide a method for preparing the environmentally friendly compound with functional integrated molecular structure.

[0007] Another object of the present invention is to provide an application of the environmentally friendly compound having a functional integrated molecular structure.

[0008] To achieve the above object, the technical solution adopted by the present invention is:

[0009] An environmentally friendly compound constructed with functional integrated molecules, the compound is shown in Formula 1,

[0010]

[0011] In the formula,

[0012]

[0013] A method for preparing the compound:

[0014] A1: Preparation of benzimidazole matrix: lauric acid and o-phenylenediamine are reacted in the presence of a solvent under nitrogen protection and gradient temperature increase to obtain a benzimidazole compound;

[0015] A2: Synthesis of intermediate I: The benzimidazole compound obtained in step A1 and sodium hydroxide are dissolved in an organic solvent, stirred at 55-65°C, and then epichlorohydrin is added to continue the reaction. After purification, the hydroxyl-containing intermediate I is obtained;

[0016] A3: Synthesis of Intermediate II: Mix Intermediate I and acryloyl chloride and dissolve them in an organic solvent. Adjust the system under alkaline conditions and react at 45-55°C to obtain Intermediate II containing a double bond.

[0017] A4: Preparation of final product: Intermediate II was mixed with CHPS-Na and subjected to quaternization reaction at 75-85°C, and the target compound was obtained after purification.

[0018] In the step A1, lauric acid and o-phenylenediamine are mixed in a molar ratio of 1:1.1-1.3, and the solvent is xylene.

[0019] In the step A1, the gradient temperature increase reaction is carried out at 155-165° C. for 3.5-4.5 hours in the first stage and at 215-225° C. for 2.5-3.5 hours in the second stage. After the reaction, the solvent is removed by distillation under reduced pressure to obtain a benzimidazole compound.

[0020] In the step A2, the benzimidazole compound obtained in the step A1 and sodium hydroxide are mixed in a molar ratio of 1:1.0-1.1; and in the step A3, the intermediate I and acryloyl chloride are mixed in a molar ratio of 1:1.0-1.05.

[0021] In the step A3, the system is adjusted with sodium hydroxide, wherein the volume ratio of the sodium hydroxide solution to the organic solution is 1.5 to 2:1.

[0022] The organic solvents in steps A2 and A3 may be the same or different and may be selected from one or more of xylene, dimethyl sulfoxide, dichloromethane, and ethyl acetate.

[0023] The amount of the intermediate II and CHPS-Na in the step A4 is 1:1 to 1.1 molar ratio.

[0024] An application of the compound according to claim 1, wherein the compound is used in the preparation of a multifunctional corrosion inhibitor in the oil and gas field (60-100°C).

[0025] An intermediate for preparing the compound, the intermediate is shown in the following structure,

[0026]

[0027] Beneficial effects of the present invention:

[0028] The environmentally friendly compound constructed with the functional integrated molecule of the present invention can be used as a corrosion inhibitor for oil and gas fields. A new type of corrosion inhibitor is molecularly designed based on the benzimidazole matrix structure. Through fine organic synthesis of the benzimidazole structure, various functional groups such as hydroxyl and sulfonic acid groups are successfully introduced, thereby significantly enhancing its performance diversity and application potential.

[0029] The core purpose of this invention is to establish an efficient and stable corrosion inhibition system to deal with the corrosion problem of metal equipment in high temperature and extreme environment during oil and gas field exploitation. This corrosion inhibitor not only has excellent corrosion inhibition performance, but also has multiple characteristics of scale inhibition and sterilization, thus realizing multi-functional integration in a single product, significantly improving its applicability and efficiency in complex industrial environments.

[0030] In addition, this new type of corrosion inhibitor has achieved a major breakthrough in formula design, reducing dependence on a variety of traditional chemical reagents, which not only reduces production costs, but also reduces potential impacts on the environment, in line with the trend of green development of modern industry. In performance tests against extreme corrosion environments such as high temperatures above 60°C, acidity, and the presence of sulfate-reducing bacteria (SRB) that are unique to oil and gas fields, the corrosion inhibitor showed impressive performance effects, far exceeding traditional corrosion inhibitors, effectively extending the service life of oil and gas field equipment, reducing maintenance costs, and improving production safety.

[0031] The present invention not only provides a new idea and method for the development of oil and gas field corrosion inhibitors, but also makes a positive contribution to promoting the sustainable development of the oil and gas field mining industry. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 The invention discloses a synthetic route for an environmentally friendly corrosion inhibitor constructed with the functional integrated molecule.

[0033] Figure 2 This is a structural characterization diagram of the environmentally friendly corrosion inhibitor constructed with the functional integrated molecules of the present invention.

[0034] Figure 3 This is a diagram showing the results of a static scale inhibition test of an environmentally friendly corrosion inhibitor constructed using the functionally integrated molecules of the present invention.

[0035] Figure 4 This is a fluorescence microscopic observation result of the environmentally friendly corrosion inhibitor constructed with the functional integrated molecule of the present invention. DETAILED DESCRIPTION

[0036] The present invention is further described below in conjunction with the accompanying drawings and specific examples, but the examples do not limit the present invention in any form. Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the art.

[0037] Unless otherwise specified, the reagents and materials used in the following examples are commercially available.

[0038] Embodiment 1:

[0039] The synthesis process of the compound Figure 1 ,

[0040] A1: Lauric acid and o-phenylenediamine were mixed in a three-necked flask at a molar ratio of 1:1.1. Xylene was added as a water carrier. Nitrogen was passed through the mixture, and then the reaction was heated to reflux and stirred. The amidation reaction was continued at 160°C for 3.5 hours, then the temperature was raised to 215°C and the reaction was continued for another 2.5 hours. After the cooling process was completed, the desired benzimidazole matrix was generated by vacuum distillation.

[0041] A2: Mix dimethyl sulfoxide with sodium hydroxide at a molar ratio of 1:1 and stir at 55°C for 1 hour. Then add epichlorohydrin and stir for another 12 hours. After the reaction is completed, cool the mixture to room temperature and pour it into cold water for filtration and purification to produce intermediate product I.

[0042] A3: Dissolve intermediate product I in dimethyl sulfoxide solution, mix intermediate product I with acryloyl chloride in a molar ratio of 1:1.05, add sodium hydroxide solution, and continue at 50°C for 10 hours to generate intermediate product II (see Figure 2 ), wherein the volume ratio of the sodium hydroxide solution to the dimethyl sulfoxide solution is 1:2.

[0043] A4: The intermediate product II and CHPS-Na were mixed and dissolved in a mixture of ethanol and water at a molar ratio of 1:4, and condensed and refluxed at 85°C for 24 hours to generate the final product shown in Formula 1 (see Figure 2 ).

[0044] Performance tests of the above-obtained compounds and intermediates:

[0045] 1. Test method for simulating the corrosion of carbon steel and other metal products in the process of simulating the actual situation of oil field produced water immersion

[0046] Firstly, Q235 carbon steel sheet was selected as the metal to be tested (Fe: 99.5%, Mn: 0.4-0.5%, C: 0.1-0.2%) and used as the working electrode of the electrochemical experiment with a size of 10mm x 10mm x 10mm. The test piece was polished step by step with 800-3000 sandpaper, then rinsed with deionized water, and then ultrasonically cleaned with anhydrous ethanol for 5 minutes, and then dried with nitrogen, and finally stored in a desiccator for use.

[0047] Electrochemical test: A three-electrode system was used, with a saturated calomel electrode (SCE) as the reference electrode and a platinum electrode (Pt) as the counter electrode. The area of ​​Pt was 4 cm 2 The working electrode was immersed in the above two media until the open circuit potential (OCP) was stable. The excitation signal used in the electrochemical impedance spectroscopy (EIS) test was a sine wave with an amplitude of 10my and a scanning frequency range of 100KHz-10mHz. The test time was the first 8 hours of immersion of the specimen and the 4th hour of each dry-wet cycle immersion time.

[0048] Specifically:

[0049] Group 1

[0050] Experimental group 1: Conditions: The experimental material was carbon steel (Fe: 99.5%, Mn: 0.4-0.5%, C: 0.1-0.2%), the corrosive environment was simulated oil field produced water with a pH of about 3 (the components are shown in Table 1), and the additive was the compound of formula 1 prepared in Example 1 above, and the amount of the compound added was 1×10 -4 mol / L; the NaCl content in the medium is 36g / L, the dosage is 500mL; the temperature is 25℃.

[0051] Table 1

[0052]

[0053] Experimental Group 2: Conditions: The experimental material was carbon steel (Fe: 99.5%, Mn: 0.4-0.5%, C: 0.1-0.2%), the corrosive environment was simulated oilfield produced water with a pH of about 3, and the additive was the compound of formula 1 prepared in Example 1 above, and the amount of the compound added was 3×10 -4 mol / L; the NaCl content in the medium is 36g / L, the dosage is 500mL; the temperature is 25℃.

[0054] Experimental group 3: Conditions: The experimental material was carbon steel (Fe: 99.5%, Mn: 0.4-0.5%, C: 0.1-0.2%), the corrosive environment was simulated oil field produced water with a pH of about 3, and the additive was the compound of formula 1 prepared in Example 1 above, and the amount of the compound added was 6×10 -4mol / L; the NaCl content in the medium is 36g / L, the dosage is 500mL; the temperature is 25℃.

[0055] Control group: Conditions: The experimental material was carbon steel (Fe: 99.5%, Mn: 0.4-0.5%, C: 0.1-0.2%), the corrosion environment was simulated oil field produced water with a pH of about 3, the NaCl content in the medium was 36 g / L, the dosage was 500 mL; no compounds were added, and the temperature was 25°C.

[0056] Group 2

[0057] Experimental group 1: Conditions: The experimental material was carbon steel (Fe: 99.5%, Mn: 0.4-0.5%, C: 0.1-0.2%), the corrosive environment was simulated oil field produced water with a pH of about 3, and the additive was the compound of formula 1 prepared in Example 1 above, and the amount of the compound added was 1×10 -4 mol / L; the NaCl content in the medium is 36g / L, the dosage is 500mL; the temperature is 45℃.

[0058] Experimental Group 2: Conditions: The experimental material was carbon steel (Fe: 99.5%, Mn: 0.4-0.5%, C: 0.1-0.2%), the corrosive environment was simulated oilfield produced water with a pH of about 3, and the additive was the compound of formula 1 prepared in Example 1 above, and the amount of the compound added was 3×10 -4 mol / L; the NaCl content in the medium is 36g / L, the dosage is 500mL; the temperature is 45℃.

[0059] Experimental group 3: Conditions: The experimental material was carbon steel (Fe: 99.5%, Mn: 0.4-0.5%, C: 0.1-0.2%), the corrosive environment was simulated oil field produced water with a pH of about 3, and the additive was the compound of formula 1 prepared in Example 1 above, and the amount of the compound added was 6×10 -4 mol / L; the NaCl content in the medium is 36g / L, the dosage is 500mL; the temperature is 45℃.

[0060] Control group: Conditions: The experimental material was carbon steel (Fe: 99.5%, Mn: 0.4-0.5%, C: 0.1-0.2%), the corrosion environment was simulated oil field produced water with a pH of about 3, the NaCl content in the medium was 36 g / L, the dosage was 500 mL; no compounds were added, and the temperature was 45°C.

[0061] Group 3

[0062] Experimental group 1: Conditions: The experimental material was carbon steel (Fe: 99.5%, Mn: 0.4-0.5%, C: 0.1-0.2%), the corrosive environment was simulated oil field produced water with a pH of about 3, and the additive was the compound of formula 1 prepared in Example 1 above, and the amount of the compound added was 1×10 -4 mol / L; the NaCl content in the medium is 36g / L, the dosage is 500mL; the temperature is 85℃.

[0063] Experimental Group 2: Conditions: The experimental material was carbon steel (Fe: 99.5%, Mn: 0.4-0.5%, C: 0.1-0.2%), the corrosive environment was simulated oilfield produced water with a pH of about 3, and the additive was the compound of formula 1 prepared in Example 1 above, and the amount of the compound added was 3×10 -4 mol / L; the NaCl content in the medium is 36g / L, the dosage is 500mL; the temperature is 85℃.

[0064] Experimental group 3: Conditions: The experimental material was carbon steel (Fe: 99.5%, Mn: 0.4-0.5%, C: 0.1-0.2%), the corrosive environment was simulated oil field produced water with a pH of about 3, and the additive was the compound of formula 1 prepared in Example 1 above, and the amount of the compound added was 6×10 -4 mol / L; the NaCl content in the medium is 36g / L, the dosage is 500mL; the temperature is 85℃.

[0065] Control group: Conditions: The experimental material was carbon steel (Fe: 99.5%, Mn: 0.4-0.5%, C: 0.1-0.2%), the corrosion environment was simulated oil field produced water with a pH of about 3, the NaCl content in the medium was 36 g / L, the dosage was 500 mL; no compounds were added, and the temperature was 85°C.

[0066] Group 4

[0067] Experimental group: Conditions: The experimental material is carbon steel (Fe: 99.5%, Mn: 0.4-0.5%, C: 0.1-0.2%), the corrosion environment is a neutral high-scale solution, and the Ca content in the medium is 2+ The content is 1.44 g / L, and the dosage is 500 mL; wherein the additive is the compound of formula 1 prepared in the above Example 1, and the amount of the compound added is 6×10 -4 mol / L; temperature is 25℃.

[0068] Control group: Conditions: The experimental material is carbon steel (Fe: 99.5%, Mn: 0.4-0.5%, C: 0.1-0.2%), the corrosion environment is a neutral high-scale solution, and the Ca content in the medium is 2+ The content is 1.44 g / L, and the dosage is 500 mL; the compound is benzimidazole, and the amount of compound added is 6×10-4 mol / L; temperature is 25℃.

[0069] The test results are shown in Table 2 below:

[0070] Table 2

[0071]

[0072] Referring to the data in the above table, it can be seen from Groups 1 to 3 that the addition of corrosion inhibitors can effectively inhibit corrosion within a certain temperature range. As the temperature rises, the corrosion inhibitor molecules maintain their adsorption behavior and form bonds with the carbon steel surface, thereby quickly adsorbing and covering the active sites. The long-chain alkyl group enhances the hydrophobicity and stability of the substance. Achieving a lower dose can produce a higher level of corrosion inhibition, which shows that the corrosion inhibitor has excellent corrosion protection. The table clearly shows that regardless of concentration or temperature, the addition of corrosion inhibitors has strong corrosion inhibition properties in simulated solutions of oil and gas fields. It can provide effective and stable corrosion protection over a wide range of concentrations. Group 4 compares the performance of benzimidazole and the new corrosion inhibitor synthesized after modification of benzimidazole in the present invention in a high-scale solution, and it can also be clearly seen that the performance is excellent after modification.

[0073] 2. Conduct static scale inhibition test of multifunctional corrosion inhibitor

[0074] The static scale inhibition test adopts the applicable standards specified in the National Standard of the People's Republic of China GB / T 16632-2019 to evaluate the scale inhibition performance of the multifunctional corrosion inhibitor. In order to evaluate the scale inhibition effect of the compound represented by Formula 1 of the present invention, the static scale inhibition efficiency of the compound represented by Formula 1 and benzimidazole was compared, and the test results are as follows Figure 3 As shown:

[0075] It can be seen from the data in the figure that under the condition of adding the same mass, the static scale inhibition efficiency of benzimidazole is above 8%, while the static scale inhibition efficiency of the compound represented by formula 1 of the present invention is above 80%, which is significantly higher than that of benzimidazole, and the scale inhibition efficiency is nearly one order of magnitude higher than that of benzimidazole.

[0076] 3. Conduct fluorescence microscope observation test on the bactericidal performance of multifunctional corrosion inhibitor

[0077] In order to verify the bactericidal performance of the multifunctional additive, a fluorescence microscope observation test was conducted, and Q235 steel was immersed in simulated oil field produced water containing SRB bacteria (the components are shown in Table 1 of Example Group 1, and the pH is about 5) with or without the compound shown in Formula 1 and cultured for 7 days. The test results are as follows Figure 4 As shown:

[0078] The SRB bacteria used in the simulated oilfield produced water containing SRB bacteria need to be cultured for 2 days before addition, and the order of magnitude is 10 6The volume ratio of SRB bacterial solution to simulated oilfield produced water was 1:100.

[0079] In the fluorescence images, green and red represent live and dead bacteria, respectively. In the control group without the addition of the multifunctional corrosion inhibitor (Figure (ac)), some live cells and very few dead cells were shown. After the addition of the multifunctional corrosion inhibitor (Figure (eg)), the number of live bacteria decreased significantly, while the number of dead bacteria increased. This indicates that the multifunctional corrosion inhibitor can effectively inhibit the growth of SRB biofilm. The observed decrease in the number of live bacteria and increase in the number of dead bacteria indicate that the multifunctional corrosion inhibitor can not only inhibit the proliferation of SRB, but also cause cell death, which is a key factor in inhibiting biofilm formation and subsequent corrosion processes.

[0080] All the above test results show that the environmentally friendly corrosion inhibitor constructed with functional integrated molecules prepared by the present invention has excellent performance, high efficiency and durability, low dosage and high efficiency, and has significant application value and broad market prospects.

Claims

1. An environmentally friendly compound constructed with functional integrated molecules, characterized in that: The compound is shown in formula 1, In the formula, 2. A method for preparing the compound according to claim 1, characterized in that: A1: Preparation of benzimidazole matrix: lauric acid and o-phenylenediamine are reacted in the presence of an organic solvent under nitrogen protection and gradient temperature increase to obtain a benzimidazole compound; A2: Synthesis of intermediate I: The benzimidazole compound obtained in step A1 and sodium hydroxide are dissolved in an organic solvent, stirred at 55-65°C, and then epichlorohydrin is added to continue the reaction. After purification, the hydroxyl-containing intermediate I is obtained; A3: Synthesis of Intermediate II: Mix Intermediate I and acryloyl chloride and dissolve them in an organic solvent. Adjust the system under alkaline conditions and react at 45-55°C to obtain Intermediate II containing a double bond. A4: Preparation of final product: Intermediate II was mixed with CHPS-Na and subjected to quaternization reaction at 75-85°C, and the target compound was obtained after purification.

3. The method for preparing the compound according to claim 2, characterized in that: In the step A1, lauric acid and o-phenylenediamine are mixed in a molar ratio of 1:1.1-1.3 and dissolved in a xylene solution.

4. The method for preparing the compound according to claim 2, characterized in that: In the step A1, the gradient temperature increase reaction is carried out at 155-165° C. for 3.5-4.5 hours in the first stage and at 215-225° C. for 2.5-3.5 hours in the second stage. After the reaction, the solvent is removed by distillation under reduced pressure to obtain a benzimidazole compound.

5. The method for preparing the compound according to claim 2, characterized in that: In the step A2, the benzimidazole compound obtained in the step A1 and sodium hydroxide are mixed in a molar ratio of 1:1.0 to 1.1; The amount of the intermediate I and acryloyl chloride in the step A3 is 1:1.0-1.05 in molar ratio.

6. The method for preparing the compound according to claim 2, characterized in that: The organic solvents in steps A2 and A3 may be the same or different and may be selected from one or more of xylene, dimethyl sulfoxide, dichloromethane, and ethyl acetate.

7. The method for preparing the compound according to claim 2, characterized in that: The amount of the intermediate II and CHPS-Na in the step A4 is 1:1 to 1.1 molar ratio.

8. Use of the compound according to claim 1, characterized in that: The compound is used in the preparation of a multifunctional corrosion inhibitor in the oil and gas field.

9. An intermediate for preparing the compound according to claim 1, characterized in that: The intermediate is shown in the following structure,

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