High-temperature-resistant microbicidal corrosion inhibitor and preparation method therefor

Abstract

A high-temperature-resistant microbicidal corrosion inhibitor and a preparation method therefor. The preparation method comprises the following steps: reacting a mercaptocarboxylic acid compound with polyethyleneimine in an organic solvent at a first temperature for a first time to obtain a system containing a first compound; adding a halogenated hydrocarbon to the system containing the first compound for a reaction at a second temperature for a second time to obtain a system containing a second compound; and then removing the organic solvent and performing drying to obtain the high-temperature-resistant microbicidal corrosion inhibitor. The preparation method for the high-temperature-resistant microbicidal corrosion inhibitor is simple and has good high-temperature stability and excellent microbicidal corrosion inhibition performance.

Description

A high temperature resistant sterilization and corrosion inhibitor and its preparation method Technical Field

[0001] The invention belongs to the technical field of chemical sterilization and anticorrosion in oil and gas fields, and particularly relates to a high-temperature resistant sterilization and corrosion inhibitor and a preparation method thereof. Background Art

[0002] Oil and gas field production systems are not only susceptible to the corrosive gas CO2, but also harbor a large number of corrosive microorganisms, such as sulfate-reducing bacteria (SRB) and saprophytic bacteria (TGB). The synergistic effects of CO2 and bacteria lead to significant corrosion failure in oil and gas field production systems, severely hindering the safe and efficient extraction of oil and gas. Currently, corrosion control primarily relies on compound biocides and corrosion inhibitors. Due to the significant difference between the downhole and surface environments, the maximum downhole temperature can exceed 150°C. Most compound biocides and corrosion inhibitors contain aldehydes and ketones, such as glutaraldehyde and isothiazolinone. These compounds crosslink or degrade after exposure to high downhole temperatures, reducing the protective effect of the returned biocides on surface pipelines. Currently, most technologies employ injection ports at the wellbore and wellhead of the production system to inject biocides and corrosion inhibitors, providing adequate protection for the downhole, production, and gathering pipelines. However, this results in large injection volumes, significantly increasing corrosion control costs. The introduction of large quantities of biocides also poses the risk of environmental pollution and complicates post-processing. On the other hand, when screening for compounding fungicides and corrosion inhibitors, they must be compatible with each other, not chemically react, and not compromise their respective fungicidal and corrosion-inhibiting properties. The screening, evaluation, and preparation of compounded agents is relatively complex. Therefore, it is necessary to develop integrated fungicides and corrosion inhibitors with excellent stability under high-temperature conditions. This can be used to control corrosion in surface pipelines through wellbore flowback, thereby reducing injection volumes and lowering corrosion control costs.

[0003] There are few reports on high-temperature resistant bactericidal corrosion inhibitors. CN104629713B discloses a high-temperature resistant corrosion inhibitor and its preparation method, which uses compounds such as dodecyldimethyl tertiary amine, polyethylene polyamine, morpholine, pyridine to prepare the high-temperature resistant corrosion inhibitor. Its preparation process is complicated, the reaction temperature is high, and its bactericidal performance is not reported. CN114231266A discloses a non-foaming corrosion inhibitor with bactericidal performance and its preparation method, which uses benzylamine compounds as the main agent, biphenyl compounds as the compounding agent and adjuvants in a solvent to mix and stir to obtain an antiseptic agent with both carbon dioxide and microbial corrosion. Although this agent has a multi-purpose performance, it has many components and a complicated preparation process. CN105439299A discloses a method for preparing a hyperbranched polyethyleneimine copolymer water treatment agent. The hyperbranched polyethyleneimine copolymer water treatment agent is prepared under microwave conditions using hydroxylated hyperbranched polyethyleneimine and 2-acrylamide-2-methylpropanesulfonic acid as monomers. The treatment agent has good scale inhibition, corrosion inhibition, and bactericidal properties. The water treatment agent is prepared by polymerization, which has significant limitations in industrial scale-up production and lacks high-temperature stability. CN103554491A discloses a polyethyleneimine antibacterial functionalized polymer and its preparation method. The preparation method reacts a guanidine substance with a high-molecular polyethyleneimine to obtain a guanidine salt polyethyleneimine solution, and then adds an epoxy compound to prepare an antibacterial polymer solution. However, the high-temperature resistance and corrosion inhibition properties of the antibacterial functionalized polymer are not reported.

[0004] Therefore, developing a high-temperature resistant bactericidal corrosion inhibitor is still one of the problems to be solved urgently in this field.

[0005] Summary of the Invention

[0006] To address the above technical problems, the present invention provides a high-temperature-resistant bactericidal and corrosion inhibitor and a method for its preparation. By grafting thiol groups onto the structure of polyethyleneimine and further quaternizing it, the present invention enhances its stability, bactericidal, and corrosion-inhibiting properties. The high-temperature-resistant bactericidal and corrosion inhibitor of the present invention has a simple preparation method, good high-temperature stability, and excellent bactericidal and corrosion-inhibiting properties.

[0007] In order to achieve the above object, the first aspect of the present invention provides a method for preparing a high temperature resistant bactericidal corrosion inhibitor, which comprises the following steps:

[0008] (1) reacting a mercaptocarboxylic acid compound and polyethyleneimine in an organic solvent at a first temperature for a first time to obtain a system containing a first compound;

[0009] (2) adding a halogenated hydrocarbon to the system containing the first compound, reacting at a second temperature for a second time to obtain a system containing the second compound, and then removing the organic solvent and drying to obtain the high-temperature resistant bactericidal corrosion inhibitor.

[0010] In the above preparation method, preferably, the structural formula of the mercaptocarboxylic acid compound is as shown in formula (I):

[0011] In formula (I), n is a natural number of 1 to 20.

[0012] In the above preparation method, preferably, the structural formula of the polyethyleneimine is as shown in formula (II):

[0013] In formula (II), x and y are each a natural number of 1 to 100. More preferably, x and y are each a natural number of 1 to 20.

[0014] In the above preparation method, preferably, the organic solvent includes an alcohol compound.

[0015] In the above preparation method, preferably, the first temperature is 25° C. to 100° C., and the first time is 5 to 24 hours.

[0016] In the above preparation method, preferably, the structural formula of the halogenated hydrocarbon is as shown in formula (III):

[0017] RZ(III)

[0018] In formula (III), R is selected from one of a C1-C10 straight-chain or branched alkyl group, a C1-C10 alkoxy group, a C2-C10 straight-chain or branched alkenyl group, a C1-C10 alkylthio group, a C3-C10 cycloalkyl group, a C6-C20 aromatic ring group, and a C5-C20 aromatic heterocyclic group, and Z is selected from one of chlorine, bromine, and iodine.

[0019] In the above preparation method, preferably, the second temperature is 50° C. to 100° C., and the second time is 3 to 24 hours.

[0020] In the above preparation method, preferably, the molar ratio of the polyethyleneimine, the mercaptocarboxylic acid compound and the halogenated hydrocarbon is (1-5):(5-50):(1-50).

[0021] The second aspect of the present invention provides a high-temperature resistant bactericidal corrosion inhibitor, which is prepared by the above-mentioned preparation method of the high-temperature resistant bactericidal corrosion inhibitor.

[0022] According to a specific embodiment of the present invention, preferably, the structural formula of the high temperature resistant bactericidal corrosion inhibitor is as shown in formula (IV):

[0023] In formula (IV), x and y are each a natural number of 1 to 100, n is a natural number of 1 to 20, R is selected from one of a C1 to C10 linear or branched alkyl group, a C1 to C10 alkoxy group, a C2 to C10 linear or branched alkenyl group, a C1 to C10 alkylthio group, a C3 to C10 cycloalkyl group, a C6 to C20 aromatic ring group, and a C5 to C20 aromatic heterocyclic group, and Z is selected from one of chlorine, bromine, and iodine. More preferably, x and y are each a natural number of 1 to 20.

[0024] The third aspect of the present invention provides a high-temperature resistant bactericidal corrosion inhibitor composition, which comprises, based on the total weight of the high-temperature resistant bactericidal corrosion inhibitor composition being 100%, 20% to 80% of the above-mentioned high-temperature resistant bactericidal corrosion inhibitor, 5% to 80% of a solvent, and 0% to 15% of an additive.

[0025] According to a specific embodiment of the present invention, preferably, based on the total weight of the high-temperature resistant bactericidal corrosion inhibitor composition being 100%, it includes: 30-80% of the high-temperature resistant bactericidal corrosion inhibitor, 5-65% of the solvent and 5-15% of the additive.

[0026] In the above-mentioned high-temperature resistant bactericidal corrosion inhibitor composition, preferably, the solvent includes one or a combination of water, alcohol compounds, amide compounds, nitrile compounds, ketone compounds, ether compounds and aromatic compounds.

[0027] In the above-mentioned high-temperature resistant bactericidal corrosion inhibitor composition, preferably, the auxiliary agent includes one or a combination of thiourea, thiazole, pyridine, piperidine, quinoline, 1,3,5-triazine and its derivatives, tributyl phosphate and thiol compounds.

[0028] The present invention provides a high-temperature resistant bactericidal corrosion inhibitor, a preparation method thereof, and a high-temperature resistant bactericidal corrosion inhibitor composition. Polyethyleneimine has a stable structure and contains abundant primary, secondary, and tertiary amine groups, but its own bactericidal and corrosion-inhibiting properties are relatively low. However, the inventors of this case have discovered through research that thiol groups have excellent corrosion-inhibiting properties. The present invention utilizes the stable structure of polyethyleneimine to graft thiol groups into the structure of polyethyleneimine through a chemical reaction, and further quaternizes it to improve its bactericidal and corrosion-inhibiting properties, thereby preparing a high-temperature resistant bactericidal corrosion inhibitor suitable for the oil and gas field industry.

[0029] The technical solution of the present invention has at least the following beneficial effects:

[0030] The present invention utilizes a mercaptocarboxylic acid compound to modify polyethyleneimine, and further quaternizes it. The bactericidal, corrosion-inhibiting, and stability properties of polyethyleneimine are enhanced by amide groups, mercapto groups, and quaternization, thereby preparing a high-temperature resistant bactericidal corrosion inhibitor. The high-temperature resistant bactericidal corrosion inhibitor has multifunctional properties, a simple preparation method, good high-temperature stability, and excellent bactericidal and corrosion-inhibiting properties. The high-temperature resistant bactericidal corrosion inhibitor of the present invention is suitable for application in microbial corrosion protection and / or chemical corrosion protection of oil and gas field pipelines, and can control and protect the synergistic corrosion of CO2 and bacteria in underground-surface gathering and transportation pipelines of oil and gas field production systems. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] FIG1 is a nuclear magnetic resonance characterization diagram of the high-temperature resistant bactericidal corrosion inhibitor provided in Example 1.

[0032] FIG2 is a thermogravimetric curve of the high-temperature resistant sterilization and corrosion inhibitor provided in Example 1.

[0033] FIG3 is a nuclear magnetic resonance characterization diagram of the high-temperature resistant sterilization and corrosion inhibitor provided in Example 2.

[0034] FIG4 is a thermogravimetric curve of the high-temperature resistant sterilization and corrosion inhibitor provided in Example 2. DETAILED DESCRIPTION

[0035] In order to have a clearer understanding of the technical features, objectives and beneficial effects of the present invention, the present invention is now described in detail below, but it should not be understood as limiting the scope of implementation of the present invention.

[0036] According to a specific embodiment of the present invention, the first aspect of the present invention provides a method for preparing a high-temperature resistant bactericidal corrosion inhibitor, which comprises the following steps:

[0037] (1) reacting a mercaptocarboxylic acid compound and polyethyleneimine in an organic solvent at a first temperature for a first time to obtain a system containing a first compound;

[0038] (2) adding a halogenated hydrocarbon to the system containing the first compound, reacting at a second temperature for a second time to obtain a system containing the second compound, and then removing the organic solvent and drying to obtain the high-temperature resistant bactericidal corrosion inhibitor.

[0039] In some embodiments, the structural formula of the mercaptocarboxylic acid compound is shown in Formula (I):

[0040] In formula (I), n is a natural number of 1 to 20, for example, n=1, 2, 3, 4, 5, 6, 7, 8, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20 or a range consisting of any two of the above values. Specifically, the mercaptocarboxylic acid compound can include one or more of mercaptoacetic acid, 3-mercaptopropionic acid, 4-mercaptobutyric acid, 5-mercaptopentanoic acid, 6-mercaptohexanoic acid, 7-mercaptoheptanoic acid, 8-mercaptooctanoic acid, 11-mercaptoundecanoic acid, 12-mercaptododecanoic acid, 13-mercaptotridecanoic acid, 14-mercaptotetradecanoic acid, 15-mercaptopentadecanoic acid, 16-mercaptohexadecanoic acid, 17-mercaptoheptadecanoic acid and 18-mercaptooctadecanoic acid.

[0041] In some embodiments, the structural formula of the polyethyleneimine is shown in Formula (II):

[0042] In formula (II), x and y are natural numbers from 1 to 100. Preferably, x and y are natural numbers from 1 to 20, for example, x and y are 1, 3, 6, 8, 10, 12, 14, 16, 18, 20, or a range consisting of any two of the above values.

[0043] In some embodiments, the organic solvent includes an alcohol compound, specifically, one or a combination of methanol, ethanol, propanol, butanol, isobutanol, and 2-methylbutanol.

[0044] In some embodiments, the first temperature is 25° C. to 100° C., and the first time is 5 to 24 hours.

[0045] In some embodiments, the structural formula of the halogenated hydrocarbon is shown in Formula (III):

[0046] RZ(III)

[0047] In formula (III), R is selected from one of a C1-C10 straight-chain or branched alkyl group, a C1-C10 alkoxy group, a C2-C10 straight-chain or branched alkenyl group, a C1-C10 alkylthio group, a C3-C10 cycloalkyl group, a C6-C20 aromatic ring group, and a C5-C20 aromatic heterocyclic group, and Z is selected from one of chlorine, bromine, and iodine. Preferably, the halogenated hydrocarbon includes one or a combination of C2-C10 straight-chain or branched halogenated olefins, C1-C10 straight-chain or branched halogenated alkanes, and C6-C20 halogenated aromatic hydrocarbons. Specifically, the halogenated alkane includes one or a combination of alkyl chlorides, alkyl iodoides, and alkyl bromides, the halogenated olefins include allyl bromide and / or allyl chloride, and the halogenated aromatic hydrocarbons include benzyl chloride and / or benzyl bromide.

[0048] In some embodiments, the second temperature is 50° C. to 100° C., and the second time is 3 to 24 hours.

[0049] In some embodiments, the molar ratio of the polyethyleneimine, the mercaptocarboxylic acid compound, and the halogenated hydrocarbon is (1-5):(5-50):(1-50).

[0050] In some embodiments, the organic solvent is removed by rotary evaporation.

[0051] In some embodiments, the drying is vacuum drying, the drying temperature is 50° C. to 60° C., and the drying time is 24 to 48 hours.

[0052] In some embodiments, the preparation method of the high temperature resistant bactericidal corrosion inhibitor comprises the following steps:

[0053] (1) adding the mercaptocarboxylic acid compound dropwise to polyethyleneimine dissolved in an appropriate amount of an organic solvent, reacting at 25° C. to 100° C. for 5 to 24 hours to obtain a system containing the first compound;

[0054] (2) Adding a halogenated hydrocarbon to the system containing the first compound, reacting at 50° C. to 100° C. for 3 to 24 hours to obtain a system containing the second compound, removing the organic solvent by rotary evaporation, and then drying to obtain the high-temperature resistant bactericidal corrosion inhibitor.

[0055] According to a specific embodiment of the present invention, the reaction process of the preparation method of the high temperature resistant bactericidal corrosion inhibitor is as follows:

[0056] According to a specific embodiment of the present invention, a second aspect of the present invention provides a high-temperature resistant bactericidal corrosion inhibitor, which is prepared by the above-mentioned preparation method of the high-temperature resistant bactericidal corrosion inhibitor.

[0057] According to a specific embodiment of the present invention, the high-temperature resistant bactericidal corrosion inhibitor includes structural units derived from the polyethyleneimine, structural units derived from the mercaptocarboxylic acid compound, and structural units derived from the halogenated hydrocarbon. Preferably, the molar ratio of the structural units derived from the polyethyleneimine, the structural units derived from the mercaptocarboxylic acid compound, and the structural units derived from the halogenated hydrocarbon is (1-5):(5-50):(1-50).

[0058] According to a specific embodiment of the present invention, preferably, the structural formula of the high temperature resistant bactericidal corrosion inhibitor is as shown in formula (IV):

[0059] In formula (IV), x and y are each a natural number of 1 to 100, n is a natural number of 1 to 20, R is selected from one of a C1 to C10 linear or branched alkyl group, a C1 to C10 alkoxy group, a C2 to C10 linear or branched alkenyl group, a C1 to C10 alkylthio group, a C3 to C10 cycloalkyl group, a C6 to C20 aromatic ring group, and a C5 to C20 aromatic heterocyclic group, and Z is selected from one of chlorine, bromine, and iodine. More preferably, x and y are each a natural number of 1 to 20.

[0060] According to a specific embodiment of the present invention, the third aspect of the present invention provides a high-temperature resistant bactericidal corrosion inhibitor composition, which includes: 20% to 80% of the above-mentioned high-temperature resistant bactericidal corrosion inhibitor, such as 20%, 40%, 60%, 80% or a range consisting of any two values ​​above; 5% to 80% of the solvent, such as 5%, 10%, 20%, 40%, 60%, 80% or a range consisting of any two values ​​above; and 0% to 15% of the auxiliary agent, such as 0%, 5%, 10%, 15% or a range consisting of any two values ​​above. Preferably, based on the total weight of the high-temperature resistant bactericidal corrosion inhibitor composition as 100%, it includes: 30% to 80% of the above-mentioned high-temperature resistant bactericidal corrosion inhibitor, 5% to 65% of the solvent and 5% to 15% of the auxiliary agent.

[0061] In some embodiments, the solvent comprises one or a combination of water, alcohol compounds, amide compounds, nitrile compounds, ketone compounds, ether compounds, and aromatic compounds. The alcohol compounds include, but are not limited to, one or a combination of methanol, ethanol, propanol, butanol, isobutanol, and 2-methylbutanol.

[0062] In some embodiments, the auxiliary agent includes one or a combination of thiourea, thiazole, pyridine, piperidine, quinoline, 1,3,5-triazine and its derivatives, tributyl phosphate and thiol compounds.

[0063] In some embodiments, the high-temperature resistant bactericidal corrosion inhibitor composition can be prepared by mixing the high-temperature resistant bactericidal corrosion inhibitor with a solvent and an optionally added auxiliary agent.

[0064] According to a specific embodiment of the present invention, the fourth aspect of the present invention provides the use of the above-mentioned high-temperature resistant bactericidal corrosion inhibitor or the above-mentioned high-temperature resistant bactericidal corrosion inhibitor composition in oil and gas field microbial corrosion protection and / or chemical corrosion protection.

[0065] In some embodiments, the oil and gas field includes an unconventional gas field. Specifically, the application is: use of the high-temperature resistant bactericidal corrosion inhibitor or the high-temperature resistant bactericidal corrosion inhibitor composition in controlling and preventing synergistic corrosion caused by CO2 and bacteria in downhole-surface gathering and transportation pipelines of unconventional gas production systems.

[0066] The present invention will be specifically described below with reference to Examples. However, the present invention is not limited to these Examples and can be implemented with various modifications within the scope of the gist of the present invention.

[0067] It should be noted that in the following examples, comparative examples and test examples, the operations involved, if the conditions are not specified, were carried out according to conventional conditions or the conditions recommended by the manufacturer, and the raw materials used, if the manufacturer and specifications are not specified, are conventional products that can be obtained commercially.

[0068] Example 1

[0069] 0.04 mol of polyethyleneimine was dissolved in 30 mL of ethanol, and 0.2 mol of thioglycolic acid was added dropwise, and the mixture was reacted at 70°C for 12 h. 0.2 mol of 3-bromopropylene was then added, and the mixture was reacted at 70°C for 10 h. The ethanol was then removed by rotary evaporation, and the mixture was vacuum dried at 50°C for 48 h to obtain a high-temperature resistant bactericidal corrosion inhibitor, which was recorded as S1.

[0070] The structural formula of the polyethyleneimine used is:

[0071] Wherein, x is a natural number from 1 to 6, and y is a natural number from 1 to 6.

[0072] The molecular weight of the polyethyleneimine was 600.

[0073] The structure of the high temperature resistant sterilization and corrosion inhibitor of this embodiment is as follows:

[0074] Wherein, x is a natural number from 1 to 6, and y is a natural number from 1 to 6.

[0075] The high temperature resistant bactericidal corrosion inhibitor of this embodiment was subjected to nuclear magnetic resonance analysis, as shown in FIG1 , and the results are: 1 HNMR(DMSO,400MHz)δ(ppm):1.04-1.08(t,-CH2-CH2-),1.81((s,-SH),2.62-2.80(d,-N(-C=O)-CH2-),2.99-3.16(m,-CH2-CH2-(-CH2-)N + (-CH2-)-,3.42-3.47(m,-(-CH2-)N +(-CH2-)-CH2-CH=CH2,-CH2-SH), 4.89(s,-CH=CH2).

[0076] Thermogravimetric analysis was performed on the high-temperature resistant bactericidal corrosion inhibitor of this embodiment. The obtained thermogravimetric curve is shown in FIG2 . As can be seen from FIG2 , the main weight loss temperatures of the substance are 200.0° C. and 360.7° C.

[0077] Example 2

[0078] 0.04 mol of polyethyleneimine was dissolved in 30 mL of ethanol, and 0.2 mol of thioglycolic acid was added dropwise, and the mixture was reacted at 70°C for 12 h. 0.1 mol of benzyl chloride was then added, and the mixture was reacted at 70°C for 10 h. The ethanol was then removed by rotary evaporation, and the mixture was vacuum dried at 50°C for 48 h to obtain a high-temperature resistant bactericidal corrosion inhibitor, which was recorded as S2.

[0079] The structural formula of the polyethyleneimine used is:

[0080] Wherein, x is a natural number from 1 to 6, and y is a natural number from 1 to 6.

[0081] The molecular weight of the polyethyleneimine was 600.

[0082] The structure of the high temperature resistant sterilization and corrosion inhibitor of this embodiment is as follows:

[0083] Wherein, x is a natural number from 1 to 6, and y is a natural number from 1 to 6.

[0084] The high temperature resistant bactericidal corrosion inhibitor of this embodiment was subjected to nuclear magnetic resonance analysis, as shown in FIG3 , and the results are: 1 HNMR(DMSO,400MHz)δ(ppm):1.04-1.08(t,-CH2-CH2-),1.82((s,-SH),2.51-2.76(m,-N(-C=O)-CH2-),2.97-3.10(m,-CH2-CH2-(-CH2-)N + (-CH2-)-,3.42-3.45(m,(-CH2-)N + (-CH2-)-CH2-CH2-NH-), 3.74-3.78(m,-CH2-CH=CH-), 7.20-7.31(M,-CH=CH-).

[0085] Thermogravimetric analysis was performed on the high-temperature resistant bactericidal corrosion inhibitor of this embodiment. The obtained thermogravimetric curve is shown in FIG4 . As can be seen from FIG4 , the main weight loss temperatures of the substance are 200.0° C. and 330.0° C.

[0086] Example 3

[0087] 0.02 mol of polyethyleneimine was dissolved in 30 mL of ethanol, and 1 mol of thioglycolic acid was added dropwise, and the mixture was reacted at 25°C for 5 h. 1 mol of benzyl chloride was then added, and the mixture was reacted at 100°C for 24 h. The ethanol was then removed by rotary evaporation, and the mixture was vacuum dried at 50°C for 48 h to obtain a high-temperature resistant bactericidal corrosion inhibitor, which was recorded as S3.

[0088] The structural formula of the polyethyleneimine used is:

[0089] Wherein, x is a natural number from 1 to 6, and y is a natural number from 1 to 6.

[0090] The molecular weight of the polyethyleneimine was 600.

[0091] The structure of the high temperature resistant sterilization and corrosion inhibitor of this embodiment is as follows:

[0092] Wherein, x is a natural number from 1 to 6, and y is a natural number from 1 to 6.

[0093] Example 4

[0094] 0.04 mol of polyethyleneimine was dissolved in 30 mL of ethanol, and 0.2 mol of thioglycolic acid was added dropwise, and the mixture was reacted at 70°C for 12 h; 0.2 mol of bromobutane was added, and the mixture was reacted at 70°C for 10 h; the ethanol was then removed by rotary evaporation, and the mixture was vacuum dried at 50°C for 48 h to obtain a high-temperature resistant bactericidal corrosion inhibitor, which was recorded as S4.

[0095] The structural formula of the polyethyleneimine used is:

[0096] Wherein, x is a natural number from 1 to 3, and y is a natural number from 1 to 3.

[0097] The molecular weight of the polyethyleneimine was 300.

[0098] The structure of the high temperature resistant sterilization and corrosion inhibitor of this embodiment is as follows:

[0099] Wherein, x is a natural number from 1 to 3, and y is a natural number from 1 to 3.

[0100] Example 5

[0101] 0.04 mol of polyethyleneimine was dissolved in 30 mL of ethanol, and 0.2 mol of thioglycolic acid was added dropwise, and the mixture was reacted at 70° C. for 12 h; 0.2 mol of 3-bromopropylene was added, and the mixture was reacted at 70° C. for 10 h; the ethanol was then removed by rotary evaporation, and the mixture was vacuum dried at 50° C. for 48 h to obtain a high-temperature resistant bactericidal corrosion inhibitor; isopropanol was then added as a solvent to obtain a high-temperature resistant bactericidal corrosion inhibitor composition, wherein the total weight of the high-temperature resistant bactericidal corrosion inhibitor composition was 100%, the content of the high-temperature resistant bactericidal corrosion inhibitor was 80%, and the content of isopropanol was 20%. The high-temperature resistant bactericidal corrosion inhibitor composition was recorded as S5.

[0102] The polyethyleneimine used is the same as that in Example 1.

[0103] Example 6

[0104] 0.04 mol of polyethyleneimine was dissolved in 30 mL of ethanol, and 0.2 mol of thioglycolic acid was added dropwise, and the mixture was reacted at 70° C. for 12 h; 0.2 mol of 3-bromopropylene was added, and the mixture was reacted at 70° C. for 10 h; the ethanol was then removed by rotary evaporation, and the mixture was vacuum dried at 50° C. for 48 h to obtain a high-temperature resistant bactericidal corrosion inhibitor; isopropanol was added as a solvent and thiourea was used as an auxiliary agent to obtain a high-temperature resistant bactericidal corrosion inhibitor composition, wherein the total weight of the high-temperature resistant bactericidal corrosion inhibitor composition was 100%, the content of the high-temperature resistant bactericidal corrosion inhibitor was 75%, the content of isopropanol was 20%, and the content of thiourea was 5%. The high-temperature resistant bactericidal corrosion inhibitor composition was recorded as S6.

[0105] The polyethyleneimine used is the same as that in Example 1.

[0106] Example 7

[0107] 0.04 mol of polyethyleneimine was dissolved in 30 mL of ethanol, and 0.2 mol of 3-mercaptopropionic acid was added dropwise, and the mixture was reacted at 25°C for 24 h. 0.2 mol of 3-bromopropylene was then added, and the mixture was reacted at 100°C for 5 h. The ethanol was then removed by rotary evaporation, and the mixture was vacuum dried at 50°C for 48 h to obtain a high-temperature resistant bactericidal corrosion inhibitor, which was recorded as S7.

[0108] The structural formula of the polyethyleneimine used is:

[0109] Wherein, x is a natural number from 1 to 12, and y is a natural number from 1 to 12.

[0110] The molecular weight of the polyethyleneimine was 1,200.

[0111] Example 8

[0112] 0.04 mol of polyethyleneimine was dissolved in 30 mL of ethanol, and 0.4 mol of 3-mercaptobutyric acid was added dropwise, and the mixture was reacted at 50°C for 24 h. 0.2 mol of 4-bromobutene was then added, and the mixture was reacted at 100°C for 12 h. The ethanol was then removed by rotary evaporation, and the mixture was vacuum dried at 50°C for 48 h to obtain a high-temperature resistant bactericidal corrosion inhibitor, which was recorded as S8.

[0113] The polyethyleneimine used is the same as that in Example 7.

[0114] Example 9

[0115] 0.04 mol of polyethyleneimine was dissolved in 30 mL of ethanol, and 2 mol of 3-mercaptobutyric acid was added dropwise, and the mixture was reacted at 100°C for 24 h. 0.5 mol of 4-bromobutene was then added, and the mixture was reacted at 100°C for 24 h. The ethanol was then removed by rotary evaporation, and the mixture was vacuum dried at 50°C for 48 h to obtain a high-temperature resistant bactericidal corrosion inhibitor, which was designated as S9.

[0116] The polyethyleneimine used is the same as that in Example 7.

[0117] Comparative Example 1

[0118] 0.04 mol of polyethyleneimine was dissolved in 30 mL of ethanol, and 0.2 mol of thioglycolic acid was added dropwise. The mixture was reacted at 70° C. for 12 h. The ethanol was then removed by rotary evaporation, and the mixture was vacuum dried at 50° C. for 48 h to obtain a bactericidal corrosion inhibitor, which was recorded as D1.

[0119] The polyethyleneimine used is the same as that in Example 1.

[0120] Comparative Example 2

[0121] 0.02 mol of polyethyleneimine was dissolved in 30 mL of ethanol, and 1 mol of thioglycolic acid was added dropwise. The mixture was reacted at 25° C. for 5 h. The ethanol was then removed by rotary evaporation. The mixture was vacuum dried at 50° C. for 48 h to obtain a bactericidal corrosion inhibitor, which was recorded as D2.

[0122] The polyethyleneimine used is the same as that in Example 3.

[0123] Comparative Example 3

[0124] 0.04 mol of polyethyleneimine was dissolved in 30 mL of ethanol, and 0.2 mol of 3-bromopropylene was added, and the mixture was reacted at 70° C. for 10 h. The ethanol was then removed by rotary evaporation, and the mixture was vacuum dried at 50° C. for 48 h to obtain a bactericidal corrosion inhibitor, which was recorded as D3.

[0125] The polyethyleneimine used is the same as that in Example 1.

[0126] Test Example 1

[0127] The bactericidal performance of the bactericidal corrosion inhibitors prepared in the above-mentioned Examples 1-4, 7 to 9 and Comparative Examples 1-3, and the bactericidal corrosion inhibitor composition prepared in Examples 5-6 were evaluated. The specific evaluation process is: after the bactericidal corrosion inhibitor and the bactericidal corrosion inhibitor composition are placed at room temperature and at 150°C for 24 hours, 100 mg / L of the bactericidal corrosion inhibitor or the bactericidal corrosion inhibitor composition is used to perform a bactericidal test on a water sample containing SRB and TGB bacteria. The method of the bactericidal test is: add a bactericidal corrosion inhibitor or a bactericidal corrosion inhibitor composition (the addition amount is 100 mg / L) to the water sample containing bacteria, and after incubating at 25°C in an anaerobic environment for 24 hours, refer to SY / T 0532-2012 "Analysis Method for Bacteria in Oilfield Injection Water (Extinction Dilution Method)" to determine the bacterial content, calculate the bactericidal rate, and the results are shown in Table 1. The bacteria-containing water sample used is the flowback fluid of a shale gas well. The formula for calculating the bactericidal rate is as follows:

[0128] Where: X is the sterilization rate (%); a2 is the number of bacteria after sterilization (cells / mL); a1 is the number of blank bacteria (cells / mL).

[0129] Table 1

[0130] As can be seen from Table 1, after the bactericidal corrosion inhibitor or bactericidal corrosion inhibitor composition prepared in the embodiment of the present invention is added to the return fluid of the shale gas well and placed at room temperature and at 150°C for 24 hours, its bactericidal performance is basically unchanged. At a usage amount of 100ppm, the bactericidal corrosion inhibitor and bactericidal corrosion inhibitor composition prepared in the embodiment of the present invention have a bactericidal rate of 97.8% to 100% for SRB; and a bactericidal rate of 100% for TGB. Therefore, the bactericidal corrosion inhibitor and bactericidal corrosion inhibitor composition prepared in the embodiment of the present invention have excellent bactericidal performance, and their bactericidal effect is not affected by high temperature placement, and they have excellent high-temperature stability.

[0131] Test Example 2

[0132] The corrosion inhibition effect of the bactericidal corrosion inhibitors prepared in Examples 1-4, 7 to 9 and Comparative Examples 1-3, and the bactericidal corrosion inhibitor compositions prepared in Examples 5-6 were evaluated. The specific evaluation process is as follows: after the bactericidal corrosion inhibitor and the bactericidal corrosion inhibitor composition are placed at room temperature and at 150°C for 24 hours, a corrosion test is performed on a 5% by mass NaCl water sample containing 800ppm CO2. The bactericidal corrosion inhibitor or the bactericidal corrosion inhibitor composition is used at a concentration of 100mg / L, the corrosive material is L360N, and after being placed at 60°C in an anaerobic environment for 72 hours, the corrosion rate is calculated with reference to the standard SY / T 7437-2019 "Technical Requirements and Evaluation Methods for Corrosion Inhibitors for Natural Gas Gathering and Transportation". The results are shown in Table 2. The corrosion rate calculation formula is as follows:

[0133] Where: V is the uniform corrosion rate in millimeters per year (mm / a); m is the weight loss of the specimen in grams (g); s is the exposed area of ​​the specimen in square centimeters (cm 2 ); t—experimental time, in hours (h); ρ—relative density of the specimen, in grams per cubic centimeter (g / cm 3 ).

[0134] Table 2

[0135] As shown in Table 2, the corrosion rates of the bactericidal corrosion inhibitor and the bactericidal corrosion inhibitor composition prepared in the examples of the present invention after being placed at room temperature and at 150°C for 24 hours were both below 0.076 mm / a. Therefore, the bactericidal corrosion inhibitor and the bactericidal corrosion inhibitor composition prepared in the examples of the present invention have excellent corrosion inhibition performance, and their corrosion inhibition effect is not affected by high temperature placement, and they have excellent high-temperature stability.

[0136] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not limitations on the implementation methods of the present invention. For ordinary technicians in the relevant field, other different forms of changes or modifications can be made based on the above description. It is impossible to list all the implementation methods here. All obvious changes or modifications derived from the technical solution of the present invention are still within the scope of protection of the present invention.

Claims

1. A preparation method of a high-temperature resistant bactericidal and corrosion inhibitor, which comprises the following steps: (1) React a mercapto carboxylic acid compound and polyethyleneimine in an organic solvent at a first temperature for a first time to obtain a system containing a first compound; (2) Add a halogenated hydrocarbon to the system containing the first compound, react at a second temperature for a second time to obtain a system containing a second compound, and then remove and dry the organic solvent to obtain the high-temperature resistant bactericidal and corrosion inhibitor.

2. The preparation method according to claim 1, wherein The structural formula of the mercapto carboxylic acid compound is as shown in formula (I): In formula (I), n is a natural number from 1 to 20.

3. The preparation method according to claim 1, wherein, The structural formula of the polyethyleneimine is shown as formula (II): In formula (II), x and y are natural numbers from 1 to 100 respectively.

4. The preparation method according to claim 3, wherein, In formula (II), x and y are natural numbers from 1 to 20 respectively.

5. The preparation method according to claim 1, wherein, The organic solvent includes alcohol compounds.

6. The preparation method according to claim 1, wherein, The first temperature is 25°C to 100°C, and the first time is 5 to 24 h.

7. The preparation method according to claim 1, wherein, The structural formula of the halogenated hydrocarbon is shown in formula (III): RZ (III) In formula (III), R is selected from one of a straight-chain or branched-chain alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, a straight-chain or branched-chain alkenyl group with 2 to 10 carbon atoms, an alkylthio group with 1 to 10 carbon atoms, a cycloalkyl group with 3 to 10 carbon atoms, an aromatic ring-containing group with 6 to 20 carbon atoms, and an aromatic heterocyclic group with 5 to 20 carbon atoms, and Z is selected from one of chlorine, bromine, and iodine.

8. The preparation method according to claim 1, wherein, The second temperature is 50°C to 100°C, and the second time is 3 to 24 h.

9. The preparation method according to claim 1, wherein, The molar ratio of the polyethyleneimine, the mercapto carboxylic acid compound, and the halogenated hydrocarbon is (1 to 5):(5 to 50):(1 to 50).

10. A high-temperature resistant bactericidal and corrosion inhibitor, which is prepared by the preparation method of the high-temperature resistant bactericidal and corrosion inhibitor according to any one of claims 1-9.

11. The high-temperature resistant bactericidal corrosion inhibitor according to claim 10, wherein, The structural formula of the high-temperature resistant bactericidal corrosion inhibitor is shown in Formula (IV) as follows: In formula (IV), x and y are natural numbers from 1 to 100 respectively, n is a natural number from 1 to 20, R is selected from one of a straight-chain or branched-chain alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, a straight-chain or branched-chain alkenyl group with 2 to 10 carbon atoms, an alkylthio group with 1 to 10 carbon atoms, a cycloalkyl group with 3 to 10 carbon atoms, an aromatic ring-containing group with 6 to 20 carbon atoms, and an aromatic heterocyclic group with 5 to 20 carbon atoms, and Z is selected from one of chlorine, bromine, and iodine.

12. A high-temperature resistant bactericidal corrosion inhibitor composition, based on 100% of the total weight of the high-temperature resistant bactericidal corrosion inhibitor composition, comprises: 20% to 80% of the high-temperature resistant bactericidal and corrosion inhibitor according to claim 10 or 11, 5% to 80% of a solvent, and 0% to 15% of an auxiliary agent.

13. The high-temperature resistant bactericidal and corrosion inhibitor composition according to claim 12, wherein, Based on the total weight of the high-temperature resistant bactericidal and corrosion inhibitor composition being 100%, it includes: 30 to 80% of the high-temperature resistant bactericidal and corrosion inhibitor, 5% to 65% of a solvent, and 5% to 15% of an auxiliary agent.

14. The high-temperature resistant bactericidal and corrosion inhibitor composition according to claim 12, wherein, The solvent includes one or a combination of several of water, alcohol compounds, amide compounds, nitrile compounds, ketone compounds, ether compounds, and aromatic compounds.

15. The high-temperature resistant bactericidal and corrosion inhibitor composition according to claim 12, wherein, The auxiliary agent includes one or a combination of several of thiourea, thiazole, pyridine, piperidine, quinoline, derivatives of 1,3,5-triazine, tributyl phosphate, and mercaptan compounds.

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