A bactericide for water injection treatment and a method for preparing the same

Abstract

The present application relates to the technical field of industrial fungicide, in particular to a kind of bactericide for injection water treatment and preparation method thereof.The preparation method includes the following steps: 2,4-imidazoline diketone is reacted with 3-chloropropionaldehyde, and 5-chloropropenyl-2,4-imidazoline diketone is prepared;5-chloropropenyl-2,4-imidazoline diketone is reacted with 1,4-dibromobutane, and 3-bromobutyl-5-chloropropenyl-2,4-imidazoline diketone is prepared;2-(4-aminophenyl)-5-aminobenzimidazole is reacted with hydrochloric acid and cyanamide, and imidazole guanidine salt is prepared;3-bromobutyl-5-chloropropenyl-2,4-imidazoline diketone is reacted with imidazole guanidine salt, extract of phellodendri chinensis and extract of sophora flavescens, to obtain the bactericide for injection water treatment.The bactericide for injection water treatment not only has excellent bactericidal performance, can effectively inhibit and kill sulfate-reducing bacteria, saprophytic bacteria and iron bacteria, but also has good corrosion inhibition performance.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of industrial fungicides, in particular to a bactericide for water injection treatment and a preparation method thereof. BACKGROUND

[0002] In the process of oil exploitation, in order to ensure the high recovery rate of oil, water needs to be injected into the oil layer to supplement and maintain the pressure of the oil layer. However, in the oilfield water injection system, there are a large number of microorganisms in the oilfield wastewater, and the growth and reproduction of sulfate-reducing bacteria (SRB), saprophytic bacteria (TGB) and iron bacteria (IB) in the water injection system will cause corrosion of metal equipment. Adding bactericides can effectively inhibit the growth and reproduction of microorganisms and achieve the protection of the equipment.

[0003] Chinese patent CN115568480B discloses a plant-based composite bacteriostatic agent for oil fields, which includes double-metal nanoparticles and plant extracts. The active substances with reducing power in the plant extracts reduce the metal ions in the metal salt solution to make the metal ions become elemental metals in zero valence state. The plant-based composite bacteriostatic agent is obtained by reducing the solutions of silver ions and copper ions. The bacteriostatic effect only depends on the double-metal nanoparticles, the bacteriostatic components are single, the bacteriostatic performance is insufficient, and the corrosion inhibition performance of the bacteriostatic agent also needs to be improved. SUMMARY

[0004] In view of the deficiencies of the prior art, the present application provides a bactericide for water injection treatment to solve the problem that the bacteriostatic performance and corrosion inhibition performance of the bactericide for water injection treatment in the prior art need to be improved.

[0005] To achieve the above purpose, the technical scheme adopted by the present application is as follows:

[0006] A preparation method of a bactericide for water injection treatment, comprising the following steps:

[0007] Step (1), 2,4-imidazolidine (hydantoin) is added to deionized water, heated and stirred until dissolved, the pH value is adjusted to 6.5-7.5, ethanolamine is added, the temperature is raised to a first set temperature, 3-chloropropanal solution is added dropwise, after the dropwise addition is completed, the temperature is raised to a second set temperature, and then the reaction is carried out. After the reaction is completed, the mixture is cooled, filtered, washed, and dried to obtain 5-chloropropenyl-2,4-imidazolidine;

[0008] Step (2), potassium carbonate is added to acetone, ultrasonic dispersion is carried out, then 5-chloropropenyl-2,4-imidazolidine is added, and the reaction is carried out. After the reaction is completed, 1,4-dibromobutane is added dropwise, and the reaction is continued after the dropwise addition is completed. After the reaction is completed, the mixture is filtered, rotary evaporated, and purified to obtain 3-bromobutyl-5-chloropropenyl-2,4-imidazolidine;

[0009] Step (3), dissolving the aminocyanide in ethanol to obtain an aminocyanide solution;

[0010] adding 2-(4-aminophenyl)-5-amino benzimidazole into ethanol, stirring, adding hydrochloric acid solution dropwise, after the dropwise addition is completed, increasing the temperature to a set temperature, adding the aminocyanide solution dropwise, after the dropwise addition is completed, reacting, after the reaction is completed, cooling, precipitating, purifying, to obtain imidazole guanidine salt;

[0011] mixing the imidazole guanidine salt, the cortex phellodendri extract, the sophora flavescens extract, and 3-bromobutyl-5-chloropropenyl-2,4-imidazoline diketone, reacting, after the reaction is completed, rotary evaporation, to obtain a bactericide for water injection treatment.

[0012] Preferably, in the step (1), the mass ratio of 2,4-imidazoline diketone, deionized water, ethanolamine, and 3-chloropropanal solution is 10:(400-600):(10-12):(65-67.5), the heating and stirring condition is heating and stirring at a temperature of 65-75℃ and a speed of 150-250r / min, the first set temperature is 80-100℃, the dropwise addition time of 3-chloropropanal solution is 30-60min, and the reaction condition is refluxing reaction at a second set temperature for 10-15h, and the second set temperature is 110-130℃.

[0013] The 3-chloropropanal solution is prepared by 3-chloropropanal and ethanol, and the mass percentage of 3-chloropropanal in the 3-chloropropanal solution is 15%.

[0014] Preferably, in the step (2), the mass ratio of 5-chloropropenyl-2,4-imidazoline diketone, 1,4-dibromobutane, potassium carbonate, and acetone is 18:(39-47):(45-55):(900-1100), the ultrasonic dispersion condition is ultrasonic dispersion at a frequency of 50kHz for 30min, the reaction condition is refluxing reaction at a temperature of 60-80℃ for 40-80min, the dropwise addition time of 1,4-dibromobutane is 20-40min, and the continued reaction condition is refluxing reaction at a temperature of 60-80℃ for 3-5h.

[0015] Preferably, in the step (3), the molar ratio of 2-(4-aminophenyl)-5-amino benzimidazole, hydrogen chloride in hydrochloric acid solution, and aminocyanide is 1:1:(1.1-1.2), the mass of ethanol is 50-60 times of the mass of 2-(4-aminophenyl)-5-amino benzimidazole, the mass percentage of aminocyanide in the aminocyanide solution is 30%-50%, the dropwise addition time of the aminocyanide solution is 40-60min, the reaction condition is controlling the pH value of the reaction system between 2 and 3 and reacting at a set temperature for 4-6h, the set temperature is 80-90℃, and the hydrochloric acid solution includes 30wt% hydrochloric acid solution.

[0016] Preferably, in the step (3), the mass ratio of the imidazole guanidine salt, the cortex phellodendri extract, the sophora flavescens extract, and 3-bromobutyl-5-chloropropenyl-2,4-imidazoline diketone is (10-20):(300-500):(250-350):(50-70), and the reaction condition is that the reaction is carried out at 55-65 DEG C for 2-4 h.

[0017] Preferably, the cortex phellodendri extract in the step (3) is prepared by the following steps:

[0018] The cortex phellodendri is crushed, added into an ethanol aqueous solution, and extracted by heating reflux, and after the extraction is completed, the filtrate is obtained by filtration to obtain the cortex phellodendri extract.

[0019] The mass ratio of the cortex phellodendri and the ethanol aqueous solution is 1:(8-12), and the heating reflux extraction condition is that the reflux extraction is carried out at 60-80 DEG C for 6-10 h.

[0020] The ethanol aqueous solution comprises 75wt% ethanol aqueous solution.

[0021] Preferably, the sophora flavescens extract in the step (3) is prepared by the following steps:

[0022] The sophora flavescens is crushed, added into an ethanol aqueous solution, and extracted by heating reflux, and after the extraction is completed, the filtrate is obtained by filtration to obtain the sophora flavescens extract.

[0023] The mass ratio of the sophora flavescens and the ethanol aqueous solution is 1:(8-12), and the heating reflux extraction condition is that the reflux extraction is carried out at 60-70 DEG C for 3-5 h.

[0024] The mass percentage content of ethanol in the ethanol aqueous solution is 50%-70%.

[0025] The application further discloses a bactericide for water injection treatment prepared by the preparation method.

[0026] Compared with the prior art, the application has the beneficial effects that:

[0027] The bactericidal component in the application comprises a plant source bactericidal component and an imidazole compound, and has an effective inhibiting effect on microorganisms; the plant source bactericidal component comprises a cortex phellodendri extract and a sophora flavescens extract, the cortex phellodendri extract contains various alkaloids such as phellodendrine and magnoflorine, has excellent bactericidal efficacy, the sophora flavescens extract contains sophoramine, and also has excellent bactericidal efficacy; hydantoin as one of the imidazole compounds has good bactericidal performance; in addition, the heteroatoms in the hydantoin ring contain multiple lone pair electrons, can be combined with the empty d orbitals of metals to form coordination bonds, can be adsorbed on the surface of metals to form a dense adsorption film, and further improve the activation energy of the corrosion reaction, so that the corrosion rate is reduced, and has corrosion inhibition effect; 2-(4-aminophenyl)-5-aminobenzimidazole as one of the imidazole compounds also has good bactericidal performance; 2-(4-aminophenyl)-5-aminobenzimidazole reacts with hydrochloric acid and cyanamide through the two aminos on the sides to generate imidazole guanidine salt, which can effectively improve the bactericidal performance;

[0028] The molecular structure of hydantoin has the characteristics of keto-enol tautomerism, and in an alkaline environment, an aldol condensation reaction occurs with the aldehyde group on the 3-chloropropanal molecule to generate an unsaturated substituted product 5-chloropropenyl-2,4-imidazolidine, and chlorine elements are introduced into the hydantoin molecule; further, a substitution reaction occurs between the active N-H bond at the 3 position of the 5-chloropropenyl-2,4-imidazolidine molecule and 1,4-dibromobutane to generate 3-bromobutyl-5-chloropropenyl-2,4-imidazolidine, and bromine elements are introduced into the hydantoin molecule; the chlorine elements and bromine elements on the 3-bromobutyl-5-chloropropenyl-2,4-imidazolidine molecule can form quaternary ammonium salt with the tertiary amine groups on the phellodendrine, sophoramine and imidazole guanidine salt molecules, further improving the bactericidal performance; at the same time, since the generated quaternary ammonium salt is cationic, and the solid surface in the water medium is generally negatively charged, the positively charged quaternary ammonium salt can be adsorbed on the surface of the solid equipment, enhancing the corrosion inhibition performance, and the introduction of the alkyl chain into the hydantoin molecule can form a hydrophobic film on the metal surface, further improving the corrosion inhibition performance. BRIEF DESCRIPTION OF DRAWINGS

[0029] Figure 1 The preparation process flow chart of the bactericide for water injection treatment in the application;

[0030] Figure 2 The bactericidal performance test result column chart of the bactericide for water injection treatment prepared in the examples 1-5 and the comparative examples 1-2 of the application;

[0031] Figure 3 The corrosion inhibition performance test result column chart of the bactericide for water injection treatment prepared in the examples 1-5 and the comparative examples 1-2 of the application. DETAILED DESCRIPTION Example 1

[0032] The embodiment discloses a preparation method of a bactericide for water injection treatment.

[0033] Step (1), 2,4-imidazolidine is added into deionized water, heating and stirring are carried out at a temperature of 65 DEG C and a speed of 250 r / min until 2,4-imidazolidine is dissolved, a saturated NaHCO3 aqueous solution is added to adjust the pH value to 6.5, ethanolamine is added, the temperature is raised to 80 DEG C, and 3-chloropropyl aldehyde solution is added dropwise, the mass ratio of 2,4-imidazolidine, deionized water, ethanolamine and 3-chloropropyl aldehyde solution is 10:400:10:65, the dropwise adding time of 3-chloropropyl aldehyde solution is 30 min, after the dropwise adding is completed, the temperature is raised to 110 DEG C, reflux reaction is carried out at the temperature of 110 DEG C for 15 h, after the reaction is completed, the temperature is cooled to 0 DEG C, the cooling precipitate is obtained by filtration, the cooling precipitate is washed with 20 wt% ethanol aqueous solution, and drying is carried out at 50 DEG C and-0.09 MPa for 12 h to obtain 5-chloropropenyl-2,4-imidazolidine;

[0034] In the preparation method, the 3-chloropropyl aldehyde solution is prepared from 3-chloropropyl aldehyde and ethanol, and the mass percentage of 3-chloropropyl aldehyde in the 3-chloropropyl aldehyde solution is 15%.

[0035] Step (2), potassium carbonate is added into acetone and ultrasonic dispersion is carried out at a frequency of 50 kHz for 30 min, then 5-chloropropenyl-2,4-imidazolidine is added, reflux reaction is carried out at a temperature of 60 DEG C for 80 min, after the reaction is completed, 1,4-dibromobutane is added dropwise, the mass ratio of 5-chloropropenyl-2,4-imidazolidine, 1,4-dibromobutane, potassium carbonate and acetone is 18:39:45:900, the dropwise adding time of 1,4-dibromobutane is 20 min, after the dropwise adding is completed, reflux reaction is carried out at the temperature of 60 DEG C for 5 h, after the reaction is completed, filtration is carried out, the solvent acetone in the filtrate is removed by rotary evaporation at a temperature of 40 DEG C, the residual part is separated by column chromatography, the eluent is prepared by mixing petroleum ether and ethyl acetate at a volume ratio of 2:1, and rotary evaporation is carried out at a temperature of 50 DEG C to obtain 3-bromobutyl-5-chloropropenyl-2,4-imidazolidine;

[0036] Step (3), cyanamide is dissolved in ethanol to obtain a cyanamide solution, and the mass percentage of cyanamide in the cyanamide solution is 30%.

[0037] 2-(4-aminophenyl)-5-aminobenzimidazole is added into ethanol, the mass of ethanol is 50 times of the mass of 2-(4-aminophenyl)-5-aminobenzimidazole, after stirring at room temperature for 30 min at a speed of 300 r / min, 30 wt% hydrochloric acid solution is added dropwise, white insoluble substances are precipitated, after the dropwise addition is completed, the temperature is increased to 80℃, cyanamide solution is added dropwise, the molar ratio of 2-(4-aminophenyl)-5-aminobenzimidazole, hydrogen chloride in the hydrochloric acid solution and cyanamide is 1:1:1.1, the dropwise addition of the cyanamide solution lasts for 40 min, after the dropwise addition is completed, the pH value of the reaction system is controlled to be between 2 and 3, and the reaction is refluxed at 80℃ for 6 h, after the reaction is completed, the temperature is cooled to room temperature, diethyl ether is added for precipitation until the precipitate no longer increases, filtration is performed, the precipitate is dissolved in methanol, and then re-precipitation is performed, the process of dissolution-precipitation is repeated for 3 times, and the precipitate after purification is placed in a 50℃ vacuum drying box for drying for 12 h to obtain imidazole guanidine salt;

[0038] The imidazole guanidine salt, the cortex phellodendri extract, the sophora flavescens extract and 3-bromobutyl-5-chloropropenyl-2,4-imidazoline diketone are mixed, the mass ratio of the imidazole guanidine salt, the cortex phellodendri extract, the sophora flavescens extract and 3-bromobutyl-5-chloropropenyl-2,4-imidazoline diketone is 10:300:250:50, and the reaction is performed at 55℃ for 4 h, after the reaction is completed, diethyl alcohol is removed by rotary evaporation at 50℃ to obtain the bactericide for water injection treatment;

[0039] The cortex phellodendri extract is prepared by the following steps:

[0040] The cortex phellodendri extract is prepared by the following steps:

[0041] The sophora flavescens extract is prepared by the following steps:

[0042] The sophora flavescens extract is prepared by the following steps:

[0043] The mass percentage content of ethanol in the ethanol aqueous solution is 60%. Example 2

[0044] The embodiment discloses a preparation method of a bactericide for water injection treatment, and the method comprises the following steps:

[0045] Step (1), 2, 4-imidazolidine dione is added into deionized water, heated and stirred at a temperature of 75 DEG C and a speed of 150 r / min until dissolved, saturated NaHCO3 aqueous solution is added to adjust the pH value to 7.5, ethanolamine is added, the temperature is raised to 100 DEG C, 3-chloropropanal solution is added dropwise, the mass ratio of 2, 4-imidazolidine dione, deionized water, ethanolamine and 3-chloropropanal solution is 10:600:12:67.5, the dropwise adding time of 3-chloropropanal solution is 60 min, after the dropwise adding is completed, the temperature is raised to 130 DEG C, refluxing reaction is carried out at 130 DEG C for 10 h, after the reaction is completed, the temperature is cooled to 0 DEG C, the cooling precipitate is filtered, the cooling precipitate is washed with 20 wt% ethanol aqueous solution, drying is carried out at 50 DEG C and -0.09 MPa for 12 h, 5-chloropropenyl-2, 4-imidazolidine dione is obtained;

[0046] In the formula, the 3-chloropropanal solution is prepared by 3-chloropropanal and ethanol, the mass percentage of 3-chloropropanal in the 3-chloropropanal solution is 15%;

[0047] Step (2), potassium carbonate is added into acetone, ultrasonic dispersion is carried out at a frequency of 50 kHz for 30 min, then 5-chloropropenyl-2, 4-imidazolidine dione is added, refluxing reaction is carried out at a temperature of 80 DEG C for 40 min, after the reaction is completed, 1, 4-dibromobutane is added dropwise, the mass ratio of 5-chloropropenyl-2, 4-imidazolidine dione, 1, 4-dibromobutane, potassium carbonate and acetone is 18:47:55:1100, the dropwise adding time of 1, 4-dibromobutane is 40 min, after the dropwise adding is completed, refluxing reaction is carried out at a temperature of 80 DEG C for 3 h, after the reaction is completed, filtration is carried out, the filtrate is rotary evaporated to remove the solvent acetone at a temperature of 40 DEG C, the residual part is separated by column chromatography, the eluent is prepared by petroleum ether and ethyl acetate in a volume ratio of 2:1, rotary evaporation is carried out at a temperature of 50 DEG C, 3-bromobutyl-5-chloropropenyl-2, 4-imidazolidine dione is obtained;

[0048] Step (3), amino cyan is dissolved in ethanol to obtain an amino cyan solution, the mass percentage of amino cyan in the amino cyan solution is 50%;

[0049] The 2-(4-aminophenyl)-5-aminobenzimidazole is added into ethanol, the mass of the ethanol is 60 times of the mass of the 2-(4-aminophenyl)-5-aminobenzimidazole, after stirring at room temperature and at a speed of 300 r / min for 30 min, a 30 wt% hydrochloric acid solution is added dropwise, white insoluble substances are precipitated, after the addition is completed, the temperature is raised to 90℃, an amino cyanide solution is added dropwise, the molar ratio of the 2-(4-aminophenyl)-5-aminobenzimidazole, hydrogen chloride in the hydrochloric acid solution and the amino cyanide is 1:1:1.2, the amino cyanide solution is added dropwise for 60 min, after the addition is completed, the pH value of the reaction system is controlled to be between 2 and 3, and the reaction is refluxed at 90℃ for 4 h, after the reaction is completed, the temperature is cooled to room temperature, diethyl ether is added for precipitation until the precipitate no longer increases, filtration is performed, the precipitate is dissolved in methanol, and then re-precipitated, the process of dissolution-precipitation is repeated for 3 times, and the precipitate after purification is placed in a 50℃ vacuum drying box for drying for 12 h to obtain the imidazole guanidine salt;

[0050] The imidazole guanidine salt, the cortex phellodendri extract, the sophora flavescens extract and the 3-bromobutyl-5-chloropropenyl-2,4-imidazoline diketone are mixed, the mass ratio of the imidazole guanidine salt, the cortex phellodendri extract, the sophora flavescens extract and the 3-bromobutyl-5-chloropropenyl-2,4-imidazoline diketone is 20:500:350:70, the reaction is performed at 65℃ for 2 h, after the reaction is completed, ethanol is removed by rotary evaporation at 50℃ to obtain the bactericide for water injection treatment;

[0051] The preparation method of the cortex phellodendri extract and the sophora flavescens extract is the same as that in Embodiment 1. Embodiment 3

[0052] The embodiment discloses a preparation method of a bactericide for water injection treatment, and the method comprises the following steps:

[0053] In step (1), the 2,4-imidazoline diketone is added into deionized water, heating and stirring are performed at 70℃ and at a speed of 200 r / min until the 2,4-imidazoline diketone is dissolved, the pH value is adjusted to 7 by adding a saturated NaHCO3 aqueous solution, ethanolamine is added, the temperature is raised to 90℃, and a 3-chloropropanal solution is added dropwise, the mass ratio of the 2,4-imidazoline diketone, the deionized water, the ethanolamine and the 3-chloropropanal solution is 10:450:10.5:65.5, the 3-chloropropanal solution is added dropwise for 45 min, after the addition is completed, the temperature is raised to 120℃, the reaction is refluxed at 120℃ for 12 h, after the reaction is completed, the temperature is cooled to 0℃, the cooled precipitate is filtered, the cooled precipitate is washed with a 20 wt% ethanol aqueous solution, and the cooled precipitate is dried at 50℃ and under a pressure of -0.09 MPa for 12 h to obtain the 5-chloropropenyl-2,4-imidazoline diketone.

[0054] The 3-chloropropanal solution is prepared by mixing 3-chloropropanal and ethanol, and the mass percentage content of the 3-chloropropanal in the 3-chloropropanal solution is 15%.

[0055] Step (2), potassium carbonate was added into acetone, and was ultrasonically dispersed for 30 min at a frequency of 50 kHz. Then, 5-chloropropenyl-2,4-imidazolidine diketone was added, and was reacted at a temperature of 70°C for 60 min. After the reaction was completed, 1,4-dibromobutane was added dropwise. The mass ratio of 5-chloropropenyl-2,4-imidazolidine diketone, 1,4-dibromobutane, potassium carbonate, and acetone was 18:41:48:950. The 1,4-dibromobutane was added dropwise for 30 min. After the addition was completed, the reaction was carried out at a temperature of 70°C for 4 h. After the reaction was completed, filtration was performed. The filtrate was subjected to rotary evaporation to remove the solvent acetone at a temperature of 40°C. The residual part was separated by column chromatography. The eluent was petroleum ether and ethyl acetate prepared by mixing at a volume ratio of 2:1. Rotary evaporation was performed at a temperature of 50°C to obtain 3-bromobutyl-5-chloropropenyl-2,4-imidazolidine diketone.

[0056] Step (3), cyanamide was dissolved in ethanol to obtain a cyanamide solution. The mass percentage content of cyanamide in the cyanamide solution was 40%.

[0057] 2-(4-aminophenyl)-5-aminobenzimidazole was added into ethanol. The mass of ethanol was 55 times the mass of 2-(4-aminophenyl)-5-aminobenzimidazole. After stirring at room temperature and at a speed of 300 r / min for 30 min, a 30 wt% hydrochloric acid solution was added dropwise, and white insoluble substances were precipitated. After the addition was completed, the temperature was increased to 85°C, and the cyanamide solution was added dropwise. The molar ratio of 2-(4-aminophenyl)-5-aminobenzimidazole, hydrogen chloride in the hydrochloric acid solution, and cyanamide was 1:1:1.12. The cyanamide solution was added dropwise for 50 min. After the addition was completed, the pH value of the reaction system was controlled to be between 2 and 3, and the reaction was carried out at a temperature of 85°C for 5 h. After the reaction was completed, the reaction system was cooled to room temperature, and diethyl ether was added for precipitation until no more precipitate was formed. Filtration was performed. The precipitate was dissolved in methanol, and was precipitated again. The process of dissolution-precipitation was repeated for 3 times. The precipitate after purification was placed in a vacuum drying box at a temperature of 50°C for drying for 12 h to obtain imidazole guanidine salt.

[0058] The imidazole guanidine salt, the extract of cortex phellodendri, the extract of sophora flavescens, and 3-bromobutyl-5-chloropropenyl-2,4-imidazolidine diketone were mixed. The mass ratio of the imidazole guanidine salt, the extract of cortex phellodendri, the extract of sophora flavescens, and 3-bromobutyl-5-chloropropenyl-2,4-imidazolidine diketone was 12:350:275:55. The mixture was reacted at a temperature of 60°C for 3 h. After the reaction was completed, ethanol was removed by rotary evaporation at a temperature of 50°C to obtain a bactericide for water injection treatment.

[0059] The preparation methods of the extract of cortex phellodendri and the extract of sophora flavescens were the same as those in Embodiment 1. Embodiment 4

[0060] The embodiment discloses a preparation method of a bactericide for water injection treatment.

[0061] Step (1), 2,4-imidazolidine dione was added into deionized water, heated and stirred at a temperature of 70°C and a speed of 200 r / min until dissolved, pH value was adjusted to 7 by adding saturated NaHCO3 aqueous solution, ethanolamine was added, the temperature was raised to 90°C, 3-chloropropanal solution was added dropwise, the mass ratio of 2,4-imidazolidine dione, deionized water, ethanolamine and 3-chloropropanal solution was 10:500:11:66, the dropwise adding time of 3-chloropropanal solution was 45 min, after the dropwise adding was completed, the temperature was raised to 120°C, and reflux reaction was carried out at 120°C for 12 h, after the reaction was completed, the temperature was cooled to 0°C, the cooling precipitate was filtered, the cooling precipitate was washed with 20 wt% ethanol aqueous solution, and drying was carried out at 50°C and -0.09 MPa for 12 h to obtain 5-chloropropenyl-2,4-imidazolidine dione;

[0062] In the formula, the 3-chloropropanal solution is prepared by 3-chloropropanal and ethanol, and the mass percentage content of 3-chloropropanal in the 3-chloropropanal solution is 15%;

[0063] Step (2), potassium carbonate was added into acetone and ultrasonic dispersion was carried out at a frequency of 50 kHz for 30 min, then 5-chloropropenyl-2,4-imidazolidine dione was added, reflux reaction was carried out at a temperature of 70°C for 60 min, after the reaction was completed, 1,4-dibromobutane was added dropwise, the mass ratio of 5-chloropropenyl-2,4-imidazolidine dione, 1,4-dibromobutane, potassium carbonate and acetone was 18:43:50:1000, the dropwise adding time of 1,4-dibromobutane was 30 min, after the dropwise adding was completed, reflux reaction was carried out at a temperature of 70°C for 4 h, after the reaction was completed, filtration was carried out, the solvent acetone in the filtrate was removed by rotary evaporation at a temperature of 40°C, and the residual part was separated by column chromatography, the eluent was prepared by mixing petroleum ether and ethyl acetate at a volume ratio of 2:1, and rotary evaporation was carried out at a temperature of 50°C to obtain 3-bromobutyl-5-chloropropenyl-2,4-imidazolidine dione;

[0064] Step (3), amino cyan was dissolved in ethanol to obtain an amino cyan solution, and the mass percentage content of amino cyan in the amino cyan solution was 40%;

[0065] The 2-(4-aminophenyl)-5-aminobenzimidazole is added into ethanol, the mass of the ethanol is 55 times of the mass of the 2-(4-aminophenyl)-5-aminobenzimidazole, after stirring at room temperature and at a speed of 300 r / min for 30 min, a 30 wt% hydrochloric acid solution is added dropwise, white insoluble substances are precipitated, after the addition is completed, the temperature is raised to 85℃, an amino cyanide solution is added dropwise, the molar ratio of the 2-(4-aminophenyl)-5-aminobenzimidazole, hydrogen chloride in the hydrochloric acid solution and the amino cyanide is 1:1:1.15, the amino cyanide solution is added dropwise for 50 min, after the addition is completed, the pH value of the reaction system is controlled to be between 2 and 3, and the reaction is refluxed at 85℃ for 5 h, after the reaction is completed, the temperature is cooled to room temperature, diethyl ether is added for precipitation until the precipitate no longer increases, filtration is performed, the precipitate is dissolved in methanol, and then re-precipitated, the process of dissolution-precipitation is repeated for 3 times, and the precipitate after purification is placed in a 50℃ vacuum drying box for drying for 12 h to obtain the imidazole guanidine salt;

[0066] The imidazole guanidine salt, the cortex phellodendri extract, the sophora flavescens extract and the 3-bromobutyl-5-chloropropenyl-2,4-imidazoline diketone are mixed, the mass ratio of the imidazole guanidine salt, the cortex phellodendri extract, the sophora flavescens extract and the 3-bromobutyl-5-chloropropenyl-2,4-imidazoline diketone is 15:400:300:60, the reaction is performed at 60℃ for 3 h, after the reaction is completed, diethyl alcohol is removed by rotary evaporation at 50℃ to obtain the bactericide for water injection treatment;

[0067] The preparation method of the cortex phellodendri extract and the sophora flavescens extract is the same as that in Embodiment 1. Embodiment 5

[0068] The embodiment discloses a preparation method of a bactericide for water injection treatment, and the method comprises the following steps:

[0069] Step (1), 2,4-imidazoline diketone is added into deionized water, heating and stirring is performed at 70℃ and at a speed of 200 r / min until the 2,4-imidazoline diketone is dissolved, saturated NaHCO3 aqueous solution is added to adjust the pH value to 7, ethanolamine is added, the temperature is raised to 90℃, and 3-chloropropanal solution is added dropwise, the mass ratio of the 2,4-imidazoline diketone, the deionized water, the ethanolamine and the 3-chloropropanal solution is 10:550:11.5:67, the 3-chloropropanal solution is added dropwise for 45 min, after the addition is completed, the temperature is raised to 120℃, the reaction is refluxed at 120℃ for 12 h, after the reaction is completed, the temperature is cooled to 0℃, the cooled precipitate is filtered, the cooled precipitate is washed with 20 wt% ethanol aqueous solution, and the cooled precipitate is dried at 50℃ and under a pressure of -0.09 MPa for 12 h to obtain 5-chloropropenyl-2,4-imidazoline diketone;

[0070] The 3-chloropropanal solution is prepared by mixing 3-chloropropanal and ethanol, and the mass percentage content of the 3-chloropropanal in the 3-chloropropanal solution is 15%;

[0071] Step (2), potassium carbonate was added into acetone, and was ultrasonically dispersed for 30 min at a frequency of 50 kHz. Then, 5-chloropropenyl-2,4-imidazolidine was added, and was refluxed at a temperature of 70 °C for 60 min. After the reaction was completed, 1,4-dibromobutane was added dropwise. The mass ratio of 5-chloropropenyl-2,4-imidazolidine, 1,4-dibromobutane, potassium carbonate, and acetone was 18:45:52:1050. The 1,4-dibromobutane was added dropwise for 30 min. After the addition was completed, the reaction was carried out at a temperature of 70 °C for 4 h. After the reaction was completed, filtration was carried out. The filtrate was rotary evaporated at a temperature of 40 °C to remove the solvent acetone. The residual part was separated by column chromatography. The eluent was petroleum ether and ethyl acetate prepared by mixing at a volume ratio of 2:1. The rotary evaporation was carried out at a temperature of 50 °C. 3-Bromobutyl-5-chloropropenyl-2,4-imidazolidine was obtained.

[0072] Step (3), cyanamide was dissolved in ethanol to obtain a cyanamide solution. The mass percentage of cyanamide in the cyanamide solution was 40%.

[0073] 2-(4-aminophenyl)-5-aminobenzimidazole was added into ethanol. The mass of ethanol was 55 times the mass of 2-(4-aminophenyl)-5-aminobenzimidazole. After stirring at room temperature at a speed of 300 r / min for 30 min, 30 wt% hydrochloric acid solution was added dropwise. White insoluble substances were precipitated. After the addition was completed, the temperature was increased to 85 °C. The cyanamide solution was added dropwise. The molar ratio of 2-(4-aminophenyl)-5-aminobenzimidazole, hydrogen chloride in the hydrochloric acid solution, and cyanamide was 1:1:1.18. The cyanamide solution was added dropwise for 50 min. After the addition was completed, the pH value of the reaction system was controlled to be between 2 and 3. The reaction was carried out at a temperature of 85 °C for 5 h. After the reaction was completed, the reaction system was cooled to room temperature. Ethyl ether was added for precipitation until no more precipitate was formed. Filtration was carried out. The precipitate was dissolved in methanol. The process of dissolution-precipitation was repeated for 3 times. The precipitate after purification was placed in a vacuum drying box at a temperature of 50 °C for drying for 12 h. Imidazole guanidine salt was obtained.

[0074] Imidazole guanidine salt, Cortex Phellodendri extract, Sophora flavescens extract, and 3-bromobutyl-5-chloropropenyl-2,4-imidazolidine were mixed. The mass ratio of imidazole guanidine salt, Cortex Phellodendri extract, Sophora flavescens extract, and 3-bromobutyl-5-chloropropenyl-2,4-imidazolidine was 18:450:330:65. The reaction was carried out at a temperature of 60 °C for 3 h. After the reaction was completed, ethanol was removed by rotary evaporation at a temperature of 50 °C. A bactericide for water injection treatment was obtained.

[0075] The preparation methods of Cortex Phellodendri extract and Sophora flavescens extract were the same as those in Example 1.

[0076] Comparative Example 1

[0077] The present comparative example discloses a preparation method of a bactericide for water injection treatment, comprising the following steps:

[0078] Step (1), 2,4-imidazolidine is added into deionized water, heated and stirred at a temperature of 65℃ and a speed of 250r / min until dissolved, pH value is adjusted to 6.5 by adding saturated NaHCO3 aqueous solution, ethanolamine is added, the temperature is raised to 80℃, 3-chloropropyl aldehyde solution is added dropwise, the mass ratio of 2,4-imidazolidine, deionized water, ethanolamine and 3-chloropropyl aldehyde solution is 10:400:10:65, the dropwise adding time of 3-chloropropyl aldehyde solution is 30min, after the dropwise adding is completed, the temperature is raised to 110℃, reflux reaction is carried out at 110℃ for 15h, after the reaction is completed, the temperature is cooled to 0℃, the cooled precipitate is obtained by filtration, the cooled precipitate is washed with 20wt% ethanol aqueous solution, dried at 50℃ and-0.09MPa for 12h, 5-chloropropenyl-2,4-imidazolidine is obtained;

[0079] In the 3-chloropropyl aldehyde solution, 3-chloropropyl aldehyde is prepared by 3-chloropropyl aldehyde and ethanol, the mass percentage of 3-chloropropyl aldehyde in the 3-chloropropyl aldehyde solution is 15%;

[0080] Step (2), cyanamide is dissolved in ethanol to obtain cyanamide solution, the mass percentage of cyanamide in the cyanamide solution is 30%;

[0081] 2-(4-aminophenyl)-5-aminobenzimidazole is added into ethanol, the mass of ethanol is 50 times of the mass of 2-(4-aminophenyl)-5-aminobenzimidazole, after stirring at room temperature and a speed of 300r / min for 30min, 30wt% hydrochloric acid solution is added dropwise, white insoluble substances are precipitated, after the dropwise adding is completed, the temperature is raised to 80℃, cyanamide solution is added dropwise, the molar ratio of 2-(4-aminophenyl)-5-aminobenzimidazole, hydrogen chloride in the hydrochloric acid solution and cyanamide is 1:1:1.1, the dropwise adding time of the cyanamide solution is 40min, after the dropwise adding is completed, the pH value of the reaction system is controlled between 2-3, reflux reaction is carried out at 80℃ for 6h, after the reaction is completed, the temperature is cooled to room temperature, ether is added for precipitation until the precipitate no longer increases, filtration is carried out, the precipitate is dissolved in methanol, then precipitated again, the process of dissolution-precipitation is repeated for 3 times, the precipitate after purification is dried in a 50℃ vacuum drying oven for 12h, imidazole guanidine salt is obtained;

[0082] imidazole guanidine salt, cortex phellodendri extract, sophora flavescens extract and 5-chloropropenyl-2,4-imidazolidine are mixed, the mass ratio of imidazole guanidine salt, cortex phellodendri extract, sophora flavescens extract and 5-chloropropenyl-2,4-imidazolidine is 10:300:250:28.3, reaction is carried out at a temperature of 55℃ for 4h, after the reaction is completed, ethanol is removed by rotary evaporation at a temperature of 50℃, a bactericide for water injection treatment is obtained;

[0083] The preparation method of the extract of Cortex Phellodendri and the extract of Sophora flavescens in the present embodiment is the same as that in Embodiment 1.

[0084] Comparative Example 2

[0085] The present comparative example discloses a preparation method of a bactericide for water injection treatment, comprising the following steps:

[0086] Step (1), dissolving aminocyanide in ethanol to obtain an aminocyanide solution, the mass percentage of aminocyanide in the aminocyanide solution is 30%;

[0087] 2-(4-aminophenyl)-5-aminobenzimidazole was added into ethanol, the mass of ethanol was 50 times that of 2-(4-aminophenyl)-5-aminobenzimidazole, after stirring at room temperature and a speed of 300 r / min for 30 min, 30 wt% hydrochloric acid solution was added dropwise, white insoluble substances were precipitated, after the addition was completed, the temperature was raised to 80℃, and the aminocyanide solution was added dropwise, the molar ratio of 2-(4-aminophenyl)-5-aminobenzimidazole, hydrogen chloride in the hydrochloric acid solution and aminocyanide was 1:1:1.1, the dropwise addition time of the aminocyanide solution was 40 min, after the dropwise addition was completed, the pH value of the reaction system was controlled between 2-3, and the reaction was carried out at 80℃ under reflux for 6 h, after the reaction was completed, the temperature was cooled to room temperature, diethyl ether was added for precipitation until no more precipitate was formed, filtration was performed, the precipitate was dissolved in methanol, and the process of dissolution-precipitation was repeated for 3 times, the precipitate after purification was placed in a 50℃ vacuum drying oven for drying for 12 h, and imidazole guanidine salt was obtained;

[0088] Step (2), mixing imidazole guanidine salt, the extract of Cortex Phellodendri, the extract of Sophora flavescens and 2,4-imidazolidine, the mass ratio of imidazole guanidine salt, the extract of Cortex Phellodendri, the extract of Sophora flavescens and 2,4-imidazolidine was 10:300:250:16.4, and the mixture was incubated at 55℃ for 4 h, after the reaction was completed, ethanol was removed by rotary evaporation at 50℃, and a bactericide for water injection treatment was obtained;

[0089] The preparation method of the extract of Cortex Phellodendri and the extract of Sophora flavescens in the present embodiment is the same as that in Embodiment 1.

[0090] In the above embodiments and comparative examples, 2,4-imidazolidine was purchased from Wuhan Kemik Biomedicine Technology Co., Ltd., CAS No.: 61-72-3; 3-chloropropanal was purchased from Hubei Qifei Pharmaceutical Chemical Co., Ltd., CAS No.: 19434-65-2; 1,4-dibromobutane was purchased from Shanghai Yihexun Biotechnology Co., Ltd., CAS No.: 110-52-1; 2-(4-aminophenyl)-5-aminobenzimidazole was purchased from Hubei Xinyuhong Biomedicine Technology Co., Ltd., product number: xyh001, CAS No.: 7621-86-5; aminocyanide was purchased from Shanghai Sirena Chemical Technology Co., Ltd., CAS No.: 420-04-2; Cortex Phellodendri and Sophora flavescens were purchased from Anhui Kangweifu Pharmaceutical Co., Ltd.

[0091] Test Example

[0092] The bactericides for water injection treatment prepared in Examples 1-5 and Comparative Examples 1-2 were subjected to performance tests:

[0093] (1) Bactericidal performance: The bactericidal performance of the bactericides for water injection treatment prepared in Examples 1-5 and Comparative Examples 1-2 was determined according to the standard SY / T5757-2010 "General technical conditions for oilfield injection water bactericides". The injection water from an oilfield was taken, and the initial bacterial number of sulfate-reducing bacteria, saprophytic bacteria and iron bacteria in the water sample was 8.1 x 10 6 , 9.2 x 10 6 and 5.1 x 10 7 , respectively. The bactericides were added at an effective dosage of 20 mg / L, and incubated at 65±5℃. The sulfate-reducing bacteria were incubated for 14 days, and the saprophytic bacteria and iron bacteria were incubated for 7 days. The total number of bacteria was determined and recorded, and the bactericidal rate was calculated. The results of the bactericidal rate determination are shown in Table 1:

[0094] Table 1

[0095]

[0096] As shown in Table 1, the bactericides prepared in the present application have good bactericidal effect, and can effectively inhibit and kill sulfate-reducing bacteria, saprophytic bacteria and iron bacteria. Compared with Example 1, in Comparative Example 1, 5-chloropropenyl-2,4-imidazoline dione was not further reacted with 1,4-dibromobutane to introduce bromine element, and the quaternary ammonium salt formed by the reaction of the tertiary amine group contained in other bactericidal components was reduced, and the bactericidal performance was decreased. Compared with Comparative Example 1, in Comparative Example 2, 2,4-imidazoline dione was not reacted with 3-chloropropyl aldehyde to introduce chlorine element, and could not react with the tertiary amine group contained in other bactericidal components to form a quaternary ammonium salt, and the bactericidal performance was further decreased.

[0097] (2) Inhibition performance: The static uniform inhibition rate of the bactericides for water injection treatment prepared in Examples 1-5 and Comparative Examples 1-2 on Q235 steel was determined according to SY / T5273-2014 "Performance index and evaluation method of corrosion inhibitors for oilfield produced water treatment". The inhibition rate was determined after standing for 10 days, and the results are shown in Table 2:

[0098] Table 2

[0099]

[0100] As shown in Table 2, the bactericide prepared by the application has good corrosion inhibition performance. Compared with Example 1, in Comparative Example 1, 5-chloropropenyl-2,4-imidazoline dione does not further react with 1,4-dibromobutane to introduce bromine element, the reaction with the tertiary amine group contained in other bactericidal components to form quaternary ammonium salt is reduced, the adsorption capacity to metal equipment is weakened, the introduced alkyl chain is reduced, the hydrophobic property of the metal surface is reduced, and the corrosion inhibition performance is reduced; compared with Comparative Example 1, in Comparative Example 2, 2,4-imidazoline dione does not react with 3-chloropropionaldehyde to introduce chlorine element, cannot react with the tertiary amine group contained in other bactericidal components to form quaternary ammonium salt, the adsorption capacity to metal equipment is further weakened, and no alkyl chain is introduced, cannot form a hydrophobic film on the metal surface, and the corrosion inhibition performance is further reduced.

[0101] Although embodiments of the application have been shown and described, it is to be understood that various modifications, substitutions, replacements and variations can be made to these embodiments without departing from the principles and spirit of the application, and the scope of the application is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a bactericide for water injection treatment, characterized by, Comprise the following steps: Step (1), 2, 4-imidazolidine dione is added to deionized water, heated and stirred until dissolved, the pH value is adjusted to 6.5-7.5, ethanolamine is added, the temperature is raised to the first set temperature, 3-chloropropanal solution is added dropwise, after the dropwise addition is completed, the temperature is raised to the second set temperature, reaction, after the reaction is completed, cooling, filtration, washing, drying, 5-chloropropenyl-2, 4-imidazolidine dione is obtained; Step (2), potassium carbonate is added to acetone, after ultrasonic dispersion, 5-chloropropenyl-2, 4-imidazolidine dione is added, reaction, after the reaction is completed, 1, 4-dibromobutane is added dropwise, after the dropwise addition is completed, the reaction is continued, after the reaction is completed, filtration, rotary evaporation, purification, 3-bromobutyl-5-chloropropenyl-2, 4-imidazolidine dione is obtained; Step (3), aminocyan is dissolved in ethanol to obtain aminocyan solution; 2-(4-aminophenyl)-5-aminobenzimidazole is added to ethanol, after stirring, hydrochloric acid solution is added dropwise, after the dropwise addition is completed, the temperature is raised to the set temperature, aminocyan solution is added dropwise, after the dropwise addition is completed, reaction, after the reaction is completed, cooling, precipitation, purification, imidazole guanidine salt is obtained; Imidazole guanidine salt, cortex phellodendri extract, sophora flavescens extract, 3-bromobutyl-5-chloropropenyl-2, 4-imidazolidine dione are mixed, reaction, after the reaction is completed, rotary evaporation, a bactericide for water injection treatment is obtained; Among them, the mass ratio of imidazole guanidine salt, cortex phellodendri extract, sophora flavescens extract, 3-bromobutyl-5-chloropropenyl-2, 4-imidazolidine dione is (10-20):(300-500):(250-350):(50-70), the reaction conditions are 2-4h at 55-65 DEG C; The cortex phellodendri extract is prepared by the following steps: The traditional Chinese medicinal material cortex phellodendri is crushed, added to ethanol aqueous solution, heated and refluxed to extract, after the extraction is completed, the filtrate is obtained by filtration, and the cortex phellodendri extract is obtained; The mass ratio of cortex phellodendri and ethanol aqueous solution is 1:(8-12), and the heating reflux extraction conditions are reflux extraction for 6-10h at 60-80 DEG C; The ethanol aqueous solution comprises 75wt% ethanol aqueous solution; The sophora flavescens extract is prepared by the following steps: The traditional Chinese medicinal material sophora flavescens is crushed, added to ethanol aqueous solution, heated and refluxed to extract, after the extraction is completed, the filtrate is obtained by filtration, and the sophora flavescens extract is obtained; The mass ratio of sophora flavescens and ethanol aqueous solution is 1:(8-12), and the heating reflux extraction conditions are reflux extraction for 3-5h at 60-70 DEG C; The mass percentage content of ethanol in the ethanol aqueous solution is 50%-70%.

2. The method for preparing a bactericide for water injection treatment according to claim 1, characterized in that, In step (1), the mass ratio of 2, 4-imidazolidine dione, deionized water, ethanolamine, 3-chloropropanal solution is 10:(400-600):(10-12):(65-67.5); The 3-chloropropanal solution is prepared by 3-chloropropanal and ethanol, and the mass percentage content of 3-chloropropanal in the 3-chloropropanal solution is 15%.

3. The method for preparing a bactericide for water injection treatment according to claim 1, characterized in that, In the step (1), the heating and stirring is performed at a temperature of 65-75℃ and a speed of 150-250r / min, the first set temperature is 80-100℃, the dropping time of 3-chloropropanal solution is 30-60min, and the reaction is performed at the second set temperature for 10-15h under reflux.

4. The method of claim 1, wherein the bactericide for water injection treatment is prepared by adding 0.1 to 0.5 parts by weight of the compound of formula (I) to 100 parts by weight of a water-soluble solvent. In the step (2), the mass ratio of 5-chloropropenyl-2,4-imidazolidine, 1,4-dibromobutane, potassium carbonate and acetone is 18:(39-47):(45-55):(900-1100), the ultrasonic dispersion is performed at a frequency of 50kHz for 30min, the reaction is performed at a temperature of 60-80℃ for 40-80min under reflux, the dropping time of 1,4-dibromobutane is 20-40min, and the continued reaction is performed at a temperature of 60-80℃ for 3-5h under reflux.

5. The method for preparing a bactericide for water injection treatment according to claim 1, characterized in that, In the step (3), the molar ratio of 2-(4-aminophenyl)-5-aminobenzimidazole, hydrogen chloride in hydrochloric acid solution and cyanamide is 1:1:(1.1-1.2); The mass of ethanol is 50-60 times of the mass of 2-(4-aminophenyl)-5-aminobenzimidazole; The mass percentage of cyanamide in the cyanamide solution is 30%-50%; The hydrochloric acid solution comprises 30wt% hydrochloric acid solution.

6. The method for preparing a bactericide for water injection treatment according to claim 1, characterized in that, In the step (3), the dropping time of cyanamide solution is 40-60min, the reaction is performed at a set temperature for 4-6h while the pH value of the reaction system is controlled between 2 and 3, and the set temperature is 80-90℃.

7. A water treatment bactericide prepared by the method of any one of claims 1-6.

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