CN114149062B - Bactericide for sulfate reducing bacteria in polymer-containing produced liquid and preparation method and application thereof - Google Patents
Bactericide for sulfate reducing bacteria in polymer-containing produced liquid and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a bactericide for sulfate reducing bacteria in polymer-containing produced liquid and a preparation method and application thereof. The bactericide is prepared by reacting straight-chain alkylamine with 1H-pyrazole-1-formamidine hydrochloride to obtain an intermediate and reacting the intermediate with acid anhydride. The bactericide does not react with anionic polymers in the polymer-containing produced liquid, does not influence the viscosity of the polymer-containing produced liquid, has good bactericidal effect, can realize excellent bactericidal effect with smaller bactericide concentration, has strong adaptability, does not cause bacteria to generate drug resistance, and simultaneously has certain corrosion inhibition effect.
Description
Technical Field
The invention relates to the technical field of oilfield sewage treatment, and particularly relates to a bactericide for sulfate reducing bacteria in polymer-containing produced liquid, and a preparation method and application thereof.
Background
The growth, metabolism and propagation of microorganisms (such as sulfate reducing bacteria, iron bacteria and saprophytic bacteria) in the oilfield reinjection system can cause corrosion and damage to drilling equipment and water injection pipelines and other metal materials, and blockage of pipelines and water injection wells; the permeability of pores of an oil layer is reduced, and water injection oil extraction is hindered; and can even degrade other oilfield chemicals and reduce the use efficiency of the medicament. These hazards can cause significant economic losses to the oil field production operation.
The method for controlling bacteria in oil field generally comprises adding bactericide, and has the characteristics of quick effect, simple operation and the like. However, the current bactericide for oilfield produced water is single in variety, and most products are quaternary ammonium salts or compound agents taking the quaternary ammonium salts as main agents; the quaternary ammonium salt bactericidal groups are mostly cationic, and are easy to react with anionic polymers in the polymer-containing produced liquid, so that the using effect of the bactericide is influenced, and the viscosity of the polymer-containing produced liquid is influenced; moreover, because a single bactericide variety is used for a long time, bacteria can generate certain drug resistance to the bactericide, so that the using effect of the medicament is obviously reduced; in addition, the existing bactericide has a large use concentration. Therefore, development of novel fungicides is urgently required. The polymer-containing produced liquid bactericide has the advantages of no reaction with anionic polymers in the polymer-containing produced liquid, no influence on the viscosity of the polymer-containing produced liquid, good bactericidal effect, realization of excellent bactericidal effect with smaller bactericide concentration, strong adaptability and no generation of bactericide with drug resistance for bacteria.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a bactericide for sulfate reducing bacteria in polymer-containing produced liquid and a preparation method and application thereof. The bactericide does not react with anionic polymers in the polymer-containing produced liquid, does not influence the viscosity of the polymer-containing produced liquid, has good bactericidal effect, can realize excellent bactericidal effect with smaller concentration of the bactericide, has strong adaptability, does not cause bacteria to generate drug resistance, and simultaneously has certain corrosion inhibition effect.
The technical scheme of the invention is as follows:
a bactericide for sulfate reducing bacteria in polymer-containing produced liquid has a structure shown as the following formula I:
wherein, the substituent R 1 Is C 6 -C 20 Alkyl of (5), substituent R 2 Is the organic acid group after the hydrolysis of the anhydride.
Preferred according to the invention are compounds of the formula I in which the substituents R 1 Is C 12 -C 16 Alkyl groups of (a); preferably, the substituent R 1 Dodecyl, tetradecyl or hexadecyl; further preferred is tetradecyl.
Preferred according to the invention are compounds of the formula I in which the substituent R 2 Selected from one of the following structural formulas:
preferably, in the compounds of the formula I, the substituents R 2 Selected from one of the following structural formulas:
according to the invention, the bactericide for sulfate reducing bacteria in polymer-containing produced liquid has a structure shown in the following formula II:
wherein, the substituent R 1 With the substituent R in the structural formula of the compound of the formula I 1 Have the same meaning.
The preparation method of the bactericide for sulfate reducing bacteria in polymer-containing produced liquid comprises the following steps:
(1) In a solvent A, reacting straight-chain alkylamine with 1H-pyrazole-1-formamidine hydrochloride to obtain an intermediate;
(2) And reacting the intermediate with acid anhydride in a solvent B in the presence of a catalyst to obtain the bactericide shown in the formula I.
Preferably, in step (1), the solvent a is methanol, ethanol, propanol, acetone or formamide, preferably methanol; the mass ratio of the 1H-pyrazole-1-formamidine hydrochloride to the volume ratio of the solvent A is 0.05-0.2 g/mL.
Preferably, in step (1), the linear alkylamine is C 6 ～C 20 An alkylamine of (a); preferably C 12 ～C 16 An alkylamine of (a); further preferably dodecylamine, tetradecylamine or hexadecylamine; most preferred is tetradecylamine.
Preferably, in step (1) according to the present invention, the molar ratio of the linear alkylamine to the 1H-pyrazole-1-carboxamidine hydrochloride is 1:1 to 2.
Preferably, according to the invention, in step (1), the reaction temperature is 30-40 ℃; the reaction time is 40 to 55 hours. Preferably, the reaction is carried out under stirring conditions, with a stirring rate of 200 to 300r/min.
According to a preferred embodiment of the present invention, in step (1), the reaction mixture obtained by reacting the linear alkylamine with 1H-pyrazole-1-carboxamidine hydrochloride is worked up as follows: and distilling the reaction liquid under reduced pressure to remove the solvent A, adding acetone for recrystallization, and finally filtering and vacuum drying to obtain an intermediate.
Preferably, in step (2), the solvent B is one or a combination of two or more of dichloromethane, dimethyl sulfoxide, dichloroethane, dichloropropane and trichloromethane; preferably a combination of dichloromethane and dimethylsulfoxide; more preferably, in the combination of the dichloromethane and the dimethyl sulfoxide, the volume ratio of the dichloromethane to the dimethyl sulfoxide is 1:1-3; the mass ratio of the acid anhydride to the solvent B is 0.05-0.1 g/mL.
Preferably, according to the invention, in step (2), the catalyst is N, N-diisopropylethylamine, formamide or N, N-dimethylformamide, preferably N, N-diisopropylethylamine; the mass ratio of the catalyst to the acid anhydride is 1.5-3:1.
Preferably, in step (2), the anhydride is maleic anhydride, 2,3-dimethylmaleic anhydride, succinic anhydride or phthalic anhydride, preferably maleic anhydride or 2,3-dimethylmaleic anhydride.
Preferably, according to the invention, in step (2), the molar ratio of intermediate to anhydride is 0.9 to 1.4.
Preferably, in step (2), the reaction temperature of the intermediate and the anhydride is 20-30 ℃; the reaction time is 20 to 30 hours; preferably, the reaction of the intermediate and the acid anhydride is carried out under stirring conditions at a rate of from 200 to 300r/min.
According to the invention, in the step (2), the post-treatment method of the reaction liquid obtained by the reaction of the intermediate and the acid anhydride is as follows: adding distilled water into the reaction liquid for quenching reaction, adding dichloromethane for extraction, taking an organic phase, distilling under reduced pressure to remove an organic solvent, adding a mixed solution of acetone, petroleum ether and dichloromethane for recrystallization, and then filtering and drying in vacuum to obtain the bactericide shown in the formula I. Preferably, in the mixed solution of acetone, petroleum ether and dichloromethane, the volume ratio of acetone, petroleum ether and dichloromethane is 1.
The application of the bactericide for sulfate reducing bacteria in the polymer-containing produced liquid is used as the bactericide for sterilizing and inhibiting the sulfate reducing bacteria in the polymer-containing produced liquid.
According to a preferred embodiment of the invention, the application method is as follows: the bactericide and the linear alkyl trimethyl ammonium bromide are mixed and then used for sterilizing and inhibiting sulfate reducing bacteria in polymer-containing produced liquid.
Preferably, the mass ratio of the bactericide to the linear alkyl trimethyl ammonium bromide is 1:8-15.
Preferably, the linear alkyltrimethylammonium bromide is dodecyltrimethylammonium bromide, tetradecyltrimethylammonium bromide, hexadecyltrimethylammonium bromide or octadecyltrimethylammonium bromide, preferably tetradecyltrimethylammonium bromide.
The invention takes the bactericide shown in the formula II as an example, and the preparation route is as follows:
wherein the substituents R 1 Is C 6 -C 20 Alkyl group of (1).
The invention has the following technical characteristics and beneficial effects:
1. the bactericide contains guanidyl, can be adsorbed on the surface of a cell membrane of sulfate reducing bacteria to change the permeability of the cell membrane, and achieves the aim of killing the sulfate reducing bacteria. The pure guanidino is a cationic group, and is easy to react with an anionic polymer in the polymer-containing produced liquid, so that the sterilization effect and the viscosity of the produced liquid are influenced; the bactericide is modified on the basis, so that the whole bactericide is electrically neutral or negatively charged, and the aim of not generating electrostatic interaction with polymers or other negatively charged substances is fulfilled. The bactericide has the advantages that the whole structure of the bactericide is taken as a whole, the groups interact with each other, so that the sterilization effect can be influenced, the combined action of the groups ensures that the bactericide does not react with anionic polymers in the polymer-containing produced liquid, the viscosity of the polymer-containing produced liquid is not influenced, the sterilization effect is good, the adaptability is high, and bacteria cannot generate drug resistance; the bactericide has good adaptability to polymer-containing produced liquid, and when the number of sulfate reducing bacteria in the polymer-containing produced liquid is 10 4 ～10 5 When the seed/mL is used, the invention is usedThe bactericide can achieve the sterilization effect when the concentration of the bactericide is 50mg/L, and the sterilization effect of the bactericide currently used in the oil field is not satisfactory when the concentration of the bactericide is 100 mg/L; namely, the bactericide of the invention can achieve excellent bactericidal effect with lower use concentration.
2. The bactericide has a certain corrosion inhibition effect, and can relieve the corrosion of drilling and production equipment, water injection pipelines and other metal materials. When the steel used by drilling and production equipment, water injection pipelines, transportation pipelines and the like is in the polymer-containing produced liquid containing the bactericide, an adsorption film can be formed on the surface of the metal, so that the steel is protected from being corroded.
3. The solid sample of the bactericide is insoluble in water, and the solubility of the bactericide in water can be improved by mixing the straight-chain alkyl trimethyl ammonium bromide serving as a cosolvent with the solid sample of the bactericide; meanwhile, the used linear alkyl trimethyl ammonium bromide also has a sterilization effect, and the linear alkyl trimethyl ammonium bromide serving as a cosolvent can form a synergistic effect with the synthesized bactericide, so that the linear alkyl trimethyl ammonium bromide is more beneficial to sterilization and bacteriostatic application.
4. The synthetic process of the bactericide of the invention does not need high temperature and high pressure, has mild reaction conditions, simple operation, short steps, high yield and low cost, is easy to realize and is suitable for industrial mass production.
Drawings
FIG. 1 is an infrared spectrum of the fungicides DGCMA, TGCMA, CGCMA prepared in examples 1-3.
Detailed Description
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto.
Meanwhile, the experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Example 1: bactericide DGCMA and preparation method and application method thereof
A bactericide DGCMA for sulfate reducing bacteria in polymer-containing produced liquid has the following structure:
preparation method of fungicide DGCMA
(1) Weighing 1.0312g of laurylamine and 1.0200g of 1H-pyrazole-1-formamidine hydrochloride, placing the materials into a flask, adding 10mL of methanol as a solvent, heating to 40 ℃, stirring at a speed of 200r/min, stirring for reaction for 48 hours, removing the solvent methanol by reduced pressure distillation after the reaction is finished, adding acetone for recrystallization, performing suction filtration to obtain a solid sample, and performing vacuum drying to obtain an intermediate product with a molar yield of 74.35%;
(2) weighing 0.5368g and 2,3-dimethylmaleic anhydride 0.2620g and N, N-diisopropylethylamine 0.5224g of the intermediates, placing the intermediates into a flask, adding 5mL of dichloromethane and 10mL of dimethylsulfoxide as solvents, stirring at 25 ℃, stirring at a speed of 200r/min, stirring for 24 hours, adding distilled water for quenching reaction, adding dichloromethane for extraction, separating water by using a separating funnel, taking an organic phase, carrying out reduced pressure distillation to remove the organic solvent, adding acetone, petroleum ether and dichloromethane (the volume ratio of acetone, petroleum ether and dichloromethane is 1.
The infrared spectrum of DGCMA obtained in this example is shown in FIG. 1, and is at 3400cm in the first peak region -1 One band appears, the characteristic peak is-N-H stretching vibration, and only one band can be identified as secondary amine. Since primary amines in this range two bands occur, corresponding to-NH 2 The antisymmetric stretching vibration and the symmetric stretching vibration of the band also can generate a third band at a lower wave number, and the third band is association-N-H stretching vibration; the tertiary amine does not have this band, and is therefore identified as a secondary amine-N-H stretching vibration peak. And is 3000-2850cm -1 The strong and wide characteristic peak appears, which is caused by the expansion and contraction vibration of alkane C-H bond, or is a dimer carboxyl absorption peak. No characteristic peak appears in the second peak area, which indicates that no triple bonds are present, and the stretching vibration of double bonds and bonds B-H, P-H, I-H, as-H, si-H and the like are accumulated. 1715cm in the third peak region -1 C = O stretching vibration of carboxylic acidAt 1680-1640cm -1 A characteristic peak appears at-C = N key stretching vibration. From the above, the fungicide DGCMA was successfully prepared in this example.
The preparation route of the bactericide is as follows:
the bactericide is applied to the sterilization and bacteriostasis of sulfate reducing bacteria in polymer-containing produced liquid as the bactericide. The application method comprises the following steps: 0.10g of the bactericide solid sample and 1.01g of dodecyl trimethyl ammonium bromide are weighed and uniformly mixed, and then the bactericide solid sample is used for sterilizing and inhibiting sulfate reducing bacteria in polymer-containing produced fluid.
Example 2: bactericide TGCMA and preparation method and application method thereof
A bactericide TGCMA for sulfate reducing bacteria in polymer-containing produced liquid has the following structure:
preparation method of the bactericide TGCMA
(1) Weighing 2.1384g of tetradecylamine and 1.6230g of 1H-pyrazole-1-formamidine hydrochloride, placing the materials into a flask, adding 20mL of methanol as a solvent, heating to 40 ℃, stirring at a speed of 200r/min, stirring for reaction for 48 hours, removing the solvent methanol by reduced pressure distillation after the reaction is finished, adding acetone for recrystallization, performing suction filtration to obtain a solid sample, and performing vacuum drying to obtain an intermediate product with a molar yield of 82.30%;
(2) weighing the intermediate 0.5884g and 2,3-dimethylmaleic anhydride 0.2534g, and N, N-diisopropylethylamine 0.5334g, placing the intermediate in a flask, adding 5mL of dichloromethane and 10mL of dimethylsulfoxide as solvents, stirring at the temperature of 25 ℃, the stirring rate of 200r/min, stirring for 24 hours, adding distilled water for quenching reaction, adding dichloromethane for extraction, separating water by using a separating funnel, taking an organic phase, removing the organic solvent by reduced pressure distillation, adding acetone, petroleum ether and dichloromethane (the volume ratio of acetone, petroleum ether and dichloromethane is 1.
The infrared spectrum of the fungicide TGCMA obtained in this example is shown in FIG. 1. As can be seen from FIG. 1, the fungicide TGCMA was successfully prepared in this example.
The preparation route of the bactericide is as follows:
the bactericide is applied to sterilization and bacteriostasis of sulfate reducing bacteria in polymer-containing produced liquid as the bactericide. The application method comprises the following steps: weighing 0.10g of the bactericide solid sample and 1.0g of dodecyl trimethyl ammonium bromide, uniformly mixing, and then, using the mixture for sterilization and bacteriostasis of sulfate reducing bacteria in polymer-containing produced liquid.
Example 3: bactericide CGCMA and preparation method and application method thereof
A bactericide CGCMA for sulfate reducing bacteria in polymer-containing produced liquid has the following structure:
preparation method of bactericide CGCMA
(1) Weighing the hexadecylamine 2.4218g and the 1H-pyrazole-1-formamidine hydrochloride 1.6357g, placing the hexadecylamine 2.4218g and the 1H-pyrazole-1-formamidine hydrochloride 1.6357g into a flask, adding 20mL of methanol as a solvent, heating to 40 ℃, stirring at a speed of 200r/min, stirring for reacting for 48 hours, removing the solvent methanol by reduced pressure distillation after the reaction is finished, adding acetone for recrystallization, performing suction filtration to obtain a solid sample, and performing vacuum drying to obtain an intermediate product with a molar yield of 84.17%;
(2) weighing 2.2163g and 2,3-dimethylmaleic anhydride 1.0034g, and N, N-diisopropylethylamine 2.1077g, placing into a flask, adding 10mL of dichloromethane and 20mL of dimethylsulfoxide as solvents, stirring at the temperature of 25 ℃, stirring at the speed of 200r/min, stirring for 24 hours, adding distilled water for quenching reaction, adding dichloromethane for extraction, separating water by using a separating funnel, taking an organic phase, removing the organic solvent by reduced pressure distillation, adding acetone, petroleum ether and dichloromethane (the volume ratio of acetone to petroleum ether to dichloromethane is 1.
The infrared spectrum of the bactericide CGCMA obtained in this example is shown in FIG. 1, and as can be seen from FIG. 1, the bactericide CGCMA was successfully prepared in this example.
The preparation route of the bactericide is as follows:
the bactericide is applied to the sterilization and bacteriostasis of sulfate reducing bacteria in polymer-containing produced liquid as the bactericide. The application method comprises the following steps: 0.10g of the bactericide solid sample and 1.0g of dodecyl trimethyl ammonium bromide are weighed and uniformly mixed, and then the bactericide solid sample is used for sterilization and bacteriostasis of sulfate reducing bacteria in polymer-containing produced liquid.
Example 4: preparation of intermediates
Weighing n-octylamine 0.6105g and 1H-pyrazole-1-formamidine hydrochloride 0.7352g, placing the materials into a flask, adding 10mL of methanol as a solvent, heating to 40 ℃, stirring at a speed of 200r/min, stirring for reaction for 48 hours, removing the solvent methanol by reduced pressure distillation after the reaction is finished, adding acetone for recrystallization, performing suction filtration to obtain a solid sample, and performing vacuum drying to obtain an intermediate product, wherein the molar yield is 2.34%.
As can be seen from a comparison of this example, C 12 -C 16 The alkylamine yield is higher and is preferred.
Comparative example 1
Preparation method and application method of bactericide DGCMA intermediate
Preparation method of bactericide DGCMA intermediate
Weighing 1.0312g of laurylamine and 1.0200g of 1H-pyrazole-1-formamidine hydrochloride, placing the materials into a flask, adding 10mL of methanol as a solvent, heating to 40 ℃, stirring at the speed of 200r/min, stirring for reacting for 48 hours, removing the solvent methanol by reduced pressure distillation after the reaction is finished, adding acetone for recrystallization, performing suction filtration to obtain a solid sample, and performing vacuum drying to obtain an intermediate product.
The bactericide is applied to sterilization and bacteriostasis of sulfate reducing bacteria in polymer-containing produced liquid as the bactericide. The application method comprises the following steps: 0.10g of the bactericide solid sample and 1.01g of dodecyl trimethyl ammonium bromide are weighed and uniformly mixed, and then the bactericide solid sample is used for sterilization and bacteriostasis of sulfate reducing bacteria in polymer-containing produced liquid.
Comparative example 2: preparation method and application method of bactericide TGCMA intermediate
Preparation method of bactericide TGCMA intermediate
Weighing the tetradecylamine 2.1384g and the 1H-pyrazole-1-formamidine hydrochloride 1.6230g, placing the materials into a flask, adding 20mL of methanol as a solvent, heating to 40 ℃, stirring at the speed of 200r/min, stirring for reacting for 48 hours, removing the solvent methanol by reduced pressure distillation after the reaction is finished, adding acetone for recrystallization, performing suction filtration to obtain a solid sample, and performing vacuum drying to obtain an intermediate product.
The bactericide is applied to sterilization and bacteriostasis of sulfate reducing bacteria in polymer-containing produced liquid as the bactericide. The application method comprises the following steps: 0.10g of the bactericide solid sample and 1.01g of dodecyl trimethyl ammonium bromide are weighed and uniformly mixed, and then the bactericide solid sample is used for sterilizing and inhibiting sulfate reducing bacteria in polymer-containing produced fluid.
Comparative example 3: preparation method and application method of bactericide CGCMA intermediate
Preparation method of bactericide CGCMA intermediate
Weighing the hexadecylamine 2.4218g and the 1H-pyrazole-1-formamidine hydrochloride 1.6357g, placing the hexadecylamine 2.4218g and the 1H-pyrazole-1-formamidine hydrochloride 1.6357g into a flask, adding 20mL of methanol as a solvent, heating to 40 ℃, stirring at the speed of 200r/min, stirring for reacting for 48 hours, removing the solvent methanol by reduced pressure distillation after the reaction is finished, adding acetone for recrystallization, performing suction filtration to obtain a solid sample, and performing vacuum drying to obtain an intermediate product.
The bactericide is applied to sterilization and bacteriostasis of sulfate reducing bacteria in polymer-containing produced liquid as the bactericide. The application method comprises the following steps: 0.10g of the bactericide solid sample and 1.01g of dodecyl trimethyl ammonium bromide are weighed and uniformly mixed, and then the bactericide solid sample is used for sterilizing and inhibiting sulfate reducing bacteria in polymer-containing produced fluid.
Test example 1: evaluation of fungicidal Effect of Fungicide
The bactericide in the embodiment and the proportion (the mixture of the bactericide and dodecyl trimethyl ammonium bromide when in application according to the application method recorded in the embodiment or the comparative example) and several bactericides provided on an oil field site are subjected to bactericidal effect evaluation according to the general technical conditions of the bactericide for treating oilfield produced water in the standard QSH 0688-2016, a water sample for a test is the water output from a certain united station which is superior to the oil-water separation treatment of polymer-containing produced liquid in the oil field, 13000 sulfate reducing bacteria/mL are contained in the water sample, and the bactericidal effect is shown in Table 1.
TABLE 1 bacteriostatic concentration of the fungicides
In the table, 50mg/L, 70mg/L and 100mg/L are the concentrations of DGCMA, TGCMA, CGCMA and other bactericide samples in the water sample for test; the "+" indicates that the test bottle for sulfate-reducing bacteria produces a positive reaction, and the "-" indicates that the test bottle for sulfate-reducing bacteria produces a negative reaction.
As shown in the table 1, the bacteriostatic concentration is the adding concentration of a bactericide capable of completely killing sulfate reducing bacteria (namely, the sterilization rate is 100%) in a water sample, GS is four bactericides provided on site and is a medicament formed by compounding quaternary ammonium salt serving as a main agent, and the results in the table show that the bactericide prepared by the invention has good adaptability in high polymer-containing sewage and has better effect than other bactericides; the three prepared bactericides have the optimal effect of TGCMA. Accordingly, the bactericide of the present invention can achieve an excellent bactericidal effect with a small amount.
Test example 2: corrosivity test
The fungicide TGCMA of the present invention (a mixture of the fungicide and dodecyltrimethylammonium bromide when applied according to the application method described in the examples) was tested for corrosivity according to the general technical conditions for fungicides for water treatment of oilfield produced under Standard QSH1020 0688-2016, and the results of the corrosivity evaluation are shown in Table 2.
TABLE 2 Corrosion test results of TGCMA
| Concentration of bactericide (mg/L) | 0 | 50 | 70 | 100 |
| Average Corrosion Rate (mm/a) | 0.1513 | 0.1061 | 0.1031 | 0.1198 |
As shown in Table 2, the average corrosion rate result is measured by three test pieces, the relative deviation of the measurement results is less than 2.5%, and the average corrosion rate is reduced after the bactericide is added compared with a blank water sample without the bactericide, which indicates that the prepared bactericide has a certain corrosion inhibition effect.
Claims (12)
1. A bactericide for sulfate reducing bacteria in polymer-containing produced liquid is characterized by having a structure shown as the following formula II:
wherein the substituents R 1 Is C 6 -C 20 Alkyl groups of (a);
the preparation method of the bactericide for sulfate reducing bacteria in polymer-containing produced liquid comprises the following steps:
(1) In a solvent A, reacting straight-chain alkylamine with 1H-pyrazole-1-formamidine hydrochloride to obtain an intermediate;
(2) And reacting the intermediate with acid anhydride in a solvent B in the presence of a catalyst to obtain the bactericide shown in the formula I.
2. The bactericide for sulfate-reducing bacteria in polymer-containing produced fluid according to claim 1, wherein in the compound of formula I, the substituent R is 1 Is C 12 -C 16 Alkyl group of (1).
3. The bactericide for sulfate-reducing bacteria in polymer-containing produced fluid according to claim 2, wherein in the compound of formula I, the substituent R is 1 Is dodecyl, tetradecyl or hexadecyl.
4. The bactericide for sulfate-reducing bacteria in polymer-containing produced fluids according to claim 1, wherein in the step (1), one or more of the following conditions are included:
i. the solvent A is methanol, ethanol, propanol, acetone or formamide; the mass ratio of the 1H-pyrazole-1-formamidine hydrochloride to the volume ratio of the solvent A is 0.05-0.2 g/mL;
ii. The linear alkylamine is C 6 ～C 20 An alkylamine of (a);
iii, linear alkylamine and 1H-pyrazole-1-carboxamidine hydrochloride in a molar ratio of 1:1 to 2;
iv, the reaction temperature is 30-40 ℃; the reaction is carried out under the condition of stirring, and the stirring speed is 200-300 r/min;
v, the post-treatment method of the reaction liquid obtained by the reaction of the straight-chain alkylamine and the 1H-pyrazole-1-formamidine hydrochloride is as follows: and distilling the reaction liquid under reduced pressure to remove the solvent A, adding acetone for recrystallization, and finally filtering and vacuum drying to obtain an intermediate.
5. The bactericide for sulfate-reducing bacteria in polymer-containing produced liquid according to claim 4, wherein in the step (1), the linear alkylamine is C 12 ～C 16 Of an alkylamine of (a).
6. The bactericide for sulfate-reducing bacteria in polymer-containing production fluids according to claim 5, wherein in the step (1), the linear alkylamine is dodecylamine, tetradecylamine or hexadecylamine.
7. The bactericide for sulfate-reducing bacteria in polymer-containing produced fluids according to claim 1, wherein the step (2) comprises one or more of the following conditions:
i. the solvent B is one or the combination of more than two of dichloromethane, dimethyl sulfoxide, dichloroethane, dichloropropane or trichloromethane; the mass ratio of the acid anhydride to the solvent B is 0.05-0.1 g/mL;
ii. The catalyst is N, N-diisopropylethylamine, formamide or N, N-dimethylformamide; the mass ratio of the catalyst to the acid anhydride is 1.5-3:1;
iii, the anhydride is 2,3-dimethylmaleic anhydride
iv, the molar ratio of the intermediate to the anhydride is 0.9 to 1.4;
v, the reaction temperature of the intermediate and the acid anhydride is 20-30 ℃; the reaction of the intermediate and the acid anhydride is carried out under the stirring condition, and the stirring speed is 200-300 r/min;
vi, the post-treatment method of the reaction liquid obtained by the reaction of the intermediate and the acid anhydride is as follows: adding distilled water into the reaction liquid for quenching reaction, adding dichloromethane for extraction, taking an organic phase, carrying out reduced pressure distillation to remove an organic solvent, adding a mixed solution of acetone, petroleum ether and dichloromethane for recrystallization, and then filtering and vacuum drying to obtain a bactericide shown in the formula I; in the mixed liquid of acetone, petroleum ether and dichloromethane, the volume ratio of acetone, petroleum ether and dichloromethane is 1.
8. The bactericide for sulfate-reducing bacteria in polymer-containing produced liquid according to claim 7, wherein in the step (2), the solvent B is a combination of dichloromethane and dimethyl sulfoxide; in the combination of the dichloromethane and the dimethyl sulfoxide, the volume ratio of the dichloromethane to the dimethyl sulfoxide is 1:1-3.
9. The use of any one of claims 1 to 8 as a bactericide for the sterilization and bacteriostasis of sulfate-reducing bacteria in polymer-containing produced fluids.
10. The application of the bactericide for sulfate reducing bacteria in polymer-containing produced liquid according to claim 9 is as follows: the bactericide and the linear alkyl trimethyl ammonium bromide are mixed and then used for sterilizing and inhibiting sulfate reducing bacteria in the polymer-containing produced liquid.
11. The use of the bactericide for sulfate-reducing bacteria in polymer-containing produced fluids according to claim 9, wherein the mass ratio of the bactericide to the linear alkyl trimethyl ammonium bromide is 1:8-15.
12. The use of a bactericide for sulfate-reducing bacteria in polymer-containing production fluids according to claim 9, wherein the linear alkyl trimethyl ammonium bromide is dodecyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide or octadecyl trimethyl ammonium bromide.
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| CN102388905A (en) * | 2011-10-17 | 2012-03-28 | 华南理工大学 | Quaternary ammonium salt grafted guanidine salt bactericide and preparation method thereof |
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| CN108402070A (en) * | 2018-03-29 | 2018-08-17 | 东营利丰化工新材料有限公司 | A kind of oil field reinjection water guanidine radicals sterilization anti-incrustation corrosion inhibitor |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102388905A (en) * | 2011-10-17 | 2012-03-28 | 华南理工大学 | Quaternary ammonium salt grafted guanidine salt bactericide and preparation method thereof |
| CN103467703A (en) * | 2013-09-26 | 2013-12-25 | 南京年吉冷冻食品有限公司 | Preparation method for anti-bacteria anti-flaming bifunctional polyurethane flexible foam plastic |
| CN104397006A (en) * | 2014-11-25 | 2015-03-11 | 苏州佑君环境科技有限公司 | Water-treated polyhexamethylene guanidine hydrochloride sterilizing agent and preparation method thereof |
| CN108402070A (en) * | 2018-03-29 | 2018-08-17 | 东营利丰化工新材料有限公司 | A kind of oil field reinjection water guanidine radicals sterilization anti-incrustation corrosion inhibitor |
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