Asymmetric bisquaternary ammonium salt surfactants, methods of making and using same

Abstract

The application relates to the technical field of oil field chemistry, and is an asymmetric double quaternary ammonium salt surfactant as well as a preparation method and application thereof. The method comprises the following steps: in step one, uniformly mixing p-dimethylaminobenzaldehyde and an organic solvent, adding 3-dimethylaminopropylamine, and refluxing to obtain a reaction mixture; in step two, adding a halogenated hydrocarbon into the reaction mixture, and refluxing to obtain the asymmetric double quaternary ammonium salt surfactant after the reaction product is concentrated and recrystallized. The asymmetric double quaternary ammonium salt surfactant has the advantages of reliable preparation method principle, simple operation, mild reaction condition, high product yield, and the like. The asymmetric double quaternary ammonium salt surfactant has significantly better bactericidal performance than traditional bactericides, can efficiently kill harmful microorganisms such as sulfate-reducing bacteria, is not prone to causing drug resistance of the harmful microorganisms, and has a wide market application prospect.

Description

Technical Field

[0001] This invention relates to the field of oilfield chemical technology, specifically to an asymmetric bis-quaternary ammonium salt surfactant, its preparation method, and its application. Background Technology

[0002] During oilfield development, the reservoir environment is rich in nutrients such as water, carbon, and nitrogen, and the temperature and pressure conditions are suitable for microbial growth and reproduction. Common harmful microorganisms in oilfields include sulfate-reducing bacteria (SRB), saprophytic bacteria (TGB), and iron bacteria (FB). The metabolic activities of these microorganisms can cause a series of serious problems: sulfate-reducing bacteria reduce sulfate to produce hydrogen sulfide, which not only corrodes metal equipment such as oil pipes and casings but also reduces crude oil quality and endangers the health of workers; the slime produced by saprophytic bacteria can clog oil layer pores and oil production channels, leading to a decrease in crude oil production; iron bacteria oxidize ferrous ions to produce ferric hydroxide precipitate, accelerating equipment corrosion and further exacerbating formation blockage. Therefore, efficient and stable bactericides for oilfields are one of the key additives for ensuring normal oilfield development and reducing production costs.

[0003] Currently, commonly used bactericides in oilfields are mainly divided into inorganic bactericides (such as hypochlorites and chlorine dioxide) and organic bactericides (such as quaternary ammonium salts, quaternary phosphate salts, and aldehydes). Quaternary ammonium salt bactericides are widely used due to their advantages such as broad bactericidal spectrum, fast bactericidal speed, and low toxicity. For example, Chinese patent document CN113956170A discloses a method for preparing a high-efficiency oilfield geminal quaternary ammonium salt bactericide. This method involves adding a solvent to a reactor and, under the action of a supported catalyst, esterifying menthol and N,N-dimethylglycine to obtain 2-isopropyl-5-methylcyclohexyl-2-(dimethylamino)acetic acid ester. Then, in the reactor, 2-isopropyl-5-methylcyclohexyl-2-(dimethylamino)acetic acid ester undergoes a solvent-free condensation reaction with 1,10-dichlorodecane at 80-140℃. After the reaction is completed, the mixture is cooled, an organic solvent is added, and the mixture is cooled and crystallized. After filtration and drying, the high-efficiency oilfield geminal quaternary ammonium salt bactericide is obtained. However, with prolonged use, microorganisms easily develop resistance, leading to a gradual decline in bactericidal efficacy. Simultaneously, traditional quaternary ammonium salt bactericides exhibit poor stability in high-salinity, high-temperature oilfield environments. Calcium and magnesium ions in high-salinity environments may also combine with quaternary ammonium salts to form insoluble salts, further reducing their bactericidal efficacy and limiting their application range. Quaternary phosphate salt bactericides, with superior performance and stability compared to traditional quaternary ammonium salts, have already begun to be used in the oilfield field. For example, Chinese patent document CN103988848A discloses a compound oilfield reinjection water bactericide and its preparation method. The bactericide is composed of quaternary phosphate salts, organic bromine compounds, butanediamine, and pure water, with a mass ratio of quaternary phosphate salts, organic bromine compounds, butanediamine, and pure water of 20–30:10–20:10–20:30–60. However, problems such as high preparation costs still exist.

[0004] Therefore, developing a novel bactericide that is highly efficient, simple to process, and low in cost has become an urgent problem to be solved. Summary of the Invention

[0005] This invention provides an asymmetric quaternary ammonium salt surfactant and its preparation method, which overcomes the shortcomings of the prior art and can effectively solve the problems of strong drug resistance and insufficient bactericidal efficiency of existing oilfield bactericides.

[0006] One of the technical solutions of this invention is achieved through the following measures: an asymmetric bisquaternary ammonium salt surfactant having the following chemical structure: Where n is an integer from 10 to 16; X is the element chlorine and / or bromine.

[0007] The following are further optimizations and / or improvements to one of the above-mentioned inventive technical solutions: The aforementioned asymmetric quaternary ammonium salt surfactants are used as bactericides in oil fields.

[0008] The above-mentioned asymmetric bis-quaternary ammonium salt surfactant was prepared according to the following steps: Step 1: Mix p-dimethylaminobenzaldehyde and organic solvent evenly, add 3-dimethylaminopropylamine, and reflux to obtain a reaction mixture; Step 2: Add haloalkanes to the reaction mixture, reflux the reaction, and the reaction product is concentrated and recrystallized to obtain an asymmetric quaternary ammonium salt surfactant.

[0009] The above molar ratio of p-dimethylaminobenzaldehyde, 3-dimethylaminopropylamine and haloalkanes is (1.0 to 1.2):1.0:(2.0 to 2.2).

[0010] The aforementioned halogenated hydrocarbons are chlorinated alkanes or bromoalkanes.

[0011] The organic solvents mentioned above are ethanol or acetonitrile.

[0012] In step one above, the reflux reaction temperature is 60°C to 80°C.

[0013] In step one above, the reflux reaction time is 4 to 12 hours.

[0014] In step two above, the reflux reaction temperature is 70°C to 90°C.

[0015] In step two above, the reflux reaction temperature is 8 to 12 hours.

[0016] The second technical solution of the present invention is achieved through the following measures: a method for preparing an asymmetric bis-quaternary ammonium salt surfactant, comprising the following steps: Step 1: Mix p-dimethylaminobenzaldehyde and organic solvent evenly, add 3-dimethylaminopropylamine, and reflux to obtain a reaction mixture; Step 2: Add haloalkanes to the reaction mixture, reflux the reaction, and the reaction product is concentrated and recrystallized to obtain an asymmetric quaternary ammonium salt surfactant.

[0017] The third technical solution of the present invention is achieved through the following measures: the application of an asymmetric quaternary ammonium salt surfactant as a bactericide for oil fields.

[0018] This invention provides an asymmetric bis-quaternary ammonium salt surfactant, its preparation method, and its application. The preparation method is reliable in principle, simple to operate, has mild reaction conditions, and a high product yield. The bactericidal performance of this asymmetric bis-quaternary ammonium salt surfactant is significantly better than that of traditional bactericides. It can effectively kill harmful microorganisms such as sulfate-reducing bacteria and is not prone to inducing drug resistance, thus having broad market application prospects. Detailed Implementation

[0019] This invention is not limited to the following embodiments, and specific implementation methods can be determined according to the technical solutions and actual conditions of this invention. Unless otherwise specified, all chemical reagents and chemicals mentioned in this invention are well-known and commonly used chemical reagents and chemicals in the prior art; unless otherwise specified, all percentages in this invention are mass percentages; unless otherwise specified, all solutions in this invention are aqueous solutions with water as the solvent, for example, hydrochloric acid solution is an aqueous solution of hydrochloric acid; room temperature in this invention generally refers to a temperature between 15°C and 25°C, generally defined as 25°C.

[0020] The present invention will be further described below with reference to embodiments: Example 1: This asymmetric bisquaternary ammonium salt surfactant has the following chemical structure: Where n is an integer from 10 to 16; X is the element chlorine and / or bromine.

[0021] Example 2: As an optimization of the above example, the asymmetric quaternary ammonium salt surfactant is used as a bactericide for oil fields.

[0022] Example 3: As an optimization of the above examples, the asymmetric bisquaternary ammonium salt surfactant was prepared according to the following steps: Step 1: Mix p-dimethylaminobenzaldehyde and organic solvent evenly, add 3-dimethylaminopropylamine, and reflux to obtain a reaction mixture; Step 2: Add haloalkanes to the reaction mixture, reflux the reaction, and the reaction product is concentrated and recrystallized to obtain an asymmetric quaternary ammonium salt surfactant.

[0023] Example 4: As an optimization of the above example, the molar ratio of p-dimethylaminobenzaldehyde, 3-dimethylaminopropylamine and haloalkanes is (1.0 to 1.2):1.0:(2.0 to 2.2).

[0024] Example 5: As an optimization of the above examples, the halogenated hydrocarbon is a chloroalkane or a bromoalkane.

[0025] Example 6: As an optimization of the above examples, the organic solvent is ethanol or acetonitrile.

[0026] Example 7: As an optimization of the above example, in step one, the reflux reaction temperature is 60°C to 80°C.

[0027] Example 8: As an optimization of the above example, in step one, the reflux reaction time is 4h to 12h.

[0028] Example 9: As an optimization of the above example, in step two, the reflux reaction temperature is 70°C to 90°C.

[0029] Example 10: As an optimization of the above example, in step two, the reflux reaction temperature is 8h to 12h.

[0030] Another objective of this invention is to provide a method for preparing the aforementioned asymmetric bis-quaternary ammonium salt surfactant. Using p-dimethylaminobenzaldehyde, 3-dimethylaminopropylamine, and haloalkanes as raw materials, the surfactant is prepared via a one-pot process involving aldehyde-amine condensation and quaternization in two steps. This method is reliable in principle, simple to operate, and operates under mild reaction conditions, thus possessing broad market application prospects. Furthermore, this surfactant exhibits excellent inhibitory and bactericidal effects against common harmful microorganisms in oilfields, such as sulfate-reducing bacteria and saprophytic bacteria.

[0031] The chemical reaction mechanism of the above preparation method is as follows: Where n is an integer from 10 to 16; X is the element chlorine and / or bromine.

[0032] Example 11: Application of this asymmetric quaternary ammonium salt surfactant as a bactericide for oil fields.

[0033] Example 12: This asymmetric bisquaternary ammonium salt surfactant was prepared according to the following steps: (1) Synthesis of Schiff base intermediates: In a 250 mL reaction vessel equipped with a stirrer and a reflux condenser, 0.12 mol of p-dimethylaminobenzaldehyde and 50 mL of anhydrous ethanol were added. Stirring was started, and 0.10 mol of 3-dimethylaminopropylamine was slowly added dropwise. After the addition was completed, the temperature was raised to 80 °C, and the mixture was stirred and refluxed for 12 h to obtain a reaction mixture.

[0034] (2) Synthesis of asymmetric bisquaternary ammonium salt surfactants: 0.22 mol of bromododecane was slowly added dropwise to the reaction mixture; after the addition was complete, the temperature was raised to 90 °C and the mixture was stirred and refluxed for 12 h. After the reaction was completed, the mixture was cooled to room temperature, and ethanol was removed by vacuum distillation. The crude product was recrystallized from ethyl acetate and dried under vacuum to obtain an asymmetric quaternary ammonium salt surfactant bactericide with a yield of 96.5%.

[0035] Example 13: This asymmetric bisquaternary ammonium salt surfactant was prepared according to the following steps: (1) Synthesis of Schiff base intermediates: In a 250 mL reaction vessel equipped with a stirrer and a reflux condenser, 0.12 mol of p-dimethylaminobenzaldehyde and 50 mL of anhydrous ethanol were added. Stirring was started, and 0.10 mol of 3-dimethylaminopropylamine was slowly added dropwise. After the addition was completed, the temperature was raised to 80 °C and the mixture was stirred and refluxed for 12 h to obtain a reaction mixture.

[0036] (2) Synthesis of asymmetric bisquaternary ammonium salt surfactants: 0.22 mol of bromotetradecane was slowly added dropwise to the reaction mixture; after the addition was complete, the temperature was raised to 90 °C and the mixture was stirred and refluxed for 12 h. After the reaction was completed, the mixture was cooled to room temperature, and ethanol was removed by vacuum distillation. The crude product was recrystallized from ethyl acetate and dried under vacuum to obtain an asymmetric quaternary ammonium salt surfactant bactericide with a yield of 97.8%.

[0037] Example 14: This asymmetric bisquaternary ammonium salt surfactant was prepared according to the following steps: (1) Synthesis of Schiff base intermediates: In a 250 mL reaction vessel equipped with a stirrer and a reflux condenser, 0.12 mol of p-dimethylaminobenzaldehyde and 50 mL of anhydrous ethanol were added. Stirring was started, and 0.10 mol of 3-dimethylaminopropylamine was slowly added dropwise. After the addition was completed, the temperature was raised to 80 °C, and the mixture was stirred and refluxed for 12 h to obtain a reaction mixture.

[0038] (2) Synthesis of asymmetric bisquaternary ammonium salt surfactants: 0.22 mol of hexadecane bromide was slowly added dropwise to the reaction mixture. After the addition was complete, the temperature was raised to 90 °C and the mixture was stirred and refluxed for 12 h. After the reaction was completed, the mixture was cooled to room temperature, and ethanol was removed by vacuum distillation. The crude product was recrystallized from ethyl acetate and dried under vacuum to obtain an asymmetric quaternary ammonium salt surfactant bactericide with a yield of 99.3%.

[0039] Example 15: This asymmetric bisquaternary ammonium salt surfactant was prepared according to the following steps: (1) Synthesis of Schiff base intermediates: In a 250 mL reaction vessel equipped with a stirrer and a reflux condenser, 0.11 mol of p-dimethylaminobenzaldehyde and 50 mL of anhydrous ethanol were added. Stirring was started, and 0.10 mol of 3-dimethylaminopropylamine was slowly added dropwise. After the addition was completed, the temperature was raised to 70 °C and the mixture was stirred and refluxed for 12 h to obtain a reaction mixture.

[0040] (2) Synthesis of asymmetric bisquaternary ammonium salt surfactants: 0.21 mol of bromotetradecane was slowly added dropwise to the reaction mixture; after the addition was complete, the temperature was raised to 90 °C and the mixture was stirred and refluxed for 12 h. After the reaction was completed, the mixture was cooled to room temperature, and ethanol was removed by vacuum distillation. The crude product was recrystallized from ethyl acetate and dried under vacuum to obtain an asymmetric quaternary ammonium salt surfactant bactericide with a yield of 97.8%.

[0041] Example 16: This asymmetric bisquaternary ammonium salt surfactant was prepared according to the following steps: (1) Synthesis of Schiff base intermediates: In a 250 mL reaction vessel equipped with a stirrer and a reflux condenser, 0.11 mol of p-dimethylaminobenzaldehyde and 50 mL of anhydrous ethanol were added. Stirring was started, and 0.10 mol of 3-dimethylaminopropylamine was slowly added dropwise. After the addition was completed, the temperature was raised to 60 °C and the mixture was stirred and refluxed for 8 h to obtain a reaction mixture.

[0042] (2) Synthesis of asymmetric bisquaternary ammonium salt surfactants: 0.2 mol of bromotetradecane was slowly added dropwise to the reaction mixture; after the addition was complete, the temperature was raised to 90 °C and the mixture was stirred and refluxed for 12 h. After the reaction was completed, the mixture was cooled to room temperature, and ethanol was removed by vacuum distillation. The crude product was recrystallized from ethyl acetate and dried under vacuum to obtain an asymmetric quaternary ammonium salt surfactant bactericide with a yield of 97.5%.

[0043] Example 17: This asymmetric bisquaternary ammonium salt surfactant was prepared according to the following steps: (1) Synthesis of Schiff base intermediates: In a 250 mL reaction vessel equipped with a stirrer and a reflux condenser, 0.11 mol of p-dimethylaminobenzaldehyde and 50 mL of anhydrous ethanol were added. Stirring was started, and 0.10 mol of 3-dimethylaminopropylamine was slowly added dropwise. After the addition was completed, the temperature was raised to 60 °C and the mixture was stirred and refluxed for 6 h to obtain a reaction mixture.

[0044] (2) Synthesis of asymmetric bisquaternary ammonium salt surfactants: 0.2 mol of bromotetradecane was slowly added dropwise to the reaction mixture; after the addition was complete, the temperature was raised to 80 °C and the mixture was stirred and refluxed for 12 h. After the reaction was completed, the mixture was cooled to room temperature, and ethanol was removed by vacuum distillation. The crude product was recrystallized from ethyl acetate and dried under vacuum to obtain an asymmetric quaternary ammonium salt surfactant bactericide with a yield of 97.5%.

[0045] Comparative example: Oilfield conventional bactericide 1227 (dodecyl dimethyl benzyl ammonium chloride).

[0046] Test example: According to the standard "Q / SY 49-2010 Technical Requirements for Bactericides Used in Oilfields", relevant bactericidal tests were conducted. The reinjection water of a certain area of ​​an oilfield was used as the test object. The conventional oilfield bactericide 1227 (dodecyl dimethyl benzyl ammonium chloride) was used as a comparative experiment. The asymmetric quaternary ammonium salt surfactant prepared in Examples 12 to 17 and the usage of the comparative example were both 50 mg / L. The performance of the bactericide was evaluated, and the results are shown in Table 1.

[0047] Table 1. Evaluation results of sterilization effect .

[0048] As shown in Table 1, the conventional bactericide 1227 achieved kill rates of 88.4%, 89.2%, and 86.8% against sulfate-reducing bacteria, saprophytic bacteria, and iron bacteria, respectively. This indicates that sulfate-reducing bacteria, saprophytic bacteria, and iron bacteria in the reinjected water of this area have developed high resistance to conventional bactericide 1227, and its bactericidal effect can no longer meet the needs of oilfield production. Compared with conventional bactericide 1227, the asymmetric bis-quaternary ammonium salt surfactants in Examples 12 to 17 performed exceptionally well, achieving kill rates of over 96.4% against all tested bacterial species, and in most cases approaching or reaching 100%. The asymmetric bis-quaternary ammonium salt surfactant of this invention contains two hydrophobic chains and two quaternary ammonium salt hydrophilic groups, which can more efficiently disrupt bacterial cell membranes, thus exhibiting higher bactericidal activity and being less likely to induce microbial resistance.

[0049] In summary, this invention provides an asymmetric bis-quaternary ammonium salt surfactant and its preparation method. The preparation process is simple, employing a one-pot synthesis method with mild reaction conditions, convenient operation, and high product yield. The prepared asymmetric bis-quaternary ammonium salt surfactant is not prone to drug resistance, and its unique bis-quaternary ammonium salt structure can efficiently disrupt bacterial cell membranes, making it less likely for microorganisms to develop drug resistance. It has an extremely high kill rate against harmful microorganisms such as sulfate-reducing bacteria and saprophytic bacteria, and its performance is superior to traditional bactericides, demonstrating significant advantages in oilfield bactericidal applications.

[0050] The above technical features constitute various embodiments of the present invention, which have strong adaptability and implementation effect. Unnecessary technical features can be added or removed according to actual needs to meet the needs of different situations.

Claims

1. An asymmetric bisquaternary ammonium salt surfactant, characterized in that... Asymmetric bisquaternary ammonium salt surfactants have the following chemical structures: Where n is an integer from 10 to 16; X is the element chlorine and / or bromine.

2. The asymmetric bis-quaternary ammonium salt surfactant according to claim 1, characterized in that... The asymmetric quaternary ammonium salt surfactant is used as a bactericide in oil fields.

3. The asymmetric bis-quaternary ammonium salt surfactant according to claim 2, characterized in that... It is prepared according to the following steps: Step 1: Mix p-dimethylaminobenzaldehyde and organic solvent evenly, add 3-dimethylaminopropylamine, and reflux to obtain a reaction mixture; Step 2: Add haloalkanes to the reaction mixture, reflux the reaction, and the reaction product is concentrated and recrystallized to obtain an asymmetric quaternary ammonium salt surfactant.

4. The asymmetric bis-quaternary ammonium salt surfactant according to claim 3, characterized in that... The molar ratio of p-dimethylaminobenzaldehyde, 3-dimethylaminopropylamine and haloalkanes is (1.0 to 1.2):1.0:(2.0 to 2.2).

5. The asymmetric bis-quaternary ammonium salt surfactant according to claim 3 or 4, characterized in that... Halogenated hydrocarbons are chlorinated alkanes or bromoalkanes.

6. The asymmetric bis-quaternary ammonium salt surfactant according to claim 3 or 4, characterized in that... The organic solvent is ethanol or acetonitrile.

7. The asymmetric bis-quaternary ammonium salt surfactant according to claim 3, characterized in that... In step one, the reflux reaction temperature is 60℃ to 80℃, and the reflux reaction time is 4h to 12h.

8. The asymmetric bis-quaternary ammonium salt surfactant according to claim 3, characterized in that... In step two, the reflux reaction temperature is 70°C to 90°C, and the reflux reaction time is 8 hours to 12 hours.

9. A method for preparing an asymmetric bis-quaternary ammonium salt surfactant according to any one of claims 1 to 8, characterized in that... Includes the following steps: Step 1: Mix p-dimethylaminobenzaldehyde and organic solvent evenly, add 3-dimethylaminopropylamine, and reflux to obtain a reaction mixture; Step 2: Add haloalkanes to the reaction mixture, reflux the reaction, and the reaction product is concentrated and recrystallized to obtain an asymmetric quaternary ammonium salt surfactant.

10. The application of an asymmetric quaternary ammonium salt surfactant according to any one of claims 1 to 8 as a bactericide for oil fields.

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