Oil field water treatment bactericide and preparation method thereof

Abstract

The invention relates to the technical field of sewage treatment, and discloses an oilfield water treatment bactericide and a preparation method thereof.The preparation method comprises the following steps that didodecyl dimethyl ammonium chloride, modified triphenylphosphine, modified sulfathiazole and water are added into a reactor and stirred for 20-30 min at the temperature of 35-45 DEG C, and the oilfield water treatment bactericide is obtained. The bactericide provided by the invention has good bactericidal performance.

Description

Technical Field

[0001] The invention relates to the technical field of sewage treatment, in particular to an oilfield water treatment bactericide and a preparation method thereof. Background Art

[0002] Bactericides can effectively control the contamination of oilfield microorganisms, but due to the increase in bacterial resistance, some bactericides have become ineffective, and due to the residues of certain oxidizing bactericides, corrosion to pipelines and equipment has increased. The most common microorganisms are sulfate-reducing bacteria (SRB), saprophytic bacteria (TGB) and iron bacteria (FB). The growth, metabolism and reproduction of these bacteria will lead to blockage of oil reservoirs and reduced production capacity, deterioration of crude oil quality, and affect crude oil production. Therefore, how to avoid this phenomenon is the key to solving the problem. Existing bactericides are highly corrosive and may cause bacteria to develop drug resistance. For example, patent CN119285473A discloses a bactericide for oilfields and its synthesis method and application. The bactericide is prepared from N, N-dimethylbenzylamine, ethanol, dibromooctane, and 4,6-dichloro-2-aminophenol. The invention has a simple synthesis process, but its antibacterial effect needs to be improved. Summary of the invention

[0003] 1. Technical issues to be resolved In view of the deficiencies of the prior art, the present invention provides an oilfield water treatment bactericide and a preparation method thereof. The bactericide of the present invention has good bactericidal performance.

[0004] (II) Technical solution To achieve the above-mentioned purpose, the present invention provides the following technical scheme: a fungicide for oilfield water treatment and a preparation method thereof, characterized in that it comprises the following components by weight: 3-5 parts by weight of didodecyldimethylammonium chloride, 1-3 parts by weight of water, 6-8 parts by weight of modified triphenylphosphine, and 2-4 parts by weight of modified sulfathiazole.

[0005] Furthermore, the preparation method of the modified triphenylphosphine is: Step 1: Add 4-vinylbenzyl chloride and triphenylphosphine to acetone solvent, stir evenly, react at 55-65°C for 20-22h, and after the reaction is completed, cool to room temperature and dry to obtain intermediate 1; Step 2: Add intermediate 1 and hexamethyldisilazane to toluene solvent, stir evenly, then add chloroplatinic acid catalyst, react at 100-110° C. for 12-13 hours, and then distill under reduced pressure, filter, wash and dry to obtain intermediate 2; Step 3: Under the protection of inert gas, add intermediate 2 and 3,4-dichlorobenzyl chloride to toluene solvent, stir evenly, react at 70-80°C for 8-14h. After the reaction is completed, cool to room temperature, filter, concentrate the filtrate, and purify by column chromatography to obtain modified triphenylphosphine.

[0006] Furthermore, in the step 1, the usage ratio of acetone, 4-vinylbenzyl chloride and triphenylphosphine is 48-50mL:8.3-8.5g:14.8-15.0g.

[0007] Furthermore, in the step 2, the dosage ratio of toluene, intermediate 1, hexamethyldisilazane, and chloroplatinic acid catalyst is 40-45 mL: 9.4-9.5 g: 5.8-6.0 g: 2-3 mL.

[0008] Furthermore, in the step three, the usage ratio of toluene and the intermediate 2,3,4-dichlorobenzyl chloride is 42-46 mL:9.4-9.8 g:6.3-6.5 g.

[0009] Furthermore, the preparation method of the modified sulfathiazole is: add sulfathiazole, 3-chlorobenzaldehyde, and p-toluenesulfonic acid catalyst to 130-150 mL of anhydrous ethanol, reflux and stir at 75-85° C. for 6-8 hours, cool and concentrate under reduced pressure, wash, and dry to obtain the modified sulfathiazole.

[0010] Furthermore, the usage ratio of sulfathiazole, 3-chlorobenzaldehyde and p-toluenesulfonic acid catalyst is 7.62-7.68g:2.85-2.90g:0.35-0.38g.

[0011] Furthermore, the preparation method of the oilfield water treatment fungicide is: adding didodecyl dimethyl ammonium chloride, modified triphenylphosphine, modified sulfathiazole and water into a reactor, stirring at 35-45° C. for 20-30 minutes to obtain the oilfield water treatment fungicide.

[0012] 3. Beneficial technical effects The invention prepares the oilfield water treatment bactericide by adding didodecyl dimethyl ammonium chloride, modified triphenylphosphine, modified sulfathiazole and water into a reactor, stirring at 35-45 DEG C for 20-30 minutes.

[0013] 4-vinylbenzyl chloride and triphenylphosphine were reacted in acetone solvent to obtain intermediate 1, which introduced a quaternary phosphonium salt group, which can destroy the cell membrane of microorganisms. For example, the cell membrane of sulfate-reducing bacteria (SRB) contains a large amount of anionic phospholipids (such as phosphatidylglycerol). +It can effectively penetrate the thick cell wall of SRB and improve the bactericidal effect. It then reacts with hexamethyldisilazane (amine) under the action of chloroplatinic acid catalyst to introduce quaternary ammonium groups to obtain intermediate 2. The quaternary ammonium groups have broad-spectrum bactericidal properties and have a killing effect on SRB, TGB, and FB commonly found in oil fields. Intermediate 2 reacts with 3,4-dichlorobenzyl chloride to obtain modified triphenylphosphine. The introduction of chlorine can penetrate the bacterial cell membrane and oxidize the unsaturated double bonds in the membrane lipids, resulting in loss of membrane integrity and leakage of intracellular substances.

[0014] Sulfathiazole and 3-chlorobenzaldehyde are reacted under the action of p-toluenesulfonic acid catalyst to obtain modified sulfathiazole. The Schiff base group in the modified sulfathiazole can play a bactericidal role through metal ion chelation. For example, the key metal enzymes of sulfate-reducing bacteria (SRB) depend on Fe²⁺ / Zn²⁺. Schiff base can strongly chelate these metal ions, resulting in inactivation of key enzymes of microorganisms. The thiazole group in the modified sulfathiazole has broad-spectrum antibacterial activity. After modification with 3-chlorobenzaldehyde, the bactericidal effect can be improved by enhancing membrane permeability and expanding the antibacterial spectrum. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 It is the H NMR spectrum of the intermediate 1 in claim 2.

[0016] Figure 2 It is the nuclear magnetic hydrogen spectrum of intermediate 2 in claim 2.

[0017] Figure 3 It is the nuclear magnetic hydrogen spectrum of the modified triphenylphosphine in claim 2.

[0018] Figure 4 It is the hydrogen nuclear magnetic spectrum of the modified sulfathiazole of claim 6. DETAILED DESCRIPTION

[0019] In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0020] In order to better understand the above technical solution, the above technical solution will be described in detail below in conjunction with the accompanying drawings and specific embodiments of the specification. Example 1

[0021] (1) Add 8.3 g of 4-vinylbenzyl chloride and 14.8 g of triphenylphosphine to 48 mL of acetone solvent, stir evenly, and react at 55 °C for 20 h. After the reaction is completed, cool to room temperature and dry to obtain intermediate 1. The reaction process is as follows:

[0022] (2) Add 9.4 g of intermediate 1 and 5.8 g of hexamethyldisilazane to 40 mL of toluene solvent, stir evenly, then add 2 mL of chloroplatinic acid catalyst, react at 100 ° C for 12 h, and then distill under reduced pressure, filter, wash and dry to obtain intermediate 2; the reaction process is as follows:

[0023] (3) Under nitrogen protection, 9.4 g of intermediate 2 and 6.3 g of 3,4-dichlorobenzyl chloride were added to 42 mL of toluene solvent, stirred evenly, and reacted at 70°C for 8 h. After the reaction was completed, the mixture was cooled to room temperature, filtered, and the filtrate was concentrated. The modified triphenylphosphine was purified by column chromatography. The reaction process was as follows:

[0024] (4) Add 7.62 g of sulfathiazole, 2.85 g of 3-chlorobenzaldehyde and 0.35 g of p-toluenesulfonic acid catalyst to 130 mL of anhydrous ethanol, reflux and stir at 75 °C for 6 h, cool, concentrate under reduced pressure, wash and dry to obtain modified sulfathiazole; the reaction process is as follows:

[0025] (5) Add didodecyl dimethyl ammonium chloride, modified triphenylphosphine, modified sulfathiazole and water into a reactor and stir for 20 minutes at 35° C. to obtain a fungicide for oilfield water treatment. Example 2

[0026] (1) Add 8.5 g of 4-vinylbenzyl chloride and 15.0 g of triphenylphosphine to 50 mL of acetone solvent, stir evenly, and react at 65 °C for 22 h. After the reaction is completed, cool to room temperature and dry to obtain intermediate 1; (2) Add 9.5 g of intermediate 1 and 6.0 g of hexamethyldisilazane to 45 mL of toluene solvent, stir evenly, then add 3 mL of chloroplatinic acid catalyst, react at 110 °C for 13 h, and then distill under reduced pressure, filter, wash and dry to obtain intermediate 2; (3) Under nitrogen protection, 9.8 g of intermediate 2 and 6.5 g of 3,4-dichlorobenzyl chloride were added to 46 mL of toluene solvent, stirred evenly, and reacted at 80 °C for 14 h. After the reaction was completed, the mixture was cooled to room temperature, filtered, and the filtrate was concentrated and purified by column chromatography to obtain modified triphenylphosphine; (4) Add 7.68 g of sulfathiazole, 2.90 g of 3-chlorobenzaldehyde, and 0.38 g of p-toluenesulfonic acid catalyst to 150 mL of anhydrous ethanol, reflux and stir at 85 °C for 8 h, cool, concentrate under reduced pressure, wash, and dry to obtain modified sulfathiazole; (5) Add didodecyl dimethyl ammonium chloride, modified triphenylphosphine, modified sulfathiazole and water into a reactor and stir for 30 minutes at 45° C. to obtain a fungicide for oilfield water treatment. Example 3

[0027] (1) Add 8.4 g of 4-vinylbenzyl chloride and 14.9 g of triphenylphosphine to 49 mL of acetone solvent, stir evenly, and react at 60 °C for 21 h. After the reaction is completed, cool to room temperature and dry to obtain intermediate 1; (2) Add 9.4 g of intermediate 1 and 5.9 g of hexamethyldisilazane to 43 mL of toluene solvent, stir evenly, then add 2 mL of chloroplatinic acid catalyst, react at 105 °C for 12 h, and then distill under reduced pressure, filter, wash and dry to obtain intermediate 2; (3) Under nitrogen protection, 9.6 g of intermediate 2 and 6.4 g of 3,4-dichlorobenzyl chloride were added to 44 mL of toluene solvent, stirred evenly, and reacted at 75 °C for 11 h. After the reaction was completed, the mixture was cooled to room temperature, filtered, and the filtrate was concentrated and purified by column chromatography to obtain modified triphenylphosphine; (4) Add 7.65 g of sulfathiazole, 2.88 g of 3-chlorobenzaldehyde, and 0.36 g of p-toluenesulfonic acid catalyst to 140 mL of anhydrous ethanol, reflux and stir at 80 °C for 7 h, cool, concentrate under reduced pressure, wash, and dry to obtain modified sulfathiazole; (5) Add didodecyl dimethyl ammonium chloride, modified triphenylphosphine, modified sulfathiazole and water into a reactor, stir at 40° C. for 25 minutes, and obtain a fungicide for oilfield water treatment. Example 4

[0028] (1) Add 8.3 g of 4-vinylbenzyl chloride and 15.0 g of triphenylphosphine to 48 mL of acetone solvent, stir evenly, and react at 65 °C for 20 h. After the reaction is completed, cool to room temperature and dry to obtain intermediate 1; (2) Add 9.4 g of intermediate 1 and 6.0 g of hexamethyldisilazane to 45 mL of toluene solvent, stir evenly, then add 3 mL of chloroplatinic acid catalyst, react at 110 °C for 13 h, and then distill under reduced pressure, filter, wash and dry to obtain intermediate 2; (3) Under nitrogen protection, 9.4 g of intermediate 2 and 6.3 g of 3,4-dichlorobenzyl chloride were added to 46 mL of toluene solvent, stirred evenly, and reacted at 70 °C for 11 h. After the reaction was completed, the mixture was cooled to room temperature, filtered, and the filtrate was concentrated and purified by column chromatography to obtain modified triphenylphosphine; (4) Add 7.65 g of sulfathiazole, 2.88 g of 3-chlorobenzaldehyde, and 0.35 g of p-toluenesulfonic acid catalyst to 150 mL of anhydrous ethanol, reflux and stir at 80 °C for 7 h, cool, concentrate under reduced pressure, wash, and dry to obtain modified sulfathiazole; (5) Add didodecyl dimethyl ammonium chloride, modified triphenylphosphine, modified sulfathiazole and water into a reactor and stir for 20 minutes at 40° C. to obtain a fungicide for oilfield water treatment.

[0029] Comparative Example 1 Compared with Example 4, this comparative example differs in that Intermediate 1 is used instead of modified triphenylphosphine.

[0030] Comparative Example 2 Compared with Example 4, this comparative example differs in that Intermediate 2 is used instead of modified triphenylphosphine.

[0031] Comparative Example 3 Compared with Example 4, this comparative example differs in that no modified triphenylphosphine is added.

[0032] Comparative Example 4 Compared with Example 4, this comparative example is different in that modified sulfathiazole is not added.

[0033] Evaluation of sterilization rate: Water samples from a joint station of Shengli Oilfield were divided into a series of 500 mL narrow-necked bottles, and 5, 10, 15, and 20 mg / L of the fungicide of the present invention and the comparative example fungicide were added respectively, shaken well, placed in a 55° C. oven, and samples were taken after 1 hour. The three-tube method MPN was used to detect the remaining bacterial content, and the sterilization rate was calculated. The test results are shown in Tables 1, 2, and 3.

[0034] Table 1: SRB bactericidal effect (bactericidal rate, %).

[0035] Concentration, mg / L 5 10 15 20 Example 1 87.0 88.3 92.6 95.3 Example 2 87.4 89.4 93.5 96.2 Example 3 89.5 90.1 93.9 97.2 Example 4 90.1 90.5 95.8 97.8 Comparative Example 1 50.9 60.2 65.3 76.6 Comparative Example 2 51.2 60.5 65.5 76.8 Comparative Example 3 50.1 59.4 64.8 76.1 Comparative Example 4 50.3 59.8 65.1 76.3 Table 2: Bactericidal effect of TGB (bactericidal rate, %).

[0036] Concentration, mg / L 5 10 15 20 Example 1 92.6 97.3 97.6 98.3 Example 2 93.4 97.5 98.1 98.4 Example 3 93.8 98.2 98.7 99.1 Example 4 94.1 98.9 99.2 99.3 Comparative Example 1 56.1 70.0 73.9 79.6 Comparative Example 2 56.2 70.3 74.2 79.7 Comparative Example 3 55.6 69.2 73.1 79.2 Comparative Example 4 55.8 69.8 73.5 79.4 Table 3: Bactericidal effect of FB (bactericidal rate, %).

[0037] Concentration, mg / L 5 10 15 20 Example 1 96.8 97.9 98.1 99.2 Example 2 97.1 98.0 98.6 99.3 Example 3 97.6 98.1 98.6 99.6 Example 4 98.3 98.4 98.8 99.6 Comparative Example 1 76.8 81.5 85.6 89.6 Comparative Example 2 76.9 81.7 85.7 89.8 Comparative Example 3 76.3 81.0 85.1 89.3 Comparative Example 4 76.5 81.2 85.4 89.5 From Table 1 we can see that: When the fungicide of the present invention (Examples 1-4) is used at a concentration of 5%, the bactericidal rate of SRB is greater than 87%, and the highest is 90.1% (Example 4); when the concentration is 10%, the bactericidal rate of SRB is greater than 88%, and the highest is 90.5% (Example 4); when the concentration is 15%, the bactericidal rate of SRB is greater than 92%, and the highest is 95.8% (Example 4); when the concentration is 20%, the bactericidal rate of SRB is greater than 95%, and the highest is 97.8% (Example 4); and the bactericidal rates of all comparative examples are significantly lower than those of the present invention at any concentration.

[0038] From Table 2 we can see that: When the bactericide of the present invention (Examples 1-4) is used at a concentration of 5%, the bactericidal rate of TGB is greater than 92%, and the highest is 94.1% (Example 4); when the concentration is 10%, the bactericidal rate of TGB is greater than 97%, and the highest is 98.9% (Example 4); when the concentration is 15%, the bactericidal rate of TGB is greater than 97%, and the highest is 99.2% (Example 4); when the concentration is 20%, the bactericidal rate of TGB is greater than 98%, and the highest is 99.3% (Example 4); and the bactericidal rates of all comparative examples are significantly lower than those of the present invention at any concentration.

[0039] From Table 3 we can see that: When the bactericide of the present invention (Examples 1-4) is used at a concentration of 5%, the bactericidal rate of FB is greater than 96%, and the highest is 98.3% (Example 4); when the concentration is 10%, the bactericidal rate of FB is greater than 97%, and the highest is 98.4% (Example 4); when the concentration is 15%, the bactericidal rate of FB is greater than 98%, and the highest is 98.8% (Example 4); when the concentration is 20%, the bactericidal rate of FB is greater than 99%, and the highest is 99.6% (Example 4); and the bactericidal rates of all comparative examples are significantly lower than those of the present invention at any concentration.

[0040] It should be noted that, in this article, the term "comprises", "includes" or any other variant thereof is intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements includes not only those elements, but also includes other elements not explicitly listed, or also includes elements inherent to such process, method, article or device. In the absence of more restrictions, an element defined by the sentence "comprises a ..." does not exclude the presence of other identical elements in the process, method, article or device including the element.

[0041] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that the technical solutions described in the aforementioned embodiments may still be modified, or some of the technical features may be replaced by equivalents. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present invention.

[0042] Those skilled in the art should understand that the above are only some specific embodiments of the present invention, rather than all embodiments. It should be noted that for those of ordinary skill in the art, many modifications and improvements can be made, and all modifications or improvements that do not exceed the scope of protection of the present invention should be regarded as the scope of protection of the present invention.

Claims

1. A fungicide for oilfield water treatment, characterized in that: The invention comprises the following components by weight: 3-5 parts by weight of didodecyldimethylammonium chloride, 1-3 parts by weight of water, 6-8 parts by weight of modified triphenylphosphine and 2-4 parts by weight of modified sulfathiazole.

2. The oilfield water treatment bactericide according to claim 1, characterized in that: The preparation method of the modified triphenylphosphine is: Step 1: Add 4-vinylbenzyl chloride and triphenylphosphine to acetone solvent, stir evenly, react at 55-65°C for 20-22h, and after the reaction is completed, cool to room temperature and dry to obtain intermediate 1; Step 2: Add intermediate 1 and hexamethyldisilazane to toluene solvent, stir evenly, then add chloroplatinic acid catalyst, react at 100-110° C. for 12-13 hours, and then distill under reduced pressure, filter, wash and dry to obtain intermediate 2; Step 3: Under the protection of inert gas, add intermediate 2 and 3,4-dichlorobenzyl chloride to toluene solvent, stir evenly, react at 70-80°C for 8-14h. After the reaction is completed, cool to room temperature, filter, concentrate the filtrate, and purify by column chromatography to obtain modified triphenylphosphine.

3. The oilfield water treatment bactericide according to claim 2, characterized in that: In the step 1, the usage ratio of acetone, 4-vinylbenzyl chloride and triphenylphosphine is 48-50 mL: 8.3-8.5 g: 14.8-15.0 g.

4. The oilfield water treatment bactericide according to claim 2, characterized in that: In the step 2, the dosage ratio of toluene, intermediate 1, hexamethyldisilazane, and chloroplatinic acid catalyst is 40-45 mL: 9.4-9.5 g: 5.8-6.0 g: 2-3 mL.

5. The oilfield water treatment bactericide according to claim 2, characterized in that: In the step 3, the usage ratio of toluene and the intermediate 2,3,4-dichlorobenzyl chloride is 42-46 mL: 9.4-9.8 g: 6.3-6.5 g.

6. The oilfield water treatment bactericide according to claim 1, characterized in that: The preparation method of the modified sulfathiazole is as follows: sulfathiazole, 3-chlorobenzaldehyde and p-toluenesulfonic acid catalyst are added to 130-150 mL of anhydrous ethanol, refluxed and stirred at 75-85° C. for 6-8 hours, cooled, concentrated under reduced pressure, washed and dried to obtain the modified sulfathiazole.

7. The bactericide for oilfield water treatment according to claim 6, characterized in that: The dosage ratio of the sulfathiazole, 3-chlorobenzaldehyde and p-toluenesulfonic acid catalyst is 7.62-7.68g:2.85-2.90g:0.35-0.38g.

8. A method for preparing an oilfield water treatment bactericide according to any one of claims 1 to 7, characterized in that: The preparation method of the oilfield water treatment bactericide comprises the following steps: adding didodecyl dimethyl ammonium chloride, modified triphenylphosphine, modified sulfathiazole and water into a reactor, stirring at 35-45° C. for 20-30 minutes, and obtaining the oilfield water treatment bactericide.

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