Bactericide for oil field as well as synthesis method and application of bactericide

Abstract

The invention belongs to the technical field of sewage treatment and relates to a bactericide for an oil field as well as a synthesis method and application thereof. The synthesis method comprises the following steps: sequentially adding cyanuric chloride and water into a reactor, slowly adding N-(2-aminoethyl) morpholine, maintaining the pH value to be 6-7, and continuously reacting after dropwise adding; 2, 6-dichloro-4-aminophenol is added into the reactor in batches, the pH is maintained to be 7-8, and the reaction continues after dropwise adding is completed; 2-amino-4-methylthiazole is added into the reactor in batches, slow stirring and heating are conducted, the pH value is maintained to be 7-8, and reaction continues after dropwise adding is completed; and after the reaction is finished, cooling to below 30 DEG C, extracting with chloroform, and distilling under reduced pressure to obtain the product bactericide. The bactericide disclosed by the invention has the characteristic of broad-spectrum sterilization, and has a relatively good sterilization effect on SRB, TGB and FB.

Description

Technical Field

[0001] The invention belongs to the technical field of sewage treatment and relates to a fungicide for oil fields and a synthesis method and application thereof. Background Art

[0002] At present, during the development of oil fields, the reservoir pressure gradually decreases, and the crude oil production will also decrease. Therefore, it is necessary to take technological measures to replenish the energy of the formation in time to keep the oil layer at a certain pressure.

[0003] The produced water from secondary and tertiary oil recovery is treated and then injected back into the oil layer. This can not only replenish the formation energy and maintain stable production of the oil field, but also reduce the harm caused by sewage discharge to humans and the ecosystem, which is beneficial to protecting the environment. Therefore, it is widely used.

[0004] Since these produced waters are recycled, the composition of the water is becoming more and more complex, and it is easy to breed various bacteria, the most common of which are sulfate-reducing bacteria (SRB), saprophytic bacteria (TGB) and iron bacteria (FB). The growth, metabolism and reproduction of these bacteria can cause corrosion and damage to drilling equipment, water injection pipelines and other metal materials, blockage of pipelines and water injection wells, reduce the pore permeability of the oil layer, hinder water injection oil production, cause the water injection pressure to increase, and directly affect crude oil production.

[0005] Therefore, produced water must be sterilized before reinjection. The most common method is to add fungicides to produced water to kill or inhibit the growth of microorganisms. There are many types of fungicides, and the extent of their killing effects on microorganisms varies. A chemical agent is toxic to a certain microorganism, but may have no effect on another microorganism. Some agents have a bactericidal effect at a slightly higher concentration, but at a certain low concentration, they have a stimulating effect on growth. Only by correctly selecting and using fungicides can the reproduction of harmful bacteria be effectively inhibited.

[0006] CN113519555A discloses a water-based low-toxicity fungicide and a production method thereof, which comprises the following group A solution and group B solution in a weight ratio of 2:1 or 1:1: group A components: 20-30 parts of copper sulfate solution, 20-30 parts of copper hydroxide, 10-20 parts of calcium hydroxide and 100-150 parts of distilled water; group B components: 50-70 parts of quicklime, 50-80 parts of distilled water, 10-15 parts of 2-methyl-4-isothiazole, 10-15 parts of dimethyl-didecyl ammonium chloride, 13 parts of dispersant and 5-10 parts of organic solvent. The invention discloses a water-based low-toxic fungicide and a production method thereof, which can effectively kill bacteria and fungi through the 2-methyl-4-isothiazole and dimethyl-didecyl ammonium chloride, and has low toxicity, and will not cause great harm to the human body for a long time. Although the fungicide has low toxicity, the bactericidal effect is difficult to be satisfactory.

[0007] CN107593703B discloses a bactericide for oilfield water treatment system and its preparation method and application, the bactericide comprises 5wt.% to 60wt.% of dodecyl dimethyl benzyl ammonium halide, 0.5wt.% to 5wt.% of D-amino acid, 10wt.% to 30wt.% of surfactant, 3wt.% to 10wt.% of buffer and the balance of water. The invention has the problem that the amount of bactericide is large and the bactericidal effect is not satisfactory, and the main component is the most common bactericide dodecyl dimethyl benzyl ammonium halide, which is easy to make bacteria resistant. Summary of the invention

[0008] The present invention aims at the deficiencies of the above-mentioned prior art and provides a fungicide for oil fields and its synthesis method and application. The fungicide of the present invention has the advantages of wide raw material sources, simple synthesis process, broad-spectrum bactericidal property, and high efficiency at low concentration.

[0009] One of the purposes of the present invention is to disclose a fungicide for oil fields, the molecular structure of the fungicide is as follows: .

[0010] Another object of the present invention is to provide a method for synthesizing the above-mentioned fungicide, wherein the method comprises the following steps: (1) Add cyanuric chloride and water to the reactor in sequence, stir to make a slurry, cool it to below 2°C with ice water, slowly add N-(2-aminoethyl)morpholine, control the temperature below 10°C, and simultaneously add sodium hydroxide solution dropwise to maintain the pH at 6-7. After the addition is complete, continue the reaction for 10-20 minutes; (2) Add 2,6-dichloro-4-aminophenol to the above reactor in batches, remove the ice bath cooling, stir and react at room temperature, and simultaneously add sodium hydroxide solution dropwise to maintain the pH at 7-8. After the addition is complete, continue the reaction for 30-60 minutes; (3) Add 2-amino-4-methylthiazole in batches to the above reactor, slowly stir and heat to 70-80°C, and simultaneously dropwise add sodium hydroxide solution to maintain the pH at 7-8. After the dropwise addition is complete, continue the reaction for 30-60 minutes; (4) After the reaction is completed, the temperature is lowered to below 30°C, extracted with chloroform, and distilled under reduced pressure to obtain the fungicide product.

[0011] In the present invention, preferably, based on 1 mole of cyanuric chloride, the amounts of N-(2-aminoethyl)morpholine, 2,6-dichloro-4-aminophenol and 2-amino-4-methylthiazole are 0.8-1.2 mole, 0.4-0.6 mole and 0.8-1.2 mole, respectively.

[0012] In the present invention, preferably, in step (1), the mass ratio of the water to the mass ratio of cyanuric chloride is 20-30:1.

[0013] The synthetic reaction equation of the oilfield bactericide of the present invention is as follows: The third object of the present invention is to disclose the application of the above-mentioned bactericide in oilfield wastewater treatment.

[0014] The oil field bactericide of the present invention belongs to a composite bactericide, and the bactericidal groups include chlorophenol, thiophene and morpholine. Among them, chlorophenol can react with proteins, enzymes and other biomacromolecules in bacterial cells to undergo oxidation reactions, thereby destroying the structure and function of these molecules, causing bacterial death or inhibiting growth and reproduction. Thiophene is enough to destroy the cell membrane structure of bacteria and fungi, causing the leakage of cell contents, and then causing the death of microorganisms. Morpholine can kill bacteria by inhibiting the biosynthesis of ergosterol of pathogens and interfering with cell wall formation, and can also interfere with the assembly of cell wall polymers by affecting the rearrangement of the molecular structure of pathogenic cell walls, thereby destroying the formation of cell walls.

[0015] Compared with the prior art, the present invention has the following advantages and beneficial effects: (1) The oilfield fungicide of the present invention has a broad spectrum and can kill SRB, TGB and FB in oily wastewater; (2) The oilfield fungicide of the present invention has the advantages of low concentration and high efficiency. When the concentration is 5 mg / L, the bactericidal rates of SRB, TGB and FB are all above 90%. When the concentration is 10 mg / L, the bactericidal rates of SRB, TGB and FB are all 100%. DETAILED DESCRIPTION

[0016] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0017] The present invention will be further described below in conjunction with specific embodiments: Example 1 (1) Add 0.05 mol of cyanuric chloride and 184 g of water to the reactor in sequence, stir to make a slurry, cool it to below 2°C with ice water, slowly add 0.04 mol of N-(2-aminoethyl)morpholine, control the temperature below 10°C, and simultaneously dropwise add sodium hydroxide solution to maintain the pH at 6-7. After the dropwise addition is completed, continue the reaction for 10 min; (2) Add 0.02 mol of 2,6-dichloro-4-aminophenol in batches to the above reactor, remove the ice bath cooling, stir and react at room temperature, and simultaneously add sodium hydroxide solution dropwise to maintain the pH at 7-8. After the addition is complete, continue the reaction for 30 minutes; (3) Add 0.04 mol of 2-amino-4-methylthiazole in batches to the above reactor, slowly stir and heat to 70°C, and simultaneously dropwise add sodium hydroxide solution to maintain the pH at 7-8. After the dropwise addition is complete, continue the reaction for 30 minutes; (4) After the reaction is completed, the temperature is lowered to below 30°C, extracted with chloroform, and distilled under reduced pressure to obtain the fungicide product.

[0018] Example 2 (1) Add 0.05 mol of cyanuric chloride and 198 g of water to the reactor in sequence, stir to make a slurry, cool it to below 2°C with ice water, slowly add 0.045 mol of N-(2-aminoethyl)morpholine, control the temperature below 10°C, and simultaneously add sodium hydroxide solution dropwise to maintain the pH at 6-7. After the addition is complete, continue the reaction for 20 min; (2) Add 0.03 mol of 2,6-dichloro-4-aminophenol in batches to the above reactor, remove the ice bath cooling, stir and react at room temperature, and simultaneously add sodium hydroxide solution dropwise to maintain the pH at 7-8. After the addition is complete, continue the reaction for 30 minutes; (3) Add 0.045 mol of 2-amino-4-methylthiazole in batches to the above reactor, slowly stir and heat to 70°C, and simultaneously dropwise add sodium hydroxide solution to maintain the pH at 7-8. After the dropwise addition is complete, continue the reaction for 60 minutes; (4) After the reaction is completed, the temperature is lowered to below 30°C, extracted with chloroform, and distilled under reduced pressure to obtain the fungicide product.

[0019] Example 3 (1) Add 0.05 mol of cyanuric chloride and 214 g of water to the reactor in sequence, stir to make a slurry, cool it to below 2°C with ice water, slowly add 0.06 mol of N-(2-aminoethyl)morpholine, control the temperature below 10°C, and simultaneously add sodium hydroxide solution dropwise to maintain the pH at 6-7. After the addition is complete, continue the reaction for 15 min; (2) Add 0.025 mol of 2,6-dichloro-4-aminophenol in batches to the above reactor, remove the ice bath cooling, stir and react at room temperature, and simultaneously add sodium hydroxide solution dropwise to maintain the pH at 7-8. After the addition is complete, continue the reaction for 60 min; (3) Add 0.045 mol of 2-amino-4-methylthiazole in batches to the above reactor, slowly stir and heat to 75°C, and simultaneously dropwise add sodium hydroxide solution to maintain the pH at 7-8. After the dropwise addition is complete, continue the reaction for 60 minutes; (4) After the reaction is completed, the temperature is lowered to below 30°C, extracted with chloroform, and distilled under reduced pressure to obtain the fungicide product.

[0020] Example 4 (1) Add 0.05 mol of cyanuric chloride and 265 g of water to the reactor in sequence, stir to make a slurry, cool it to below 2°C with ice water, slowly add 0.05 mol of N-(2-aminoethyl)morpholine, control the temperature below 10°C, and simultaneously add sodium hydroxide solution dropwise to maintain the pH at 6-7. After the addition is complete, continue the reaction for 12 min; (2) Add 0.02 mol of 2,6-dichloro-4-aminophenol in batches to the above reactor, remove the ice bath cooling, stir and react at room temperature, and simultaneously add sodium hydroxide solution dropwise to maintain the pH at 7-8. After the addition is complete, continue the reaction for 45 minutes; (3) Add 0.055 mol of 2-amino-4-methylthiazole in batches to the above reactor, slowly stir and heat to 75°C, and simultaneously dropwise add sodium hydroxide solution to maintain the pH at 7-8. After the dropwise addition is completed, continue the reaction for 50 minutes; (4) After the reaction is completed, the temperature is lowered to below 30°C, extracted with chloroform, and distilled under reduced pressure to obtain the fungicide product.

[0021] Example 5 (1) Add 0.05 mol of cyanuric chloride and 276 g of water to the reactor in sequence, stir to make a slurry, cool it to below 2°C with ice water, slowly add 0.055 mol of N-(2-aminoethyl)morpholine, control the temperature below 10°C, and simultaneously add sodium hydroxide solution dropwise to maintain the pH at 6-7. After the addition is complete, continue the reaction for 20 min; (2) Add 0.03 mol of 2,6-dichloro-4-aminophenol in batches to the above reactor, remove the ice bath cooling, stir and react at room temperature, and simultaneously add sodium hydroxide solution dropwise to maintain the pH at 7-8. After the addition is complete, continue the reaction for 40 minutes; (3) Add 0.06 mol of 2-amino-4-methylthiazole in batches to the above reactor, slowly stir and heat to 78°C, and simultaneously add sodium hydroxide solution dropwise to maintain the pH at 7-8. After the addition is complete, continue the reaction for 30 minutes; (4) After the reaction is completed, the temperature is lowered to below 30°C, extracted with chloroform, and distilled under reduced pressure to obtain the fungicide product.

[0022] Example 6 (1) Add 0.05 mol of cyanuric chloride and 264 g of water to the reactor in sequence, stir to make a slurry, cool it to below 2°C with ice water, slowly add 0.05 mol of N-(2-aminoethyl)morpholine, control the temperature below 10°C, and simultaneously add sodium hydroxide solution dropwise to maintain the pH at 6-7. After the addition is complete, continue the reaction for 15 min; (2) Add 0.025 mol of 2,6-dichloro-4-aminophenol in batches to the above reactor, remove the ice bath cooling, stir and react at room temperature, and simultaneously add sodium hydroxide solution dropwise to maintain the pH at 7-8. After the addition is complete, continue the reaction for 50 min; (3) Add 0.055 mol of 2-amino-4-methylthiazole in batches to the above reactor, slowly stir and heat to 80°C, and simultaneously dropwise add sodium hydroxide solution to maintain the pH at 7-8. After the dropwise addition is complete, continue the reaction for 50 minutes; (4) After the reaction is completed, the temperature is lowered to below 30°C, extracted with chloroform, and distilled under reduced pressure to obtain the fungicide product.

[0023] Example 7 (1) Add 0.05 mol of cyanuric chloride and 260 g of water to the reactor in sequence, stir to make a slurry, cool it to below 2°C with ice water, slowly add 0.05 mol of N-(2-aminoethyl)morpholine, control the temperature below 10°C, and simultaneously add sodium hydroxide solution dropwise to maintain the pH at 6-7. After the addition is complete, continue the reaction for 10 min; (2) Add 0.02 mol of 2,6-dichloro-4-aminophenol in batches to the above reactor, remove the ice bath cooling, stir and react at room temperature, and simultaneously add sodium hydroxide solution dropwise to maintain the pH at 7-8. After the addition is complete, continue the reaction for 35 minutes; (3) Add 0.06 mol of 2-amino-4-methylthiazole in batches to the above reactor, slowly stir and heat to 80°C, and simultaneously dropwise add sodium hydroxide solution to maintain the pH at 7-8. After the dropwise addition is completed, continue the reaction for 60 minutes; (4) After the reaction is completed, the temperature is lowered to below 30°C, extracted with chloroform, and distilled under reduced pressure to obtain the fungicide product.

[0024] Example 8: Evaluation of sterilization rate Take the external water without adding bactericide from a joint station of Shengli Oilfield and put it into a series of 500ml narrow-mouth bottles, add 5, 8, and 10mg / L of the bactericide of the present invention respectively, shake well, put it in a 60℃ oven, take samples after 1h, use the three-tube MPN method to detect SRB (sulfate-reducing bacteria), TGB (saprophytic bacteria), and FB (iron bacteria), and calculate the bactericidal rate. At the same time, dodecyl dimethyl benzyl ammonium chloride (1227) was used for comparative experiments. The test results are shown in Tables 1, 2, and 3.

[0025] Table 1 SRB sterilization results (sterilization rate, %) 5 8 10 Example 1 93.3 98.7 100 Example 2 92.2 98.7 100 Example 3 91.1 99.3 100 Example 4 93.3 100 100 Example 5 93.3 100 100 Example 6 97.7 100 100 Example 7 97.3 100 100 Comparative Example 0 44.4 81.8 Table 2 TGB sterilization results (sterilization rate, %) 5 8 10 Example 1 93.3 99.3 100 Example 2 93.3 99.3 100 Example 3 95.3 100 100 Example 4 95.9 100 100 Example 5 96.9 100 100 Example 6 97.3 100 100 Example 7 96.9 100 100 Comparative Example 9.6 59.1 81.8 Table 3 FB sterilization results (sterilization rate, %) 5 8 10 Example 1 93.3 100 100 Example 2 93.3 100 100 Example 3 94.7 100 100 Example 4 95.6 100 100 Example 5 96.9 100 100 Example 6 98.4 100 100 Example 7 98.7 100 100 Comparative Example 44.4 81.8 89.5 From Table 1 we can see that: (1) When the fungicide of the present invention (Examples 1-7) was used at a concentration of 5%, the bactericidal rate against SRB was greater than 90%, with the highest reaching 97.7% (Example 6); while the bactericidal rate of the comparative example dodecyl dimethyl benzyl ammonium chloride (1227) was 0, which was significantly lower than that of the present invention; (2) When the fungicide of the present invention (Examples 1-7) was used at a concentration of 8%, the bactericidal rate against SRB was greater than 98%, with the highest reaching 100% (Examples 4, 5, 6 and 7); while the bactericidal rate of the comparative example dodecyl dimethyl benzyl ammonium chloride (1227) was 44.4%, which was significantly lower than that of the present invention; (3) When the fungicide of the present invention (Examples 1-7) was used at a concentration of 10%, the bactericidal rate against SRB reached 100%; while the bactericidal rate of the comparative example dodecyl dimethyl benzyl ammonium chloride (1227) was 81.8%, which was significantly lower than that of the present invention.

[0026] From Table 2 we can see that: (1) When the fungicide of the present invention (Examples 1-7) was used at a concentration of 5%, the bactericidal rate against TGB was greater than 93%, with the highest reaching 97.3% (Example 6); while the bactericidal rate of the comparative example dodecyl dimethyl benzyl ammonium chloride (1227) was 9.6%, which was significantly lower than that of the present invention; (2) When the fungicide of the present invention (Examples 1-7) was used at a concentration of 8%, the bactericidal rate against TGB was greater than 99%, with the highest reaching 100%; while the bactericidal rate of the comparative example dodecyl dimethyl benzyl ammonium chloride (1227) was 59.1%, which was significantly lower than that of the present invention; (3) When the fungicide of the present invention (Examples 1-7) was used at a concentration of 10%, the bactericidal rate against TGB reached 100%; while the bactericidal rate of the comparative example dodecyl dimethyl benzyl ammonium chloride (1227) was 81.8%, which was significantly lower than that of the present invention.

[0027] From Table 3 we can see that: (1) When the fungicide of the present invention (Examples 1-7) was used at a concentration of 5%, the bactericidal rate against FB was greater than 93%, with the highest reaching 98.7%; while the bactericidal rate of the comparative example dodecyl dimethyl benzyl ammonium chloride (1227) was 44.4%, which was significantly lower than that of the present invention; (2) When the fungicide of the present invention (Examples 1-7) was used at a concentration of 8%, the bactericidal rate against FB reached 100%; while the bactericidal rate of the comparative example dodecyl dimethyl benzyl ammonium chloride (1227) was 81.8%, which was significantly lower than that of the present invention; (3) When the fungicide of the present invention (Examples 1-7) was used at a concentration of 10%, the bactericidal rate against FB reached 100%; while the bactericidal rate of the comparative example dodecyl dimethyl benzyl ammonium chloride (1227) was 89.5%, which was significantly lower than that of the present invention.

[0028] The preferred embodiments of the present invention are described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the technical concept of the present invention, a variety of simple modifications can be made to the technical solution of the present invention, and these simple modifications all belong to the protection scope of the present invention.

[0029] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not further describe various possible combinations.

[0030] In addition, various embodiments of the present invention may be arbitrarily combined, and as long as they do not violate the concept of the present invention, they should also be regarded as the contents disclosed by the present invention.

Claims

1. A method for synthesizing an oilfield fungicide, characterized in that: The synthetic method specifically comprises the following steps: (1) Add cyanuric chloride and water to the reactor in sequence, stir to make a slurry, cool it to below 2°C with ice water, slowly add N-(2-aminoethyl)morpholine, control the temperature below 10°C, and simultaneously add sodium hydroxide solution dropwise to maintain the pH at 6-7. After the addition is complete, continue the reaction for 10-20 minutes; (2) Add 2,6-dichloro-4-aminophenol to the above reactor in batches, remove the ice bath cooling, stir and react at room temperature, and simultaneously add sodium hydroxide solution dropwise to maintain the pH at 7-8. After the addition is complete, continue the reaction for 30-60 minutes; (3) Add 2-amino-4-methylthiazole in batches to the above reactor, slowly stir and heat to 70-80°C, and simultaneously dropwise add sodium hydroxide solution to maintain the pH at 7-8. After the dropwise addition is complete, continue the reaction for 30-60 minutes; (4) After the reaction is completed, the temperature is lowered to below 30°C, chloroform extraction is performed, and vacuum distillation is performed to obtain the product fungicide; Based on 1 mole of cyanuric chloride, the amounts of N-(2-aminoethyl)morpholine, 2,6-dichloro-4-aminophenol and 2-amino-4-methylthiazole are 0.8-1.2 mole, 0.4-0.6 mole and 0.8-1.2 mole respectively.

2. The method for synthesizing an oilfield bactericide according to claim 1, characterized in that: In step (1), the mass ratio of the water to the cyanuric chloride is 20-30:

1.

3. The fungicide prepared by the synthesis method according to any one of claims 1 or 2, characterized in that: The molecular structure of the bactericide is as follows: 。 4. Use of the bactericide according to claim 3 in oilfield wastewater treatment.

Images