阅读说明：本技术 用于油路管道的杀菌剂及其制备方法和应用 (Bactericide for oil pipeline and preparation method and application thereof ) 是由 徐文峰 杨梅 廖晓玲 张园园 于 2019-10-12 设计创作，主要内容包括：本发明属于化工技术领域,具体涉及用于油路管道的杀菌剂及其制备方法、和在抑制杀灭油田管道中硫酸盐还原菌中的应用。所述杀菌剂由量子点和十二烷基二甲基苄基氯化铵制备而成。所述杀菌剂非常适用于油田管道的杀菌,在一定施药量的基础上,可实现精准附着在菌落处,或吸附细菌,使细菌表面局部达到高浓度的化学杀菌剂,提高了杀菌的经济效果比,以达到防腐蚀的作用；所述油田管道用新型精准杀菌剂的制备方法简单易操作,且可稳定生产所述杀菌剂,适用于工业化大生产。(The invention belongs to the technical field of chemical industry, and particularly relates to a bactericide for oil pipelines, a preparation method of the bactericide and application of the bactericide in inhibiting and killing sulfate reducing bacteria in oil field pipelines. The bactericide is prepared from quantum dots and dodecyl dimethyl benzyl ammonium chloride. The bactericide is very suitable for sterilizing oilfield pipelines, can be accurately attached to bacterial colonies or adsorb bacteria on the basis of a certain application dosage, so that the surface of the bacteria locally reaches high-concentration chemical bactericide, the economic effect ratio of sterilization is improved, and the anti-corrosion effect is achieved; the preparation method of the novel accurate bactericide for the oilfield pipeline is simple and easy to operate, can stably produce the bactericide, and is suitable for industrial mass production.)

1. The bactericide for the oil pipeline is characterized in that the bactericide is an effective amount of chemical bactericide which is dissolved in a quantum dot solution of an phenanthroline-carbon system.

2. The bactericide as claimed in claim 1, wherein the chemical bactericide is dodecyl dimethyl benzyl ammonium chloride.

3. The germicide according to claim 1, wherein the quantum dot solution is prepared from citric acid, urea and phenanthroline.

4. The bactericide as claimed in claim 2, wherein the concentration of the dodecyl dimethyl benzyl ammonium chloride is not less than 12.5 mg/L.

5. The method for removing sulfate-reducing bacteria by using the bactericide as claimed in any one of claims 1 to 4, which comprises the following steps:

1) identification and binding of sulfate-reducing bacteria

The bactericide is fully contacted with a suspected part corroded by the sulfate reducing bacteria, namely the quantum dots in the bactericide and Fe generated after the pipeline is corroded by the sulfate reducing bacteria²⁺And/or Fe³⁺Combined with the quantum dots in the bactericide to react with Fe²⁺And/or Fe³⁺The combined action, if the bactericide and the sulfate-reducing bacteria are aggregated, is judged to be corroded by the sulfate-reducing bacteria;

2) eliminating sulfate reducing bacteria

When an effective amount of the bactericide is accurately attached to the part corroded by the sulfate reducing bacteria, the dodecyl dimethyl benzyl ammonium chloride in the bactericide has a killing effect on the sulfate reducing bacteria, and the bactericide is cleaned.

6. The method of claim 5, wherein in step 1), the suspected location is an oilfield pipeline.

7. The method according to claim 6, characterized in that in step 1) there are a plurality of other suspected sites of corrosion in the oilfield pipeline, to which potassium chloride and/or sodium chloride and/or magnesium chloride and/or aluminium chloride and/or calcium chloride and/or lead acetate and/or copper sulphate and/or nickel sulphate and/or cobalt acetate and/or cadmium sulphate and/or barium chloride and/or chromium nitrate and/or manganese sulphate and/or mercury iodide are attached, the biocide not being bound to the attachments of the other suspected sites.

8. A complex of the bactericidal agent of claim 1 and sulfate-reducing bacteria.

9. A method for detecting iron ions, characterized in that the bactericidal agent of claim 1 is used as a fluorescent probe, and Fe²⁺And/or Fe³⁺And (4) fully combining, and reading the fluorescence spectrum to perform qualitative or quantitative judgment.

10. According to claimThe method of claim 9, wherein the Fe can be compared to a standard fluorescence intensity-concentration curve when reading the fluorescence spectrum for qualitative or quantitative determination²⁺The standard fluorescence intensity-concentration curve equation is that Y is 0.35622X +1.08606, R²0.993, X is not less than 0.13 μ M and not more than 21mM, and Fe³⁺The standard fluorescence intensity-concentration curve equation is that Y is 10.29529X +1.00487, R²X is 67nM < X > 41M < 0.990.

Technical Field

The invention belongs to the technical field of chemical industry, and particularly relates to a novel precise bactericide for an oil field pipeline, a preparation method of the novel precise bactericide and application of the novel precise bactericide in inhibiting and killing sulfate reducing bacteria in the oil field pipeline.

Background

Oil field pipeline corrosion refers to the aging of pipelines for transporting petroleum and petroleum products due to corrosion caused by chemical reaction or other reasons, and is one of the problems frequently encountered in the petrochemical industry. Because petroleum and its products are complex mixtures containing acids, alkalis, salts and other corrosive substances, and are exposed to the open air and exposed to the sun and rain, corrosion reactions are easily caused. And equipment damage caused by corrosion easily causes potential safety hazards and accidents, loss caused by various corrosion accounts for 3% -4% of total GDP every year all over the world, and how to delay corrosion and resist corrosion becomes one of important subjects in industrial production and pipeline oil transportation industries.

In recent years, most oil fields in China enter a high-water-content development period, and the corrosion damage of bacteria is serious in the process of oil field exploitation, so that great economic loss is caused. Among them, sulfate reducing bacteria are the most harmful to corrosion of oil field pipelines. Sulfate reducing bacteria are gram-negative anaerobic bacteria that react with SO under dissimilation₄ ^2-、SO₃ ^2-Reduction to H₂S, metabolization to produce high concentrations of H₂S、Fe(OH)₂And FeS, which causes severe corrosion, blockage, etc. to the pipeline and causes deterioration of water quality, and the primary key to the corrosion prevention of the oilfield pipeline is to inhibit and kill sulfate reducing bacteria. At present, various bactericides capable of inhibiting sulfate-reducing bacteria exist, for example, Chinese patent application with application number of 201910475514.5, N-alkyl biquaternary ammonium salt and dodecyl dimethyl benzyl ammonium chloride (1227 for short) are compounded, and the N-alkyl biquaternary ammonium salt and the dodecyl dimethyl benzyl ammonium chloride can efficiently kill the sulfate-reducing bacteriaSulfate reducing bacteria. Chemical biocides such as those described above are not the best choice for a "special site" of oilfield tubulars. The oil pipeline needs large dosage and high concentration, and general chemical reagents have low efficiency and are sterile. At present, a high-efficiency and accurate sulfate bactericide special for oil pipelines does not exist.

Disclosure of Invention

In view of the above, an object of the present invention is to provide a bactericide for oil pipelines, which can accurately identify sulfate-reducing bacteria.

In order to achieve the purpose, the technical scheme of the invention is as follows:

the bactericide is a chemical bactericide with effective dose, and is dissolved in a quantum dot (quantum dot is CD for short) solution of an o-diazaphenanthrene-carbon system. In the technical scheme, the chemical bactericide can be any bactericide in the prior art and aims to inhibit or eliminate oil pipeline bacteria. An effective amount of a chemical germicide is an amount effective in the art to inhibit or eliminate bacteria.

Further, in the bactericide, the chemical bactericide is dodecyl dimethyl benzyl ammonium chloride.

Further, in the bactericide, the action concentration of the dodecyl dimethyl benzyl ammonium chloride is not lower than 12.5 mg/L.

Further, the quantum dots are prepared from citric acid, urea and phenanthroline.

Further, the mass ratio of the citric acid to the urea to the phenanthroline is 0.3:0.2: 0.1.

Experiments prove that the minimum inhibitory concentration of the bactericide is 12.5mg/L (calculated by mass percentage of dodecyl dimethyl benzyl ammonium chloride), and the minimum bactericidal concentration of the bactericide is 25 mug/mL (calculated by mass percentage of dodecyl dimethyl benzyl ammonium chloride).

The second purpose of the invention is to provide a preparation method of the bactericide, which is simple and easy to operate, can stably produce the bactericide and is suitable for industrial mass production.

In order to achieve the purpose, the invention adopts the following scheme:

the preparation method comprises the following steps:

1) preparing quantum dots: dissolving citric acid, urea and phenanthroline in a formula amount in water, sealing the solution in a stainless steel autoclave with polytetrafluoroethylene, keeping the solution at 180 ℃ for 4 hours, and naturally cooling the solution to room temperature;

2) and (3) preparation of a bactericide: weighing dodecyl dimethyl benzyl ammonium chloride, and dissolving in the quantum dot solution to obtain the bactericide.

Further, step 1) was maintained at 180 ℃ for 4 hours.

Further, the final concentration of the dodecyl dimethyl benzyl ammonium chloride dissolved in the quantum dot solution is 5-20 mg/mL.

The third purpose of the present invention is to provide a method for eliminating sulfate-reducing bacteria, which can specifically eliminate the sulfate-reducing bacteria.

In order to achieve the purpose, the technical scheme of the invention is as follows:

1. the method for removing the sulfate bacteria by using the bactericide specifically comprises the following steps:

1) identification and binding of sulfate-reducing bacteria

The bactericide is fully contacted with a suspected part corroded by the sulfate reducing bacteria, namely the quantum dots in the bactericide and Fe generated after the pipeline is corroded by the sulfate reducing bacteria²⁺And/or Fe³⁺Combined with the quantum dots in the bactericide to react with Fe²⁺And/or Fe³⁺The combined action, if the bactericide and the sulfate-reducing bacteria are aggregated, is judged to be corroded by the sulfate-reducing bacteria;

2) eliminating sulfate reducing bacteria

When an effective amount of the bactericide is accurately attached to the part corroded by the sulfate reducing bacteria, the dodecyl dimethyl benzyl ammonium chloride in the bactericide has a killing effect on the sulfate reducing bacteria, and the bactericide is cleaned.

Further, in step 1), the suspected part is an oilfield pipeline.

Further, in step 1), at a plurality of other suspected places where the oilfield pipeline is corroded, potassium chloride and/or sodium chloride and/or magnesium chloride and/or aluminum chloride and/or calcium chloride and/or lead acetate and/or copper sulfate and/or nickel sulfate and/or cobalt acetate and/or cadmium sulfate and/or barium chloride and/or chromium nitrate and/or manganese sulfate and/or mercury iodide are attached to the suspected places, and the bactericide is not combined with attachments of the other suspected places, so that the bactericide achieves a precise effect.

The fourth purpose of the invention is to provide a compound which is prepared from a bactericide and Fe²⁺And/or Fe³⁺And (4) aggregating to obtain the finished product.

In order to realize the scheme, the technical scheme of the invention is as follows:

a complex of the bactericide and sulfate-reducing bacteria.

The fifth object of the present invention is to provide a method for detecting iron ions, which has high specificity.

In order to achieve the purpose, the technical scheme of the invention is as follows:

the method for detecting iron ions uses the bactericide as a fluorescent probe and Fe²⁺And/or Fe³⁺And (4) fully combining, and reading the fluorescence spectrum to perform qualitative or quantitative judgment.

Further, in the method, when the fluorescence spectrum is read for qualitative or quantitative judgment, the standard fluorescence intensity-concentration curve can be compared, and the Fe can be obtained²⁺The standard fluorescence intensity-concentration curve equation is that Y is 0.35622X +1.08606, R²X is 0.993, and the value of X is more than or equal to 0.13 mu M and less than or equal to 21 mM; said Fe³⁺The standard fluorescence intensity-concentration curve equation is that Y is 10.29529X +1.00487, R²0.990, X is 67nM ≤ and 41 μ M, and the bactericide can be mixed with low dose of Fe²⁺And/or Fe³⁺The full combination, namely when a small amount of sulfate reducing bacteria exist, the sulfate reducing bacteria can be identified and killed, the sterilization effect is improved, and the subsequent corrosion is prevented.

The invention has the beneficial effects that:

1) the bactericide for the oil pipeline is very suitable for sterilizing the oil pipeline, can be accurately attached to bacterial colonies or adsorb bacteria while reducing the application amount as much as possible, enables the surface of the bacteria to locally reach high-concentration chemical bactericide, improves the economic effect ratio of sterilization, and achieves the anti-corrosion effect, namely the bactericide has the double effects of specifically identifying the bacteria and killing the bacteria.

2) The preparation method of the novel accurate bactericide for the oilfield pipeline is simple and easy to operate, can stably produce the bactericide, and is suitable for industrial mass production.

Drawings

FIG. 1 is Fe²⁺The influence on the fluorescence spectrum of the bactericide (namely the quantum dot +1227 solution) after the bactericide is continuously added, and the fluorescence intensity and Fe²⁺Fitted linear relationship graph of concentration.

FIG. 2 is Fe³⁺The influence on the fluorescence spectrum of the quantum dot +1227 solution after the quantum dot is continuously added and a fitted linear relation graph of the fluorescence intensity and the concentration of Fe3 +.

Fig. 3 is a fluorescence emission spectrum of quantum dot +1227 with the addition of 14 different metal ions and a fluorescence response histogram of different metal ions to quantum dot + 1227.

Fig. 4 shows the results of the bacteriostatic test of the quantum dot +1227 on SRB.

FIG. 5 is Fe²⁺And Fe³⁺Influence on UV/vis absorption spectra of quantum dot +1227 solutions.

Detailed Description

The examples are given for the purpose of better illustration of the invention, but the invention is not limited to the examples. Therefore, those skilled in the art should make insubstantial modifications and adaptations to the embodiments of the present invention in light of the above teachings and remain within the scope of the invention.