CN119896236B - Sterilization corrosion inhibitor of polyhexamethylene biguanide inorganic salt, preparation method and application thereof in oilfield produced water - Google Patents
Sterilization corrosion inhibitor of polyhexamethylene biguanide inorganic salt, preparation method and application thereof in oilfield produced waterInfo
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- CN119896236B CN119896236B CN202510049223.5A CN202510049223A CN119896236B CN 119896236 B CN119896236 B CN 119896236B CN 202510049223 A CN202510049223 A CN 202510049223A CN 119896236 B CN119896236 B CN 119896236B
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Abstract
The invention relates to a polyhexamethylene biguanide inorganic salt sterilizing corrosion inhibitor, a preparation method and application thereof in oilfield produced water, belonging to the technical field of oilfield water treatment. The invention relates to a sterilizing corrosion inhibitor of polyhexamethylene biguanide inorganic salt, which comprises a compound system of polyhexamethylene biguanide hydrochloride and zinc sulfate-sodium molybdate. The bactericidal corrosion inhibitor takes the polyhexamethylene biguanide as a synthetic substrate, has the advantages of high stability, degradability, low cost, green environmental protection and the like, and the compound system of sodium molybdate and zinc sulfate not only can effectively inhibit corrosion, but also reduces cost. Because the agent has limited water solubility, the agent is a slow-release long-acting sterilization and corrosion inhibition integrated agent, can be adsorbed on the surface of a metal material, slowly releases polyhexamethylene biguanide, inhibits the formation of bacterial biofilms, effectively kills microorganisms in water and inhibits metal corrosion.
Description
Technical Field
The invention relates to the technical field of oilfield water treatment, in particular to a polyhexamethylene biguanide inorganic salt sterilization corrosion inhibitor for an oilfield water treatment system with high microorganism content and serious corrosion, a preparation method and application thereof in oilfield produced water.
Background
Corrosion is a material failure behavior that is widely found in marine, oilfield, and freshwater environments, jeopardizing throughout daily life and nearly all industrial industries. According to statistics, the global corrosion cost is 2.5 trillion dollars, and in China, the economic loss caused by corrosion each year accounts for about 5% of the total national production value. The microbial corrosion accounts for about 20% of economic loss, and especially in the field of oil field development, the service life of metal materials and equipment is further shortened, and the economic, environmental protection and safety risks are greatly improved. It is currently widely believed that microbial corrosion is closely related to biofilm formation by microorganisms, which tend to grow on the surface of materials, gathering together in a biofilm fashion to capture nutrients in the environment, providing conditions for growth metabolism, which make the microorganisms less susceptible to external interference independent of the external environment. Meanwhile, the biomembrane attached to the metal surface can also change the physicochemical property of the metal surface, promote the electrochemical corrosion, and further reduce the service life of the equipment.
Oilfield microbial corrosion is mainly composed of bacteria including Sulfate Reducing Bacteria (SRB), saprophytic bacteria (TGB), iron bacteria (FB), and the like. SRB is an anaerobic bacterium that oxidizes carbonaceous organic compounds or hydrogen and reduces sulfate to produce H 2 S. The survival pH range is very wide and can be between 5.5 and 9.0. Sulfate reducing bacteria commonly existing in oil fields are desulfonate bacteria, mainly clusters or colony forming bacteria are attached to the pipe wall, depolarize the metal surface, accelerate corrosion of pipelines and equipment, and the corrosion products FeS can block pipelines and water injection wells, so that the damage to the ground system of the oil fields is the greatest. TGB is also called mucus forming bacteria, is aerobic heterotrophic bacteria, can secrete a large amount of mucus to adhere to pipelines and equipment, causes biological scale to block water injection wells and filters, can generate oxygen concentration batteries to cause corrosion of equipment and pipelines, and can provide living and propagation environments for sulfate reducing bacteria. FB is a kind of saprophytic bacteria, and is widely distributed, ferrous iron is mainly oxidized into high-valence iron, energy released by iron oxidation is utilized to meet the living requirement, and the harm is greater than that of general saprophytic bacteria, so that corrosion of equipment and pipelines can be accelerated, and a water injection well and a filter are blocked.
The methods applied to the microbial corrosion protection are numerous, and the chemical method is one of the simplest and effective corrosion protection methods. Bactericides, also known as biocides, bacteriocidal algicides, microbiocides, and the like, are chemical agents that are capable of effectively controlling or killing microorganisms in water systems. The bactericides used in the current oil field are generally agents which use domestic water and industrial circulating water, and can be divided into oxidation bactericides and non-oxidation bactericides according to the sterilization mechanism. The oxidizing bactericides include chlorine, ozone, sodium hypochlorite, chlorine dioxide and the like, and destroy the cell structure of microorganisms or inhibit the metabolic processes of microorganisms by utilizing the strong oxidizing capability of the oxidizing bactericides, but the oxidizing bactericides are low in practical application because the oxidizing bactericides are low in safety and easy to cause chemical corrosion. The non-oxidizing bactericides can be divided into aldehyde ketones, quaternary ammonium salts, quaternary phosphonium salts, organic sulfides, medicament compound, and the like. In recent years, organic guanidine and heterocyclic bactericides have been developed and have been shown to have a good bactericidal effect.
Currently, most of the oil fields in China enter a secondary oil extraction stage, as the water content of produced liquid continuously rises, the water consumption of water drive is continuously increased, microbial corrosion is more common, and in order to prevent the damage of injected water to devices, pipe columns and stratum, the reinjection requirements on the produced water are more strict, and the demand of bactericide also continuously rises. In Jiangsu oil fields, the water body has high microorganism content and various types, and the quaternary ammonium salt bactericides are adopted in advance, so that the bacterial drug resistance is enhanced, the bacterial numbers of sulfate reducing bacteria, iron bacteria, saprophytic bacteria and the like of partial water treatment stations reach the order of magnitude of 5 times of 10, the water body is also degraded, a large number of corrosion problems are brought about, and at present, the corrosion rate of partial stations exceeds 0.076 mm/a, so that a sterilizing corrosion inhibition medicament for killing the water body microorganisms and inhibiting the corrosion is urgently required to be developed, so that the safe operation of oil field injection and production is ensured.
Disclosure of Invention
Aiming at the problems that the microbial corrosion in the oilfield water treatment system is more and more serious and the requirement on bactericide is higher and more in the prior art, the invention provides the sterilizing corrosion inhibitor of the polyhexamethylene biguanide inorganic salt, the preparation method and the application thereof in oilfield produced water, which can slowly release the polyhexamethylene biguanide in the water treatment system to effectively kill bacteria in the water body, inhibit the formation of bacterial biomembrane, greatly relieve the equipment corrosion and prolong the service life of the equipment when the oilfield water is sterilized.
The invention firstly provides a sterilizing corrosion inhibitor of polyhexamethylene biguanide inorganic salt, which is characterized by comprising a compound system of polyhexamethylene biguanide hydrochloride and zinc sulfate-sodium molybdate.
Further, the mass ratio of the polyhexamethylene biguanide hydrochloride to the zinc sulfate and sodium molybdate compound system is 10:2-6.
The bactericidal corrosion inhibitor takes the polyhexamethylene biguanide as a synthetic substrate, has the advantages of high stability, degradability, low cost, green environmental protection and the like, and the compound system of sodium molybdate and zinc sulfate not only can effectively inhibit corrosion, but also reduces cost. Because the agent has limited water solubility, the agent is a slow-release long-acting sterilization and corrosion inhibition integrated agent, can be adsorbed on the surface of a metal material, slowly releases polyhexamethylene biguanide, inhibits the formation of bacterial biofilms, effectively kills microorganisms in water and inhibits metal corrosion.
The invention further provides a preparation method of the sterilizing corrosion inhibitor of the polyhexamethylene biguanide inorganic salt, which is characterized in that the polyhexamethylene biguanide hydrochloride aqueous solution is mixed with the aqueous solution of a zinc sulfate and sodium molybdate compound system, the mixed solution is decanted to remove water, the precipitate is washed by deionized water and dried in vacuum, and finally the dried substance is ground into fine powder to obtain the polyhexamethylene biguanide-inorganic salt.
Further, the concentration of the polyhexamethylene biguanide hydrochloride aqueous solution is 60-100 g/L.
Further, the concentration of the aqueous solution of the zinc sulfate-sodium molybdate compound system is 80-240 g/L, and the mass ratio of the zinc sulfate to the sodium molybdate is 1:1.5-3.
Further, the temperature of vacuum drying is 75-85 ℃, and the drying time is more than 24 hours.
The preparation method of the polyhexamethylene biguanidine hydrochloride comprises the steps of respectively dissolving guanidine hydrochloride and 1, 6 hexamethylenediamine in deionized water, mechanically stirring and mixing, heating the mixed solution to enable water to be evaporated continuously, heating to 100-120 ℃, stirring and reacting at constant temperature for 3-4 h, heating to 160-180 ℃ for 3-6 h to obtain a solid phase, adding distilled water into the solid phase to be completely dissolved, adding saturated sodium chloride aqueous solution into the dissolved solution, filtering and precipitating, centrifuging to remove supernatant, and vacuum drying the solid phase at 75-85 ℃ for more than 24-h to obtain the polyhexamethylene biguanidine hydrochloride.
As the preferable preparation method of the polyhexamethylene biguanidine hydrochloride, the weight ratio of the guanidine hydrochloride to 1, 6 hexamethylenediamine is 1:1-3;
Further preferably, the weight ratio of guanidine hydrochloride to 1, 6 hexamethylenediamine is 1:1.1-1.5.
The preparation method of the sterilizing corrosion inhibitor of the polyhexamethylene biguanide inorganic salt adopts guanidine hydrochloride and 1, 6-hexamethylenediamine to react to generate polyhexamethylene biguanide hydrochloride, and then reacts with a compound system of sodium molybdate and zinc sulfate to generate polyhexamethylene biguanide inorganic salt, and the polyhexamethylene biguanide is used as a synthetic substrate, so that the sterilizing corrosion inhibitor has the advantages of high stability, degradability, low cost, environmental protection and the like, and the compound system of sodium molybdate and zinc sulfate not only can effectively inhibit corrosion, but also reduces cost. The agent has limited water solubility, is a slow-release long-acting sterilization and corrosion inhibition integrated agent, can be adsorbed on the surface of a metal material, slowly releases polyhexamethylene biguanide, inhibits the formation of bacterial biofilm, effectively kills microorganisms in a water body, and inhibits metal corrosion.
The third object of the invention is to use the bactericidal corrosion inhibitor of the polyhexamethylene biguanide inorganic salt in an oilfield water treatment system. The method is mainly used in a ground treatment system for produced water or a reinjection oil pipe or an oil sleeve annular water system. Through regular quantitative addition in the production operation process, the water is gradually dissolved into the produced liquid, and the protection effect on the underground pipe column and the ground pipeline is achieved. The particle size of the medicament can be adjusted according to the bottom hole temperature, the flow rate of the fluid, the corrosiveness of the fluid, the required dosing concentration and other factors, so that the release speed of the medicament is controlled, and the optimal protection effect and protection period are obtained.
Drawings
FIG. 1 is an FT-IR chart of the inorganic salts of polyhexamethylene biguanide and polyhexamethylene biguanide hydrochloride prepared in example 1.
FIG. 2 is a graph showing corrosion of N80 hanger plates of comparative example 1 and example 1. Wherein, the graph (a) is the appearance of the hanging piece after corrosion in the comparative example 1, (b) is the pitting 3D graph of the hanging piece after corrosion in the comparative example 1, and the graph (c) is the appearance of the hanging piece after corrosion in the example 1, and (D) is the pitting 3D graph of the hanging piece after corrosion in the example 1.
FIG. 3 is a graph showing the sustained release performance test of the polyhexamethylene biguanide-inorganic salt of the present invention.
Detailed Description
The invention will be described in more detail by means of specific examples which are not intended to limit the scope of the invention in any way.
Example 1
(1) Respectively weighing guanidine hydrochloride 20.0 g and 1, 6 hexamethylenediamine 22 g, dissolving in deionized water, adding into a three-neck flask equipped with a mechanical stirrer, slowly heating to evaporate water continuously, keeping the temperature at 120 ℃ for stirring reaction 4h, reacting at 160 ℃ for 5 h, adding a proper amount of distilled water until the mixture is completely dissolved, adding saturated sodium chloride aqueous solution for filtering and precipitating, centrifuging to remove supernatant, and vacuum-drying at 80 ℃ for 24 h to obtain polyhexamethylene biguanide hydrochloride solid.
(2) Respectively dissolving zinc sulfate 3.0 g and sodium molybdate 9.0 g in 50 mL deionized water, and uniformly mixing the two in stirring to obtain a zinc sulfate-sodium molybdate composite system.
(3) Dissolving the polyhexamethylene biguanide hydrochloride 20 g prepared in the step (1) in 200 mL deionized water, adding 100 mL of the zinc sulfate-sodium molybdate composite system prepared in the step (2) under the condition of mechanical stirring, decanting the obtained reaction solution to remove upper water, washing 3 times by using deionized water, vacuum drying at 80 ℃ for 24 h, and grinding into fine powder by using an agate mortar to obtain the polyhexamethylene biguanide-inorganic salt.
As shown in FIG. 1, which shows the FT-IR chart of the present example, it can be seen from FIG. 1 that the polyhexamethylene biguanide hydrochloride synthesized in step (1) exhibits a broad peak at 3000-3500 cm -1, which is mainly derived from the stretching vibration peaks of-NH, -CH 2, -OH. The absorption peaks at 2930 and 2860 cm -1 are the-CH 2 stretching vibration peak asymmetric and symmetric absorption peaks. The strong stretching vibration peak of c=n appears at 1540-1660 cm -1, from which successful synthesis of polyhexamethylene biguanide hydrochloride can be seen. The infrared spectrogram of the polyhexamethylene biguanide-inorganic salt synthesized in the step (2) is compared with the infrared spectrogram of the polyhexamethylene biguanide hydrochloride synthesized in the step (1), the difference is mainly represented in a fingerprint area, a stretching vibration peak of S=O bond appears at 1090 cm -1, and a vibration peak corresponding to MoO 4 2- appears at 830 and cm -1, so that the successful preparation of the polyhexamethylene biguanide-inorganic salt composite system can be seen.
Example 2
(1) Respectively weighing guanidine hydrochloride 20.0 g and 1, 6 hexamethylenediamine 30 g, dissolving in deionized water, adding into a three-neck flask equipped with a mechanical stirrer, slowly heating to evaporate water continuously, keeping the temperature at 100 ℃ for stirring reaction 4h, reacting at 180 ℃ for 3h, adding a proper amount of distilled water for dissolving, adding saturated sodium chloride aqueous solution for filtering and precipitating, centrifuging to remove supernatant, and vacuum drying at 80 ℃ for 24h to obtain polyhexamethylene biguanide hydrochloride solid.
(2) Respectively dissolving zinc sulfate 3.0 g and sodium molybdate 6.0 g in 50 mL deionized water, and uniformly mixing the two in stirring to obtain a zinc sulfate-sodium molybdate composite system.
(3) Dissolving the polyhexamethylene biguanide hydrochloride 20 g prepared in the step (1) in 200 mL deionized water, adding 100 mL of the zinc sulfate-sodium molybdate composite system prepared in the step (2) under the condition of mechanical stirring, decanting the obtained reaction solution to remove upper water, washing 3 times by using deionized water, vacuum drying at 80 ℃ for 24 h, and grinding into fine powder by using an agate mortar to obtain the polyhexamethylene biguanide-inorganic salt.
Example 3
(1) Respectively weighing guanidine hydrochloride 20.0 g and 1, 6 hexamethylenediamine 28 g, dissolving in deionized water, adding into a three-neck flask equipped with a mechanical stirrer, slowly heating to evaporate water continuously, keeping the temperature at 110 ℃ for stirring reaction 4h, reacting at 170 ℃ for 4h, adding a proper amount of distilled water for dissolving, adding saturated sodium chloride aqueous solution for filtering and precipitating, centrifuging to remove supernatant, and vacuum-drying at 75 ℃ for 24h to obtain polyhexamethylene biguanide hydrochloride solid.
(2) Respectively dissolving zinc sulfate 3.0 g and sodium molybdate 7.0 g in 50 mL deionized water, and uniformly mixing the two in stirring to obtain a zinc sulfate-sodium molybdate composite system.
(3) Dissolving the polyhexamethylene biguanide hydrochloride 20 g prepared in the step (1) in 200 mL deionized water, adding 100 mL of the zinc sulfate-sodium molybdate composite system prepared in the step (2) under the condition of mechanical stirring, decanting the obtained reaction solution to remove upper water, washing 3 times by using deionized water, vacuum drying at 85 ℃ for 24 h, and grinding into fine powder by using an agate mortar to obtain the polyhexamethylene biguanide-inorganic salt.
Example 4
(1) Respectively weighing 20.0 g g guanidine hydrochloride and 1g 6 hexamethylenediamine 40g, dissolving in deionized water, adding into a three-neck flask with a mechanical stirrer, slowly heating to evaporate water continuously, keeping the temperature at 110 ℃ for stirring reaction 4h, reacting for 6 hours at 160 ℃, adding a proper amount of distilled water for dissolving, adding a saturated sodium chloride aqueous solution for filtering and precipitating, centrifuging to remove supernatant, and vacuum drying 24 h at 85 ℃ to obtain the polyhexamethylene biguanide hydrochloride solid.
(2) Respectively dissolving zinc sulfate 2.0 g and sodium molybdate 5.0 g in 50 mL deionized water, and uniformly mixing the two in stirring to obtain a zinc sulfate-sodium molybdate composite system.
(3) Dissolving the polyhexamethylene biguanide hydrochloride 20 g prepared in the step (1) in 200 mL deionized water, adding 100 mL of the zinc sulfate-sodium molybdate composite system prepared in the step (2) under the condition of mechanical stirring, decanting the obtained reaction solution to remove upper water, washing 3 times by using deionized water, vacuum drying at 85 ℃ for 24 h, and grinding into fine powder by using an agate mortar to obtain the polyhexamethylene biguanide-inorganic salt.
Example 5
(1) Respectively weighing guanidine hydrochloride 20.0 g and 1, 6 hexamethylenediamine 60 g, dissolving in deionized water, adding into a three-neck flask equipped with a mechanical stirrer, slowly heating to evaporate water, keeping the temperature at 120 ℃ for stirring reaction 4h, reacting at 160 ℃ for 5h, adding a proper amount of distilled water for dissolving, adding saturated sodium chloride aqueous solution for filtering and precipitating, centrifuging to remove supernatant, and vacuum drying at 80 ℃ for 24h to obtain polyhexamethylene biguanide hydrochloride solid.
(2) Respectively dissolving zinc sulfate 2.0 g and sodium molybdate 2.0 g in 50 mL deionized water, and uniformly mixing the two in stirring to obtain a zinc sulfate-sodium molybdate composite system.
(3) Dissolving the polyhexamethylene biguanide hydrochloride 20 g prepared in the step (1) in 200 mL deionized water, adding 100 mL of the zinc sulfate-sodium molybdate composite system prepared in the step (2) under the condition of mechanical stirring, decanting the obtained reaction solution to remove upper water, washing 3 times by using deionized water, vacuum drying at 80 ℃ for 24 h, and grinding into fine powder by using an agate mortar to obtain the polyhexamethylene biguanide-inorganic salt.
Example 6
(1) Respectively weighing guanidine hydrochloride 20.0 g and 1, 6 hexamethylenediamine 20 g, dissolving in deionized water, adding into a three-neck flask equipped with a mechanical stirrer, slowly heating to evaporate water, keeping the temperature at 120 ℃ for stirring reaction 4h, reacting at 160 ℃ for 5h, adding a proper amount of distilled water for dissolving, adding saturated sodium chloride aqueous solution for filtering and precipitating, centrifuging to remove supernatant, and vacuum drying at 75 ℃ for 24h to obtain polyhexamethylene biguanide hydrochloride solid.
(2) Respectively dissolving zinc sulfate 3.0 g and sodium molybdate 9.0 g in 50 mL deionized water, and uniformly mixing the two in stirring to obtain a zinc sulfate-sodium molybdate composite system.
(3) Dissolving the polyhexamethylene biguanide hydrochloride 12g prepared in the step (1) in 200mL deionized water, adding 100mL of the zinc sulfate-sodium molybdate composite system prepared in the step (2) under the condition of mechanical stirring, decanting the obtained reaction solution to remove upper water, washing 3 times by using deionized water, vacuum drying at 85 ℃ for 24 h, and grinding into fine powder by using an agate mortar to obtain the polyhexamethylene biguanide-inorganic salt.
Comparative example 1
This comparative example was used to compare the sterilizing effect with that of a conventional non-oxidizing type sterilizing agent.
1G dodecyl dimethyl benzyl ammonium chloride is taken and dissolved in 100 mL deionized water to prepare 10000 mg/L dodecyl dimethyl benzyl ammonium chloride solution, and a certain amount of dodecyl dimethyl benzyl ammonium chloride solution is taken and added into an experimental water sample for testing the sterilization performance of the experimental water sample. The experimental water sample is a fine filtration outlet water sample of a certain site of Jiangsu oilfield, and the water sample contains 11000 SRB/mL, 600 TGB/mL and 600 FB/mL.
Comparative example 2
The comparative example is used for comparing the corrosion inhibition effect with that of the conventional inorganic corrosion inhibitor.
1G sodium molybdate is taken to be dissolved in 100mL deionized water to prepare 10000 mg/L sodium molybdate solution, and a certain amount of sodium molybdate solution is taken to be added into an experimental water sample for testing corrosion inhibition performance. The experimental water sample is an outlet water sample of a three-phase separator at a certain site of Jiangsu oilfield, and the total mineralization degree of the water sample is 19213 mg/L.
Comparative example 3
This comparative example was used to compare the corrosion inhibition effect with polyhexamethylene biguanide hydrochloride-zinc chloride.
(1) Respectively weighing guanidine hydrochloride 20.0 g and 1, 6 hexamethylenediamine 24 g, dissolving in deionized water, adding into a three-neck flask equipped with a mechanical stirrer, slowly heating to evaporate water, keeping the temperature at 120 ℃ for stirring reaction 4h, reacting at 160 ℃ for 5h, adding a proper amount of distilled water for dissolving, adding saturated sodium chloride aqueous solution for filtering and precipitating, centrifuging to remove supernatant, and vacuum drying at 80 ℃ for 24h to obtain polyhexamethylene biguanide hydrochloride solid.
(2) Dissolving the polyhexamethylene biguanide hydrochloride 20 g prepared in the step (1) in 200 mL deionized water, adding 12 g zinc chloride under a mechanical stirring state, decanting the obtained reaction solution to remove upper water, washing 3 times by using deionized water, vacuum-drying 24h at 80 ℃, and grinding into fine powder by using an agate mortar to obtain the polyhexamethylene biguanide-zinc chloride.
Comparative example 4
This comparative example was used to compare the corrosion inhibition effect with polyhexamethylene biguanide hydrochloride-zinc sulfate.
(1) Respectively weighing guanidine hydrochloride 20.0 g and 1, 6 hexamethylenediamine 24 g, dissolving in deionized water, adding into a three-neck flask equipped with a mechanical stirrer, slowly heating to evaporate water, keeping the temperature at 120 ℃ for stirring reaction 4h, reacting at 160 ℃ for 5h, adding a proper amount of distilled water for dissolving, adding saturated sodium chloride aqueous solution for filtering and precipitating, centrifuging to remove supernatant, and vacuum drying at 80 ℃ for 24h to obtain polyhexamethylene biguanide hydrochloride solid.
(2) Dissolving the polyhexamethylene biguanide hydrochloride 20 g prepared in the step (1) in 200 mL deionized water, adding 12 g zinc sulfate under a mechanical stirring state, decanting the obtained reaction solution to remove upper water, washing 3 times by using deionized water, vacuum-drying 24h at 80 ℃, and grinding into fine powder by using an agate mortar to obtain the polyhexamethylene biguanide-zinc sulfate.
Comparative example 5
This comparative example was used to compare the corrosion inhibition effect with polyhexamethylene biguanide hydrochloride-sodium molybdate.
(1) Respectively weighing guanidine hydrochloride 20.0 g and 1, 6 hexamethylenediamine 24 g, dissolving in deionized water, adding into a three-neck flask equipped with a mechanical stirrer, slowly heating to evaporate water, keeping the temperature at 120 ℃ for stirring reaction 4h, reacting at 160 ℃ for 5h, adding a proper amount of distilled water for dissolving, adding saturated sodium chloride aqueous solution for filtering and precipitating, centrifuging to remove supernatant, and vacuum drying at 80 ℃ for 24h to obtain polyhexamethylene biguanide hydrochloride solid.
(2) Dissolving the polyhexamethylene biguanide hydrochloride 20 g prepared in the step (1) in 200 mL deionized water, adding 12 g sodium molybdate under the condition of mechanical stirring, decanting the obtained reaction solution to remove upper water, washing 3 times by using deionized water, vacuum-drying 24h at 80 ℃, and grinding into fine powder by using an agate mortar to obtain the polyhexamethylene biguanide-sodium molybdate.
Comparative example 6
(1) Respectively weighing guanidine hydrochloride 20.0 g and 1, 6 hexamethylenediamine 10 g, dissolving in deionized water, adding into a three-neck flask equipped with a mechanical stirrer, slowly heating to evaporate water continuously, keeping the temperature at 120 ℃ for stirring reaction 4h, reacting at 160 ℃ for 5h, adding a proper amount of distilled water for dissolving, adding saturated sodium chloride aqueous solution for filtering and precipitating, centrifuging to remove supernatant, and vacuum drying at 80 ℃ for 24h to obtain polyhexamethylene biguanide hydrochloride solid.
(2) And respectively dissolving 1.0 g of zinc sulfate and 9.0 g of sodium molybdate in 50 mL of deionized water, and uniformly mixing the two in stirring to obtain a zinc sulfate-sodium molybdate composite system.
(3) Dissolving the polyhexamethylene biguanide hydrochloride 12 g prepared in the step (1) in 200 mL deionized water, adding 100 mL of the zinc sulfate-sodium molybdate composite system prepared in the step (2) under the condition of mechanical stirring, decanting the obtained reaction solution to remove upper water, washing 3 times by using deionized water, vacuum drying at 80 ℃ for 24 h, and grinding into fine powder by using an agate mortar to obtain the polyhexamethylene biguanide-inorganic salt.
Comparative example 7
(1) Respectively weighing guanidine hydrochloride 20.0 g and 1, 6 hexamethylenediamine 24 g, dissolving in deionized water, adding into a three-neck flask equipped with a mechanical stirrer, slowly heating to evaporate water, keeping the temperature at 120 ℃ for stirring reaction 4h, reacting at 160 ℃ for 5h, adding a proper amount of distilled water for dissolving, adding saturated sodium chloride aqueous solution for filtering and precipitating, centrifuging to remove supernatant, and vacuum drying at 80 ℃ for 24h to obtain polyhexamethylene biguanide hydrochloride solid.
(2) Respectively dissolving zinc sulfate 3.0 g and sodium molybdate 12.0 g in 50 mL deionized water, and uniformly mixing the two in stirring to obtain a zinc sulfate-sodium molybdate composite system.
(3) Dissolving the polyhexamethylene biguanide hydrochloride 12 g prepared in the step (1) in 200 mL deionized water, adding 100 mL of the zinc sulfate-sodium molybdate composite system prepared in the step (2) under the condition of mechanical stirring, decanting the obtained reaction solution to remove upper water, washing 3 times by using deionized water, vacuum drying at 80 ℃ for 24 h, and grinding into fine powder by using an agate mortar to obtain the polyhexamethylene biguanide-inorganic salt.
Comparative example 8
(1) Respectively weighing guanidine hydrochloride 20.0 g and 1, 6 hexamethylenediamine 75 g, dissolving in deionized water, adding into a three-neck flask equipped with a mechanical stirrer, slowly heating to evaporate water, keeping the temperature at 120 ℃ for stirring reaction 4h, reacting at 160 ℃ for 5h, adding a proper amount of distilled water for dissolving, adding saturated sodium chloride aqueous solution for filtering and precipitating, centrifuging to remove supernatant, and vacuum drying at 80 ℃ for 24h to obtain polyhexamethylene biguanide hydrochloride solid.
(2) And respectively dissolving zinc sulfate 0.3 g and sodium molybdate 0.9 and g in 5 mL deionized water, and uniformly mixing the two in stirring to obtain a zinc sulfate-sodium molybdate composite system.
(3) Dissolving the polyhexamethylene biguanide hydrochloride 12g prepared in the step (1) in 200mL deionized water, adding 10 mL of the zinc sulfate-sodium molybdate composite system prepared in the step (2) under the condition of mechanical stirring, decanting the obtained reaction solution to remove upper water, washing 3 times by using deionized water, vacuum drying at 80 ℃ for 24 h, and grinding into fine powder by using an agate mortar to obtain the polyhexamethylene biguanide-inorganic salt.
1. Evaluation of sterilizing Performance
Table 1 shows the results of the sterilization performance test of comparative example 1 and examples 1 to 6. The water sample used was the one described in comparative example 1, which contained 11000 SRB/mL, 600 TGB/mL, and 600 FB/mL. The sterilizing performance of the sterilizing agent in each comparative example and example is tested by adopting a method of Q/SHCG 132,132-2017 technical requirement of the sterilizing agent for oilfield produced water treatment, the number of bacteria in raw water is measured by repeatedly counting the secondary bacterial load by a dilution method, and whether the added sterilizing agent can completely kill the bacteria is judged by adopting a three-tube parallel method (the "+" is that bacteria exist and the "-" is that no bacteria exist). As can be seen from Table 1, at 50 ppm, the polyhexamethylene biguanide-inorganic salt has a certain inhibition effect on TGB and FB, at 80: 80 ppm, the polyhexamethylene biguanide-inorganic salt can kill SRB, TGB, FB, and at 50: 50 ppm, the sterilization effect of examples 1-6 is significantly better than that of each comparative example.
Table 1 evaluation of sterilizing Performance
2. Corrosion inhibition evaluation
Table 2 shows the corrosion inhibition performance test results of comparative examples 2 to 5 and examples 1, 3 and 4. The water sample used was the water sample described in comparative example 2, which had a mineralization of 19213 mg/L and a water type of calcium chloride, and contained sodium ion 5867 mg/L, calcium ion 1252 mg/L, magnesium ion 99 mg/L, barium ion 67 mg/L, chloride ion 10989 mg/L, sulfate ion 314 mg/L, and bicarbonate ion 625 mg/L. And carrying out weightlessness analysis on the steel sheet before and after corrosion according to a method of GB-T35509-2017 oil and gas field corrosion inhibitor application and evaluation, and calculating the corrosion rate. The results are shown in Table 2, and it can be seen from Table 2 that the polyhexamethylene biguanide-inorganic salt provided by the invention has good corrosion inhibition performance and can maintain the corrosion inhibition rate of more than 80% at the temperature of a conventional water treatment system. The addition of zinc sulfate in combination with sodium molybdate reduces both the corrosion rate and the cost compared to comparative example 5. The corrosion rate is 0.011 mm/a at the minimum, the corrosion inhibition rate reaches 88.54%, and the corrosion inhibition requirement of equipment can be met.
TABLE 2
| Numbering device | Temperature, C | Concentration, ppm | Corrosion rate, mm/a | Corrosion inhibition rate% |
| Blank space | 35 | 0 | 0.096 | 0 |
| Comparative example 2 | 35 | 40 | 0.077 | 19.79 |
| Comparative example 3 | 35 | 40 | 0.032 | 66.67 |
| Comparative example 4 | 35 | 40 | 0.029 | 69.80 |
| Comparative example 5 | 35 | 40 | 0.027 | 71.88 |
| Comparative example 6 | 55 | 40 | 0.043 | 72.08 |
| Comparative example 7 | 55 | 40 | 0.039 | 74.68 |
| Example 1 | 35 | 40 | 0.011 | 88.54 |
| Blank space | 45 | 0 | 0.121 | 0 |
| Example 3 | 45 | 40 | 0.018 | 85.12 |
| Blank space | 55 | 0 | 0.154 | 0 |
| Example 4 | 55 | 40 | 0.029 | 81.17 |
| Example 5 | 55 | 40 | 0.038 | 75.32 |
| Example 6 | 55 | 40 | 0.036 | 76.62 |
FIG. 2 is a graph showing corrosion of N80 hanger of comparative example 1 and example 1. The water sample was used as described in comparative example 2, and the temperature of the water sample was 35 ℃. As can be seen from fig. 2, the surface of the hanging piece in example 1 is smoother, no pitting corrosion basically occurs, and the highest depth is 0.97 mm, so that the polyhexamethylene biguanide inorganic salt provided by the invention has good corrosion inhibition performance, and can be adsorbed on the surface of the hanging piece to effectively prevent equipment corrosion.
10 Mg polyhexamethylene biguanide inorganic salts were placed in 50 mL deionized water and the concentration of polyhexamethylene biguanide inorganic salts in the deionized water was measured at 230 and nm wavelength for different times using an ultraviolet-visible spectrophotometer. As shown in the test result in FIG. 3, the polyhexamethylene biguanide inorganic salt is released quickly in the initial stage and then released slowly with time, the water body concentration reaches 84.9 mg/L after 48 h, and the release rate reaches 42.7%.
Claims (8)
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