CN113817097A - Salt-resistant antibacterial functional polymer for oil displacement and preparation method thereof - Google Patents
Salt-resistant antibacterial functional polymer for oil displacement and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an anti-salt antibacterial functional polymer for oil displacement and a preparation method thereof, and relates to the technical field of oil exploitation. The preparation method comprises the steps of uniformly stirring the functional monomer 1, the functional monomer 2, the surfactant, water and acrylamide, and adjusting the pH value to 10 by using a pH regulator; and then adding the solution into a heat-insulating polymerization kettle, deoxidizing for 30min, adding an oxidant and a reducing agent, reacting for 4-6h, continuing to cure for 2h at 85 ℃, and performing granulation, drying, crushing and screening to obtain the polymer dry powder of the salt-resistant antibacterial functional polymer for oil displacement. The invention ensures the stability and the emulsifying capacity of the functional polymer in the stratum, and can effectively improve the temperature resistance, salt resistance and antibacterial capacity of the functional polymer, thereby improving the recovery ratio.
Description
The technical field is as follows:
the invention relates to the technical field of oil exploitation, in particular to an anti-salt and antibacterial functional polymer for oil displacement and a preparation method thereof.
Background art:
with the development of tertiary oil recovery technology, oil fields have higher requirements on the performance of polymers for oil displacement. The existing oil displacement polymer has poor viscosity, cannot extend into an oil reservoir, has high water phase permeability of a large pore passage, and has unsatisfactory surface activity and emulsification solubilization property, so that the effect of improving the crude oil recovery rate cannot be realized. Therefore, a functional polymer which can realize deep profile control and plugging control of an oil field and simultaneously can create benefits and increase efficiency of a low-efficiency well of the oil field is needed to provide technical support for improving the productivity of the oil well in an ultra-high water-cut period.
The invention content is as follows:
the invention aims to overcome the defects of the prior art and provide the salt-resistant antibacterial functional polymer for oil displacement, and the salt-resistant antibacterial functional polymer for oil displacement has good temperature resistance, salt resistance, antibacterial and emulsifying functions, so that the stability and emulsifying capacity of the polymer are ensured, and the recovery ratio is improved.
The invention is realized by the following technical scheme:
an anti-salt antibacterial functional polymer for oil displacement comprises the following components in parts by weight:
as a further improvement of the invention, the components and parts by weight are as follows:
as a further improvement of the invention, the functional monomer 1 has the following structural formula:
as a further improvement of the invention, the functional monomer 2 has the following structural formula:
wherein R is1Alkyl alcohol with 6-20 carbon atoms; n is polymerization degree, n is more than or equal to 6 and less than or equal to 20.
As a further improvement of the invention, the surfactant is fatty alcohol polyoxyethylene ether methacrylate.
As a further improvement of the invention, the functional monomer 2 is prepared by the following steps:
(1) dissolving alkyl alcohol with the carbon number of 6-20 in an organic phase with the mass of 10-12 times that of the alkyl alcohol, adding DMF (dimethyl formamide) with the mass of 0.01-0.1 time that of the alkyl alcohol into the organic phase, placing the mixture into a four-neck flask, stirring the mixture at room temperature, dropwise adding thionyl chloride with the mass of 1.1-1.5 times that of the alkyl alcohol into the mixed solution at a constant speed within 0.5-1 h, continuing to react for 1-2 h after dropwise adding is completed, then heating the mixture to 50-80 ℃ to react for 1-2 h, cooling the mixture, pouring the reaction solution into a 20% sodium hydroxide aqueous solution with the temperature of 0 ℃, extracting the mixture with an organic solvent, washing the organic phase with water, drying and extracting the organic phase with a drying agent, evaporating the organic solvent, and distilling the organic phase under reduced pressure to obtain alkyl chloride; dissolving alkyl chloride with the carbon number of 6-20 in an organic solvent with the mass of 10-12 times that of the alkyl chloride, adding sodium hydroxide with the mass of 1.1-1.5 times that of the alkyl chloride, 4-vinylphenol with the mass of 1.1-1.5 times that of the alkyl chloride and an entrainer with the mass of 10-12 times that of the alkyl chloride, heating to reflux, separating water generated by the reaction through a water separator, cooling and filtering a reaction product after the reaction is finished, adding water, extracting with the organic solvent, washing the organic phase with water, drying and extracting the obtained organic phase with a drying agent, and evaporating the organic solvent to obtain a functional monomer 2 intermediate 1;
(2) dissolving the functional monomer 2 intermediate 1 in an organic solvent with the mass 10-12 times that of the functional monomer 2 intermediate 1, placing the mixture in a four-neck flask, controlling the temperature to be less than or equal to 20 ℃, dropwise adding a sulfonating agent with the mass 1.1-1.5 times that of the functional monomer 2 intermediate 1 at a constant speed under the condition of continuous stirring, reacting at room temperature for 2-4 hours after dropwise adding, then adding a 20% sodium hydroxide aqueous solution with the mass 0.5-2 times that of the functional monomer 2 intermediate 1 for neutralization reaction, removing water and the organic solvent by rotary evaporation, dissolving the obtained mixture with anhydrous ethanol, filtering to remove inorganic salt generated by the reaction, extracting with the organic solvent to remove the unreacted functional monomer 2 intermediate 1, collecting an alcohol-water phase, and evaporating ethanol and water to obtain the functional monomer 2 intermediate 2;
(3) dissolving the intermediate 2 of the functional monomer 2 in tetrahydrofuran with the mass 10-12 times of that of the intermediate 2 of the functional monomer 2, placing the mixture in a four-neck flask, dissolving single-ended amino silicone oil with the mass 1.1-1.3 times of that of the intermediate 2 of the functional monomer 2 in tetrahydrofuran with the mass 3-5 times of that of the intermediate 2 of the functional monomer 2, and adding the mixture into the mixed system dropwise at a constant speed under the condition of ice bath stirring. After the dropwise addition, stirring is carried out for 24 hours under ice-bath conditions, then stirring is carried out for 48 hours at room temperature, and the solvent is removed to obtain the functional monomer 2.
As a further improvement of the invention, the organic solvent is petroleum ether, methane chloride, dichloromethane or trichloromethane.
As a further improvement of the invention, the entrainer is benzene, toluene, xylene or cyclohexane.
As a further improvement of the invention, the sulfonating agent is any one of fuming sulfuric acid, 5-20% of chlorosulfonic acid or sulfur trioxide.
As a further improvement of the invention, the oxidant is any one of ammonium persulfate, potassium persulfate and sodium persulfate.
As a further improvement of the invention, the reducing agent is any one of sodium bisulfite, sodium thiosulfate or triethanolamine.
As a further improvement of the invention, the pH regulator is a sodium hydroxide solution with the mass percentage concentration of 10%.
The preparation method of the salt-resistant antibacterial functional polymer for oil displacement comprises the following steps:
(1) uniformly mixing and stirring the functional monomer 1, the functional monomer 2, the surfactant, water and acrylamide, and adjusting the pH value to 10 by using a pH regulator;
(2) adding the solution prepared in the step (1) into a heat-insulating polymerization kettle, introducing nitrogen, deoxidizing for 30min, adding an oxidant and a reducing agent, reacting for 4-6h to obtain an elastic transparent rubber block, continuously curing at 85 ℃ for 2h, and then granulating, drying, crushing and screening to obtain the polymer dry powder of the salt-resistant antibacterial functional polymer for oil displacement.
The invention has the beneficial effects that: the salt-resistant antibacterial functional polymer for oil displacement, which is prepared by the invention, introduces a functional monomer 1 and a functional monomer 2 with stable structures on a chain. The functional monomer 1 has two benzene rings and is not easily affected by ionic groups in the stratum. The functional monomer 2 belongs to sulfonamide monomers and has the functions of temperature resistance, salt resistance and bacteria resistance. The introduction of the functional monomer 1, the functional monomer 2 and the polymerizable surfactant changes the structure and the performance of the functional polymer, ensures the stability and the emulsifying capacity of the functional polymer in a stratum, and can effectively improve the temperature resistance, salt resistance and antibacterial capacity of the functional polymer, thereby improving the recovery ratio.
The specific implementation mode is as follows:
example 1
An anti-salt antibacterial functional polymer for oil displacement comprises the following components in parts by weight:
the structural formula of the functional monomer 1 is shown as follows:
the structural formula of the functional monomer 2 is shown as follows:
wherein R is1Alkyl alcohol with 6 carbon atoms; n is the degree of polymerization, and n is 6.
The surfactant is fatty alcohol polyoxyethylene ether methacrylate.
The preparation method of the functional monomer 2 comprises the following steps:
(4) dissolving alkyl alcohol with the carbon number of 6 in an organic phase with the mass of 10 times that of the alkyl alcohol, adding DMF (dimethyl formamide) with the mass of 0.01 time that of the alkyl alcohol, placing the mixture in a four-neck flask, stirring at room temperature, dropwise adding thionyl chloride with the mass of 1.1 time that of the alkyl alcohol into the mixed solution at a constant speed within 0.5h, continuing to react for 1h after dropwise adding, then heating to 50 ℃ to react for 1h, cooling, pouring the reaction liquid into 20% sodium hydroxide aqueous solution with the temperature of 0 ℃, extracting with organic solvent petroleum ether, washing the organic phase with water, drying the extracted organic phase with a drying agent, evaporating the organic solvent, and distilling under reduced pressure to obtain alkyl chloride; dissolving alkyl chloride with the carbon number of 6 in organic solvent petroleum ether with the mass of 10 times that of the alkyl chloride, adding sodium hydroxide with the mass of 1.1 times that of the alkyl chloride, 4-vinylphenol with the mass of 1.1 times that of the alkyl chloride and entrainer benzene with the mass of 10 times that of the alkyl chloride, heating to reflux, separating water generated by the reaction through a water separator, cooling and filtering a reaction product after the reaction is finished, adding water, extracting with an organic solvent, washing the organic phase with water, drying and extracting the obtained organic phase with a drying agent, and evaporating the organic solvent to obtain a functional monomer 2 intermediate 1;
(5) dissolving the intermediate 1 of the functional monomer 2 in organic solvent petroleum ether with the mass 10 times that of the intermediate 1 of the functional monomer 2, placing the mixture in a four-neck flask, controlling the temperature to be less than or equal to 20 ℃, dropwise adding sulfonating agent fuming sulfuric acid with the mass 1.1 times that of the intermediate 1 of the functional monomer 2 at a constant speed under the condition of continuous stirring, reacting for 2 hours at room temperature after dropwise adding, then adding 20% sodium hydroxide aqueous solution with the mass 0.5 times that of the intermediate 1 of the functional monomer 2 for neutralization reaction, removing water and the petroleum ether of the organic solvent by rotary evaporation to obtain a mixture, dissolving the mixture with absolute ethyl alcohol, filtering to remove inorganic salt generated by the reaction, extracting with the petroleum ether of the organic solvent to remove the intermediate 1 of the unreacted functional monomer 2, collecting an alcohol-water phase, and evaporating the ethyl alcohol and the water to obtain the intermediate 2 of the functional monomer 2;
(6) dissolving the intermediate 2 of the functional monomer 2 in tetrahydrofuran with the mass 10 times of that of the intermediate 2 of the functional monomer 2, placing the mixture in a four-neck flask, dissolving the single-end amino silicone oil with the mass 1.1 times of that of the intermediate 2 of the functional monomer 2 in the tetrahydrofuran with the mass 3 times of that of the intermediate 2 of the functional monomer 2, and dropwise adding the mixture into the mixed system at a constant speed under the condition of ice bath stirring. After the dropwise addition, stirring is carried out for 24 hours under ice-bath conditions, then stirring is carried out for 48 hours at room temperature, and the solvent is removed to obtain the functional monomer 2. The specific chemical reaction formula is as follows:
the oxidant is ammonium persulfate.
The reducing agent is sodium bisulfite.
The pH regulator is a sodium hydroxide solution with the mass percentage concentration of 10%.
The preparation method of the salt-resistant antibacterial functional polymer for oil displacement comprises the following steps:
(1) uniformly mixing and stirring the functional monomer 1, the functional monomer 2, the surfactant, water and acrylamide, and adjusting the pH value to 10 by using a pH regulator;
(2) adding the solution prepared in the step (1) into a heat-insulating polymerization kettle, introducing nitrogen, deoxidizing for 30min, adding an oxidant and a reducing agent, reacting for 4h to obtain an elastic transparent rubber block, continuously curing at 85 ℃ for 2h, and then granulating, drying, crushing and screening to obtain the polymer dry powder of the salt-resistant antibacterial functional polymer for oil displacement.
Example 2
An anti-salt antibacterial functional polymer for oil displacement comprises the following components in parts by weight:
the structural formula of the functional monomer 1 is shown as follows:
the structural formula of the functional monomer 2 is shown as follows:
wherein R is1Alkyl alcohol with 20 carbon atoms; n is the degree of polymerization, and n is 20. The surfactant is fatty alcohol polyoxyethylene ether methacrylate. The preparation method of the functional monomer 2 comprises the following steps:
(1) dissolving an alkyl alcohol with the carbon number of 20 in an organic phase with the mass of 12 times that of the alkyl alcohol, adding DMF (dimethyl formamide) with the mass of 0.1 time that of the alkyl alcohol, placing the mixture in a four-neck flask, stirring at room temperature, dropwise adding thionyl chloride with the mass of 1.5 times that of the alkyl alcohol into the mixed solution at a constant speed within 1 hour, continuing to react for 2 hours after dropwise adding is completed, then heating to 80 ℃ to react for 2 hours, cooling, pouring the reaction solution into a 20% sodium hydroxide aqueous solution with the temperature of 0 ℃, extracting with an organic solvent, namely chloromethane, washing the organic phase with water, drying and extracting the organic phase with a drying agent, evaporating the organic solvent namely chloromethane, and distilling under reduced pressure to obtain alkyl chloride; dissolving alkyl chloride with the carbon number of 20 in organic solvent monochloromethane with the mass of 12 times that of the alkyl chloride, adding sodium hydroxide with the mass of 1.5 times that of the alkyl chloride, 4-vinylphenol with the mass of 1.5 times that of the alkyl chloride and entrainer toluene with the mass of 12 times that of the alkyl chloride, heating to reflux, separating water generated by the reaction through a water separator, cooling and filtering a reaction product after the reaction is finished, adding water, extracting with the organic solvent monochloromethane, washing an organic phase with water, drying and extracting the obtained organic phase with a drying agent, and evaporating the organic solvent monochloromethane to obtain a functional monomer 2 intermediate 1;
(2) dissolving the intermediate 1 of the functional monomer 2 in an organic solvent, namely methyl chloride, in an amount which is 12 times that of the intermediate 1 of the functional monomer 2, placing the mixture in a four-necked flask, controlling the temperature to be less than or equal to 20 ℃, dropwise adding chlorosulfonic acid in an amount which is 5% -20% of a sulfonating agent and is 1.5 times that of the intermediate 1 of the functional monomer 2 at a constant speed under the condition of continuous stirring, reacting for 4 hours at room temperature after dropwise adding, then adding a 20% sodium hydroxide aqueous solution in an amount which is 2 times that of the intermediate 1 of the functional monomer 2 for neutralization reaction, removing water and the organic solvent by rotary evaporation to obtain a mixture, dissolving the mixture with absolute ethyl alcohol, filtering to remove inorganic salt generated by the reaction, extracting and removing the unreacted intermediate 1 of the functional monomer 2 by using an organic solvent, collecting an alcohol-water phase, and evaporating the ethyl alcohol and the water to obtain the intermediate 2 of the functional monomer 2;
(3) dissolving the intermediate 2 of the functional monomer 2 in tetrahydrofuran with the mass 12 times of that of the intermediate 2 of the functional monomer 2, placing the mixture in a four-neck flask, dissolving single-end amino silicone oil with the mass 1.3 times of that of the intermediate 2 of the functional monomer 2 in tetrahydrofuran with the mass 5 times of that of the intermediate 2 of the functional monomer 2, and dropwise adding the mixture into the mixed system at a constant speed under the condition of ice bath stirring. After the dropwise addition, stirring is carried out for 24 hours under ice-bath conditions, then stirring is carried out for 48 hours at room temperature, and the solvent is removed to obtain the functional monomer 2. The specific chemical reaction formula is shown in example 1.
The oxidant is potassium persulfate.
The reducing agent is sodium thiosulfate.
The pH regulator is a sodium hydroxide solution with the mass percentage concentration of 10%.
The preparation method of the salt-resistant antibacterial functional polymer for oil displacement comprises the following steps:
(1) uniformly mixing and stirring the functional monomer 1, the functional monomer 2, the surfactant, water and acrylamide, and adjusting the pH value to 10 by using a pH regulator;
(2) adding the solution prepared in the step (1) into a heat-insulating polymerization kettle, introducing nitrogen, deoxidizing for 30min, adding an oxidant and a reducing agent, reacting for 6h to obtain an elastic transparent rubber block, continuously curing at 85 ℃ for 2h, and then granulating, drying, crushing and screening to obtain the polymer dry powder of the salt-resistant antibacterial functional polymer for oil displacement.
Example 3
An anti-salt antibacterial functional polymer for oil displacement comprises the following components in parts by weight:
the structural formula of the functional monomer 1 is shown as follows:
the structural formula of the functional monomer 2 is shown as follows:
wherein R is1Alkyl alcohol with 12 carbon atoms; n is the degree of polymerization, and n is 12.
The surfactant is fatty alcohol polyoxyethylene ether methacrylate.
The preparation method of the functional monomer 2 comprises the following steps:
(1) dissolving alkyl alcohol with the carbon number of 12 in an organic phase with the mass being 11 times that of the alkyl alcohol, adding DMF (dimethyl formamide) with the mass being 0.05 time that of the alkyl alcohol, placing the mixture in a four-neck flask, stirring at room temperature, dropwise adding thionyl chloride with the mass being 1.3 times that of the alkyl alcohol into the mixed solution at a constant speed within 0.8h, continuing to react for 1.5 h after dropwise adding is completed, then heating to 65 ℃ to react for 1.5 h, cooling, pouring the reaction liquid into 20% sodium hydroxide aqueous solution with the temperature of 0 ℃, extracting with an organic solvent dichloromethane, washing the organic phase with water, drying and extracting the organic phase with a drying agent, evaporating the organic solvent dichloromethane, and distilling under reduced pressure to obtain alkyl chloride; dissolving alkyl chloride with the carbon number of 12 in organic solvent dichloromethane with the mass of 11 times that of the alkyl chloride, adding sodium hydroxide with the mass of 1.3 times that of the alkyl chloride, 4-vinylphenol with the mass of 1.3 times that of the alkyl chloride and entrainer xylene with the mass of 11 times that of the alkyl chloride, heating to reflux, separating water generated by the reaction through a water separator, cooling and filtering a reaction product after the reaction is finished, adding water, extracting with the organic solvent, washing the organic phase with water, drying and extracting the obtained organic phase with a drying agent, and evaporating the organic solvent dichloromethane to obtain a functional monomer 2 intermediate 1;
(2) dissolving the functional monomer 2 intermediate 1 in an organic solvent dichloromethane with the mass 11 times that of the functional monomer 2 intermediate 1, placing the mixture in a four-neck flask, controlling the temperature to be less than or equal to 20 ℃, dropwise adding a sulfonating agent sulfur trioxide with the mass 1.3 times that of the functional monomer 2 intermediate 1 at a constant speed under the condition of continuous stirring, reacting at room temperature for 3 hours after dropwise adding, then adding a 20% sodium hydroxide aqueous solution with the mass 1.2 times that of the functional monomer 2 intermediate 1 for neutralization reaction, removing water and the organic solvent dichloromethane by rotary evaporation, dissolving the obtained mixture with absolute ethanol, filtering to remove inorganic salt generated by the reaction, extracting with the organic solvent dichloromethane to remove the unreacted functional monomer 2 intermediate 1, collecting an alcohol-water phase, and evaporating ethanol and water to obtain the functional monomer 2 intermediate 2;
(3) dissolving the intermediate 2 of the functional monomer 2 in tetrahydrofuran with the mass 11 times that of the intermediate 2 of the functional monomer 2, placing the mixture in a four-neck flask, dissolving single-end amino silicone oil with the mass 1.2 times that of the intermediate 2 of the functional monomer 2 in tetrahydrofuran with the mass 4 times that of the intermediate 2 of the functional monomer 2, and dropwise adding the mixture into the mixed system at a constant speed under the condition of ice bath stirring. After the dropwise addition, stirring is carried out for 24 hours under ice-bath conditions, then stirring is carried out for 48 hours at room temperature, and the solvent is removed to obtain the functional monomer 2. The specific chemical reaction formula is shown in example 1.
The oxidant is sodium persulfate.
The reducing agent is triethanolamine.
The pH regulator is a sodium hydroxide solution with the mass percentage concentration of 10%.
The preparation method of the salt-resistant antibacterial functional polymer for oil displacement comprises the following steps:
(1) uniformly mixing and stirring the functional monomer 1, the functional monomer 2, the surfactant, water and acrylamide, and adjusting the pH value to 10 by using a pH regulator;
(2) adding the solution prepared in the step (1) into a heat-insulating polymerization kettle, introducing nitrogen, deoxidizing for 30min, adding an oxidant and a reducing agent, reacting for 5h to obtain an elastic transparent rubber block, continuously curing at 85 ℃ for 2h, and then granulating, drying, crushing and screening to obtain the polymer dry powder of the salt-resistant antibacterial functional polymer for oil displacement.
The performance of the salt-resistant antibacterial functional polymer for oil displacement produced by the preparation method of the invention is evaluated as follows:
the salt-resistant antibacterial functional polymer for flooding of examples 1 to 3 prepared by the above formulation has excellent properties such as high dissolution rate, high-efficiency thickening property, viscosity stability, salt resistance, antibacterial property, and remarkable emulsifying property, compared with general flooding polymers, and the salt-resistant antibacterial functional polymer for flooding of examples 1 to 3 will be tested in terms of dissolution rate, viscosity stability, salt resistance, emulsion water-precipitation rate, antibacterial property, and the like.
1. Dissolution rate
The products of examples 1 to 3 were prepared into polymer solutions with a concentration of 5000mg/L using simulated sewage (calcium magnesium free) with a degree of mineralization of 10000mg/L at normal temperature, sampled every 5min, and measured for viscosity using Brookfield viscosity BROOKFIELD LVDV II at a constant temperature of 45 ℃ with the same viscosity measured twice, and the time for measuring the viscosity first was regarded as the complete dissolution time. Ordinary polyacrylamide was used as a control experiment under the same conditions.
Table 1 dissolution time test results
| Sample size | Example 1 | Example 2 | Example 3 | Ordinary polyacrylamide |
| Dissolution time min | 60 | 55 | 55 | 120 |
Experiments show that the salt-resistant antibacterial functional polymer for oil displacement, which is modified by adding the functional monomer 1, the functional monomer 2 and the surfactant, has the advantages that the solubility is well improved, and the dissolving time is shortened by over 60min compared with that of common polyacrylamide.
2. Viscosity stability and antibacterial ability
On-site sewage of an oil production plant, the mineralization degree is 6500mg/L (wherein, the content of calcium and magnesium ions is about 50mg/L), and the bacteria containing decomposable polymers comprise: sulfate reducing bacteria, iron bacteria, saprophytic bacteria and the like, wherein the products of the examples 1-3 are prepared into polymer solution with the concentration of 1000mg/L in a pollution-preparation and sewage-dilution mode in the experimental process, the polymer solution is stored at the constant temperature of 45 ℃ in a sealing way, and the viscosity of different days is measured by using a Brookfield viscometer BROOKFIELD LVDV II at the constant temperature of 45 ℃. Ordinary polyacrylamide was used as a control experiment under the same conditions. The viscosity stability of the polymer solution measured over 90d is shown in table two:
table 2 viscosity stability results
As shown in Table 2, the viscosity retention of the salt-resistant antibacterial functional polymer 90d for flooding, which is modified by adding the functional monomer 1, the functional monomer 2 and the surfactant, is more than one hundred percent, which is better than that of the common polyacrylamide. And the experiment is carried out by using the bacteria-containing sewage of an oil production plant, and the antibacterial property of the functional polymer surfactant for oil displacement is proved to be superior to that of the common polyacrylamide.
3. Salt resistance
Different concentration gradient sodium chloride solutions (concentration from 5000mg/L to 20000mg/L) were prepared, and the experimental procedure adopted a dirty-and-dirty dilution method to dilute the products of examples 1 to 3 to 1000mg/L solution, and the viscosity was measured at a constant temperature of 45 ℃ using Brookfield viscometer BROOKFIELD LVDV II. Ordinary polyacrylamide was used as a control experiment under the same conditions. The viscosity test results are shown in table 3:
table 3 viscosity test results
As shown in table 3, the viscosity increased slightly with increasing degree of mineralization; the viscosity of the polymers of the conventional type always tends to decrease with increasing degree of mineralization. The salt resistance of the salt-resistant antibacterial functional polymer for oil displacement, which is modified by adding the functional monomer 1, the functional monomer 2 and the surfactant, is obviously better than that of a common polymer.
4. Emulsifiability
Using a certain oil production plant wastewater, with a mineralization degree of 6500mg/L (wherein the content of calcium and magnesium ions is about 50mg/L), the products of examples 1-3 were formulated into a polymer solution with a concentration of 1000mg/L by a sewage-to-sewage dilution method, and the formulated solution was mixed with the oil produced by the oil well of the plant in a 50ml colorimetric cylinder in a volume ratio of 1: 1, keeping the temperature in a constant-temperature oven at 45 ℃ for 30min, oscillating the mixture up and down for 300 times, keeping the temperature in the constant-temperature oven at 45 ℃ and observing the water precipitation rate after emulsification to serve as an experimental group.
The method is the same as the above, ordinary polyacrylamide is prepared into a polymer solution with the concentration of 1000mg/L according to the above conditions, and the prepared solution and the oil produced by the oil well of the factory are mixed in a colorimetric tube of 50ml according to the volume ratio of 1: 1, keeping the temperature in a constant-temperature oven at 45 ℃ for 30min, oscillating up and down for 300 times, keeping the temperature in the constant-temperature oven at 45 ℃ and observing the water precipitation rate after emulsification to serve as a control experiment. The results are shown in Table 4:
TABLE 4 test results of water separation rate by emulsification
As can be seen from Table 4, the emulsifying property of the salt-repellent antibacterial functional polymer modified by adding the functional monomer 1, the functional monomer 2 and the surfactant in each example is better than that of the common polymer.
5. Oil displacement performance
An oil displacement scheme: the artificial core is 30 multiplied by 4.5cm, the water content is driven to 98 percent, the water content is converted into chemical flooding (functional polymer flooding), and the water content is driven to 98 percent. The displacement speed is 0.3mL/min, and the chemical flooding injection amount is 0.57 pv.
Chemical flooding: the products of examples 1-3 and ordinary polyacrylamide were formulated into polymer solutions of 1000mg/L concentration using four-plant wastewater from oil recovery with a degree of mineralization of 6500mg/L (with calcium and magnesium ion content of about 50 mg/L). The recovery factor is shown in Table 5.
TABLE 5 recovery results
The experimental result shows that the oil displacement recovery ratio of the salt-resistant antibacterial functional polymer for oil displacement added with the functional monomer 1, the functional monomer 2 and the surfactant is obviously higher than that of the common polyacrylamide.
Claims (8)
1. An anti-salt antibacterial functional polymer for oil displacement comprises the following components in parts by weight:
2. the salt-resistant antibacterial functional polymer for oil displacement according to claim 1, which is characterized by comprising the following components in parts by weight:
3. the salt-resistant antibacterial functional polymer for flooding according to claim 1 or 2, characterized in that the functional monomer 1 has the following structural formula:
4. the salt-resistant antibacterial functional polymer for flooding according to claim 1 or 2, characterized in that the functional monomer 2 has the following structural formula:
wherein R is1Alkyl alcohol with 6-20 carbon atoms; n is polymerization degree, n is more than or equal to 6 and less than or equal to 20.
5. The salt-resistant antibacterial functional polymer for flooding according to claim 1 or 2, characterized in that the surfactant is fatty alcohol-polyoxyethylene ether methacrylate; the oxidant is any one of ammonium persulfate, potassium persulfate or sodium persulfate; the reducing agent is any one of sodium bisulfite, sodium thiosulfate or triethanolamine; the pH regulator is a sodium hydroxide solution with the mass percentage concentration of 10%.
6. The preparation method of the salt-resistant antibacterial functional polymer for oil displacement according to claim 4, wherein the preparation method of the functional monomer 2 is as follows:
(1) dissolving alkyl alcohol with the carbon number of 6-20 in an organic phase with the mass of 10-12 times that of the alkyl alcohol, adding DMF (dimethyl formamide) with the mass of 0.01-0.1 time that of the alkyl alcohol into the organic phase, placing the mixture into a four-neck flask, stirring the mixture at room temperature, dropwise adding thionyl chloride with the mass of 1.1-1.5 times that of the alkyl alcohol into the mixed solution at a constant speed within 0.5-1 h, continuing to react for 1-2 h after dropwise adding is completed, then heating the mixture to 50-80 ℃ to react for 1-2 h, cooling the mixture, pouring the reaction solution into a 20% sodium hydroxide aqueous solution with the temperature of 0 ℃, extracting the mixture with an organic solvent, washing the organic phase with water, drying and extracting the organic phase with a drying agent, evaporating the organic solvent, and distilling the organic phase under reduced pressure to obtain alkyl chloride; dissolving alkyl chloride with the carbon number of 6-20 in an organic solvent with the mass of 10-12 times that of the alkyl chloride, adding sodium hydroxide with the mass of 1.1-1.5 times that of the alkyl chloride, 4-vinylphenol with the mass of 1.1-1.5 times that of the alkyl chloride and an entrainer with the mass of 10-12 times that of the alkyl chloride, heating to reflux, separating water generated by the reaction through a water separator, cooling and filtering a reaction product after the reaction is finished, adding water, extracting with the organic solvent, washing the organic phase with water, drying and extracting the obtained organic phase with a drying agent, and evaporating the organic solvent to obtain a functional monomer 2 intermediate 1.
(2) Dissolving the functional monomer 2 intermediate 1 in an organic solvent with the mass 10-12 times that of the functional monomer 2 intermediate 1, placing the mixture in a four-neck flask, controlling the temperature to be less than or equal to 20 ℃, dropwise adding a sulfonating agent with the mass 1.1-1.5 times that of the functional monomer 2 intermediate 1 at a constant speed under the condition of continuous stirring, reacting at room temperature for 2-4 hours after dropwise adding, then adding a 20% sodium hydroxide aqueous solution with the mass 0.5-2 times that of the functional monomer 2 intermediate 1 for neutralization reaction, removing water and the organic solvent by rotary evaporation, dissolving the obtained mixture with anhydrous ethanol, filtering to remove inorganic salt generated by the reaction, extracting with the organic solvent to remove the unreacted functional monomer 2 intermediate 1, collecting an alcohol-water phase, and evaporating ethanol and water to obtain the functional monomer 2 intermediate 2.
(3) Dissolving the intermediate 2 of the functional monomer 2 in tetrahydrofuran with the mass 10-12 times of that of the intermediate 2 of the functional monomer 2, placing the mixture in a four-neck flask, dissolving single-ended amino silicone oil with the mass 1.1-1.3 times of that of the intermediate 2 of the functional monomer 2 in tetrahydrofuran with the mass 3-5 times of that of the intermediate 2 of the functional monomer 2, and adding the mixture into the mixed system dropwise at a constant speed under the condition of ice bath stirring. After the dropwise addition, stirring is carried out for 24 hours under ice-bath conditions, then stirring is carried out for 48 hours at room temperature, and the solvent is removed to obtain the functional monomer 2.
7. The salt-resistant antibacterial functional polymer for flooding according to claim 6, wherein the organic solvent is petroleum ether, methyl chloride, dichloromethane or chloroform; the entrainer is benzene, toluene, xylene or cyclohexane; the sulfonating agent is any one of fuming sulfuric acid, 5-20% of chlorosulfonic acid or sulfur trioxide.
8. A method for preparing the salt-resistant antibacterial functional polymer for oil displacement according to claim 1 or 2, which comprises the following steps:
(1) uniformly mixing and stirring a functional monomer 1, a functional monomer 2, a surfactant, water and acrylamide, and adjusting the pH value to 10 by using a pH regulator to obtain a solution;
(2) adding the solution prepared in the step (1) into a heat-insulating polymerization kettle, introducing nitrogen, deoxidizing for 30min, adding an oxidant and a reducing agent, reacting for 4-6h to obtain an elastic transparent rubber block, curing for 2h at 85 ℃, granulating, drying, crushing and screening to obtain the salt-resistant antibacterial functional polymer for oil displacement, wherein the molecular weight of the salt-resistant antibacterial functional polymer for oil displacement is 300-2500 ten thousand.
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| CN115386043A (en) * | 2022-04-12 | 2022-11-25 | 黑龙江吉地油田服务股份有限公司 | Functional polyacrylamide and preparation method thereof |
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