CN109748991B - Polymer with selective water plugging function and preparation method and application thereof - Google Patents
Polymer with selective water plugging function and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the research field of profile control and water shutoff materials of oil fields and improvement of oil well productivity of oil reservoirs in high water cut periods, and discloses a polymer with a selective water shutoff function, wherein the polymer is prepared by carrying out polymerization reaction on emulsion containing a monomer A, a monomer B, a monomer C and an emulsifier in the presence of an initiator and water serving as a solvent, wherein the monomer A is acrylamide; the monomer B is N-vinylformamide; the monomer C is an oil-soluble monomer, and the oil-soluble monomer is styrene and/or octyl methacrylate; the emulsifier comprises a primary emulsifier and/or a co-emulsifier. The polymer prepared by the invention has excellent effects of selectively blocking water but not oil, and has higher scouring resistance times.
Description
Technical Field
The invention relates to the research field of oil field profile control water shutoff materials and improvement of oil well production of oil reservoirs in high water cut periods, in particular to a polymer with a selective water shutoff function, a method for preparing the polymer with the selective water shutoff function, the polymer with the selective water shutoff function prepared by the method, and application of the polymer with the selective water shutoff function as a selective water shutoff agent.
Background
The water plugging process for the oil well is a key technology for optimizing the development result of water injection of the oil and gas field. The water layer and the oil layer in the stratum are mutually interwoven, the heterogeneity is serious, the two reservoirs are difficult to be effectively isolated by the existing construction technology, but oil field enterprises need to stabilize the yield of crude oil and reduce the comprehensive water content of an oil well as far as possible, and therefore higher requirements are provided for the water shutoff agent with high oil/water selectivity. Although the existing water-based, oil-based and polymer gel water-blocking systems have certain selectivity, the water-blocking and oil-blocking systems block water and oil, and indoor physical model experiment results show that the oil-blocking rate of the existing water-blocking agents is more than 35%, the temperature resistance and salt resistance of the systems are poor, and the popularization and application range is small. Although the water-soluble polymer water shutoff agent can preferentially enter a stratum with higher water saturation, part of the water-soluble polymer water shutoff agent can enter an oil layer in stratum migration, and the water-soluble polymer water shutoff agent is very difficult to discharge because the water shutoff agent has no self-plugging removal capability. Although the oil-based cement water shutoff agent can also improve the crude oil recovery efficiency to a greater extent, the oil-based cement water shutoff agent has the great disadvantage that a stratum with higher water saturation is generally plugged, and when the oil-based cement water shutoff agent flows into an oil-water mixed stratum, even if only a small part of stratum water is mixed in an oil layer, the oil-based cement water shutoff agent can react with the stratum water to solidify the cement, which shows that the water shutoff selectivity of the oil-based cement water shutoff agent is also greatly deficient. The polymer gel water shutoff agent enables the oil-water phase permeability to be reduced unevenly by means of the change of the effective movable volume under the action of oil and water, but the oil-water channel physical shutoff can be caused by the treatment mode, so that the seepage capability of a porous medium is reduced, the oil production capability is also reduced while the water production of an oil well is greatly reduced, the liquid production amount is too low due to improper treatment, and the yield of crude oil is reduced.
At present, selective water shutoff agents and deep profile control technologies at home and abroad are improved day by day, and the selective water shutoff materials are developed greatly on the technologies of research development, construction process and the like, but along with the development of oil fields, the characteristics of oil layers and the environment are changed constantly, particularly, the water shutoff materials are adopted for a long time to make the contradiction of oil reservoir development more prominent in the later development period, the practical development experience of the oil fields is summarized according to the characteristics of the selective water shutoff materials, and the technical problem which must be overcome at present by the selective water shutoff agents is provided so as to develop new technologies in a targeted manner to adapt to the special oil fields and improve the water shutoff effect of a selective system.
In summary, most of the selective plugging agents used for water plugging of oil wells at present are gels or jelly generated by water-soluble polymers such as polyacrylamide and derivatives thereof in the stratum to plug the stratum water, or oil-based plugging agents are used for gelling or curing when meeting water to plug water channeling passages, but due to poor selectivity, the oil phase permeability can be greatly reduced while water plugging is carried out, so that low liquid after plugging is caused, and the application of the water plugging technology of the oil wells is restricted.
Therefore, a novel high-selectivity water plugging material is developed, so that water plugging and oil plugging of an oil layer are realized, and the method has important significance for improving the productivity of an oil well in an ultrahigh water cut period.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a polymer with a selective water plugging function, a preparation method and application thereof, namely, a certain amount of water-soluble monomer, oil-soluble monomer and emulsifier are added into an aqueous solution, a stable emulsion system in an oil-in-water form is formed after stirring, an initiator is added, and a polymerization mode is adopted to finally synthesize a water-based oil-soluble polymer particle type water plugging material. According to the water plugging material with high selectivity, water plugging agents with different mass concentrations can be prepared by adopting field water according to the field requirements of an oil field, and the water plugging agents are injected into an oil reservoir stratum and enter a water phase layer, so that oil-soluble particles in the water plugging material can effectively plug pore passages, further the water phase permeability is reduced, and the water phase plugging effect is enhanced; after entering the oil phase layer, the oil-soluble particles are dissolved in the crude oil without affecting the oil phase permeability, thereby achieving the effect of selectively blocking water and not blocking oil.
In order to achieve the above object, a first aspect of the present invention provides a polymer having a selective water shutoff function, wherein the polymer is obtained by polymerizing an emulsion containing a monomer a, a monomer B, a monomer C and an emulsifier in the presence of an initiator and water as a solvent, wherein the monomer a is acrylamide; the monomer B is N-vinylformamide; the monomer C is an oil-soluble monomer, and the oil-soluble monomer is styrene and/or octyl methacrylate; the emulsifier comprises a primary emulsifier and/or a co-emulsifier.
Preferably, based on 100 parts by weight of water, the content of the monomer A is 0.4-5 parts by weight, the content of the monomer B is 0.1-5 parts by weight, the content of the monomer C is 1-10 parts by weight, the content of the main emulsifier is 0.5-4.5 parts by weight, and the content of the co-emulsifier is 0-1.5 parts by weight;
more preferably, the content of the monomer A is 3.5-4.5 parts by weight, the content of the monomer B is 2.5-4.5 parts by weight, the content of the monomer C is 3-4 parts by weight, the content of the main emulsifier is 2.5-3.5 parts by weight, and the content of the co-emulsifier is 0.6-0.9 part by weight based on 100 parts by weight of water;
most preferably, the content of the monomer A is 3.8-4.2 parts by weight, the content of the monomer B is 3-4 parts by weight, the content of the monomer C is 3.3-3.8 parts by weight, the content of the main emulsifier is 2.8-3.2 parts by weight, and the content of the co-emulsifier is 0.7-0.8 part by weight based on 100 parts by weight of water.
Preferably, the polymer has a wash-out resistance factor of greater than 50 PV.
Preferably, the main emulsifier is selected from one or more of sodium dodecyl sulfate, sodium dodecyl sulfate and sodium dodecyl benzene sulfonate; preferably, the primary emulsifier is selected from sodium dodecyl sulfonate and/or sodium dodecyl benzene sulfonate;
the auxiliary emulsifier is selected from one or more of span 20, span 40, span 60, span 80, tween 20, tween 40, tween 60 and tween 80; preferably, the co-emulsifier is selected from one or more of span 20, span 40 and tween 80.
Preferably, the initiator is a water-soluble initiator and/or an oil-soluble initiator, the water-soluble initiator is a persulfate-sulfite oxidation-reduction initiation system, and the oil-soluble initiator is azobisisobutyronitrile and/or dimethyl azobisisobutyrate;
preferably, the initiator is a combination of a water-soluble initiator and an oil-soluble initiator;
preferably, the persulfate is contained in an amount of 0.01 to 0.1% by weight and the sulfite is contained in an amount of 0.005 to 0.05% by weight, based on the total content of the monomer A and the monomer B; and
the content of the oil-soluble initiator is 0.01 to 0.1% by weight based on the total content of the monomer C.
The invention provides a preparation method of a polymer with selective water plugging function, wherein the preparation method comprises the following steps:
(1) mixing a monomer A, a monomer B and water to form an aqueous solution;
(2) mixing a monomer C and an emulsifier with the aqueous solution to form an emulsion;
(3) carrying out polymerization reaction on the emulsion in the presence of an initiator;
wherein the monomer A is acrylamide; the monomer B is N-vinylformamide; the monomer C is an oil-soluble monomer, and the oil-soluble monomer is styrene and/or octyl methacrylate; the emulsifier comprises a primary emulsifier and/or a co-emulsifier.
Preferably, the amount of the monomer A is 0.4-5 parts by weight, the amount of the monomer B is 0.1-5 parts by weight, the amount of the monomer C is 1-10 parts by weight, the amount of the main emulsifier is 0.5-4.5 parts by weight, and the amount of the co-emulsifier is 0-1.5 parts by weight based on 100 parts by weight of water;
more preferably, the monomer A is used in an amount of 3.5 to 4.5 parts by weight, the monomer B is used in an amount of 2.5 to 4.5 parts by weight, the monomer C is used in an amount of 3 to 4 parts by weight, the primary emulsifier is used in an amount of 2.5 to 3.5 parts by weight, and the co-emulsifier is used in an amount of 0.6 to 0.9 part by weight, based on 100 parts by weight of water;
most preferably, the monomer A is used in an amount of 3.8 to 4.2 parts by weight, the monomer B is used in an amount of 3 to 4 parts by weight, the monomer C is used in an amount of 3.3 to 3.8 parts by weight, the main emulsifier is used in an amount of 2.8 to 3.2 parts by weight, and the co-emulsifier is used in an amount of 0.7 to 0.8 part by weight, based on 100 parts by weight of water.
Preferably, the polymer has a wash-out resistance factor of greater than 50 PV.
Preferably, the main emulsifier is selected from one or more of sodium dodecyl sulfate, sodium dodecyl sulfate and sodium dodecyl benzene sulfonate; preferably, the primary emulsifier is selected from sodium dodecyl sulfonate and/or sodium dodecyl benzene sulfonate;
the auxiliary emulsifier is selected from one or more of span 20, span 40, span 60, span 80, tween 20, tween 40, tween 60 and tween 80; preferably, the co-emulsifier is selected from one or more of span 20, span 40 and tween 80.
Preferably, the initiator is a water-soluble initiator and/or an oil-soluble initiator, the water-soluble initiator is a persulfate-sulfite oxidation-reduction initiation system, and the oil-soluble initiator is azobisisobutyronitrile and/or dimethyl azobisisobutyrate;
preferably, the initiator is a combination of a water-soluble initiator and an oil-soluble initiator;
preferably, the persulfate is used in an amount of 0.01 to 0.1 wt% and the sulfite is used in an amount of 0.005 to 0.05 wt%, based on the total amount of the monomer A and the monomer B; and
the oil-soluble initiator is used in an amount of 0.01 to 0.1% by weight, based on the total amount of the monomer C.
Preferably, in step (1), the pH value of the aqueous solution is 6-10; and in the step (3), the conditions of the polymerization reaction are as follows: the temperature is 40-60 deg.C, preferably 45-55 deg.C, and the time is 6-8 hr, preferably 7-8 hr.
The third aspect of the invention provides the polymer with the selective water plugging function prepared by the method.
The fourth aspect of the invention provides an application of the polymer with the selective water plugging function as a selective water plugging agent.
According to the invention, the oil-soluble polymer particles are introduced into the emulsion of the water-based acrylamide copolymer, so that the oil-soluble polymer particles can be stably suspended in the water-based emulsion and can be smoothly injected into an oil reservoir stratum through a high-pressure pump. The existence of the oil-soluble particles can greatly improve the temperature resistance, salt resistance and scouring resistance of the water plugging agent material. In the stratum, when the water shutoff agent is influenced by the environmental temperature and the pressure of a water layer, the water shutoff agent can deform, and a large amount of gathered oil-soluble particle water shutoff agents interact with each other to effectively block the stratum with the rock pore with higher water saturation, so that the water yield of an oil well is greatly reduced. After part of the oil-soluble particle water plugging agent flows into an oil layer, the oil-soluble particle water plugging agent can be dissolved into crude oil due to good oil solubility of the oil-soluble particle water plugging agent and is discharged back to the ground together with underground crude oil, so that the oil/water selectivity of a water plugging material is obviously improved, the effect of plugging water and not plugging oil is achieved, measures are provided for the low-efficiency well exploitation and benefit increase under the low oil price, and technical support is provided for the improvement of the oil well productivity in the extremely high water-containing period.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In a first aspect, the present invention provides a polymer having a selective water shutoff function, wherein the polymer can be prepared by polymerizing an emulsion containing a monomer a, a monomer B, a monomer C and an emulsifier in the presence of an initiator and water as a solvent, wherein the monomer a is acrylamide; the monomer B is N-vinyl formamide (NVF); the monomer C is an oil-soluble monomer, and the oil-soluble monomer is styrene and/or octyl methacrylate; the emulsifier comprises a primary emulsifier and/or a co-emulsifier.
In the present invention, the monomer a, the monomer B, and the monomer C may be obtained commercially or synthesized by a method of the related art. For example, the monomer A, the monomer B and the monomer C used in the examples of the present invention are commercially available, wherein the monomer A acrylamide is commercially available from Shandong Baomo Biochemical industries, Ltd, and the monomer BN-vinylformamide and the monomer C styrene and/or octyl methacrylate are commercially available from Beijing Chemicals.
According to the invention, based on 100 parts by weight of water, the content of the monomer A is 0.4-5 parts by weight, the content of the monomer B is 0.1-5 parts by weight, the content of the monomer C is 1-10 parts by weight, the content of the main emulsifier is 0.5-4.5 parts by weight, and the content of the co-emulsifier is 0-1.5 parts by weight; in the present invention, the specific selection and content of the monomer a, the monomer B, the monomer C, the main emulsifier and the co-emulsifier are controlled within the above-mentioned ranges, but it is preferable that the effects are better when the content of the monomer a is 3.5 to 4.5 parts by weight, the content of the monomer B is 2.5 to 4.5 parts by weight, the content of the monomer C is 3 to 4 parts by weight, the content of the main emulsifier is 2.5 to 3.5 parts by weight and the content of the co-emulsifier is 0.6 to 0.9 part by weight, based on 100 parts by weight of water; more preferably, the effects are better when the content of the monomer A is 3.8 to 4.2 parts by weight, the content of the monomer B is 3 to 4 parts by weight, the content of the monomer C is 3.3 to 3.8 parts by weight, the content of the main emulsifier is 2.8 to 3.2 parts by weight, and the content of the co-emulsifier is 0.7 to 0.8 part by weight, based on 100 parts by weight of water.
Further preferably, the total content of the monomer A and the monomer B is 0.5 to 10% by weight, preferably 6.8 to 8.2% by weight, based on 100 parts by weight of water.
Preferably, the polymer has a wash-out resistance factor of greater than 50 PV.
According to the present invention, the primary emulsifier may be selected from one or more of sodium dodecyl sulfate (SBS), Sodium Dodecyl Sulfate (SDS), and Sodium Dodecyl Benzene Sulfonate (SDBS); preferably, the primary emulsifier is selected from one or more of sodium dodecyl sulfonate (SBS) and/or Sodium Dodecyl Benzene Sulfonate (SDBS);
the coemulsifier can be selected from one or more of span 20, span 40, span 60, span 80, tween 20, tween 40, tween 60 and tween 80; preferably, the co-emulsifier is selected from one or more of span 20, span 40 and tween 80.
According to the invention, the initiator may be a water-soluble initiator which is a persulfate-sulfite oxidation-reduction initiation system and/or an oil-soluble initiator which may be azobisisobutyronitrile and/or dimethyl azobisisobutyrate.
Preferably, the initiator is a combination of a water-soluble initiator and an oil-soluble initiator;
further preferably, the persulfate is contained in an amount of 0.01 to 0.1% by weight and the sulfite is contained in an amount of 0.005 to 0.05% by weight based on the total content of the monomer A and the monomer B; more preferably, the effect is more excellent when the content of the persulfate is 0.025 to 0.1% by weight and the content of the sulfite is 0.025 to 0.05% by weight based on the total content of the monomer a and the monomer B; still more preferably, the effect is best when the content of the persulfate is 0.05 to 0.08 wt% and the content of the sulfite is 0.03 to 0.04 wt%, based on the total content of the monomer A and the monomer B;
the content of the oil-soluble initiator is 0.01 to 0.1 percent by weight based on the total content of the monomer C; preferably, the effect is better when the content of the oil-soluble initiator is 0.01-0.05 wt% based on the total content of the monomer C; more preferably, the oil-soluble initiator is contained in an amount of 0.02 to 0.04% by weight based on the total content of the monomer C, the most effective being obtained. In the present invention, when the oil-soluble initiator may be a composition of azobisisobutyronitrile and dimethyl azobisisobutyrate, the ratio of the contents of the azobisisobutyronitrile and the dimethyl azobisisobutyrate is not particularly limited as long as the total content of the azobisisobutyronitrile and the dimethyl azobisisobutyrate is 0.01 to 0.1% by weight, preferably 0.01 to 0.05% by weight, more preferably 0.02 to 0.04.
In a second aspect, the present invention provides a method for preparing a polymer with a selective water shutoff function, wherein the preparation method comprises the following steps:
(1) mixing a monomer A, a monomer B and water to form an aqueous solution;
(2) mixing a monomer C and an emulsifier with the aqueous solution to form an emulsion;
(3) carrying out polymerization reaction on the emulsion in the presence of an initiator;
wherein the monomer A is acrylamide; the monomer B is N-vinylformamide; the monomer C is an oil-soluble monomer, and the oil-soluble monomer is styrene and/or octyl methacrylate; the emulsifier comprises a primary emulsifier and/or a co-emulsifier.
The polymerization reaction involved in the method for preparing the polymer with the selective water plugging function adopts an emulsion suspension polymerization mode.
The polymerization reaction can also be carried out in the presence of a protective gas, which can preferably be nitrogen.
According to the invention, based on 100 parts by weight of water, the monomer A is used in an amount of 0.4-5 parts by weight, the monomer B is used in an amount of 0.1-5 parts by weight, the monomer C is used in an amount of 1-10 parts by weight, the main emulsifier is used in an amount of 0.5-4.5 parts by weight, and the co-emulsifier is used in an amount of 0-1.5 parts by weight; in the present invention, the specific selection and amount of the monomer a, the monomer B, the monomer C, the main emulsifier and the co-emulsifier are controlled within the above range, but preferably, the amount of the monomer a is 3.5 to 4.5 parts by weight, the amount of the monomer B is 2.5 to 4.5 parts by weight, the amount of the monomer C is 3 to 4 parts by weight, the amount of the main emulsifier is 2.5 to 3.5 parts by weight, and the amount of the co-emulsifier is 0.6 to 0.9 part by weight, based on 100 parts by weight of water, to achieve the desired effects; more preferably, the monomer A is used in an amount of 3.8 to 4.2 parts by weight, the monomer B is used in an amount of 3 to 4 parts by weight, the monomer C is used in an amount of 3.3 to 3.8 parts by weight, the main emulsifier is used in an amount of 2.8 to 3.2 parts by weight, and the co-emulsifier is used in an amount of 0.7 to 0.8 part by weight, based on 100 parts by weight of water, more preferably.
Further preferably, the total amount of the main emulsifier and the co-emulsifier is 1 to 5 parts by weight, preferably 3 to 4 parts by weight, based on 100 parts by weight of water.
Preferably, the polymers produced have a wash-out factor of greater than 50 PV.
According to the present invention, the primary emulsifier may be selected from one or more of sodium dodecyl sulfonate, sodium dodecyl sulfate and sodium dodecyl benzene sulfonate; preferably, the main emulsifier is selected from one or more of sodium dodecyl sulfonate and/or sodium dodecyl benzene sulfonate.
The coemulsifier can be selected from one or more of span 20, span 40, span 60, span 80, tween 20, tween 40, tween 60 and tween 80; preferably, the co-emulsifier is selected from one or more of span 20, span 40 and tween 80.
According to the invention, the initiator may be a water-soluble initiator and/or an oil-soluble initiator, and the water-soluble initiator may be an oxidation-reduction initiation system consisting of a persulfate oxidizer and a sulfite reducer. In a preferred aspect, the persulfate is used in an amount of 0.01 to 0.1% by weight and the sulfite is used in an amount of 0.005 to 0.05% by weight, based on the total amount of the monomer A and the monomer B, that is, the persulfate is used in an amount of 0.01 to 0.1% by weight and the sulfite is used in an amount of 0.005 to 0.05% by weight, based on the total amount of the monomer A and the monomer B. For example, the oxidizing agent in the redox initiator may be a 0.2 wt% aqueous solution of potassium persulfate and/or a 0.2 wt% aqueous solution of ammonium persulfate; the reducing agent in the redox initiator may be 0.1 wt% aqueous potassium bisulfite solution and/or 0.1 wt% aqueous sodium bisulfite solution.
Preferably, the persulfate is used in an amount of 0.025 to 0.1 wt%, and the sulfite is used in an amount of 0.025 to 0.05 wt%, based on the total amount of the monomer A and the monomer B, more preferably; still more preferably, the persulfate is used in an amount of 0.05 to 0.08 wt% and the sulfite is used in an amount of 0.03 to 0.04 wt%, based on the total amount of the monomer A and the monomer B, and the most effective is obtained.
The oil-soluble initiator can be azobisisobutyronitrile and/or dimethyl azobisisobutyrate; and the amount of the oil-soluble initiator is 0.01 to 0.1 percent by weight based on the total amount of the monomer C; preferably, the oil-soluble initiator is used in an amount of 0.01 to 0.05% by weight, based on the total amount of the monomers C, to obtain a better effect; more preferably, the oil-soluble initiator is used in an amount of 0.02 to 0.04% by weight based on the total amount of the monomers C, the most effective being obtained. In the present invention, when the oil-soluble initiator may be a combination of azobisisobutyronitrile and dimethyl azobisisobutyrate, the ratio of the amounts of the azobisisobutyronitrile and the dimethyl azobisisobutyrate is not particularly limited as long as the total amount of the azobisisobutyronitrile and the dimethyl azobisisobutyrate is 0.01 to 0.1% by weight, preferably 0.01 to 0.05% by weight, more preferably 0.02 to 0.04.
Further preferably, the initiator is a combination of a water-soluble initiator and an oil-soluble initiator.
According to the present invention, in step (1), the pH of the aqueous solution is preferably 6 to 10, more preferably 7 to 9. The pH may be obtained by adding a pH adjuster, which may be various pH adjusters conventional in the art, to the mixed system, for example, at least one of sodium hydroxide, sodium carbonate, potassium carbonate and ammonia water, preferably sodium hydroxide and/or sodium carbonate.
According to the present invention, in step (3), the conditions of the polymerization reaction may include: the temperature is 40-60 deg.C, preferably 45-55 deg.C, and the time is 6-8 hr, preferably 7-8 hr.
In the present invention, the environmental conditions of the oil field may include: the temperature is 40-130 ℃, preferably 70-110 ℃, and more preferably 95-110 ℃; the degree of mineralization is 100-200,000mg/L, preferably 10,000-150,000mg/L, more preferably 60,000-150,000mg/L, and most preferably 100,000-150,000 mg/L.
According to a preferred embodiment of the present invention, the preparation method of the polymer with selective water plugging function comprises the following steps:
step 1: adding the monomer A, the monomer B and water into a polymerization reaction bottle (a heat-preservation polymerization bottle) to prepare an aqueous solution, and adjusting the pH value of the aqueous solution to 6-10 by using alkali;
step 2: adding the monomer C and the emulsifier into the aqueous solution obtained in the step 1, and uniformly stirring to form emulsion;
and 3, step 3: and (2) blowing nitrogen for 5-60min at the temperature of 40-60 ℃, adding an initiator into the emulsion obtained in the step 2, blowing nitrogen to uniformly mix the initiator and the emulsion, and carrying out sealing polymerization for 6-8h to obtain the water-based oil-soluble polymer water plugging material.
And 4, step 4: the water plugging material is prepared into an aqueous solution with the mass concentration of 0.1 percent by adopting simulated saline with the mineralization degree of 150,000mg/L, namely the water plugging agent.
In a third aspect, the invention provides a polymer with a selective water plugging function prepared by the method.
In a fourth aspect, the invention provides an application of the polymer with the selective water plugging function as a selective water plugging agent.
In the application of the polymer with the selective water plugging function as the selective water plugging agent, a specific application method is well known by the technical personnel in the field.
The invention adopts a polymerization method to synthesize a water-based water plugging material containing oil-soluble polymer particles in a system, namely, acrylamide monomers are polymerized in a water phase to form a water-soluble polymer continuous phase; meanwhile, oil-soluble monomers are polymerized in the emulsified colloidal particles to form oil-soluble polymer particles, and different action mechanisms of the water plugging material in an oil layer and a water layer are changed through two-phase polymerization, so that the oil/water selectivity of the water plugging material is improved, and the effect of plugging water and not plugging oil is achieved. According to the technical scheme, oil-soluble polymer particles are obtained by polymerizing oil-soluble monomers and are used for improving the temperature resistance, salt resistance and oil/water selectivity of the polymer.
The present invention will be described in detail below by way of examples.
Sodium Dodecyl Sulfate (SDS), Sodium Dodecyl Benzene Sulfonate (SDBS), and sodium dodecyl sulfate (SBS), span 20, span 40, and span 80 persulfate, and sulfites azobisisobutyronitrile and dimethyl azobisisobutyrate were purchased from national drug group chemical agents, Inc.
In the following examples, the test methods involved are as follows:
the plugging rate is carried out on a rock core flow test device according to the plugging rate test procedure in SY/T5840-2007 bridge plugging material indoor test method for drilling fluid. Specifically, the method comprises the following steps:
and (3) measuring the water plugging rate: loading the artificial core into core holder, saturating with water, and measuring its pore volume PV and water phase permeability (K)w1) Then injecting 1.0PV water shutoff agent, curing for 24h at 95 ℃, and measuring the permeability (K) of the mixture after adding the water shutoff agent by using waterw2)，Kw2And Kw1Ratio (K)w2/Kw1) Namely the water plugging rate.
And (3) measuring the oil plugging rate: loading the artificial core into core holder, saturating with oil, and measuring its pore volume PV and oil phase permeability (K)o1) Then injecting 1.0PV water shutoff agent, curing for 24h at 95 ℃, and measuring the permeability (K) after adding the water shutoff agent by using oilo2)，Ko2And Ko1Of (K)o2/Ko1) Namely the oil plugging rate.
And (3) measuring the scouring resistance multiple: after the water plugging rate is measured, water with 50 times of pore volume multiple (PV) is continuously injected into the rock core, the permeability under different PV numbers is recorded, the water plugging rate under different PV numbers is calculated according to the measuring method of the water plugging rate, and the scouring resistance multiple is the maximum PV number of the injected water when the water plugging rate is more than or equal to 80%. Normally, the water blocking rate at 50PV number is measured, and the value is more than or equal to 80 percent, which indicates that the material has excellent flushing resistance.
Wherein the artificial core is obtained by filling quartz sand of 40-60 meshes in a mould.
Example 1
This example illustrates a polymer having selective water shutoff functionality prepared by the method of the present invention.
1. 2.9g of acrylamide (the amount of the monomer A is 0.97 parts by weight based on 100 parts by weight of water) and 0.3g of N-vinylformamide (the amount of the monomer B is 0.1 part by weight based on 100 parts by weight of water) are weighed and added into 300mL of water to be stirred and fully dissolved, and then the pH value of the aqueous solution is adjusted to 6.0 by alkali (sodium hydroxide) to obtain a stable aqueous solution;
2. weighing 6.0g of styrene (based on 100 parts by weight of water, the using amount of the monomer C is 2 parts by weight), 1.5g of a main emulsifier SDBS (based on 100 parts by weight of water, the using amount of the main emulsifier is 0.5 part by weight) and 1.5g of a co-emulsifier span 20 (based on 100 parts by weight of water, the using amount of the co-emulsifier is 0.5 part by weight), adding the mixture into the solution, and fully stirring to form a stable emulsion;
3. 0.15g of 0.2 weight percent potassium persulfate aqueous solution, 0.15g of 0.1 weight percent sodium bisulfite aqueous solution (based on 3.2g of the total amount of the monomer A and the monomer B, 0.01 weight percent of the persulfate, and 0.005 weight percent of the sulfite) and 0.6mg of oil-soluble initiator (azobisisobutyronitrile) (based on 6g of the total amount of the monomer C, 0.01 weight percent of the oil-soluble initiator) are added into the emulsion in the step 2 in sequence, fully stirred and emulsified, and then heated to 40 ℃ to initiate polymerization for 6 hours to obtain the water-based oil-soluble polymer.
4. The water plugging material is prepared into an aqueous solution with the mass concentration of 0.1 percent by adopting simulated saline with the mineralization degree of 150,000mg/L, namely DSJ 1.
As a result of the test, under the conditions of high temperature (95 ℃) and high salt (the degree of mineralization is 150,000mg/L), the water blocking rate of the DSJ1 is 94.1%, the oil blocking rate is 11.0%, and the scouring resistance multiple is more than 50 PV.
The water plugging material prepared in the embodiment has excellent selective plugging rate and flushing resistance on oil/water, and particularly still has better selective plugging rate on oil/water under high temperature and high salt conditions.
Example 2
This example illustrates a polymer having selective water shutoff functionality prepared by the method of the present invention.
1. 9.0g of acrylamide (the amount of the monomer A is 3 parts by weight based on 100 parts by weight of water) and 6.0g of N-vinylformamide (the amount of the monomer B is 2 parts by weight based on 100 parts by weight of water) are weighed and added into 300mL of water to be stirred and fully dissolved, and then the pH value of the aqueous solution is adjusted to 7.0 by alkali (sodium carbonate) to obtain a stable aqueous solution;
2. weighing 15.0g of styrene (based on 100 parts by weight of water, the using amount of the monomer C is 5 parts by weight), 6.0g of SBS (based on 100 parts by weight of water, the using amount of the main emulsifier is 2 parts by weight) and 3.0g of span 40 (based on 100 parts by weight of water, the using amount of the auxiliary emulsifier is 1 part by weight) which are added into the solution, and fully stirring to form stable emulsion;
3. to the emulsion in the step 2, 3.75g of a 0.2 wt% potassium persulfate aqueous solution, 3.75g of a 0.1 wt% sodium bisulfite aqueous solution (based on 15g of the total amount of the monomer A and the monomer B, the amount of the persulfate is 0.05 wt%, and the amount of the sulfite is 0.025 wt%) and 7.5mg of an oil-soluble initiator (dimethyl azodiisobutyrate) (based on 15g of the total amount of the monomer C, the amount of the oil-soluble initiator is 0.05 wt%) were added in this order, and after sufficient stirring and emulsification, the temperature was raised to 45 ℃ to initiate polymerization for 7 hours, thereby obtaining a water-based oil-soluble polymer.
4. The water plugging material is prepared into an aqueous solution with the mass concentration of 0.1 percent by adopting simulated saline with the mineralization degree of 150,000mg/L, namely DSJ 2.
As a result of the test, under the conditions of high temperature (95 ℃) and high salt (the degree of mineralization is 150,000mg/L), the water blocking rate of the DSJ2 is 98.2%, the oil blocking rate is 7.5%, and the scouring resistance multiple is more than 50 PV.
The water plugging material prepared in the embodiment has excellent selective plugging rate and flushing resistance on oil/water, and particularly still has better selective plugging rate on oil/water under high temperature and high salt conditions.
Example 3
This example illustrates a polymer having selective water shutoff functionality prepared by the method of the present invention.
1. Weighing 15.0g of acrylamide (based on 100 parts by weight of water, the amount of the monomer A is 5 parts by weight) and 15.0g of N-vinylformamide (based on 100 parts by weight of water, the amount of the monomer B is 5 parts by weight) into 300mL of water, stirring and fully dissolving, and then adjusting the pH value of the aqueous solution to 7.0 by using alkali (sodium hydroxide) to obtain a stable aqueous solution;
2. weighing 30.0g of styrene (based on 100 parts by weight of water, the using amount of the monomer C is 10 parts by weight), 10.0g of SDS (based on 100 parts by weight of water, the using amount of the main emulsifier is 3.33 parts by weight) as a main emulsifier and 5.0g of Tween 80 (based on 100 parts by weight of water, the using amount of the auxiliary emulsifier is 1.67 parts by weight) as auxiliary emulsifiers, adding the materials into the solution, and fully stirring to form stable emulsion;
3. and (2) adding 15.0g of 0.2% potassium persulfate aqueous solution, 15.0g of 0.1% sodium bisulfite aqueous solution (based on 30g of the total dosage of the monomer A and the monomer B, 0.1 wt% of the persulfate and 0.05 wt% of the sulfite) and 30mg of oil-soluble initiator (based on 30g of the total dosage of the monomer C, 0.1 wt% of the oil-soluble initiator) into the emulsion in the step 2 in sequence, stirring and emulsifying fully, raising the temperature to 60 ℃, and initiating polymerization for 8 hours to obtain the water-based oil-soluble polymer.
4. The water plugging material is prepared into an aqueous solution with the mass concentration of 0.1 percent by adopting simulated saline with the mineralization degree of 150,000mg/L, namely DSJ 3.
As a result of the test, under the conditions of high temperature (95 ℃) and high salt (the degree of mineralization is 150,000mg/L), the water blocking rate of the DSJ3 is 999.9%, the oil blocking rate is 6.2%, and the scouring resistance multiple is more than 50 PV.
The water plugging material prepared in the embodiment has excellent selective plugging rate and flushing resistance on oil/water, and particularly still has better selective plugging rate on oil/water under high temperature and high salt conditions.
Example 4
This example illustrates a polymer having selective water shutoff functionality prepared by the method of the present invention.
1. Weighing 10.0g of acrylamide (the amount of the monomer A is 3.33 parts by weight based on 100 parts by weight of water) and 8.0g of N-vinylformamide (the amount of the monomer B is 2.67 parts by weight based on 100 parts by weight of water) into 300mL of water, stirring and fully dissolving, and then adjusting the pH value of the aqueous solution to 7.0 by using alkali (sodium carbonate) to obtain a stable aqueous solution;
2. weighing 12.0g of octyl methacrylate (based on 100 parts by weight of water, the using amount of the monomer C is 4 parts by weight), 6.0g of a main emulsifier SDBS (based on 100 parts by weight of water, the using amount of the main emulsifier is 2 parts by weight) and 6.0g of a co-emulsifier Tween 40 (based on 100 parts by weight of water, the using amount of the co-emulsifier is 2 parts by weight), adding the materials into the solution, and fully stirring to form a stable emulsion;
3. and (2) adding 1.8g of 0.2% potassium persulfate aqueous solution, 1.8g of 0.1% sodium bisulfite aqueous solution (based on 18g of the total dosage of the monomer A and the monomer B, 0.02 wt% of persulfate and 0.01 wt% of sulfite) and 6.0mg of oil-soluble initiator (based on 12g of the total dosage of the monomer C, 0.05 wt% of oil-soluble initiator) into the emulsion in the step 2 in sequence, stirring and emulsifying fully, raising the temperature to 50 ℃, and initiating polymerization for 7 hours to obtain the water-based oil-soluble polymer.
4. The water plugging material is prepared into an aqueous solution with the mass concentration of 0.1 percent by adopting simulated saline with the mineralization degree of 150,000mg/L, namely DSJ 4.
As a result of the test, under the conditions of high temperature (95 ℃) and high salt (the degree of mineralization is 150,000mg/L), the water blocking rate of the DSJ4 is 97.6%, the oil blocking rate is 4.8%, and the scouring resistance multiple is more than 50 PV.
The water plugging material prepared in the embodiment has excellent selective plugging rate and flushing resistance on oil/water, and particularly still has better selective plugging rate on oil/water under high temperature and high salt conditions.
Example 5
This example illustrates a polymer having selective water shutoff functionality prepared by the method of the present invention.
The same method as that of example 1 for preparing a polymer having a selective water shutoff function was employed, except that: the monomers used in the present examples were different, specifically:
the amount of acrylamide used was 12g (based on 100 parts by weight of water, the amount of monomer A used was 4 parts by weight), the amount of N-vinylformamide used was 12g (based on 100 parts by weight of water, the amount of monomer B used was 4 parts by weight), the amount of styrene used was 6g (based on 100 parts by weight of water, the amount of monomer C used was 2 parts by weight), the amount of primary emulsifier SDBS used was 6g (based on 100 parts by weight of water, the amount of primary emulsifier used was 2 parts by weight) and the amount of co-emulsifier span 20 used was 3.0g (based on 100 parts by weight of water, the amount of co-emulsifier used was 1 part by weight);
and the persulfate is used in an amount of 0.01 wt% and the sulfite is used in an amount of 0.005 wt%, based on the total amount of the monomer A and the monomer B; the amount of the oil-soluble initiator is 0.01 percent by weight based on the total amount of the monomer C;
the rest of the procedure was the same as in example 1, to obtain a water-based oil-soluble polymer.
The water plugging material is prepared into an aqueous solution with the mass concentration of 0.1 percent by adopting simulated saline with the mineralization degree of 150,000mg/L, namely DSJ 5.
And (3) testing results: under the conditions of high temperature (95 ℃) and high salt (the degree of mineralization is 150,000mg/L), the water blocking rate of the DSJ5 is 98.9%, the oil blocking rate is 8.4%, the scouring resistance multiple is more than 60PV, and specifically, the scouring resistance multiple is 60-70 PV.
The water plugging material prepared in the embodiment has excellent selective plugging rate and flushing resistance on oil/water, and particularly still has better selective plugging rate on oil/water under high temperature and high salt conditions.
Example 6
This example illustrates a polymer having selective water shutoff functionality prepared by the method of the present invention.
The same method as that of example 1 for preparing a polymer having a selective water shutoff function was employed, except that: the monomers used in the present examples were different, specifically:
the amount of acrylamide used is 15g (based on 100 parts by weight of water, the amount of monomer A used is 5 parts by weight), the amount of N-vinylformamide used is 6g (based on 100 parts by weight of water, the amount of monomer B used is 3 parts by weight), the amount of styrene used is 9g (based on 100 parts by weight of water, the amount of monomer C used is 3 parts by weight), the amount of main emulsifier SDBS used is 9g (based on 100 parts by weight of water, the amount of main emulsifier used is 3 parts by weight) and the amount of co-emulsifier span 20 used is 9g (based on 100 parts by weight of water, the amount of co-emulsifier used is 3 parts by weight);
and the use amount of the persulfate is 0.1 weight percent and the use amount of the sulfite is 0.05 weight percent based on the total use amount of the monomer A and the monomer B; the amount of the oil-soluble initiator is 0.1 wt% based on the total amount of the monomer C;
the rest of the procedure was the same as in example 1, to obtain a water-based oil-soluble polymer.
The water plugging material is prepared into an aqueous solution with the mass concentration of 0.1 percent by adopting simulated saline with the mineralization degree of 150,000mg/L, namely DSJ 6.
And (3) testing results: under the conditions of high temperature (95 ℃) and high salt (the mineralization degree is 150,000mg/L), the water blocking rate of the DSJ6 is 99.2%, the oil blocking rate is 6.1%, the scouring resistance multiple is more than 80PV, and specifically, the scouring resistance multiple is 80-90 PV.
The water plugging material prepared in the embodiment has excellent selective plugging rate and flushing resistance on oil/water, and particularly still has better selective plugging rate on oil/water under high temperature and high salt conditions.
Example 7
This example illustrates a polymer having selective water shutoff functionality prepared by the method of the present invention.
The same method as that of example 1 for preparing a polymer having a selective water shutoff function was employed, except that: the monomers used in the present examples were different, specifically:
the amount of acrylamide used was 11.4g (based on 100 parts by weight of water, the amount of monomer A used was 3.8 parts by weight), the amount of N-vinylformamide used was 6g (based on 100 parts by weight of water, the amount of monomer B used was 3 parts by weight), the amount of styrene used was 9.9g (based on 100 parts by weight of water, the amount of monomer C used was 3.3 parts by weight), the amount of primary emulsifier SDBS used was 8.4g (based on 100 parts by weight of water, the amount of primary emulsifier used was 2.8 parts by weight) and the amount of co-emulsifier span 20 used was 2.1g (based on 100 parts by weight of water, the amount of co-emulsifier used was 0.7 part by weight).
And the persulfate is used in an amount of 0.05 wt% and the sulfite is used in an amount of 0.03 wt%, based on the total amount of the monomer A and the monomer B; the amount of the oil-soluble initiator is 0.02 wt% based on the total amount of the monomer C;
the rest of the procedure was the same as in example 1, to obtain a water-based oil-soluble polymer.
The water plugging material is prepared into an aqueous solution with the mass concentration of 0.1 percent by adopting simulated saline with the mineralization degree of 150,000mg/L, namely DSJ 7.
And (3) testing results: under the conditions of high temperature (95 ℃) and high salt (the mineralization degree is 150,000mg/L), the water blocking rate of the DSJ7 is 99.8%, the oil blocking rate is 10.2%, the scouring resistance multiple is more than 80PV, and specifically, the scouring resistance multiple is 85-95 PV.
The water plugging material prepared in the embodiment has excellent selective plugging rate and flushing resistance on oil/water, and particularly still has better selective plugging rate on oil/water under high temperature and high salt conditions.
Example 8
This example illustrates a polymer having selective water shutoff functionality prepared by the method of the present invention.
The same method as that of example 1 for preparing a polymer having a selective water shutoff function was employed, except that: the monomers used in the present examples were different, specifically:
the amount of acrylamide used was 12.6g (based on 100 parts by weight of water, the amount of monomer A used was 4.2 parts by weight), the amount of N-vinylformamide used was 12g (based on 100 parts by weight of water, the amount of monomer B used was 4 parts by weight), the amount of styrene used was 11.4g (based on 100 parts by weight of water, the amount of monomer C used was 3.8 parts by weight), the amount of primary emulsifier SDBS used was 9.4g (based on 100 parts by weight of water, the amount of primary emulsifier used was 3.2 parts by weight) and the amount of co-emulsifier span 20 used was 2.4g (based on 100 parts by weight of water, the amount of co-emulsifier used was 0.8 part by weight);
and the use amount of the persulfate is 0.08 wt% and the use amount of the sulfite is 0.04 wt% based on the total use amount of the monomer A and the monomer B; the amount of the oil-soluble initiator is 0.04 wt% based on the total amount of the monomer C;
the rest of the procedure was the same as in example 1, to obtain a water-based oil-soluble polymer.
The water plugging material is prepared into an aqueous solution with the mass concentration of 0.1 percent by adopting simulated saline with the mineralization degree of 150,000mg/L, namely DSJ 8.
And (3) testing results: under the conditions of high temperature (95 ℃) and high salt (the mineralization degree is 150,000mg/L), the water blocking rate of the DSJ8 is 99.8%, the oil blocking rate is 9.8%, the scouring resistance multiple is more than 80PV, and specifically, the scouring resistance multiple is 85-95 PV.
The water plugging material prepared in the embodiment has excellent selective plugging rate and flushing resistance on oil/water, and particularly still has better selective plugging rate on oil/water under high temperature and high salt conditions.
Example 9
This example illustrates a polymer having selective water shutoff functionality prepared by the method of the present invention.
The same method as that of example 1 for preparing a polymer having a selective water shutoff function was employed, except that: the monomer C in this embodiment is styrene and octyl methacrylate, and the weight ratio of the amounts of styrene and octyl methacrylate is 1: 1.
the rest of the procedure was the same as in example 1, to obtain a water-based oil-soluble polymer.
The water plugging material is prepared into an aqueous solution with the mass concentration of 0.1 percent by adopting simulated saline with the mineralization degree of 100,000mg/L, namely DSJ 9.
And (3) testing results: under the conditions of high temperature (95 ℃) and high salt (the mineralization degree is 100,000mg/L), the water blocking rate of the DSJ9 is 995.2%, the oil blocking rate is 9.1%, the scouring resistance multiple is more than 80PV, and specifically, the scouring resistance multiple is 85-95 PV.
The water plugging material prepared in the embodiment has excellent selective plugging rate and flushing resistance on oil/water, and particularly still has better selective plugging rate on oil/water under high temperature and high salt conditions.
Comparative example 1
The same method as that of example 1 for preparing a polymer having a selective water shutoff function was employed, except that: the monomers used in this example were varied, specifically, the amount of acrylamide used was 18g (the amount of monomer A used was 6 parts by weight based on 100 parts by weight of water), the amount of N-vinylformamide used was 18g (the amount of monomer B used was 6 parts by weight based on 100 parts by weight of water), the amount of styrene used was 33g (the amount of monomer C used was 11 parts by weight based on 100 parts by weight of water), the amount of primary emulsifier SDBS used was 15g (the amount of primary emulsifier used was 5 parts by weight based on 100 parts by weight of water) and the amount of co-emulsifier span 20 used was 15g (the amount of co-emulsifier used was 5 parts by weight based on 100 parts by weight of water).
The rest of the procedure was the same as in example 1, to obtain a water-based oil-soluble polymer.
The water plugging material is prepared into an aqueous solution with the mass concentration of 0.1 percent by adopting simulated saline with the mineralization degree of 150,000mg/L, namely D1.
And (3) testing results: under the conditions of high temperature (95 ℃) and high salt (the degree of mineralization is 150,000mg/L), the water blocking rate of the water blocking material D1 is 65.8%, the oil blocking rate is 32.1%, and the scouring resistance multiple is 0 PV.
The water plugging material prepared by the comparative example does not have excellent selective plugging rate and flushing resistance on oil/water, and particularly does not have good selective plugging rate on oil/water under high-temperature and high-salt conditions.
Comparative example 2
The same method as that of example 1 for preparing a polymer having a selective water shutoff function was employed, except that: the monomers used in this example were varied, specifically, acrylamide was used in an amount of 0.3g (monomer a was used in an amount of 0.1 part by weight based on 100 parts by weight of water), N-vinylformamide was used in an amount of 18g (monomer B was used in an amount of 6 parts by weight based on 100 parts by weight of water), styrene was used in an amount of 0.3g (monomer C was used in an amount of 0.1 part by weight based on 100 parts by weight of water), a main emulsifier SDBS was used in an amount of 0.9g (main emulsifier was used in an amount of 0.3 part by weight based on 100 parts by weight of water) and a co-emulsifier span 20 was used in an amount of 18g (co-emulsifier was used in an amount of 6 parts by weight based on 100 parts by weight of water).
The rest of the procedure was the same as in example 1, to obtain a water-based oil-soluble polymer.
The water plugging material is prepared into an aqueous solution with the mass concentration of 0.1 percent by adopting simulated saline with the mineralization degree of 150,000mg/L, namely D2.
And (3) testing results: under the conditions of high temperature (95 ℃) and high salt (the degree of mineralization is 150,000mg/L), the water blocking rate of the water blocking material D2 is 43.5%, the oil blocking rate is 20.9%, and the scouring resistance multiple is 0 PV.
Comparative example 3
The same method as that of example 1 for preparing a polymer having a selective water shutoff function was employed, except that: in this example, monomer C was not added.
And (3) testing results: under the conditions of high temperature (95 ℃) and high salt (the degree of mineralization is 150,000mg/L), the water blocking rate of the water blocking material D3 is 42.3%, the oil blocking rate is 31.8%, and the scouring resistance multiple is 0 PV.
Comparative example 4
The same method as that of example 1 for preparing a polymer having a selective water shutoff function was employed, except that: in this example, monomer B was not added.
And (3) testing results: under the conditions of high temperature (95 ℃) and high salt (the degree of mineralization is 150,000mg/L), the water blocking material D4 has the water blocking rate of 48.7 percent, the oil blocking rate of 28.4 percent and the scouring resistance multiple of 0 PV.
The water plugging material prepared by the comparative example does not have excellent selective plugging rate and flushing resistance on oil/water, and particularly does not have good selective plugging rate on oil/water under high-temperature and high-salt conditions.
According to the embodiments and the comparative examples, the water-soluble monomer, the oil-soluble monomer and the emulsifier are added into the aqueous solution, the stable emulsion system in the oil-in-water form is formed after stirring, the initiator is added, the initiation and the polymerization are carried out at the temperature of 40-60 ℃ by adopting the polymerization mode, and finally the water-based oil-soluble polymer particle type water plugging material is synthesized; and the amounts of the water-soluble monomer, the oil-soluble monomer and the emulsifier satisfy the above-defined ranges, the present invention can be accomplished, and has excellent effects.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (6)
1. A preparation method of a water-based water plugging material containing oil-soluble polymer particles and having a selective water plugging function is characterized by comprising the following steps:
(1) mixing the monomer A, the monomer B and water to form an aqueous solution with the pH value of 6-10;
(2) mixing a monomer C and an emulsifier with the aqueous solution to form an emulsion;
(3) carrying out polymerization reaction on the emulsion for 6-8 hours at the temperature of 40-60 ℃ in the presence of an initiator;
wherein the monomer A is acrylamide; the monomer B is N-vinylformamide; the monomer C is an oil-soluble monomer, and the oil-soluble monomer is styrene and/or octyl methacrylate; the emulsifier comprises a main emulsifier and a co-emulsifier; the main emulsifier is sodium dodecyl sulfate and/or sodium dodecyl benzene sulfonate; the auxiliary emulsifier is selected from one or more of span 20, span 40, span 60, span 80, tween 20, tween 40, tween 60 and tween 80;
wherein, based on 100 parts by weight of water, the using amount of the monomer A is 0.4-5 parts by weight, the using amount of the monomer B is 0.1-5 parts by weight, the using amount of the monomer C is 1-10 parts by weight, the using amount of the main emulsifier is 0.5-4.5 parts by weight, and the using amount of the co-emulsifier is 0-1.5 parts by weight;
the initiator is a water-soluble initiator and an oil-soluble initiator, the water-soluble initiator is an oxidation-reduction initiation system of persulfate-sulfite, and the oil-soluble initiator is azobisisobutyronitrile and/or dimethyl azobisisobutyrate; based on the total amount of the monomer A and the monomer B, the amount of the persulfate is 0.01-0.1 wt%, and the amount of the sulfite is 0.005-0.05 wt%; and the oil-soluble initiator is used in an amount of 0.01 to 0.1% by weight, based on the total amount of the monomer C.
2. The preparation method according to claim 1, wherein the monomer A is used in an amount of 3.5 to 4.5 parts by weight, the monomer B is used in an amount of 2.5 to 4.5 parts by weight, the monomer C is used in an amount of 3 to 4 parts by weight, the primary emulsifier is used in an amount of 2.5 to 3.5 parts by weight, and the co-emulsifier is used in an amount of 0.6 to 0.9 part by weight, based on 100 parts by weight of water.
3. The preparation method according to claim 1, wherein the primary emulsifier is sodium dodecylbenzenesulfonate; the coemulsifier is selected from one or more of span 20, span 40 and tween 80.
4. The production method according to claim 1, wherein the conditions of the polymerization reaction include: the temperature is 45-55 ℃ and the time is 7-8 hours.
5. The water-based water plugging material containing the oil-soluble polymer particles and having the selective water plugging function, which is prepared by the method of any one of claims 1 to 4.
6. The use of the water-based water shutoff material containing oil-soluble polymer particles with selective water shutoff function according to claim 5 as a selective water shutoff agent.
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| CN104448126A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Harsh oil deposit reversed-phase microemulsion profile-control flooding system and preparation method thereof |
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