CN108690584B - Composite profile control agent - Google Patents

Composite profile control agent Download PDF

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CN108690584B
CN108690584B CN201810481234.0A CN201810481234A CN108690584B CN 108690584 B CN108690584 B CN 108690584B CN 201810481234 A CN201810481234 A CN 201810481234A CN 108690584 B CN108690584 B CN 108690584B
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parts
agent
surfactant
gemini surfactant
carboxylate gemini
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CN108690584A (en
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高燕
张冕
兰建平
李泽锋
王亚军
邵秀丽
王改红
宇文昔涵
齐加德
李志杰
杨敏
高红平
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China National Petroleum Corp
CNPC Chuanqing Drilling Engineering Co Ltd
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China National Petroleum Corp
CNPC Chuanqing Drilling Engineering Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/50Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
    • C09K8/504Compositions based on water or polar solvents
    • C09K8/506Compositions based on water or polar solvents containing organic compounds
    • C09K8/508Compositions based on water or polar solvents containing organic compounds macromolecular compounds
    • C09K8/512Compositions based on water or polar solvents containing organic compounds macromolecular compounds containing cross-linking agents
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/50Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
    • C09K8/504Compositions based on water or polar solvents
    • C09K8/5045Compositions based on water or polar solvents containing inorganic compounds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/50Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
    • C09K8/504Compositions based on water or polar solvents
    • C09K8/506Compositions based on water or polar solvents containing organic compounds
    • C09K8/508Compositions based on water or polar solvents containing organic compounds macromolecular compounds
    • C09K8/5083Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/50Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
    • C09K8/504Compositions based on water or polar solvents
    • C09K8/506Compositions based on water or polar solvents containing organic compounds
    • C09K8/508Compositions based on water or polar solvents containing organic compounds macromolecular compounds
    • C09K8/514Compositions based on water or polar solvents containing organic compounds macromolecular compounds of natural origin, e.g. polysaccharides, cellulose

Abstract

The invention provides a composite profile control and flooding agent, which comprises, by weight, 20-50 parts of a surfactant type plugging agent, 30-70 parts of a pressure-reducing injection-increasing agent and 5-20 parts of a particle plugging agent; the surfactant type plugging agent is prepared from polyacrylamide, water, a composite cross-linking agent, modified cyclodextrin, m-phenylenediamine, an oxygen scavenger and a carboxylate gemini surfactant according to a weight ratio of 1: (110-131): (0.05-0.12): (0.2-0.8): (0.1-0.3): (0.05-0.2): (0.3-1), the oil displacement agent is prepared by adopting three coupling profile control key materials of a surfactant type plugging agent, a pressure reducing injection increasing agent and a particle plugging agent, and the effective unification of water plugging profile control, pressure reducing injection increasing and oil displacement technologies is realized by combining a water plugging profile control technology and a pressure reducing injection increasing technology.

Description

Composite profile control agent
Technical Field
The invention relates to the technical field of profile control, depressurization, injection enhancement and oil displacement used in oil exploitation, in particular to a composite profile control and flooding agent.
Background
The low-permeability oil field refers to an oil field with low oil reservoir permeability, low abundance and low single-well productivity. The low-permeability oil-gas field has important significance in oil-gas development in China, low-permeability oil-gas resource distribution in China has the characteristics of more oil and gas, more oil-gas reservoir types, wide distribution area and 'upper gas and lower oil and sea gas are main and continental phase oil and gas are combined', the proportion of the reserve of the low-permeability oil reservoir is very high in the ascertained reserve, the reserve occupies more than 2/3 of the reserve in China, and the development potential is huge.
In the development process of low-permeability oil fields, waterflooding development is the most successful technology for improving the recovery efficiency with high efficiency and economy at present. During the water injection process of the oil field, the contradiction between the layer, the layer and the plane caused by the injected water gradually appears in the middle and later periods of the water injection, and is particularly more obvious for compact reservoirs with developed cracks and micro cracks, for example, the injected water coning, the formation of well network waterlines and the like cause the rising of the development cost of the hypotonic oil field and the reduction of the recovery ratio. In order to solve the problems, a water plugging and profile control technology is generally required to plug the large pore throat and the cracks. Meanwhile, the hypotonic oil field faces another problem, namely the problem of 'insufficient injection' of the water injection well, namely, the actual water injection quantity cannot reach the 'daily water injection quantity' set by the oil field development, so that reservoir energy developed by the oil field cannot be effectively supplied and supplemented, the reduction of the yield of the corresponding affected oil well and well group is influenced, and the most effective technology is a pressure reduction and injection increase technology, so that the water injection pressure of the water injection well is reduced, and the water injection quantity is increased.
Therefore, aiming at the problems, the invention provides a composite profile control agent, which combines a water shutoff profile control technology with a depressurization and injection increasing technology, realizes the water shutoff profile control of a water flooded fracture, improves the water injection rate of a matrix reservoir and improves the oil displacement effect of a heterogeneous reservoir.
Disclosure of Invention
Aiming at the problems, through the evaluation of the geological characteristics of the low-permeability micro-fracture reservoir and the water injection effect, the invention aims to provide the composite profile control and flooding agent, and the effective unification of water plugging and profile control, pressure reduction and flooding technologies is realized through the effective combination of the water plugging and profile control technology and the pressure reduction and flooding technology.
The invention also aims to provide the development of the pressure-reducing and injection-increasing acid liquid, the development of the profile control and flooding agent and the development of the particle plugging agent.
The composite profile control and flooding agent is applied to the development of low-permeability oil fields, can be used for removing the blockage of a water injection well and simultaneously achieves the oil displacement effect on the oil well.
The technical scheme adopted by the invention is as follows:
a composite profile control and flooding agent comprises, by weight, 20-50 parts of a surfactant type plugging agent, 30-70 parts of a pressure-reducing injection-increasing agent and 5-20 parts of a particle plugging agent; the surfactant type plugging agent is prepared from polyacrylamide, water, a composite cross-linking agent, modified cyclodextrin, m-phenylenediamine, an oxygen scavenger and a carboxylate gemini surfactant according to a weight ratio of 1: (110-131): (0.05-0.12): (0.2-0.8): (0.1-0.3): (0.05-0.2): (0.3-1).
The pressure-reducing injection-increasing agent comprises, by weight, 30-35 parts of dioctyldimethylammonium chloride, 3-7 parts of fluorocarbon surfactant, 3-5 parts of nonionic surfactant, 5-10 parts of sodium ethylene diamine tetramethylene phosphonate, (Z) -3,3, 4-trimethyl-piperazinone oxime, and 38-57 parts of deionized water; the fluorocarbon surfactant is fluorocarbon FC-4430, and the nonionic surfactant is polyoxyethylene lauryl ether.
The particle blocking agent comprises, by weight, 20-50 parts of acrylamide, 20-50 parts of acrylic acid, 1-15 parts of sodium hydroxide, 2-10 parts of modified zeolite, 0.1-0.5 part of ammonium persulfate, 0.05-0.25 part of sodium bisulfite, 0.1-0.5 part of N, N-methylene bisacrylamide, 1-5 parts of dodecyl methacrylate and 40-60 parts of water;
the modified zeolite is acrylic acid modified zeolite, and the acrylic acid modified zeolite is prepared from zeolite powder, acrylic acid and dibenzoyl peroxide according to a weight ratio of 100: (12-20): (0.13-0.2); the preparation method comprises the following steps: adding zeolite powder into a mixing machine with a charging basket at the temperature of 50-70 ℃, adding acrylic acid and dibenzoyl peroxide according to the weight ratio, stirring for 2-3h, discharging, raising the charging basket temperature of the mixing machine to 110-120 ℃, pouring the materials into the mixing machine, stirring at a high speed for 1-2h, and discharging to obtain the acrylic acid modified zeolite.
The preparation method of the surfactant type plugging agent comprises the following steps: firstly, adding polyacrylamide and water with a formula amount into a reactor, stirring and dissolving, adjusting the pH value to 5.0 by using oxalic acid, and standing for 1-3 hours for full curing; and then sequentially adding the oxygen scavenger, the composite cross-linking agent, the modified cyclodextrin and the m-phenylenediamine in the formula amount, uniformly stirring, heating to 80-90 ℃, preserving heat for 20-40h, then cooling to 55-60 ℃, adding the carboxylate gemini surfactant in the formula amount, stirring for 1-2h, and cooling to room temperature to obtain the surfactant type plugging agent.
The modified cyclodextrin is citric acid modified beta-cyclodextrin, and the citric acid modified beta-cyclodextrin is prepared from citric acid, sodium hypophosphite, deionized water, beta-cyclodextrin and absolute ethyl alcohol in a weight ratio of 1: (0.1-0.3): (1-3): (0.5-1): (3-6); the preparation method of the citric acid modified beta-cyclodextrin comprises the following steps: sequentially adding citric acid, sodium hypophosphite and deionized water into a reactor according to the weight ratio, stirring to completely dissolve, adding beta-cyclodextrin with the formula amount, heating to 70-80 ℃, carrying out heat preservation reaction for 2-3h, heating to 100-.
The carboxylate gemini surfactant is prepared from a carboxylate gemini surfactant A and a carboxylate gemini surfactant B according to the weight ratio of 1: (0.1-0.7) mixing.
The carboxylate gemini surfactant A is prepared from 1, 3-propane sultone, absolute ethyl alcohol, p-phenylenediamine, methanol, anhydrous potassium carbonate, bromododecane and acetone according to a weight ratio of 1: (4-8): (0.3-0.7): (8-12): (1-1.3): (0.8-1.2): (3-6);
the preparation method of the carboxylate gemini surfactant A comprises the following steps: firstly, sequentially adding 1, 3-propane sultone, absolute ethyl alcohol and p-phenylenediamine in formula amount into a reactor, stirring, heating to 55-60 ℃, reacting for 20-25h under heat preservation, and concentrating under reduced pressure to dryness; then sequentially adding methanol, anhydrous potassium carbonate and bromododecane according to the formula ratio, heating to 60-70 ℃, reacting for 30-35h under heat preservation, filtering, and concentrating the filtrate under reduced pressure to dryness; and finally adding acetone with the formula amount for recrystallization, and drying at 60 ℃ under reduced pressure for 10-12h to obtain the carboxylate gemini surfactant A.
The carboxylate gemini surfactant B is prepared from raw materials including 1, 3-propane sultone, absolute ethyl alcohol, p-phenylenediamine, methanol, anhydrous potassium carbonate, 1-bromohexane and acetone according to a weight ratio of 1: (4-7): (0.4-0.6): (9-12): (1-1.3): (0.9-1.1): (3-6);
the preparation method of the carboxylate gemini surfactant B comprises the following steps: firstly, sequentially adding 1, 3-propane sultone, absolute ethyl alcohol and p-phenylenediamine in formula amount into a reactor, stirring, heating to 55-60 ℃, reacting for 20-25h under heat preservation, and concentrating under reduced pressure to dryness; then sequentially adding methanol, anhydrous potassium carbonate and 1-bromohexane according to the formula ratio, heating to 60-70 ℃, reacting for 30-35h under heat preservation, filtering, and concentrating the filtrate under reduced pressure to dryness; and finally adding acetone with the formula amount for recrystallization, and drying at 60 ℃ under reduced pressure for 10-12h to obtain the carboxylate gemini surfactant B.
The composite cross-linking agent is prepared from benzaldehyde and benzenediol in a weight ratio of 1: (0.3-0.6) in proportion.
The oxygen scavenger comprises one or more of thiourea, 2, 4-dithiobiuret, semicarbazide, thiosemicarbazide and 1, 4-phenylene bis (thiourea).
The oxygen scavenger is semicarbazide and 1, 4-phenylene bis (thiourea) according to the weight ratio of 1: (0.3-2) in proportion.
The composite profile control agent is applied to the development of low-permeability oil fields.
The invention has the following advantages:
according to the invention, through three coupling profile control key materials of the surfactant type plugging agent, the pressure-reducing injection-increasing agent and the particle plugging agent, the combination of a water-plugging profile control technology and a pressure-reducing injection-increasing technology is developed, and the effective unification of the water-plugging profile control, the pressure-reducing injection-increasing and the oil displacement technology is realized. The injected water is adjusted to flow to a favorable direction through the continuous change of multiple parameters such as material viscosity, state, flow resistance, wettability, flow pressure and the like in the injection process, the injected water amount flowing to a large pore passage is reduced through the processes of automatic energy coupling, automatic fluid direction steering and automatic fluid pressure balancing, the low-permeability area which is not used for low-permeability is enlarged, the water plugging and regulating agent of a water flooding crack is realized, the water injection amount of a matrix reservoir is increased, and the oil displacement effect of a heterogeneous reservoir is improved.
Detailed Description
The disclosure may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, and in the event of conflict, the definitions set forth herein shall control.
The term "prepared from …" as used herein is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The conjunction "consisting of …" excludes any unspecified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of …" appears in a clause of the subject matter of the claims rather than immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
The singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. "optional" or "any" means that the subsequently described event or events may or may not occur, and that the description includes instances where the event occurs and instances where it does not.
Approximating language, as used herein throughout the specification and claims, is intended to modify a quantity, such that the invention is not limited to the specific quantity, but includes portions that are literally received for modification without substantial change in the basic function to which the invention is related. Accordingly, the use of "about" to modify a numerical value means that the invention is not limited to the precise value. In some instances, the approximating language may correspond to the precision of an instrument for measuring the value. In the present description and claims, range limitations may be combined and/or interchanged, including all sub-ranges contained therein if not otherwise stated.
In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the stated number clearly indicates that the singular form is intended.
"Polymer" means a polymeric compound prepared by polymerizing monomers of the same or different types. The generic term "polymer" embraces the terms "homopolymer", "copolymer", "terpolymer" and "interpolymer".
"interpolymer" means a polymer prepared by polymerizing at least two different monomers. The generic term "interpolymer" includes the term "copolymer" (which is generally used to refer to polymers prepared from two different monomers) and the term "terpolymer" (which is generally used to refer to polymers prepared from three different monomers). It also includes polymers made by polymerizing more monomers. "blend" means a polymer formed by two or more polymers being mixed together by physical or chemical means.
The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.
In addition, the raw materials used are commercially available from national chemical reagents, unless otherwise specified.
Example 1
The invention provides a composite profile control and flooding agent, which comprises, by weight, 20-50 parts of a surfactant type plugging agent, 30-70 parts of a pressure-reducing injection-increasing agent and 5-20 parts of a particle plugging agent; the surfactant type plugging agent is prepared from polyacrylamide, water, a composite cross-linking agent, modified cyclodextrin, m-phenylenediamine, an oxygen scavenger and a carboxylate gemini surfactant according to a weight ratio of 1: (110-131): (0.05-0.12): (0.2-0.8): (0.1-0.3): (0.05-0.2): (0.3-1).
According to the invention, through three coupling profile control key materials of the surfactant type plugging agent, the pressure-reducing injection-increasing agent and the particle plugging agent, the combination of a water-plugging profile control technology and a pressure-reducing injection-increasing technology is developed, and the effective unification of the water-plugging profile control, the pressure-reducing injection-increasing and the oil displacement technology is realized. The injected water is adjusted to flow to a favorable direction through the continuous change of multiple parameters such as material viscosity, state, flow resistance, wettability, flow pressure and the like in the injection process, the injected water amount flowing to a large pore passage is reduced through the processes of automatic energy coupling, automatic fluid direction steering and automatic fluid pressure balancing, the low-permeability area which is not used for low-permeability is enlarged, the water plugging and regulating agent of a water flooding crack is realized, the water injection amount of a matrix reservoir is increased, and the oil displacement effect of a heterogeneous reservoir is improved.
Example 2
On the basis of the example 1, the preparation raw materials of the surfactant type plugging agent comprise polyacrylamide, a composite cross-linking agent, modified cyclodextrin, m-phenylenediamine, an oxygen scavenger and a carboxylate gemini surfactant. The polyacrylamide is a raw material widely used by a conventional water shutoff profile control agent, and molecules of the polyacrylamide shrink and curl when meeting an oil phase, and extend and expand molecular chains to retain water when meeting a water phase, so that the selectivity is good. However, the polymer is mainly adsorbed to the stratum by hydrogen bonds, the adsorption strength is weak, and the polymer cannot be washed by water, in addition, the mineralization degree of the stratum water is high, the salt resistance effect of polyacrylamide is weak, the electric property of polyacrylamide groups is neutralized by salt, so that the charges on polyacrylamide ion groups are shielded, the electrostatic repulsion between ions is weakened, and the long chain of the polymer is curled. In this example, the polyacrylamide is a partially hydrolyzed polyacrylamide having a degree of hydrolysis of 18% and a molecular weight of 1400 ten thousand.
The composite cross-linking agent is prepared from benzaldehyde and benzenediol in a weight ratio of 1: 0.4, and mixing.
The beta-cyclodextrin is one of cyclodextrin, and is a cyclic oligosaccharide formed by connecting 7D-glucopyranoses through alpha-1, 4 glycosidic bonds and generated by the action of cyclodextrin glucosyltransferase produced by bacillus amyloliquefaciens on starch. In this example, the modified cyclodextrin is citric acid modified β -cyclodextrin.
The citric acid modified beta-cyclodextrin is prepared from citric acid, sodium hypophosphite, deionized water, beta-cyclodextrin and absolute ethyl alcohol in a weight ratio of 1: (0.1-0.3): (1-3): (0.5-1): (3-6); the preparation method of the citric acid modified beta-cyclodextrin comprises the following steps: sequentially adding citric acid, sodium hypophosphite and deionized water into a reactor according to the weight ratio, stirring to completely dissolve, adding beta-cyclodextrin with the formula amount, heating to 70-80 ℃, carrying out heat preservation reaction for 2-3h, heating to 100-. According to the invention, citric acid is adopted to modify cyclodextrin, and the cyclodextrin contains-NH 2, -COOH, -OH and a cyclodextrin cavity, so that the crystallinity of the cyclodextrin can be reduced, the water solubility of the cyclodextrin can be increased, and the polysaccharide cross-linking agent which is green, environment-friendly and low in price can be obtained.
The oxygen scavenger comprises one or more of thiourea, 2, 4-dithiobiuret, semicarbazide, thiosemicarbazide and 1, 4-phenylene bis (thiourea).
Example 3
On the basis of example 2, the carboxylate gemini surfactant comprises a carboxylate gemini surfactant A and a carboxylate gemini surfactant B, wherein the carboxylate gemini surfactant A is prepared from 1, 3-propane sultone, absolute ethyl alcohol, p-phenylenediamine, methanol, anhydrous potassium carbonate, bromododecane and acetone in a weight ratio of 1: (4-8): (0.3-0.7): (8-12): (1-1.3): (0.8-1.2): (3-6); the preparation method of the carboxylate gemini surfactant A comprises the following steps: firstly, sequentially adding 1, 3-propane sultone, absolute ethyl alcohol and p-phenylenediamine in formula amount into a reactor, stirring, heating to 55-60 ℃, reacting for 20-25h under heat preservation, and concentrating under reduced pressure to dryness; then sequentially adding methanol, anhydrous potassium carbonate and bromododecane according to the formula ratio, heating to 60-70 ℃, reacting for 30-35h under heat preservation, filtering, and concentrating the filtrate under reduced pressure to dryness; and finally adding acetone with the formula amount for recrystallization, and drying at 60 ℃ under reduced pressure for 10-12h to obtain the carboxylate gemini surfactant A.
The carboxylate gemini surfactant B is prepared from raw materials including 1, 3-propane sultone, absolute ethyl alcohol, p-phenylenediamine, methanol, anhydrous potassium carbonate, 1-bromohexane and acetone according to a weight ratio of 1: (4-7): (0.4-0.6): (9-12): (1-1.3): (0.9-1.1): (3-6); the preparation method of the carboxylate gemini surfactant B comprises the following steps: firstly, sequentially adding 1, 3-propane sultone, absolute ethyl alcohol and p-phenylenediamine in formula amount into a reactor, stirring, heating to 55-60 ℃, reacting for 20-25h under heat preservation, and concentrating under reduced pressure to dryness; then sequentially adding methanol, anhydrous potassium carbonate and 1-bromohexane according to the formula ratio, heating to 60-70 ℃, reacting for 30-35h under heat preservation, filtering, and concentrating the filtrate under reduced pressure to dryness; and finally adding acetone with the formula amount for recrystallization, and drying at 60 ℃ under reduced pressure for 10-12h to obtain the carboxylate gemini surfactant B.
The weight ratio of the carboxylate gemini surfactant A to the carboxylate gemini surfactant B in the carboxylate gemini surfactant is 1: (0.1-0.7); preferably, the weight ratio of the carboxylate gemini surfactant a to the carboxylate gemini surfactant B is 1: 0.24.
in this embodiment, the surfactant type plugging agent is prepared from polyacrylamide, water, an oxygen scavenger, a composite cross-linking agent, modified cyclodextrin, m-phenylenediamine, and a carboxylate gemini surfactant in a weight ratio of 1: (110-131): (0.05-0.12): (0.2-0.8): (0.1-0.3): (0.05-0.2): (0.3-1). The preparation method of the surfactant type plugging agent comprises the following steps: firstly, adding a formula amount of partially hydrolyzed polyacrylamide with the molecular weight of 1400 ten thousand and the hydrolysis degree of 18 percent and water with the mineralization degree of 125520mg/L into a reactor, stirring and dissolving, adjusting the pH value to 5.0 by using oxalic acid, and standing for 1-3 hours for full curing; and then sequentially adding the oxygen scavenger, the composite cross-linking agent, the modified cyclodextrin and the m-phenylenediamine in the formula amount, uniformly stirring, heating to 80-90 ℃, preserving heat for 20-40h, then cooling to 55-60 ℃, adding the carboxylate gemini surfactant in the formula amount, stirring for 1-2h, and cooling to room temperature to obtain the surfactant type plugging agent. The addition of the surfactant can reduce the interfacial tension among underground phases, cause emulsification, reduce the adsorption force of rock formations on oil, increase the solubility of the oil in water, and reduce the viscosity of crude oil, thereby extracting oil bound by pores.
The surfactant type plugging agent disclosed by the invention can be prepared by using high-salinity water through the synergistic effect of polyacrylamide, a composite cross-linking agent, modified cyclodextrin, m-phenylenediamine, an oxygen scavenger and a carboxylate gemini surfactant, and has the advantages of strong cross-linking capability, long-term stability, high-temperature and high-salinity resistance and strength required by long-term washing of formation water.
Example 4
On the basis of the embodiment 1, the raw material composition of the pressure-reducing injection-increasing agent comprises 30-35 parts of dioctyldimethylammonium chloride, 3-7 parts of fluorocarbon surfactant, 3-5 parts of nonionic surfactant, 5-10 parts of sodium ethylene diamine tetra methylene phosphonate, 2-5 parts of (Z) -3,3, 4-trimethyl-piperazinone oxime and 38-57 parts of deionized water in parts by weight; preferably, the preparation raw materials of the pressure-reducing injection-increasing agent comprise 32 parts of dioctyldimethylammonium chloride, 4 parts of fluorocarbon surfactant, 3 parts of nonionic surfactant, 7 parts of sodium ethylene diamine tetramethylammonium phosphate, 3 parts of (Z) -3,3, 4-trimethyl-piperazinone oxime (CAS:74987-05-6) and 50 parts of deionized water.
The fluorocarbon surfactant is fluorocarbon FC-4430, and the nonionic surfactant is polyoxyethylene lauryl ether.
The preparation method of the blood pressure reducing and injection increasing agent comprises the following steps:
adding dioctyldimethylammonium chloride, fluorocarbon FC-4430, polyoxyethylene lauryl ether, ethylene diamine tetra methylene phosphonic acid sodium, (Z) -3,3, 4-trimethyl-piperazinone oxime and deionized water into a reactor in sequence according to the weight parts, heating to 50 ℃, keeping the temperature for reaction for 3 hours, and cooling to room temperature to obtain the pressure-reducing and injection-increasing agent.
The pressure-reducing injection-increasing agent takes an aqueous solution as a transfer medium to deposit and form an ultrathin molecular film on the surface of rock; the pressure-reducing and injection-increasing agent has the effects of changing core wettability and preventing clay from swelling besides the water film peeling-off, so that the water injection pressure is reduced, the pressure-reducing and injection-increasing agent also has various effects of corrosion inhibition, scale inhibition, sterilization and the like, the influence of corrosion products, scaling, bacteria and the like of injected water on the formation porosity can be effectively prevented, the antibacterial effect is further improved due to the introduction of piperazine groups, and the water injection effect of the low-permeability reservoir water injection well is greatly improved.
Example 5
On the basis of the embodiment 1, the raw material composition of the particle plugging agent comprises, by weight, 20-50 parts of acrylamide, 20-50 parts of acrylic acid, 1-15 parts of sodium hydroxide, 2-10 parts of modified zeolite, 0.1-0.5 part of ammonium persulfate, 0.05-0.25 part of sodium bisulfite, 0.1-0.5 part of N, N-methylene bisacrylamide, 1-5 parts of dodecyl methacrylate and 40-60 parts of water; preferably, the raw materials for preparing the particle blocking agent comprise 35 parts of acrylamide, 21 parts of acrylic acid, 5 parts of sodium hydroxide, 5 parts of modified zeolite, 0.3 part of ammonium persulfate, 0.1 part of sodium bisulfite, 0.25 part of N, N-methylene bisacrylamide, 3 parts of dodecyl methacrylate and 50 parts of water.
The modified zeolite is acrylic acid modified zeolite, and the acrylic acid modified zeolite is prepared from zeolite powder, acrylic acid and dibenzoyl peroxide according to a weight ratio of 100: (12-20): (0.13-0.2), the preparation method comprises the following steps: adding zeolite powder into a mixing machine with a charging basket at the temperature of 50-70 ℃, adding acrylic acid and dibenzoyl peroxide according to the weight ratio, stirring for 2-3h, discharging, raising the charging basket temperature of the mixing machine to 110-120 ℃, pouring the materials into the mixing machine, stirring at a high speed for 1-2h, and discharging to obtain the acrylic acid modified zeolite.
The preparation method of the particle plugging agent comprises the following steps:
adding deionized water and sodium hydroxide according to the formula amount into a reactor, uniformly stirring, adding acrylic acid according to the formula amount, fully stirring, sequentially adding dodecyl methacrylate, acrylamide and modified zeolite according to the formula amount, heating to 45 ℃, then adding N, N-methylene bisacrylamide according to the formula amount, heating to 80 ℃, adding sodium bisulfite and ammonium persulfate according to the formula amount, reacting for 2 hours under heat preservation, cooling to room temperature, shearing, drying, and crushing into powder to obtain the particle plugging agent.
The particle plugging agent disclosed by the invention can not pollute a horizontal-section precision screen pipe when a screen pipe well completion horizontal well blocks water, is long in consolidation time, moderate in strength and high-temperature resistant, and has the advantages of good suspension property, good fluidity, good sieving property, high-temperature resistance, easiness in entering a stratum and low cost, so that the aims of low plugging risk, long validity period and high plugging success rate of the precision screen pipe horizontal well are fulfilled.
Example 6
On the basis of the embodiment, the composite profile control agent is applied to the development of low-permeability oil fields. The invention also provides a coupling profile control and flooding process, which comprises the following steps:
(1) opening a well mouth of the measure well, and injecting the depressurization and injection increasing agent into the underground through an adjusting and driving pump truck;
(2) sequentially injecting a surfactant type plugging agent and a particle plugging agent by a profile control pump truck;
(3) after the injection operation is finished, the well is not closed, the water injection operation is continued, and the composite profile control and flooding agent reacts at the longitudinal and deep part of the reservoir under the promotion of subsequent water injection, so that the purpose of profile control, flooding and increasing injection is achieved.
Example 7
A composite profile control and flooding agent comprises, by weight, 35 parts of a surfactant type plugging agent, 55 parts of a pressure-reducing injection-increasing agent and 10 parts of a particle plugging agent;
the surfactant type plugging agent is prepared from the following raw materials of polyacrylamide, a composite cross-linking agent, modified cyclodextrin, m-phenylenediamine, an oxygen scavenger and a carboxylate gemini surfactant, wherein the weight ratio of the polyacrylamide, water, the composite cross-linking agent, citric acid modified beta-cyclodextrin, the m-phenylenediamine, the oxygen scavenger and the carboxylate gemini surfactant is 1: 120: 0.1: 0.5: 0.2: 0.1: 0.6.
the polyacrylamide is partially hydrolyzed polyacrylamide with 18 percent of hydrolysis degree, and the molecular weight is 1400 ten thousand; the modified cyclodextrin is citric acid modified beta-cyclodextrin; the composite cross-linking agent is benzaldehyde and hydroquinone, and the weight ratio of the benzaldehyde to the hydroquinone is 1: 0.4; the oxygen scavenger is semicarbazide and 1, 4-phenylene bis (thiourea), and the weight ratio of the semicarbazide to the 1, 4-phenylene bis (thiourea) is 1: 0.72; the carboxylate gemini surfactant comprises a carboxylate gemini surfactant A and a carboxylate gemini surfactant B, wherein the preparation raw materials of the carboxylate gemini surfactant A comprise 1, 3-propane sultone, absolute ethyl alcohol, p-phenylenediamine, methanol, anhydrous potassium carbonate, bromododecane and acetone; the carboxylate gemini surfactant B is prepared from raw materials including 1, 3-propane sultone, absolute ethyl alcohol, p-phenylenediamine, methanol, anhydrous potassium carbonate, 1-bromohexane and acetone; the weight ratio of the carboxylate gemini surfactant A to the carboxylate gemini surfactant B is 1: 0.24;
the preparation method of the surfactant type plugging agent comprises the following steps:
adding part of hydrolyzed polyacrylamide with the molecular weight of 1400 ten thousand and the hydrolysis degree of 18 percent and water with the mineralization degree of 125520mg/L into a reactor, stirring and dissolving, adjusting the pH value to 5.0 by oxalic acid, standing for 2 hours to fully cure, then sequentially adding an oxygen scavenger, a composite cross-linking agent, citric acid modified beta-cyclodextrin and m-phenylenediamine in formula amount, stirring uniformly, heating to 88 ℃, keeping the temperature for 30 hours, cooling to 60 ℃, adding a carboxylate gemini surfactant, stirring for 1 hour, and cooling to room temperature to obtain the surfactant type plugging agent.
The citric acid modified beta-cyclodextrin is prepared from citric acid, sodium hypophosphite, deionized water, beta-cyclodextrin and absolute ethyl alcohol in a weight ratio of 1: 0.2: 2: 0.95: 5, preparing a composition; the preparation method of the citric acid modified beta-cyclodextrin comprises the following steps: sequentially adding citric acid, sodium hypophosphite and deionized water in a formula amount into a reactor, stirring to completely dissolve, adding beta-cyclodextrin, heating to 80 ℃, keeping the temperature for reaction for 2 hours, heating to 110 ℃, keeping the temperature for reaction for 6 hours, cooling to room temperature, slowly dripping into absolute ethyl alcohol in a formula amount, stirring for 2 hours after dripping is finished, filtering, and drying under reduced pressure at 60 ℃ for 16 hours to obtain the citric acid modified beta-cyclodextrin.
The carboxylate gemini surfactant A is prepared from 1, 3-propane sultone, absolute ethyl alcohol, p-phenylenediamine, methanol, anhydrous potassium carbonate, bromododecane and acetone according to a weight ratio of 1: 6: 0.5: 10: 1.2: 1: 4, preparing the mixture; the preparation method of the carboxylate gemini surfactant A comprises the following steps:
sequentially adding 1, 3-propane sultone, absolute ethyl alcohol and p-phenylenediamine in formula amount into a reactor, stirring, heating to 60 ℃, carrying out heat preservation reaction for 20h, carrying out reduced pressure concentration to dryness, sequentially adding methanol, anhydrous potassium carbonate and bromododecane in formula amount, heating to 70 ℃, carrying out heat preservation reaction for 30h, filtering, carrying out reduced pressure concentration to dryness on filtrate, adding acetone in formula amount, carrying out recrystallization, and carrying out reduced pressure drying at 60 ℃ for 10h to obtain the carboxylate gemini surfactant A.
The carboxylate gemini surfactant B is prepared from 1, 3-propane sultone, absolute ethyl alcohol, p-phenylenediamine, methanol, anhydrous potassium carbonate, 1-bromohexane and acetone according to a weight ratio of 1: 6: 0.5: 10: 1.2: 1: 4, preparing the mixture; the preparation method of the carboxylate gemini surfactant B comprises the following steps:
sequentially adding 1, 3-propane sultone, absolute ethyl alcohol and p-phenylenediamine in formula amount into a reactor, stirring, heating to 60 ℃, carrying out heat preservation reaction for 20h, carrying out reduced pressure concentration to dryness, sequentially adding methanol, anhydrous potassium carbonate and 1-bromohexane in formula amount, heating to 70 ℃, carrying out heat preservation reaction for 30h, filtering, carrying out reduced pressure concentration to dryness on filtrate, adding acetone in formula amount, carrying out recrystallization, and carrying out reduced pressure drying at 60 ℃ for 10h to obtain the carboxylate gemini surfactant B.
The preparation raw materials of the pressure-reducing injection-increasing agent comprise 32 parts of dioctyldimethylammonium chloride, 3 parts of fluorocarbon FC-44304, 3 parts of polyoxyethylene lauryl ether, 7 parts of ethylene diamine tetramethylene sodium phosphonate, 3 parts of (Z) -3,3, 4-trimethyl-piperazinone oxime and 50 parts of deionized water;
the preparation method of the blood pressure reducing and injection increasing agent comprises the following steps:
adding the dioctyl dimethyl ammonium chloride, the fluorocarbon FC-4430, the polyoxyethylene lauryl ether, the ethylene diamine tetra methylene phosphonic acid sodium, (Z) -3,3, 4-trimethyl-piperazinone oxime and deionized water in parts by weight into a reactor in sequence, heating to 50 ℃, keeping the temperature for reaction for 3 hours, and cooling to room temperature to obtain the pressure-reducing and injection-increasing agent.
The particle blocking agent is prepared from raw materials including 35 parts of acrylamide, 21 parts of acrylic acid, 5 parts of sodium hydroxide, 5 parts of acrylic acid modified zeolite, 0.3 part of ammonium persulfate, 0.1 part of sodium bisulfite, 0.25 part of N, N-methylene bisacrylamide, 3 parts of dodecyl methacrylate and 50 parts of water;
the preparation method of the particle plugging agent comprises the following steps:
adding 50 parts by weight of deionized water and 5 parts by weight of sodium hydroxide into a reactor in sequence, stirring uniformly, adding 21 parts by weight of acrylic acid, stirring fully, adding 3 parts by weight of dodecyl methacrylate, 35 parts by weight of acrylamide and 5 parts by weight of acrylic acid modified zeolite in sequence, heating to 45 ℃, adding 0.25 part by weight of N, N-methylene bisacrylamide, heating to 80 ℃, adding 0.1 part by weight of sodium bisulfite and 0.3 part by weight of ammonium persulfate, reacting for 2 hours at a constant temperature, cooling to room temperature, shearing, drying, and crushing into powder to obtain the particle plugging agent.
The acrylic acid modified zeolite is prepared from zeolite powder, acrylic acid and dibenzoyl peroxide (BPO) according to the weight ratio of 100: 16: 0.18 is prepared; the preparation method of the acrylic acid modified zeolite comprises the following steps:
adding zeolite powder into a mixing machine with a charging basket at a temperature of 60 ℃, adding acrylic acid and dibenzoyl peroxide (BPO) according to a weight ratio, stirring for 2 hours, discharging, heating the charging basket of the mixing machine to 120 ℃, pouring the materials into the mixing machine, stirring at a high speed for 1 hour, and discharging to obtain the acrylic acid modified zeolite.
Example 8
A composite profile control and flooding agent comprises, by weight, 20 parts of a surfactant type plugging agent, 70 parts of a pressure-reducing injection-increasing agent and 10 parts of a particle plugging agent;
the surface active agent type plugging agent is prepared from raw materials including polyacrylamide, a composite cross-linking agent, modified cyclodextrin, m-phenylenediamine, an oxygen scavenger and a carboxylate gemini surfactant, wherein the polyacrylamide is partially hydrolyzed polyacrylamide with the hydrolysis degree of 18% and the molecular weight of the partially hydrolyzed polyacrylamide is 1400 ten thousand; the modified cyclodextrin is citric acid modified beta-cyclodextrin; the composite cross-linking agent is benzaldehyde and hydroquinone, and the weight ratio of the benzaldehyde to the hydroquinone is 1: 0.4; the oxygen scavenger is semicarbazide and 1, 4-phenylene bis (thiourea), and the weight ratio of the semicarbazide to the 1, 4-phenylene bis (thiourea) is 1: 0.72; the carboxylate gemini surfactant comprises a carboxylate gemini surfactant A and a carboxylate gemini surfactant B, wherein the preparation raw materials of the carboxylate gemini surfactant A comprise 1, 3-propane sultone, absolute ethyl alcohol, p-phenylenediamine, methanol, anhydrous potassium carbonate, bromododecane and acetone; the carboxylate gemini surfactant B is prepared from raw materials including 1, 3-propane sultone, absolute ethyl alcohol, p-phenylenediamine, methanol, anhydrous potassium carbonate, 1-bromohexane and acetone; the weight ratio of the carboxylate gemini surfactant A to the carboxylate gemini surfactant B is 1: 0.24;
the preparation raw materials of the pressure-reducing injection-increasing agent comprise 32 parts of dioctyldimethylammonium chloride, 3 parts of fluorocarbon FC-44304, 3 parts of polyoxyethylene lauryl ether, 7 parts of ethylene diamine tetramethylene sodium phosphonate, 3 parts of (Z) -3,3, 4-trimethyl-piperazinone oxime and 50 parts of deionized water;
the particle blocking agent is prepared from raw materials including 35 parts of acrylamide, 21 parts of acrylic acid, 5 parts of sodium hydroxide, 5 parts of acrylic acid modified zeolite, 0.3 part of ammonium persulfate, 0.1 part of sodium bisulfite, 0.25 part of N, N-methylene bisacrylamide, 3 parts of dodecyl methacrylate and 50 parts of water;
the preparation method of the surfactant type plugging agent, the preparation method of the pressure-reducing injection-increasing agent and the preparation method of the particle plugging agent are the same as those in example 7.
Example 9
A composite profile control and flooding agent comprises, by weight, 50 parts of a surfactant type plugging agent, 30 parts of a pressure-reducing injection-increasing agent and 10 parts of a particle plugging agent;
the surface active agent type plugging agent is prepared from raw materials including polyacrylamide, a composite cross-linking agent, modified cyclodextrin, m-phenylenediamine, an oxygen scavenger and a carboxylate gemini surfactant, wherein the polyacrylamide is partially hydrolyzed polyacrylamide with the hydrolysis degree of 18% and the molecular weight of the partially hydrolyzed polyacrylamide is 1400 ten thousand; the modified cyclodextrin is citric acid modified beta-cyclodextrin; the composite cross-linking agent is benzaldehyde and hydroquinone, and the weight ratio of the benzaldehyde to the hydroquinone is 1: 0.4; the oxygen scavenger is semicarbazide and 1, 4-phenylene bis (thiourea), and the weight ratio of the semicarbazide to the 1, 4-phenylene bis (thiourea) is 1: 0.72; the carboxylate gemini surfactant comprises a carboxylate gemini surfactant A and a carboxylate gemini surfactant B, wherein the preparation raw materials of the carboxylate gemini surfactant A comprise 1, 3-propane sultone, absolute ethyl alcohol, p-phenylenediamine, methanol, anhydrous potassium carbonate, bromododecane and acetone; the carboxylate gemini surfactant B is prepared from raw materials including 1, 3-propane sultone, absolute ethyl alcohol, p-phenylenediamine, methanol, anhydrous potassium carbonate, 1-bromohexane and acetone; the weight ratio of the carboxylate gemini surfactant A to the carboxylate gemini surfactant B is 1: 0.24;
the preparation raw materials of the pressure-reducing injection-increasing agent comprise 32 parts of dioctyldimethylammonium chloride, 3 parts of fluorocarbon FC-44304, 3 parts of polyoxyethylene lauryl ether, 7 parts of ethylene diamine tetramethylene sodium phosphonate, 3 parts of (Z) -3,3, 4-trimethyl-piperazinone oxime and 50 parts of deionized water;
the particle blocking agent is prepared from raw materials including 35 parts of acrylamide, 21 parts of acrylic acid, 5 parts of sodium hydroxide, 5 parts of acrylic acid modified zeolite, 0.3 part of ammonium persulfate, 0.1 part of sodium bisulfite, 0.25 part of N, N-methylene bisacrylamide, 3 parts of dodecyl methacrylate and 50 parts of water;
the preparation method of the surfactant type plugging agent, the preparation method of the pressure-reducing injection-increasing agent and the preparation method of the particle plugging agent are the same as those in example 7.
Example 10
A composite profile control and flooding agent comprises, by weight, 35 parts of a surfactant type plugging agent, 55 parts of a pressure-reducing injection-increasing agent and 10 parts of a particle plugging agent;
the surface active agent type plugging agent is prepared from raw materials including polyacrylamide, a composite cross-linking agent, modified cyclodextrin, m-phenylenediamine, an oxygen scavenger and a carboxylate gemini surfactant, wherein the polyacrylamide is partially hydrolyzed polyacrylamide with the hydrolysis degree of 18% and the molecular weight of the partially hydrolyzed polyacrylamide is 1400 ten thousand; the modified cyclodextrin is citric acid modified beta-cyclodextrin; the composite cross-linking agent is benzaldehyde and hydroquinone, and the weight ratio of the benzaldehyde to the hydroquinone is 1: 0.4; the oxygen scavenger is semicarbazide and 1, 4-phenylene bis (thiourea), and the weight ratio of the semicarbazide to the 1, 4-phenylene bis (thiourea) is 1: 0.72; the carboxylate gemini surfactant comprises a carboxylate gemini surfactant A and a carboxylate gemini surfactant B, wherein the preparation raw materials of the carboxylate gemini surfactant A comprise 1, 3-propane sultone, absolute ethyl alcohol, p-phenylenediamine, methanol, anhydrous potassium carbonate, bromododecane and acetone; the carboxylate gemini surfactant B is prepared from raw materials including 1, 3-propane sultone, absolute ethyl alcohol, p-phenylenediamine, methanol, anhydrous potassium carbonate, 1-bromohexane and acetone; the weight ratio of the carboxylate gemini surfactant A to the carboxylate gemini surfactant B is 1: 0.1;
the preparation raw materials of the pressure-reducing injection-increasing agent comprise 32 parts of dioctyldimethylammonium chloride, 3 parts of fluorocarbon FC-44304, 3 parts of polyoxyethylene lauryl ether, 7 parts of ethylene diamine tetramethylene sodium phosphonate, 3 parts of (Z) -3,3, 4-trimethyl-piperazinone oxime and 50 parts of deionized water;
the particle blocking agent is prepared from raw materials including 35 parts of acrylamide, 21 parts of acrylic acid, 5 parts of sodium hydroxide, 5 parts of acrylic acid modified zeolite, 0.3 part of ammonium persulfate, 0.1 part of sodium bisulfite, 0.25 part of N, N-methylene bisacrylamide, 3 parts of dodecyl methacrylate and 50 parts of water;
the preparation method of the surfactant type plugging agent, the preparation method of the pressure-reducing injection-increasing agent and the preparation method of the particle plugging agent are the same as those in example 7.
Example 11
A composite profile control and flooding agent comprises, by weight, 35 parts of a surfactant type plugging agent, 55 parts of a pressure-reducing injection-increasing agent and 10 parts of a particle plugging agent;
the surface active agent type plugging agent is prepared from raw materials including polyacrylamide, a composite cross-linking agent, modified cyclodextrin, m-phenylenediamine, an oxygen scavenger and a carboxylate gemini surfactant, wherein the polyacrylamide is partially hydrolyzed polyacrylamide with the hydrolysis degree of 18% and the molecular weight of the partially hydrolyzed polyacrylamide is 1400 ten thousand; the modified cyclodextrin is citric acid modified beta-cyclodextrin; the composite cross-linking agent is benzaldehyde and hydroquinone, and the weight ratio of the benzaldehyde to the hydroquinone is 1: 0.4; the oxygen scavenger is semicarbazide and 1, 4-phenylene bis (thiourea), and the weight ratio of the semicarbazide to the 1, 4-phenylene bis (thiourea) is 1: 0.72; the carboxylate gemini surfactant comprises a carboxylate gemini surfactant A and a carboxylate gemini surfactant B, wherein the preparation raw materials of the carboxylate gemini surfactant A comprise 1, 3-propane sultone, absolute ethyl alcohol, p-phenylenediamine, methanol, anhydrous potassium carbonate, bromododecane and acetone; the carboxylate gemini surfactant B is prepared from raw materials including 1, 3-propane sultone, absolute ethyl alcohol, p-phenylenediamine, methanol, anhydrous potassium carbonate, 1-bromohexane and acetone; the weight ratio of the carboxylate gemini surfactant A to the carboxylate gemini surfactant B is 1: 0.7;
the preparation raw materials of the pressure-reducing injection-increasing agent comprise 32 parts of dioctyldimethylammonium chloride, 3 parts of fluorocarbon FC-44304, 3 parts of polyoxyethylene lauryl ether, 7 parts of ethylene diamine tetramethylene sodium phosphonate, 3 parts of (Z) -3,3, 4-trimethyl-piperazinone oxime and 50 parts of deionized water;
the particle blocking agent is prepared from raw materials including 35 parts of acrylamide, 21 parts of acrylic acid, 5 parts of sodium hydroxide, 5 parts of acrylic acid modified zeolite, 0.3 part of ammonium persulfate, 0.1 part of sodium bisulfite, 0.25 part of N, N-methylene bisacrylamide, 3 parts of dodecyl methacrylate and 50 parts of water;
the preparation method of the surfactant type plugging agent, the preparation method of the pressure-reducing injection-increasing agent and the preparation method of the particle plugging agent are the same as those in example 7.
Example 12
A composite profile control and flooding agent comprises, by weight, 35 parts of a surfactant type plugging agent, 55 parts of a pressure-reducing injection-increasing agent and 10 parts of a particle plugging agent;
the surface active agent type plugging agent is prepared from raw materials including polyacrylamide, a composite cross-linking agent, modified cyclodextrin, m-phenylenediamine, an oxygen scavenger and a carboxylate gemini surfactant, wherein the polyacrylamide is partially hydrolyzed polyacrylamide with the hydrolysis degree of 18% and the molecular weight of the partially hydrolyzed polyacrylamide is 1400 ten thousand; the modified cyclodextrin is citric acid modified beta-cyclodextrin; the composite cross-linking agent is benzaldehyde and hydroquinone, and the weight ratio of the benzaldehyde to the hydroquinone is 1: 0.4; the oxygen scavenger is semicarbazide and 1, 4-phenylene bis (thiourea), and the weight ratio of the semicarbazide to the 1, 4-phenylene bis (thiourea) is 1: 0.5; the carboxylate gemini surfactant comprises a carboxylate gemini surfactant A and a carboxylate gemini surfactant B, wherein the preparation raw materials of the carboxylate gemini surfactant A comprise 1, 3-propane sultone, absolute ethyl alcohol, p-phenylenediamine, methanol, anhydrous potassium carbonate, bromododecane and acetone; the carboxylate gemini surfactant B is prepared from raw materials including 1, 3-propane sultone, absolute ethyl alcohol, p-phenylenediamine, methanol, anhydrous potassium carbonate, 1-bromohexane and acetone; the weight ratio of the carboxylate gemini surfactant A to the carboxylate gemini surfactant B is 1: 0.24;
the preparation raw materials of the pressure-reducing injection-increasing agent comprise 32 parts of dioctyldimethylammonium chloride, 3 parts of fluorocarbon FC-44304, 3 parts of polyoxyethylene lauryl ether, 7 parts of ethylene diamine tetramethylene sodium phosphonate, 3 parts of (Z) -3,3, 4-trimethyl-piperazinone oxime and 50 parts of deionized water;
the particle blocking agent is prepared from raw materials including 35 parts of acrylamide, 21 parts of acrylic acid, 5 parts of sodium hydroxide, 5 parts of acrylic acid modified zeolite, 0.3 part of ammonium persulfate, 0.1 part of sodium bisulfite, 0.25 part of N, N-methylene bisacrylamide, 3 parts of dodecyl methacrylate and 50 parts of water;
the preparation method of the surfactant type plugging agent, the preparation method of the pressure-reducing injection-increasing agent and the preparation method of the particle plugging agent are the same as those in example 7.
Example 13
A composite profile control and flooding agent comprises, by weight, 35 parts of a surfactant type plugging agent, 55 parts of a pressure-reducing injection-increasing agent and 10 parts of a particle plugging agent;
the surface active agent type plugging agent is prepared from raw materials including polyacrylamide, a composite cross-linking agent, modified cyclodextrin, m-phenylenediamine, an oxygen scavenger and a carboxylate gemini surfactant, wherein the polyacrylamide is partially hydrolyzed polyacrylamide with the hydrolysis degree of 18% and the molecular weight of the partially hydrolyzed polyacrylamide is 1400 ten thousand; the modified cyclodextrin is citric acid modified beta-cyclodextrin; the composite cross-linking agent is benzaldehyde and hydroquinone, and the weight ratio of the benzaldehyde to the hydroquinone is 1: 0.4; the oxygen scavenger is semicarbazide and 1, 4-phenylene bis (thiourea), and the weight ratio of the semicarbazide to the 1, 4-phenylene bis (thiourea) is 1: 1.2; the carboxylate gemini surfactant comprises a carboxylate gemini surfactant A and a carboxylate gemini surfactant B, wherein the preparation raw materials of the carboxylate gemini surfactant A comprise 1, 3-propane sultone, absolute ethyl alcohol, p-phenylenediamine, methanol, anhydrous potassium carbonate, bromododecane and acetone; the carboxylate gemini surfactant B is prepared from raw materials including 1, 3-propane sultone, absolute ethyl alcohol, p-phenylenediamine, methanol, anhydrous potassium carbonate, 1-bromohexane and acetone; the weight ratio of the carboxylate gemini surfactant A to the carboxylate gemini surfactant B is 1: 0.24;
the preparation raw materials of the pressure-reducing injection-increasing agent comprise 32 parts of dioctyldimethylammonium chloride, 3 parts of fluorocarbon FC-44304, 3 parts of polyoxyethylene lauryl ether, 7 parts of ethylene diamine tetramethylene sodium phosphonate, 3 parts of (Z) -3,3, 4-trimethyl-piperazinone oxime and 50 parts of deionized water;
the particle blocking agent is prepared from raw materials including 35 parts of acrylamide, 21 parts of acrylic acid, 5 parts of sodium hydroxide, 5 parts of acrylic acid modified zeolite, 0.3 part of ammonium persulfate, 0.1 part of sodium bisulfite, 0.25 part of N, N-methylene bisacrylamide, 3 parts of dodecyl methacrylate and 50 parts of water;
the preparation method of the surfactant type plugging agent, the preparation method of the pressure-reducing injection-increasing agent and the preparation method of the particle plugging agent are the same as those in example 7.
Example 14 (comparative example 1)
A composite profile control and flooding agent comprises, by weight, 35 parts of a surfactant type plugging agent, 55 parts of a pressure-reducing injection-increasing agent and 10 parts of a particle plugging agent;
the surface active agent type plugging agent is prepared from raw materials including polyacrylamide, a composite cross-linking agent, beta-cyclodextrin, m-phenylenediamine, an oxygen scavenger and a carboxylate gemini surfactant, wherein the polyacrylamide is partially hydrolyzed polyacrylamide with the hydrolysis degree of 18% and the molecular weight of the partially hydrolyzed polyacrylamide is 1400 ten thousand; the composite cross-linking agent is benzaldehyde and hydroquinone, and the weight ratio of the benzaldehyde to the hydroquinone is 1: 0.4; the carboxylate gemini surfactant A is prepared from raw materials including 1, 3-propane sultone, p-phenylenediamine and bromododecane; the carboxylate gemini surfactant A is prepared from raw materials including 1, 3-propane sultone, p-phenylenediamine and 1-bromohexane; the weight ratio of the carboxylate gemini surfactant A to the carboxylate gemini surfactant B is 1: 0.24; the oxygen scavenger is semicarbazide and 1, 4-phenylene bis (thiourea), and the weight ratio of the semicarbazide to the 1, 4-phenylene bis (thiourea) is 1: 0.72;
the preparation raw materials of the pressure-reducing injection-increasing agent comprise 32 parts of dioctyldimethylammonium chloride, 4 parts of fluorocarbon surfactant, 3 parts of nonionic surfactant, 7 parts of ethylene diamine tetra methylene phosphonic acid sodium, 3 parts of (Z) -3,3, 4-trimethyl-piperazinone oxime and 50 parts of deionized water; the fluorocarbon surfactant is fluorocarbon FC-4430, and the nonionic surfactant is polyoxyethylene lauryl ether;
the particle blocking agent is prepared from raw materials including 35 parts of acrylamide, 21 parts of acrylic acid, 5 parts of sodium hydroxide, 5 parts of modified zeolite, 0.3 part of ammonium persulfate, 0.1 part of sodium bisulfite, 0.25 part of N, N-methylene-bisacrylamide, 3 parts of dodecyl methacrylate and 50 parts of water; the modified zeolite is acrylic acid modified zeolite;
the surfactant type plugging agent is prepared from polyacrylamide, water, a composite cross-linking agent, beta-cyclodextrin, m-phenylenediamine, an oxygen scavenger and a carboxylate gemini surfactant according to a weight ratio of 1: 120: 0.1: 0.5: 0.2: 0.1: 0.6 is prepared; the preparation method of the surfactant type plugging agent comprises the following steps:
adding part of hydrolyzed polyacrylamide with the molecular weight of 1400 ten thousand and the hydrolysis degree of 18 percent and water with the mineralization degree of 125520mg/L into a reactor, stirring and dissolving, adjusting the pH value to 5.0 by oxalic acid, standing for 2 hours to be fully cured, then sequentially adding an oxygen scavenger, a composite cross-linking agent, beta-cyclodextrin and m-phenylenediamine in a formula amount, uniformly stirring, heating to 88 ℃, keeping the temperature for 30 hours, cooling to 60 ℃, adding a carboxylate gemini surfactant in a formula amount, stirring for 1 hour, and cooling to room temperature to obtain the surfactant type plugging agent.
The carboxylate gemini surfactant A is prepared from 1, 3-propane sultone, absolute ethyl alcohol, p-phenylenediamine, methanol, anhydrous potassium carbonate, bromododecane and acetone according to a weight ratio of 1: 6: 0.5: 10: 1.2: 1: 4, preparing the mixture; the preparation method of the carboxylate gemini surfactant A comprises the following steps:
sequentially adding 1, 3-propane sultone, absolute ethyl alcohol and p-phenylenediamine in formula amount into a reactor, stirring, heating to 60 ℃, carrying out heat preservation reaction for 20h, carrying out reduced pressure concentration to dryness, sequentially adding methanol, anhydrous potassium carbonate and bromododecane in formula amount, heating to 70 ℃, carrying out heat preservation reaction for 30h, filtering, carrying out reduced pressure concentration to dryness on filtrate, adding acetone in formula amount, carrying out recrystallization, and carrying out reduced pressure drying at 60 ℃ for 10h to obtain the carboxylate gemini surfactant A; in this embodiment, the weight ratio of 1, 3-propane sultone, absolute ethanol, p-phenylenediamine, methanol, anhydrous potassium carbonate, bromododecane, and acetone is 1: 6: 0.5: 10: 1.2: 1: 4.
the carboxylate gemini surfactant B is prepared from 1, 3-propane sultone, absolute ethyl alcohol, p-phenylenediamine, methanol, anhydrous potassium carbonate, 1-bromohexane and acetone according to a weight ratio of 1: 6: 0.5: 10: 1.2: 1: 4, preparing the mixture according to a proportion; the preparation method of the carboxylate gemini surfactant B comprises the following steps:
sequentially adding 1, 3-propane sultone, absolute ethyl alcohol and p-phenylenediamine in formula amount into a reactor, stirring, heating to 60 ℃, carrying out heat preservation reaction for 20h, carrying out reduced pressure concentration to dryness, sequentially adding methanol, anhydrous potassium carbonate and 1-bromohexane in formula amount, heating to 70 ℃, carrying out heat preservation reaction for 30h, filtering, carrying out reduced pressure concentration to dryness on filtrate, adding acetone in formula amount, carrying out recrystallization, and carrying out reduced pressure drying at 60 ℃ for 10h to obtain the carboxylate gemini surfactant B.
The difference between the preparation method of the surfactant type plugging agent and the preparation method of the surfactant type plugging agent in example 7 is that: replacing the modified cyclodextrin with beta-cyclodextrin; the preparation method of the pressure-reducing injection-increasing agent and the preparation method of the particle plugging agent are the same as those in example 7.
Example 15 (comparative example 2)
A composite profile control and flooding agent comprises, by weight, 35 parts of a surfactant type plugging agent, 55 parts of a pressure-reducing injection-increasing agent and 10 parts of a particle plugging agent;
the surface active agent type plugging agent is prepared from raw materials including polyacrylamide, a composite cross-linking agent, modified cyclodextrin, m-phenylenediamine, an oxygen scavenger and a carboxylate gemini surfactant, wherein the polyacrylamide is partially hydrolyzed polyacrylamide with the hydrolysis degree of 18% and the molecular weight of the partially hydrolyzed polyacrylamide is 1400 ten thousand; the modified cyclodextrin is citric acid modified beta-cyclodextrin; the composite cross-linking agent is benzaldehyde and hydroquinone, and the weight ratio of the benzaldehyde to the hydroquinone is 1: 0.4; the oxygen scavenger is semicarbazide and 1, 4-phenylene bis (thiourea), and the weight ratio of the semicarbazide to the 1, 4-phenylene bis (thiourea) is 1: 0.72; the carboxylate gemini surfactant comprises a carboxylate gemini surfactant A and a carboxylate gemini surfactant B, wherein the preparation raw materials of the carboxylate gemini surfactant A comprise 1, 3-propane sultone, absolute ethyl alcohol, p-phenylenediamine, methanol, anhydrous potassium carbonate, bromododecane and acetone; the carboxylate gemini surfactant B is prepared from raw materials including 1, 3-propane sultone, absolute ethyl alcohol, p-phenylenediamine, methanol, anhydrous potassium carbonate, 1-bromohexane and acetone; the weight ratio of the carboxylate gemini surfactant A to the carboxylate gemini surfactant B is 1: 0.24;
the particle blocking agent is prepared from raw materials including 35 parts of acrylamide, 21 parts of acrylic acid, 5 parts of sodium hydroxide, 5 parts of acrylic acid modified zeolite, 0.3 part of ammonium persulfate, 0.1 part of sodium bisulfite, 0.25 part of N, N-methylene bisacrylamide, 3 parts of dodecyl methacrylate and 50 parts of water;
the preparation raw materials of the pressure-reducing injection-increasing agent comprise 32 parts of dioctyldimethylammonium chloride, 3 parts of fluorocarbon FC-44304, 3 parts of polyoxyethylene lauryl ether, 7 parts of sodium ethylene diamine tetramethylidene phosphonate, 3 parts of dimethyl ketoxime and 50 parts of deionized water;
the preparation method of the blood pressure reducing and injection increasing agent comprises the following steps:
adding 32 parts by weight of dioctyldimethylammonium chloride, 4 parts by weight of fluorocarbon FC-4430, 3 parts by weight of polyoxyethylene lauryl ether, 7 parts by weight of sodium ethylene diamine tetramethylene phosphonate, 3 parts by weight of dimethylketoxime and 50 parts by weight of deionized water into a reactor in sequence, heating to 50 ℃, carrying out heat preservation reaction for 3 hours, and cooling to room temperature to obtain the pressure-reducing and injection-increasing agent.
The preparation method of the surfactant type plugging agent and the preparation method of the particle plugging agent are the same as those of example 7; the preparation method of the pressure-reducing injection-increasing agent is different from that of the embodiment 7 in that: dimethyl ketoxime is used to replace (Z) -3,3, 4-trimethyl-piperazine ketoxime.
Example 16 (comparative example 3)
A composite profile control and flooding agent comprises, by weight, 35 parts of a surfactant type plugging agent, 55 parts of a pressure-reducing injection-increasing agent and 10 parts of a particle plugging agent;
the surface active agent type plugging agent is prepared from raw materials including polyacrylamide, a composite cross-linking agent, modified cyclodextrin, m-phenylenediamine, an oxygen scavenger and a carboxylate gemini surfactant, wherein the polyacrylamide is partially hydrolyzed polyacrylamide with the hydrolysis degree of 18% and the molecular weight of the partially hydrolyzed polyacrylamide is 1400 ten thousand; the modified cyclodextrin is citric acid modified beta-cyclodextrin; the composite cross-linking agent is benzaldehyde and hydroquinone, and the weight ratio of the benzaldehyde to the hydroquinone is 1: 0.4; the oxygen scavenger is semicarbazide and 1, 4-phenylene bis (thiourea), and the weight ratio of the semicarbazide to the 1, 4-phenylene bis (thiourea) is 1: 0.72; the carboxylate gemini surfactant comprises a carboxylate gemini surfactant A and a carboxylate gemini surfactant B, wherein the preparation raw materials of the carboxylate gemini surfactant A comprise 1, 3-propane sultone, absolute ethyl alcohol, p-phenylenediamine, methanol, anhydrous potassium carbonate, bromododecane and acetone; the carboxylate gemini surfactant B is prepared from raw materials including 1, 3-propane sultone, absolute ethyl alcohol, p-phenylenediamine, methanol, anhydrous potassium carbonate, 1-bromohexane and acetone; the weight ratio of the carboxylate gemini surfactant A to the carboxylate gemini surfactant B is 1: 0.24;
the preparation raw materials of the pressure-reducing injection-increasing agent comprise 32 parts of dioctyldimethylammonium chloride, 3 parts of fluorocarbon FC-44304, 3 parts of polyoxyethylene lauryl ether, 7 parts of ethylene diamine tetramethylene sodium phosphonate, 3 parts of (Z) -3,3, 4-trimethyl-piperazinone oxime and 50 parts of deionized water;
the preparation raw materials of the particle plugging agent comprise 35 parts of acrylamide, 21 parts of acrylic acid, 5 parts of sodium hydroxide, 5 parts of zeolite, 0.3 part of ammonium persulfate, 0.1 part of sodium bisulfite, 0.25 part of N, N-methylene-bisacrylamide, 3 parts of dodecyl methacrylate and 50 parts of water;
the preparation method of the particle plugging agent comprises the following steps:
adding 50 parts by weight of deionized water and 5 parts by weight of sodium hydroxide into a reactor in sequence, stirring uniformly, adding 21 parts by weight of acrylic acid, stirring fully, adding 3 parts by weight of dodecyl methacrylate, 35 parts by weight of acrylamide and 5 parts by weight of zeolite in sequence, heating to 45 ℃, adding 0.25 part by weight of N, N-methylene bisacrylamide, heating to 80 ℃, adding 0.1 part by weight of sodium bisulfite and 0.3 part by weight of ammonium persulfate, carrying out heat preservation reaction for 2 hours, cooling to room temperature, shearing, drying, and crushing into powder to obtain the particle plugging agent.
The preparation method of the surfactant type plugging agent and the preparation method of the pressure-reducing injection-increasing agent are the same as those in example 7; the preparation method of the particle plugging agent is different from that of the example 7 in that: the modified zeolite is replaced with zeolite.
Example 17 (comparative example 4)
A composite profile control and flooding agent comprises, by weight, 35 parts of a surfactant type plugging agent, 55 parts of a pressure-reducing injection-increasing agent and 10 parts of a particle plugging agent;
20-50 parts of pressure-reducing injection-increasing agent, 30-70 parts of particle plugging agent and 5-20 parts of particle plugging agent
A composite profile control and flooding agent comprises, by weight, 35 parts of a surfactant type plugging agent, 55 parts of a pressure-reducing injection-increasing agent and 10 parts of a particle plugging agent;
the surface active agent type plugging agent is prepared from raw materials including polyacrylamide, a composite cross-linking agent, beta-cyclodextrin, m-phenylenediamine, an oxygen scavenger and a carboxylate gemini surfactant, wherein the polyacrylamide is partially hydrolyzed polyacrylamide with the hydrolysis degree of 18% and the molecular weight of the partially hydrolyzed polyacrylamide is 1400 ten thousand; the composite cross-linking agent is benzaldehyde and hydroquinone, and the weight ratio of the benzaldehyde to the hydroquinone is 1: 0.4; the oxygen scavenger is semicarbazide and 1, 4-phenylene bis (thiourea), and the weight ratio of the semicarbazide to the 1, 4-phenylene bis (thiourea) is 1: 0.72; the carboxylate gemini surfactant comprises a carboxylate gemini surfactant A and a carboxylate gemini surfactant B, wherein the preparation raw materials of the carboxylate gemini surfactant A comprise 1, 3-propane sultone, absolute ethyl alcohol, p-phenylenediamine, methanol, anhydrous potassium carbonate, bromododecane and acetone; the carboxylate gemini surfactant B is prepared from raw materials including 1, 3-propane sultone, absolute ethyl alcohol, p-phenylenediamine, methanol, anhydrous potassium carbonate, 1-bromohexane and acetone; the weight ratio of the carboxylate gemini surfactant A to the carboxylate gemini surfactant B is 1: 0.24;
the surfactant type plugging agent is prepared from polyacrylamide, water, a composite cross-linking agent, beta-cyclodextrin, m-phenylenediamine, an oxygen scavenger and a carboxylate gemini surfactant according to a weight ratio of 1: 120: 0.1: 0.5: 0.2: 0.1: 0.6 is prepared; the preparation method of the surfactant type plugging agent comprises the following steps:
adding part of hydrolyzed polyacrylamide with the molecular weight of 1400 ten thousand and the hydrolysis degree of 18 percent and water with the mineralization degree of 125520mg/L into a reactor, stirring and dissolving, adjusting the pH value to 5.0 by oxalic acid, standing for 2 hours to be fully cured, then sequentially adding an oxygen scavenger, a composite cross-linking agent, beta-cyclodextrin and m-phenylenediamine in a formula amount, uniformly stirring, heating to 88 ℃, keeping the temperature for 30 hours, cooling to 60 ℃, adding a carboxylate gemini surfactant in a formula amount, stirring for 1 hour, and cooling to room temperature to obtain the surfactant type plugging agent.
The preparation method of the carboxylate gemini surfactant A and the preparation method of the carboxylate gemini surfactant B are the same as those in example 7.
The preparation raw materials of the pressure-reducing injection-increasing agent comprise 32 parts of dioctyldimethylammonium chloride, 3 parts of fluorocarbon FC-44304, 3 parts of polyoxyethylene lauryl ether, 7 parts of sodium ethylene diamine tetramethylidene phosphonate, 3 parts of dimethyl ketoxime and 50 parts of deionized water;
the preparation method of the blood pressure reducing and injection increasing agent comprises the following steps:
adding 32 parts by weight of dioctyldimethylammonium chloride, 4 parts by weight of fluorocarbon FC-4430, 3 parts by weight of polyoxyethylene lauryl ether, 7 parts by weight of sodium ethylene diamine tetramethylene phosphonate, 3 parts by weight of dimethylketoxime and 50 parts by weight of deionized water into a reactor in sequence, heating to 50 ℃, carrying out heat preservation reaction for 3 hours, and cooling to room temperature to obtain the pressure-reducing and injection-increasing agent.
The preparation raw materials of the particle plugging agent comprise 35 parts of acrylamide, 21 parts of acrylic acid, 5 parts of sodium hydroxide, 5 parts of zeolite, 0.3 part of ammonium persulfate, 0.1 part of sodium bisulfite, 0.25 part of N, N-methylene-bisacrylamide, 3 parts of dodecyl methacrylate and 50 parts of water;
the preparation method of the particle plugging agent comprises the following steps:
adding 50 parts by weight of deionized water and 5 parts by weight of sodium hydroxide into a reactor in sequence, stirring uniformly, adding 21 parts by weight of acrylic acid, stirring fully, adding 3 parts by weight of dodecyl methacrylate, 35 parts by weight of acrylamide and 5 parts by weight of zeolite in sequence, heating to 45 ℃, adding 0.25 part by weight of N, N-methylene bisacrylamide, heating to 80 ℃, adding 0.1 part by weight of sodium bisulfite and 0.3 part by weight of ammonium persulfate, carrying out heat preservation reaction for 2 hours, cooling to room temperature, shearing, drying, and crushing into powder to obtain the particle plugging agent.
The preparation method of the surfactant type plugging agent, the preparation method of the pressure-reducing injection-increasing agent and the preparation method of the particle plugging agent are different from those of the example 7 in that beta-cyclodextrin is used for replacing modified cyclodextrin, dimethyl ketoxime is used for replacing (Z) -3,3, 4-trimethyl-piperazine ketoxime and zeolite is used for replacing modified zeolite.
And (3) performance testing:
1. and (3) measuring thermodynamic stability: the composite profile control and flooding agent systems prepared in the examples 7 to 17 are respectively placed in a constant temperature water bath at 90 ℃, and the layered precipitation and the uniform and transparent conditions of the systems are observed;
the thermodynamic stability is good: uniform, transparent and non-layered;
thermodynamic stability is generally: uniform, slightly turbid and not layered;
poor thermodynamic stability: non-uniform, opaque, layered.
2. And (3) measuring the pressure reduction and injection increase capacity, namely measuring the injection pressure after the water drive pressure is stable before and after the 0.2PV compound profile control and flooding agent slug is injected by utilizing a rock core experiment.
3. Measurement of enhanced oil recovery capacity: and measuring the recovery efficiency improving capability of continuously injecting the composite profile control and flooding agent and injecting a 0.2PV composite profile control and flooding agent slug by using a rock core experiment.
Table 1 results of performance testing
Figure BDA0001665585510000331
Figure BDA0001665585510000341
From the data, the invention provides the composite profile control agent, combines the water shutoff profile control technology with the depressurization and injection increasing technology, has better thermodynamic stability, realizes the water shutoff profile control of water flooded cracks, improves the water injection rate of a matrix reservoir and improves the oil displacement effect of a heterogeneous reservoir.
Example 18
A composite profile control and flooding agent comprises, by weight, 40 parts of a surfactant type plugging agent, 50 parts of a pressure-reducing injection-increasing agent and 20 parts of a particle plugging agent;
the surfactant type plugging agent is prepared from the following raw materials of polyacrylamide, a composite cross-linking agent, modified cyclodextrin, m-phenylenediamine, an oxygen scavenger and a carboxylate gemini surfactant, wherein the weight ratio of the polyacrylamide, water, the composite cross-linking agent, citric acid modified beta-cyclodextrin, the m-phenylenediamine, the oxygen scavenger and the carboxylate gemini surfactant is 1: 110: 0.12: 0.8: 0.3: 0.2: 1.0.
the polyacrylamide is partially hydrolyzed polyacrylamide with 18 percent of hydrolysis degree, and the molecular weight is 1400 ten thousand; the modified cyclodextrin is citric acid modified beta-cyclodextrin; the composite cross-linking agent is prepared from benzaldehyde and hydroquinone in a weight ratio of 1: 0.3, mixing; the oxygen scavenger is semicarbazide and 1, 4-phenylene bis (thiourea) according to the weight ratio of 1: 0.3, mixing; the carboxylate gemini surfactant comprises a carboxylate gemini surfactant A and a carboxylate gemini surfactant B, wherein the preparation raw materials of the carboxylate gemini surfactant A comprise 1, 3-propane sultone, absolute ethyl alcohol, p-phenylenediamine, methanol, anhydrous potassium carbonate, bromododecane and acetone; the carboxylate gemini surfactant B is prepared from raw materials including 1, 3-propane sultone, absolute ethyl alcohol, p-phenylenediamine, methanol, anhydrous potassium carbonate, 1-bromohexane and acetone; the weight ratio of the carboxylate gemini surfactant A to the carboxylate gemini surfactant B is 1: 0.4;
the preparation method of the surfactant type plugging agent comprises the following steps:
adding part of hydrolyzed polyacrylamide with the molecular weight of 1400 ten thousand and the hydrolysis degree of 18 percent and water with the mineralization degree of 125520mg/L into a reactor, stirring and dissolving, adjusting the pH value to 5.0 by oxalic acid, standing for 2 hours to fully cure, then sequentially adding the oxygen scavenger, the composite cross-linking agent, the citric acid modified beta-cyclodextrin and the m-phenylenediamine in formula amount, stirring uniformly, heating to 88 ℃, keeping the temperature for 30 hours, cooling to 60 ℃, adding the carboxylate gemini surfactant in formula amount, stirring for 1 hour, and cooling to room temperature to obtain the surfactant type plugging agent.
The citric acid modified beta-cyclodextrin is prepared from citric acid, sodium hypophosphite, deionized water, beta-cyclodextrin and absolute ethyl alcohol in a weight ratio of 1: 0.1: 1: 0.8: 3, preparing a composition; the preparation method of the citric acid modified beta-cyclodextrin comprises the following steps: sequentially adding citric acid, sodium hypophosphite and deionized water according to the formula amount into a reactor, stirring to completely dissolve, adding beta-cyclodextrin, heating to 80 ℃, keeping the temperature for reaction for 2 hours, heating to 110 ℃, keeping the temperature for reaction for 6 hours, cooling to room temperature, slowly dripping into absolute ethyl alcohol according to the formula amount, stirring for 2 hours after dripping is finished, filtering, and drying under reduced pressure at 60 ℃ for 16 hours.
The carboxylate gemini surfactant A is prepared from 1, 3-propane sultone, absolute ethyl alcohol, p-phenylenediamine, methanol, anhydrous potassium carbonate, bromododecane and acetone according to a weight ratio of 1: 4: 0.4: 8: 1: 0.8: 3 in proportion; the preparation method of the carboxylate gemini surfactant A comprises the following steps:
sequentially adding 1, 3-propane sultone, absolute ethyl alcohol and p-phenylenediamine in formula amount into a reactor, stirring, heating to 60 ℃, carrying out heat preservation reaction for 20h, carrying out reduced pressure concentration to dryness, sequentially adding methanol, anhydrous potassium carbonate and bromododecane in formula amount, heating to 70 ℃, carrying out heat preservation reaction for 30h, filtering, carrying out reduced pressure concentration to dryness on filtrate, adding acetone in formula amount, carrying out recrystallization, and carrying out reduced pressure drying at 60 ℃ for 10h to obtain the carboxylate gemini surfactant A.
The carboxylate gemini surfactant B is prepared from 1, 3-propane sultone, absolute ethyl alcohol, p-phenylenediamine, methanol, anhydrous potassium carbonate, 1-bromohexane and acetone according to a weight ratio of 1: 7: 0.6: 12: 1.3: 1.1: 6, preparing the mixture; the preparation method of the carboxylate gemini surfactant B comprises the following steps:
sequentially adding 1, 3-propane sultone, absolute ethyl alcohol and p-phenylenediamine in formula amount into a reactor, stirring, heating to 60 ℃, carrying out heat preservation reaction for 20h, carrying out reduced pressure concentration to dryness, sequentially adding methanol, anhydrous potassium carbonate and 1-bromohexane in formula amount, heating to 70 ℃, carrying out heat preservation reaction for 30h, filtering, carrying out reduced pressure concentration to dryness on filtrate, adding acetone in formula amount, carrying out recrystallization, and carrying out reduced pressure drying at 60 ℃ for 10h to obtain the carboxylate gemini surfactant B.
The preparation raw materials of the pressure-reducing injection-increasing agent comprise 35 parts of dioctyldimethylammonium chloride, 5 parts of fluorocarbon FC-44307, 5 parts of polyoxyethylene lauryl ether, 10 parts of sodium ethylene diamine tetra methylene phosphonate, 5 parts of (Z) -3,3, 4-trimethyl-piperazinone oxime and 57 parts of deionized water;
the preparation method of the blood pressure reducing and injection increasing agent comprises the following steps:
adding 35 parts by weight of dioctyldimethylammonium chloride, 7 parts by weight of fluorocarbon FC-4430, 5 parts by weight of polyoxyethylene lauryl ether, 10 parts by weight of sodium ethylene diamine tetramethylene phosphonate, 5 parts by weight of (Z) -3,3, 4-trimethyl-piperazinone oxime and 57 parts by weight of deionized water into a reactor in sequence, heating to 50 ℃, carrying out heat preservation reaction for 3 hours, and cooling to room temperature to obtain the pressure-reducing and injection-increasing agent.
The particle blocking agent is prepared from raw materials including 50 parts of acrylamide, 20 parts of acrylic acid, 10 parts of sodium hydroxide, 8 parts of acrylic acid modified zeolite, 0.5 part of ammonium persulfate, 0.2 part of sodium bisulfite, 0.4 part of N, N-methylene-bisacrylamide, 5 parts of dodecyl methacrylate and 60 parts of water;
the preparation method of the particle plugging agent comprises the following steps:
adding 60 parts by weight of deionized water and 10 parts by weight of sodium hydroxide into a reactor in sequence, stirring uniformly, adding 20 parts by weight of acrylic acid, stirring fully, adding 5 parts by weight of dodecyl methacrylate, 50 parts by weight of acrylamide and 8 parts by weight of acrylic acid modified zeolite in sequence, heating to 45 ℃, adding 0.4 part by weight of N, N-methylene bisacrylamide, heating to 80 ℃, adding 0.2 part by weight of sodium bisulfite and 0.5 part by weight of ammonium persulfate, reacting for 2 hours while keeping the temperature, cooling to room temperature, shearing, drying, and crushing into powder to obtain the particle plugging agent.
The acrylic acid modified zeolite is prepared from zeolite powder, acrylic acid and dibenzoyl peroxide (BPO) according to the weight ratio of 100: 20: 0.2 is prepared; the preparation method of the acrylic acid modified zeolite comprises the following steps:
adding zeolite powder into a mixing machine with a charging basket at a temperature of 60 ℃, adding acrylic acid and dibenzoyl peroxide (BPO) according to a weight ratio, stirring for 2 hours, discharging, heating the charging basket of the mixing machine to 120 ℃, pouring the materials into the mixing machine, stirring at a high speed for 1 hour, and discharging to obtain the acrylic acid modified zeolite.
Example 19
A composite profile control and flooding agent comprises, by weight, 30 parts of a surfactant type plugging agent, 40 parts of a pressure-reducing injection-increasing agent and 5 parts of a particle plugging agent;
the surfactant type plugging agent is prepared from the following raw materials of polyacrylamide, a composite cross-linking agent, modified cyclodextrin, m-phenylenediamine, an oxygen scavenger and a carboxylate gemini surfactant, wherein the weight ratio of the polyacrylamide, water, the composite cross-linking agent, citric acid modified beta-cyclodextrin, the m-phenylenediamine, the oxygen scavenger and the carboxylate gemini surfactant is 1: 131: 0.09: 0.6: 0.25: 0.15: 0.95.
the citric acid modified beta-cyclodextrin is prepared from citric acid, sodium hypophosphite, deionized water, beta-cyclodextrin and absolute ethyl alcohol in a weight ratio of 1: 0.2: 2: 0.95: 5, preparing a composition; the polyacrylamide is partially hydrolyzed polyacrylamide with 18 percent of hydrolysis degree, and the molecular weight is 1400 ten thousand; the modified cyclodextrin is citric acid modified beta-cyclodextrin; the composite cross-linking agent is prepared from benzaldehyde and hydroquinone in a weight ratio of 1: 0.45 is mixed; the oxygen scavenger is semicarbazide and 1, 4-phenylene bis (thiourea) according to the weight ratio of 1: 1.3, mixing; the carboxylate gemini surfactant comprises a carboxylate gemini surfactant A and a carboxylate gemini surfactant B, wherein the preparation raw materials of the carboxylate gemini surfactant A comprise 1, 3-propane sultone, absolute ethyl alcohol, p-phenylenediamine, methanol, anhydrous potassium carbonate, bromododecane and acetone; the carboxylate gemini surfactant B is prepared from raw materials including 1, 3-propane sultone, absolute ethyl alcohol, p-phenylenediamine, methanol, anhydrous potassium carbonate, 1-bromohexane and acetone; the weight ratio of the carboxylate gemini surfactant A to the carboxylate gemini surfactant B is 1: 0.5;
the preparation method of the surfactant type plugging agent comprises the following steps:
adding part of hydrolyzed polyacrylamide with the molecular weight of 1400 ten thousand and the hydrolysis degree of 18 percent and water with the mineralization degree of 125520mg/L into a reactor, stirring and dissolving, adjusting the pH value to 5.0 by oxalic acid, standing for 2 hours to fully cure, then sequentially adding the oxygen scavenger, the composite cross-linking agent, the citric acid modified beta-cyclodextrin and the m-phenylenediamine in formula amount, stirring uniformly, heating to 88 ℃, keeping the temperature for 30 hours, cooling to 60 ℃, adding the carboxylate gemini surfactant in formula amount, stirring for 1 hour, and cooling to room temperature to obtain the surfactant type plugging agent.
The citric acid modified beta-cyclodextrin is prepared from citric acid, sodium hypophosphite, deionized water, beta-cyclodextrin and absolute ethyl alcohol in a weight ratio of 1: 0.3: 3: 1: 6, preparing a mixture; the preparation method of the citric acid modified beta-cyclodextrin comprises the following steps:
sequentially adding citric acid, sodium hypophosphite and deionized water in a formula amount into a reactor, stirring to completely dissolve, adding beta-cyclodextrin, heating to 80 ℃, keeping the temperature for reaction for 2 hours, heating to 110 ℃, keeping the temperature for reaction for 6 hours, cooling to room temperature, slowly dripping into absolute ethyl alcohol in a formula amount, stirring for 2 hours after dripping is finished, filtering, and drying under reduced pressure at 60 ℃ for 16 hours to obtain the citric acid modified beta-cyclodextrin.
The carboxylate gemini surfactant A is prepared from 1, 3-propane sultone, absolute ethyl alcohol, p-phenylenediamine, methanol, anhydrous potassium carbonate, bromododecane and acetone according to a weight ratio of 1: 8: 0.7: 12: 1.3: 1.2: 6, preparing the mixture; the preparation method of the carboxylate gemini surfactant A comprises the following steps:
sequentially adding 1, 3-propane sultone, absolute ethyl alcohol and p-phenylenediamine in formula amount into a reactor, stirring, heating to 60 ℃, carrying out heat preservation reaction for 20h, carrying out reduced pressure concentration to dryness, sequentially adding methanol, anhydrous potassium carbonate and bromododecane in formula amount, heating to 70 ℃, carrying out heat preservation reaction for 30h, filtering, carrying out reduced pressure concentration to dryness on filtrate, adding acetone in formula amount, carrying out recrystallization, and carrying out reduced pressure drying at 60 ℃ for 10h to obtain the carboxylate gemini surfactant A.
The carboxylate gemini surfactant B is prepared from 1, 3-propane sultone, absolute ethyl alcohol, p-phenylenediamine, methanol, anhydrous potassium carbonate, 1-bromohexane and acetone according to a weight ratio of 1: 4: 0.4: 9: 1: 0.9: 3 in proportion; the preparation method of the carboxylate gemini surfactant B comprises the following steps:
sequentially adding 1, 3-propane sultone, absolute ethyl alcohol and p-phenylenediamine in formula amount into a reactor, stirring, heating to 60 ℃, carrying out heat preservation reaction for 20h, carrying out reduced pressure concentration to dryness, sequentially adding methanol, anhydrous potassium carbonate and 1-bromohexane in formula amount, heating to 70 ℃, carrying out heat preservation reaction for 30h, filtering, carrying out reduced pressure concentration to dryness on filtrate, adding acetone in formula amount, carrying out recrystallization, and carrying out reduced pressure drying at 60 ℃ for 10h to obtain the carboxylate gemini surfactant B.
The preparation raw materials of the pressure-reducing injection-increasing agent comprise 30 parts of dioctyldimethylammonium chloride, 3 parts of fluorocarbon FC-44303, 3 parts of polyoxyethylene lauryl ether, 5 parts of ethylene diamine tetramethylene sodium phosphonate, 2 parts of (Z) -3,3, 4-trimethyl-piperazinone oxime and 38 parts of deionized water;
the preparation method of the blood pressure reducing and injection increasing agent comprises the following steps:
adding 30 parts by weight of dioctyldimethylammonium chloride, 3 parts by weight of fluorocarbon FC-4430, 3 parts by weight of polyoxyethylene lauryl ether, 5 parts by weight of sodium ethylene diamine tetramethylene phosphonate, 2 parts by weight of (Z) -3,3, 4-trimethyl-piperazinone oxime and 38 parts by weight of deionized water into a reactor in sequence, heating to 50 ℃, carrying out heat preservation reaction for 3 hours, and cooling to room temperature to obtain the pressure-reducing and injection-increasing agent.
The particle blocking agent is prepared from raw materials including 20 parts of acrylamide, 35 parts of acrylic acid, 8 parts of sodium hydroxide, 2 parts of acrylic acid modified zeolite, 0.1 part of ammonium persulfate, 0.05 part of sodium bisulfite, 0.1 part of N, N-methylene-bisacrylamide, 2 parts of dodecyl methacrylate and 40 parts of water;
the preparation method of the particle plugging agent comprises the following steps:
adding 40 parts by weight of deionized water and 8 parts by weight of sodium hydroxide into a reactor in sequence, stirring uniformly, adding 35 parts by weight of acrylic acid, stirring fully, adding 2 parts by weight of dodecyl methacrylate, 20 parts by weight of acrylamide and 2 parts by weight of acrylic acid modified zeolite in sequence, heating to 45 ℃, adding 0.1 part by weight of N, N-methylene bisacrylamide, heating to 80 ℃, adding 0.05 part by weight of sodium bisulfite and 0.1 part by weight of ammonium persulfate, carrying out heat preservation reaction for 2 hours, cooling to room temperature, shearing, drying, and crushing into powder to obtain the particle plugging agent.
The acrylic acid modified zeolite is prepared from zeolite powder, acrylic acid and dibenzoyl peroxide (BPO) according to the weight ratio of 100: 12: 0.13 is prepared; the preparation method of the acrylic acid modified zeolite comprises the following steps: adding zeolite powder into a mixing machine with a charging basket at a temperature of 60 ℃, adding acrylic acid and dibenzoyl peroxide (BPO) according to a weight ratio, stirring for 2 hours, discharging, heating the charging basket of the mixing machine to 120 ℃, pouring the materials into the mixing machine, stirring at a high speed for 1 hour, and discharging to obtain the acrylic acid modified zeolite.
Example 20
The composite profile control and flooding agent comprises 55 parts by weight of a surfactant type plugging agent, 60 parts by weight of a pressure-reducing injection-increasing agent and 8 parts by weight of a particle plugging agent;
the surfactant type plugging agent is prepared from the following raw materials of polyacrylamide, a composite cross-linking agent, modified cyclodextrin, m-phenylenediamine, an oxygen scavenger and a carboxylate gemini surfactant, wherein the weight ratio of the polyacrylamide, water, the composite cross-linking agent, citric acid modified beta-cyclodextrin, the m-phenylenediamine, the oxygen scavenger and the carboxylate gemini surfactant is 1: 115: 0.05: 0.2: 0.1: 0.05: 0.3.
the polyacrylamide is partially hydrolyzed polyacrylamide with 18 percent of hydrolysis degree, and the molecular weight is 1400 ten thousand; the modified cyclodextrin is citric acid modified beta-cyclodextrin; the composite cross-linking agent is prepared from benzaldehyde and hydroquinone in a weight ratio of 1: 0.6 is mixed; the oxygen scavenger is semicarbazide and 1, 4-phenylene bis (thiourea) according to the weight ratio of 1: 2 in proportion; the carboxylate gemini surfactant comprises a carboxylate gemini surfactant A and a carboxylate gemini surfactant B, wherein the preparation raw materials of the carboxylate gemini surfactant A comprise 1, 3-propane sultone, absolute ethyl alcohol, p-phenylenediamine, methanol, anhydrous potassium carbonate, bromododecane and acetone; the carboxylate gemini surfactant B is prepared from raw materials including 1, 3-propane sultone, absolute ethyl alcohol, p-phenylenediamine, methanol, anhydrous potassium carbonate, 1-bromohexane and acetone; the weight ratio of the carboxylate gemini surfactant A to the carboxylate gemini surfactant B is 1: 0.7;
the preparation method of the surfactant type plugging agent comprises the following steps:
adding part of hydrolyzed polyacrylamide with the molecular weight of 1400 ten thousand and the hydrolysis degree of 18 percent and water with the mineralization degree of 125520mg/L into a reactor, stirring and dissolving, adjusting the pH value to 5.0 by oxalic acid, standing for 2 hours to fully cure, then sequentially adding the oxygen scavenger, the composite cross-linking agent, the citric acid modified beta-cyclodextrin and the m-phenylenediamine in formula amount, stirring uniformly, heating to 88 ℃, keeping the temperature for 30 hours, cooling to 60 ℃, adding the carboxylate gemini surfactant in formula amount, stirring for 1 hour, and cooling to room temperature to obtain the surfactant type plugging agent.
The citric acid modified beta-cyclodextrin is prepared from citric acid, sodium hypophosphite, deionized water, beta-cyclodextrin and absolute ethyl alcohol in a weight ratio of 1: 0.15: 2: 0.5: 4, preparing a composition; the preparation method of the citric acid modified beta-cyclodextrin comprises the following steps:
sequentially adding citric acid, sodium hypophosphite and deionized water in a formula amount into a reactor, stirring to completely dissolve, adding beta-cyclodextrin, heating to 80 ℃, keeping the temperature for reaction for 2 hours, heating to 110 ℃, keeping the temperature for reaction for 6 hours, cooling to room temperature, slowly dripping into absolute ethyl alcohol in a formula amount, stirring for 2 hours after dripping is finished, filtering, and drying under reduced pressure at 60 ℃ for 16 hours to obtain the citric acid modified beta-cyclodextrin.
The carboxylate gemini surfactant A is prepared from 1, 3-propane sultone, absolute ethyl alcohol, p-phenylenediamine, methanol, anhydrous potassium carbonate, bromododecane and acetone according to a weight ratio of 1: 5: 0.3: 9: 1.1: 0.9: 5, preparing the mixture; the preparation method of the carboxylate gemini surfactant A comprises the following steps:
sequentially adding 1, 3-propane sultone, absolute ethyl alcohol and p-phenylenediamine in formula amount into a reactor, stirring, heating to 60 ℃, carrying out heat preservation reaction for 20h, carrying out reduced pressure concentration to dryness, sequentially adding methanol, anhydrous potassium carbonate and bromododecane in formula amount, heating to 70 ℃, carrying out heat preservation reaction for 30h, filtering, carrying out reduced pressure concentration to dryness on filtrate, adding acetone in formula amount, carrying out recrystallization, and carrying out reduced pressure drying at 60 ℃ for 10h to obtain the carboxylate gemini surfactant A.
The carboxylate gemini surfactant B is prepared from 1, 3-propane sultone, absolute ethyl alcohol, p-phenylenediamine, methanol, anhydrous potassium carbonate, 1-bromohexane and acetone according to a weight ratio of 1: 5: 0.5: 10: 1.1: 1.0: 5, preparing the mixture; the preparation method of the carboxylate gemini surfactant B comprises the following steps:
sequentially adding 1, 3-propane sultone, absolute ethyl alcohol and p-phenylenediamine in formula amount into a reactor, stirring, heating to 60 ℃, carrying out heat preservation reaction for 20h, carrying out reduced pressure concentration to dryness, sequentially adding methanol, anhydrous potassium carbonate and 1-bromohexane in formula amount, heating to 70 ℃, carrying out heat preservation reaction for 30h, filtering, carrying out reduced pressure concentration to dryness on filtrate, adding acetone in formula amount, carrying out recrystallization, and carrying out reduced pressure drying at 60 ℃ for 10h to obtain the carboxylate gemini surfactant B.
The preparation raw materials of the pressure-reducing injection-increasing agent comprise 33 parts of dioctyldimethylammonium chloride, 4 parts of fluorocarbon FC-44305 parts of polyoxyethylene lauryl ether, 8 parts of ethylene diamine tetra methylene phosphonic acid sodium, 2 parts of (Z) -3,3, 4-trimethyl-piperazinone oxime and 47 parts of deionized water;
the preparation method of the blood pressure reducing and injection increasing agent comprises the following steps:
adding 33 parts by weight of dioctyldimethylammonium chloride 57 parts by weight of fluorocarbon FC-4430, 4 parts by weight of polyoxyethylene lauryl ether, 8 parts by weight of sodium ethylene diamine tetramethylene phosphonate, 2 parts by weight of (Z) -3,3, 4-trimethyl-piperazinone oxime and 47 parts by weight of deionized water into a reactor in sequence, heating to 50 ℃, keeping the temperature for reaction for 3 hours, and cooling to room temperature to obtain the pressure-reducing and injection-increasing agent.
The particle blocking agent is prepared from raw materials including 30 parts of acrylamide, 50 parts of acrylic acid, 4 parts of sodium hydroxide, 10 parts of acrylic acid modified zeolite, 0.4 part of ammonium persulfate, 0.15 part of sodium bisulfite, 0.3 part of N, N-methylene-bisacrylamide, 4 parts of dodecyl methacrylate and 55 parts of water;
the preparation method of the particle plugging agent comprises the following steps:
adding 55 parts by weight of deionized water and 4 parts by weight of sodium hydroxide into a reactor in sequence, stirring uniformly, adding 50 parts by weight of acrylic acid, stirring fully, adding 4 parts by weight of dodecyl methacrylate, 30 parts by weight of acrylamide and 10 parts by weight of acrylic acid modified zeolite in sequence, heating to 45 ℃, adding 0.3 part by weight of N, N-methylene bisacrylamide, heating to 80 ℃, adding 0.15 part by weight of sodium bisulfite and 0.4 part by weight of ammonium persulfate, reacting for 2 hours at a constant temperature, cooling to room temperature, shearing, drying, and crushing into powder to obtain the particle plugging agent.
The acrylic acid modified zeolite is prepared from zeolite powder, acrylic acid and dibenzoyl peroxide (BPO) according to the weight ratio of 100: 15: 0.16 is prepared; the preparation method of the acrylic acid modified zeolite comprises the following steps: adding zeolite powder into a mixing machine with a charging basket at a temperature of 60 ℃, adding acrylic acid and dibenzoyl peroxide (BPO) according to a weight ratio, stirring for 2 hours, discharging, heating the charging basket of the mixing machine to 120 ℃, pouring the materials into the mixing machine, stirring at a high speed for 1 hour, and discharging to obtain the acrylic acid modified zeolite.
The above examples are merely illustrative and serve to explain some of the features of the method of the invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.

Claims (8)

1. A composite profile control and flooding agent is characterized in that: the composite profile control and flooding agent comprises, by weight, 20-50 parts of a surfactant type plugging agent, 30-70 parts of a pressure-reducing injection-increasing agent and 5-20 parts of a particle plugging agent; the surfactant type plugging agent is prepared from polyacrylamide, water, a composite cross-linking agent, modified cyclodextrin, m-phenylenediamine, an oxygen scavenger and a carboxylate gemini surfactant according to a weight ratio of 1: (110-131): (0.05-0.12): (0.2-0.8): (0.1-0.3): (0.05-0.2): (0.3-1); the polyacrylamide is partially hydrolyzed polyacrylamide with 18 percent of hydrolysis degree, and the molecular weight is 1400 ten thousand;
the particle blocking agent comprises, by weight, 20-50 parts of acrylamide, 20-50 parts of acrylic acid, 1-15 parts of sodium hydroxide, 2-10 parts of modified zeolite, 0.1-0.5 part of ammonium persulfate, 0.05-0.25 part of sodium bisulfite, 0.1-0.5 part of N, N-methylene bisacrylamide, 1-5 parts of dodecyl methacrylate and 40-60 parts of water;
the modified zeolite is acrylic acid modified zeolite, and the acrylic acid modified zeolite is prepared from zeolite powder, acrylic acid and dibenzoyl peroxide according to a weight ratio of 100: (12-20): (0.13-0.2), the preparation method comprises the following steps: adding zeolite powder into a mixing machine with a charging basket at the temperature of 50-70 ℃, adding acrylic acid and dibenzoyl peroxide according to the weight ratio, stirring for 2-3h, discharging, raising the charging basket temperature of the mixing machine to 110-120 ℃, pouring the materials into the mixing machine, stirring at a high speed for 1-2h, and discharging to obtain acrylic acid modified zeolite;
the modified cyclodextrin is citric acid modified beta-cyclodextrin, and the citric acid modified beta-cyclodextrin is prepared from citric acid, sodium hypophosphite, deionized water, beta-cyclodextrin and absolute ethyl alcohol in a weight ratio of 1: (0.1-0.3): (1-3): (0.5-1): (3-6); the preparation method of the citric acid modified beta-cyclodextrin comprises the following steps: sequentially adding citric acid, sodium hypophosphite and deionized water into a reactor according to the weight ratio, stirring to completely dissolve, adding beta-cyclodextrin according to the formula amount, heating to 70-80 ℃, carrying out heat preservation reaction for 2-3h, heating to 100-.
2. The composite profile control and flooding agent according to claim 1, characterized in that: the pressure-reducing injection-increasing agent comprises, by weight, 30-35 parts of dioctyldimethylammonium chloride, 3-7 parts of fluorocarbon surfactant, 3-5 parts of nonionic surfactant, 5-10 parts of sodium ethylene diamine tetramethylene phosphonate, (Z) -3,3, 4-trimethyl-piperazinone oxime, and 38-57 parts of deionized water; the fluorocarbon surfactant is fluorocarbon FC-4430, and the nonionic surfactant is polyoxyethylene lauryl ether.
3. The composite profile control and flooding agent according to claim 1, characterized in that: the preparation method of the surfactant type plugging agent comprises the following steps: firstly, adding polyacrylamide and water with a formula amount into a reactor, stirring and dissolving, adjusting the pH value to 5.0 by using oxalic acid, and standing for 1-3 hours for full curing; and then sequentially adding the oxygen scavenger, the composite cross-linking agent, the modified cyclodextrin and the m-phenylenediamine in the formula amount, uniformly stirring, heating to 80-90 ℃, preserving heat for 20-40h, then cooling to 55-60 ℃, adding the carboxylate gemini surfactant in the formula amount, stirring for 1-2h, and cooling to room temperature to obtain the surfactant type plugging agent.
4. The composite profile control and flooding agent according to claim 1, characterized in that: the carboxylate gemini surfactant is prepared from a carboxylate gemini surfactant A and a carboxylate gemini surfactant B according to the weight ratio of 1: (0.1-0.7) in proportion.
5. The composite profile control and flooding agent according to claim 4, characterized in that: the carboxylate gemini surfactant A is prepared from 1, 3-propane sultone, absolute ethyl alcohol, p-phenylenediamine, methanol, anhydrous potassium carbonate, bromododecane and acetone according to a weight ratio of 1: (4-8): (0.3-0.7): (8-12): (1-1.3): (0.8-1.2): (3-6);
the preparation method of the carboxylate gemini surfactant A comprises the following steps: firstly, sequentially adding 1, 3-propane sultone, absolute ethyl alcohol and p-phenylenediamine in formula amount into a reactor, stirring, heating to 55-60 ℃, reacting for 20-25h under heat preservation, and concentrating under reduced pressure to dryness; then sequentially adding methanol, anhydrous potassium carbonate and bromododecane according to the formula ratio, heating to 60-70 ℃, reacting for 30-35h under heat preservation, filtering, and concentrating the filtrate under reduced pressure to dryness; and finally adding acetone with the formula amount for recrystallization, and drying at 60 ℃ under reduced pressure for 10-12h to obtain the carboxylate gemini surfactant A.
6. The composite profile control and flooding agent according to claim 4, characterized in that: the carboxylate gemini surfactant B is prepared from raw materials including 1, 3-propane sultone, absolute ethyl alcohol, p-phenylenediamine, methanol, anhydrous potassium carbonate, 1-bromohexane and acetone according to a weight ratio of 1: (4-7): (0.4-0.6): (9-12): (1-1.3): (0.9-1.1): (3-6);
the preparation method of the carboxylate gemini surfactant B comprises the following steps: firstly, sequentially adding 1, 3-propane sultone, absolute ethyl alcohol and p-phenylenediamine in formula amount into a reactor, stirring, heating to 55-60 ℃, reacting for 20-25h under heat preservation, and concentrating under reduced pressure to dryness; then sequentially adding methanol, anhydrous potassium carbonate and 1-bromohexane according to the formula ratio, heating to 60-70 ℃, reacting for 30-35h under heat preservation, filtering, and concentrating the filtrate under reduced pressure to dryness; and finally adding acetone with the formula amount for recrystallization, and drying at 60 ℃ under reduced pressure for 10-12h to obtain the carboxylate gemini surfactant B.
7. The composite profile control and flooding agent according to claim 1, characterized in that: the composite cross-linking agent is prepared from benzaldehyde and benzenediol in a weight ratio of 1: (0.3-0.6) in proportion.
8. The composite profile control and flooding agent according to claim 1, characterized in that: the oxygen scavenger comprises one or more of thiourea, 2, 4-dithiobiuret, semicarbazide, thiosemicarbazide and 1, 4-phenylene bis (thiourea).
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