CN109181672B - Monomer charge-identical association polymer composite oil displacement agent and alternate injection oil displacement method - Google Patents
Monomer charge-identical association polymer composite oil displacement agent and alternate injection oil displacement method Download PDFInfo
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- CN109181672B CN109181672B CN201811174340.0A CN201811174340A CN109181672B CN 109181672 B CN109181672 B CN 109181672B CN 201811174340 A CN201811174340 A CN 201811174340A CN 109181672 B CN109181672 B CN 109181672B
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- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims description 6
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 3
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- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 2
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- PSBDWGZCVUAZQS-UHFFFAOYSA-N (dimethylsulfonio)acetate Chemical compound C[S+](C)CC([O-])=O PSBDWGZCVUAZQS-UHFFFAOYSA-N 0.000 description 1
- RNMDNPCBIKJCQP-UHFFFAOYSA-N 5-nonyl-7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-ol Chemical compound C(CCCCCCCC)C1=C2C(=C(C=C1)O)O2 RNMDNPCBIKJCQP-UHFFFAOYSA-N 0.000 description 1
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- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
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- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 1
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- 239000012224 working solution Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/588—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants
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- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
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- Oil, Petroleum & Natural Gas (AREA)
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Abstract
The invention belongs to the technical field of chemical flooding for improving the recovery ratio of crude oil, and provides a composite oil displacement agent consisting of a hydrophobically associating polymer with the same monomer charge, an optimal surfactant or a composition thereof and water, and an alternative injection oil displacement method. The interaction of the hydrophobic association polymer and the preferred surfactant can increase the viscosity of the association polymer by more than two orders of magnitude, the poly/surface effect tackifying efficiency is highest, the viscosity of the composite oil displacement agent is increased and then reduced along with the addition of the surfactant, and the preferred surfactant is easily replaced by the hydrophobic association polymer on the surface of the rock. The oil displacement method adopts multiple rounds of alternate injection, effectively regulates and controls the position of the fluidity mutation in the oil displacement process, and improves the fluidity ratio of the oil displacement agent and the crude oil. The invention solves the problems of high consumption, difficult injection of high-viscosity oil displacement agent and difficult treatment of produced fluid in the traditional composite flooding, and can be used for tertiary oil recovery production of medium-low permeability and chemical flooding and heavy oil reservoirs.
Description
Technical Field
The invention belongs to the technical field of improving the recovery ratio of crude oil by chemical flooding, and particularly relates to a composite oil displacement agent containing a hydrophobic association polymer and a surfactant and an oil displacement method.
Background
In the process of oil field development, compound flooding is one of effective methods for greatly improving the recovery ratio of crude oil. The composite oil displacement agent generally refers to any two or more of polymer oil displacement agents, surfactant oil displacement agents, alkali oil displacement agents, biological oil displacement agents and other oil displacement agents. However, the large-scale application of the technology is restricted due to the problems of high cost, well bore and stratum scaling, difficult treatment of produced fluid and the like in the application of the composite flooding. Therefore, developing a compound flooding technology with lower cost, higher oil displacement efficiency and wider application range is one of the key technologies in the field of improving the recovery ratio of crude oil.
Fluidity refers to the ratio of the effective permeability of a fluid to the viscosity of the fluid in a certain phase. Mobility ratio refers to the ratio of mobility of the displacement fluid to mobility of the fluid (crude oil) being displaced. The size of the mobility ratio directly affects the swept volume of the displacement fluid, which in turn affects the recovery ratio of the crude oil. Controlling and adjusting the mobility ratio is an important direction in increasing oil recovery, and the best method at present is to increase the viscosity of the displacement fluid.
The compound flooding related research shows that: improved fluidity is the primary mechanism for enhanced oil recovery by chemical Flooding, and it is difficult to significantly enhance oil recovery without Polymer assisted low interfacial Tension surfactant Flooding (MA Bataweel, AY Shivaprasad, HA Nasr-El-din. Low-Tension Polymer Flooding Using aqueous surfactant in High purity/High Hardness and High Temperature conditioning in Sandstone Cores [ J ]. Society of Petroleum Engineers, 2012). The cost of chemicals is a key factor in controlling the cost of compounding flooding, with surfactants capable of achieving ultra-low interfacial tensions being a major component of the chemical cost. The oil displacement efficiency problem of the compound flooding is more complex, and the existing research shows that: whether a chemical flooding is successful depends mainly on whether mobility control is maintained during the flooding of the reservoir at the depth (Farajzadeh. R, Rikovetsky. P, Lotfollahi. M, Lake, L.W.Simultaneous absorption and mechanical reservoir dual polymer flow through porous media [ J ]. Water Resources Research,2016,52(3):2279 + 2298.). If the mobility control capability of the oil displacement system at the deep part of the reservoir is not weakened or even greatly enhanced, the oil displacement efficiency is inevitably and favorably improved greatly.
Hydrophobically Associating Polymers (HAWSP) are Water-Soluble Polymers with a small number of hydrophobic groups on the hydrophilic macromolecular chain of the polymer. In aqueous solutions, when the polymer Concentration is higher than a certain Critical Association Concentration (CAC), macromolecular chains aggregate by hydrophobic Association to form a supramolecular structure (dynamic physical cross-linked network) dominated by intermolecular Association, the hydrodynamic volume increases, the solution viscosity increases dramatically (Alain Hill, Francois Candau, Joseph Selb, Properties of hydrophic Association polyamides: fluorescence of the Method of Synthesis, Macromolecules,1993,26(17): 4521) 4532). As the supramolecular network structure formed by the HAWSP has the characteristic of reversible Recovery, the supramolecular network structure shows good capability of controlling the denaturation of the working fluid in different solution environments and at different shear rates, and has huge application potential in the aspects of drilling fluid and improving crude Oil Recovery (Taylor K C, Nasr-El-Din H A, Water-Soluble hydrogel association Polymers for Improved Oil Recovery: A Librature Review, Society of Petroleum Engineers, SPE29008, 675-. Hydrobically-Modified Polyacrylamide (HMPAM) is a class of Hydrophobically associating polymers with acrylamide and acrylic acid as the main polymer molecular chains, and such polymers are one of the most important types of HAWSP. The polymer is already industrially produced and is applied to the actual production of oil fields to a certain extent, and good effects are achieved (Zhou defending is, Korea, Wako Weekao, Zhang Jian and the like, research and application of Bohai sea oil field polymer flooding enhanced recovery technology, China offshore oil and gas, 2006, 18(6): 386-389).
It is found that certain surfactants can greatly increase the viscosity of the HAWSP solution in a specific concentration range, because the surfactants react with hydrophobic groups of polymers in the solution to enhance hydrophobic association among polymer molecular chains, so that the strength of an intermolecular association dynamic physical crosslinking network is increased. Thereby, the performances of thickening property, shearing dilution property, suspension property, salt resistance, temperature resistance and the like of the hydrophobically modified water-soluble polymer/surfactant composition are obviously improved compared with those of a single polymer. The research considers that: the change of the macroscopic rheological behavior of the composite system is caused by the change of a microscopic space network structure, and the change process of the microscopic space network structure is formation, reinforcement and destruction. (Biggs S, Selb J, Candau F. Effect of surfactant on the solution properties of hydrocalumied polyacylamide [ J ]. Langmuir,1992,8: 838.).
Aiming at the problems existing in the technology of improving the recovery ratio of the compound flooding, a novel compound oil displacement agent with a new fluidity regulating and controlling mechanism can be designed based on the synergistic effect of HAWSP and a surfactant on the adsorption of a solid/liquid interface and the intermolecular interaction according to the principle of intermolecular interaction, the consumption of the surfactant can be greatly reduced, and the fluidity control capability of a displacement front edge can be greatly improved in the seepage process, so that the compound oil displacement agent has the characteristics of low consumption, good injectivity and high oil displacement efficiency, can be used for various oil reservoir conditions applicable to the conventional chemical flooding, and can also be used in the technology of improving the recovery ratio of low-permeability oil reservoirs and oil reservoirs after polymer flooding.
Disclosure of Invention
The invention aims to provide a composite oil displacement agent containing a hydrophobic association polymer with the same monomer charge and a surfactant and an alternative injection oil displacement method. Compared with the traditional binary composite flooding, the oil displacement agent has the advantages that the using amount of the oil displacement agent is remarkably reduced, the injectivity is remarkably improved, the mobility regulation and control capability is stronger, and the oil displacement agent is more suitable for wider oil reservoir range.
In order to achieve the object of the present invention, the present invention firstly provides a composite oil displacement agent comprising a hydrophobically associating polymer and a surfactant. The hydrophobic association polymer (HAWSP) is Hydrophobic Modified Polyacrylamide (HMPAM) and derivative dry powder thereof, the molecular structure of the HAWSP comprises an acrylamide monomer unit, at least one amphiphilic unsaturated hydrophobic monomer unit and at least one olefinic unsaturated functional monomer unit, and the charges of the hydrophobic monomer unit and the functional monomer unit have the same sign; the hydrophobic monomer is alkyl dimethyl allyl ammonium chloride, N-alkyl substituted acrylamide or alkyl methacrylate, 2-acrylamide alkyl sulfonic acid and sodium salt thereof, wherein the carbon atom number of an alkyl chain is 8-22, preferably 12-18; the ethylenically unsaturated functional monomer is one or more of acrylic acid, acrylic acid sodium salt, acrylic acid ammonium salt, methacrylic acid sodium salt, methacrylic acid ammonium salt, 2-acrylamido-2-methylpropanesulfonic Acid (AMPS), 2-acrylamido-2-methylpropanesulfonic acid sodium salt, vinylsulfonic acid sodium salt, styrenesulfonic acid, and styrenesulfonic acid sodium salt, and is preferably acrylic acid, acrylic acid sodium salt, 2-acrylamido-2-methylpropanesulfonic Acid (AMPS), 2-acrylamido-2-methylpropanesulfonic acid sodium salt, or methacryloyloxyethyltrimethylammonium chloride.
In the HMPAM and the derivative thereof, the acrylamide monomer unit, the amphiphilic unsaturated hydrophobic monomer unit and the ethylenically unsaturated functional monomer unit are 60-80 parts, 1-5 parts and 39-15 parts in sequence by weight.
The molecular structural formula of the HMPAM and the derivatives thereof is as follows:
i acrylamide/sodium acrylate/amphiphilic unsaturated hydrophobic monomer; wherein, the amphiphilic unsaturated hydrophobic monomer is preferably 2-acrylamide alkyl sulfonic acid and sodium salt thereof; or
II acrylamide/sodium acrylate/amphiphilic unsaturated hydrophobic monomer/ethylenically unsaturated functional monomer; wherein the hydrophobic monomer is preferably alkyl dimethyl allyl ammonium chloride, N-alkyl substituted acrylamide, alkyl methacrylate, 2-acrylamide alkyl sulfonic acid and sodium salt thereof; the ethylenically unsaturated monomer is preferably AMPS, methacrylic acid and sodium salt thereof, styrene sulfonic acid and sodium salt thereof, vinyl sulfonic acid and sodium salt thereof, methacryloyloxyethyl trimethyl ammonium chloride and the like; or
III acrylamide/amphiphilic unsaturated hydrophobic monomer/ethylenically unsaturated functional monomer; wherein the hydrophobic monomer is preferably alkyl dimethyl allyl ammonium chloride, N-alkyl substituted acrylamide, alkyl methacrylate, 2-acrylamide alkyl sulfonic acid and sodium salt thereof; the ethylenically unsaturated functional monomer is preferably AMPS, methacrylic acid and sodium salt thereof, styrene sulfonic acid and sodium salt thereof, vinyl sulfonic acid and sodium salt thereof, methacryloyloxyethyl trimethyl ammonium chloride, and the like.
In the molecular structure II or III, anionic ethylenically unsaturated functional monomers AMPS, sodium vinylsulfonate and the like are selected to further improve the viscosity increasing property, the temperature resistance and the salt resistance of HMPAM and derivatives thereof so as to obtain the composite oil displacement agent suitable for oil reservoirs with higher temperature and higher salinity.
The HMPAM and the derivative thereof optionally contain one or more of a synthetic instant assistant, a hydrolysis instant assistant, a drying instant assistant and an anti-sticking agent.
In the composite oil displacement agent, the content of HMPAM and derivatives thereof is higher than that of CAC, and the preferable content of HMPAM and derivatives thereof is 0.05-0.5%.
The surfactant in the composite oil displacement agent is an ionic surfactant and/or a non-ionic surfactant. The ionic surfactant is one or more of but not limited to alkyl benzene sulfonate, alkyl sulfate, petroleum sulfonate, alkyl trimethyl ammonium chloride, alkyl hydroxypropyl sulfobetaine and the like. The nonionic surfactant is, but not limited to, polyoxyethylene nonylphenol ether and/or polyoxyethylene octylphenol ether, alkanolamide, alkyl glycoside, etc.
Further, a composition using a surfactant is preferable, and it has been found that the viscosity increase range and the thickening concentration range of the composite oil-displacing agent can be made larger than those of the surfactant alone by using the composition.
It should be noted that the above-mentioned surfactants or their compositions cannot be directly fixed in the present invention, but can be selected and optimized according to the method and principles disclosed in the present invention, and the specific method is: under the premise of determining the specific oil reservoir temperature, the mineralization degree of preparation water and the addition amount of the fixed hydrophobic association polymer, scanning the relationship between the viscosity of the composite oil-displacing agent and the addition amount of the surfactant, generally, under the condition that the surfactant is selected, the viscosity of the composite oil-displacing agent is increased and then reduced along with the addition amount of the surfactant, and after a certain specific concentration is exceeded, the viscosity of the composite oil-displacing agent is gradually reduced and is finally maintained at a lower viscosity (see fig. 1). The addition amount of the preferable surfactant in the composite oil displacement agent is determined according to the scanning experiment result. The hydrophobic association polymer has different types, different oil reservoir temperatures and different mineralization degrees of water for preparation, and the addition amount of the corresponding surfactant or the composition thereof is different.
In the composite oil displacement agent, the content of the surfactant or the composition thereof is 0.001-0.5%.
Most preferably, the formulation of the composite oil displacement agent is hydrophobically modified polyacrylamide, preferably a surfactant or a combination thereof and water.
The water may be deionized water or mineral-containing water, wherein the mineral-containing water may be tap water, river water, oil field formation water.
In order to achieve the object of the present invention, the present invention also provides a multiple-round alternate injection method of the hydrophobically associating polymer slug and the surfactant slug. Sequentially injecting the hydrophobically associating polymer 0.01PV-0.5PV (Pore Volume) and the surfactant 0.01PV-0.5PV into the oil-bearing stratum to displace crude oil in the oil-bearing stratum; the total injection amount is 0.1PV-1.0PV after 1-50 times of total injection.
The fluidity control principle of the hydrophobic association polymer and surfactant slug multi-round alternate injection is as follows: injecting a slug of said surfactant or combination thereof, part of which will be adsorbed at the solid/liquid interface of the porous media; then injecting the hydrophobic association polymer slug, on one hand, the polymer and the surfactant adsorbed on the solid/liquid interface generate competitive adsorption, so that part of the surfactant enters the polymer slug; on the other hand, in the diffusion mixing zone where the two slugs are in contact with each other, a relatively strong mixing of the surfactant slug and the polymer slug will occur due to diffusion. Both of the two action mechanisms can change the concentration ratio between the two components, and when the concentration of the hydrophobically modified polyacrylamide and the concentration of the surfactant are in a viscosity increasing area (see figure 1), the viscosity of the oil displacement agent can be increased, and the fluidity ratio of the oil displacement agent to crude oil can be improved. Meanwhile, the dynamic adsorption effect of the two oil displacement agents on a solid/liquid interface respectively or in a mixed mode also changes the effective permeability of the oil displacement agent, and the fluidity ratio of the oil displacement agent to crude oil is improved. The above principle remains true by varying the order of injection of the hydrophobically associative polymer and the surfactant slug.
Further, the preferred hydrophobically associating polymer and surfactant can control the highest increase of the viscosity of the composite oil displacement agent compared with the viscosity of the hydrophobically associating polymer alone (see fig. 1); according to the competitive adsorption relation of the hydrophobically associating polymer and the surfactant and the diffusion mixing rule of the two slugs, the specific stratum position where the mobility mutation is generated in the oil displacement process of the two oil displacement agents and the mobility change amplitude caused by each round of alternate injection can be designed.
Compared with the traditional combination flooding technology of poly/epi (SP) and alkali/epi/poly (ASP), the invention overcomes the technical bias of the original combination flooding technology and mainly shows the following three aspects:
the positioning of the actions of each component of the composite oil displacement agent is obviously different: in the traditional composite flooding system, the main function of the surfactant is to reduce the oil/water interfacial tension to be ultra-low, so that the selection of the surfactant is greatly limited, and the dosage of the surfactant is necessarily large; the polymer has the main function of improving the viscosity of the displacement fluid, so that higher requirements are also placed on the tackifying capability and the concentration of the displacement fluid. In the composite oil displacement agent, the surfactant or the composition thereof is added for the main purpose of not reducing the oil/water interfacial tension, but realizing the regulation and control of the viscosity of the composite oil displacement agent by influencing the intermolecular interaction with the hydrophobically associating polymer (see figure 2). The viscosity of the composite oil-displacing agent can be improved by more than two orders of magnitude by adding a small amount of the preferable surfactant into the preferable hydrophobically associating polymer solution, so that the dosage of the polymer and the surfactant in the composite oil-displacing agent can be greatly reduced, and particularly, the dosage of the surfactant can be reduced by more than one order of magnitude compared with that of the traditional composite oil-displacing system, namely, the dosage is reduced from thousands of mg/L to hundreds of mg/L.
(II) the regulation and control mechanisms of the performance of the complex oil displacement agent are completely different: the traditional compound flooding theory considers that the retention of the displacement fluid in the porous medium (mainly the adsorption effect of a solid/liquid interface on a chemical agent) is a key factor influencing the chemical flooding effect, the viscosity of the displacement front edge is reduced along with the adsorption loss of the chemical agent, meanwhile, the interfacial tension is increased, and the oil displacement efficiency is obviously reduced. In order to ensure the oil displacement effect of an oil displacement system in the deep part of a stratum, the adsorption capacity of effective components of a composite flooding agent on a solid/liquid interface needs to be reduced as much as possible, and the initial concentration of each component is greatly improved, so that the displacement fluid still has the capabilities of controlling stronger fluidity and reducing interfacial tension in the deep part of the stratum. In the composite oil-displacing agent and the oil displacing method, the diffusion mixing rule of the two slugs of the hydrophobic association polymer and the surfactant is a main technical principle for regulating and controlling the fluidity of the composite oil-displacing agent, and the oil displacing method can greatly change the fluidity of the oil-displacing agent in the deep part of the stratum, so that the composite oil-displacing agent has better fluidity regulating and controlling effect. Meanwhile, the initial viscosity of the oil displacement agent can be greatly reduced, and the problem of injectability of the high-viscosity oil displacement agent cannot be caused.
(III) the oil displacement mechanisms of the composite oil displacement agent are different: the traditional compound flooding theory considers that the synergistic effect of fluidity improvement and ultralow interfacial tension has a decisive effect on oil displacement efficiency, and simultaneously, oil displacement mechanisms such as wettability, viscoelasticity, emulsification and the like are considered; the composite oil displacement agent and the oil displacement method mainly strengthen the mobility regulation and control capability of the oil displacement agent in the oil displacement process, and the key for improving the oil displacement efficiency is considered to be the improvement of the swept capability of the displacement fluid through the mobility change of the deep stratum, and meanwhile, the composite oil displacement agent and the oil displacement method have oil displacement mechanisms of reducing the oil/water interfacial tension, improving the wettability, high viscoelasticity, emulsification and the like to a certain degree.
Compared with the prior art, the invention has the beneficial effects that:
the composite oil displacement agent containing the hydrophobic association polymer and the surfactant is provided, and the amount of the chemical agent required for realizing the same fluidity control capability is obviously reduced compared with the traditional poly/epi (SP) and alkali/epi/poly (ASP) composite flooding.
(II) the hydrophobic association polymer and the nonionic surfactant are adopted, and when the charges of the hydrophobic monomer unit, the functional monomer unit and the surfactant in the hydrophobic association polymer are the same, only the hydrophobic association effect exists between the polymer and the surfactant; when the charges of the hydrophobic monomer unit, the functional monomer unit and the surfactant are opposite, the interaction between the hydrophobic association polymer and the surfactant is strongest, the poly-surface has hydrophobic association, the electrostatic attraction between the surfactant and the hydrophobic monomer increases the hydrophobic association strength between molecules, and meanwhile, the electrostatic attraction between the surfactant and the functional monomer increases a new association point and further increases the poly-surface interaction (see fig. 2). When charges of the hydrophobic monomer unit, the functional monomer unit and the surfactant in the hydrophobic association polymer are opposite, the surfactant can increase the viscosity of the association polymer by more than two orders of magnitude, the tackifying efficiency of poly/surface interaction is highest, the adjustable range of fluidity is greatly increased, and the using amount of a chemical agent is reduced.
And (III) providing an oil displacement method of multi-round section plug alternate injection of the composite oil displacement agent, wherein in the oil displacement process, the mobility control capability of a displacement front edge can be effectively regulated and controlled within a larger stratum range and a larger range, the oil displacement efficiency is remarkably improved compared with that of polymer flooding, and the enhanced oil recovery range reaches or approaches to that of the traditional binary composite flooding.
And (IV) the injectability of the composite oil displacement agent in the medium-low oil-permeability reservoir and the heavy oil reservoir is obviously improved, and the composite oil displacement agent is more widely applicable to the oil reservoir than the conventional composite oil displacement technology.
And fifthly, the compound oil-displacing agent and the oil-displacing method can effectively utilize the chemical agent retained in the oil reservoir after conventional polymer flooding or compound flooding, so that the compound oil-displacing agent and the oil-displacing method can also be used for the oil reservoir recovery-improving technology after chemical flooding.
And (VI) because the consumption of the associative polymer and the surfactant is greatly reduced, the technical difficulty of treating the oil well output liquid is lower than that of the existing compound flooding technology when the oil well output liquid treatment agent is applied.
Drawings
FIG. 1 is a schematic diagram showing the relationship between the viscosity of the composite oil displacement agent and the concentration of the surfactant.
FIG. 2 is a schematic diagram of the interaction mechanism of the hydrophobically associating polymer and different types of surfactants in the composite oil displacement agent.
FIG. 3 is a graph showing the relationship between the apparent viscosity and the SDBS mass concentration of the composite oil-displacing agent (1200mg/L HP-Y) in example 1 of the present invention.
FIG. 4 is a graph showing the relationship between the apparent viscosity and the 1831 mass concentration of the composite oil-displacing agent (1200mg/L HP-Y) in example 1 of the present invention.
FIG. 5 is a graph showing the relationship between the apparent viscosity and the mass concentration of SB-18 for the composite oil-displacing agent (1200mg/L HP-Y) in example 1 of the present invention.
FIG. 6 is a graph showing the relationship between the apparent viscosity of the composite oil-displacing agent (1200mg/L HP-Y) and the mass concentration of APG-1214 in example 1 of the present invention.
FIG. 7 is a graph showing the static adsorption curve of HP-Y on the surface of silica sand in example 2 of the present invention.
FIG. 8 is a static adsorption curve of 1831 on the surface of quartz sand in example 2 of the present invention.
FIG. 9 is a plot of injection pressure versus PV number for injection of 2PV 100 mg/L1831 oil displacement agent after injection of 0.5PV 1200mg/L HP-Y oil displacement agent in example 3 of the present invention.
FIG. 10 is a graph of injection pressure versus PV number for injection of 0.5PV 1200mg/L HP-Y oil displacement agent after injection of 2PV 100 mg/L1831 oil displacement agent in accordance with example 3 of the present invention.
FIG. 11 is a plot of injection pressure versus PV number for five alternating injections of 0.1PV 1200mg/L HP-Y oil displacement agent and 0.4PV 100 mg/L1831 oil displacement agent of example 3 in accordance with the present invention.
Detailed Description
In the technical scheme, the hydrophobically modified polyacrylamide can be purchased from the market, and can also be prepared by a conventional aqueous solution polymerization method. The resulting products, whether block or random, are useful in and meet the objectives of the present invention. The hydrophobic modified polyacrylamide HP-Y molecular structure in the embodiment of the invention contains an anionic hydrophobic monomer and an anionic functional monomer, and is prepared by mixing an acrylamide monomer, a sodium acrylate monomer and a 2-acrylamidotetradecyl sulfonic acid sodium salt monomer according to a molar ratio of 79: 20: 1, and then initiating a free radical polymerization reaction by using water as a solvent and using a conventional free radical initiator.
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art, and the raw materials used are commercially available products.
Example 1 the hydrophobically associative polymer interacts with the surfactant.
Preparation of a mother solution of the hydrophobically associating polymer: firstly weighing 5000mg/L of NaCl saline water with a certain weight in a container with a stirrer, starting the stirrer, slowly adding the purified hydrophobic modified polyacrylamide HP-Y dry powder into water, wherein the dry powder is added along a vortex, and the dry powder is required to be fully dispersed in the water, otherwise, fish eyes are easily formed. Stirring the mixture for 6 hours in a constant speed (400r/min) constant temperature water bath at the temperature of 45 ℃ to prepare polymer mother liquor with the mass concentration of 5000mg/L, and standing the polymer mother liquor for 24 hours for later use.
Preparing a surfactant mother solution: weighing a certain mass of an anionic surfactant Sodium Dodecyl Benzene Sulfonate (SDBS), a cationic surfactant octadecyl trimethyl ammonium chloride (1831), a zwitterionic surfactant octadecyl hydroxypropyl sulphobetaine (SB-18) and a nonionic surfactant alkyl glycoside (APG-1214), respectively, preparing a surfactant mother solution with the mass concentration of 5000mg/L in 5000mg/L NaCl saline, stirring for 6 hours at a constant speed (400r/min) in a constant-temperature water bath at 45 ℃, and standing for 24 hours for later use.
Preparing a composite oil displacement agent: and (3) preparing a series of composite oil displacement agents (the mass concentration of the HP-Y is 1200mg/L) with different mass concentrations of the surfactant from the HP-Y polymer mother liquor and the surfactant mother liquor in 5000mg/L NaCl saline.
Measurement of apparent viscosity: the test temperature was 45 ℃ and was carried out on a Brookfield LVDV-III rheometer, with a shear rate set at 7.34 s-1. In order to eliminate the influence of the standing time of the solution on the viscosity, a pretreatment program of shearing at 100 rpm for 30s is added in the test, the test is started after the program is stood for 90s, the apparent viscosity measured values at 3min, 5min and 8min are read, and the average value is taken as the final test result.
Under the condition of different surfactant mass concentrations, the apparent viscosity of the composite oil-displacing agent consisting of 1200mg/LHP-Y and SDBS is shown in figure 3, the apparent viscosity of the composite oil-displacing agent consisting of 1200mg/LHP-Y and 1831 is shown in figure 4, the apparent viscosity of the composite oil-displacing agent consisting of 1200mg/LHP-Y and SB-18 is shown in figure 5, and the apparent viscosity of the composite oil-displacing agent consisting of 1200mg/LHP-Y and APG-1214 is shown in figure 6.
In FIG. 3, the apparent viscosity of the composite oil-displacing agent shows a tendency to increase first and then decrease, and finally decrease to an initial viscosity (26.2 mPas) value lower than 1200mg/L HP-Y with increasing concentration of SDBS. When the concentration of the SDBS is 50mg/L, the viscosity of the composite oil displacement agent reaches the maximum value of 53.5mPa & s; when the concentration of the SDBS is more than 100mg/L, the viscosity of the composite oil displacement agent tends to be stable (25.4mPa · s), and is slightly less than the initial viscosity value of 1200mg/L HP-Y. Therefore, when the mass concentration of the hydrophobically modified polyacrylamide HP-Y is 1200mg/L, the mass concentration of the SDBS is 0-100mg/L, and the viscosity increasing area is formed, and the viscosity decreasing area is formed when the mass concentration of the SDBS is more than 100 mg/L.
From the experimental results of fig. 3, it can be determined that the preferable composition of the composite oil displacement agent is: the concentration of the hydrophobic association polymer HP-Y is 1200 mg/L; the concentration of the surfactant SDBS was 100 mg/L.
In FIG. 4, with the increase of 1831 concentration, the apparent viscosity of the composite oil displacement agent shows a tendency to increase first and then decrease, and finally decrease to an initial viscosity (26.2 mPas) value lower than 1200mg/L HP-Y with the increase of 1831 concentration. When the 1831 concentration is 100mg/L, the viscosity of the composite oil displacement agent reaches the maximum value of 2588.0mPa & s; when the 1831 concentration is more than 300mg/L, the viscosity of the composite oil displacement agent tends to be stable (22.1mPa · s), and is slightly less than the initial viscosity value of 1200mg/L HP-Y. Therefore, when the mass concentration of the hydrophobically modified polyacrylamide HP-Y is 1200mg/L, the mass concentration of 1831 is 0-300mg/L to form an adhesion increasing area, and more than 300mg/L to form a viscosity reducing area.
From the experimental results of fig. 4, it can be determined that the preferable composition of the composite oil displacement agent is: the concentration of the hydrophobic association polymer HP-Y is 1200 mg/L; the concentration of the surfactant 1831 was 300 mg/L.
In FIG. 5, the apparent viscosity of the composite oil-displacing agent shows a tendency to increase first and then decrease, and finally decrease to an initial viscosity (26.2 mPas) value lower than 1200mg/L HP-Y with increasing concentration of SB-18. When the concentration of SB-18 is 100mg/L, the viscosity of the composite oil displacement agent reaches the maximum value of 82.0 mPas; when the concentration of SB-18 is more than 300mg/L, the viscosity of the composite oil displacement agent tends to be stable (23.4mPa · s), and is slightly less than the initial viscosity value of 1200mg/L HP-Y. Therefore, when the mass concentration of the hydrophobically modified polyacrylamide HP-Y is 1200mg/L, the mass concentration of SB-18 is 0-300mg/L to form an adhesion increasing area, and more than 300mg/L to form a viscosity reducing area.
From the experimental results of fig. 5, it can be determined that the preferable composition of the composite oil displacement agent is: the concentration of the hydrophobic association polymer HP-Y is 1200 mg/L; the concentration of the surfactant SB-18 was 300 mg/L.
In FIG. 6, the apparent viscosity of the composite oil-displacing agent shows a tendency of increasing and then decreasing with the increase of the concentration of APG-1214, and finally decreasing to an initial viscosity (26.2 mPas) value lower than 1200mg/L HP-Y. When the concentration of APG-1214 is 150mg/L, the viscosity of the composite oil displacement agent reaches the maximum value of 58.3mPa & s; when the concentration of APG-1214 is more than 250mg/L, the viscosity of the composite oil displacement agent tends to be stable (25.4mPa · s), and is slightly less than the initial viscosity value of 1200mg/L HP-Y. Therefore, when the mass concentration of the hydrophobically modified polyacrylamide HP-Y is 1200mg/L, the mass concentration of APG-1214 is 0-250mg/L to form a tackifying area, and more than 250mg/L to form a viscosity reducing area.
From the experimental results of fig. 6, it can be determined that the preferable composition of the composite oil displacement agent is: the concentration of the hydrophobic association polymer HP-Y is 1200 mg/L; the concentration of the surfactant APG-1214 was 250 mg/L.
Example 2 competitive adsorption experiments of hydrophobically associative polymers with surfactants.
According to the experimental results of example 1, the surfactant 1831 was selected as a representative to perform the competitive adsorption experiment, and the surfactant concentration was 300mg/L and the concentration of the hydrophobically associative polymer HP-Y was 1200 mg/L.
And (3) measuring the static adsorption quantity:
(1) preparing a series of HP-Y and 1831 solutions with different mass concentrations in 5000mg/L NaCl saline, and sequentially measuring the concentrations of HP-Y and 1831 in each solution, namely the initial concentration before the oil-displacing agent is adsorbed, which is marked as C0;
(2) Adding quartz sand and an oil displacement agent into a ground conical flask with a plug according to a solid-to-liquid ratio of 1:5 (10g of quartz sand: 50mL of oil displacement agent), shaking and uniformly mixing, covering the plug, and further sealing the bottle opening by using a sealant tape;
(3) placing the conical flask in a constant-temperature water bath oscillator at 45 ℃ and oscillating for 96 hours at the oscillation frequency of 120 times/minute, taking out the conical flask every 6 hours during the oscillation, fully oscillating the conical flask, and then placing the conical flask in the oscillator to continue oscillating;
(4) after 96 hours of shaking, the flask was removed and allowed to stand for 1 hour, and the supernatant was poured into a centrifuge tube and centrifuged at 3000 rpm for approximately 30 minutes.
(5) Pouring the supernatant in the centrifuge tube into a beaker, uniformly mixing, and respectively measuring the concentration of HP-Y or 1831 in the supernatant, namely the equilibrium concentration when the oil-displacing agent is adsorbed to reach equilibrium, and recording as Ce。
The static adsorption amount was calculated as follows:
wherein gamma is the static adsorption capacity, mg/g;
v, volume of oil displacement agent, mL;
C0initial concentration of the oil-displacing agent, mg/L;
Ceequilibrium concentration of the oil-displacing agent, mg/L;
m, mass of quartz sand, g;
1000, unit conversion factor.
The HP-Y concentration detection method comprises the following steps:
(1) preparing a buffer solution: accurately weighing 12.5g of sodium acetate trihydrate crystals, putting the sodium acetate trihydrate crystals into a 500mL beaker, adding 400mL of pure water for dissolution, then adding 0.38g of hydrated aluminum sulfate, measuring the pH value by using a corrected pH meter, and adjusting the pH value to 5.0 by using acetic acid;
(2) preparing a starch-cadmium iodide solution: weighing 11g of cadmium iodide in a 1L beaker, adding 400mL of pure water, stirring, heating and boiling for 15min, adding about 500mL of pure water, and heating and boiling. 2.5g of soluble starch was weighed into a 100mL beaker, dissolved in a small amount of purified water, and then added to the above 1L beaker. Heating and boiling for 5min, cooling, and diluting to 1L;
(3) the experimental steps are as follows: accurately transferring 2mL of the diluted sample to be detected, 25mL of pure water and 5mL of buffer solution with the pH value of 5 into a 50mL volumetric flask, shaking up, accurately adding 1mL of saturated bromine aqueous solution, shaking up, standing for 15min, continuously adding 5mL of 1% sodium formate solution, shaking up, standing for 5min, adding 5mL of starch-cadmium iodide solution, diluting to a scale with pure water, standing for 20min, testing the absorbance of the solution (pure water is used as a reference) at a wavelength of 590nm by using an ultraviolet spectrophotometer, and determining the mass concentration of the polymer HP-Y according to a standard curve of the relationship between the mass concentration and the absorbance.
1831 concentration detection method:
(1) buffer solution and color developing agent: preparing a disodium hydrogen phosphate-sodium dihydrogen phosphate buffer solution with the pH value of 6.38 and a bromocresol green color developing agent of 70 mg/L;
(2) the experimental steps are as follows: adding 2.5mL of buffer solution into a 25mL volumetric flask in sequence, diluting 2mL of sample to be detected and 3mL of developer solution, fixing the volume to a scale mark by using pure water, standing for 20min, testing the absorbance of the sample at 366nm by using an ultraviolet spectrophotometer, and determining the mass concentration of 1831 according to a standard curve of the relationship between the mass concentration of 1831 and the absorbance.
FIGS. 7 and 8 are adsorption isotherms of HP-Y composite oil displacement agents with different concentrations 1831 and HP-Y on the surface of quartz sand, which both conform to the Langmuir model.
As can be seen from FIG. 7, the maximum adsorption amount of HP-Y alone was 950. mu.g/g, and adsorption was substantially saturated when the equilibrium concentration of HP-Y was greater than 800 mg/L; when the concentration of 1831 in the compound oil displacement agent is 60mg/L and 300mg/L respectively, the maximum adsorption capacity of HP-Y is reduced to 675 mug/g and 405 mug/g respectively, which shows that 1831 and HP-Y have competitive adsorption on the surface of quartz sand, and the adsorption capacity of HP-Y is reduced.
As can be seen from FIG. 8, the maximum adsorbed amount of 1831 alone is 2.93 mg/g. The adsorption also reaches equilibrium when the equilibrium concentration of 1831 is greater than 600 mg/L; when the HP-Y concentration in the compound oil displacement agent is respectively 500mg/L and 1200mg/L, the maximum adsorption capacity of 1831 is respectively 2.1mg/g and 1.7mg/g, which are smaller than the maximum static adsorption capacity of 1831 alone on quartz sand, thus indicating that the HP-Y and 1831 have competitive adsorption on the quartz sand surface, and the adsorption capacity of 1831 is reduced.
It can be seen from comparison of FIG. 8 with FIG. 7 that the static adsorption capacity is 1831> HP-Y in order of magnitude under the same silica sand condition.
The experimental results of fig. 7 and fig. 8 show that the composite oil displacement agent (1200mg/L HP-Y and 300 mg/L1831) preferred in example 1 can regulate the viscosity of the displacement front by using the competitive adsorption relationship of different components in the seepage process according to the oil displacement method of the present invention, so as to achieve the oil displacement effect of the present invention.
Example 3 Effect of the mode of injection on the interaction of hydrophobically associative polymer with surfactant.
In the embodiment, three different injection modes and the same mass of HP-Y and 1831 components are adopted, and the influence rule of the three injection modes of firstly polymerizing and then surface injecting, firstly polymerizing and then polymerizing injecting and alternately polymerizing surface injecting on the interaction of the hydrophobic association polymer and the surfactant in the porous medium is examined.
Three pressure measurement point flat plate sand inclusion object mold injection experiment steps:
(1) selecting 160-180-mesh quartz sand to fill a flat plate sand inclusion model, connecting and debugging an instrument, and filling each working solution into a high-precision injection pump for later use;
(2) saturating the filled flat plate sand inclusion model with 5000mg/L NaCl salt water, measuring the wet weight of the saturated flat plate sand inclusion model after 2 hours of saturation, and determining the Pore Volume (PV) and the porosity of the model;
(3) injecting 4PV 5000mg/L NaCl saline, and measuring the water permeability K of the object model;
(4) injecting a composite oil displacement agent with certain pore volume into the flat sand inclusion model at a certain injection speed under the condition of a constant-temperature oven at 45 ℃ by adopting a certain injection mode (see table 1), detecting pressure values of three pressure measurement points, and stopping injection when the pressure is basically kept unchanged.
Table 1 experimental protocol table for different injection modes
As can be seen from FIG. 9, after the injection of 0.5PV 1200mg/L HP-Y displacement agent, the pressure values of the three pressure measurement points show a trend of increasing and then decreasing with the beginning of the injection of 2PV 100 mg/L1831 displacement agent, and when 1PV 100 mg/L1831 displacement agent is injected, pressure peaks respectively appear at pressure measurement points 1, 2 and 3, which are respectively about 460, 359 and 278 kPa. The pressure values of the three pressure measuring points in the subsequent water drive process show a slow descending and stable trend, and when the subsequent water drive 2.5PV 5000mg/L NaCl brine is used, the pressure values of the pressure measuring points 1, 2 and 3 are stabilized at about 225 kPa, 176 kPa and 138kPa, which are far higher than the pressure values corresponding to the early water drive stage. The results of the experiment in FIG. 9 show that: the HP-Y and 1831 slugs injected respectively have obvious diffusion mixing effect in the porous medium, so that the viscosity of the oil displacement agent is increased, and the injection pressure is continuously increased. Most oil displacement agents are displaced out of the flat sand inclusion model in the subsequent water flooding process, part of the oil displacement agent adsorption retention amount is still in the model, the pressure values of the three pressure measurement points are shown as the process of slowly descending and tending to be stable, and the final pressure is still higher than the early water flooding stage.
As can be seen from FIG. 10, when the 2PV 100 mg/L1831 oil-displacing agent is injected first and then the 0.5PV 1200mg/L HP-Y oil-displacing agent is injected, the pressure values of the three pressure measurement points show a gradually increasing trend; however, when 1PV 5000mg/L NaCl saline is injected, pressure peaks respectively appear at pressure measuring points 1, 2 and 3, and are about 363 kPa, 296 kPa and 209kPa respectively; with further injection of the NaCl brine with the concentration of 5000mg/L, the pressure values of the three pressure measuring points gradually decrease and tend to a stable trend; when 1.5PV 5000mg/L NaCl brine is injected subsequently, the pressure values of the pressure measuring points 1, 2 and 3 are stabilized at about 157 kPa, 130 kPa and 87kPa and are still higher than the pressure values corresponding to the early water flooding stage. The analysis compared with fig. 9 can find that: compared with the injection mode of polymerization before the table in fig. 9, when the injection mode of polymerization before the table in fig. 10 is adopted, the degree of diffusion and mixing effects of the HP-Y and 1831 oil displacement agents in the porous medium is poor, so that the viscosity and injection pressure peak value of the oil displacement agent are obviously reduced, the PV number corresponding to the peak value is delayed, and the adsorption retention amount in the water displacement stage is also small. This is because the low viscosity fluid (1831 displacement agent) displaces the high viscosity fluid (HP-Y displacement agent) more easily by the phenomenon of "viscous fingering" which favours diffusive mixing of the two slugs with each other.
As can be seen from FIG. 11, after 5 consecutive injections of 0.1PV 1200mg/L HP-Y oil-displacing agent and 0.4PV 100 mg/L1831 oil-displacing agent, the pressure values at the three pressure measurement points showed a slow increase trend with the subsequent injection of 4PV 5000mg/L NaCl brine. The results of the experiment in FIG. 11 show that: in the process of alternately injecting two oil displacement agents for multiple times, the diffusion mixing action between different slugs is stronger and more durable, and the oil displacement agent keeps higher pressure in a wider range, so that the pressure measuring points 1, 2 and 3 continuously have higher pressure values in the subsequent water flooding process.
The above experimental results demonstrate that the interaction of the HP-Y and 1831 components in the porous medium is different under different injection modes: under the condition of alternate injection, the diffusion mixing action among the slugs is a main factor for controlling the fluidity of the oil displacement agent; injecting the high-viscosity fluid first and then injecting the low-viscosity fluid and increasing the alternate injection turns are favorable for realizing the full diffusion mixing action between the slugs and also for increasing the adsorption retention of the oil displacement agent.
Example 4 oil displacement experiment of the composite oil displacement agent.
The invention adopts a physical simulation displacement experiment to evaluate the effects of different oil displacement methods, and the specific evaluation method comprises the following steps:
(1) drying a homogeneous artificial rock core (with the diameter of 3.8cm and the length of 30cm) to constant weight at constant temperature in a constant-temperature oven at 45 ℃, and measuring the gas logging permeability of the rock core;
(2) calculating the pore volume of a saturated core by using 5000mg/L NaCl brine, recording the volume of the saturated crude oil by using a saturated core of crude oil (prepared from degassed crude oil and diesel oil and having the viscosity of 150mPa & s) at the oil displacement temperature,
(3) pumping 5000mg/L NaCl salt water at the speed of 0.2ml/min until the water content reaches 98%, calculating the water drive to improve the recovery ratio of crude oil,
(4) the oil displacement agent is injected according to the oil displacement method (1) or the oil displacement method (2) at the speed of 0.2ml/min (the experimental scheme is shown in the table 2),
(5) and (3) flooding the NaCl with the speed of 0.2ml/min of 5000mg/L to the water content of more than 99 percent by using the saline, and calculating the percentage for improving the crude oil recovery ratio on the basis of water flooding.
And (3) interfacial tension test: TX500C interfacial tension meter, rotating speed 5000r/min, density difference 0.1 (g/cm)3) The temperature is 45 ℃, the experimental water is 5000mg/L NaCl brine, the experimental crude oil is simulated formation crude oil prepared from degassed crude oil and diesel oil, and the viscosity is 150mPa & s;
table 2 oil displacement experimental results of different oil displacement agents
From the results of the oil displacement experiments of the four oil displacement agents in table 2, it can be seen that: when a hydrophobic association polymer HP-Y slug (1200mg/L HP-Y with the initial viscosity of 26.8mPa & s and the oil/water interfacial tension of 11.31mN/m) is injected alone, the recovery ratio is improved by 16.3 percent compared with that of water flooding; injecting a conventional binary composite flooding slug (1200mg/L HP-Y/3000mg/L petroleum sulfonate composite oil displacement agent with the initial viscosity of 27.2mPa & s and the oil/water interfacial tension of 7.61 multiplied by 10)-3mN/m), the recovery ratio is increased by 26.3 percent compared with that of water flooding and by 10.1 percent compared with that of polymer flooding; when the two oil-displacing agent components (0.15PV 1200mg/L HP-Y and 0.15PV 100 mg/L1831 oil-displacing agent are injected alternately for four times) are injected alternately for multiple times, the recovery ratio is increased by 29.8% compared with that of water drive and 13.5% compared with that of polymer drive. In addition, from the state of the produced fluid in an oil displacement experiment, the produced fluid emulsification phenomenon is the most serious when the conventional binary composite flooding slug is injected, the produced fluid emulsification is the weakest when the hydrophobic association polymer HP-Y slug is injected alone, and the produced fluid emulsification degree is between the two when the oil displacement agent optimized by the invention is injected.
Claims (4)
1. The alternate injection oil displacement method of the compound oil displacement agent containing the hydrophobic association polymer and the surfactant is characterized in that the formula of the compound oil displacement agent is hydrophobic modified polyacrylamide HMPAM, the surfactant or the composition thereof and water;
in the composite oil displacement agent, the content of HMPAM is higher than the critical association concentration CAC, and the content of HMPAM is 0.05-0.5%;
the molecular structure of the HMPAM comprises an acrylamide monomer unit, at least one amphiphilic unsaturated hydrophobic monomer unit and at least one ethylenically unsaturated functional monomer unit, and the charges of the hydrophobic monomer unit and the functional monomer unit are the same;
the surfactant is cationic surfactant octadecyl trimethyl ammonium chloride 1831; the screening and optimizing method of the surfactant or the composition thereof is that under the conditions that the determined oil reservoir temperature, the mineralization degree of preparation water and the concentration of the fixed hydrophobic association polymer are higher than CAC, the viscosity of the composite oil displacement agent is increased and then reduced along with the increase of the concentration of the surfactant, after a certain specific concentration is exceeded, the viscosity of the composite oil displacement agent is gradually reduced and finally maintained at a lower viscosity, wherein the specific concentration is the required concentration of the surfactant;
the oil displacement method of the composite oil displacement agent is a multi-round alternate injection method, the hydrophobic association polymer oil displacement agent and the surfactant oil displacement agent are sequentially injected into an oil-bearing stratum in a multi-round alternate mode under the conditions that the oil reservoir temperature is 20-100 ℃ and the total mineralization is more than 500mg/L of oil field stratum water, and crude oil in the oil-bearing stratum is displaced;
the oil displacement method for alternately injecting the hydrophobic association polymer and the surfactant for multiple rounds is characterized in that in a diffusion mixing area in which a polymer slug and a surfactant slug are contacted with each other in the oil displacement process, the concentration ratio of the polymer to the surfactant is gradually changed, so that the viscosity of the composite oil displacement agent is gradually increased, the effective permeability of the composite oil displacement agent is reduced, and the fluidity ratio of the oil displacement agent to crude oil is improved; in the oil displacement process, the mobility change amplitude and the specific stratum position generating mobility mutation caused by alternate injection in each round are optimally designed according to the oil reservoir conditions; the hydrophobic association polymer slug and the surfactant slug are 0.01PV-0.5PV, the total injection amount of the oil displacement agent injected alternately in multiple rounds is 0.1PV-1.0PV, and 1-50 rounds are injected together.
2. The alternate injection oil displacement method of the composite oil displacement agent containing the hydrophobic association polymer and the surfactant according to claim 1, characterized in that the amphiphilic unsaturated hydrophobic monomer is selected from alkyl dimethyl allyl ammonium chloride, N-alkyl substituted acrylamide or alkyl methacrylate, 2-acrylamido alkyl sulfonic acid and sodium salt thereof, wherein the number of carbon atoms in an alkyl chain is 8-22; the ethylenically unsaturated functional monomer is selected from acrylic acid, sodium acrylate salt, 2-acrylamido-2-methylpropanesulfonic acid AMPS, 2-acrylamido-2-methylpropanesulfonic acid sodium salt or methacryloyloxyethyl trimethyl ammonium chloride;
in the HMPAM, an acrylamide monomer unit, a hydrophobic monomer unit and an ethylenically unsaturated functional monomer unit are 60-80 parts, 1-5 parts and 39-15 parts in sequence by weight.
3. The alternate injection flooding method of the composite oil displacement agent containing the hydrophobically associative polymer and the surfactant according to claim 2, wherein the HMPAM has an anionic hydrophobic monomer and an anionic functional monomer or a cationic hydrophobic monomer and a cationic functional monomer.
4. The alternate injection oil displacement method of the composite oil displacement agent containing the hydrophobically associating polymer and the surfactant as claimed in claim 1, wherein the prepared water is deionized water or water containing minerals, wherein the water containing minerals is selected from tap water, river water and oil field formation water, and the total mineralization is 0-50000 mg/l.
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