CN111087995B - Low-tension polymer microemulsion, profile control and flooding system, preparation method and application thereof - Google Patents
Low-tension polymer microemulsion, profile control and flooding system, preparation method and application thereof Download PDFInfo
- Publication number
- CN111087995B CN111087995B CN201811234932.7A CN201811234932A CN111087995B CN 111087995 B CN111087995 B CN 111087995B CN 201811234932 A CN201811234932 A CN 201811234932A CN 111087995 B CN111087995 B CN 111087995B
- Authority
- CN
- China
- Prior art keywords
- oil
- polymer
- microemulsion
- water
- profile control
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/504—Compositions based on water or polar solvents
- C09K8/506—Compositions based on water or polar solvents containing organic compounds
- C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/512—Compositions based on water or polar solvents containing organic compounds macromolecular compounds containing cross-linking agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/334—Polymers modified by chemical after-treatment with organic compounds containing sulfur
- C08G65/3344—Polymers modified by chemical after-treatment with organic compounds containing sulfur containing oxygen in addition to sulfur
- C08G65/3346—Polymers modified by chemical after-treatment with organic compounds containing sulfur containing oxygen in addition to sulfur having sulfur bound to carbon and oxygen
-
- 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
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/504—Compositions based on water or polar solvents
- C09K8/506—Compositions based on water or polar solvents containing organic compounds
- C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/5083—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/504—Compositions based on water or polar solvents
- C09K8/506—Compositions based on water or polar solvents containing organic compounds
- C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/5086—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
Abstract
The invention relates to a low-tension polymer microemulsion, a profile control and flooding system, a preparation method and application thereof, and mainly solves the problems of large dosage of conventional emulsifier for inverse microemulsion polymerization and no oil washing effect in the prior art. The invention adopts a polymer microemulsion which comprises an oil-soluble solvent, water, an emulsifier and polymer microspheres; wherein the oil-soluble solvent is a continuous phase, the water is a dispersed phase, and the emulsifier comprises a fatty alcohol-polyoxyethylene ether sulfonate surfactant shown in a structure of formula (1): wherein R is C 10 ～C 25 N =1 to 24, M is selected from H, alkali metal or NH 4 The technical scheme of the method well solves the problem, and the system can be used as an oil displacement agent and a deep water plugging profile control agent to be applied to tertiary oil recovery in an oil field to improve the crude oil recovery rate. RO (CH) 2 CH 2 O) n CH 2 CH 2 SO 3 M……………(1)。
Description
Technical Field
The invention relates to a low-tension polymer microemulsion, a profile control and flooding system, a preparation method and application thereof.
Background
The water content of crude oil is continuously increased after primary and secondary oil extraction in various domestic oil fields, and part of the large oil fields sequentially enter a tertiary oil extraction stage. The polymer flooding is a main technical method for tertiary oil recovery, the oil displacement mechanism is clear, the process is relatively simple, the technology is mature day by day, and the polymer flooding oil recovery method is an effective technical measure for improving the oil recovery rate. However, in the case of a heterogeneous formation, displacement can only act on a high permeable layer and cannot reach an oil-containing low permeable layer, so that the recovery rate of crude oil is reduced, and the cost is increased. Generally, a water injection well profile control and production well water plugging technology is adopted for a heterogeneous stratum, but the effective range of the technology is limited to a near-wellbore zone, the technology cannot reach deep parts of an oil well, and the purpose of greatly improving the crude oil recovery rate cannot be achieved.
The nanometer-sized cross-linked polymer microsphere is used as a step-by-step deep profile control and displacement material for developing oil reservoirs by water injection, and the use principle of the nanometer-sized cross-linked polymer microsphere is that the nanometer-sized polymer microsphere is utilized, the initial size of the nanometer-sized polymer microsphere is far smaller than the pore throat size of a stratum, the nanometer-sized polymer microsphere can smoothly enter the deep part of the stratum along with injected water and continuously moves forwards in the stratum, and after water absorption and gradual expansion, plugging is formed at the pore throat of a water seepage channel to cause liquid flow redirection, so that the purposes of expanding water waves and volume and improving the crude oil recovery rate are achieved.
In general, reverse microemulsion polymerization tends to use surfactants in mass fractions greater than 10%, and the addition of these surfactants leads to a substantial increase in production costs. How to fully utilize the surface active agent can make the surface active agent play a role not only in the preparation process but also in the application aspect, such as the deep profile control process. Most of the conventional emulsifiers are lipophilic surfactants Span (sorbitan fatty acid ester) or a compound of Span and hydrophilic surfactants Tween (polyoxyethylene sorbitan fatty acid ester) and OP (polyoxyethylene alkylphenol ether), and the used amount of Span accounts for most of the emulsifiers. However, the oil-water interfacial activity is deteriorated due to the lipophilicity of Span, and the oil displacement effect is greatly reduced after the oil-water interfacial activity is prepared into an aqueous solution together with microspheres and injected underground; OP type surfactants have recently been limited in their use in most countries and regions due to their toxicity to aquatic organisms and irritation to the skin, teratogenicity, and poor biodegradability. Therefore, a stable and transparent reverse microemulsion system which can replace or partially replace the conventional surfactant is sought for preparing, so that the microemulsion system for profile control and flooding, which has good interfacial activity and good water shutoff and profile control effects, namely has dual effects of oil displacement and profile control, is significant and profound.
Disclosure of Invention
One of the technical problems to be solved by the invention is the problem that the conventional emulsifier for inverse microemulsion polymerization in the prior art is large in dosage and has no oil washing effect, and provides a novel polymer microemulsion adopting the fatty alcohol-polyoxyethylene ether sulfonate composite emulsifier.
The second technical problem to be solved by the invention is to provide a polymer micro-emulsion profile control and flooding agent which adopts the fatty alcohol-polyoxyethylene ether sulfonate composite emulsifier and corresponds to the first technical problem.
The third technical problem to be solved by the invention is to provide a preparation method of the polymer micro-emulsion profile control and flooding agent adopting the fatty alcohol-polyoxyethylene ether sulfonate composite emulsifier, which corresponds to the second technical problem to be solved
The fourth technical problem to be solved by the invention is to provide the application of the polymer micro-emulsion profile control agent adopting the fatty alcohol-polyoxyethylene ether sulfonate composite emulsifier in oil reservoir profile control and flooding, which corresponds to the solution of the second technical problem.
In order to solve one of the above technical problems, the technical solution of the present invention is as follows: a polymer microemulsion, comprising an oil-soluble solvent, water, an emulsifier and polymer microspheres; wherein the oil-soluble solvent is a continuous phase, the water is a dispersed phase, and the emulsifier comprises fatty alcohol polyoxyethylene ether sulfonate surfactant shown in a structure of formula (1):
RO(CH 2 CH 2 O) n CH 2 CH 2 SO 3 m, formula (1);
wherein R is C 10 ～C 25 N =1 to 24, M is selected from H, alkali metal or NH 4 . R is more preferably C 12 ～C 18 N is preferably 4 to 16, and the alkali metal is preferably potassium, sodium or lithium.
In the above technical solution, it is preferable that: in the microemulsion, the microemulsion contains 22-68 wt% of the oil-soluble solvent, 13-28 wt% of water, 4-13 wt% of the emulsifier and 15-45 wt% of the polymer microspheres in percentage by mass of the total microemulsion.
In the technical scheme, the polymer microsphere preferably contains an acrylamide monomer unit and a temperature-resistant and salt-resistant monomer unit; the mass ratio of the acrylamide monomer unit to the temperature-resistant and salt-resistant monomer unit is preferably (10-70) to (0.5-20); more preferably, the temperature-resistant and salt-resistant monomer is at least one selected from N-vinyl pyrrolidone, N-dimethylacrylamide, acrylamide-N-dodecyl sulfonic acid or/and a salt thereof, N-phenyl maleimide, dodecyl (meth) acrylate, styrene, p-tert-butyl styrene, 2-acrylamido-2-methylpropane sulfonic acid and/or an alkali metal salt or ammonium salt thereof, and 2-acrylamido-2-methylpropyl trimethyl ammonium halide.
In the above technical scheme, the polymer microsphere preferably contains a cross-linking agent unit; further preferably: the content of the cross-linking agent unit is preferably 0.1-1.0% in terms of the total mass percentage of the polymer microsphere; more preferably: the crosslinking agent is preferably at least one selected from divinylbenzene, pentaerythritol triacrylate, N' -m-phenylene bismaleimide, and methylenebisacrylamide.
In the above technical scheme, the emulsifier preferably includes any one of a combination of a fatty alcohol-polyoxyethylene ether sulfonate surfactant represented by the structure of formula (1) and a conventional surfactant, wherein the mass ratio of the fatty alcohol-polyoxyethylene ether sulfonate surfactant to the conventional surfactant is 1; more preferably, the conventional surfactant is one or more selected from sorbitan fatty acid esters and polyoxyethylene sorbitan fatty acid esters.
In the above technical solution, the oil-soluble solvent is preferably at least one selected from hydrocarbons or esters; the further preferable scheme is as follows: the hydrocarbon is preferably aliphatic hydrocarbon or/and aromatic hydrocarbon, and the aliphatic hydrocarbon is more preferably C 4 ～C 8 Aliphatic hydrocarbons such as cyclohexane, hexane, heptane, octane, isooctane and the like; the aromatic hydrocarbon is more preferably C 6 ～C 10 Aromatic hydrocarbons of (2), e.g. benzene, toluene, xylene, trimethylbenzene, ethylbenzene, diethylbenzene, isopropylbenzene, etcAnd the hydrocarbon can also be preferably petroleum fractions, such as white oil, liquid paraffin, gasoline, kerosene, diesel oil, petroleum ether and the like; the ester is preferably a carboxylic acid ester, and may be more preferably C 4 ～C 8 Monoesters of (A) and (B), for example, ethyl acetate, propyl acetate and the like, and further more preferably C 4 ～C 10 And diesters of (a) such as dimethyl oxalate, diethyl oxalate, ethyl methyl oxalate and the like, and also more preferably vegetable oils selected from peanut oil, soybean oil, sunflower seed oil and castor oil.
In the technical scheme, the polymer microemulsion is preferably prepared by polymerizing reverse microemulsion under the action of a redox composite initiator; the reverse microemulsion comprises the following components in parts by weight:
a) 50 parts of the oil-soluble solvent;
b) 3-30 parts of the emulsifier;
c) 10-70 parts of acrylamide monomer;
d) 0.5-20 parts of the temperature-resistant and salt-resistant monomer;
e) 10-60 parts of water; and preferably: 0.1 to 1.0 percent of cross-linking agent in percentage by mass of the total monomers;
as a preferable scheme, the redox composite initiator preferably comprises the following components in percentage by weight of all the monomers:
(a) 0.02 to 1.0 percent of oxidant;
(b) 0.02-2.0% of reducing agent;
(c) 0.1-10% of urea and thiourea;
(d) 0.01 to 0.5 percent of complexone;
as a more preferable mode: the oxidizing agent is preferably selected from potassium persulfate, sodium persulfate, ammonium persulfate or benzoyl peroxide, the reducing agent is preferably selected from at least one of sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium thiosulfate or ferrous chloride, and the complexone is selected from ethylenediaminetetraacetic acid and alkali metal salts thereof, diethylenetriaminepentaacetic acid and alkali metal salts thereof.
In the above technical scheme, the emulsifier may further comprise a co-emulsifier. The coemulsifier can be small molecular alcohol or salt. The small molecular alcohol is preferably C 3 ～C 12 Such as isopropanol, tert-butanol, n-pentanol and the like. The salts are preferably water-soluble inorganic salts or organic acid salts. The inorganic salt is preferably an alkali metal salt (e.g., sodium chloride, potassium chloride), an alkali metal sulfate (e.g., sodium sulfate, potassium sulfate); the organic acid salt is preferably an alkali metal organic acid salt, more preferably C 2 ～C 6 Alkali metal salts of carboxylic acids, for example potassium acetate or sodium acetate. The content of the co-emulsifier is preferably 3 to 20wt% of the nonionic surfactant in the emulsifier.
In the technical scheme, the preparation method of the fatty alcohol-polyoxyethylene ether sulfonate surfactant shown in the structure of the formula (1) comprises the following steps:
(a) Synthetic reaction of sodium alcohol ether
Adding fatty alcohol-polyoxyethylene ether and sodium hydroxide in a certain molar ratio into a 500mL four-neck flask connected with a water separator and a condenser pipe, adding a certain amount of cyclohexane, stirring and heating to 80-100 ℃ in an oil bath, and removing water generated by the reaction by utilizing azeotropic distillation. After the reaction was completed, the residual cyclohexane in the reaction flask was removed.
(b) Sulfonation reaction
Transferring the sodium alcohol ether to a constant-pressure titration funnel, adding a certain amount of toluene and 2-chloroethyl sodium sulfonate (controlling the molar ratio of the 2-chloroethyl sodium sulfonate to the sodium alcohol ether to be 1.0-1.5) into a reaction bottle, heating, dropwise adding the sodium alcohol ether, and reacting for 2-8 hours to obtain a crude product. Removing toluene in the crude product by rotary evaporation, adding absolute ethyl alcohol, refluxing at 80 ℃ for 20 minutes, carrying out suction filtration while the crude product is hot, and removing inorganic salts, excessive sodium chloroethyl sulfonate and a small amount of sample mixture. And cooling and crystallizing the filtrate, recrystallizing for 3 times by using absolute ethyl alcohol, and drying in vacuum at the temperature of 80 ℃ to obtain the refined fatty alcohol-polyoxyethylene ether sulfonate surfactant. And (3) measuring the total mass fraction of the anionic surfactant in the product by using methylene blue as an indicator through a two-phase titration method, thereby calculating the purity and yield of the product.
In order to solve the second technical problem, the invention adopts the following technical scheme: a polymer microemulsion profile control agent, comprising the polymer microemulsion according to any one of the above technical solutions to solve the technical problems.
In order to solve the third technical problem, the invention adopts the following technical scheme: the preparation method of the polymer microemulsion profile control agent comprises the following steps:
(a) Preparing an oil phase: dissolving the emulsifier in an oil-soluble solvent, and uniformly stirring to obtain an oil phase I; dissolving optional oil-soluble temperature-resistant salt-resistant monomers, oil-soluble oxidants and oil-soluble cross-linking agents in an oil-soluble solvent, and uniformly stirring to obtain an oil phase II;
(b) Preparing a water phase: uniformly mixing water-soluble components in acrylamide, optional water-soluble temperature-resistant salt-resistant monomer, redox composite initiator except reducer and water to obtain water phase;
(c) And uniformly mixing the oil phase I, the water phase and the optional oil phase II, adding a reducing agent, and reacting to obtain the polymer microemulsion profile control and flooding agent.
In the above technical solution, as a preferred solution: the reaction temperature is preferably 40 to 80 ℃, the reaction time is preferably 1 to 8 hours, and the reducing agent is preferably added in the form of an aqueous solution.
More preferably, the step (c) is as follows:
(c) Adding the oil phase I into a reactor, adding the oil phase II and the water phase, uniformly stirring, dropwise adding a reducing agent aqueous solution, and reacting for 3-6 hours at 50-60 ℃.
To solve the fourth technical problem, the technical scheme of the invention is as follows: the polymer micro-emulsion profile control agent adopting the fatty alcohol-polyoxyethylene ether sulfonate composite emulsifier is applied to oil reservoir profile control and flooding in any one of the two technical schemes for solving the technical problems.
In the above technical scheme, the polymer microemulsion profile control and flooding system using the fatty alcohol-polyoxyethylene ether sulfonate complex emulsifier can be directly diluted with water to form an aqueous solution with a desired concentration, and can be applied to tertiary oil recovery in an oil field, or can be used in combination with other oil recovery agents, and has no special requirements on oil reservoir conditions, such as but not limited to a high-temperature and high-salinity oil reservoir.
The key point of the method is that the fatty alcohol-polyoxyethylene ether sulfonate surfactant with excellent temperature resistance and salt resistance is added, so that the interfacial activity of a system can be enhanced, and the method has double effects of water plugging and profile control and oil displacement, and achieves the effect of one agent with multiple effects. The low-tension micro-emulsion profile control and flooding system is directly diluted into an aqueous solution with required concentration by water, and can meet the field operation requirement of improving the recovery ratio when being applied to tertiary oil recovery of an oil field as an oil displacement agent and a deep water plugging profile control agent.
By adopting the technical scheme of the invention, the interfacial tension (total salinity of brine 180000mg/L, concentration of calcium and magnesium ions 5000mg/L and measurement temperature: 90 ℃) between the obtained polymer microemulsion profile control and displacement agent and Pucheng 2+3 block dehydrated crude oil can reach 10 DEG C -3 mN/m or less; the particle size of the microsphere is calculated after the salt with the total mineralization degree of 180000mg/L (the concentration of calcium and magnesium ions is 5000 mg/L) is placed under water for 1 day, 7 days, 15 days and 30 days at the temperature of 90 ℃ under the anaerobic condition, the expansion multiple of the microsphere is good, the slow expansion effect is achieved, the state of the obtained microemulsion system is very stable after standing for 3 months, no layering is caused, and good technical effect is achieved.
The invention is further illustrated by the following specific examples.
Detailed Description
[ example 1 ]
1. Preparation of sodium fatty alcohol polyoxyethylene (5) ether sulfonate surfactant:
(a) Synthetic reaction of sodium alcohol ether
100g of fatty alcohol polyoxyethylene (5) ether (AEO-5) and 10g of sodium hydroxide were put into a 500mL four-neck flask connected with a water separator and a condenser, and 120mL of cyclohexane was added thereto, and the mixture was stirred in an oil bath and heated to 90 ℃ to remove water produced by the reaction by azeotropic distillation. After the reaction was completed, the residual cyclohexane in the reaction flask was removed.
(b) Sulfonation reaction
And (3) transferring the sodium alcohol ether into a constant pressure titration funnel, adding 120mL of toluene and 55g of 2-chloroethyl sodium sulfonate (the molar ratio of the 2-chloroethyl sodium sulfonate to the sodium alcohol ether is 1.2) into a reaction bottle, heating to 65 ℃, dropwise adding the sodium alcohol ether, and reacting for 5 hours to obtain a crude product. The toluene in the crude product was removed by rotary evaporation, 150mL of anhydrous ethanol was added, reflux was carried out at 80 ℃ for 20 minutes, and suction filtration was carried out while hot to remove inorganic salts, excess sodium chloroethyl sulfonate and a small amount of the sample mixture. Cooling and crystallizing the filtrate, recrystallizing for 3 times by using absolute ethyl alcohol, and drying in vacuum at the temperature of 80 ℃ to obtain the refined fatty alcohol polyoxyethylene (5) ether sodium sulfonate surfactant. The following are obtained by calculation: the product purity was 90.5% and the yield was 78.6%.
2. Preparing a low-tension polymer micro-emulsion profile control and flooding system:
(a) Preparing an oil phase: dissolving an emulsifier consisting of 15g of fatty alcohol polyoxyethylene (5) ether sodium sulfonate, 12g of span60 and 3g of Tween80 in 80g of white oil, and uniformly stirring to obtain an oil phase I; 5g of 2-acrylamide-N-hexadecyl sodium sulfonate is dissolved in 20g of white oil and stirred uniformly to obtain an oil phase II.
(b) Preparing a water phase: dissolving 50g of acrylamide, 20g of 2-acrylamido-2-methylpropanesulfonic acid sodium salt, 10gN, N-dimethylacrylamide, 0.5g of ammonium persulfate, 0.6gN, N' -methylenebisacrylamide, 5g of urea, 0.2g of ethylene diamine tetraacetic acid disodium and 0.5g of isopropanol in 80g of water, and uniformly stirring to obtain a water phase; 0.6g of sodium bisulfite was dissolved in 10g of water to form an aqueous reducing agent solution.
(c) And adding the oil phase I into a reactor, adding the oil phase II and the water phase, uniformly stirring, dropwise adding a reducing agent aqueous solution, and reacting at 60 ℃ for 4 hours to obtain the low-tension polymer micro-emulsion profile control and flooding system.
3. Characterization of the polymer micro-emulsion profile control and flooding system and the polymer microspheres therein:
the polymer micro-emulsion profile control system is directly diluted into 0.3wt% aqueous solution by saline water and is stirred uniformly. The interfacial tension between the polymer microemulsion profile control system and Pucheng 2+3 block of dehydrated crude oil (total salinity of brine 180000mg/L, concentration of calcium and magnesium ions 5000mg/L, measurement temperature: 90 ℃) was measured using a TX500 rotary drop interfacial tensiometer, produced by Texas university, USA.
Testing the initial particle size of the microspheres of the polymer microemulsion profile control and flooding system by using a Nano ZS type nanometer particle size analyzer produced by British Markov instruments; the particle size of the microspheres after standing for 1 day, 7 days, 15 days, 30 days at 90 ℃ under oxygen-free condition with total salinity of 180000mg/L (calcium magnesium ion concentration of 5000 mg/L), the expansion times of the microspheres were calculated, and the state of the obtained microemulsion system after standing for 3 months was observed, and the results are shown in Table 1.
[ example 2 ]
The preparation of the fatty alcohol polyoxyethylene (5) ether sodium sulfonate surfactant and the preparation process of the low-tension polymer micro-emulsion profile control system are the same as in example 1, except that the dosages of the emulsifiers of the fatty alcohol polyoxyethylene (5) ether sodium sulfonate and the Tween80 are respectively changed into 8g and 10g. The polymer microemulsion profile control and flooding system and the characterization method of the polymer microspheres in the polymer microemulsion profile control and flooding system are the same as in example 1, and the results are shown in table 1.
[ example 3 ]
The preparation of the fatty alcohol polyoxyethylene (5) ether sodium sulfonate surfactant and the preparation process of the low-tension polymer micro-emulsion profile control system are the same as in example 1, except that the dosages of the emulsifiers of the fatty alcohol polyoxyethylene (5) ether sodium sulfonate and the Tween80 are respectively changed into 10g and 8g. The polymer microemulsion profile control and flooding system and the characterization method of the polymer microspheres in the polymer microemulsion profile control and flooding system are the same as in example 1, and the results are shown in table 1.
[ COMPARATIVE EXAMPLE 1 ]
The preparation process of the low-tension polymer micro-emulsion profile control and flooding system is the same as example 1, except that the emulsifier consisting of the sodium fatty alcohol polyoxyethylene (5) ether sulfonate, the Span60 and the Tween80 is changed into the emulsifier consisting of the Span60 and the Tween80 with the same HLB value. The polymer microemulsion profile control and flooding system and the characterization method of the polymer microspheres in the polymer microemulsion profile control and flooding system are the same as in example 1, and the results are shown in table 1.
The inventor discovers that the low-tension polymer microemulsion profile control system prepared by compounding the fatty alcohol-polyoxyethylene ether sodium sulfonate surfactant and the conventional surfactant has better interfacial activity, and when the low-tension polymer microemulsion profile control system is applied to field application for improving the recovery ratio, the low-tension polymer microemulsion profile control system can play a role in improving the oil washing efficiency and finally improving the recovery ratio. This is visualized by the interfacial tension data of examples 1-3 and comparative example 1.
[ example 4 ]
1. Preparation of sodium fatty alcohol polyoxyethylene (9) ether sulfonate surfactant:
(a) Synthetic reaction of sodium alcohol ether
100g of fatty alcohol-polyoxyethylene (9) ether (AEO-9) and 7g of sodium hydroxide were put into a 500mL four-necked flask equipped with a water separator and a condenser, and 120mL of cyclohexane was added thereto, and the mixture was heated to 100 ℃ with stirring in an oil bath, and water produced by the reaction was removed by azeotropic distillation. After the reaction was completed, the residual cyclohexane in the reaction flask was removed.
(b) Sulfonation reaction
And (3) transferring the sodium alcohol ether to a constant pressure titration funnel, adding 120mL of toluene and 48g of 2-chloroethyl sodium sulfonate (the molar ratio of the 2-chloroethyl sodium sulfonate to the sodium alcohol ether is 1.5) into a reaction bottle, heating to 70 ℃, dropwise adding the sodium alcohol ether, and reacting for 4 hours to obtain a crude product. Removing toluene in the crude product by rotary evaporation, adding 150mL of absolute ethyl alcohol, refluxing for 20 minutes at 80 ℃, and performing suction filtration while the crude product is hot to remove inorganic salts, excessive sodium chloroethyl sulfonate and a small amount of sample mixture. Cooling and crystallizing the filtrate, recrystallizing for 3 times by using absolute ethyl alcohol, and drying in vacuum at the temperature of 80 ℃ to obtain the refined fatty alcohol polyoxyethylene (9) ether sodium sulfonate surfactant. The calculation results are that: the product purity was 89.7% and yield 76.8%.
2. Preparing a low-tension polymer micro-emulsion profile control and flooding system:
(a) Preparing an oil phase: dissolving an emulsifier consisting of 15g of fatty alcohol polyoxyethylene (9) ether sodium sulfonate, 7g of span80 and 4g of Tween60 in 80g of white oil, and uniformly stirring to obtain an oil phase I; 10g of stearyl methacrylate is dissolved in 20g of white oil and stirred uniformly to obtain an oil phase II.
(b) Preparing a water phase: dissolving 60g of acrylamide, 20g of 2-acrylamido-2-methylpropyl trimethyl ammonium chloride, 0.5g of ammonium persulfate, 0.6g of N, N' -methylene bisacrylamide, 5g of urea, 0.2g of disodium ethylene diamine tetraacetate and 0.5g of isopropanol in 80g of water, and uniformly stirring to obtain a water phase; 0.6g of sodium hydrogen sulfite was dissolved in 10g of water to form an aqueous reducing agent solution.
(c) Adding the oil phase I into a reactor, adding the oil phase II and the water phase, uniformly stirring, dropwise adding a reducing agent aqueous solution, and reacting at 50 ℃ for 6 hours to obtain the low-tension polymer microemulsion profile control and flooding system.
3. The characteristics of the polymer micro-emulsion profile control and displacement system and the polymer microspheres in the system are the same as example 1, and the results are shown in table 1.
[ example 5 ] A method for producing a polycarbonate
The preparation of the fatty alcohol polyoxyethylene (9) ether sodium sulfonate surfactant and the preparation process of the low-tension polymer micro-emulsion profile control system are the same as in example 4, except that the dosages of the emulsifiers of the fatty alcohol polyoxyethylene (9) ether sodium sulfonate and the Tween60 are respectively changed into 12g and 7g. The polymer microemulsion profile control and flooding system and the characterization method of the polymer microspheres in the polymer microemulsion profile control and flooding system are the same as in example 1, and the results are shown in table 1.
[ example 6 ]
The preparation of the fatty alcohol polyoxyethylene (9) ether sodium sulfonate surfactant and the preparation process of the low-tension polymer micro-emulsion profile control system are the same as in example 4, except that the dosages of the emulsifiers fatty alcohol polyoxyethylene (9) ether sodium sulfonate and Tween60 are respectively changed into 7g and 12g. The polymer micro-emulsion profile control and displacement system and the characterization method of the polymer microspheres in the system are the same as in example 1, and the results are shown in table 1.
[ COMPARATIVE EXAMPLE 2 ]
The preparation of the sodium fatty alcohol polyoxyethylene (9) ether sulfonate surfactant and the preparation of the low-tension polymer microemulsion profile control system are the same as in example 4, except that 10g of stearyl methacrylate and 20g of 2-acrylamido-2-methylpropyl trimethyl ammonium chloride are all changed into 30g of acrylamide and dissolved in the water phase. The polymer microemulsion profile control and flooding system and the characterization method of the polymer microspheres in the polymer microemulsion profile control and flooding system are the same as in example 1, and the results are shown in table 1.
The inventor of the invention finds that the low-tension micro-emulsion profile control and flooding system prepared by selecting a proper comonomer can well solve the problems of poor expansibility and poor long-term blocking effect of the polymer microsphere in the prior art under the conditions of high temperature and high salt, which can be seen visually from the data of the same ratio of the embodiment 4 and the comparative example 2.
TABLE 1
Claims (17)
1. A polymer microemulsion comprises an oil-soluble solvent, water, an emulsifier and polymer microspheres; wherein the oil-soluble solvent is a continuous phase, the water is a dispersed phase, and the emulsifier comprises fatty alcohol polyoxyethylene ether sulfonate surfactant shown in a structure of formula (1):
RO(CH 2 CH 2 O) n CH 2 CH 2 SO 3 m, formula (1);
wherein R is C 12 ~C 18 N =4 to 16, M is selected from H, alkali metal or NH 4 ；
The emulsifier comprises a combination of a fatty alcohol-polyoxyethylene ether sulfonate surfactant shown in a structure of a formula (1) and a conventional surfactant, wherein the mass ratio of the fatty alcohol-polyoxyethylene ether sulfonate surfactant to the conventional surfactant is 1 to 9; the conventional surfactant consists of sorbitan fatty acid ester and polyoxyethylene sorbitan fatty acid ester;
the microemulsion contains 4-13 wt% of the emulsifier by mass percent of the total microemulsion;
the polymer microsphere contains an acrylamide monomer unit and a temperature-resistant and salt-resistant monomer unit; the mass ratio of the acrylamide monomer unit to the temperature-resistant salt-resistant monomer unit is (10 to 70) to (0.5 to 20); the polymer microsphere contains a cross-linking agent unit; the content of the cross-linking agent unit is 0.1 to 1.0 percent in terms of the total mass percentage of the polymer microsphere; the polymer microemulsion is prepared by polymerizing reverse microemulsion under the action of a redox composite initiator.
2. The polymeric microemulsion according to claim 1, wherein said microemulsion contains said oil-soluble solvent in an amount of 22-68 wt%, said water in an amount of 13-28 wt%, and said polymeric microspheres in an amount of 15-45 wt%, based on the total mass percentage of said microemulsion.
3. The polymer microemulsion according to claim 1 wherein the temperature and salt resistant monomer is selected from at least one of N-vinylpyrrolidone, N-dimethylacrylamide, acrylamido-N-dodecylsulfonic acid and/or a salt thereof, N-phenylmaleimide, dodecyl (meth) acrylate, styrene, p-tert-butylstyrene, 2-acrylamido-2-methylpropanesulfonic acid and/or an alkali metal or ammonium salt thereof, 2-acrylamido-2-methylpropyltrimethylammonium halide.
4. The polymer microemulsion according to claim 1, wherein the crosslinking agent is at least one member selected from the group consisting of divinylbenzene, pentaerythritol triacrylate, N' -m-phenylene bismaleimide, and methylenebisacrylamide.
5. The polymer microemulsion of claim 1 wherein said oil-soluble solvent is selected from at least one of a hydrocarbon or an ester.
6. The polymer microemulsion of claim 5 wherein said hydrocarbon is an aliphatic hydrocarbon or/and an aromatic hydrocarbon and said ester is a carboxylic acid ester.
7. The polymer microemulsion according to claim 6, characterised in that said aliphatic hydrocarbon is C 4 ~C 8 The aliphatic hydrocarbon of (2) is selected from one or a mixture of more than two of hexane, heptane and octane; the aromatic hydrocarbon is C 6 ~C 10 The aromatic hydrocarbon of (2) is one or a mixture of two or more selected from benzene, toluene, xylene, trimethylbenzene, ethylbenzene, diethylbenzene and isopropylbenzene.
8. The polymer microemulsion according to claim 6 wherein said aliphatic hydrocarbon is one or both of cyclohexane and isooctane.
9. The polymer microemulsion according to claim 5 wherein said hydrocarbon is a petroleum distillate selected from the group consisting of liquid paraffin, gasoline, kerosene, diesel, petroleum ether; the ester is C 4 ~C 8 The monoester of (2) is selected from ethyl acetate and propyl acetate.
10. The polymer microemulsion of claim 5 wherein said ester is C 4 ~C 10 The diester of (a) is selected from dimethyl oxalate, diethyl oxalate, ethyl methyl oxalate.
11. The polymer microemulsion according to claim 5, wherein said ester is a vegetable oil selected from the group consisting of peanut oil, soybean oil, sunflower oil and castor oil.
12. A polymer microemulsion profile control agent, comprising the polymer microemulsion as defined in any one of claims 1 to 11.
13. A method for preparing the polymer microemulsion profile control agent of claim 12, comprising the following steps:
(a) Preparing an oil phase: dissolving the emulsifier in an oil-soluble solvent, and uniformly stirring to obtain an oil phase I; dissolving an oil-soluble temperature-resistant salt-resistant monomer, an oil-soluble oxidant and an oil-soluble cross-linking agent in an oil-soluble solvent, and uniformly stirring to obtain an oil phase II;
(b) Preparing a water phase: uniformly mixing water-soluble components in acrylamide, optional water-soluble temperature-resistant salt-resistant monomer, redox composite initiator except reducing agent and water to obtain water phase;
(c) And uniformly mixing the oil phase I, the water phase and the oil phase II, adding a reducing agent, and reacting to obtain the polymer microemulsion profile control and flooding agent.
14. The process according to claim 13, wherein the reaction temperature is from 40 to 80 ℃.
15. The method according to claim 13, wherein the reaction time is 1 to 8 hours.
16. The method of claim 13, wherein the reducing agent is added as an aqueous solution.
17. The use of the polymer microemulsion profile control agent of claim 12 in reservoir profile control.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811234932.7A CN111087995B (en) | 2018-10-23 | 2018-10-23 | Low-tension polymer microemulsion, profile control and flooding system, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811234932.7A CN111087995B (en) | 2018-10-23 | 2018-10-23 | Low-tension polymer microemulsion, profile control and flooding system, preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111087995A CN111087995A (en) | 2020-05-01 |
| CN111087995B true CN111087995B (en) | 2022-10-11 |
Family
ID=70391348
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811234932.7A Active CN111087995B (en) | 2018-10-23 | 2018-10-23 | Low-tension polymer microemulsion, profile control and flooding system, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111087995B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112280544B (en) * | 2020-10-29 | 2022-05-17 | 中国石油大学(华东) | Emulsion type precipitation profile control agent and preparation method and application thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015048131A1 (en) * | 2013-09-26 | 2015-04-02 | Shell Oil Company | Composition and method for enhanced hydrocarbon recovery |
| CN106589226A (en) * | 2015-10-20 | 2017-04-26 | 中国石油化工股份有限公司 | Profile controlling and flooding composition and application thereof |
| CN107118134A (en) * | 2017-05-10 | 2017-09-01 | 兰州交通大学 | One pot process AEO（3）Sodium sulfonate（AESO‑3）Method |
-
2018
- 2018-10-23 CN CN201811234932.7A patent/CN111087995B/en active Active
Non-Patent Citations (1)
| Title |
|---|
| Salinity And Hardness Tolerant Microemulsion Formulations;B.B. Maini;《 the SPE Annual Technical Conference and Exhibition, September 21–24, 1980》;Society of Petroleum Engineers (SPE);19800921;全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111087995A (en) | 2020-05-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106866879B (en) | Low-tension polymer microemulsion system for oil reservoir deep profile control and flooding and preparation method thereof | |
| CN104277174B (en) | Polyacrylamide nanometer microballoon system and preparation method thereof | |
| CN106590590B (en) | Oil displacement composition containing polyether carboxylate surfactant and preparation method thereof | |
| CN109666475B (en) | Temperature-resistant salt-resistant low-tension nano-microsphere profile control and flooding agent and preparation method thereof | |
| CN106866877B (en) | Oil deposit deep part transfer drive polymer microemulsion system and preparation method thereof | |
| CN109666099B (en) | Core-shell polymer microsphere and preparation method thereof | |
| CN106589231B (en) | Polymer microsphere and preparation method thereof | |
| CN106590586B (en) | Oil displacement agent for tertiary oil recovery | |
| CN106867496A (en) | Online injection type oil displacement agent containing hydrophobic associated polymer emulsion and preparation method thereof | |
| EP2738237A1 (en) | Amphiphilic macromolecule and use thereof | |
| CN106589228B (en) | Microemulsion system for profile control and flooding for low-permeability oil reservoir and preparation method | |
| CN106589227A (en) | Polyacrylamide oil displacement agent of oil reservoir with high temperature and high hypersalinity as well as preparation method thereof | |
| CN106467599A (en) | A kind of self-association type linked polymer coil and preparation method thereof | |
| CN111087995B (en) | Low-tension polymer microemulsion, profile control and flooding system, preparation method and application thereof | |
| CN106590597A (en) | High-temperature high-mineralization-degree oil displacement agent composition for oil reservoirs and preparation method thereof | |
| CN106317308B (en) | A kind of acrylamide copolymer and its preparation method and application | |
| CN106593374B (en) | The method of intensified oil reduction | |
| CN111087534B (en) | Polymer microemulsion adopting gemini sulfonate type composite emulsifier, profile control and flooding system, preparation method and application thereof | |
| CN106478869B (en) | A kind of temperature-resistant anti-salt reversed-phase emulsion transfer drive system and its preparation method and application | |
| CN104628943B (en) | A kind of acrylamide based copolymer and its preparation method and application | |
| CN106590591A (en) | Oil displacement agent composition used for oil recovery, and preparation method thereof | |
| CN112226222B (en) | Low-tension viscoelastic surfactant composition for high-temperature high-mineralization oil reservoir chemical flooding tertiary oil recovery and preparation method thereof | |
| CN108314997A (en) | Increase substantially fluid, the preparation method and application of oil recovery factor | |
| CN106589232B (en) | Hydrophobic association acrylamide copolymer and preparation method thereof | |
| CN111087533B (en) | Polymer microemulsion system adopting anionic non-sulfonate type composite emulsifier, profile control and flooding system, preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |