CN106833586B - nano-micron polymer particle and surfactant composite oil displacement method - Google Patents
nano-micron polymer particle and surfactant composite oil displacement method Download PDFInfo
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- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
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- 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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Abstract
the invention relates to a nano-micron polymer particle and surfactant composite oil displacement method, which comprises the steps of alternately injecting a nano-micron polymer particle dispersed aqueous solution and a surfactant aqueous solution in different slug combination modes to improve the oil displacement efficiency, wherein the permeability of a low-permeability oil reservoir is within the range of 1-50mD, the concentration of the nano-micron polymer particles is within the range of 500-2000mg/L, and the concentration of the surfactant is within the range of 0.05-0.5 wt%. The nano-micron polymer particle and surfactant composite oil displacement method disclosed by the invention is simple to operate, combines the advantages of non-homogeneous solution oil displacement and active water oil displacement, and exerts the advantages of large swept volume, strong step-by-step depth profile control of the non-homogeneous solution oil displacement method and high oil washing efficiency in a large pore channel of a reservoir in the active water oil displacement method. The oil displacement method disclosed by the invention can obviously improve the recovery ratio of the low-permeability reservoir and can provide an effective method for the tertiary oil recovery development of the low-permeability reservoir.
Description
Technical Field
the invention relates to a method for improving the oil recovery ratio of a low-permeability reservoir, belongs to the technical field of oil exploitation, and particularly relates to a nano-micron polymer particle and surfactant compound oil displacement method.
Background
the exploration reserves of the low-permeability petroleum and the yield of crude oil are increased year by year, as long as 2010, the accumulated low-permeability petroleum reserves of the medium petroleum account for 40.6 percent of the total exploration petroleum reserves, and the newly increased 73 percent of the petroleum reserves in nearly 3 years are the low-permeability reserves. In the national petroleum prospect residual resources, the low-permeability reserves also account for 54% of the total amount of the residual resources. Low permeability reserves have become the mainstay of current new zone capacity construction and oil field production. But the low-permeability reservoir has small permeability, large fluid constrained force and poor fluidity, and the heterogeneous degree is far greater than that of a medium-high permeability reservoir, so that the exploitation effect of the low-permeability reservoir is poor. The low-permeability oil reservoir belongs to a low-permeability, low-productivity and low-abundance 'three-low' oil reservoir, and the recovery ratio at the present stage is only 20 percent and is far lower than that of a medium-permeability and high-permeability oil reservoir. The polymer flooding, binary combination flooding, ternary combination flooding and other technologies which have been successfully popularized and applied in medium and high permeability oil reservoirs can not be applied to low permeability oil reservoirs due to the large injection pressure caused by the high viscosity of the polymer.
the surfactant flooding is considered to be a chemical agent which can greatly improve the recovery ratio, has wide application range and has the greatest development prospect. The surfactant industrialized products for tertiary oil recovery at home and abroad mainly have two categories: the surfactant is a surfactant mainly containing petroleum sulfonate and a surfactant mainly containing alkylbenzene sulfonate, the raw materials of the surfactants are all taken from crude oil, and the surfactants are wide in source and large in quantity, so that the surfactant is also the surfactant with the largest use amount for tertiary oil recovery at home and abroad. However, the single surfactant flooding of the low permeability reservoir has low recovery efficiency improvement on the basis of water flooding because after surfactant flooding, a dominant channel is formed in the reservoir, so that the reservoir coverage is reduced, and a large amount of residual oil is left.
the nano-micron polymer particle profile control and flooding technology is a novel oil reservoir deep profile control and flooding water shutoff technology developed in recent years, and is one of main means for improving the development effect of low-permeability oil fields. The profile control and drive mechanism is as follows: the nano-micron polymer particle water solution has the advantages that the flow speed in the large-permeability pore channel is reduced, the flow speed is not reduced, the flow field flow speed is adjusted, the flow speed distribution caused by non-homogeneity is obviously changed, the effect of enlarging swept volume is achieved, and residual oil in the small and medium pore channels is better exploited. The polymer particles have the characteristics of small volume, hydration expansion, deformation and good fluidity, and can enter a low-permeability pore channel, so that the flow speed and the state of fluid in the pore channel can be adjusted, the liquid flow redirection and the gradual profile control are realized, and the aim of improving the oil reservoir recovery ratio is fulfilled.
Disclosure of Invention
The invention aims to provide a nano-micron polymer particle and surfactant composite oil displacement method, which is applied to low-permeability oil reservoirs and has the advantages of good injection performance and high crude oil recovery rate improvement at the formation temperature.
in order to achieve the purpose, the invention adopts the following technical scheme:
a nano-micron polymer particle and surfactant composite oil displacement method is applied to a low-permeability oil reservoir, nano-micron polymer particle dispersed aqueous solution and surfactant aqueous solution are alternately injected in different slug combination modes, the oil displacement efficiency is improved, and the permeability of the low-permeability oil reservoir is in the range of 1-50 mD.
preferably, the total slug injection amount of the nano-micron polymer particle dispersion aqueous solution and the surfactant aqueous solution is 0.2-0.6 PV.
preferably, the slug injection amount of the nano-micron polymer particle dispersed aqueous solution is 0.05-0.3 PV.
Preferably, the slug injection amount of the aqueous surfactant solution is 0.05 to 0.3 PV.
preferably, the number of times of alternately injecting the nano-micron polymer particle dispersed aqueous solution slug and the surfactant aqueous solution slug is 1-3.
Preferably, the nano-micron polymer particle dispersion aqueous solution comprises nano-micron polymer particles, the particle diameter is 250-360nm, the concentration is 500-2000mg/L, and the concentration is 0.1wt%, and the balance is water.
Preferably, the surfactant aqueous solution comprises a surfactant with a concentration of 0.05-0.5wt%, and the balance of water.
Preferably, the nano-micron polymer particles are acrylamide/acrylic acid/2-acrylamido-2-methylpropanesulfonic acid ternary copolymer particles, and the preparation steps are as follows:
(1) Taking 1.5mol of acrylamide and 1.5mol of acrylic acid, and 4.5mol of 2-acrylamido-2-methylpropanesulfonic acid, adding the acrylamide and the acrylic acid into a single-neck round-bottom flask, adding 54.75mol of acetonitrile solvent into the flask, and fully mixing;
(2) After ultrasonic dispersion, adding 0.12mol of N, N-methylene bisacrylamide and 0.0105mol of azobisisobutyronitrile into a round-bottom flask, and simultaneously carrying out ultrasonic mixing uniformly;
(3) adding the reaction solution into a round-bottom flask, placing the round-bottom flask into a constant-temperature oil bath, keeping the temperature of the oil bath at 95 ℃, heating the temperature of the reaction solution from normal temperature to boiling, and keeping the boiling state for 20 min;
(4) After the reaction solution turns from colorless to light blue and gradually turns to milk white, adjusting the temperature of the oil bath to 110 ℃, keeping the reflux ratio of the reaction solution at 2, and reacting for 95 min;
(5) After all the solvent is distilled, the powder at the bottom of the bottle is dispersed, cleaned and centrifuged by ethanol, dried for 15 hours in a drying oven at the temperature of 60 ℃, and fully ground to obtain the nano-micron polymer particles.
Preferably, the surfactant is bio-oil hydroxy sulfonate prepared by using kitchen waste grease, and the preparation steps are as follows:
(1) Processing and purifying frying oil to obtain treated oil, wherein the treated oil is a mixture of multiple triglycerides;
(2) Mixing the processed and purified frying oil and 1, 2-dichloroethane in a volume ratio of 1:2 in a three-neck flask provided with a magnetic rotor, a condenser pipe and a thermometer, placing the three-neck flask in a heat collection type constant temperature heating magnetic stirrer, and rapidly stirring for 10-20min to completely dissolve the kitchen waste grease to obtain a light brown mixed solution;
(3) Slowly dropping fuming sulfuric acid into the mixed solution of the three-neck flask at room temperature according to the volume ratio of the kitchen waste grease to the fuming sulfuric acid of 7:1, simultaneously carrying out rapid stirring, after beginning to drop the fuming sulfuric acid for 10-15min at the timing, heating to the reaction temperature of 60 ℃, and keeping the reaction for 4 h;
(4) after reaching 4 hours, dropwise adding ammonia water into the reaction solution for hydrolysis neutralization reaction until the reaction solution is not acidic, stopping dropwise adding ammonia water, stirring the reaction solution for 2-5min for fully mixing, pouring the product into a separating funnel, diluting the solution with distilled water, oscillating and stirring uniformly;
(5) standing for 10-15min, separating to obtain crude product of bio-oil hydroxy sulfonate, and distilling the crude product in a constant temperature water bath under reduced pressure for 1.5-2h by using a simulated reduced pressure distillation device to obtain the bio-oil hydroxy sulfonate.
The invention has the beneficial effects that: the nano-micron polymer particle and surfactant composite oil displacement method is simple to operate, and has the advantages of large swept volume, strong step-by-step depth profile control capability of a non-homogeneous solution oil displacement method and high oil washing efficiency in a large pore channel of a reservoir in an active water oil displacement method. Meanwhile, the problems that more crude oil remains in a large pore channel of a reservoir when a non-homogeneous solution oil displacement method is used and water channeling is easily caused when an active water oil displacement method is used are solved. The crude oil recovery rate of the low-permeability reservoir is obviously improved, and the crude oil recovery rate is improved by more than 12% on the basis of the water flooding recovery rate.
drawings
FIG. 1 is a graph showing the change in the extraction degree and water content in example 1;
FIG. 2 is a graph showing the change in the extraction degree and water content in example 2;
FIG. 3 is a graph showing the change in the extraction degree and water content in example 3;
Detailed Description
The technical solution of the present invention will be further specifically described below by way of specific examples.
In the present invention, the raw materials and equipment used are commercially available or commonly used in the art, unless otherwise specified. The methods in the following examples are conventional in the art unless otherwise specified.
Example 1
A nano-micron polymer particle and surfactant composite oil displacement method utilizes a rock core displacement device to perform an indoor simulated oil displacement experiment, and comprises the following specific steps:
(1) Selecting a natural core of a typical low-permeability reservoir block, wherein the core permeability is 10.37 multiplied by 10 -3 mu m 2, the porosity is 14.68%, the diameter is 2.52cm, the length is 12.45cm, the core is subjected to oil washing, is dried for 12h at 105 ℃ by an oven, is cooled to normal temperature, is vacuumized for 8h by a vacuumizing saturated water device, saturates formation simulated water, and the mineralization degree of formation water is 5000 mg/L;
(2) and putting the rock core with the saturated formation water into the rock core holder, connecting the rock core holder with the rock core displacement device, and draining air in the pipeline. Placing the holder in a thermostat, injecting the degassed and dehydrated crude oil into the core at a constant speed of 0.5mL/min at a formation simulation temperature of 45 ℃ until no water is discharged from the outlet of the core holder, receiving the liquid by using a graduated measuring cylinder at the outlet end, recording the volume of the water in the measuring cylinder, calculating to obtain the original oil saturation of the core of 50.36%, displacing for 15-30min after the outlet end is free from water, closing a displacement device after the bound water is produced, screwing two ends of the core holder, and aging for 24h at a constant temperature; (3) preparing a dispersed aqueous solution of acrylamide/acrylic acid/2-acrylamide-2-methylpropanesulfonic acid ternary copolymer particles by using formation water, wherein the diameter of the nano-micron polymer particles is 250-360nm, the concentration is 1000mg/L, the concentration of polyethylene glycol serving as a dispersant is 0.1wt%, preparing a biological oil hydroxyl sulfonate surfactant aqueous solution by using the formation water, the concentration is 0.3 wt%, and placing the prepared two solutions into two intermediate containers;
(4) after the core is aged for 24 hours, injecting formation water at a constant speed of 0.5mL/min at a formation simulation temperature of 45 ℃ until the water content of the outlet end of the holder is more than 98%, continuously connecting the liquid by using a graduated measuring cylinder at the outlet end, recording the volume of oil and water, and calculating to obtain the water flooding efficiency of 30.35%;
(5) under the stratum simulation temperature of 45 ℃, acrylamide/acrylic acid/2-acrylamide-2-methylpropanesulfonic acid ternary copolymer particle dispersed aqueous solution slugs are injected at a constant speed of 0.5mL/min, the injection amount of the slugs is 0.3PV, then biological oil hydroxyl sulfonate surfactant aqueous solution slugs are injected at the same speed and a constant speed, the injection amount of the slugs is 0.3PV, the slugs are alternately injected for 1 time, the injection amount of the total slug is 0.6PV, the water content of the outlet end is more than 98% after the subsequent water flooding, the outlet end is continuously connected with graduated cylinders, the volume of oil and water is recorded, the total oil displacement efficiency is 43.27% at this time, the recovery ratio is improved by 12.92% on the basis of the water flooding, and the change curve of the extraction degree and the water content in the displacement process is shown in figure 1.
Example 2
A nano-micron polymer particle and surfactant composite oil displacement method utilizes a rock core displacement device to perform an indoor simulated oil displacement experiment, and comprises the following specific steps:
(1) Selecting a natural core of a typical low-permeability reservoir block, wherein the core permeability is 11.62 multiplied by 10 -3 mu m 2, the porosity is 16.78%, the diameter is 2.54cm, the length is 11.71cm, the core is subjected to oil washing, is dried for 12h at 105 ℃ by an oven, is cooled to normal temperature, is vacuumized for 8h by a vacuumizing saturated water device, saturates formation simulated water, and the mineralization degree of formation water is 5000 mg/L;
(2) And putting the rock core with the saturated formation water into the rock core holder, connecting the rock core holder with the rock core displacement device, and draining air in the pipeline. Placing the holder in a thermostat, injecting the degassed and dehydrated crude oil into the core at a constant speed of 0.5mL/min at a formation simulation temperature of 45 ℃ until no water is discharged from the outlet of the core holder, receiving the liquid by using a graduated measuring cylinder at the outlet end, recording the volume of the water in the measuring cylinder, calculating to obtain the original oil saturation of the core of 55.83%, displacing for 15-30min after the outlet end is free from water, closing a displacement device after the bound water is produced, screwing two ends of the core holder, and aging for 24h at a constant temperature;
(3) Preparing a dispersed aqueous solution of acrylamide/acrylic acid/2-acrylamide-2-methylpropanesulfonic acid ternary copolymer particles by using formation water, wherein the diameter of the nano-micron polymer particles is 250-360nm, the concentration is 800mg/L, the concentration of polyethylene glycol serving as a dispersant is 0.1wt%, preparing a biological oil hydroxyl sulfonate surfactant aqueous solution by using the formation water, the concentration is 0.1wt%, and placing the prepared two solutions into two intermediate containers;
(4) After the core is aged for 24 hours, injecting formation water at a constant speed of 0.5mL/min at a formation simulation temperature of 45 ℃ until the water content of the outlet end of the holder is more than 98%, continuously connecting the liquid by using a graduated measuring cylinder at the outlet end, recording the volume of oil and water, and calculating to obtain the water flooding efficiency of 38.95%;
(5) Under the stratum simulation temperature of 45 ℃, injecting a slug of an acrylamide/acrylic acid/2-acrylamide-2-methylpropanesulfonic acid ternary copolymer polymer particle dispersed aqueous solution at a constant injection speed of 0.5mL/min, wherein the injection amount of the slug is 0.2PV, then injecting a slug of a biological oil hydroxyl sulfonate surfactant aqueous solution at the same constant speed, the injection amount of the slug is 0.1PV, alternately injecting for 2 times, the total slug injection amount is 0.6PV, subsequently driving water until the water content at the outlet end is more than 98%, continuously connecting the outlet end with a graduated cylinder, recording the volumes of oil and water, calculating to obtain the total oil displacement efficiency of 55.26%, improving the recovery ratio by 16.31% on the basis of water displacement, and the change curve of the extraction degree and the water content in the displacement process is shown in figure 2.
example 3
a nano-micron polymer particle and surfactant composite oil displacement method utilizes a rock core displacement device to perform an indoor simulated oil displacement experiment, and comprises the following specific steps:
(1) selecting a natural core of a typical low-permeability reservoir block, wherein the core permeability is 12.88 multiplied by 10 -3 mu m 2, the porosity is 15.41%, the diameter is 2.56cm, the length is 13.06cm, the core is subjected to oil washing, is dried for 12h at 105 ℃ by an oven, is cooled to normal temperature, is vacuumized for 8h by a vacuumizing saturated water device, saturates formation simulated water, and the mineralization degree of formation water is 5000 mg/L;
(2) And putting the rock core with the saturated formation water into the rock core holder, connecting the rock core holder with the rock core displacement device, and draining air in the pipeline. Placing the holder in a thermostat, injecting the degassed and dehydrated crude oil into the core at a constant speed of 0.5mL/min at a formation simulation temperature of 45 ℃ until no water is discharged from the outlet of the core holder, receiving the liquid by using a graduated measuring cylinder at the outlet end, recording the volume of the water in the measuring cylinder, calculating to obtain the original oil saturation of the core of 54.29%, displacing for 15-30min after the outlet end is not filled with water, closing a displacement device after the bound water is produced, screwing two ends of the core holder, and aging for 24h at a constant temperature;
(3) Preparing an acrylamide/acrylic acid/2-acrylamide-2-methylpropanesulfonic acid ternary copolymer polymer particle dispersion aqueous solution by using formation water, wherein the diameter of a nano-micron polymer particle is 250-360nm, the concentration is 500mg/L, the concentration of a dispersant polyethylene glycol is 0.1wt%, preparing a biological oil hydroxyl sulfonate surfactant aqueous solution by using the formation water, the concentration is 0.06 wt%, and placing the prepared two solutions into two intermediate containers;
(4) After the core is aged for 24 hours, injecting formation water at a constant speed of 0.5mL/min at a formation simulation temperature of 45 ℃ until the water content of the outlet end of the holder is more than 98%, continuously connecting the liquid by using a graduated measuring cylinder at the outlet end, and recording the volume of oil and water, wherein the calculated water flooding efficiency is 34.72%;
(5) under the stratum simulation temperature of 45 ℃, acrylamide/acrylic acid/2-acrylamide-2-methylpropanesulfonic acid ternary copolymer particle dispersed aqueous solution slugs are injected at a constant speed of 0.5mL/min, the injection amount of the slugs is 0.1PV, then biological oil hydroxyl sulfonate surfactant aqueous solution slugs are injected at the same speed and a constant speed, the injection amount of the slugs is 0.1PV, the slugs are alternately injected for 3 times, the injection amount of the total slug is 0.6PV, the water content of the outlet end is more than 98% after the subsequent water flooding, the outlet end is continuously connected with graduated cylinders, the volume of oil and water is recorded, the total oil displacement efficiency is calculated to be 48.06%, the recovery ratio is improved by 13.34% on the basis of the water flooding, and the change curve of the extraction degree and the water content in the displacement process is shown in an attached figure 3.
The above-described embodiments are only preferred embodiments of the present invention, and are not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the spirit of the invention as set forth in the claims.
Claims (8)
1. A nano-micron polymer particle and surfactant compound oil displacement method is characterized in that the method is applied to a low-permeability reservoir, a nano-micron polymer particle dispersed aqueous solution slug is injected at a constant injection speed of 0.5mL/min at a stratum simulation temperature of 45 ℃, then the surfactant aqueous solution slug is injected at the same constant injection speed as well as alternately injected once, the alternate injection is carried out for a plurality of times, the total slug injection amount is 0.2-0.6PV, and the permeability of the low-permeability reservoir is in a range of 1-50 mD.
2. The method for oil displacement by combining nano-micro polymer particles and a surfactant according to claim 1, wherein the slug injection amount of the nano-micro polymer particle dispersed aqueous solution is 0.05-0.3 PV.
3. The method for oil displacement by combining nano-micro polymer particles and a surfactant according to claim 1, wherein the slug injection amount of the surfactant aqueous solution is 0.05-0.3 PV.
4. the method for oil displacement by combining nano-micro polymer particles and surfactants according to claim 1, wherein the number of times of alternately injecting the nano-micro polymer particle dispersed aqueous solution slug and the surfactant aqueous solution slug is 1-3 times.
5. The method for the oil displacement by combining the nano-micron polymer particles and the surfactant as claimed in claim 1, wherein the nano-micron polymer particles are contained in the nano-micron polymer particle dispersion water solution, the particle diameter is 250-360nm, the concentration is 500-2000mg/L, the concentration of the dispersant polyethylene glycol is 0.1wt%, and the balance is water.
6. The method for oil displacement by combining nano-micro polymer particles and a surfactant according to claim 1, wherein the surfactant aqueous solution comprises the surfactant, the concentration of the surfactant is 0.05-0.5wt%, and the balance is water.
7. The method for oil displacement by combining nano-micron polymer particles and a surfactant according to claim 1 or 5, wherein the nano-micron polymer particles are acrylamide/acrylic acid/2-acrylamido-2-methylpropanesulfonic acid terpolymer polymer particles, and the preparation steps are as follows:
(1) Taking 1.5mol of acrylamide and 1.5mol of acrylic acid, and 4.5mol of 2-acrylamido-2-methylpropanesulfonic acid, adding the acrylamide and the acrylic acid into a single-neck round-bottom flask, adding 54.75mol of acetonitrile solvent into the flask, and fully mixing;
(2) After ultrasonic dispersion, adding 0.12mol of N, N-methylene bisacrylamide and 0.0105mol of azobisisobutyronitrile into a round-bottom flask, and simultaneously carrying out ultrasonic mixing uniformly;
(3) adding the reaction solution into a round-bottom flask, placing the round-bottom flask into a constant-temperature oil bath, keeping the temperature of the oil bath at 95 ℃, heating the temperature of the reaction solution from normal temperature to boiling, and keeping the boiling state for 20 min;
(4) after the reaction solution turns from colorless to light blue and gradually turns to milk white, adjusting the temperature of the oil bath to 110 ℃, keeping the reflux ratio of the reaction solution at 2, and reacting for 95 min;
(5) After all the solvent is distilled, the powder at the bottom of the bottle is dispersed, cleaned and centrifuged by ethanol, dried for 15 hours in a drying oven at the temperature of 60 ℃, and fully ground to obtain the nano-micron polymer particles.
8. the method for the compound oil displacement of the nano-micron polymer particles and the surfactant according to claim 1 or 6, wherein the surfactant is bio-oil hydroxy sulfonate prepared from kitchen waste oil, and the preparation steps are as follows:
(1) Processing and purifying frying oil to obtain treated oil, wherein the treated oil is a mixture of multiple triglycerides;
(2) Mixing the processed and purified frying oil and 1, 2-dichloroethane in a volume ratio of 1:2 in a three-neck flask provided with a magnetic rotor, a condenser pipe and a thermometer, placing the three-neck flask in a heat collection type constant temperature heating magnetic stirrer, and rapidly stirring for 10-20min to completely dissolve the kitchen waste grease to obtain a light brown mixed solution;
(3) Slowly dropping fuming sulfuric acid into the mixed solution of the three-neck flask at room temperature according to the volume ratio of the kitchen waste grease to the fuming sulfuric acid of 7:1, simultaneously carrying out rapid stirring, after beginning to drop the fuming sulfuric acid for 10-15min at the timing, heating to the reaction temperature of 60 ℃, and keeping the reaction for 4 h;
(4) after reaching 4 hours, dropwise adding ammonia water into the reaction solution for hydrolysis neutralization reaction until the reaction solution is not acidic, stopping dropwise adding ammonia water, stirring the reaction solution for 2-5min for fully mixing, pouring the product into a separating funnel, diluting the solution with distilled water, oscillating and stirring uniformly;
(5) standing for 10-15min, separating to obtain crude product of bio-oil hydroxy sulfonate, and distilling the crude product in a constant temperature water bath under reduced pressure for 1.5-2h by using a simulated reduced pressure distillation device to obtain the bio-oil hydroxy sulfonate.
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