CN115368504B - Preparation method of high-rheological polymer composite emulsion profile control agent - Google Patents
Preparation method of high-rheological polymer composite emulsion profile control agent Download PDFInfo
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Abstract
A preparation method of a high-rheological polymer composite emulsion profile control agent relates to the field of petroleum exploitation. The nanometer polyacrylamide gel is prepared by the water-in-oil inverse emulsion polymerization technology and dispersed in an oil phase medium, and meanwhile, a high-rheology hyperbranched polymer is introduced to prepare the gel, polymer and surfactant integrated emulsion. The high-rheological polymer composite emulsion has high rheological property, the viscosity is rapidly reduced under high shear rate, the viscosity is rapidly recovered after the shearing action is finished, the water-oil fluidity ratio is reduced while the injectability is ensured, the sweep efficiency is improved, and the recovery ratio is improved in oil field profile control and flooding application.
Description
Technical field:
the invention relates to the field of petroleum exploitation, in particular to a preparation method of a high-rheological polymer composite emulsion profile control agent.
The background technology is as follows:
most of the oil fields in China enter a high-water-content or ultra-high-water-content development stage at present, oil reservoirs show obvious heterogeneous characteristics, and particularly in the field of low-permeability oil reservoirs, water control and oil stabilization are main contradictions facing the present stage. The problems of poor shearing resistance, poor temperature resistance and salt resistance, slow dissolution in a construction site, non-ideal injectability of a low-permeability layer and the like of the traditional polyacrylamide limit the wide application of the polyacrylamide in a low-permeability oil reservoir, so that the novel profile control agent which has the advantages of quick dissolution, good water-in dispersibility, low injection viscosity, high rheological property and capability of smoothly entering the deep part of a stratum is developed, and is one of important products for realizing water control and oil stabilization at the present stage. In recent years, a series of micro-nano polymer gel dispersion liquid-phase related products with different dimensions, which can be molded on the ground by water flooding, can be favorably developed in application tests and popularization of low-permeability reservoirs, and a new direction is opened for exploitation of the low-permeability reservoirs, so that on one hand, fluid can be turned through gel blocking of a high-permeability layer, the swept volume and swept efficiency of water flooding are improved, on the other hand, the interfacial tension of oil and water is reduced through a surfactant in a system, the oil displacement efficiency is improved, and the crude oil recovery efficiency is cooperatively improved.
In order to further improve the residual oil drive of the heterogeneous oil reservoir and further improve the recovery ratio, the water-oil fluidity ratio is further reduced on the basis of profile control and profile control of gel particles. The molecular chain shrinkage of the traditional polyacrylamide under the conditions of high temperature and high mineralization degree can cause the viscosity to be reduced, so that the profile control capability is reduced. In order to achieve the purpose, the invention prepares the integrated compound flooding agent according to the concept of multi-element compound flooding through the technical route of inverse emulsion polymer, wherein the compound emulsion contains polyacrylamide gel microspheres, surfactant and hyperbranched polymer, the high-rheology polymer is introduced into the polymer hydrogel emulsion to be dispersed and then exists in the form of water-in-oil compound emulsion, and the viscosity of a dispersed liquid system is improved, the water-oil fluidity ratio is reduced, the emulsification effect of the surfactant is exerted, and the recovery ratio is improved cooperatively on the basis that the gel plugging effect is guaranteed through the synergistic effect of the multi-dimensional flooding agent. Compared with the traditional polymer flooding or polymer microsphere emulsion, the invention introduces microgel, polymer and surfactant, wherein the high-rheology polymer is hyperbranched polyacrylamide or xanthan gum, and has the characteristics of high dissolution speed and good temperature and salt resistance, and most importantly, when the polymer microsphere emulsion is sheared, the fluid viscosity becomes small, and when the shearing is stopped, the fluid viscosity is restored to the state before the shearing. The Gao Liubian characteristic enables the low permeability oil to be sheared when entering the low permeability oil reservoir and passing through the pore throats, reduces the viscosity of the fluid, enables the fluid to smoothly enter the deep part of the stratum, enters the bulk phase state after passing through the pore throats, and recovers the original viscosity of the fluid, thereby being beneficial to deep profile control and flooding. In the composite emulsion, the hyperbranched polymer part exists in a nano gel loaded form, and after the nano-scale dispersion is carried into water, the viscosity is low, so that the injection is facilitated, the polymer is released in the deep part of the stratum, the water flooding wave and efficiency is improved, the water-oil fluidity ratio is reduced, and the deep flooding effect is improved.
The invention comprises the following steps:
the invention provides a preparation method of a high-rheological polymer composite emulsion profile control agent, which is characterized in that hyperbranched polyacrylamide or xanthan gum is introduced into a water-in-oil inverse emulsion polymerization system to endow the system with high rheological property, namely, the viscosity is rapidly reduced under the shearing action, the viscosity is rapidly recovered after the shearing action is finished, the water-oil fluidity ratio is reduced while the plugging action is ensured, the sweep efficiency is improved, and the requirement of profile control of residual oil in a hypotonic region is met.
The technical scheme for achieving the aim of the invention is as follows:
a preparation method of a high-rheological polymer composite emulsion profile control agent is characterized by comprising the following steps: the nanometer polyacrylamide gel is prepared by the water-in-oil inverse emulsion polymerization technology and dispersed in an oil phase medium, and meanwhile, a high-rheology hyperbranched polymer is introduced to prepare the gel, polymer and surfactant integrated emulsion. The preparation method comprises the following steps:
(1) Preparing a composite emulsion oil phase: sequentially weighing 30-50 parts of oily medium, 15-25 parts of surfactant 1 and 5-10 parts of surfactant 2, mixing at 50-60 ℃, stirring at 300-500rpm for 30-50 minutes, and cooling to room temperature after uniform mixing.
(2) Preparing a composite emulsion water phase: sequentially weighing 20-30 parts of nonionic monomer, 10-20 parts of ionic monomer, 3-8 parts of dispersing agent and 1-5 parts of cross-linking agent, sequentially dissolving in 15-25 parts of water, regulating the pH to 6-7 after dissolving, and finally adding 0.1-0.3 part of 10wt.% of oxidative initiator aqueous solution.
(3) The preparation method of the high-rheological polymer composite emulsion profile control agent can be realized by the following method 1 or the method 2.
The preparation method of the high-rheological polymer composite emulsion profile control agent comprises the following steps of: pouring the water phase prepared in the step (2) into the cooled oil phase (1), mixing and stirring for 30-50 minutes, wherein the stirring speed is 500-900rpm, introducing inert gas for 3-10 minutes, adding 0.1-0.3 part of a reducing initiator with the concentration of 5wt.% at the temperature of 25-30 ℃, quickly heating to 50-80 ℃, continuously reacting for 10 minutes, stopping ventilation, reducing the stirring speed to 200-500 revolutions per minute, and continuously stirring for 30-50 minutes; weighing 30-50 parts of the emulsion, adding 20-30 parts of surfactant 1, stirring for 30-60 minutes at 50-60 ℃, setting the stirring speed to 300-500 revolutions per minute, adding 20-35 parts of 0.5wt.% hyperbranched polyacrylamide or xanthan gum aqueous solution after the temperature is reduced to room temperature, stirring for 30-60 minutes, setting the stirring speed to 500-800 revolutions per minute, and stirring until the system becomes uniform emulsion, thereby obtaining the high-rheological polymer composite emulsion, wherein the emulsion has higher self viscosity, obviously improves the viscosity in the injection process, and can improve the recovery ratio of crude oil of a hypertonic reservoir.
The preparation method 2 of the high rheological polymer composite emulsion profile control agent comprises the steps of introducing hyperbranched polyacrylamide or xanthan gum in the preparation of the aqueous phase of the composite emulsion in the step 2; the specific method comprises the following steps: sequentially weighing 20-30 parts of nonionic monomer, 10-20 parts of ionic monomer, 3-8 parts of dispersing agent and 1-5 parts of cross-linking agent, sequentially dissolving in 15-25 parts of water, regulating the pH to 6-7 after dissolving, and finally adding 0.5 part of hyperbranched polyacrylamide or xanthan gum and 0.1-0.3 part of 10wt.% of oxidative initiator aqueous solution. Pouring the completely dissolved water phase into the cooled oil phase, namely the oil phase prepared in the step (1), mixing and stirring for 30-50 minutes, wherein the stirring speed is 500-900rpm, introducing inert gas for 3-10 minutes, adding 0.1-0.3 part of 5wt.% of reducing initiator at 25-30 ℃, quickly heating to 50-80 ℃, continuously reacting for 10 minutes, recording temperature change, stopping ventilation, reducing the stirring speed to 200-500 revolutions per minute, continuing stirring for 30-50 minutes, and obtaining uniform composite emulsion, wherein the emulsion has lower viscosity in the injection process, gradually increases in viscosity after long-time swelling or pore-throat shearing, and can be used for improving the recovery ratio of a hypotonic reservoir.
The oily medium in the step (1) is one or more selected from aliphatic hydrocarbon, alicyclic hydrocarbon, aromatic hydrocarbon, vegetable oil and mineral oil, and the aliphatic hydrocarbon is one or more selected from pentane, hexane, n-hexane and octane; the alicyclic hydrocarbon is selected from one of cyclohexane, cyclohexanone and toluene cyclohexanone; the aromatic hydrocarbon is selected from one of benzene, toluene, xylene and styrene; the vegetable oil is selected from one of peanut oil, soybean oil, sunflower seed oil and castor oil; the mineral oil is one of white oil, fuel oil and lubricating oil.
The surfactant 1 in the step (1) is one or more selected from sorbitan monolaurate (Span-20), sorbitan monopalmitate (Span-40), sorbitan monostearate (Span-60), sorbitan monooleate (Span-80) and sorbitan trioleate (Span-85). The surfactant 2 is selected from one or more of alkylphenol ethoxylates, polyoxyethylene oleyl alcohol ethers, polyoxyethylene monooleate and polyoxyethylene monolaurate.
The nonionic monomer in the step (2) is selected from one or more of acrylamide, N-methylolacrylamide, N-butoxymethylacrylamide, methacrylamide and N, N-dimethylacrylamide; the ionic monomer is selected from one or more of acrylic acid, oxalic acid, maleic acid, 2-acrylamido-2-methylpropanesulfonic acid, allylbenzenesulfonic acid or metal salts thereof.
The dispersing agent in the step (2) is sodium acetate.
The cross-linking agent in the step (2) is a multifunctional water-soluble cross-linking agent and is selected from at least one of polyethylene glycol diacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, divinylbenzene, N-methylene bisacrylamide and dimethyl diallyl ammonium chloride.
The oxidizing initiator in the step (2) is selected from one of sodium peroxide, ammonium persulfate, potassium persulfate and sodium persulfate.
The reducing initiator in the step (3) is selected from one of sodium sulfite, potassium sulfite, sodium bisulfite and ferrous sulfate.
The inert gas in the step (3) is nitrogen or argon.
The high-rheological polymer in the step (3) is selected from one of hyperbranched polyacrylamide and xanthan gum with molecular weight of 1000-3000 ten thousand.
The particle size of gel particles in the high-rheology polymer composite emulsion obtained by the invention is 50nm to 800nm; the particle diameter of the water-dispersed polymer is 100nm to 5 mu m after swelling; the polymer gel accounts for 12-63% of the total mass of the polymer composite emulsion, and the high-rheological polymer accounts for 0.1-0.5% of the total mass of the polymer composite emulsion.
A compound profile control agent for oil field recovery ratio improvement.
The application of the composite profile control agent is used for oil field profile control.
The invention prepares the novel profile control agent by compounding polyacrylamide gel with high-rheology polymer aqueous solution, and has the following advantages:
(1) The high-rheological polymer composite emulsion has good dispersion stability, does not have layering phenomenon after being placed for a long time, and gel particles in the composite emulsion do not spontaneously swell, so that the injection property is ensured, and the effect of plugging pore throats is achieved.
(2) The high-rheological polymer is compounded to raise the apparent viscosity, shearing resistance and viscosity stability of the emulsion, and the emulsion can maintain high viscosity under long-term standing condition.
(3) The high-rheological polymer composite emulsion has high rheological property, the viscosity is rapidly reduced under high shear rate, the viscosity is rapidly recovered after the shearing action is finished, the water-oil fluidity ratio is reduced while the injectability is ensured, the sweep efficiency is improved, and the recovery ratio is improved in oil field profile control and flooding application.
Description of the drawings:
FIG. 1 is a transmission electron microscope image of a high rheology polymer composite emulsion
FIG. 2 is a scanning electron microscope image of a high rheology polymer composite emulsion
FIG. 3 is a rheological profile of a gel emulsion (P0) without high rheological polymer for control and a high rheological polymer composite emulsion (E2) prepared according to the invention
The specific embodiment is as follows:
the invention is further illustrated by the following examples, which are intended to be illustrative only and not limiting in any way.
Example 1 (comparative): 40 parts of peanut oil, 20 parts of sorbitan monolaurate and 10 parts of alkylphenol ethoxylate are weighed, poured into a four-necked flask, the temperature is raised to 50 ℃, the stirring speed is set to 300 revolutions per minute, the temperature is reduced to room temperature after 50 minutes of stirring, 25 parts of acrylamide, 15 parts of oxalic acid, 5 parts of sodium acetate and 3 parts of polyethylene glycol diacrylate are sequentially weighed, dissolved in 20 parts of deionized water in sequence, the pH of the solution is adjusted to 6.5, and 0.2 part of 10wt.% sodium persulfate solution is added.
Pouring the water phase into a four-neck flask, mixing and stirring for 50 minutes, setting the rotating speed to 600 revolutions per minute, introducing nitrogen for 5 minutes after uniformly mixing, adding 0.2 part of sodium sulfite aqueous solution with the concentration of 5wt.% to initiate reaction, continuously reacting for 10 minutes, recording temperature change, stopping ventilation, adjusting the rotating speed to 350 revolutions per minute, continuously stirring for 30 minutes, and reducing the temperature to room temperature to obtain the polymer gel emulsion P0. Wherein the gel particles account for 49wt.%, the average particle diameter is 50nm, and the zero shear viscosity is 125 mPa.s as measured by a rheometer.
Example 2:
35 parts of toluene, 18 parts of sorbitan monostearate and 8 parts of alkylphenol ethoxylate are weighed, poured into a four-necked flask, the temperature is raised to 60 ℃, the stirring speed is set to 500 revolutions per minute, the temperature is reduced to room temperature after stirring for 30 minutes, 23 parts of methacrylamide, 11 parts of oxalic acid, 4 parts of sodium acetate and 1 part of divinylbenzene are sequentially weighed and dissolved in 15 parts of deionized water, the pH of the solution is adjusted to 6.3, and 0.1 part of sodium persulfate solution with the mass fraction of 10wt.% is added.
Pouring the water phase into a four-neck flask, mixing and stirring for 30 minutes, setting the rotating speed to 800 revolutions per minute, introducing nitrogen for 5 minutes after uniformly mixing, adding 0.1 part of sodium sulfite aqueous solution with the concentration of 5wt.% to initiate reaction, continuously reacting for 10 minutes, recording temperature change, stopping ventilation, reducing the rotating speed to 300 revolutions per minute, and continuing stirring for 30 minutes; 30 parts of the emulsion is weighed, 20 parts of sorbitan monostearate is added and stirred at 50 ℃ for 30 minutes, the stirring speed is set to 300 revolutions per minute, after the temperature is reduced to room temperature, 20 parts of 0.5wt.% hyperbranched polyacrylamide aqueous solution (1000 ten thousand molecular weight) is added and stirred for 30 minutes, and the stirring speed is set to 600 revolutions per minute, so that the high-rheological polymer composite emulsion is obtained. Wherein the high rheological polymer content is 0.14wt.%, the gel particle content is 20.1wt.%, the average particle diameter is 55nm, and the zero shear viscosity is 523 mPa.s as measured by a rheometer.
Example 3:
40 parts of white oil, 23 parts of sorbitan monolaurate and 10 parts of polyoxyethylene oleyl ether are weighed, poured into a four-necked flask, the temperature is raised to 50 ℃, the stirring speed is set to 450 revolutions per minute, the temperature is reduced to room temperature after stirring for 30 minutes, 30 parts of methacrylamide, 15 parts of maleic acid, 5 parts of sodium acetate and 3 parts of N, N-methylene bisacrylamide are sequentially weighed, sequentially dissolved in 25 parts of deionized water, the pH of the solution is adjusted to 6.5, and 0.3 part of 10wt.% potassium persulfate solution is added.
Pouring the water phase into a four-neck flask, mixing and stirring for 50 minutes, setting the rotating speed to 600 revolutions per minute, introducing nitrogen for 5 minutes after uniformly mixing, adding 0.3 part of sodium bisulphite aqueous solution with the concentration of 5wt.% to initiate reaction, continuously reacting for 10 minutes, recording temperature change, stopping ventilation, reducing the rotating speed to 300 revolutions per minute, and continuously stirring for 30 minutes; 35 parts of the emulsion was weighed, 25 parts of sorbitan monolaurate was added and stirred at 55 ℃ for 45 minutes, the stirring speed was set at 500 revolutions per minute, after the temperature was lowered to room temperature, 25 parts of a 0.5wt.% aqueous solution of hyperbranched polyacrylamide (2000 ten thousand molecular weight) was added and stirred for 30 minutes, and the stirring speed was set at 600 revolutions per minute, to obtain a high-rheology polymer composite emulsion. Wherein the high rheological polymer content is 0.15wt.%, the gel particle content is 21.2wt.%, the average particle diameter is 62nm, and the zero shear viscosity is 908 mPa.s as measured by a rheometer.
Example 4:
30 parts of diesel oil, 18 parts of sorbitan monopalmitate and 9 parts of polyoxyethylene monooleate are weighed, poured into a four-necked flask, the temperature is raised to 50 ℃, the stirring speed is set to be 350 revolutions per minute, the temperature is reduced to room temperature after 50 minutes of stirring, 23 parts of methacrylamide, 11 parts of 2-acrylamide-2-methylpropanesulfonic acid, 4 parts of sodium acetate and 2 parts of N, N-methylene bisacrylamide are weighed in sequence, dissolved in 20 parts of deionized water in sequence, the pH of the solution is adjusted to 6.8, and 0.2 part of ammonium persulfate solution with the mass fraction of 10wt.% is added.
Pouring the water phase into a four-neck flask, mixing and stirring for 50 minutes, setting the rotating speed to 600 revolutions per minute, introducing nitrogen for 5 minutes after uniformly mixing, adding 0.2 part of sodium bisulphite aqueous solution with the concentration of 5wt.% to initiate reaction, continuously reacting for 10 minutes, recording temperature change, stopping ventilation, reducing the rotating speed to 300 revolutions per minute, and continuously stirring for 50 minutes; 35 parts of the emulsion was weighed, 27 parts of sorbitan monopalmitate was added and stirred at 60℃for 50 minutes at a stirring speed of 500 revolutions per minute, 30 parts of a 0.5wt.% aqueous solution of hyperbranched polyacrylamide (3000 w molecular weight) was added and stirred for 30 minutes after the temperature was lowered to room temperature at a stirring speed of 600 revolutions per minute, to obtain a high-rheology polymer composite emulsion. Wherein the high rheological polymer content is 0.16%, the gel particle content is 19.6wt.%, the average particle diameter is 59nm, and the zero shear viscosity is 1912 mPa.s by a rheometer.
Example 5:
45 parts of diesel oil, 18 parts of sorbitan monooleate and 9 parts of polyoxyethylene monooleate are weighed, poured into a four-necked flask, the temperature is raised to 55 ℃, the stirring speed is set to 450 revolutions per minute, the temperature is reduced to room temperature after stirring for 30 minutes, 20 parts of methacrylamide, 10 parts of 2-acrylamide-2-methylpropanesulfonic acid, 3 parts of sodium acetate and 1 part of polyethylene glycol diacrylate are sequentially weighed, dissolved in 15 parts of deionized water in sequence, the pH of the solution is adjusted to 6.8, and 0.2 part of ammonium persulfate solution with the mass fraction of 10wt.% is added.
Pouring the water phase into a four-neck flask, mixing and stirring for 50 minutes, setting the rotating speed to 600 revolutions per minute, introducing nitrogen for 5 minutes after uniformly mixing, adding 0.2 part of sodium bisulphite aqueous solution with the concentration of 5wt.% to initiate reaction, continuously reacting for 10 minutes, recording temperature change, stopping ventilation, reducing the rotating speed to 350 revolutions per minute, and continuously stirring for 45 minutes; 41 parts of the emulsion was weighed, 27 parts of sorbitan monooleate was added and stirred at 55℃for 50 minutes at a stirring speed of 500 revolutions per minute, after the temperature was lowered to room temperature, 35 parts of a 0.5wt.% aqueous solution of hyperbranched polyacrylamide (3000 w molecular weight) was added and stirred for 30 minutes at a stirring speed of 600 revolutions per minute, to obtain a high-rheology polymer composite emulsion. Wherein the high rheological polymer content is 0.17%, the gel particle content is 16.2wt.%, the average particle diameter is 63nm, and the zero shear viscosity is 2021 mPa.s by a rheometer.
Example 6:
40 parts of peanut oil, 20 parts of sorbitan trioleate and 10 parts of polyoxyethylene monolaurate are weighed, poured into a four-necked flask, the temperature is raised to 50 ℃, the stirring speed is set to 350 revolutions per minute, the temperature is reduced to room temperature after stirring for 35 minutes, 21 parts of acrylamide, 10 parts of allylbenzenesulfonic acid, 3 parts of sodium acetate and 2 parts of dimethyl diallyl ammonium chloride are sequentially weighed, dissolved in 20 parts of deionized water in sequence, the pH of the solution is adjusted to 6.5, and 0.2 part of ammonium persulfate solution with the mass fraction of 10wt.% is added.
Pouring the water phase into a four-neck flask, mixing and stirring for 50 minutes, setting the rotating speed to 600 revolutions per minute, introducing nitrogen for 5 minutes after uniformly mixing, adding 0.2 part of sodium bisulphite aqueous solution with the concentration of 5wt.% to initiate reaction, continuously reacting for 10 minutes, recording temperature change, stopping ventilation, reducing the rotating speed to 300 revolutions per minute, and continuously stirring for 30 minutes; 36 parts of the emulsion was weighed, 23 parts of sorbitan trioleate was added and stirred at 55℃for 45 minutes at a stirring speed of 450 rpm, 27 parts of a 0.5wt.% aqueous solution of hyperbranched polyacrylamide (3000 w molecular weight) was added and stirred for 30 minutes after the temperature was lowered to room temperature at a stirring speed of 600 rpm, to obtain a high-rheology polymer composite emulsion. Wherein the high rheological polymer content is 0.16wt.%, the gel particle content is 18.5wt.%, the average particle diameter is 59nm, and the zero shear viscosity is 2195 mPa.s by rheometer.
The change of the shear viscosity with the shear rate was measured using an MCR-301 rheometer, the rheometer shear rate being set to 0.01s -1 To 1000s -1 The temperature was set at 25 ℃. The emulsion was dispersed at 100000 mg.L at 1wt.% prior to testing -1 After stirring for 30 minutes at 25 ℃ in mineralized aqueous solution, ultrasonic dispersion is carried out for 10 minutes, and the dispersion is placed in a rheometer to start testing, and the rheological curves of the polymer gel emulsion (P0) and the high-rheological polymer composite emulsion (E2) are shown in figure 3.
Example 7 (corresponding to step three method 2):
30 parts of vegetable oil, 18 parts of sorbitan monolaurate and 7 parts of polyoxyethylene oleyl ether are weighed, poured into a four-necked flask, the temperature is raised to 55 ℃, the stirring speed is set to 300 revolutions per minute, the temperature is reduced to room temperature after stirring for 45 minutes, 23 parts of methacrylamide, 11 parts of acrylic acid, 5 parts of sodium acetate and 2 parts of divinylbenzene are sequentially weighed and dissolved in 21 parts of deionized water, the pH of the solution is adjusted to 6.5, and finally 0.5 part of hyperbranched polyacrylamide and 0.3 part of 10wt.% sodium persulfate solution are added.
Pouring the water phase into a four-neck flask, mixing and stirring for 50 minutes, setting the rotating speed to 600 revolutions per minute, introducing nitrogen for 5 minutes after uniformly mixing, adding 0.3 part of potassium sulfite aqueous solution with the concentration of 5wt.% to initiate reaction, continuously reacting for 10 minutes, recording temperature change, stopping ventilation, reducing the rotating speed to 300 revolutions per minute, and continuously stirring for 30 minutes to obtain high-rheological polymer composite emulsion, wherein the high-rheological polymer content is 0.44% and the gel particle content is 55.3wt.%, the average particle diameter is 65nm, the zero shear viscosity of the rheometer is 295 mPa.s, and after 10 shear cycles are carried out on the emulsion dispersion liquid by using the rheometer, the shear rate is increased from 0.01 to 1000s -1 Then reduce to 0.01s -1 The zero shear viscosity was raised to 2392 mPas.
Example 8 (corresponding to step three method 2):
35 parts of mineral oil, 20 parts of sorbitan monopalmitate and 9 parts of polyoxyethylene monooleate are weighed, poured into a four-necked flask, the temperature is raised to 50 ℃, the stirring speed is set to 500 revolutions per minute, the temperature is reduced to room temperature after stirring for 35 minutes, 25 parts of N-methylolacrylamide, 13 parts of maleic acid, 6 parts of sodium acetate and 3 parts of dimethyl diallyl ammonium chloride are sequentially weighed, sequentially dissolved in 25 parts of deionized water, the pH of the solution is adjusted to 6.5, and finally 0.5 part of xanthan gum and 0.3 part of 10wt.% potassium persulfate solution are added.
Pouring the water phase into a four-neck flask, mixing and stirring for 50 minutes, setting the rotating speed to 600 revolutions per minute, introducing nitrogen for 5 minutes after uniformly mixing, adding 0.3 part of sodium bisulphite aqueous solution with the concentration of 5wt.% to initiate reaction, continuously reacting for 10 minutes, recording temperature change, stopping ventilation and reducing the rotating speed to 300 revolutions per minute, and continuously stirring for 30 minutes, wherein the high-rheological polymer content is 0.37%, the gel particle content is 53.7wt.%, the average particle diameter is 65nm, and the zero shear viscosity measured by a rheometer is 312 mPa.sAfter 10 shear cycles of the emulsion dispersion using a rheometer, i.e. the shear rate was increased from 0 to 1000s -1 Then reduce to 0s -1 The zero shear viscosity was raised to 2155 mpa.s.
Example 9:
35 parts of diesel oil, 19 parts of sorbitan trioleate and 10 parts of alkylphenol ethoxylate are weighed, poured into a four-necked flask, the temperature is raised to 60 ℃, the stirring speed is set to 300 revolutions per minute, the temperature is reduced to room temperature after stirring for 30 minutes, 25 parts of methacrylamide, 12 parts of 2-acrylamide-2-methylpropanesulfonic acid, 5 parts of sodium acetate and 2 parts of N, N-methylene bisacrylamide are weighed in sequence, dissolved in 25 parts of deionized water in sequence, the pH of the solution is adjusted to 6.8, and 0.3 part of ammonium persulfate solution with the mass fraction of 10wt.% is added.
Pouring the water phase into a four-neck flask, mixing and stirring for 50 minutes, setting the rotating speed to 600 revolutions per minute, introducing nitrogen for 5 minutes after uniformly mixing, adding 0.3 part of sodium bisulphite aqueous solution with the concentration of 5wt.% to initiate reaction, continuously reacting for 10 minutes, recording temperature change, stopping ventilation, reducing the rotating speed to 350 revolutions per minute, and continuously stirring for 30 minutes; 30 parts of the emulsion is weighed, 23 parts of sorbitan trioleate is added and stirred at 50 ℃ for 30 minutes, the stirring speed is set to 300 revolutions per minute, 27 parts of 0.5wt.% hyperbranched polyacrylamide aqueous solution (3000 ten thousand molecular weight) is added and stirred for 30 minutes after the temperature is reduced to room temperature, and the stirring speed is set to 600 revolutions per minute, so that the high-rheological polymer composite emulsion is obtained. Wherein the high rheological polymer content is 0.17wt.%, the gel particle content is 19.5wt.%, the average particle diameter is 69nm, and the zero shear viscosity is 2286 mPa.s.
The blocking properties of the high rheology polymer composite emulsion were measured using hypotonic cores of length and diameter 7.8 cm and 2.5 cm, respectively, with a permeability of 10-50mD, the composite emulsion was dispersed at a concentration of 5.0wt.% in 100000 mg.l prior to testing -1 Mineralized salt solution and swelled at 65 ℃ for 48 hours. In the test, the salt solution is firstly added with the concentration of 0.1 mL-min -1 Is injected into the sand pipe until the pressure is stable, and the initial permeability k is recorded 0 Then 2 Pore Volumes (PV) of the composite emulsion dispersion were injected. FinallySaline was again injected until the pressure remained stable and the permeability k' after the test was recorded. The pressure was measured continuously throughout the test, with an injection rate of 0.1mL min -1 The test temperature was 65 ℃, and after two water flooding actions, the blocking rates of the control polymer gel emulsion (P0) and the high-rheology polymer composite emulsion (E2) prepared in this example were 75% and 81%, respectively.
Under the condition of room temperature, the core is pumped out to saturate mineralized water, so as to obtain the pore volume and the porosity, a saturated mineralized water model is placed at the constant temperature of 65 ℃ for more than 12 hours, oil-driven water flows out to be anhydrous, the original oil-containing saturation is calculated, and the mineralized water is injected into the water-driven water until the water content is 98%, so that the primary water-driven recovery ratio is obtained; after injecting the 1PV emulsion dispersion, water driving is carried out again until the water content is 98%, the recovery ratio is calculated, and the injection rate is maintained at 0.5 mL.min. The oil displacement efficiency of the control sample polymer gel emulsion (P0) after secondary water flooding and the high-rheology polymer composite emulsion (E2) prepared by the embodiment can reach 45% and 53% respectively.
Claims (6)
1. A preparation method of a high-rheological polymer composite emulsion profile control agent is characterized by comprising the following steps: preparing nano polyacrylamide gel by a water-in-oil inverse emulsion polymerization technology, dispersing the nano polyacrylamide gel in an oil phase medium, and introducing a high-rheology hyperbranched polymer to prepare gel, polymer and surfactant integrated emulsion; the preparation method comprises the following steps:
(1) Preparing a composite emulsion oil phase: sequentially weighing 30-50 parts of oily medium, 15-25 parts of surfactant 1 and 5-10 parts of surfactant 2, mixing at 50-60 ℃, stirring at 300-500rpm for 30-50 minutes, and cooling to room temperature after uniform mixing;
(2) Preparing a composite emulsion water phase: sequentially weighing 20-30 parts of nonionic monomer, 10-20 parts of ionic monomer, 3-8 parts of dispersing agent and 1-5 parts of cross-linking agent, sequentially dissolving in 15-25 parts of water, adjusting the pH to 6-7 after dissolving, and finally adding 0.1-0.3 part of 10 wt% of oxidative initiator aqueous solution;
(3) The preparation method of the high-rheological polymer composite emulsion profile control agent is realized by the following method 1 or method 2;
the preparation method of the high-rheological polymer composite emulsion profile control agent comprises the following steps of: pouring the water phase prepared in the step (2) into the cooled oil phase (1), mixing and stirring for 30-50 minutes, wherein the stirring speed is 500-900rpm, introducing inert gas for 3-10 minutes, adding 0.1-0.3 part of a reducing initiator with the concentration of 5 wt% at the temperature of 25-30 ℃, quickly heating to 50-80 ℃, continuously reacting for 10 minutes, stopping ventilation, reducing the stirring speed to 200-500 revolutions per minute, and continuously stirring for 30-50 minutes; weighing 30-50 parts of the emulsion, adding 20-30 parts of surfactant 1, stirring for 30-60 minutes at 50-60 ℃, setting the stirring speed to 300-500 revolutions per minute, cooling to room temperature, adding 20-35 parts of 0.5-wt% hyperbranched polyacrylamide or xanthan gum aqueous solution with the molecular weight of 1000-3000 ten thousand, stirring for 30-60 minutes, setting the stirring speed to 500-800 revolutions per minute, and stirring until the system becomes uniform emulsion, thus obtaining high-rheological polymer composite emulsion;
the preparation method 2 of the high rheological polymer composite emulsion profile control agent comprises the steps of introducing hyperbranched polyacrylamide or xanthan gum in the preparation of the aqueous phase of the composite emulsion in the step 2; the specific method comprises the following steps: sequentially weighing 20-30 parts of nonionic monomer, 10-20 parts of ionic monomer, 3-8 parts of dispersing agent and 1-5 parts of cross-linking agent, sequentially dissolving in 15-25 parts of water, regulating the pH to 6-7 after dissolving, and finally adding 0.5 part of hyperbranched polyacrylamide or xanthan gum with the molecular weight of 1000-3000 ten thousand and 0.1-0.3 part of oxidative initiator aqueous solution with the concentration of 10 wt%; pouring the completely dissolved water phase into the cooled oil phase, namely the oil phase prepared in the step (1), mixing and stirring for 30-50 minutes, wherein the stirring speed is 500-900rpm, introducing inert gas for 3-10 minutes, adding 0.1-0.3 part of 5-wt% of reductive initiator at 25-30 ℃, quickly heating to 50-80 ℃, continuously reacting for 10 minutes, recording temperature change, stopping ventilation, reducing the stirring speed to 200-500 revolutions per minute, and continuously stirring for 30-50 minutes to obtain uniform composite emulsion;
the surfactant 1 in the step (1) is one or more selected from sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate and sorbitan trioleate; the surfactant 2 is selected from one or more of alkylphenol ethoxylates, polyoxyethylene oleyl alcohol ethers, polyoxyethylene monooleate and polyoxyethylene monolaurate;
the nonionic monomer in the step (2) is selected from one or more of acrylamide, N-methylolacrylamide, N-butoxymethylacrylamide, methacrylamide and N, N-dimethylacrylamide; the ionic monomer is selected from one or more of acrylic acid, maleic acid, 2-acrylamido-2-methylpropanesulfonic acid, allylbenzenesulfonic acid or metal salts thereof;
the dispersing agent in the step (2) is sodium acetate;
the cross-linking agent in the step (2) is a multifunctional water-soluble cross-linking agent and is selected from at least one of polyethylene glycol diacrylate, N-methylene bisacrylamide and dimethyl diallyl ammonium chloride.
2. The method for preparing the high-rheological polymer composite emulsion profile control agent according to claim 1, which is characterized in that: the oily medium in the step (1) is selected from one or more of pentane, hexane, n-hexane, octane, cyclohexane, cyclohexanone, toluene cyclohexanone, benzene, toluene, xylene, peanut oil, soybean oil, sunflower seed oil, castor oil, white oil, fuel oil and lubricating oil.
3. The method for preparing the high-rheological polymer composite emulsion profile control agent according to claim 1, which is characterized in that: the oxidizing initiator in the step (2) is selected from one of sodium peroxide, ammonium persulfate, potassium persulfate and sodium persulfate.
4. The method for preparing the high-rheological polymer composite emulsion profile control agent according to claim 1, which is characterized in that: the reducing initiator in the step (3) is selected from one of sodium sulfite, potassium sulfite, sodium bisulfite and ferrous sulfate;
the inert gas in the step (3) is nitrogen or argon.
5. A high rheology polymer composite emulsion profile control agent prepared according to the method of any one of claims 1-4.
6. The application of the high-rheological polymer composite emulsion profile control agent prepared by the method according to any one of claims 1-4, wherein the product obtained by the method 1 in the step (3) is used for improving the recovery ratio of crude oil of a hypertonic reservoir; and (3) improving the recovery ratio of the product obtained by the method 2 in the step (3) aiming at the hypotonic reservoir.
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