CN114478904A - Semi-interpenetrating network anion-cation core-shell type polymer microsphere profile control and flooding agent, and preparation method and application thereof - Google Patents
Semi-interpenetrating network anion-cation core-shell type polymer microsphere profile control and flooding agent, and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a semi-interpenetrating network anion-cation core-shell type polymer microsphere profile control and flooding agent, a preparation method and application thereof, belonging to the field of oilfield additives. The semi-interpenetrating network anion-cation core-shell type polymer microsphere profile control and flooding agent is characterized in that one of a core and a shell of the core-shell type polymer microsphere contains a hydrophobic structure unit, and the hydrophobic structure unit is derived from an amphiphilic hydrophobic monomer; the amphiphilic hydrophobic monomer is selected from anionic hydrophobic monomers and/or cationic hydrophobic monomers. The semi-interpenetrating network yin-yang core-shell polymer microsphere profile control and flooding agent prepared by the preparation process provided by the invention still has good expansion performance and plugging performance after long-term aging at high temperature and high salinity, and can be directly used for field application of improving the recovery rate of high-temperature high-salt, high-permeability oil-reservoir tertiary oil recovery, oil displacement and the like after being compounded with other oil field chemicals.
Description
Technical Field
The invention relates to the field of oilfield additives, in particular to a semi-interpenetrating network anion-cation core-shell polymer microsphere profile control and flooding agent, and a preparation method and application thereof.
Background
The polymer microsphere has the following advantages as a recognized deep profile control agent: the microsphere can meet the requirements of 'getting in and getting out and blocking' at the pore throat part for blocking a water flow channel, can expand when meeting water, does not change when meeting oil, and is a selective blocking agent; the microsphere expansion layer is continuously diluted and peeled off after being washed by injected water for a long time, and finally, oil and water are produced by an oil well, so that pollution and damage to the stratum can be avoided, and a special treatment fluid is not needed to treat the profile control water well in the later stage. However, because the general microsphere system adopts inverse microemulsion or inverse emulsion polymerization, the generated particles have smaller sizes and generally have homogeneous structures, and the microsphere system has poor adaptability to high-temperature high-salt and medium-high-permeability oil-reservoir polymer microspheres and cannot play an effective role in deep profile control and displacement.
Compared with homogeneous microspheres, the core-shell type polymer microspheres have more complex preparation process, but different monomers can be introduced into the core and the shell of the polymer respectively to form different crosslinking densities, and certain interaction force can be formed between the core and the shell through molecular design, so that the structure is more flexible and adjustable, and the core-shell type polymer microspheres have far better temperature resistance, salt resistance, hydrolysis resistance, stability and the like than the homogeneous microspheres; and the multi-step feeding polymerization mode leads the content of the emulsifier in the system to be reduced and the content of the water phase to be increased, and actually increases the solid content, namely the effective content, of the product.
The core-shell type polymer microsphere can be divided into a core-shell distinct type, a transition layer type and a gradient type. The core and the shell of the core-shell distinct microsphere have distinct and distinct interfaces, and the core and the shell are two different substances; the transition layer type microsphere is characterized in that a transition layer (graft, interpenetrating network or ionic bonding) is arranged between a core and a shell, and the core layer and the shell are tightly combined in a chemical bond mode, so that the mechanical defect caused by existence of a clear phase interface can be eliminated, and the performance of the core-shell polymer microsphere can be obviously improved; the gradient polymer microsphere is prepared by adopting a gradient feeding method (also called a power feeding method) during inverse emulsion polymerization, and the copolymerization composition (or blending composition) of the polymer is gradually changed by multiplying the gradient from the center of the microsphere to the surface of the shell of the microsphere according to a certain functional relationship, so that the prepared core-shell microsphere has excellent performance.
In recent years, much research is carried out on the aspect of research on polyacrylamide microsphere profile control and flooding agents in China, and a plurality of colleges and research institutions make better progress and achievement on the aspects of preparation of polyacrylamide microspheres and tertiary oil recovery and oil displacement application, so that polymer microsphere emulsions with various sizes from nano-scale, submicron-scale to micron-scale are prepared, but most of the obtained polymer microsphere structures applied on site are homogeneous, and the solid content is low; the preparation process of the core-shell structure microspheres reported in a few documents is complex, most researches are focused on researches on reaction mechanism, dynamics, characterization and the like, the basic physical properties such as molecular weight, particle size and the like of the polymer are paid more attention, and few factors which directly influence the application such as the stability of the polymer microspheres under oil reservoir conditions, the expansion performance of the microspheres and the like are considered or the research results are not ideal.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a semi-interpenetrating network anion-cation core-shell type polymer microsphere profile control and flooding agent. In particular to a semi-interpenetrating network anion-cation core-shell type polymer microsphere profile control and flooding agent, a preparation method and application thereof.
One of the purposes of the invention is to provide a semi-interpenetrating network anion-cation core-shell type polymer microsphere profile control and flooding agent, wherein one of the core and the shell of the core-shell type polymer microsphere contains a hydrophobic structure unit, and the hydrophobic structure unit is derived from an amphiphilic hydrophobic monomer;
the amphiphilic hydrophobic monomer is selected from anionic hydrophobic monomers and/or cationic hydrophobic monomers;
preferably, the anionic hydrophobic monomer is selected from at least one of long-chain alkyl sodium sulfonate with a vinyl carbon chain number of 8-16 or sodium p-acrylamido alkyl benzene sulfonate; the cationic hydrophobic monomer is selected from at least one of allyl alkyl ammonium chlorides with a vinyl carbon chain number of 12-20.
The semi-interpenetrating network anion-cation core-shell type polymer microsphere profile control and flooding agent is prepared by reacting the following components in the presence of a composite initiator; wherein, the total mass of the semi-interpenetrating network anion-cation core-shell type polymer microsphere profile control and flooding agent is 100 percent, and the dosage of each component is as follows:
a) 20-50% of an oil-soluble solvent; preferably 20-40%;
b) 1-10% of a composite emulsifier system; preferably 1-5%;
c) 40-75% of a water phase; preferably 55-75%; the water phase contains nonionic water-soluble monomers, amphiphilic hydrophobic monomers and ionic monomers; the weight content of all monomers in the water phase is 50-70%;
d) 0.02-2% of a cross-linking agent; preferably 0.02-1.5%;
the composite initiator comprises the following components in percentage by weight based on the weight of all the monomers:
(a) 0.02-1.0% of an oxidant;
(b) 0.02-2.0% of a reducing agent;
(c) 0.03-2.0% of azo compounds.
Preferably, the first and second electrodes are formed of a metal,
the weight of the amphiphilic hydrophobic monomer accounts for 0.1-5% of the total mass of the nonionic water-soluble monomer, the amphiphilic hydrophobic monomer and the ionic monomer (namely the total mass of all monomers in a water phase), preferably 0.2-3%, and more preferably 0.3-1.5%.
Wherein the content of the first and second substances,
the oil-soluble solvent may be selected from at least one of aliphatic hydrocarbon, aromatic hydrocarbon, halogenated hydrocarbon, etc., and preferably may be a mixture of one or more of toluene, o-xylene, isoparaffin, cycloalkane, paraffin, petroleum ether, toluene, xylene, white oil, and kerosene, etc.
The composite emulsifier system is partially selected from at least one of nonionic lipophilic surfactants and hydrophilic surfactants, and specifically selected from at least one of fatty acid polyoxyethylene ester, alkyl acid polyoxyethylene ether, fatty alcohol polyoxyethylene ether and the like; and adjusting the mass ratio of the two surfactants to ensure that the hydrophilic-lipophilic balance (HLB) of the composite emulsifier system is between 4 and 9.
And/or, in order to increase the stability of the system, a co-emulsifier can be added, and the co-emulsifier can be selected from at least one of alcohols, salts and/or small molecule polymers. The total dosage of the co-emulsifier can be 10-90 wt%, preferably 10-60 wt% of the total dosage of the composite emulsifier system. Wherein, the salt can be at least one of chloride or acetate of sodium or potassium;
the small molecule polymer may comprise an oligomer, preferably at least one of polyacrylamide, polyacrylic acid, polyethylene glycol, etc., having a molecular weight of several thousand (e.g., a molecular weight of 1000 to 10000).
The nonionic water soluble monomer may include, but is not limited to, at least one of acrylamide, methacrylamide, t-butylacrylamide, N-isopropylacrylamide, N-dimethylacrylamide, N-diethylacrylamide and N-methylolacrylamide, N-vinylformamide, N-vinylacetamide, N-vinylpyridine and N-vinylpyrrolidone, nitrogen vinylpyrrolidone, etc.; and/or the presence of a gas in the gas,
the ionic monomer may include, but is not limited to, anionic monomers and/or cationic monomers; the anionic monomer may include, but is not limited to, at least one of 2-acrylamido-2-methylpropanesulfonic acid, acrylic acid, methacrylic acid, itaconic acid, maleic acid, vinylbenzenesulfonic acid, vinylsulfonic acid, and/or water-soluble alkali metal, alkaline earth metal, and ammonium salts thereof; and/or the presence of a gas in the atmosphere,
the cationic monomer may include, but is not limited to, at least one of dimethyldiallylammonium chloride, acryloyloxyethyltrimethylammonium chloride, methacryloyloxyethyltrimethylammonium chloride, methacryloylpropyltrimethylammonium chloride, and 2-acrylamido-2-methylpropyltrimethylammonium chloride.
The amphiphilic hydrophobic monomer may include, but is not limited to, anionic hydrophobic monomers and/or cationic hydrophobic monomers; preferably, the anionic hydrophobic monomer may include, but is not limited to, at least one of sodium alkyl sulfonate with a long chain vinyl carbon chain number of 8-16 or sodium p-acrylamido alkyl benzene sulfonate, and the cationic hydrophobic monomer may be selected from allyl alkyl ammonium chloride with a vinyl carbon chain number of 12-20, and the like, and may be specifically selected from octadecyl dimethyl trimethoxy silyl propyl ammonium chloride, dimethyl tetradecyl (2-acrylamidoethyl) ammonium chloride, and the like.
The crosslinking agent may include, but is not limited to, at least one of N, N-methylenebisacrylamide, divinylbenzene, polyethylene glycol diacrylate, aldehydes having two or more aldehyde groups, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, and the like. Wherein the aldehyde may be at least one selected from glyoxal, glutaraldehyde, and the like.
The oxidant can be at least one of potassium persulfate, sodium persulfate, ammonium persulfate or benzoyl peroxide; the reducing agent can be selected from at least one of sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium thiosulfate, ferrous chloride and the like;
the azo compound may be at least one selected from 2, 2' -azo [2- (2-imidazolin-2-yl) propane ] dihydrochloride (V044), azobisisobutylamidine hydrochloride (V50), Azobisisobutyronitrile (AIBN), Azobisisoheptonitrile (ABVN), and the like.
The invention also aims to provide a preparation method of the semi-interpenetrating network anion-cation core-shell type polymer microsphere profile control and flooding agent, which comprises the following steps:
(a) adding the oil-soluble solvent and the lipophilic surfactant in the composite emulsifier system into a container with a certain size, and uniformly mixing to form a continuous oil phase;
(b) in a container with a certain size, dissolving a polymerization monomer (containing or not containing an amphiphilic hydrophobic monomer) required for preparing a microsphere core part and auxiliaries such as a hydrophilic surfactant, a co-emulsifier, a cross-linking agent and the like in a composite emulsifier system in water, and uniformly stirring to form a water phase I; in another container, the components of the polymeric monomer (with or without amphiphilic hydrophobic monomer), the co-emulsifier, the cross-linking agent and the like required for preparing the shell part of the microsphere are dissolved in water and stirred uniformly to form a water phase II. The oxidant and the reducer can be respectively dissolved in water to form an initiator aqueous solution, and the oil-soluble initiator can be dissolved in a small amount of solvent for later use.
Wherein, preferably, the aqueous phase I and the aqueous phase II do not comprise an amphiphilic hydrophobic monomer at the same time; preferably, one of the aqueous phases I or II comprises amphiphilic hydrophobic monomers, i.e. the invention introduces amphiphilic hydrophobic monomers in only one of the aqueous phases.
Preferably, the weight of the amphiphilic hydrophobic monomer accounts for 0.3 to 6 percent of the total mass of all monomers in the aqueous phase (i.e. one of aqueous phase I or aqueous phase II), preferably 0.3 to 4 percent, and more preferably 0.5 to 3 percent. And/or the ratio of the total weight of the monomers contained in the water phase I to the total weight of the monomers contained in the water phase II is 6: 1-0.5: 1, preferably 4: 1 to 1:1, more preferably 3:1 to 1.5: 1.
(c) Slowly adding the water phase I into the continuous oil phase, and simultaneously shearing at a high speed to form milky emulsion to be put into a reaction kettle (a homogenizing emulsifying machine can be used for shearing at a high speed of 10000-20000 revolutions per minute for 3-30 minutes); controlling the temperature in the reaction kettle to be 5-30 ℃, stirring the reaction kettle at a rotating speed of 400-600 rpm, introducing nitrogen to remove oxygen for 0.5-1 h, then dropwise adding a certain amount of oxidant, stirring the mixture uniformly for 5-10 min, continuously dropwise adding a reducing agent at a certain speed (the specific speed can be determined according to the concentration and the total amount of the reducing agent, such as 0.01-10 ml/min), initiating polymerization, controlling the heat release of the polymerization reaction by the dropwise adding speed of the reducing agent, controlling the temperature rise speed to be less than or equal to 2 ℃/min, keeping the final reaction temperature at 30-60 ℃, keeping the temperature after the temperature reaches the peak, and continuing the reaction for 0.5-1 h to obtain the core part of the semitransparent semi-interpenetrating network yin-yang core-shell polymer microsphere profile control agent;
(d) and (3) adding a water-soluble azo initiator or an oil-soluble azo initiator dissolved by a small amount of solvent into the water phase II, uniformly stirring, dripping the mixture into the core emulsion of the polymer microsphere obtained in the step (c) at a certain speed, controlling the polymerization to be stably carried out by controlling the temperature of a water bath, controlling the temperature of the water bath to be between 40 and 70 ℃, finishing the reaction after 4 to 8 hours, cooling to room temperature, dripping a certain amount of phase transfer agent, and uniformly stirring to obtain the polymer microsphere. The second step reaction adopts a dropping process, and the dropping speed of the water phase can be controlled to ensure that the diffusion speed of the water phase to the core is lower than the reaction speed of the monomer, so that the second step reaction is basically carried out on the outer layer of the core, and the product structure obtained by the two steps reaction is basically a core-shell structure. Specifically, the water phase II is added dropwise within 1.5-3 hours, preferably 2-2.5 hours. The dropping speed can be 3-10 g/min, preferably 4-6 g/min.
The dosage of the phase inversion agent is 5-95% of the weight of the composite emulsifier, and preferably 20-80%; the phase inversion agent can be a surfactant with a structure similar to that of the hydrophilic surfactant in the composite emulsifier system. The phase transfer agent can be at least one of hydrophilic surfactants such as fatty acid polyoxyethylene ester, alkyl acid polyoxyethylene ether and fatty alcohol polyoxyethylene ether, the number of ethoxy groups is equal to or slightly smaller than that of the hydrophilic surfactants used as the emulsifier, namely the HLB value is close to or slightly smaller than that of the hydrophilic surfactants, and the HLB value of the phase transfer agent is 10-20, preferably 10-15.
The invention also aims to provide the application of the semi-interpenetrating network yin-yang core-shell type polymer microsphere profile control agent in deep profile control and oil displacement for tertiary oil recovery of a high-permeability oil reservoir under high temperature and high salinity. Specifically, the semi-interpenetrating network anion-cation core-shell polymer microsphere profile control and flooding agent can be directly applied to field application of improving the recovery rate for high-temperature high-salt and medium-high-permeability oil reservoirs, tertiary oil recovery, oil displacement and the like after being compounded with other oilfield chemicals.
The polymer microsphere profile control agent can be compounded with other oilfield chemical additives according to requirements, such as oil-flooding polymers or surfactants, and the weight ratio of the oilfield chemical additives to the microspheres can be 1: 10-10: 1.
on the basis of extensive and intensive research on the synthesis, structural characterization and properties of polyacrylamide inverse emulsion and core-shell structure microspheres, an inverse emulsion or inverse microemulsion polymerization method is adopted, an amphiphilic hydrophobic monomer is introduced into a monomer of a microsphere core or shell, in the process of nucleation or cladding reaction carried out step by step, a reaction group of the hydrophobic monomer is copolymerized with acrylamide and other monomers in the monomer of the microsphere core or shell, a hydrophobic long-chain tail group points to an oil phase, so that the hydrophobic monomer is easily arranged on an oil-water interface as a whole, and is further copolymerized with the cladding or the nucleated monomer or has the adsorption effect of anions and cations; thus, the core and the shell of the polymer microsphere are connected through the amphiphilic hydrophobic monomer to form intermolecular association crosslinking, which is equivalent to a semi-interpenetrating network. Compared with the common core-shell microsphere, the structure of the yin-yang core-shell microsphere is more definite and stable, and the profile control plugging performance is improved.
The semi-interpenetrating network yin-yang core-shell polymer microsphere profile control and flooding agent can solve the problems that the core-shell polymer microsphere is poor in binding power between the core and the shell, the positive core-shell structure is difficult to guarantee, and a blending product of two types of microspheres is easy to form finally when the core-shell polymer microsphere is prepared in the prior art. The semi-interpenetrating network yin-yang core-shell polymer microsphere profile control and flooding agent prepared by the preparation process provided by the invention has the advantages that the initial particle size of the polymer microsphere is hundreds of nanometers (specifically 200-900 nanometers), the polymer microsphere still has good expansion performance and plugging performance after long-term aging at high temperature and high salinity, and the prepared semi-interpenetrating network yin-yang core-shell polymer microsphere profile control and flooding agent can be directly used or used for field application for improving the recovery rate of high-temperature high-salt and medium-high-permeability oil-reservoir tertiary oil recovery, and the like after being compounded with other oil field chemicals.
Drawings
FIG. 1 is a schematic diagram of interpenetrating network associated microspheres;
FIG. 2 is a schematic representation of a semi-interpenetrating network core-shell microsphere described herein.
Detailed Description
While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The starting materials used in the examples are all commercially available.
[ example 1 ]
Adding 650g of 5# white oil and 72g of SPAN80(HLB is 4.3) into a beaker, stirring until the materials are completely and uniformly mixed to form a mixed oil phase, and reserving 1/4 for supplementing; 500g of water, 6g of dimethylallyloctadecyl ammonium chloride, 630g of acrylamide, 260g of dimethyldiallyl ammonium chloride (with a content of 60%), 10g of potassium acetate, 0.8g of sodium diethylenetriamine pentaacetate, 8g of methylene bisacrylamide, 8g of TWEEN80(HLB is 15) and an emulsifier system consisting of SPAN80 in an oil phase, HLB is 5.37 and 0.4g of V044 are added into a container with a certain size, and the mixture is uniformly stirred and dissolved to form a water phase I; adding 280g of water, 330g of acrylamide, 100g of 2-acrylamido-2-methylpropanesulfonic acid sodium salt, 5g of potassium acetate, 0.4g of sodium diethylenetriamine pentaacetate and 1.0g of methylene bisacrylamide into another container, stirring the solvent uniformly, adding 5g of isopropanol solution in which 0.4g of azobisisobutyronitrile is dissolved, and stirring and dissolving uniformly to obtain a water phase II; ammonium persulfate and sodium bisulfite are respectively prepared into 1.0 percent and 0.05 percent aqueous solutions for standby. Slowly adding the water phase I into the mixed oil phase in the beaker, simultaneously starting a homogenizing emulsifying machine, and shearing at a high speed of 20000 revolutions per minute for 3 minutes to form milky emulsion which is put into a reaction kettle; controlling the temperature in the reaction kettle at 20 ℃, controlling the stirring speed to be 400rpm, introducing nitrogen to remove oxygen for 0.5h, then dripping 4g of oxidant aqueous solution, stirring for 10min to be uniform, then continuously dripping reducing agent aqueous solution at a certain speed to initiate polymerization, controlling the heat release of the polymerization reaction by the dripping speed of the reducing agent aqueous solution, controlling the temperature rise speed to be less than or equal to 2 ℃/min, raising the temperature to 43 ℃ after about 3 hours, and keeping the temperature to continue reacting for 1.5 hours to obtain the core part of the semitransparent semi-interpenetrating network yin-yang core-shell polymer microsphere profile control and flooding agent; adding the reserved oil phase into a reaction kettle, uniformly stirring, continuously dropwise adding a water phase II into the formed nuclear emulsion of the microsphere profile control and flooding agent at a certain speed, controlling the polymerization to be stably carried out at about 56 ℃ through water bath temperature, dropwise adding the water phase II within about 2 hours, then preserving heat for 2 hours to finish reaction, cooling to room temperature, dropwise adding 36g of OP10(HLB is 13.5), continuously stirring for 20min to obtain a semitransparent product, and stably storing for more than 6 months.
The content of the precipitated solid is 42.5 percent, the initial average particle size is 530nm, the total mineralization is 250000mg/L at 95 ℃, and the Ca content is determined by the method of sampling analysis and reference of Q/SH1020 enterprise standard & lt & gt technical conditions for polymer microsphere deep profile control and flooding agent & gt of China petrochemical group Shengli Petroleum administration2++Mg2+: aging in 10000mg/L saline for 5 days, 15 days,After 45 days, the expansion times of the particle diameters are respectively 4.2, 8.6 and 10.5 times, 0.5PV of polymer microspheres with the concentration of 0.2 percent after aging for 45 days is injected by a sand filling pipe with 2000mD, and the plugging rate is measured to reach 89 percent.
[ example 2 ]
650g of 5# white oil and 72g of SPAN80(HLB is 4.3) are added into a reaction kettle, stirred until the mixture is completely and uniformly mixed to serve as a mixed oil phase, and 1/4 is reserved for supplement; adding 520g of water, 630g of acrylamide, 180g of methacryl propyl trimethyl ammonium chloride, 6g of dimethyl allyl hexadecyl ammonium chloride, 8g of sodium acetate, 5g of TWEEN60(HLB is 14.9) and an emulsifier system consisting of SPAN80 in an oil phase, wherein the HLB is 4.99, 0.5g of ethylene diamine tetraacetic acid disodium salt, 10g of isopropanol and 11g of methylene bisacrylamide into a container with a certain size, and uniformly stirring and dissolving to obtain a water phase I; adding 320g of water, 300g of acrylamide, 65g of 2-acrylamido-2-methylpropanesulfonic acid sodium salt, 18g of sodium acetate, 0.5g of ethylene diamine tetraacetic acid disodium salt and 1.0g of methylene bisacrylamide into another container, stirring the solvent uniformly, adding 10g of isopropanol solution dissolved with 1g of azobisisoheptonitrile, and stirring and dissolving uniformly to obtain a water phase II; ammonium persulfate and sodium bisulfite are respectively prepared into 1.0 percent and 0.1 percent aqueous solutions for standby. Slowly adding the water phase I into the mixed oil phase, starting a homogenizing emulsifying machine at the same time, and shearing at a high speed of 10000 r/min for 15 min to form milky white emulsion which is put into a reaction kettle; controlling the temperature in the reaction kettle at 18 ℃, controlling the stirring speed to be 500rpm, introducing nitrogen to remove oxygen for 0.5h, then dripping 2g of oxidant aqueous solution, stirring for 10min to be uniform, then continuously dripping reducing agent aqueous solution at a certain speed to initiate polymerization, controlling the heat release of the polymerization reaction by the dripping speed of the reducing agent aqueous solution, controlling the temperature rise speed to be less than or equal to 1.5 ℃/min, raising the temperature to 42 ℃ after about 4 hours, preserving the temperature and continuing the reaction for 1 hour to obtain the core part of the semitransparent semi-interpenetrating network yin-yang core-shell polymer microsphere profile control and flooding agent; adding the reserved oil phase into a reaction kettle, uniformly stirring, continuously dropwise adding a water phase II into the formed nuclear emulsion of the microsphere profile control and flooding agent at a certain speed, controlling the polymerization to be stably carried out at about 56 ℃ through water bath temperature, dropwise adding the water phase II for about 2 hours, then preserving heat for 2 hours to finish reaction, cooling to room temperature, dropwise adding 30g of OP10(HLB is 13.5), continuously stirring for 20min to obtain a semitransparent product, and stably storing for more than 6 months.
The content of precipitated solid is 40.7 percent, the initial average grain diameter is 620nm, the total mineralization is 250000mg/L at 95 ℃, and Ca is measured by sampling analysis and referring to a method for measuring the standard polymer microsphere deep profile control agent technical condition of the enterprise Standard of Q/SH1020 China petrochemical group Shengli Petroleum administration2++Mg2+: aging in 10000mg/L saline for 5 days, 15 days and 45 days, wherein the expansion times of the particle diameter are respectively 4.6 times, 7.2 times and 10.9 times, injecting 0.2 percent polymer 0.5PV after aging for 45 days by using a 2000mD sand filling pipe, and measuring that the plugging rate reaches 89 percent.
[ example 3 ]
Firstly, 680g of 120# solvent oil and 78g of SPAN60(HLB is 4.7) are added into a reaction kettle, stirred until the mixture is completely and uniformly mixed to serve as a mixed oil phase, and 1/4 is reserved for supplement; adding 530g of water, 15g of tetradecyl dimethyl allyl ammonium chloride, 630g of acrylamide, 270g of acryloyloxyethyl trimethyl ammonium chloride, 10g of sodium acetate, 10g of TWEEN60(HLB is 14.9) and an emulsifier system consisting of SPAN60 in an oil phase, wherein the emulsifier system consists of 5.86 HLB, 1.0g of disodium ethylene diamine tetraacetate, 15g of isopropanol and 2.1g of pentaerythritol triacrylate into a container with a certain size, and uniformly stirring and dissolving to obtain a water phase I; 300g of water, 380g of acrylamide, 50g of N, N-dimethylacrylamide, 20g of sodium acetate, 0.5g of disodium ethylenediamine tetraacetic acid and 1.0g of methylenebisacrylamide are added into a separate container, stirred and dissolved uniformly, and then 0.4g of 2, 2' -azo [2- (2-imidazolin-2-yl) propane ] dihydrochloride (V044) is added and stirred and dissolved uniformly to obtain a water phase II; ammonium persulfate and sodium bisulfite are respectively prepared into 1.0 percent and 0.1 percent aqueous solutions for standby. Slowly adding the water phase I into the mixed oil phase, starting a homogenizing emulsifying machine at the same time, and shearing at a high speed of 10000 r/min for 15 min to form milky white emulsion which is put into a reaction kettle; controlling the temperature in the reaction kettle at 25 ℃, controlling the stirring speed to 520rpm, introducing nitrogen to remove oxygen for 0.5h, then dripping 3g of oxidant aqueous solution, stirring for 10min until the mixture is uniform, then continuously dripping reducing agent aqueous solution at a certain speed to initiate polymerization, controlling the heat release of the polymerization reaction by the dripping speed of the reducing agent aqueous solution, controlling the temperature rise speed to be less than or equal to 1.8 ℃/min, raising the temperature to 41 ℃ after about 3.5 hours, preserving the temperature and continuing the reaction for 1 hour to obtain the core part of the semitransparent semi-interpenetrating network yin-yang core-shell type polymer microsphere profile control and flooding agent; adding the reserved oil phase into a reaction kettle, uniformly stirring, continuously dropwise adding a water phase II into the formed nuclear emulsion of the microsphere profile control and flooding agent at a certain speed, controlling the polymerization to be stably carried out at about 52 ℃ through the water bath temperature, dropwise adding the water phase II after about 2.5 hours, preserving the heat for 2 hours after dropwise adding to finish the reaction, cooling to room temperature, dropwise adding 30g of AEO9(HLB is 13.5), continuously stirring for 20min to obtain a semitransparent product, and stably storing for more than 6 months.
The content of precipitated solid is 40.2 percent, the initial average particle size is 570nm, the total mineralization is 250000mg/L at 95 ℃, and Ca is contained in the sample, the analysis is carried out by referring to a method for determining the standard polymer microsphere deep profile control and flooding agent technical condition of the enterprise of Q/SH1020 China petrochemical group Shengli Petroleum administration2++Mg2+: aging in 10000mg/L saline for 5 days, 15 days and 45 days, wherein the expansion times of the particle diameter are respectively 4.3, 7.2 and 10.3 times, injecting 0.2 percent polymer 0.5PV after aging for 45 days by a 2000mD sand filling pipe, and measuring that the plugging rate reaches 91 percent.
[ example 4 ] A method for producing a polycarbonate
650g of 3# white oil and 72g of SPAN80(HLB is 4.3) are added into a reaction kettle, stirred until the mixture is completely and uniformly mixed to serve as a mixed oil phase, and 1/4 is reserved for supplement; 550g of water, 685g of acrylamide, 200g of 2-acrylamido-2-methylpropanesulfonic acid sodium salt, 5g of OP10(HLB is 13.5), an emulsifier system consisting of SPAN80 in an oil phase, HLB is 4.90, 12g of sodium acetate, 0.8g of ethylene diamine tetraacetic acid disodium salt, 10g of isopropanol and 2.0g of methylene bisacrylamide are added into a container with a certain size, and the mixture is uniformly stirred and dissolved to form a water phase I; adding 310g of water, 10g of octadecyl dimethyl trimethoxy silyl propyl ammonium chloride, 380g of acrylamide, 40g of dimethyl diallyl ammonium chloride, 12g of sodium acetate, 0.5g of disodium ethylene diamine tetraacetate and 0.8g of polyethylene glycol diacrylate into a separate container, stirring the solvent uniformly, adding 0.5g of azo diisobutyl amidine hydrochloride (V50), and stirring and dissolving uniformly to obtain a water phase II; ammonium persulfate and sodium bisulfite are respectively prepared into 1.0 percent and 0.1 percent aqueous solutions for standby. Slowly adding the water phase I into the mixed oil phase, starting a homogenizing emulsifying machine, and shearing at a high speed of 10000 r/min for 20min to form milky emulsion which is put into a reaction kettle; controlling the temperature in the reaction kettle at 26 ℃, controlling the stirring speed to be 550rpm, introducing nitrogen to remove oxygen for 0.5h, then dripping 3g of oxidant aqueous solution, stirring for 10min until the mixture is uniform, continuously dripping reducing agent aqueous solution at a certain speed to initiate polymerization, controlling the heat release of the polymerization reaction by controlling the dripping speed of the reducing agent aqueous solution, controlling the temperature rise to be 48 ℃ after about 3.8 hours, and keeping the temperature for continuous reaction for 0.5h to obtain the core part of the semitransparent semi-interpenetrating network yin-yang core-shell polymer microsphere profile control and flooding agent; adding the reserved oil phase into a reaction kettle, uniformly stirring, continuously dropwise adding a water phase II into the formed nuclear emulsion of the microsphere profile control and flooding agent at a certain speed, controlling the polymerization to be stably carried out at about 56 ℃ through water bath temperature, dropwise adding the water phase II after about 2.5 hours, preserving heat for 2 hours after dropwise adding to finish reaction, cooling to room temperature, dropwise adding 28g of AEO9(HLB is 13.5), continuously stirring for 20min to obtain a semitransparent product, and stably storing for more than 6 months.
The content of the precipitated solid is 42.5 percent, the initial average particle size is 720nm, the total mineralization is 250000mg/L at 95 ℃, and the Ca content is determined by the method of sampling analysis and reference of Q/SH1020 enterprise standard & lt & gt technical conditions for polymer microsphere deep profile control and flooding agent & gt of China petrochemical group Shengli Petroleum administration2++Mg2+: aging in 10000mg/L saline for 5 days, 15 days and 45 days, the expansion times of the particle diameter are respectively 4.9 times, 7.8 times and 9.6 times, injecting 0.2 percent concentration polymer 0.5PV after aging for 45 days by a 2000mD sand filling pipe, and measuring that the plugging rate reaches 88 percent.
[ example 5 ]
640g of 90# solvent oil and 75g of SPAN80(HLB is 4.3) are added into a reaction kettle, stirred until the mixture is completely and uniformly mixed to serve as a mixed oil phase, and 1/4 is reserved for supplement; in a container of a certain size, 570g of water, 12g of dimethyltetradecyl (2-acrylamidoethyl) ammonium chloride, 720g of acrylamide, 130g of dimethyldiallylammonium chloride, 15g of potassium acetate, 0.7g of sodium diethylenetriamine pentaacetate, 10g of isopropanol, 7g of OP15(HLB is 15), an emulsifier system HLB is 5.94 consisting of SPAN80 in an oil phase, and 8g of pentaerythritol triacrylate are added, and the mixture is uniformly stirred and dissolved to form a water phase I; 300g of water, 350g of acrylamide, 65g of nitrogen vinyl pyrrolidone, 5g of sodium acetate, 0.8g of divinylbenzene, 8g of isopropanol, 0.8g of pentaerythritol triacrylate and 0.5g of azobisisobutylamidine hydrochloride (V50) were put into a separate container and stirred together to dissolve uniformly to form a water phase II; ammonium persulfate and sodium bisulfite are respectively prepared into 2.0 percent and 0.2 percent aqueous solutions for standby. Slowly adding the water phase I into the mixed oil phase, starting a homogenizing emulsifying machine, and shearing at a high speed of 10000 r/min for 20min to form milky emulsion which is put into a reaction kettle; controlling the temperature in the reaction kettle at 18 ℃, stirring the mixture at a rotating speed of 500rpm, introducing nitrogen to remove oxygen for 0.5h, then dripping 1.5g of oxidant aqueous solution, stirring the mixture for 10min to be uniform, then continuously dripping reducing agent aqueous solution at a certain speed to initiate polymerization, controlling the heat release of the polymerization reaction by the dripping speed of the reducing agent aqueous solution, controlling the temperature rise speed to be less than or equal to 1.8 ℃/min, raising the temperature to 46 ℃ after about 4.2 hours, preserving the temperature and continuing the reaction for 0.5h to obtain the core part of the semitransparent semi-interpenetrating network yin-yang core-shell type polymer microsphere profile control and flooding agent; adding the reserved oil phase into a reaction kettle, uniformly stirring, continuously dropwise adding a water phase II into the formed nuclear emulsion of the microsphere profile control and flooding agent at a certain speed, controlling the polymerization to be stably carried out at about 56 ℃ through water bath temperature, dropwise adding the water phase II after about 2.5 hours, preserving heat for 2 hours after dropwise adding to finish reaction, cooling to room temperature, dropwise adding 35g of OP10(HLB is 13.5), continuously stirring for 20min to obtain a semitransparent product, and stably storing for more than 6 months.
The content of the precipitated solid is 42.1 percent, the initial average particle size is 530nm, the total mineralization is 250000mg/L at 95 ℃, and the Ca content is determined by the method of sampling analysis and reference of Q/SH1020 enterprise standard & lt & gt technical conditions for polymer microsphere deep profile control and flooding agent & gt of China petrochemical group Shengli Petroleum administration2++Mg2+: aging in 10000mg/L saline for 5 days, 15 days and 45 days, wherein the expansion times of the particle diameter are respectively 4.6 times, 7.9 times and 10.8 times, injecting 0.2 percent concentration polymer 0.5PV after aging for 45 days by using a 2000mD sand filling pipe, and measuring that the plugging rate reaches 91 percent.
The above examples show that the semi-interpenetrating network yin-yang core-shell polymer microsphere profile control agent obtained by the invention has a submicron level initial particle size of hundreds of nanometers, has a solid content of more than 40%, can effectively block 2000mD high-permeability sand-filling pipes after being aged for a period of time under the condition of a high-temperature and high-salt oil reservoir, and has a blocking rate of about 90% after being injected with 0.5PV with a concentration of 0.2% after being aged for 45 days.
Comparative example 1
Except that dimethylallyloctadecylammonium chloride was removed in example 1, the rest were the same.
The content of the precipitated solid is 42.1 percent, the initial average particle size is 430nm, the total mineralization is 250000mg/L at 95 ℃, and the Ca content is determined by the method of sampling analysis and reference of Q/SH1020 enterprise standard & lt & gt technical conditions for polymer microsphere deep profile control and flooding agent & gt & lt & gt of China petrochemical group Shengli Petroleum administration2++Mg2+: aging in 10000mg/L saline for 5 days, 15 days and 45 days, wherein the expansion times of the particle diameter are respectively 2.6 times, 3.2 times and 4.7 times, injecting 0.2 percent polymer microsphere 0.5PV after aging for 45 days by using a 2000mD sand filling pipe, and measuring the plugging rate to be 27 percent.
Comparative example 2
The dimethylallyloctadecylammonium chloride from example 1 was replaced by styrene, and the rest was the same.
The content of precipitated solid is 42.3 percent, the initial average particle size is 470nm, the total mineralization is 250000mg/L at 95 ℃, and the Ca content is determined by the method of sampling analysis and reference of Q/SH1020 enterprise standard & lt & gt technical conditions for polymer microsphere deep profile control and flooding agent & gt of China petrochemical group Shengli Petroleum administration corporation2++Mg2+: aging in 10000mg/L saline for 5 days, 15 days and 45 days, wherein the expansion times of the particle diameter are respectively 2.9 times, 3.6 times and 4.9 times, injecting 0.2 percent polymer microsphere 0.5PV after aging for 45 days by using a 2000mD sand filling pipe, and measuring that the plugging rate reaches 34 percent.
Comparative example 3
The interpenetrating network associated polymer microspheres obtained in CN109666096A example 1 are evaluated by the conditions of the invention, and the total mineralization degree is 250000mg/L, Ca is carried out at 95 DEG C2++Mg2+: aging in 10000mg/L saline for 5 days, 15 days and 45 days,the expansion times of the particle diameters are respectively 3.6 times, 4.7 times and 5.9 times, 0.5PV of polymer microspheres with the concentration of 0.2 percent after aging for 45 days is injected into a sand filling pipe with the diameter of 2000mD, and the plugging rate is measured to reach 52 percent.
Therefore, the microspheres obtained without adding amphiphilic hydrophobic monomers or adding lipophilic hydrophobic monomers have much poorer plugging performance. Without adding amphiphilic hydrophobic monomers, a semi-interpenetrating network between the core and the shell cannot be formed, and the expansion performance and the plugging performance of the microspheres are deteriorated after long-term aging under high temperature and high mineralization. The interpenetrating network type microspheres obtained by adopting the method of the embodiment of CN109666096A are of a homogeneous structure, and the aggregation adsorption effect of the microspheres after long-term aging is weaker than that of the microspheres with a semi-interpenetrating core-shell structure, so that the blocking capability is relatively weaker.
Claims (12)
1. A semi-interpenetrating network negative and positive core-shell type polymeric microsphere profile control and flooding agent, wherein one of the core or the shell of the core-shell type polymeric microsphere contains a hydrophobic structure unit, and the hydrophobic structure unit is derived from an amphiphilic hydrophobic monomer;
the amphiphilic hydrophobic monomer is selected from anionic hydrophobic monomers and/or cationic hydrophobic monomers;
preferably, the anionic hydrophobic monomer is selected from at least one of long-chain alkyl sodium sulfonate with a vinyl carbon chain number of 8-16 or sodium p-acrylamido alkyl benzene sulfonate; the cationic hydrophobic monomer is selected from at least one of allyl alkyl ammonium chlorides with a vinyl carbon chain number of 12-20.
2. The semi-interpenetrating network yin-yang core-shell type polymer microsphere profile control and flooding agent according to claim 1, characterized in that: in the presence of a composite initiator, the composite initiator is prepared by the reaction of the following components; wherein, the components comprise the following components in percentage by weight:
a) 20-50% of an oil-soluble solvent; preferably 20-40%;
b) 1-10% of a composite emulsifier system; preferably 1-5%;
c) 40-75% of a water phase; preferably 55-75%; the water phase contains nonionic water-soluble monomers, amphiphilic hydrophobic monomers and ionic monomers; the weight content of all monomers in the water phase is 50-70%;
d) 0.02-2% of a cross-linking agent; preferably 0.02 to 1.5%.
3. The semi-interpenetrating network yin-yang core-shell type polymer microsphere profile control and flooding agent according to claim 2, characterized in that:
the weight of the amphiphilic hydrophobic monomer accounts for 0.1-5%, preferably 0.2-3%, and more preferably 0.3-1.5% of the total mass of the nonionic water-soluble monomer, the amphiphilic hydrophobic monomer and the ionic monomer.
4. The semi-interpenetrating network yin-yang core-shell type polymer microsphere profile control and flooding agent according to claim 2, characterized in that:
the composite initiator comprises the following components in percentage by weight of all monomers:
(a) 0.02-1.0% of an oxidant;
(b) 0.02-2.0% of a reducing agent;
(c) 0.03-2.0% of azo compounds.
5. The semi-interpenetrating network yin-yang core-shell type polymer microsphere profile control and flooding agent according to claim 2, characterized in that:
the hydrophilic-lipophilic balance value of the composite emulsifier system is between 4 and 9;
the composite emulsifier system is at least one selected from nonionic lipophilic surfactants and hydrophilic surfactants, and preferably at least one selected from fatty acid polyoxyethylene esters, alkyl acid polyoxyethylene ethers and fatty alcohol polyoxyethylene ethers.
6. The agent according to claim 2, which is characterized by comprising a co-emulsifier;
the coemulsifier is selected from at least one of alcohols, salts and/or small molecular polymers;
the total dosage of the co-emulsifier is 10-90 wt%, preferably 10-60 wt% of the total dosage of the composite emulsifier system.
7. The semi-interpenetrating network yin-yang core-shell type polymer microsphere profile control and flooding agent according to claim 2, characterized in that:
the non-ionic water-soluble monomer is at least one selected from acrylamide, methacrylamide, N-isopropyl acrylamide, N-dimethyl acrylamide, N-diethyl acrylamide, N-hydroxymethyl acrylamide, N-vinyl formamide, N-vinyl acetamide, N-vinyl pyridine and N-vinyl pyrrolidone; and/or the presence of a gas in the gas,
the ionic monomer is selected from anionic monomers and/or cationic monomers;
the anionic monomer is selected from at least one of 2-acrylamide-2-methyl propane sulfonic acid, acrylic acid, methacrylic acid, itaconic acid, maleic acid, vinyl benzene sulfonic acid, vinyl sulfonic acid and/or water-soluble alkali metal salt, alkaline earth metal salt and ammonium salt thereof; and/or the presence of a gas in the gas,
the cationic monomer is at least one selected from dimethyl diallyl ammonium chloride, acryloyloxyethyl trimethyl ammonium chloride, methacryloyloxyethyl trimethyl ammonium chloride, methacryloyl propyl trimethyl ammonium chloride and 2-acrylamido-2-methylpropyl trimethyl ammonium chloride.
8. The semi-interpenetrating network yin-yang core-shell type polymer microsphere profile control and flooding agent according to claim 2, characterized in that:
the oil-soluble solvent is selected from at least one of aliphatic hydrocarbon, aromatic hydrocarbon and halogenated hydrocarbon, preferably one or more of toluene, o-xylene, isoparaffin, cycloparaffin, paraffin, petroleum ether, toluene, xylene, white oil and kerosene;
and/or the presence of a gas in the gas,
the cross-linking agent is selected from at least one of N, N-methylene bisacrylamide, divinyl benzene, polyethylene glycol diacrylate, aldehydes containing two or more aldehyde groups, trimethylolpropane trimethacrylate and pentaerythritol triacrylate.
9. The semi-interpenetrating network yin-yang core-shell type polymer microsphere profile control and flooding agent according to claim 4, characterized in that:
the oxidant is at least one of potassium persulfate, sodium persulfate, ammonium persulfate or benzoyl peroxide; and/or the presence of a gas in the gas,
the reducing agent is selected from at least one of sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium thiosulfate and ferrous chloride; and/or the presence of a gas in the gas,
the azo compound is at least one selected from 2, 2' -azo [2- (2-imidazoline-2-yl) propane ] dihydrochloride, azobisisobutylamidine hydrochloride, azobisisobutyronitrile and azobisisoheptonitrile.
10. The preparation method of the semi-interpenetrating network yin-yang core-shell type polymer microsphere profile control and flooding agent according to any one of claims 1 to 9, characterized by comprising the following steps:
(a) uniformly mixing the oil-soluble solvent and the lipophilic surfactant in the composite emulsifier system to form a continuous oil phase;
(b) dissolving and uniformly stirring components including a monomer to be polymerized for preparing a microsphere core part, a hydrophilic surfactant, a co-emulsifier and a cross-linking agent in a composite emulsifier system in water to form a water phase I; in addition, the components including the polymerization monomer, the co-emulsifier and the cross-linking agent required by the shell part of the microsphere are dissolved in water and stirred uniformly to form a water phase II;
(c) slowly adding the water phase I into the continuous oil phase, shearing to form emulsion, and putting the emulsion into a reaction kettle; controlling the temperature in the reaction kettle at 5-30 ℃, deoxidizing, adding an oxidant, uniformly stirring, adding a reducing agent to initiate polymerization, controlling the heat release of the polymerization reaction by the adding speed of the reducing agent, controlling the heating speed to be less than or equal to 2 ℃/min, keeping the final reaction temperature at 30-60 ℃, keeping the temperature after the temperature reaches the peak, and continuing the reaction for 0.5-1 hour to obtain the core emulsion of the semi-interpenetrating network yin-yang core-shell type polymer microsphere profile control and flooding agent;
(d) and (c) adding an azo initiator into the water phase II, uniformly stirring, dropwise adding the azo initiator into the core emulsion of the polymer microsphere obtained in the step (c), carrying out polymerization reaction, cooling after reaction, dropwise adding a phase inversion agent, and uniformly stirring to obtain the polymer microsphere.
11. The preparation method of the semi-interpenetrating network yin-yang core-shell type polymer microsphere profile control and flooding agent according to claim 10, wherein the preparation method comprises the following steps:
in the step (d), the step (c),
during the polymerization reaction, the reaction temperature range is controlled to be 40-70 ℃, and the reaction time is 4-8 hours; and/or the presence of a gas in the gas,
the dosage of the phase inversion agent is 5-95% of the weight of the composite emulsifier, and preferably 20-80%; the phase inversion agent is selected from hydrophilic surfactants, preferably at least one of fatty acid polyoxyethylene ester, alkyl acid polyoxyethylene ether and fatty alcohol polyoxyethylene ether; the HLB value of the phase transfer agent is 10-20.
12. The semi-interpenetrating network yin-yang core-shell type polymer microsphere profile control and flooding agent according to any one of claims 1 to 9 or the polymer microsphere profile control and flooding agent prepared by the preparation method according to claim 10 or 11 is applied to deep profile control and flooding for tertiary oil recovery of a high-permeability oil reservoir under high temperature and high salinity.
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| WO2015189060A1 (en) * | 2014-06-11 | 2015-12-17 | Basf Se | Amphiphilic macromonomers, method for producing amphiphilic macromonomers, copolymers comprising amphiphilic macromonomers and the use of such copolymers for tertiary petroleum production |
| CN108315003A (en) * | 2017-01-17 | 2018-07-24 | 中国石油化工股份有限公司 | Polyacrylamide microballoon in-depth profile control and its preparation method and application |
| CN109666096A (en) * | 2017-10-17 | 2019-04-23 | 中国石油化工股份有限公司 | Interpenetrating networks association type polymer microballoon profile control agent and preparation method thereof |
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| WO2015189060A1 (en) * | 2014-06-11 | 2015-12-17 | Basf Se | Amphiphilic macromonomers, method for producing amphiphilic macromonomers, copolymers comprising amphiphilic macromonomers and the use of such copolymers for tertiary petroleum production |
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