CN103614124A - Retarded crosslinking deep profile control agent and preparation method thereof - Google Patents
Retarded crosslinking deep profile control agent and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a retarded crosslinking deep profile control agent and a preparation method thereof, and belongs to the technical field of oilfield chemistry. The deep profile control agent is prepared from the following components by mass concentration: 0.1-1.0% of hydrophobically associating polyacrylamide, 0.1-1.0% of cyclodextrin/phenol clathrate, 0.1-0.5% of urotropine, 0.1-0.4% of citric acid, and water serving as a solvent. Hydrophobically associating polyacrylamide is novel water-soluble polyacrylamide, and has critical association concentration; when the concentration of a polymer is greater than the critical association concentration, a hydrophobic group generates intermolecular association, so that the viscosity of the solution is greatly increased and the solution displays good performances such as temperature resistance, salt resistance, shearing resistance and the like. Phenol is slowly released by the competitive clathration of the hydrophobic group in hydrophobically associating polyacrylamide on phenol, so that the gelation time can be effectively retarded; meanwhile, the gelation time can be regulated and controlled, so that deep profile control is selectively carried out on high-permeability reservoirs, large ducts, cracks and the like.
Description
Technical field
The present invention is specifically related to the agent of a kind of delayed cross-linking deep profile controlling, and the preparation method of this amendment, belongs to oilfield chemical technology field.
Background technology
At home and abroad in oil and water well profile control technique, common concern crosslinked polymer gel technique, being about to polymers soln mixes on ground with linking agent, be mixed with single liquid profile control working fluid and inject earth formation deep with heavy dose, under formation condition, polymkeric substance and linking agent are slowly cross-linked to form and have cancellated polymer gel, so as to shutoff high infiltration high permeability formation and macropore.
The main component of gel profile-controlling system is polymkeric substance and linking agent.Conventional polymkeric substance has xanthan gum and polyacrylamide at present.Linking agent one class is phenols, water soluble phenol resin, terpolycyantoamino-formaldehyde resin, phenol-amine resin etc., and another kind of is transition metal organic crosslinking agent, is mainly Al
+ 3, Cr
3+, Zr
4+deng metal and suitable intercalating agent, form.
Chinese patent (application number: the water plugging profile control agent that 201210000833.9) discloses a kind of high temperature resistant high salinity, comprise that (molecular weight is 1500～3,000 ten thousand to polyacrylamide, degree of hydrolysis is 15～30%), multiple crosslinking agent, cyclodextrin, mphenylenediamine and oxygen scavenger (as thiocarbamide), wherein multiple crosslinking agent is comprised of aldehydes (as a kind of or arbitrary combination in phenyl aldehyde, paraformaldehyde), phenols (as a kind of or arbitrary combination in phenol, Resorcinol, Resorcinol) and Tiorco 677.The crosslinked ability of this water plugging profile control agent is strong, and high temperature resistant high salinity, has permanent stability, and resistance to local water washes away required intensity for a long time.Yet the ability of its delayed cross-linking is very limited, be unsuitable for height infiltration oil reservoir, macropore and crack etc. to carry out deep profile controlling.
Summary of the invention
The object of this invention is to provide the agent of a kind of delayed cross-linking deep profile controlling.
Meanwhile, the present invention also provides the preparation method of a kind of delayed cross-linking deep profile controlling agent.
In order to realize above object, the technical solution adopted in the present invention is:
The agent of delayed cross-linking deep profile controlling, is comprised of the component of following mass concentration: hydrophobic association polyacrylamide 0.1～1.0%, cyclodextrin/phenol inclusion compound 0.1～1.0%, urotropine 0.1～0.5%, citric acid 0.1～0.4%, solvent is water.
The molecular weight of described hydrophobic association polyacrylamide is 2.0 * 10
6～1.0 * 10
7, degree of hydrolysis is 25～30%.In hydrophobic association polyacrylamide molecule, the mol ratio of hydrophobic grouping and phenol is (1～2): 1; The inclusion constant of hydrophobic grouping (as alkylphenol polyoxyethylene, OP-10, OP-20 etc.) and cyclodextrin is greater than the inclusion constant of phenol and cyclodextrin.
In described cyclodextrin/phenol inclusion compound, the mol ratio of cyclodextrin and phenol is 1:(1～2).
Described hydrophobic association polyacrylamide can be commercial goods, also can adopt preparation with the following method:
(1) getting acrylamide, hydrophobic monomer and three kinds of monomers of vinylformic acid is added to the water, by the pH value of NaOH regulator solution, be 8～9, take and guarantee that vinylformic acid alkalizes completely as sodium acrylate, in atmosphere of inert gases, stir hydrophobic monomer is dissolved, then at 25～65 ℃ of temperature, stir 30～60min and clarify to solution;
(2) add initiator, in atmosphere of inert gases, stirring reaction is 1～24 hour, obtains.
In described step (1), hydrophobic monomer is alkylphenol polyoxyethylene acrylate.Preferred polyoxyethylene octylphenol ether acrylate.
Described alkylphenol polyoxyethylene acrylate is commercial goods, and structural formula is shown in following formula 1:
In formula: when m=8, be polyoxyethylene octylphenol ether acrylate; Now, when n value is 10, commercial disignation is OP-10, and n value is 20 o'clock, and commercial disignation is OP-20; By that analogy.
Described polyoxyethylene octylphenol ether acrylate can be adopted preparation with the following method, comprises the following steps: get polyoxyethylene octylphenol ether and toluene, reflux is divided water 1～12 hour, to without globule wall built-up, is cooled to 50～70 ℃; Add vinylformic acid, catalyzer and stopper, reflux divides water 6～12h, removes toluene and excessive vinylformic acid after cooling and get final product.
Described catalyzer is benzene methanesulfonic acid; Stopper is Resorcinol.Wherein, polyoxyethylene octylphenol ether and acrylic acid mol ratio are (0.95～1): 1; Toluene accounts for 60～120% of two kinds of monomer total masses; Benzene methanesulfonic acid accounts for 0.1～1.0% of two kinds of monomer total masses; Resorcinol accounts for 0.01～0.1% of two kinds of monomer total masses.Remove toluene and excessive vinylformic acid mainly adopts Rotary Evaporators, under vacuum condition, steam toluene and vinylformic acid.
In described step (1), acrylamide, hydrophobic monomer and acrylic acid mol ratio are (45～74): (1～25): (25～30).
In described step (1), three kinds of total mass concentrations of monomer are 5～30%.
In described step (1), be stirred in atmosphere of inert gases and carry out, as nitrogen etc.
In described step (2), initiator is Potassium Persulphate and sodium bisulfite; The quality of initiator accounts for 0.05～0.5% of three kinds of monomer total masses; Potassium Persulphate and sodium bisulfite mol ratio be (1～2): 1.Potassium Persulphate first adds, and excessively after 5～15min, adds sodium bisulfite again.
The middle atmosphere of inert gases of described step (2) is nitrogen etc.
After reaction, sealing and standing 6～10h obtains transparent colloid material in described step (2), and fragmentation is placed on soaks 20～28h in acetone and obtain white solid, is dried, pulverizes and to obtain Powdered thick product.Preferably, thick product is soluble in water, with acetone precipitation, purify 2～5 times, dry, granulation and get final product.
The preparation method of described cyclodextrin/phenol inclusion compound comprises the following steps:
(1) mix cyclodextrin is soluble in water, obtain solution A standby;
(2) phenol is dissolved in 70～80% ethanolic solns, then joining in solution A stirring and evenly mixing, to obtain solution B standby;
(3) get solution B at 25～40 ℃ standing 30～60 minutes, to guarantee the complete inclusion phenol of cyclodextrin, then be drying to obtain.
Dry decompression solvent evaporates and two steps of freeze-day with constant temperature of comprising in described step (3), concrete grammar is: at 0.1～0.5atm pressure, 60～80 ℃ of temperature, be dried to solvent-free volatilization, then be placed in 40～50 ℃ of environment freeze-day with constant temperature 20～28 hours.
Preferably, in the solution B of described step (2), the mass concentration of cyclodextrin is 1.6～2.0g/mL, and the mass concentration of phenol is 0.12～0.18g/mL.Above-mentioned inclusion method is saturated solution solvent evaporation method.
Described cyclodextrin can be alpha-cylodextrin, beta-cyclodextrin etc., preferably beta-cyclodextrin.
A preparation method for delayed cross-linking deep profile controlling agent, comprises the following steps: accurately get each component, and first that hydrophobic association polyacrylamide is soluble in water, then add successively urotropine, citric acid, cyclodextrin/phenol inclusion compound, stir evenly and get final product.
Hydrophobicity power can represent with lipid, and lipid shows that more greatly the hydrophobicity of this material is stronger.The lipid of phenol is 1.61, for polyoxyethylene octylphenol ether, during n=1, its Log P=4.8, its Log P of oxyethyl group of every increase reduces approximately 0.16, and the hydrophobicity of n≤20 o'clock hydrophobic monomer is all better than phenol, can guarantee phenol to replace out from the hydrophobic cavity of cyclodextrin.
Beneficial effect of the present invention:
Hydrophobic association polyacrylamide is a kind of novel water-soluble polyacrylamide, has good heatproof, salt tolerant, the performance such as anti-shearing, can be widely used in the every field of tertiary oil recovery, as the displacement of reservoir oil, profile control and water plugging etc.Hydrophobic association polyacrylamide has critical association concentration in solution, after polymer concentration is greater than critical association concentration, hydrophobic grouping generation Interpolymer Association causes soltion viscosity to increase considerably and presents good heatproof, salt tolerant, the performance such as anti-shearing.The required hydrophobic monomer of synthetizing hydrophobic associated polyacrylamide is generally water insoluble, need to it, carry out solubilising as sodium lauryl sulphate etc. with tensio-active agent, and vinylformic acid and polyoxyethylene octylphenol ether (OP-10, OP-13, OP-15, OP-20, OP-30 etc.) the polyoxyethylene octylphenol ether acrylate that obtains of reaction, can with acrylamide, sodium acrylate generation solution polymerization, and in OP-n series, the higher corresponding hydrophobic monomer of oxyethyl group content is water-soluble better.
Delayed cross-linking deep profile controlling of the present invention agent is phenolic resin type gel.Hydrophobic association polyacrylamide and formaldehyde, phenol reactant form phenolic resin gel.In this delayed cross-linking gelling system, formaldehyde is that linking agent urotropine is heated and slowly releases under weak acid environment; Phenol, is slowly released under the competitive inclusion effect of the hydrophobic grouping in hydrophobic association polyacrylamide molecule by inclusion among the hydrophobic cavity of cyclodextrin.In the present invention, the hydrophobic monomer of hydrophobic association polyacrylamide is alkylphenol polyoxyethylene acrylate, and its hydrophobicity is better than phenol, phenol can be replaced out from the hydrophobic cavity of cyclodextrin.In hydrophobic association polyacrylamide solution, after polymer concentration is greater than critical association concentration, hydrophobic grouping be take Interpolymer Association as main, after adding cyclodextrin/phenol inclusion compound, hydrophobic grouping is competed gradually and is entered cyclodextrin hydrophobic cavity phenol is replaced out, thereby can reach the object of delayed cross-linking.
In the present invention, the agent of delayed cross-linking deep profile controlling slowly discharges phenol by the competitive inclusion effect of hydrophobic grouping Pyrogentisinic Acid in hydrophobic association polyacrylamide, can effectively delay gelation time, gelation time can regulate and control simultaneously, thereby selectively deep profile controlling is carried out in height infiltration oil reservoir, macropore and crack etc.
The preparation method of delayed cross-linking deep profile controlling of the present invention agent is simple, easy to operate, is suitable for large-scale industrial production and application.
Accompanying drawing explanation
Fig. 1 is the synthetic route schematic diagram of hydrophobic monomer alkyl polyoxyethylene ether acrylate in the embodiment of the present invention 1;
Fig. 2 is the synthetic route schematic diagram of hydrophobic association polyacrylamide in embodiment 1.
Embodiment
Following embodiment is only described in further detail the present invention, but does not form any limitation of the invention.
Delayed cross-linking deep profile controlling agent in the present embodiment is composed of the following components: hydrophobic association polyacrylamide 0.4g, beta-cyclodextrin/phenol inclusion compound 0.5g, urotropine 0.4g, citric acid 0.15g, solvent is 100mL deionized water.
In the present embodiment, the preparation method of delayed cross-linking deep profile controlling agent comprises the following steps: accurately get each component, first hydrophobic association polyacrylamide is dissolved in deionized water, add successively urotropine, citric acid, cyclodextrin/phenol inclusion compound, stirring and dissolving evenly and get final product again.
The preparation method of described hydrophobic association polyacrylamide is:
(1) prepare hydrophobic monomer (octyl group Soxylat A 25-7 acrylate): in the 250mL there-necked flask of mechanical stirrer, water-and-oil separator, reflux condensing tube is housed, add the toluene of polyoxyethylene octylphenol ether (OP-20) 100g and 100mL, reflux divide water to flask without globule wall built-up; Then reaction solution is cooled to 60 ℃, again vinylformic acid 10g, catalyzer tosic acid 0.3g and hydroquinone of polymerization retarder 0.03g are added in flask, reflux is divided water 8 hours, be cooled to normal temperature, with Rotary Evaporators, steam toluene and excessive vinylformic acid, obtain orange oily liquids, obtain hydrophobic monomer, synthetic route chart refers to Fig. 1;
(2) getting acrylamide, hydrophobic monomer, three kinds of monomers of vinylformic acid adds in deionized water, wherein acrylamide, hydrophobic monomer and acrylic acid mol ratio are 5:2:3, by the pH value of the NaOH solution regulator solution of 6mol/L, be 8, take and guarantee that vinylformic acid alkalizes completely as sodium acrylate, be transferred in 250mL there-necked flask, pass into N
2and constantly stirring is dissolved hydrophobic monomer, then add deionized water to 100mL, making the mass concentration of three kinds of monomers is 25%, then there-necked flask is placed in to constant temperature water bath, and keeping temperature is 45 ℃, passes into N
2and stir 60min and make solution become clarification;
(3) initiator potassium persulfate and sodium bisulfite are dissolved in respectively in 5mL deionized water, wherein the mol ratio of Potassium Persulphate and sodium bisulfite is 1:1, the quality of initiator accounts for 0.5% of three kinds of monomer total masses, with syringe, potassium persulfate solution is injected to there-necked flask, the sodium sulfite solution that reinjects after 10min, passes into N
2constantly stir, when becoming sticky, mixture stops stirring, flask sealing is placed to 8h and obtain transparent colloid shape material, taking-up is cut into small pieces, be placed on and in excessive acetone, soak 24h and obtain white solid, then be placed in that 45 ℃ of baking ovens are dry, the thick product of powder all to pieces, thick product is dissolved in deionized water, with acetone precipitation, purify 3 times, (molecular weight is 3.7 * 10 through vacuum-drying, granulation, to obtain hydrophobic association polyacrylamide
6).
The preparation method of described beta-cyclodextrin/phenol inclusion compound is: under normal temperature, beta-cyclodextrin is dissolved in deionized water, the mass concentration of beta-cyclodextrin in solution is 1.8g/100mL; Phenol is dissolved in 75% ethanolic soln, then adds in beta-cyclodextrin solution, the concentration of phenol in solution is 0.15g/100mL, and standing 60min after stirring makes the complete inclusion phenol of beta-cyclodextrin; Get solution after the standing solvent evaporates that reduces pressure, under temperature 70 C, pressure 0.2atm, be dried to solvent-free volatilization, then be placed in 45 ℃ of thermostat container freeze-day with constant temperature and obtain hydrophobic association polyacrylamide in 24 hours, synthetic route chart refers to Fig. 2.In Fig. 2, a, b, c only represent to have mol ratio between three kinds of monomers, do not affect its molecular order, i.e. lack of alignment between each group in hydrophobic association polyacrylamide.
Embodiment 2
Delayed cross-linking deep profile controlling agent in the present embodiment is composed of the following components: hydrophobic association polyacrylamide 0.5g, beta-cyclodextrin/phenol inclusion compound 0.5g, urotropine 0.2g, citric acid 0.2g, solvent is 100mL deionized water.
The preparation method of described hydrophobic association polyacrylamide is:
(1) prepare hydrophobic monomer (octyl group Soxylat A 25-7 acrylate): in the 250mL there-necked flask of mechanical stirrer, water-and-oil separator, reflux condensing tube is housed, add the toluene of polyoxyethylene octylphenol ether (OP-15) 100g and 100mL, reflux divide water to flask without globule wall built-up; Then reaction solution is cooled to 50 ℃, again vinylformic acid 10g, catalyzer tosic acid 0.5g and hydroquinone of polymerization retarder 0.05g are added in flask, reflux is divided water 12 hours, be cooled to normal temperature, with Rotary Evaporators, steam toluene and excessive vinylformic acid, obtain orange oily liquids, obtain hydrophobic monomer, synthetic route chart refers to Fig. 1;
(2) getting acrylamide, hydrophobic monomer, three kinds of monomers of vinylformic acid adds in deionized water, wherein acrylamide, hydrophobic monomer and acrylic acid mol ratio are 11:4:5, by the pH value of the NaOH solution regulator solution of 6mol/L, be 8.5, take and guarantee that vinylformic acid alkalizes completely as sodium acrylate, be transferred in 250mL there-necked flask, pass into N
2and constantly stirring is dissolved hydrophobic monomer, then add deionized water to 100mL, making the mass concentration of three kinds of monomers is 30%, then there-necked flask is placed in to constant temperature water bath, and keeping temperature is 65 ℃, passes into N
2and stir 30min and make solution become clarification;
(3) initiator potassium persulfate and sodium bisulfite are dissolved in respectively in 5mL deionized water, wherein the mol ratio of Potassium Persulphate and sodium bisulfite is 2:1, the quality of initiator accounts for 0.1% of three kinds of monomer total masses, with syringe, potassium persulfate solution is injected to there-necked flask, the sodium sulfite solution that reinjects after 5min, passes into N
2constantly stir, when becoming sticky, mixture stops stirring, flask sealing is placed to 10h and obtain transparent colloid shape material, taking-up is cut into small pieces, be placed on and in excessive acetone, soak 24h and obtain white solid, then be placed in that 50 ℃ of baking ovens are dry, the thick product of powder all to pieces, thick product is dissolved in deionized water, with acetone precipitation, purify 3 times, through vacuum-drying, granulation, obtain hydrophobic association polyacrylamide.
The preparation method of described beta-cyclodextrin/phenol inclusion compound is: under normal temperature, beta-cyclodextrin is dissolved in deionized water, the mass concentration of beta-cyclodextrin in solution is 1.8g/100mL; Phenol is dissolved in 80% ethanolic soln, then adds in beta-cyclodextrin solution, the concentration of phenol in solution is 0.15g/100mL, and standing 50min after stirring makes the complete inclusion phenol of beta-cyclodextrin; Get solution after the standing solvent evaporates that reduces pressure, under temperature 60 C, pressure 0.3atm, be dried to solvent-free volatilization, then be placed in 40 ℃ of thermostat container freeze-day with constant temperature and within 28 hours, obtain hydrophobic association polyacrylamide.
Embodiment 3
Delayed cross-linking deep profile controlling agent in the present embodiment is composed of the following components: hydrophobic association polyacrylamide 0.8g, beta-cyclodextrin/phenol inclusion compound 0.8g, urotropine 0.5g, citric acid 0.4g, solvent is 100mL deionized water.
The preparation method of described hydrophobic association polyacrylamide is:
(1) prepare hydrophobic monomer (octyl group Soxylat A 25-7 acrylate): in the 250mL there-necked flask of mechanical stirrer, water-and-oil separator, reflux condensing tube is housed, add the toluene of polyoxyethylene octylphenol ether (OP-13) 100g and 100mL, reflux divide water to flask without globule wall built-up; Then reaction solution is cooled to 70 ℃, again vinylformic acid 10g, catalyzer tosic acid 0.1g and hydroquinone of polymerization retarder 0.01g are added in flask, reflux is divided water 6 hours, be cooled to normal temperature, with Rotary Evaporators, steam toluene and excessive vinylformic acid, obtain orange oily liquids, obtain hydrophobic monomer, synthetic route chart refers to Fig. 1;
(2) getting acrylamide, hydrophobic monomer, three kinds of monomers of vinylformic acid adds in deionized water, wherein acrylamide, hydrophobic monomer and acrylic acid mol ratio are 9:5:6, by the pH value of the NaOH solution regulator solution of 6mol/L, be 9, take and guarantee that vinylformic acid alkalizes completely as sodium acrylate, be transferred in 250mL there-necked flask, pass into N
2and constantly stirring is dissolved hydrophobic monomer, then add deionized water to 100mL, making the mass concentration of three kinds of monomers is 15%, then there-necked flask is placed in to constant temperature water bath, and keeping temperature is 30 ℃, passes into N
2and stir 60min and make solution become clarification;
(3) initiator potassium persulfate and sodium bisulfite are dissolved in respectively in 5mL deionized water, wherein the mol ratio of Potassium Persulphate and sodium bisulfite is 1:1, the quality of initiator accounts for 0.3% of three kinds of monomer total masses, with syringe, potassium persulfate solution is injected to there-necked flask, the sodium sulfite solution that reinjects after 15min, passes into N
2constantly stir, when becoming sticky, mixture stops stirring, flask sealing is placed to 10h and obtain transparent colloid shape material, taking-up is cut into small pieces, be placed on and in excessive acetone, soak 20h and obtain white solid, then be placed in that 40 ℃ of baking ovens are dry, the thick product of powder all to pieces, thick product is dissolved in deionized water, with acetone precipitation, purify 4 times, (molecular weight is 3.7 * 10 through vacuum-drying, granulation, to obtain hydrophobic association polyacrylamide
6).
The preparation method of described beta-cyclodextrin/phenol inclusion compound is: under normal temperature, beta-cyclodextrin is dissolved in deionized water, the mass concentration of beta-cyclodextrin in solution is 1.8g/100mL; Phenol is dissolved in 75% ethanolic soln, then adds in beta-cyclodextrin solution, the concentration of phenol in solution is 0.15g/100mL, and standing 50min after stirring makes the complete inclusion phenol of beta-cyclodextrin; Get solution after the standing solvent evaporates that reduces pressure, under 80 ℃ of temperature, pressure 0.5atm, be dried to solvent-free volatilization, then be placed in 50 ℃ of thermostat container freeze-day with constant temperature and within 20 hours, obtain hydrophobic association polyacrylamide.
Embodiment 4
Delayed cross-linking deep profile controlling agent in the present embodiment is composed of the following components: hydrophobic association polyacrylamide 0.6g, beta-cyclodextrin/phenol inclusion compound 0.5g, urotropine 0.1g, citric acid 0.15g, solvent is 100mL deionized water.The preparation method of hydrophobic association polyacrylamide, beta-cyclodextrin/phenol inclusion compound and amendment is with embodiment 1.
Embodiment 5
Delayed cross-linking deep profile controlling agent in the present embodiment is composed of the following components: hydrophobic association polyacrylamide 0.9g, beta-cyclodextrin/phenol inclusion compound 0.9g, urotropine 0.5g, citric acid 0.1g, solvent is 100mL deionized water.The preparation method of hydrophobic association polyacrylamide, beta-cyclodextrin/phenol inclusion compound and amendment is with embodiment 1.
Embodiment 6
Delayed cross-linking deep profile controlling agent in the present embodiment is composed of the following components: hydrophobic association polyacrylamide 0.7g, beta-cyclodextrin/phenol inclusion compound 0.7g, urotropine 0.4g, citric acid 0.2g, solvent is 100mL deionized water.The preparation method of hydrophobic association polyacrylamide, beta-cyclodextrin/phenol inclusion compound and amendment is with embodiment 1.
Embodiment 7
Delayed cross-linking deep profile controlling agent in the present embodiment is composed of the following components: hydrophobic association polyacrylamide 0.1g, beta-cyclodextrin/phenol inclusion compound 0.1g, urotropine 0.1g, citric acid 0.15g, solvent is 100mL deionized water.The preparation method of hydrophobic association polyacrylamide, beta-cyclodextrin/phenol inclusion compound and amendment is with embodiment 1.
Embodiment 8
Delayed cross-linking deep profile controlling agent in the present embodiment is composed of the following components: hydrophobic association polyacrylamide 1.0g, beta-cyclodextrin/phenol inclusion compound 1.0g, urotropine 0.5g, citric acid 0.1g, solvent is 100mL deionized water.The preparation method of hydrophobic association polyacrylamide, beta-cyclodextrin/phenol inclusion compound and amendment is with embodiment 1.
Embodiment 9
Delayed cross-linking deep profile controlling agent in the present embodiment is composed of the following components: hydrophobic association polyacrylamide 0.2g, beta-cyclodextrin/phenol inclusion compound 0.5g, urotropine 0.4g, citric acid 0.2g, solvent is 100mL deionized water.The preparation method of hydrophobic association polyacrylamide, beta-cyclodextrin/phenol inclusion compound and amendment is with embodiment 1.
Test example
Get the delayed cross-linking deep profile controlling agent of embodiment 1～6 preparation and carry out gellifying property mensuration, method is as follows: the homogeneous solution that measures fast embodiment 1～6 preparation proceeds in ampoule, and ampoule is sealed; The ampoule of sealing is placed in respectively at 45 ℃ and investigates its gel time and gel-strength, and treatment condition and measurement result are as shown in table 1 below, and gel-strength represents with code method.
The gellifying property of the delayed cross-linking gel profile control agent of table 1 embodiment 1～3 preparation
(2) sealing characteristics
At 45 ℃, the middle gelling system of embodiment 1 is 8.54 μ m to rate of permeation
2the sealing ratiod of fill out sand tube is 99.1%, and plugging strength is 4.75MPa/m; Gelling system in embodiment 2 is 6.74 μ m to rate of permeation
2the sealing ratiod of fill out sand tube is 99.2%, and plugging strength is 5.14MPa/m.Gelling system in embodiment 3 is 8.65 μ m to rate of permeation
2the sealing ratiod of fill out sand tube is 99.5%, and plugging strength is 7.14MPa/m.Gelling system in embodiment 4 is 11.5 μ m to rate of permeation
2the sealing ratiod of fill out sand tube is 99.2%, and plugging strength is 5.45MPa/m.Gelling system in embodiment 5 is 9.34 μ m to rate of permeation
2the sealing ratiod of fill out sand tube is 99.8%, and plugging strength is 8.56MPa/m.Gelling system in embodiment 6 is 7.13 μ m to rate of permeation
2the sealing ratiod of fill out sand tube is 99.4%, and plugging strength is 6.58MPa/m.Above-mentioned six fill out sand tube are further carried out to displacement test, and experiment confirms that above-mentioned blocking agent system all has very strong erosion resistibility.
Claims (10)
1. delayed cross-linking deep profile controlling agent, it is characterized in that: the component by following mass concentration forms: hydrophobic association polyacrylamide 0.1～1.0%, cyclodextrin/phenol inclusion compound 0.1～1.0%, urotropine 0.1～0.5%, citric acid 0.1～0.4%, solvent is water.
2. delayed cross-linking deep profile controlling according to claim 1 agent, is characterized in that: the molecular weight of described hydrophobic association polyacrylamide is 2.0 * 10
6～1.0 * 10
7, degree of hydrolysis is 25～30%, in hydrophobic association polyacrylamide molecule, the mol ratio of hydrophobic grouping and phenol is (1～2): 1.
3. delayed cross-linking deep profile controlling according to claim 2 agent, is characterized in that: the inclusion constant of described hydrophobic grouping and cyclodextrin is greater than the inclusion constant of phenol and cyclodextrin.
4. delayed cross-linking deep profile controlling according to claim 3 agent, is characterized in that: the preparation method of described hydrophobic association polyacrylamide is:
(1) getting acrylamide, hydrophobic monomer and three kinds of monomers of vinylformic acid and be added to the water, is 8～9 by the pH value of NaOH regulator solution, stirs hydrophobic monomer is dissolved, then at 25～65 ℃ of temperature, stir 30～60min and clarify to solution in atmosphere of inert gases;
(2) add initiator, in atmosphere of inert gases, stirring reaction is 1～24 hour, obtains.
5. delayed cross-linking deep profile controlling according to claim 4 agent, is characterized in that: in described step (1), acrylamide, hydrophobic monomer and acrylic acid mol ratio are (45～74): (1～25): (25～30).
6. delayed cross-linking deep profile controlling according to claim 4 agent, is characterized in that: in described step (1), hydrophobic monomer is polyoxyethylene octylphenol ether acrylate.
7. delayed cross-linking deep profile controlling according to claim 6 agent, it is characterized in that: the preparation method of described polyoxyethylene octylphenol ether acrylate is: get polyoxyethylene octylphenol ether and toluene, reflux is divided water 1～12 hour, to without globule wall built-up, is cooled to 50～70 ℃; Add vinylformic acid, catalyzer and stopper, reflux divides water 6～12h, removes toluene and excessive vinylformic acid after cooling and get final product.
8. delayed cross-linking deep profile controlling according to claim 4 agent, is characterized in that: sealing and standing 6～10h after reaction in described step (2), fragmentation, be placed in acetone and soak 20～28h, dry, soluble in water again after pulverizing, with acetone precipitation, purify 2～5 times, dry, granulation and get final product.
9. delayed cross-linking deep profile controlling according to claim 1 agent, is characterized in that: the preparation method of described cyclodextrin/phenol inclusion compound comprises the following steps:
(1) mix cyclodextrin is soluble in water, obtain solution A standby;
(2) phenol is dissolved in 70～80% ethanolic solns, then joining in solution A stirring and evenly mixing, to obtain solution B standby;
(3) get solution B at 25～40 ℃ standing 30～60 minutes, to guarantee the complete inclusion phenol of cyclodextrin, then be drying to obtain.
10. the preparation method of a delayed cross-linking deep profile controlling as claimed in claim 1 agent, it is characterized in that: comprise the following steps: accurately get each component, first that hydrophobic association polyacrylamide is soluble in water, then add successively urotropine, citric acid, cyclodextrin/phenol inclusion compound, stir evenly and get final product.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105646775A (en) * | 2015-12-29 | 2016-06-08 | 四川光亚聚合物化工有限公司 | Hydrophobic associated polymer and preparation method thereof |
| CN107556996A (en) * | 2017-08-11 | 2018-01-09 | 中国石油天然气股份有限公司 | CO (carbon monoxide)2Response in-situ gel channeling sealing agent and preparation method and application thereof |
| CN107794025A (en) * | 2016-09-06 | 2018-03-13 | 中国石油化工股份有限公司 | Multiple crosslinking agent and its preparation method and application |
| CN108690584A (en) * | 2018-05-18 | 2018-10-23 | 中国石油集团川庆钻探工程有限公司长庆井下技术作业公司 | A kind of compound profile control agent |
| CN111269335A (en) * | 2020-04-08 | 2020-06-12 | 中国石油大学(华东) | Slow-crosslinking host-guest inclusion gel deep profile control and flooding agent and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1821456A (en) * | 2006-02-10 | 2006-08-23 | 党智军 | Novel fabric with skin-care function and its preparing method |
| CN102533233A (en) * | 2012-01-04 | 2012-07-04 | 中国石油天然气股份有限公司 | High-temperature-resistant high-salinity water shutoff profile control agent and preparation method and application thereof |
-
2013
- 2013-11-18 CN CN201310581760.1A patent/CN103614124B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1821456A (en) * | 2006-02-10 | 2006-08-23 | 党智军 | Novel fabric with skin-care function and its preparing method |
| CN102533233A (en) * | 2012-01-04 | 2012-07-04 | 中国石油天然气股份有限公司 | High-temperature-resistant high-salinity water shutoff profile control agent and preparation method and application thereof |
Cited By (7)
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|---|---|---|---|---|
| CN105646775A (en) * | 2015-12-29 | 2016-06-08 | 四川光亚聚合物化工有限公司 | Hydrophobic associated polymer and preparation method thereof |
| CN105646775B (en) * | 2015-12-29 | 2019-05-10 | 四川光亚聚合物化工有限公司 | A kind of hydrophobic associated polymer and preparation method thereof |
| CN107794025A (en) * | 2016-09-06 | 2018-03-13 | 中国石油化工股份有限公司 | Multiple crosslinking agent and its preparation method and application |
| CN107556996A (en) * | 2017-08-11 | 2018-01-09 | 中国石油天然气股份有限公司 | CO (carbon monoxide)2Response in-situ gel channeling sealing agent and preparation method and application thereof |
| CN107556996B (en) * | 2017-08-11 | 2021-03-09 | 中国石油天然气股份有限公司 | CO (carbon monoxide)2Response in-situ gel channeling sealing agent and preparation method and application thereof |
| CN108690584A (en) * | 2018-05-18 | 2018-10-23 | 中国石油集团川庆钻探工程有限公司长庆井下技术作业公司 | A kind of compound profile control agent |
| CN111269335A (en) * | 2020-04-08 | 2020-06-12 | 中国石油大学(华东) | Slow-crosslinking host-guest inclusion gel deep profile control and flooding agent and preparation method and application thereof |
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