CN105315403A - Temperature-resistant salt-resistant active microsphere, and preparation method and applications thereof - Google Patents
Temperature-resistant salt-resistant active microsphere, and preparation method and applications thereof Download PDFInfo
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Abstract
The invention provides a temperature-resistant salt-resistant active microsphere, and a preparation method and applications thereof. The temperature-resistant salt-resistant active microsphere is mainly used for solving problems of the prior art that common microsphere is easily hydrated and broken under complex stratum conditions, and plugging effect on high permeability oil reservoir or cracks generated by pressure break is poor. The temperature-resistant salt-resistant active microsphere is obtained via reaction of acrylamide and/or an anionic hydrophilic monomer, a cationic hydrophilic monomer, a hydrophobic monomer, a cross-linking agent, a dispersing agent, water, a dispersion medium, and an initiator. Particle size of the temperature-resistant salt-resistant active microsphere ranges from 0.5 to 200<mu>m; thermal stability and injection performance is excellent; the temperature-resistant salt-resistant active microsphere possesses water encounter swelling performance, is capable of blocking lager pore-throat via bridging, increasing water wave, volume, and displacement efficiency of other injection agents effectively, is suitable for middle-high permeability reservoirs. The temperature-resistant salt-resistant active microsphere is convenient for industrial production, and can be applied to oil field tertiary oil recovery water shut-off and profile control.
Description
Technical field
The present invention relates to polymer technology of preparing and tertiary oil recovery field, be specifically related to a kind of temperature resistant antisalt active microsphere and its preparation method and application.
Background technology
How effectively to improve the seepage flow situation of oil field heterogeneous reservoir, improve sweep efficiency and the swept volume of driven water-replacing, thus improve oil recovery factor, become key subjects urgently to be resolved hurrily in current tertiary oil recovery process.Current, generally use chemical reagent to carry out shutoff oilfield high infiltration permeable layers, i.e. so-called water plugging and profile controlling method both at home and abroad.The water plugging profile control agent be employed, mainly comprises inorganics class, polymer class, foam class etc., all there is its respective defect.Cross linked gel microballoon is the cross-linked polymer particle be polymerized by acrylamide, vinylformic acid, linking agent etc., and the dispersion in water is less by ectocine, directly can use waste water, pollution-free, cost is lower.The resistance coefficient of polymer microballoon and residual resistance factor are large, and system viscosity does not increase, and can not increase the resistance of pipeline during injection, but its plugging strength and having much room for improvement with the compatibleness on stratum.
Domestic and international hydrogel microsphere was applied to the research of raising recovery ratio less than 30 years, but had achieved suitable great successes.Document (JamesP, FramptonH, BrinkmanJ, etal.Fieldapplicationofanewin-depthwaterfloodconformance improvementtool.SPE84897,2003) in, the site pilot test of report shows that gel micro-ball has good nearly well augmented injection and the performance of deep profile correction, and oil increasing effect is obvious.Chinese patent CN1903974A adopts low temperature light trigger, synthesizes the polymer microgel of nano-scale, and its microemulsion is stablized, and particle diameter is convenient to control, but can not effectively profile control or shutoff to large-size crack or high permeability zones.Chinese patent CN101029109A is with redox/azo composite initiator, via Inverse-Phase Suspension Polymerization is adopted to obtain the cationic acrylamide crosspolymer microballoon that particle diameter is 1 ~ 50um, adopt the impact can avoiding mineral ion, mechanical impurity etc. during waste water, but do not investigate its temperature resistant antisalt performance.In addition, hydrophobic monomer unit is distributed in hydrophobic associated polymer macromolecular chain with random or micro-block structure, be conducive to the temperature resistant antisalt ageing resistance improving polymkeric substance, and the association between hydrophobic grouping, be easy to Interpolymer Association build bridge, under shearing action, solution is formed, and can reply after shearing, favourable to the retention rate of polymer solution viscosity.But about the report then shorter mention of hydrophobic association structure microspheres.
Summary of the invention
One of technical problem to be solved by this invention is conventional microballoon easy aquation under complex stratum condition in prior art, very easily be broken, to the problem of the crack shutoff weak effect that high permeability oil reservoir or pressure break produce, a kind of novel temperature resistant antisalt active microsphere is provided, for in tertiary oil production in oil field field, there is good temperature resistant antisalt performance, electrostatic interaction can be there is in positively charged ion component with electronegative stratum, improve the gripping power in microballoon and duct, and hydrophobic grouping can make to occur between microballoon to associate to build bridge, strengthen microballoon shut-off capacity, thus effective shutoff stratum macropore, water plugging and profile controlling Be very effective.
Two of technical problem to be solved by this invention is to provide a kind of preparation method corresponding with the temperature resistant antisalt active microsphere of one of technical solution problem.
Three of technical problem to be solved by this invention is to provide a kind of with the application of temperature resistant antisalt active microsphere in tertiary oil production in oil field one of technical solution problem Suo Shu.
For one of solving the problems of the technologies described above, technical scheme of the present invention is as follows: a kind of temperature resistant antisalt active microsphere, obtained by the substance reaction comprising following component: with weight parts, 1 ~ 40 part of acrylamide and/or anionic hydrophilic monomer, 1 ~ 30 part of cationic hydrophilic monomer, 0.01 ~ 2 part of hydrophobic monomer, 0.001 ~ 5 part of linking agent, 0.1 ~ 10 part of dispersion agent, 10 ~ 50 parts of water, 30 ~ 90 parts of dispersion medium, 0.001 ~ 5 part of initiator; Wherein, the particle diameter of described temperature resistant antisalt active microsphere is 0.5 ~ 200 μm.
In technique scheme, at least one of described anionic hydrophilic monomer preferably in vinylformic acid, methacrylic acid, 2-acrylamide-2-methylpro panesulfonic acid and salt thereof.
In technique scheme, at least one of described cationic hydrophilic monomer preferably in dimethyl ethyl allyl ammonium chloride, dimethyl diallyl ammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac, acryloxyethyldimethyl ethyl phosphonium bromide ammonium, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, 2-acrylamido-2-trimethoxysilyl propyl methacrylate ammonium chloride.
In technique scheme, at least one of described hydrophobic monomer preferably in structures alone shown in formula (1), formula (2):
Wherein, R
1, R
2all independent preferred from C
1~ C
6fatty group, more independent preferably from hydrogen or C
1~ C
6alkyl; R
3be selected from C
1~ C
18fatty group, more independent preferably from being selected from C
1~ C
18alkyl.What be such as selected from formula (1) has vinylbenzene, vinyl toluene, ethyl styrene, isopropyl styrene, t-butyl styrene etc.; What be selected from formula (2) has (methyl) methyl acrylate, (methyl) tert-butyl acrylate, (methyl) aliphatic acrylate etc.
In technique scheme, described linking agent is preferably from methylene-bisacrylamide, methylenebismethacrylamide, triallylamine, pentaerythritol triacrylate, glycol diacrylate, ethylene glycol dimethacrylate, polyethyleneglycol diacrylate, Vinylstyrene or N, N ' at least one in-penylene a bismaleimides.
In technique scheme, at least one of described dispersion agent preferably in sapn, tween, alkylphenol polyoxyethylene, fatty alcohol-polyoxyethylene ether, sodium lauryl sulphate, sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, trimethyl quaternary ammonium salt, two dodecyl dimethyl quaternary ammonium salt, hexadecanyl trimethyl quaternary ammonium salt, di-cetyl dimethyl quaternary ammonium salt, octadecyl trimethyl quaternary ammonium salt, two octadecyldimethyl quaternary ammonium salt; Described quaternary ammonium salt is preferably chlorination ammonium salt or bromination ammonium salt.
In technique scheme, described dispersion agent is more preferably such as formula at least one in the fatty acid polyglycol oxypropylene polyoxyethylene ester shown in the aromatic alcohol polyoxyethylene polyoxypropylene ether shown in the fatty alcohol polyoxypropylene Soxylat A 25-7 shown in (i), (ii), formula (iii), the aliphatic amide polyoxyethylene polyoxypropylene ether shown in formula (iv):
Wherein, R
1, R
2and R
3respective independence is preferably from C
1~ C
28fatty group, be more preferably C
1~ C
28alkyl, more preferably C
1~ C
28saturated hydrocarbyl; R
4and R
5independent preferred from hydrogen atom or C
1~ C
28fatty group, be more preferably hydrogen atom or C
1~ C
28alkyl, more preferably hydrogen atom or C
1~ C
28saturated hydrocarbyl, and R
4and R
5can not be hydrogen atom simultaneously; M is preferably from 0 ~ 50; N is preferably from 1 ~ 50;
In technique scheme, two or more the mixture in the fatty alcohol polyoxypropylene Soxylat A 25-7 of described dispersion agent more preferably shown in formula (i), the aromatic alcohol polyoxyethylene polyoxypropylene ether shown in (ii), the fatty acid polyglycol oxypropylene polyoxyethylene ester shown in formula (iii), the aliphatic amide polyoxyethylene polyoxypropylene ether shown in formula (iv).
In technique scheme, at least one of described dispersion medium preferably in fatty compounds, alicyclic compound, aromatics; Wherein, at least one of described fatty compounds preferably in butane, pentane, hexane, heptane, octane, mineral oil, vegetables oil; At least one of described alicyclic compound preferably in pentamethylene, cyclohexane, methylcyclohexane, cyclooctane; At least one of described aromatics preferably in benzene, toluene, ethylbenzene, dimethylbenzene and isopropyl benzene; At least one of described mineral oil preferably in whiteruss, white oil, gasoline, diesel oil, kerosene; At least one of described vegetables oil preferably in peanut oil, soybean oil, sunflower seed oil and Viscotrol C.
In technique scheme, at least one of described initiator preferably in peroxide initiator, redox composite initiator and azo compound; Wherein, at least one of described peroxide initiator preferably in ammonium persulphate, Potassium Persulphate, Sodium Persulfate, hydrogen peroxide, benzoyl peroxide; At least one of oxygenant preferably in ammonium persulphate, Potassium Persulphate, Sodium Persulfate, hydrogen peroxide, benzoyl peroxide in described redox composite initiator, at least one of reductive agent preferably in sodium bisulfite, Potassium hydrogen sulfite, S-WAT, potassium sulfite, Sulfothiorine, iron protochloride; Described azo compound is preferably from Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), 2,2'-Azobis(2,4-dimethylvaleronitrile), azo-bis-iso-dimethyl, azo diisobutyl amidine hydrochloride, 2,2 '-azo [2-(2-tetrahydroglyoxaline-2-base) propane] dihydrochloride, azo two (2,5-dimethyl-6-carboxyl) own nitrile, 4, at least one in 4 '-azo two (4-cyanopentanoic acid); Described initiator is more preferably the mixed initiator of peroxide initiator, redox composite initiator and azo compound three, wherein, the reductive agent in described peroxide initiator, described redox composite initiator and the mass ratio of described azo compound are preferably 1:(0 ~ 5): (0 ~ 5).
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: a kind of preparation method of temperature resistant antisalt active microsphere, comprises the following steps:
1) preparation of aqueous phase: reductive agent and/or azo compound in acrylamide and/or anionic hydrophilic monomer, cationic hydrophilic monomer, water-soluble cross-linker, initiator are dissolved in the deionized water of 90 ~ 99.9% of described deionized water gross weight, with alkali lye regulator solution to neutral, obtain aqueous phase I; Oxygenant in initiator is dissolved in the deionized water of surplus and obtains aqueous phase II;
2) preparation of polymer fluid: hydrophobic monomer, dispersion agent and lipophilicity linking agent are dissolved in dispersion medium, then by step 1) in the aqueous phase I of preparation join in dispersion medium, fully stir and obtain polymer fluid;
3) polyreaction: remove and be dissolved in step 2) polymer fluid in oxygen, add step 1) in preparation aqueous phase II, initiated polymerization at 30 ~ 80 DEG C, react 0.5 ~ 8 hour, sedimentation, washing, drying obtain temperature resistant antisalt active microsphere.
For solve the problems of the technologies described above three, the technical solution used in the present invention is as follows: the application of a kind of temperature resistant antisalt active microsphere in tertiary oil production in oil field.
In technique scheme, describedly be applied as application method well-known to those skilled in the art, such as described temperature resistant antisalt active microsphere directly can use clear water, salt solution or oil field extracted water dissolved dilution, is applied in tertiary oil production in oil field and makes water plugging profile control agent to improve oil recovery factor after independent or composite with other oil field chemical.The salinity of described salt solution can be such as that total mineralization is 50000 ~ 250000mg/L, calcium ions and magnesium ions concentration is 500 ~ 8000mg/L.
The key of the inventive method is to introduce cationic monomer and hydrophobic monomer unit in the acrylamide polymer microballoon of routine, can in 50 ~ 95 DEG C, swelling gradually in the salt solution of high salinity, under oxygen free condition, aging 30 days expansion multiplying powers are up to more than 8 times, show excellent heatproof, salt resistance and ageing resistance; Occurring between microballoon associates builds bridge, and improves between microballoon, microballoon and cell walls gripping power and be unlikelyly washed breakthrough, can effective macropore plugging, 85 DEG C, total mineralization is 150000mg/L, calcium ions and magnesium ions concentration be the brines of 2000mg/L under to 2.360 μm
2the shutoff efficiency of reservoir core plugging can reach more than 80%, and water plugging and profile controlling Be very effective achieves good technique effect.
According to application needs, described temperature resistant antisalt active microsphere directly can be used clear water, salt solution or oil field extracted water dissolved dilution, be applied in tertiary oil production in oil field after independent or composite with other oil field chemical and make water plugging profile control agent to improve oil recovery factor.
Below by embodiment, the invention will be further elaborated.
Embodiment
[embodiment 1]
In there-necked flask, add 100mL normal hexane, 2.5g sorbitan monooleate, 0.5g styrene monomer, 0.6g Vinylstyrene, stir and make it to mix, in controlling, temperature is 30 DEG C, and stir speed (S.S.) is 600 revs/min.25g vinylformic acid is placed in beaker, in ice-water bath, is neutralized to neutrality with the aqueous sodium hydroxide solution that mass concentration is 40%.By 30g deionized water, 35g acrylamide, 5g dimethyl ethyl allyl ammonium chloride, 0.6g sodium bisulfite, stir and make it to be uniformly dissolved; In addition, 0.8g Sodium Persulfate is dissolved in 4.2g deionized water, for subsequent use.Imported in there-necked flask by above-mentioned monomer solution, fully stir, the deoxygenation of drum nitrogen, adds sodium persulfate aqueous solution, system temperature rise to 65 DEG C, continues reaction 3 hours.After reaction terminates, with methyl alcohol sedimentation, washing, suction filtration, 50 DEG C of vacuum-dryings, obtain powdered product.The particle diameter of thus obtained microsphere is measured with laser particle analyzer; Respectively 70 DEG C, 90 DEG C, total mineralization is 150000mg/L, calcium ions and magnesium ions concentration is 2000mg/L salt solution, within aging 30 days, investigate aging resistance and expansion multiplying power under oxygen free condition, and 85 DEG C, total mineralization is 150000mg/L, calcium ions and magnesium ions concentration be the brines of 2000mg/L under to 2.360 μm
2reservoir core plugging performance.Result is as shown in table 1.
[embodiment 2]
The consumption of sorbitan monooleate, with [embodiment 1], is just replaced with 1.5g by the preparation process of microballoon.The particle diameter of thus obtained microsphere is measured with laser particle analyzer; Respectively 70 DEG C, 90 DEG C, total mineralization is 150000mg/L, calcium ions and magnesium ions concentration is 2000mg/L salt solution, within aging 30 days, investigate aging resistance and expansion multiplying power under oxygen free condition, and 85 DEG C, total mineralization is 150000mg/L, calcium ions and magnesium ions concentration be the brines of 2000mg/L under to 2.515 μm
2reservoir core plugging performance.Result is as shown in table 1.
[embodiment 3]
110mL ethylbenzene, 1.5g sorbitan monostearate, 0.4g Soxylat A 25-7 sorbitan monooleate, 0.8g tert-butyl acrylate monomer, 0.1g Vinylstyrene is added in there-necked flask, stirring makes it to mix, in controlling, temperature is 30 DEG C, and stir speed (S.S.) is 650 revs/min.20g vinylformic acid is placed in beaker, in ice-water bath, is neutralized to neutrality with the aqueous sodium hydroxide solution that mass concentration is 40%.By 30g deionized water, 30g acrylamide, 10g acrylyl oxy-ethyl-trimethyl salmiac, 0.4g S-WAT, stir and make it to be uniformly dissolved; In addition, 0.7g Sodium Persulfate is dissolved in 4.3g deionized water, for subsequent use.Imported in there-necked flask by above-mentioned monomer solution, fully stir, the deoxygenation of drum nitrogen, adds sodium persulfate aqueous solution, system temperature rise to 58 DEG C, continues reaction 4 hours.After reaction terminates, with methyl alcohol sedimentation, washing, suction filtration, 50 DEG C of vacuum-dryings, obtain powdered product.The particle diameter of thus obtained microsphere is measured with laser particle analyzer; Respectively 70 DEG C, 90 DEG C, total mineralization is 150000mg/L, calcium ions and magnesium ions concentration is 2000mg/L salt solution, within aging 30 days, investigate aging resistance and expansion multiplying power under oxygen free condition, and 85 DEG C, total mineralization is 150000mg/L, calcium ions and magnesium ions concentration be the brines of 2000mg/L under to 2.806 μm
2reservoir core plugging performance.Result is as shown in table 1.
[embodiment 4]
The consumption of tert-butyl acrylate monomer, with [embodiment 3], is just increased to 1.5g by the preparation process of microballoon.The particle diameter of thus obtained microsphere is measured with laser particle analyzer; Respectively 70 DEG C, 90 DEG C, total mineralization is 150000mg/L, calcium ions and magnesium ions concentration is 2000mg/L salt solution, within aging 30 days, investigate aging resistance and expansion multiplying power under oxygen free condition, and 85 DEG C, total mineralization is 150000mg/L, calcium ions and magnesium ions concentration be the brines of 2000mg/L under to 2.660 μm
2reservoir core plugging performance.Result is as shown in table 1.
[embodiment 5]
110mL ethylbenzene, 1.5g sorbitan monostearate, 0.4g Soxylat A 25-7 sorbitan monooleate, 0.8g methacrylic acid cetyl ester monomer, 0.1g Vinylstyrene is added in there-necked flask, stirring makes it to mix, in controlling, temperature is 30 DEG C, and stir speed (S.S.) is 650 revs/min.By 30g deionized water, 50g acrylamide, 10g acrylyl oxy-ethyl-trimethyl salmiac, 0.4g S-WAT, stir and make it to be uniformly dissolved; In addition, 0.7g Sodium Persulfate is dissolved in 4.3g deionized water, for subsequent use.Imported in there-necked flask by above-mentioned monomer solution, fully stir, the deoxygenation of drum nitrogen, adds sodium persulfate aqueous solution, system temperature rise to 58 DEG C, continues reaction 4 hours.After reaction terminates, with methyl alcohol sedimentation, washing, suction filtration, 50 DEG C of vacuum-dryings, obtain powdered product.The particle diameter of thus obtained microsphere is measured with laser particle analyzer; Respectively 70 DEG C, 90 DEG C, total mineralization is 150000mg/L, calcium ions and magnesium ions concentration is 2000mg/L salt solution, within aging 30 days, investigate aging resistance and expansion multiplying power under oxygen free condition, and 85 DEG C, total mineralization is 150000mg/L, calcium ions and magnesium ions concentration be the brines of 2000mg/L under to 2.811 μm
2reservoir core plugging performance.Result is as shown in table 1.
[embodiment 6]
In there-necked flask, add 100mL normal hexane, 2.5g sorbitan monooleate, 0.5g styrene monomer, 0.6g Vinylstyrene, stir and make it to mix, in controlling, temperature is 30 DEG C, and stir speed (S.S.) is 600 revs/min.60g vinylformic acid is placed in beaker, in ice-water bath, is neutralized to neutrality with the aqueous sodium hydroxide solution that mass concentration is 40%.By 30g deionized water, 5g dimethyl ethyl allyl ammonium chloride, 0.6g sodium bisulfite, stir and make it to be uniformly dissolved; In addition, 0.8g Sodium Persulfate is dissolved in 4.2g deionized water, for subsequent use.Imported in there-necked flask by above-mentioned monomer solution, fully stir, the deoxygenation of drum nitrogen, adds sodium persulfate aqueous solution, system temperature rise to 65 DEG C, continues reaction 3 hours.After reaction terminates, with methyl alcohol sedimentation, washing, suction filtration, 50 DEG C of vacuum-dryings, obtain powdered product.The particle diameter of thus obtained microsphere is measured with laser particle analyzer; Respectively 70 DEG C, 90 DEG C, total mineralization is 150000mg/L, calcium ions and magnesium ions concentration is 2000mg/L salt solution, within aging 30 days, investigate aging resistance and expansion multiplying power under oxygen free condition, and 85 DEG C, total mineralization is 150000mg/L, calcium ions and magnesium ions concentration be the brines of 2000mg/L under to 2.556 μm
2reservoir core plugging performance.Result is as shown in table 1.
[embodiment 7]
130mL heptane, 1.2g is added to n-butyl benzene base polyoxypropylene (3) Soxylat A 25-7 (8), 1.5g Brij 35 (5), 0.8g p-tert-butylstyrene monomer, 0.5g Vinylstyrene in there-necked flask, stirring makes it to mix, in controlling, temperature is 25 DEG C, and stir speed (S.S.) is 500 revs/min.18g vinylformic acid is placed in beaker, in ice-water bath, is neutralized to neutrality with the aqueous sodium hydroxide solution that mass concentration is 40%.By 32g deionized water, 33g acrylamide, 5gN-vinyl pyrrolidone, 4g dimethyl ethyl allyl ammonium chloride, 0.6g sodium bisulfite, 0.2gN, N '-methylene-bisacrylamide adds in the acrylic acid aqueous solution of becoming reconciled, and stirs and makes it to be uniformly dissolved.In addition, 1.5g Sodium Persulfate is dissolved in 8.5g water, for subsequent use.Imported in there-necked flask by above-mentioned monomer solution, fully stir, the deoxygenation of drum nitrogen, adds sodium persulfate aqueous solution, system temperature rise to 68 DEG C, continues reaction 4 hours.After reaction terminates, with methyl alcohol sedimentation, washing, suction filtration, 50 DEG C of vacuum-dryings, obtain powdered product.The particle diameter of thus obtained microsphere is measured with laser particle analyzer; Respectively 70 DEG C, 90 DEG C, total mineralization is 150000mg/L, calcium ions and magnesium ions concentration is 2000mg/L salt solution, within aging 30 days, investigate aging resistance and expansion multiplying power under oxygen free condition, and 85 DEG C, total mineralization is 150000mg/L, calcium ions and magnesium ions concentration be the brines of 2000mg/L under to 2.556 μm
2reservoir core plugging performance.Result is as shown in table 1.
[comparative example 1]
The preparation process of microballoon, with [embodiment 1], just do not add styrene monomer, Vinylstyrene and dimethyl ethyl allyl ammonium chloride, and the consumption of acrylamide is adjusted to 40.5g.The particle diameter of thus obtained microsphere is measured with laser particle analyzer; Respectively 70 DEG C, 90, total mineralization is 150000mg/L, calcium ions and magnesium ions concentration is 2000mg/L salt solution, within aging 30 days, investigate aging resistance and expansion multiplying power under oxygen free condition, and 85 DEG C, total mineralization is 150000mg/L, calcium ions and magnesium ions concentration be the brines of 2000mg/L under to 2.453 μm
2reservoir core plugging performance.Result is as shown in table 1.
[comparative example 2]
The preparation process of microballoon, with [embodiment 1], just do not add styrene monomer, Vinylstyrene and vinylformic acid, and the consumption of acrylamide is adjusted to 60.5g.The particle diameter of thus obtained microsphere is measured with laser particle analyzer; Respectively 70 DEG C, 90 DEG C, total mineralization is 150000mg/L, calcium ions and magnesium ions concentration is 2000mg/L salt solution, within aging 30 days, investigate aging resistance and expansion multiplying power under oxygen free condition, and 85 DEG C, total mineralization is 150000mg/L, calcium ions and magnesium ions concentration be the brines of 2000mg/L under to 2.530 μm
2reservoir core plugging performance.Result is as shown in table 1.
[comparative example 3]
The preparation process of microballoon, with [embodiment 3], just do not add vinylformic acid and acrylyl oxy-ethyl-trimethyl salmiac, and the consumption of acrylamide is adjusted to 60g.The particle diameter of thus obtained microsphere is measured with laser particle analyzer; Respectively 70 DEG C, 90 DEG C, total mineralization is 150000mg/L, calcium ions and magnesium ions concentration is 2000mg/L salt solution, within aging 30 days, investigate aging resistance and expansion multiplying power under oxygen free condition, and 85 DEG C, total mineralization is 150000mg/L, calcium ions and magnesium ions concentration be the brines of 2000mg/L under to 2.398 μm
2reservoir core plugging performance.Result is as shown in table 1.
[comparative example 4]
The preparation process of microballoon, with [embodiment 3], does not just add acrylamide and acrylyl oxy-ethyl-trimethyl salmiac,
And acrylic acid consumption is adjusted to 60g.The particle diameter of thus obtained microsphere is measured with laser particle analyzer; Respectively 70 DEG C, 90 DEG C, total mineralization is 150000mg/L, calcium ions and magnesium ions concentration is 2000mg/L salt solution, within aging 30 days, investigate aging resistance and expansion multiplying power under oxygen free condition, and 85 DEG C, total mineralization is 150000mg/L, calcium ions and magnesium ions concentration be the brines of 2000mg/L under to 2.580 μm
2reservoir core plugging performance.Result is as shown in table 1.
Table 1
Claims (10)
1. a temperature resistant antisalt active microsphere, obtained by the substance reaction comprising following component: with weight parts, 1 ~ 40 part of acrylamide and/or anionic hydrophilic monomer, 1 ~ 30 part of cationic hydrophilic monomer, 0.01 ~ 2 part of hydrophobic monomer, 0.001 ~ 5 part of linking agent, 0.1 ~ 10 part of dispersion agent, 10 ~ 50 parts of water, 30 ~ 90 parts of dispersion medium, 0.001 ~ 5 part of initiator; Wherein, the particle diameter of described temperature resistant antisalt active microsphere is 0.5 ~ 200 μm.
2. temperature resistant antisalt active microsphere according to claim 1, is characterized in that described anionic hydrophilic monomer is selected from least one in vinylformic acid, methacrylic acid, 2-acrylamide-2-methylpro panesulfonic acid and salt thereof.
3. temperature resistant antisalt active microsphere according to claim 1, is characterized in that described cationic hydrophilic monomer is selected from least one in dimethyl ethyl allyl ammonium chloride, dimethyl diallyl ammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac, acryloxyethyldimethyl ethyl phosphonium bromide ammonium, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, 2-acrylamido-2-trimethoxysilyl propyl methacrylate ammonium chloride.
4. temperature resistant antisalt active microsphere according to claim 1, is characterized in that described hydrophobic monomer is selected from least one in structures alone shown in formula (1), formula (2):
Wherein, R
1, R
2all independently be selected from hydrogen or C
1~ C
6fatty group, and R
3be selected from C
1~ C
18fatty group.
5. temperature resistant antisalt active microsphere according to claim 1, it is characterized in that described linking agent is selected from methylene-bisacrylamide, methylenebismethacrylamide, triallylamine, pentaerythritol triacrylate, glycol diacrylate, ethylene glycol dimethacrylate, polyethyleneglycol diacrylate, Vinylstyrene or N, N ' at least one in-penylene a bismaleimides.
6. temperature resistant antisalt active microsphere according to claim 1, is characterized in that described dispersion agent is selected from least one in sapn, tween, alkylphenol polyoxyethylene, fatty alcohol-polyoxyethylene ether, sodium lauryl sulphate, sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, trimethyl quaternary ammonium salt, two dodecyl dimethyl quaternary ammonium salt, hexadecanyl trimethyl quaternary ammonium salt, di-cetyl dimethyl quaternary ammonium salt, octadecyl trimethyl quaternary ammonium salt, two octadecyldimethyl quaternary ammonium salt.
7. temperature resistant antisalt active microsphere according to claim 1, is characterized in that described dispersion medium is selected from least one in fatty compounds, alicyclic compound, aromatics.
8. temperature resistant antisalt active microsphere according to claim 1, is characterized in that described initiator is selected from least one in peroxide initiator, redox composite initiator and azo compound.
9. the preparation method of temperature resistant antisalt active microsphere according to any one of claim 1 ~ 8, comprises the following steps:
1) preparation of aqueous phase: reductive agent and/or azo compound in acrylamide and/or anionic hydrophilic monomer, cationic hydrophilic monomer, water-soluble cross-linker, initiator are dissolved in the water of 90 ~ 99.9% of described water gross weight, with alkali lye regulator solution to neutral, obtain aqueous phase I; Oxygenant in initiator is dissolved in excess water and obtains aqueous phase II;
2) preparation of polymer fluid: hydrophobic monomer, dispersion agent and lipophilicity linking agent are dissolved in dispersion medium, then by step 1) in the aqueous phase I of preparation join in dispersion medium, fully stir and obtain polymer fluid;
3) polyreaction: remove and be dissolved in step 2) polymer fluid in oxygen, add step 1) in preparation aqueous phase II, initiated polymerization at 30 ~ 80 DEG C, react 0.5 ~ 8 hour, sedimentation, washing, drying obtain temperature resistant antisalt active microsphere.
10. according to the arbitrary described application of temperature resistant antisalt active microsphere in tertiary oil production in oil field of claim 1 ~ 8.
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Cited By (9)
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| CN105778016A (en) * | 2016-03-28 | 2016-07-20 | 中国石油天然气股份有限公司 | Polymer microsphere for profile control and water shutoff of oil field and preparation method thereof |
| CN105801742A (en) * | 2016-03-29 | 2016-07-27 | 中国石油大学胜利学院 | Quadripolymer type oil product drag reducer and synthesizing method |
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| CN109666475A (en) * | 2017-10-17 | 2019-04-23 | 中国石油化工股份有限公司 | Temperature-resistant anti-salt low-tension nanosphere profile control agent and preparation method thereof |
| CN111234790A (en) * | 2020-02-19 | 2020-06-05 | 中国石油大学(华东) | Gel particles suitable for low-permeability fractured carbon dioxide flooding oil reservoir, profile control agent, preparation method and application |
| CN111793164A (en) * | 2020-06-08 | 2020-10-20 | 长江大学 | Polymer microsphere and preparation method and application thereof |
| CN111909306A (en) * | 2020-08-14 | 2020-11-10 | 西安石油大学 | Double-aqueous-phase PAM/AMPS nano microsphere latex as well as preparation method and application thereof |
| CN117886993A (en) * | 2024-03-12 | 2024-04-16 | 四川省威沃敦石油科技股份有限公司成都分公司 | Supermolecule microsphere profile control agent convenient for deep profile control of oil field and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101037493A (en) * | 2007-03-31 | 2007-09-19 | 中国石油大学(华东) | Cation polypropylene amides gel micro-ball and preparation method thereof |
| CN101270178A (en) * | 2008-04-24 | 2008-09-24 | 中国海洋石油总公司 | Water dispersion dewatering cationic polymer and preparing method |
| CN101619118A (en) * | 2009-05-26 | 2010-01-06 | 中国石油大学(华东) | Polymer microspheres for water flooding reservoir deep oil displacement and profile control and preparation method thereof |
| CN102399345A (en) * | 2010-09-14 | 2012-04-04 | 中国科学院理化技术研究所 | Preparation method of emulsion deep profile control and flooding agent containing gel microspheres with core-shell structures and emulsion deep profile control and flooding agent |
| CN103739778A (en) * | 2014-01-08 | 2014-04-23 | 天津大学 | Core-shell polyacrylamide microsphere profile controlling oil displacement agent and preparation method thereof |
-
2014
- 2014-07-24 CN CN201410353237.8A patent/CN105315403B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101037493A (en) * | 2007-03-31 | 2007-09-19 | 中国石油大学(华东) | Cation polypropylene amides gel micro-ball and preparation method thereof |
| CN101270178A (en) * | 2008-04-24 | 2008-09-24 | 中国海洋石油总公司 | Water dispersion dewatering cationic polymer and preparing method |
| CN101619118A (en) * | 2009-05-26 | 2010-01-06 | 中国石油大学(华东) | Polymer microspheres for water flooding reservoir deep oil displacement and profile control and preparation method thereof |
| CN102399345A (en) * | 2010-09-14 | 2012-04-04 | 中国科学院理化技术研究所 | Preparation method of emulsion deep profile control and flooding agent containing gel microspheres with core-shell structures and emulsion deep profile control and flooding agent |
| CN103739778A (en) * | 2014-01-08 | 2014-04-23 | 天津大学 | Core-shell polyacrylamide microsphere profile controlling oil displacement agent and preparation method thereof |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105778016A (en) * | 2016-03-28 | 2016-07-20 | 中国石油天然气股份有限公司 | Polymer microsphere for profile control and water shutoff of oil field and preparation method thereof |
| CN105778016B (en) * | 2016-03-28 | 2018-05-04 | 中国石油天然气股份有限公司 | Polymer microsphere for profile control and water shutoff of oil field and preparation method thereof |
| CN105801742A (en) * | 2016-03-29 | 2016-07-27 | 中国石油大学胜利学院 | Quadripolymer type oil product drag reducer and synthesizing method |
| CN105801742B (en) * | 2016-03-29 | 2018-04-03 | 中国石油大学胜利学院 | A kind of quadripolymer type oil product drag reducer and synthetic method |
| CN109666475A (en) * | 2017-10-17 | 2019-04-23 | 中国石油化工股份有限公司 | Temperature-resistant anti-salt low-tension nanosphere profile control agent and preparation method thereof |
| CN108250344A (en) * | 2017-12-27 | 2018-07-06 | 山东诺尔生物科技有限公司 | A kind of low bulk speed nanoscale water suction microballoon and preparation method thereof |
| CN108250344B (en) * | 2017-12-27 | 2020-11-13 | 山东诺尔生物科技有限公司 | Low-expansion-speed nanoscale water-absorbing microsphere and preparation method thereof |
| CN108192588A (en) * | 2018-01-24 | 2018-06-22 | 西南石油大学 | A kind of selfreparing Low Damage superhigh temperature resistant fracturing fluid |
| CN108192588B (en) * | 2018-01-24 | 2020-08-18 | 西南石油大学 | Self-repairing low-damage ultrahigh-temperature-resistant fracturing fluid |
| CN111234790A (en) * | 2020-02-19 | 2020-06-05 | 中国石油大学(华东) | Gel particles suitable for low-permeability fractured carbon dioxide flooding oil reservoir, profile control agent, preparation method and application |
| CN111234790B (en) * | 2020-02-19 | 2022-07-15 | 中国石油大学(华东) | Gel particles suitable for low-permeability fractured carbon dioxide flooding oil reservoir, profile control agent, preparation method and application |
| CN111793164A (en) * | 2020-06-08 | 2020-10-20 | 长江大学 | Polymer microsphere and preparation method and application thereof |
| CN111909306A (en) * | 2020-08-14 | 2020-11-10 | 西安石油大学 | Double-aqueous-phase PAM/AMPS nano microsphere latex as well as preparation method and application thereof |
| CN117886993A (en) * | 2024-03-12 | 2024-04-16 | 四川省威沃敦石油科技股份有限公司成都分公司 | Supermolecule microsphere profile control agent convenient for deep profile control of oil field and preparation method thereof |
| CN117886993B (en) * | 2024-03-12 | 2024-05-31 | 四川省威沃敦石油科技股份有限公司成都分公司 | Supermolecule microsphere profile control agent convenient for deep profile control of oil field and preparation method thereof |
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