CN106589228A - Low permeability reservoir flooding microemulsion system and preparation method thereof - Google Patents
Low permeability reservoir flooding microemulsion system and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a low permeability reservoir flooding microemulsion system and a preparation method thereof and aims to solve the problems that in the prior art, the usage of conventional emulsifier adopted for reversed phase microemulsion polymerization is large, the stability of the reversed phase microemulsion is low, microspheres expanse rapidly in earlier period but expanse slowly or hydrated seriously in later period and hole sealing strength is low. The components of the low permeability reservoir flooding microemulsion system include, by weight: 15 to 90% oily solvent, 1 to 15% carboxylate complex emulsifier, 10 to 50% water-swellable polymer microspheres and 15 to 85% of deionized water; wherein, the carboxylate complex emulsifier includes carboxylate surfactant of structure of general formula shown as formula 1. By means of the technical scheme, the problems are solved completely; the system and method can be applied to tertiary oil recovery of low-permeability reservoirs, and the oil recovery rate can be increased. (img file = 'DDA0000825426570000011.TIF'wi =' 1254'he = '222 /).
Description
Technical field
The present invention relates to a kind of can be used for transfer drive microemulsion system of low-permeability oil deposit and preparation method thereof, especially with the transfer drive microemulsion system and preparation method thereof of carboxylate compound emulsifying agent.
Background technology
Currently, most domestic oil field has successively entered tertiary phase.For inhomogeneous formation, typically frequently with Profile Control in Injection Well and producing well water-plugging technique, but this technology effective range is only limitted near wellbore zone, well deep part can not be deep into, the purpose for increasing substantially oil recovery factor is not reached, ultimately resulting in the recovery ratio of crude oil reduces, and cost is raised.Therefore, the research and development to water plugging and profile controlling class reagent and related supporting technology just seem extremely urgent.
The cross-linked polymer microsphere that nano-scale is obtained using conversed phase micro emulsion copolymerization is used for waterflooding reservoir deep profile correction material step by step, its use principle is using receiving the polymer microballoon of size, original dimension is much smaller than formation pore throat size, earth formation deep can be smoothly entered with injection water, constantly migrate forward in the earth formation, water suction forms closure after progressively expanding at penetrating passage pore throat, causes liquid stream to alter course, and realizes expanding water swept volume.Therefore, the technological means are significant to the recovery ratio of the harsh conditions oil reservoir such as hypotonic, high temperature, high salinity in raising.
At present, when preparing nanoscale/micrograde polymer microemulsion transfer drive system, typically all employ substantial amounts of surfactant and make oil-water interfaces emulsifying agent, such as alkylphenol polyoxyethylene class, sorbitan fatty ester, polyoxyethylene sorbitan fatty acid ester and its complex, considerably increase production cost.And alkylphenol polyoxyethylene class is to aquatic toxicity and to skin irritation, teratogenecity and itself poor biological degradability, in recent years in majority state and territorial restrictions, it is used；It is and sugar esters interfacial activity is poor and low or without effect to improving displacement efficiency effectiveness.Therefore, substitute or part substitutes above-mentioned conventional surfactants, prepare and significant with the microemulsion system for adjusting stifled effect using the interfacial activity having had.
The content of the invention
One of the technical problem to be solved is that conversed phase micro emulsion copolymerization conventional emulsifier consumption present in prior art is big, the expansion of polymer microballoon early stage is more rapid in reverse micro emulsion stability difference and prior art, late expansion is slow or aquation is serious, the low problem of plugging strength in duct, a kind of new transfer drive microemulsion system that can be used for low-permeability oil deposit is provided, interfacial activity and water plugging and profile controlling effect that the system has had, have the displacement of reservoir oil concurrently and adjust stifled double effects, disclosure satisfy that in low-permeability oil deposit tertiary oil recovery and make water blockoff, deep profile controlling and displacement etc. improve oil recovery factor field operation and require, economy is good.
The two of the technical problem to be solved are to provide the preparation method of the transfer drive microemulsion system that can be used for low-permeability oil deposit in a kind of one of solution technical problem.
To solve one of above-mentioned technical problem, the technical solution used in the present invention is as follows：A kind of transfer drive microemulsion system that can be used for low-permeability oil deposit, by weight percentage, including following components：
(1) 15～90% oil-based solvent；
(2) 1～15% carboxylate compound emulsifying agent；
(3) 10～50% water-swelling polymer microsphere；
(4) 15～85% deionized water；
Wherein, described carboxylate compound emulsifying agent includes carboxylate surface active agent of the formula as shown in Formulas I structure：
In formula, R is C1～C18Aliphatic hydrocarbon；X is epoxide, imido grpup, carbonyl epoxide or phenyl epoxide；M=0～50；N=1～55；M is selected from alkali metal or ammonium.
In above-mentioned technical proposal, described water-swelling polymer microsphere is preferably by obtained in Reverse Microemulsion System Jing Raolical polymerizables；Described Reverse Microemulsion System, by weight percentage, including following components：
(1) 15～90% oil-based solvent；
(2) 1～15% carboxylate compound emulsifying agent；
(3) 10～50% acrylamide；
(4) 10～50% temperature-resistant anti-salt monomer；
(5) 15～85% deionized water；
(6) 0.01～10% emulsion adjuvant；
(7) 0.001～5% oxidant；
(8) 0.001～5% reducing agent；
(9) 0.001～5% cross-linking agent.
In above-mentioned technical proposal, described oil-based solvent is selected from least one in thiacyclohexane, hexane, heptane, octane, isobutyltrimethylmethane., benzene, toluene, ethylbenzene, dimethylbenzene, isopropylbenzene, liquid paraffin, vegetable oil, white oil, gasoline, diesel oil and kerosene.Described carboxylate compound emulsifying agent also includes conventional surfactants, wherein, carboxylate surface active agent is 1 with the mass ratio of conventional surfactants：9～9：1；The conventional surfactants are selected from Span series and TWEEN Series.Wherein spans surfactant and Tweenses surfactant are surfactants commonly used in the art, those skilled in the art can carry out conventional selection, it is more preferably span 20, sorbester p17, sorbester p37 etc. for example but not limit spans surfactant, and Tweenses surfactant is more preferably polysorbas20, polysorbate60, Tween 80 etc..HLB value after described carboxylate compound emulsifying agent compounding is preferably 3～9.In order to increase the stability of emulsification system, appropriate emulsion adjuvant can be added, its consumption is the 0.01～10% of emulsifier.At least one of the described emulsion adjuvant in ethanol, propanol, isopropanol, n-butyl alcohol, isobutanol, the tert-butyl alcohol, amylalcohol, hexanol, ethylene glycol, Propylene Glycol, butanediol, pentanediol, hexanediol, glycerol, polyglycerin ester, sodium formate, potassium formate, ammonium formate, sodium acetate, potassium acetate, ammonium acetate, adipic acid sodium, sodium malonate.
In above-mentioned technical proposal, the preparation method of described carboxylate surface active agent comprises the steps：
It is 1～15 in mol ratio with the alkyl polycyclic oxygen alkene based surfactants shown in Formula II structure by halogenated acetic acids or its alkali metal salt：1st, reaction temperature is reacted Jing acid solutions, alkali liquor, saturated common salt water process after terminating and obtains described carboxylate surface active agent at 10～160 DEG C, to react 2～15 hours.Described halogenated acetic acids is monoxone or bromoacetic acid；Described alkali metal salt is sodium salt, potassium salt or ammonium salt；Described alkali liquor is potassium hydroxide, the aqueous solution of sodium hydroxide or ammonia.
In formula, R is C1～C18Aliphatic hydrocarbon；X is epoxide, imido grpup, carbonyl epoxide or phenyl epoxide；M=0～50；N=1～55.
In above-mentioned technical proposal, described temperature-resistant anti-salt monomer is selected from least one in vinylbenzenesulfonic acid, 2- acrylamide-2-methylpro panesulfonic acids and/or its alkali metal salt and ammonium salt, 2- acrylamido -2- trimethoxysilyl propyl methacrylate ammonium chlorides, NVP.
In above-mentioned technical proposal, described oxidant is selected from least one in Ammonium persulfate., potassium peroxydisulfate, sodium peroxydisulfate, hydrogen peroxide, benzoyl peroxide.At least one of the described reducing agent in sodium sulfite, Potassium acid sulfite, sodium sulfite, potassium sulfite, sodium thiosulfate, ferrous chloride.At least one of the described cross-linking agent in divinylbenzene, methylene-bisacrylamide, polyethyleneglycol diacrylate, pentaerythritol triacrylate.
To solve the two of above-mentioned technical problem, the technical solution used in the present invention is as follows：The preparation method of arbitrary described transfer drive microemulsion system that can be used for low-permeability oil deposit in above-mentioned technical proposal, it is characterised in that comprise the following steps：
In dissolving reduce agent in portions of de-ionized water, reducing agent aqueous solution is obtained；Acrylamide, temperature-resistant anti-salt monomer, cross-linking agent, oxidant are dissolved in the deionized water of surplus again, are stirred to solution and is clarified without insoluble matter, and the sodium hydrate aqueous solution with 5% adjusts solution ph to 7～12, obtains water phase；Carboxylate compound emulsifying agent and emulsion adjuvant are dissolved in oil-based solvent, are stirred, obtain oil phase；The aforementioned water for having prepared is added in oil phase, is stirred, obtain transparent or semitransparent Reverse Microemulsion System；Noble gases deoxygenation is passed through in the system, add the aforementioned reducing agent aqueous solution for having prepared, it is uniformly mixed, the initiated polymerization at a temperature of 25～70 DEG C, continue to react 0.5～6 hour up to after exothermic peak temperature, obtain stable, the transparent or semitransparent transfer drive microemulsion system that can be used for low-permeability oil deposit；Wherein, the particle diameter of water-swelling polymer microsphere be 50～300nm, particle diameter distribution be 0.1～0.5.
By using conversed phase micro emulsion copolymerization method, the emulsifier for being adopted is less than 20% to the inventive method, and microspherulite diameter is that 50～300nm is adjustable, narrow distribution, and can in high temperature and high salinity saline controllable expansion.It is critical only that using the surfactant of special construction as reverse micro emulsion emulsifying agent for the inventive method, not only increases the interfacial activity of system, also has water plugging and profile controlling and displacement double effects concurrently, reaches " one multiple-effect " effect.The reverse micro emulsion transfer drive system disclosure satisfy that making water blockoff, deep profile controlling and displacement etc. in low-permeability oil deposit tertiary oil recovery improves oil recovery factor field operation requirement, and economy is good.
Using technical scheme, water-swelling polymer microsphere initial particle can slowly expand up to 266nm in the transfer drive microemulsion system for obtaining, 30 days expansion multiples up to 9.6 times, with Pu 2-529 outputs oil oil water interfacial tension up to 8.85 × 10-3MN/m, achieves preferable technique effect.
Description of the drawings
Fig. 1 is the infrared spectrogram of water-swelling polymer microsphere in embodiment 1.
Below by specific embodiment, the present invention will be further elaborated.
Specific embodiment
【Embodiment 1】
1st, the synthesis of carboxylate surface active agent：
In equipped with reflux condensate device, thermometer, the glass reaction kettle of agitator, add 85g dodecyl alcohol polyoxypropylene base (3) polyoxyethylene groups (2) ethers, at a temperature of 72 DEG C, the sodium chloroacetate aqueous solution into 40g 70% is slowly added dropwise with Dropping funnel, stir in Deca and be allowed to mix homogeneously, continue to react 6 hours after completion of dropping, terminate reaction, with 20% hydrochloric acid solution regulation system pH to neutrality, dodecyl alcohol polyoxypropylene base (3) polyoxyethylene groups (2) carboxylic acid is obtained；Again with 30% sodium hydroxide solution regulation system pH to alkalescence, inorganic salt is separated out, the saturated common salt water washing upper strata of reusable heat 3 times is dried, dodecyl alcohol polyoxypropylene base (3) polyoxyethylene groups (2) carboxylic acid sodium is obtained, yield is 85.1%.
2nd, can be used for the preparation of the transfer drive microemulsion system of low-permeability oil deposit：
125g gasoline, 22g dodecyl alcohol polyoxypropylene base (3) polyoxyethylene groups (2) carboxylic acid sodium, 35g sorbester p18s, 4g Tween 80s are added in reactor, stirring is allowed to mix homogeneously, temperature in the kettle is controlled for 35 DEG C, stir speed (S.S.) is 250rpm.80g water, 120g acrylamides, 18g NVPs, 1.55g polyethyleneglycol diacrylates, 2g sodium malonates, 2.2g potassium acetates, 2.8g potassium peroxydisulfates are added in batching kettle, stirring is allowed to be uniformly dissolved, and pH value is adjusted to 7.3 with sodium hydrate aqueous solution；In addition, 3g sodium sulfite is dissolved in 20g deionized waters, it is standby.226.5g water is mutually imported in reactor, stirring is allowed to fully emulsified, add 16g sodium sulfite aqueous solutions, system temperature rise continues to react 2.5 hours to 86 DEG C, after terminating reaction, discharging.
The infrared spectrogram of water-swelling polymer microsphere is tested using Nicolet-20DXB types infrared spectrophotometer；Under 85 DEG C, oxygen free condition under total salinity 150000mg/L sodium chloride brine place 1 day, 7 days, 15 days, after 30 days microsphere particle diameter, calculate water-swelling polymer microsphere expansion multiple；Initial particle and the distribution of water-swelling polymer microsphere are tested using the type Particle Size Analyzers of Zetasizer Nano 2000；Interfacial tension between TX-500 types rotating interfacial tensimeter measure transfer drive microemulsion system and Pu 2-529 outputs oil is produced using Texas ,Usa university.As a result as shown in table 1, Fig. 1.
【Embodiment 2】
The synthesis of carboxylate surface active agent and can be used for low-permeability oil deposit transfer drive microemulsion system preparation process, together【Embodiment 1】, simply the consumption of emulsifying agent dodecyl alcohol polyoxypropylene base (3) polyoxyethylene groups (2) carboxylic acid sodium and sorbester p18 is transformed to into respectively 20.2g, 38.5g.Under 85 DEG C, oxygen free condition under total salinity 150000mg/L sodium chloride brine place 1 day, 7 days, 15 days, after 30 days microsphere particle diameter, calculate water-swelling polymer microsphere expansion multiple；Initial particle and the distribution of water-swelling polymer microsphere are tested using the type Particle Size Analyzers of Zetasizer Nano 2000；Interfacial tension between TX-500 types rotating interfacial tensimeter measure transfer drive microemulsion system and Pu 2-529 outputs oil is produced using Texas ,Usa university.As a result it is as shown in table 1.
【Embodiment 3】
The synthesis of carboxylate surface active agent and can be used for low-permeability oil deposit transfer drive microemulsion system preparation process, together【Embodiment 1】, simply the consumption of emulsifying agent dodecyl alcohol polyoxypropylene base (3) polyoxyethylene groups (2) carboxylic acid sodium and sorbester p18 is transformed to into respectively 26.4g, 30.5g.Under 85 DEG C, oxygen free condition under total salinity 150000mg/L sodium chloride brine place 1 day, 7 days, 15 days, after 30 days microsphere particle diameter, calculate water-swelling polymer microsphere expansion multiple；Initial particle and the distribution of water-swelling polymer microsphere are tested using the type Particle Size Analyzers of Zetasizer Nano 2000；Interfacial tension between TX-500 types rotating interfacial tensimeter measure transfer drive microemulsion system and Pu 2-529 outputs oil is produced using Texas ,Usa university.As a result it is as shown in table 1.
【Embodiment 4】
1st, the synthesis of carboxylate surface active agent：
In equipped with reflux condensate device, thermometer, the glass reaction kettle of agitator, add carbon carboxylic acid polyoxyethylene groups (20) ethers of 81g 12, at a temperature of 75 DEG C, the sodium chloroacetate aqueous solution into 33g 70% is slowly added dropwise with Dropping funnel, stir in Deca and be allowed to mix homogeneously, continue to react 7 hours after completion of dropping, terminate reaction, with 20% hydrochloric acid solution regulation system pH to neutrality, lauric acid polyoxyethylene groups (20) carboxylic acid is obtained；Again with 30% potassium hydroxide solution regulation system pH to alkalescence, inorganic salt is separated out, the saturated common salt water washing upper strata of reusable heat 3 times is dried, and obtains lauric acid polyoxyethylene groups (20) carboxylic acid potassium, and yield is 89.6%.
2nd, can be used for the preparation of the transfer drive microemulsion system of low-permeability oil deposit：
Add 145g vegetable oil, 16g lauric acid polyoxyethylene groups (20) carboxylic acid potassium, 38g sorbester p37s, 5g polysorbas20s, stirring to be allowed to mix homogeneously in reactor, control temperature in the kettle for 35 DEG C, stir speed (S.S.) is 250rpm.100g water, 136g acrylamides, 14g 2- acrylamido -2- trimethoxysilyl propyl methacrylate ammonium chlorides, 1.8g methylene-bisacrylamides, 1.5g amylalcohols, 1.5g sodium formates, 2.2g potassium peroxydisulfates are added in batching kettle, stirring is allowed to be uniformly dissolved, and pH value is adjusted to 7.5 with sodium hydrate aqueous solution；In addition, 2.5g sodium sulfite is dissolved in 20g deionized waters, it is standby.257g water is mutually imported in reactor, stirring is allowed to fully emulsified, add 14g sodium sulfite aqueous solutions, system temperature rise continues to react 3 hours to 80 DEG C, after terminating reaction, discharging.
Under 85 DEG C, oxygen free condition under total salinity 150000mg/L sodium chloride brine place 1 day, 7 days, 15 days, after 30 days microsphere particle diameter, calculate water-swelling polymer microsphere expansion multiple；Initial particle and the distribution of water-swelling polymer microsphere are tested using the type Particle Size Analyzers of Zetasizer Nano 2000；Interfacial tension between TX-500 types rotating interfacial tensimeter measure transfer drive microemulsion system and Pu 2-529 outputs oil is produced using Texas ,Usa university.As a result it is as shown in table 1.
【Embodiment 5】
The synthesis of carboxylate surface active agent and can be used for low-permeability oil deposit transfer drive microemulsion system preparation process, together【Embodiment 4】, simply the consumption of emulsifying agent lauric acid polyoxyethylene groups (20) carboxylic acid potassium and sorbester p37 is transformed to into respectively 13.8g, 41.6g.Under 85 DEG C, oxygen free condition under total salinity 150000mg/L sodium chloride brine place 1 day, 7 days, 15 days, after 30 days microsphere particle diameter, calculate water-swelling polymer microsphere expansion multiple；Initial particle and the distribution of water-swelling polymer microsphere are tested using the type Particle Size Analyzers of Zetasizer Nano 2000；Interfacial tension between TX-500 types rotating interfacial tensimeter measure transfer drive microemulsion system and Pu 2-529 outputs oil is produced using Texas ,Usa university.As a result it is as shown in table 1.
【Embodiment 6】
The synthesis of carboxylate surface active agent and can be used for low-permeability oil deposit transfer drive microemulsion system preparation process, together【Embodiment 4】, simply the consumption of emulsifying agent lauric acid polyoxyethylene groups (20) carboxylic acid potassium and sorbester p37 is transformed to into respectively 18.5g, 34.8g.Under 85 DEG C, oxygen free condition under total salinity 150000mg/L sodium chloride brine place 1 day, 7 days, 15 days, after 30 days microsphere particle diameter, calculate water-swelling polymer microsphere expansion multiple；Initial particle and the distribution of water-swelling polymer microsphere are tested using the type Particle Size Analyzers of Zetasizer Nano 2000；Interfacial tension between TX-500 types rotating interfacial tensimeter measure transfer drive microemulsion system and Pu 2-529 outputs oil is produced using Texas ,Usa university.As a result it is as shown in table 1.
【Embodiment 7】
The synthesis of carboxylate surface active agent and can be used for low-permeability oil deposit transfer drive microemulsion system preparation process, together【Embodiment 3】Simply three kinds of emulsifying agent dodecyl alcohol polyoxypropylene base (3) polyoxyethylene groups (2) carboxylic acid sodium, sorbester p18, Tween 80 are replaced with into two kinds of emulsifying agent dodecyl alcohol polyoxypropylene base (3) polyoxyethylene groups (2) carboxylic acid sodium, sorbester p18s, both consumptions are respectively 25g, 36g.Under 85 DEG C, oxygen free condition under total salinity 150000mg/L sodium chloride brine place 1 day, 7 days, 15 days, after 30 days microsphere particle diameter, calculate water-swelling polymer microsphere expansion multiple；Initial particle and the distribution of water-swelling polymer microsphere are tested using the type Particle Size Analyzers of Zetasizer Nano 2000；Interfacial tension between TX-500 types rotating interfacial tensimeter measure transfer drive microemulsion system and Pu 2-529 outputs oil is produced using Texas ,Usa university.As a result it is as shown in table 1.
【Embodiment 8】
The synthesis of carboxylate surface active agent and can be used for low-permeability oil deposit transfer drive microemulsion system preparation process, together【Embodiment 6】Simply three kinds of emulsifying agent lauric acid polyoxyethylene groups (20) carboxylic acid potassium, sorbester p37, polysorbas20 are replaced with into two kinds of emulsifying agent lauric acid polyoxyethylene groups (20) carboxylic acid potassium, sorbester p37s, both consumptions are respectively 18.3g, 40.7g.Under 85 DEG C, oxygen free condition under total salinity 150000mg/L sodium chloride brine place 1 day, 7 days, 15 days, after 30 days microsphere particle diameter, calculate water-swelling polymer microsphere expansion multiple；Initial particle and the distribution of water-swelling polymer microsphere are tested using the type Particle Size Analyzers of Zetasizer Nano 2000；Interfacial tension between TX-500 types rotating interfacial tensimeter measure transfer drive microemulsion system and Pu 2-529 outputs oil is produced using Texas ,Usa university.As a result it is as shown in table 1.
【Embodiment 9】
The synthesis of carboxylate surface active agent is same【Embodiment 1】With【Embodiment 4】, the preparation process that can be used for the transfer drive microemulsion system of low-permeability oil deposit is same【Embodiment 1】, simply three kinds of emulsifying agent dodecyl alcohol polyoxypropylene base (3) polyoxyethylene groups (2) carboxylic acid sodium, sorbester p18, Tween 80s are replaced with into other three kinds of emulsifying agents ---【Embodiment 1】Dodecyl alcohol polyoxypropylene base (3) polyoxyethylene groups (2) carboxylic acid sodium of middle synthesis,【Embodiment 4】Lauric acid polyoxyethylene groups (20) the carboxylic acid potassium of middle synthesis and sorbester p37, the consumption of three is respectively 9g, 8g, 44g.Under 85 DEG C, oxygen free condition under total salinity 150000mg/L sodium chloride brine place 1 day, 7 days, 15 days, after 30 days microsphere particle diameter, calculate water-swelling polymer microsphere expansion multiple；Initial particle and the distribution of water-swelling polymer microsphere are tested using the type Particle Size Analyzers of Zetasizer Nano 2000；Interfacial tension between TX-500 types rotating interfacial tensimeter measure transfer drive microemulsion system and Pu 2-529 outputs oil is produced using Texas ,Usa university.As a result it is as shown in table 1.
【Embodiment 10】
The synthesis of carboxylate surface active agent is same【Embodiment 1】With【Embodiment 4】, the preparation process that can be used for the transfer drive microemulsion system of low-permeability oil deposit is same【Embodiment 4】, simply three kinds of emulsifying agent lauric acid polyoxyethylene groups (20) carboxylic acid potassium, sorbester p37, polysorbas20 are replaced with into other four kinds of emulsifying agents ---【Embodiment 1】Dodecyl alcohol polyoxypropylene base (3) polyoxyethylene groups (2) carboxylic acid sodium of middle synthesis,【Embodiment 4】Lauric acid polyoxyethylene groups (20) the carboxylic acid potassium of middle synthesis, sorbester p37 and polysorbate60, four consumption is respectively 7g, 5g, 44g and 3g.Under 85 DEG C, oxygen free condition under total salinity 150000mg/L sodium chloride brine place 1 day, 7 days, 15 days, after 30 days microsphere particle diameter, calculate water-swelling polymer microsphere expansion multiple；Initial particle and the distribution of water-swelling polymer microsphere are tested using the type Particle Size Analyzers of Zetasizer Nano 2000；Interfacial tension between TX-500 types rotating interfacial tensimeter measure transfer drive microemulsion system and Pu 2-529 outputs oil is produced using Texas ,Usa university.As a result it is as shown in table 1.
【Comparative example 1】
The preparation process of transfer drive microemulsion system is same【Embodiment 4】, simply emulsifying agent lauric acid polyoxyethylene groups (20) carboxylic acid potassium is replaced with into Tween 80.Under 85 DEG C, oxygen free condition under total salinity 150000mg/L sodium chloride brine place 1 day, 7 days, 15 days, after 30 days microsphere particle diameter, calculate water-swelling polymer microsphere expansion multiple；Initial particle and the distribution of water-swelling polymer microsphere are tested using the type Particle Size Analyzers of Zetasizer Nano 2000；Interfacial tension between TX-500 types rotating interfacial tensimeter measure transfer drive microemulsion system and Pu 2-529 outputs oil is produced using Texas ,Usa university.As a result it is as shown in table 1.
【Comparative example 2】
The preparation process of transfer drive microemulsion system is same【Comparative example 1】, simply lauric acid polyoxyethylene groups (20) carboxylic acid potassium 16g will be added in the microemulsion system after discharging.Under 85 DEG C, oxygen free condition under total salinity 150000mg/L sodium chloride brine place 1 day, 7 days, 15 days, after 30 days microsphere particle diameter, calculate water-swelling polymer microsphere expansion multiple；Initial particle and the distribution of water-swelling polymer microsphere are tested using the type Particle Size Analyzers of Zetasizer Nano 2000；Interfacial tension between TX-500 types rotating interfacial tensimeter measure transfer drive microemulsion system and Pu 2-529 outputs oil is produced using Texas ,Usa university.As a result it is as shown in table 1.
【Comparative example 3】
The preparation process of transfer drive microemulsion system is same【Embodiment 1】, simply dodecyl alcohol polyoxypropylene base (3) polyoxyethylene groups (2) carboxylic acid sodium is replaced with into dodecyl alcohol polyoxyethylene base (2) polyoxypropylene base (3) carboxylic acid sodium (as shown in formula III).Under 85 DEG C, oxygen free condition under total salinity 150000mg/L sodium chloride brine place 1 day, 7 days, 15 days, after 30 days microsphere particle diameter, calculate water-swelling polymer microsphere expansion multiple；Initial particle and the distribution of water-swelling polymer microsphere are tested using the type Particle Size Analyzers of Zetasizer Nano 2000；Interfacial tension between TX-500 types rotating interfacial tensimeter measure transfer drive microemulsion system and Pu 2-529 outputs oil is produced using Texas ,Usa university.As a result it is as shown in table 1.
Table 1
Claims (10)
1. a kind of transfer drive that can be used for low-permeability oil deposit microemulsion system microemulsion system, by weight percentage,
Including following components：
(1) 15～90% oil-based solvent；
(2) 1～15% carboxylate compound emulsifying agent；
(3) 10～50% water-swelling polymer microsphere；
(4) 15～85% deionized water；
Wherein, the carboxylate compound emulsifying agent includes carboxylate surface active agent of the formula as shown in Formulas I structure：
In formula, R is C1～C18Aliphatic hydrocarbon；X is epoxide, imido grpup, carbonyl epoxide or phenyl epoxide；M=0～50；
N=1～55；M is selected from alkali metal or ammonium.
2. the transfer drive microemulsion system that can be used for low-permeability oil deposit according to claim 1, its feature exists
In the water-swelling polymer microsphere be by obtained in Reverse Microemulsion System Jing Raolical polymerizables；It is described anti-phase
Microemulsion system, by weight percentage, including following components：
(1) 15～90% oil-based solvent；
(2) 1～15% carboxylate compound emulsifying agent；
(3) 10～50% acrylamide；
(4) 10～50% temperature-resistant anti-salt monomer；
(5) 15～85% deionized water；
(6) 0.01～10% emulsion adjuvant；
(7) 0.001～5% oxidant；
(8) 0.001～5% reducing agent；
(9) 0.001～5% cross-linking agent.
3. the transfer drive microemulsion system that can be used for low-permeability oil deposit according to claim 1 and 2, it is special
Levy be the oil-based solvent selected from thiacyclohexane, hexane, heptane, octane, isobutyltrimethylmethane., benzene, toluene, ethylbenzene,
At least one in dimethylbenzene, isopropylbenzene, liquid paraffin, vegetable oil, white oil, gasoline, diesel oil and kerosene.
4. the transfer drive microemulsion system that can be used for low-permeability oil deposit according to claim 1 and 2, it is special
Levy be the carboxylate compound emulsifying agent also include conventional surfactants, wherein, carboxylate surface active agent with
The mass ratio of conventional surfactants is 1：9～9：1；The conventional surfactants are selected from Span series and tween
Series；The emulsion adjuvant selected from ethanol, propanol, isopropanol, n-butyl alcohol, isobutanol, the tert-butyl alcohol, amylalcohol,
Hexanol, ethylene glycol, Propylene Glycol, butanediol, pentanediol, hexanediol, glycerol, polyglycerin ester, sodium formate, first
At least one in sour potassium, ammonium formate, sodium acetate, potassium acetate, ammonium acetate, adipic acid sodium, sodium malonate, its
Consumption is the 0.01～10% of emulsifying agent total amount.
5. the transfer drive microemulsion system that can be used for low-permeability oil deposit according to claim 1 and 2, it is special
Levy be the carboxylate surface active agent preparation method, comprise the steps：
Halogenated acetic acids or its alkali metal salt are existed with the alkyl polycyclic oxygen alkene based surfactants shown in Formula II structure
Mol ratio is 1～15：1st, reaction temperature be 10～160 DEG C at, react 2～15 hours, reaction terminate after Jing acid solutions,
Alkali liquor, saturated common salt water process obtain the carboxylate surface active agent.
In formula, R is C1～C18Aliphatic hydrocarbon；X is epoxide, imido grpup, carbonyl epoxide or phenyl epoxide；M=0～50；
N=1～55.
6. the transfer drive microemulsion system that can be used for low-permeability oil deposit according to claim 5, its feature exists
In described halogenated acetic acids be monoxone or bromoacetic acid；Described alkali metal salt is sodium salt, potassium salt or ammonium salt；It is described
Acid solution be hydrochloric acid or sulphuric acid；Described alkali liquor is potassium hydroxide, the aqueous solution of sodium hydroxide or ammonia.
7. the transfer drive microemulsion system that can be used for low-permeability oil deposit according to claim 2, its feature exists
Vinylbenzenesulfonic acid, 2- acrylamide-2-methylpro panesulfonic acids and/or its alkali metal are selected from the temperature-resistant anti-salt monomer
In salt and ammonium salt, 2- acrylamido -2- trimethoxysilyl propyl methacrylate ammonium chlorides, NVP at least one
Kind.
8. the transfer drive microemulsion system that can be used for low-permeability oil deposit according to claim 2, its feature exists
It is selected from Ammonium persulfate., potassium peroxydisulfate, sodium peroxydisulfate, hydrogen peroxide, benzoyl peroxide in the oxidant
It is at least one；The reducing agent is selected from sodium sulfite, Potassium acid sulfite, sodium sulfite, potassium sulfite, thio
At least one in sodium sulfate, ferrous chloride.
9. the transfer drive microemulsion system that can be used for low-permeability oil deposit according to claim 2, its feature exists
Divinylbenzene, methylene-bisacrylamide, polyethyleneglycol diacrylate, Ji Wusi are selected from the cross-linking agent
At least one in alcohol triacrylate.
10. the transfer drive microemulsion system that can be used for low-permeability oil deposit according to any one of claim 1～9
Preparation method, it is characterised in that comprise the following steps：
In dissolving reduce agent in portions of de-ionized water, reducing agent aqueous solution is obtained；Again by acrylamide, temperature-resistant anti-salt
Monomer, cross-linking agent, oxidant are dissolved in the deionized water of surplus, are stirred to solution and are clarified without insoluble matter, and use 5%
Sodium hydrate aqueous solution adjust solution ph to 7～12, obtain water phase；By carboxylate compound emulsifying agent and emulsifying
Auxiliary agent is dissolved in oil-based solvent, is stirred, and obtains oil phase；The aforementioned water for having prepared is added in oil phase,
Stirring, obtains transparent or semitransparent Reverse Microemulsion System；Noble gases deoxygenation is passed through in the system, is added
The aforementioned reducing agent aqueous solution for having prepared, is uniformly mixed, the initiated polymerization at a temperature of 25～70 DEG C,
Continue to react 0.5～6 hour up to after exothermic peak temperature, obtain it is stable, transparent or semitransparent can be used for it is hypotonic
The transfer drive microemulsion system of saturating oil reservoir；Wherein, the particle diameter of water-swelling polymer microsphere is 50～300nm, particle diameter
It is distributed as 0.1～0.5.
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| CN110079291A (en) * | 2019-05-31 | 2019-08-02 | 西南石油大学 | Emulsify increasing stick system in situ containing high transformation temperature and in the application of water-drive pool |
| CN111154473A (en) * | 2020-01-14 | 2020-05-15 | 北京勃兴石油科技有限公司 | Blockage removal oil displacement agent and preparation method and application thereof |
| CN111154473B (en) * | 2020-01-14 | 2022-04-08 | 北京勃兴石油科技有限公司 | Blockage removal oil displacement agent and preparation method and application thereof |
| CN114716991A (en) * | 2021-01-04 | 2022-07-08 | 中国石油化工股份有限公司 | Medium-low-permeability reservoir enhanced self-emulsifying oil displacement system and application thereof |
| CN114573268A (en) * | 2022-05-07 | 2022-06-03 | 中国石油大学(华东) | Oil well cement composite permeation enhancer suitable for hydrate layer and preparation method thereof |
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