CN112521560B - Efficient salt-resistant one-dose dual-purpose thickening agent and preparation method and application thereof - Google Patents
Efficient salt-resistant one-dose dual-purpose thickening agent and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a high-efficiency salt-resistant one-dose dual-purpose thickener, a preparation method and application thereof, wherein the preparation method of the thickener comprises the steps of S1 preparing a water phase; s2, preparing an oil phase; s3, emulsifying; s4, polymerization; s5, post-treatment. The thickener is introduced with hydrophobic monomer, functional monomer and salt-resistant monomer, and forms compact and complex space network structure in water solution, so that the heat stability and salt resistance of the thickener are improved, and the water solution can maintain higher viscosity under the condition of high mineralization. And the addition of the chain extender enables the molecular chain of the polymer to be longer, so that the viscosity is greatly improved. The dissolution rate of the polymer emulsion is further improved by introducing the cosolvent, the polymer emulsion can be completely dissolved in 30 seconds, the water quality requirement is low, and the polymer emulsion can be prepared from oilfield reinjection water and oilfield wastewater. The suspending agent is added, so that the emulsion system is more stable, and the emulsion can not be layered within 2 years. The thickener has the characteristics of dual purposes, and can be used as a slick water drag reducer of fracturing fluid and a thickener of the fracturing fluid.
Description
Technical Field
The invention belongs to the technical field of oil field enhanced recovery ratio, and particularly relates to a high-efficiency salt-resistant one-dose dual-purpose thickening agent, and a preparation method and application thereof.
Background
The proportion of the low-permeability oil gas resources in China is more than 50%, and the low-permeability oil gas resources become the main exploration and development object in China at present. Because low permeability reservoirs are affected by factors such as large burial depth, high formation temperature, high formation water mineralization, strong diagenetic and compaction effects, etc., effective development can be realized usually by means of yield-increasing reformation measures such as fracturing, acidification and acid fracturing. At present, the fracturing yield increasing technology is an important means for oil and gas field development.
The requirements for high-performance fracturing fluid are increased by expanding the American shale gas fracturing market and increasing the market demands for petroleum at home and abroad. In recent years, clean fracturing fluid technology, polymer fracturing fluid technology and low-molecular polymer fracturing technology gradually replace the traditional guar gum fracturing fluid technology. Meanwhile, due to the progress of the fracturing fluid technology and the requirements of oilfield construction, the online fracturing fluid construction technology is rapidly developed, a liquid preparation station, a preparation tank or other preparation equipment is not needed, high-content concentrated liquid active chemicals are directly pumped to a sand mixing vehicle according to proportion through a gear pump in an on-site online adding mode, propping agents and water are added, and the water, propping agents and the chemicals are mixed together according to the proportion under the stirring of the sand mixing vehicle. However, because the drag reducer and the thickener have different effects, the agents are frequently switched in the oilfield construction process, and certain inconvenience is brought to site construction. Therefore, the fracturing fluid agent is required to have high requirements, not only excellent drag reduction performance, but also high viscosity sand suspension performance. Therefore, the efficient salt-resistant one-dose dual-purpose thickener has important significance for oil field development.
Disclosure of Invention
Aiming at the technical problems, the invention provides a high-efficiency salt-resistant one-dose dual-purpose thickener, and a preparation method and application thereof.
The technical scheme adopted by the invention is as follows:
the invention firstly discloses a preparation method of a high-efficiency salt-resistant one-dose dual-purpose thickener, which comprises the following steps:
s1, preparing an aqueous phase: 120-160 parts of acrylamide, 60-80 parts of acrylic acid, 80-120 parts of 2-acrylamido-2-methylpropanesulfonic acid, 5-10 parts of functional monomers, 1-4 parts of hydrophobic monomers, 3-6 parts of chain extenders, 2-5 parts of cosolvent and 280-340 parts of water are uniformly mixed, and then the pH value is regulated to 6.5-6.7 by using a pH regulator, and the mixture is uniformly mixed to obtain a water phase;
s2, preparing an oil phase: 200-240 parts of white oil, 20-35 parts of main emulsifier, 4-7 parts of auxiliary emulsifier and 3-6 parts of suspending agent are uniformly mixed to obtain an oil phase;
s3, emulsifying: sequentially adding a water phase, an oil phase and an initiator into a mixing kettle, controlling the rotating speed to be 500rpm/min in the adding process, stirring for 1.5-2.5 h at room temperature, and cooling to 15-25 ℃ to obtain emulsion;
s4, polymerization: introducing nitrogen into the emulsion obtained in the step S3 to deoxidize, controlling the temperature to be 45-50 ℃, and adding a reducing agent to initiate polymerization reaction; the stirring rotation speed is always kept at 150rpm/min in the polymerization reaction process,
s5, post-treatment: after the polymerization reaction is completed, 23-33 parts of fatty alcohol polyoxyethylene ether is added, and the light yellow semitransparent liquid is obtained after uniform stirring, namely the efficient salt-resistant one-dose dual-purpose thickener.
Further, the functional monomer is prepared from a grafting monomer and dimethylaminoethyl methacrylate according to a molar ratio of 1:1; wherein the grafting monomer is one or a mixture of two or more than two of N-tertiary butyl-2-methylbenzamide, 2- (chloromethyl) benzoyl chloride and 2-methylbenzamide in any proportion.
Specifically, the preparation method of the functional monomer comprises the following steps: uniformly mixing dimethylaminoethyl methacrylate and solvent water according to a proportion, introducing nitrogen to remove oxygen, heating to 50 ℃ under the stirring condition of the rotating speed of 100rpm/min, continuously introducing nitrogen to protect, beginning to dropwise add grafted monomers at the water bath temperature of 50-70 ℃, controlling the dropwise adding time within 2 hours, and obtaining functional monomers after the reaction is finished;
wherein the dosage of the solvent water is 20 percent of the total mass of the functional monomer.
Preferably, the hydrophobic monomer is one or a mixture of two or more of N-tertiary butyl acrylamide, methyl methacrylate, styrene, N-dodecyl acrylamide and octadecyl dimethyl allyl ammonium chloride in any proportion.
Preferably, the chain extender is one or a mixture of two or more of polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate and polyglycerol acrylate in any proportion.
Preferably, the cosolvent is one of fatty alcohol polyoxyethylene ether AEO-15 and isomeric tridecanol polyoxyethylene ether 1310 or a mixture of the fatty alcohol polyoxyethylene ether AEO-15 and the isomeric tridecanol polyoxyethylene ether 1310 in any proportion.
Preferably, the main emulsifier is a composite emulsifier system and is prepared from Tween 80 and Span 65 according to a mass ratio of 1:5.
Preferably, the auxiliary emulsifier is n-octanol and ethylene glycol according to the ratio of 7:3, and is prepared by mass ratio.
Preferably, the suspending agent is one of hydrophobic silica, modified hectorite or a mixture thereof.
Preferably, the initiator is a composite initiation system and comprises azo initiator and oxidant, wherein the addition amount of the azo initiator is 0.01-0.05 part, and the addition amount of the oxidant is 0.01-0.05 part;
preferably, the azo initiator is one or a mixture of azodiisobutylamidine dihydrochloride, azodiisoheptonitrile and azodiiso Ding Mi-hydrochloride, and the oxidant is potassium persulfate or ammonium persulfate.
Further, the reducing agent is sodium bisulphite.
Preferably, sodium bisulfate is added in a plurality of times in the reaction process, and the specific adding method is as follows: 10% sodium bisulfite is added in 20min from the beginning of the reaction to initiate the polymerization reaction; after 1.5h of reaction, adding 30% of sodium bisulfite, continuously reacting for 2h, adding 30% of sodium bisulfite, reacting for 2h till the reaction is finished, and adding the rest sodium bisulfite till the polymerization reaction is finished.
The efficient salt-resistant dual-purpose thickener is prepared by the preparation method.
The invention also discloses application of the efficient salt-resistant one-agent dual-purpose thickening agent, which can be used as a slickwater drag reducer of fracturing fluid and a thickening agent of the fracturing fluid, and when the efficient salt-resistant one-agent dual-purpose thickening agent is used as the drag reducer, the additive concentration is 0.05-0.1%; when the thickener is used, the additive concentration is 0.6 to 1 percent.
Due to the adoption of the technical scheme, the invention has the following beneficial effects:
1. the high-efficiency salt-resistant dual-purpose thickener provided by the invention is characterized in that the hydrophobic monomer, the functional monomer and the salt-resistant monomer are introduced into the thickener, a compact and complex space network structure is formed in the aqueous solution, the thermal stability and the salt resistance of the thickener are improved, and the aqueous solution can keep higher viscosity under the condition of high mineralization. Meanwhile, the addition of the chain extender enables the molecular chain of the polymer to be longer, and the viscosity is greatly improved. The dissolution rate of the polymer emulsion is further improved by introducing the cosolvent, the polymer emulsion can be completely dissolved in 30 seconds, the water quality requirement is low, and the polymer emulsion can be prepared from oilfield reinjection water and oilfield wastewater. The suspending agent is added, so that the emulsion system is more stable, and the emulsion can not be layered within 2 years.
2. The efficient salt-resistant dual-purpose thickener provided by the invention has the advantages of quick dissolution, small addition amount, high drag reduction rate, strong salt resistance, good sand suspension effect, low viscosity after gel breaking, complete flowback, less residues and the like, and is an environment-friendly efficient comb-type variable-viscosity thickener.
3. The efficient salt-resistant one-agent dual-purpose thickening agent prepared by adopting the inverse emulsion polymerization process has the characteristic of one-agent dual-purpose, and can be used as a slick water drag reducer of fracturing fluid and a thickening agent of the fracturing fluid: it is used as drag reducer in the use process, the water-soluble fiber is prepared, the addition amount is 0.05 percent, the drag reduction rate of the system can reach 78%; when used as a thickening agent, the additive amount is 1 percent, the six-speed viscosity of tap water can reach 120 mpa.s, and the sand suspending effect is good.
4. The preparation method provided by the invention has the advantages that various raw materials involved in the preparation method can be purchased from the market, the operation of each step is simple, the requirements on reaction conditions are low, the cost of the product can be effectively reduced, and the preparation method is suitable for industrial production.
The foregoing description is only an overview of the present invention and is intended to provide a better understanding of the present invention, as it is hereinafter described in terms of preferred embodiments of the present invention.
Drawings
FIG. 1 is a graph of drag reduction performance testing for a high efficiency anti-salt one-dose dual-purpose thickener according to the present invention;
FIG. 2 is a graph showing the rheological property test of the high-efficiency anti-salt one-dose dual-purpose thickener according to the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below in connection with the embodiments of the present invention. It will be apparent that the described embodiments are some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It should be noted that the implementation conditions used in the examples may be further adjusted according to the specific experimental environment, and the implementation conditions that are not noted are generally conditions in the conventional experiments. The preparation methods mentioned in the invention are all conventional methods unless otherwise specified; all the starting materials mentioned in the examples below were obtained from the commercial sources disclosed, unless otherwise specified.
The invention firstly discloses a preparation method of a high-efficiency salt-resistant one-dose dual-purpose thickener, which comprises the following steps:
s1, preparing an aqueous phase: 120-160 parts of acrylamide, 60-80 parts of acrylic acid, 80-120 parts of 2-acrylamido-2-methylpropanesulfonic acid, 5-10 parts of functional monomers, 1-4 parts of hydrophobic monomers, 3-6 parts of chain extenders, 2-5 parts of cosolvent and 280-340 parts of water are uniformly mixed, and then the pH value is regulated to 6.5-6.7 by using a pH regulator, and the mixture is uniformly mixed to obtain a water phase;
s2, preparing an oil phase: 200-240 parts of white oil, 20-35 parts of main emulsifier, 4-7 parts of auxiliary emulsifier and 3-6 parts of suspending agent are uniformly mixed to obtain an oil phase;
s3, emulsifying: sequentially adding a water phase, an oil phase and an initiator into a mixing kettle, controlling the rotating speed to be 500rpm/min in the adding process, stirring for 1.5-2.5 h at room temperature, and cooling to 15-25 ℃ to obtain emulsion;
s4, polymerization: introducing nitrogen into the emulsion obtained in the step S3 to deoxidize, controlling the temperature to be 45-50 ℃, and adding a reducing agent to initiate polymerization reaction; the stirring rotation speed is always kept at 150rpm/min in the polymerization reaction process,
s5, post-treatment: after the polymerization reaction is completed, 23-33 parts of fatty alcohol polyoxyethylene ether is added, and the light yellow semitransparent liquid is obtained after uniform stirring, namely the efficient salt-resistant one-dose dual-purpose thickener.
Further, the functional monomer is prepared from a grafting monomer and dimethylaminoethyl methacrylate according to a molar ratio of 1:1; wherein the grafting monomer is one or a mixture of two or more than two of N-tertiary butyl-2-methylbenzamide, 2- (chloromethyl) benzoyl chloride and 2-methylbenzamide in any proportion.
Specifically, the preparation method of the functional monomer comprises the following steps: uniformly mixing dimethylaminoethyl methacrylate and solvent water according to a proportion, introducing nitrogen to remove oxygen, heating to 50 ℃ under the stirring condition of the rotating speed of 100rpm/min, continuously introducing nitrogen to protect, beginning to dropwise add grafted monomers at the water bath temperature of 50-70 ℃, controlling the dropwise adding time within 2 hours, and obtaining functional monomers after the reaction is finished;
wherein the dosage of the solvent water is 20 percent of the total mass of the functional monomer.
Preferably, the hydrophobic monomer is one or a mixture of two or more of N-tertiary butyl acrylamide, methyl methacrylate, styrene, N-dodecyl acrylamide and octadecyl dimethyl allyl ammonium chloride in any proportion.
Preferably, the chain extender is one or a mixture of two or more of polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate and polyglycerol acrylate in any proportion.
Preferably, the cosolvent is one of fatty alcohol polyoxyethylene ether AEO-15 and isomeric tridecanol polyoxyethylene ether 1310 or a mixture of the fatty alcohol polyoxyethylene ether AEO-15 and the isomeric tridecanol polyoxyethylene ether 1310 in any proportion.
Preferably, the main emulsifier is a composite emulsifier system and is prepared from Tween 80 and Span 65 according to a mass ratio of 1:5.
Preferably, the auxiliary emulsifier is n-octanol and ethylene glycol according to the ratio of 7:3, and is prepared by mass ratio.
Preferably, the suspending agent is one of hydrophobic silica, modified hectorite or a mixture thereof.
Preferably, the initiator is a composite initiation system and comprises azo initiator and oxidant, wherein the addition amount of the azo initiator is 0.01-0.05 part, and the addition amount of the oxidant is 0.01-0.05 part;
preferably, the azo initiator is one or a mixture of azodiisobutylamidine dihydrochloride, azodiisoheptonitrile and azodiiso Ding Mi-hydrochloride, and the oxidant is potassium persulfate or ammonium persulfate.
Further, the reducing agent is sodium bisulphite.
Preferably, sodium bisulfate is added in a plurality of times in the reaction process, and the specific adding method is as follows: 10% sodium bisulfite is added in 20min from the beginning of the reaction to initiate the polymerization reaction; after 1.5h of reaction, adding 30% of sodium bisulfite, continuously reacting for 2h, adding 30% of sodium bisulfite, reacting for 2h till the reaction is finished, and adding the rest sodium bisulfite till the polymerization reaction is finished.
The invention also provides a high-efficiency salt-resistant one-dose dual-purpose thickening agent, which is prepared by the preparation method.
The invention also discloses application of the efficient salt-resistant one-agent dual-purpose thickening agent, which can be used as a slickwater drag reducer of fracturing fluid and a thickening agent of the fracturing fluid, and when the efficient salt-resistant one-agent dual-purpose thickening agent is used as the drag reducer, the additive concentration is 0.05-0.1%; when the thickener is used, the additive concentration is 0.6 to 1 percent.
The following related tests were performed on the high-efficiency anti-salt one-dose dual-purpose thickener prepared in the following examples according to the following methods:
(1) Viscosity test
The obtained high-efficiency salt-resistant dual-purpose thickener is prepared into a thickener with a certain concentrationAgent solution: adding a certain amount of polymer emulsion into required saline water, stirring for 5 min under the condition of a vertical stirrer of 1000r/min, and using a six-speed viscometer at 25 ℃ and shearing rate of 170s -1 The viscosity of the polymer solution was measured as follows.
The apparent viscosity is calculated according to formula (1):
wherein: eta-apparent viscosity, mpa.s
k-readings from a six-fold rotational viscometer.
(2) Testing of rheological Properties
A polymer solution of a certain concentration was prepared and the rheological properties of the drag reducer solution were tested using a HAAKE MARS model 40 rheometer. Wherein the shear rate is controlled at 170s in the performance evaluation experiment -1 The shearing time is 60min, and the temperature is controlled at 90 ℃.
(3) Testing of sand suspension Performance
Preparing a polymer solution with concentration of 1% by using tap water, adding 20-40 ceramsite sand into a glass cup according to a sand ratio of 35%, uniformly stirring, pouring into a 100ml measuring cylinder, and observing and recording sand sedimentation rate (the percentage of the settled height of the ceramsite sand to the total height of sand-carrying fluid). And observing and recording the suspension state of sand grains in 24 hours and the sand setting rate.
(4) Testing of drag reduction performance
Drag reduction rate determination: slick water was formulated as required and performed as described with reference to 7.8 in NB/T14003.1-2015, as follows:
and adopting an indoor pipeline friction resistance meter to perform resistance reduction performance test. The inner diameter of the pipeline is R=8mm, the test length of the horizontal pipe is L=2.5m, the pressure difference of the fluid passing through the pipeline is recorded, and the drag reduction rate is calculated as shown in the following formula. Drag reduction efficiency of drag reducer under turbulent flow was tested.
Wherein: DR is drag reduction rate,%; Δp1 is the pressure difference, pa, across the loop line when water is being cleaned; Δp2 is the pressure difference across the mobile phase, pa, when it is slick water.
Example 1:
the invention provides a high-efficiency salt-resistant one-dose dual-purpose thickener, which comprises the following components in parts by weight: 120 parts of acrylamide, 60 parts of acrylic acid, 80 parts of 2-acrylamido-2-methylpropanesulfonic acid, 5 parts of functional monomers, 1 part of N-tert-butyl acrylamide, 3 parts of polyethylene glycol diacrylate, 152 parts of fatty alcohol polyoxyethylene ether AEO-152 parts of sodium hydroxide, 48 parts of water 340 parts of white oil, 20 parts of a main emulsifier, 4 parts of a co-emulsifier, 3 parts of hydrophobic silica, 0.03 part of azo diiso Ding Mi hydrochloride, 0.02 part of potassium persulfate and 0.02 part of sodium bisulfate.
The preparation method comprises the following steps: s1, preparing a water phase; s2, preparing an oil phase; s3, emulsifying and polymerizing: fully and uniformly mixing the water phase, the oil phase and the initiator, emulsifying for 2 hours, cooling to 20 ℃, transferring into a reaction kettle, introducing nitrogen to deoxidize for 30 minutes, and pumping sodium bisulphite to initiate polymerization; s4, post-treatment: after the polymerization reaction is finished, 26 parts by weight of fatty alcohol polyoxyethylene ether is added, and the mixture is stirred uniformly to obtain pale yellow semitransparent emulsion.
Apparent viscosity 1420 mpa.s, drag reducing properties of the synthetic high efficiency thickeners: a drag reduction of 76.46% at 0.05% (test water: mineralized water 50000ppm, containing 3000ppm calcium magnesium ions); thickening performance: 1% tap water viscosity 120 mpa.s, 2% 8.5% mineralized water viscosity 60 mpa.s; rheological properties: viscosity 82 mpa.s after shearing at 90℃for 60 minutes; sand suspending performance: 24h sedimentation rate 0.5% (1% tap water solution, sand ratio 35%. Drag reduction curve, rheological curve are shown in figure 1 and figure 2.
Example 2
The invention provides a high-efficiency salt-resistant one-dose dual-purpose thickener, which comprises the following components: 140 parts of acrylamide, 70 parts of acrylic acid, 100 parts of 2-acrylamido-2-methylpropanesulfonic acid, 7 parts of functional monomers, 2 parts of N-dodecyl acrylamide, 5 parts of polyethylene glycol dimethacrylate, 13104 parts of isomeric tridecanol polyoxyethylene ether, 58 parts of sodium hydroxide, 310 parts of water, 220 parts of white oil, 27 parts of a main emulsifier, 5 parts of a co-emulsifier, 5 parts of modified hectorite, 0.03 part of azodiiso Ding Mi hydrochloride, 0.02 part of potassium persulfate and 0.02 part of sodium bisulfate.
The preparation method comprises the following steps: s1, preparing a water phase; s2, preparing an oil phase; s3, emulsifying and polymerizing: fully and uniformly mixing the water phase, the oil phase and the initiator, emulsifying for 2 hours, cooling to 20 ℃, transferring into a reaction kettle, introducing nitrogen to deoxidize for 30 minutes, and pumping sodium bisulphite to initiate polymerization; s4, post-treatment: and after the polymerization reaction is finished, adding 27 parts by weight of fatty alcohol polyoxyethylene ether, and uniformly stirring to obtain pale yellow semitransparent emulsion.
Apparent viscosity 1270 mpa.s of the synthesized high-efficiency thickener, and drag reduction performance: 0.05% drag reduction 75.15% (test water: mineralized water 50000ppm, containing 3000ppm calcium magnesium ions); thickening performance: 1% tap water viscosity 105 mpa.s, 2% 8.5% mineralized water viscosity 66 mpa.s; rheological properties: viscosity 91 mpa.s after shearing at 90℃for 60 minutes; sand suspending performance: the 24h sedimentation rate was 0.5% (1% tap water solution, sand ratio 35%). The drag reduction curve and the rheological curve are shown in fig. 1 and 2.
Example 3
The invention provides a high-efficiency salt-resistant one-dose dual-purpose thickener, which comprises the following components in parts by weight: 160 parts of acrylamide, 80 parts of acrylic acid, 120 parts of 2-acrylamido-2-methylpropanesulfonic acid, 10 parts of functional monomers, 4 parts of octadecyl dimethyl allyl ammonium chloride, 6 parts of polyethylene glycol dimethacrylate, 13105 parts of isomeric tridecanol polyoxyethylene ether, 67 parts of sodium hydroxide, 280 parts of water, 240 parts of white oil, 35 parts of a main emulsifier, 7 parts of a co-emulsifier, 6 parts of hydrophobic silica, 0.03 part of azo diiso Ding Mi hydrochloride, 0.02 part of potassium persulfate and 0.02 part of sodium bisulfate.
The preparation method comprises the following steps: s1, preparing a water phase; s2, preparing an oil phase; s3, emulsifying and polymerizing: fully and uniformly mixing the water phase, the oil phase and the initiator, emulsifying for 2 hours, cooling to 20 ℃, transferring into a reaction kettle, introducing nitrogen to deoxidize for 30 minutes, pumping sodium bisulphite to initiate polymerization, and S4, post-treating: after the polymerization reaction is finished, 31 parts by weight of fatty alcohol polyoxyethylene ether is added, and the mixture is stirred uniformly to obtain pale yellow semitransparent emulsion.
Apparent viscosity 1350 mpa.s, drag reduction performance of the synthesized high-efficiency thickener: a drag reduction of 76.77% at 0.05% (test water: mineralized water 50000ppm, containing 3000ppm calcium magnesium ions); thickening performance: 1% tap water viscosity 132 mpa.s, 2% 8.5% mineralized water viscosity 75 mpa.s; rheological properties: viscosity 112 mpa.s after shearing at 90℃for 60 minutes; sand suspending performance: the 24h sedimentation rate was 0.5% (1% tap water solution, sand ratio 35%). The drag reduction curve and the rheological curve are shown in fig. 1 and 2.
The high-efficiency salt-resistant dual-purpose thickener provided by the invention is characterized in that the hydrophobic monomer, the functional monomer and the salt-resistant monomer are introduced into the thickener, a compact and complex space network structure is formed in the aqueous solution, the thermal stability and the salt resistance of the thickener are improved, and the aqueous solution can keep higher viscosity under the condition of high mineralization. Meanwhile, the addition of the chain extender enables the molecular chain of the polymer to be longer, and the viscosity is greatly improved. The dissolution rate of the polymer emulsion is further improved by introducing the cosolvent, the polymer emulsion can be completely dissolved in 30 seconds, the water quality requirement is low, and the polymer emulsion can be prepared from oilfield reinjection water and oilfield wastewater. The suspending agent is added, so that the emulsion system is more stable, and the emulsion can not be layered within 2 years.
The thickener obtained by the invention has the characteristic of 'one agent for two purposes', and can be used as a slick water drag reducer of fracturing fluid and also can be used as a thickener of the fracturing fluid: when the modified starch is used as a drag reducer, the preferable addition amount is 0.05%, the drag reduction rate of the system can reach 78%; when used as a thickening agent, the preferable addition amount is 1%, the six-speed viscosity of tap water can reach 120 mpa.s, and the sand suspending effect is good.
In conclusion, the efficient salt-resistant dual-purpose thickener has the advantages of quick dissolution, small addition amount, high drag reduction rate, strong salt resistance, good sand suspension effect, low viscosity after gel breaking, complete flowback, less residues and the like, and is an environment-friendly efficient comb-type variable-viscosity thickener. The method not only can improve the overall development economic benefit of the oil field, but also has better field popularization value.
While the preferred embodiments of the present invention have been illustrated and described, the present invention is not limited to the embodiments, and various equivalent modifications and substitutions can be made by one skilled in the art without departing from the spirit of the present invention, and these are intended to be included in the scope of the present invention as defined in the appended claims.
Claims (9)
1. The preparation method of the efficient salt-resistant one-dose dual-purpose thickener is characterized by comprising the following steps of:
s1, preparing an aqueous phase: 120-160 parts of acrylamide, 60-80 parts of acrylic acid, 80-120 parts of 2-acrylamido-2-methylpropanesulfonic acid, 5-10 parts of functional monomers, 1-4 parts of hydrophobic monomers, 3-6 parts of chain extenders, 2-5 parts of cosolvent and 280-340 parts of water are uniformly mixed, and then the pH value is regulated to 6.5-6.7 by using a pH regulator, and the mixture is uniformly mixed to obtain a water phase;
wherein the functional monomer is prepared from a grafting monomer and dimethylaminoethyl methacrylate according to a molar ratio of 1:1; the grafting monomer is 2- (chloromethyl) benzoyl chloride;
s2, preparing an oil phase: 200-240 parts of white oil, 20-35 parts of main emulsifier, 4-7 parts of auxiliary emulsifier and 3-6 parts of suspending agent are uniformly mixed to obtain an oil phase;
s3, emulsifying: sequentially adding a water phase, an oil phase and an initiator into a mixing kettle, controlling the rotating speed to be 500rpm in the adding process, stirring for 1.5-2.5 h at room temperature, and cooling to 15-25 ℃ to obtain emulsion;
s4, polymerization: introducing nitrogen into the emulsion obtained in the step S3 to deoxidize, controlling the temperature to be 45-50 ℃, and adding a reducing agent to initiate polymerization reaction; the stirring rotation speed is always kept at 150rpm in the polymerization reaction process;
s5, post-treatment: after the polymerization reaction is completed, adding 23-33 parts of fatty alcohol polyoxyethylene ether, and uniformly stirring to obtain light yellow semitransparent liquid, namely the efficient salt-resistant dual-purpose thickener;
the efficient salt-resistant dual-purpose thickening agent can be used as a slickwater drag reducer of fracturing fluid and can also be used as a thickening agent of the fracturing fluid.
2. The preparation method of the efficient salt-resistant one-agent dual-purpose thickener according to claim 1, wherein the preparation method of the functional monomer is as follows: uniformly mixing dimethylaminoethyl methacrylate and solvent water according to a proportion, introducing nitrogen to remove oxygen, heating to 50 ℃ under the stirring condition of the rotating speed of 100rpm, continuously introducing nitrogen to protect, beginning to dropwise add grafted monomers at the water bath temperature of 50-70 ℃, controlling the dropwise adding time within 2 hours, and obtaining functional monomers after the reaction is finished;
wherein the dosage of the solvent water is 20 percent of the total mass of the functional monomer.
3. The method for preparing the efficient salt-resistant one-dose dual-purpose thickener according to claim 1, which is characterized in that: the hydrophobic monomer is one or a mixture of two or more of N-tertiary butyl acrylamide, methyl methacrylate, styrene, N-dodecyl acrylamide and octadecyl dimethyl allyl ammonium chloride in any proportion.
4. The method for preparing the efficient salt-resistant one-dose dual-purpose thickener according to claim 1, which is characterized in that: the chain extender is one or a mixture of two or more than two of polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate and polyglycerol acrylate in any proportion;
the cosolvent is one of fatty alcohol polyoxyethylene ether AEO-15 and isomeric tridecanol polyoxyethylene ether 1310 or a mixture of the fatty alcohol polyoxyethylene ether AEO-15 and the isomeric tridecanol polyoxyethylene ether 1310 in any proportion.
5. The method for preparing the efficient salt-resistant one-dose dual-purpose thickener according to claim 1, which is characterized in that: the main emulsifier is a composite emulsifier system and is prepared from Tween 80 and Span 65 according to a mass ratio of 1:5;
the auxiliary emulsifier is n-octanol and ethylene glycol according to the proportion of 7:3, preparing the mixture by mass ratio;
the suspending agent is one of hydrophobic silicon dioxide and modified hectorite or a mixture thereof.
6. The method for preparing the efficient salt-resistant one-dose dual-purpose thickener according to claim 1, which is characterized in that: the initiator is a composite initiation system and comprises an azo initiator and an oxidant, wherein the addition amount of the azo initiator is 0.01-0.05 part, and the addition amount of the oxidant is 0.01-0.05 part;
the azo initiator is one or a mixture of azodiisobutylamidine dihydrochloride, azodiisoheptonitrile and azodiiso Ding Mi hydrochloride, and the oxidant is potassium persulfate or ammonium persulfate.
7. The method for preparing the efficient salt-resistant one-dose dual-purpose thickener according to claim 1, which is characterized in that: the reducing agent is sodium bisulphite, and the sodium bisulphite is added for a plurality of times in the reaction process, specifically: 10% sodium bisulfite is added in 20min from the beginning of the reaction to initiate the polymerization reaction; after 1.5h of reaction, adding 30% of sodium bisulfite, continuously reacting for 2h, adding 30% of sodium bisulfite, reacting for 2h till the reaction is finished, and adding the rest sodium bisulfite till the polymerization reaction is finished.
8. A high-efficiency anti-salt one-agent dual-purpose thickener, characterized in that it is prepared by the preparation method according to any one of claims 1 to 7.
9. The use of a high-efficiency anti-salt one-dose dual-purpose thickener according to claim 8, wherein: when the efficient salt-resistant dual-purpose thickener is used as a drag reducer, the additive concentration is 0.05% -0.1%; when the thickener is used as a thickening agent, the addition concentration is 0.6% -1%.
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| CN115260418B (en) * | 2022-09-30 | 2022-12-09 | 山东诺尔生物科技有限公司 | Drag reducer for fracturing fluid and preparation method thereof |
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