CN114907531A - Preparation method of salt-responsive hydrophobically associating polymer and application of salt-responsive hydrophobically associating polymer in fracturing fluid - Google Patents
Preparation method of salt-responsive hydrophobically associating polymer and application of salt-responsive hydrophobically associating polymer in fracturing fluid Download PDFInfo
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Abstract
The invention discloses a preparation method of a salt-responsive hydrophobically associating polymer and application of the salt-responsive hydrophobically associating polymer in fracturing fluid. The technical scheme is as follows: (1) the intermediate D12PA is obtained by the reaction of methyl piperazine and bromododecane, and thenReacting the intermediate D12PA with methacryloyl chloride to obtain an amphiphilic monomer D12 PAAC; (2) the polyoxyethylene ether monomer MAA-EO is obtained by the reaction of methacryloyl chloride and lauryl alcohol polyoxyethylene ether 23 C 12 (ii) a (3) Amphiphilic monomer D12PAAC and polyoxyethylene ether monomer MAA-EO 23 C 12 And reacting the acrylamide, the acrylic acid and the 2-acrylamido-2-methylpropanesulfonic acid for 6 to 8 hours under the light initiation, and drying and powdering to obtain polymer powder HSRPM. The fracturing fluid prepared from the polymer has the characteristics of excellent salt responsiveness and low viscosity. The preparation method has the characteristics of low cost and high yield, and the prepared product has the characteristics of low viscosity and high elasticity and has a good application prospect in oil field fracturing.
Description
Technical Field
The invention relates to a preparation method of a salt-responsive hydrophobically associating polymer and application of the salt-responsive hydrophobically associating polymer in fracturing fluid, belonging to the field of oilfield chemical additives.
Technical Field
Along with large-scale exploitation and consumption of conventional oil and gas reservoirs, unconventional oil and gas resources with low permeability, ultra-low permeability and deep-layer high temperature, such as compact sandstone gas, coal bed gas, shale gas and the like, need to be developed and utilized urgently. Fracturing is an important means for increasing the production of oil and gas wells and increasing the injection of water injection wells. Particularly, in recent years, a plurality of compact oil-gas reservoirs are discovered, the yield is very low or even no at the initial production stage, and a certain production value can be achieved after fracturing modification. The fracturing fluid is a working fluid in the process of hydraulic fracturing modification of an oil-gas layer, and plays roles in forming formation cracks, transferring pressure and carrying a propping agent into the cracks in the fracturing process. The performance of the fracturing fluid directly influences success or failure of fracturing construction and yield increasing effect after fracturing. The water-based fracturing fluid based on guanidine gum is widely applied to fracturing operation at present, and the vegetable gum type fracturing fluid has good thickening effect but has prominent defects: the insoluble matter content is high, the gel breaking is not thorough, the residue and clarification amount is large, the formation is easily damaged, and the cost is increased day by day. The emergence of fracturing fluids with superior properties is therefore an urgent need.
The hydrophobic association polymer is a water-soluble polymer with a small amount of hydrophobic groups on the macromolecular chains of the polymer, and in a polymer aqueous solution, the molecular chains aggregate due to the hydrophobic effect of the hydrophobic groups to form intramolecular or intermolecular association. When the concentration of the solution is less than the critical association concentration, the polymer can mainly form intramolecular association, a macromolecular chain is curled, the hydrodynamic volume of the polymer is reduced, and the viscosity of the aqueous solution is low; when the concentration is higher than the critical association concentration, the polymer mainly adopts intermolecular association, a network is formed among molecular chains, the hydrodynamic volume is increased sharply, and the viscosity is increased. The existing hydrophobic association polymer fracturing fluid has the defects of overlarge base fluid viscosity, difficulty in pumping, poor salt tolerance and the like, and in order to improve the applicability of the hydrophobic association polymer, the prepared amphipathic polymerizable monomer is adopted, so that the salt-responsive hydrophobic association polymer is prepared, and the fracturing fluid with excellent performance is provided for improving the oil and gas recovery ratio.
Disclosure of Invention
The invention provides a preparation method of a salt-responsive hydrophobically associating polymer, aiming at the defects of overlarge base fluid viscosity, difficult pumping, poor salt tolerance and the like of the existing hydrophobically associating polymer fracturing fluid. The polymer fracturing fluid has the characteristics of excellent salt responsiveness and viscoelasticity and low viscosity. The fracturing fluid has high yield, low cost and simple synthesis process.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a salt-responsive hydrophobically associative polymer HSRPM. The specific structural formula is as follows:
in the formula:
R 1 dodecyl, hexadecyl, octadecyl.
R 2 (OCH 2 CH 2 ) a O is fatty alcohol-polyoxyethylene ether, alkylphenol ethoxylate, fatty acid-polyoxyethylene ether. The number a of ethoxy groups is 5 to 30.
x, y, z, m and n are monomer molar ratios, wherein x is 60-80%, y is 10-22%, z is 8-12%, m is 1-3%, and n is 1-3%.
The synthesis steps of the amphiphilic monomer D12PAAC are as follows:
(1) dissolving methyl piperazine in ethanol, heating to 50 ℃, adding bromododecane according to the molar ratio of 1: 1.1-1.2, refluxing and reacting at 50 ℃ for 12 hours, cooling after the reaction is finished, performing rotary evaporation by using a rotary evaporator to remove ethanol, performing suction filtration to obtain a light yellow liquid, adding ethyl acetate to soak for 1 day, cleaning a resultant, and performing vacuum drying to constant weight to finally obtain an intermediate D12 PA;
(2) and reacting the intermediate D12PA obtained in the first step with methacryloyl chloride in a molar ratio of 1: 1.1-1.2 to obtain the amphiphilic monomer D12 PAAC. Firstly, dissolving D12PA in dichloromethane, adding the solution into a three-neck round-bottom flask, cooling the temperature of a reaction system to be below 5 ℃ by using an ice-water bath, adding triethylamine according to the molar ratio of 1: 1.2-1.3, slowly dropwise adding a mixed solution of methacryloyl chloride and dichloromethane by using a constant-pressure funnel, heating to room temperature after the addition is finished, reacting for 8-11 h, washing the solution to be neutral by using deionized water, and drying and carrying out rotary evaporation to obtain a relatively pure amphiphilic monomer D12 PAAC.
The monomer reaction formula is as follows:
further, in the preferred embodiment of the present invention, bromododecane may be replaced with bromohexadecane, bromooctadecane.
Wherein the polyoxyethylene ether monomer MAA-EO 23 C 12 The specific preparation method comprises the following steps:
dissolving polyoxyethylene lauryl ether in dichloromethane, adding the solution into a three-neck round-bottom flask, cooling the temperature of a reaction system to below 5 ℃ in ice-water bath, adding triethylamine in a molar ratio of 1: 1.2-1.3, slowly dropwise adding a mixed solution of methacryloyl chloride and dichloromethane by using a constant-pressure funnel, heating to room temperature after the addition is finished, reacting for 8-10 hours, washing the solution to be neutral by using deionized water, and dryingDrying and rotary evaporation to obtain polyoxyethylene ether monomer MAA-EO 23 C 12 (ii) a Wherein the molar ratio of the lauryl alcohol polyoxyethylene ether to the methacryloyl chloride is 1: 1.1-1.2;
the monomer reaction formula is as follows:
further, in the preferred embodiment of the present invention, the polyoxyethylene lauryl ether can be other fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, or fatty acid polyoxyethylene ether.
The invention discloses a preparation method of a salt-responsive hydrophobically associating polymer HSRPM, which comprises the following steps:
(1) adding acrylamide, acrylic acid, 2-acrylamide-2-methylpropanesulfonic acid, amphiphilic monomer D12PAAC and polyoxyethylene ether monomer MAA-EO into deionized water 23 C 12 60 to 80 percent of acrylamide, 10 to 22 percent of acrylic acid, 8 to 12 percent of 2-acrylamide-2-methylpropanesulfonic acid, 1 to 3 percent of amphiphilic monomer D12PAAC, and 1 to 3 percent of polyoxyethylene ether monomer MAA-EO 23 C 12 Preparing an aqueous solution with the monomer concentration of 25-30%, adding Sodium Dodecyl Sulfate (SDS) accounting for 0.5-2% of the total monomer concentration, and stirring to obtain a clear solution;
(2) after the solution is fully and uniformly mixed, introducing nitrogen for 30min to remove dissolved oxygen in water;
(3) taking 2, 2-azo diisobutyl amidine dihydrochloride (V50) as an initiator, wherein the initiator accounts for 0.1-0.3% of the total monomer concentration, carrying out free radical aqueous solution polymerization under the ultraviolet light photo-initiation condition, reacting for 6-8 hours to obtain the required polyether-containing hydrophobic association polymer, finally shearing the obtained hydrophobic association polymer, soaking and drying the hydrophobic association polymer in absolute ethyl alcohol, and crushing the hydrophobic association polymer into powder to obtain the salt-responsive hydrophobic association polymer HSRPM for the fracturing fluid.
The chemical reaction process of the invention is as follows:
x, y, z, m and n are monomer molar ratios, wherein x is 60-80%, y is 10-22%, z is 8-12%, m is 1-3%, and n is 1-3%.
The other technical scheme of the invention is realized as follows: the salt-responsive hydrophobically associating polymer is fracturing fluid, and consists of 0.3 to 0.6 mass percent of hydrophobically associating polymer and the balance of mineralized water.
The invention has the beneficial effects that:
(1) the invention provides a preparation method of a salt-responsive hydrophobically associating polymer, which has high yield, low cost and simple production process.
(2) The invention provides a preparation method of an amphiphilic monomer with a hydrophobic long chain.
(3) The salt-responsive hydrophobically associating polymer prepared by the invention has excellent salt response performance.
(4) The salt-responsive hydrophobically associating polymer provided by the invention has the characteristics of low viscosity and high elasticity in a salt solution as a fracturing fluid, and can meet the engineering requirements of oilfield field construction.
Drawings
FIG. 1 is a graph of the viscosity change of the fracturing fluid obtained in example nine at different degrees of mineralization;
FIG. 2 is a viscoelastic diagram of fracturing fluids obtained in example ten under different degrees of mineralization;
FIG. 3 is a rheological graph of shear resistance tests of the fracturing fluid obtained in example eleven at different degrees of mineralization.
Detailed Description
The first embodiment is as follows:
synthesis of amphiphilic monomer D12PAAC
(1) Dissolving methyl piperazine in ethanol, heating to 50 ℃, adding bromododecane according to the molar ratio of 1:1.1, refluxing and reacting at 50 ℃ for 12 hours, cooling after the reaction is finished, carrying out rotary evaporation by using a rotary evaporator to remove ethanol, carrying out suction filtration to obtain light yellow liquid, then adding ethyl acetate to soak for 1 day, cleaning a resultant, and carrying out vacuum drying to constant weight to finally obtain an intermediate D12 PA;
(2) and reacting the intermediate D12PA obtained in the first step with methacryloyl chloride in a molar ratio of 1:1.1 to obtain the amphiphilic monomer D12 PAAC. Firstly, dissolving D12PA in dichloromethane, adding the solution into a three-neck round-bottom flask, cooling the temperature of a reaction system to be below 5 ℃ by ice-water bath, adding triethylamine according to the molar ratio of 1:1.2, slowly dropwise adding a mixed solution of methacryloyl chloride and dichloromethane by using a constant-pressure funnel, heating to room temperature after the addition is finished, reacting for 8 hours, washing the solution to be neutral by deionized water, drying, and performing rotary evaporation to obtain a relatively pure amphiphilic monomer D12 PAAC; the yield was 85%.
Example two:
synthesis of amphiphilic monomer D12PAAC
(1) Dissolving methyl piperazine in ethanol, heating to 50 ℃, adding bromododecane according to the molar ratio of 1:1.1, refluxing and reacting at 50 ℃ for 12 hours, cooling after the reaction is finished, carrying out rotary evaporation by using a rotary evaporator to remove ethanol, carrying out suction filtration to obtain light yellow liquid, then adding ethyl acetate to soak for 1 day, cleaning a resultant, and carrying out vacuum drying to constant weight to finally obtain an intermediate D12 PA;
(2) and reacting the intermediate D12PA obtained in the first step with methacryloyl chloride in a molar ratio of 1:1.1 to obtain the amphiphilic monomer D12 PAAC. Firstly, dissolving D12PA in dichloromethane, adding the solution into a three-neck round-bottom flask, cooling the temperature of a reaction system to be below 5 ℃ by ice-water bath, adding triethylamine according to the molar ratio of 1:1.2, slowly dropwise adding a mixed solution of methacryloyl chloride and dichloromethane by using a constant-pressure funnel, heating to room temperature after the addition is finished, reacting for 9 hours, washing the solution to be neutral by deionized water, drying, and performing rotary evaporation to obtain a relatively pure amphiphilic monomer D12 PAAC; the yield was 89%.
Example three:
synthesis of amphiphilic monomer D12PAAC
(1) Dissolving methyl piperazine in ethanol, heating to 50 ℃, adding bromododecane according to the molar ratio of 1:1.1, refluxing and reacting at 50 ℃ for 12 hours, cooling after the reaction is finished, carrying out rotary evaporation by using a rotary evaporator to remove ethanol, carrying out suction filtration to obtain light yellow liquid, then adding ethyl acetate to soak for 1 day, cleaning a resultant, and carrying out vacuum drying to constant weight to finally obtain an intermediate D12 PA;
(2) and reacting the intermediate D12PA obtained in the first step with methacryloyl chloride in a molar ratio of 1:1.1 to obtain the amphiphilic monomer D12 PAAC. Firstly, dissolving D12PA in dichloromethane, adding the solution into a three-neck round-bottom flask, cooling the temperature of a reaction system to be below 5 ℃ by ice-water bath, adding triethylamine according to the molar ratio of 1:1.2, slowly dropwise adding a mixed solution of methacryloyl chloride and dichloromethane by using a constant-pressure funnel, heating to room temperature after the addition is finished, reacting for 10 hours, washing the solution to be neutral by deionized water, drying, and performing rotary evaporation to obtain a relatively pure amphiphilic monomer D12 PAAC; the yield was 91%.
Example four:
synthesis of amphiphilic monomer D12PAAC
(1) Dissolving methyl piperazine in ethanol, heating to 50 ℃, adding bromododecane according to a molar ratio of 1:1.1, carrying out reflux reaction at 50 ℃ for 12 hours, cooling after the reaction is finished, carrying out rotary evaporation by using a rotary evaporator to remove ethanol, carrying out suction filtration to obtain a light yellow liquid, then adding ethyl acetate, soaking for 1 day, cleaning a resultant, and carrying out vacuum drying to constant weight to finally obtain an intermediate D12 PA;
(2) and reacting the intermediate D12PA obtained in the first step with methacryloyl chloride in a molar ratio of 1:1.1 to obtain the amphiphilic monomer D12 PAAC. Firstly, dissolving D12PA in dichloromethane, adding the solution into a three-neck round-bottom flask, cooling the temperature of a reaction system to be below 5 ℃ by ice-water bath, adding triethylamine according to the molar ratio of 1:1.2, slowly dropwise adding a mixed solution of methacryloyl chloride and dichloromethane by using a constant-pressure funnel, heating to room temperature after the addition is finished, reacting for 11 hours, washing the solution to be neutral by deionized water, drying, and performing rotary evaporation to obtain a relatively pure amphiphilic monomer D12 PAAC; the yield was 96%, and this reaction time was the optimum reaction time.
Example five:
polyoxyethylene ether monomer MAA-EO 23 C 12 Synthesis of (2)
Dissolving 0.1mol of polyoxyethylene lauryl ether in dichloromethane, adding the solution into a three-neck round-bottom flask, cooling the temperature of a reaction system to be below 5 ℃ by ice-water bath, adding triethylamine according to the molar ratio of 1:1.2, slowly dropwise adding a mixed solution of 0.11mol of methacryloyl chloride and dichloromethane by using a constant-pressure funnel, heating to room temperature after the addition is finished, reacting for 8 hours, washing the solution to be neutral by deionized water, drying, and performing rotary evaporation to obtain a polyoxyethylene ether monomer MAA-EO 23 C 12 The yield was 81%.
Example six:
polyoxyethylene ether monomer MAA-EO 23 C 12 Synthesis of (2)
Dissolving 0.1mol of polyoxyethylene lauryl ether in dichloromethane, adding the solution into a three-neck round-bottom flask, cooling the temperature of a reaction system to be below 5 ℃ by ice-water bath, adding triethylamine according to the molar ratio of 1:1.2, slowly dropwise adding a mixed solution of 0.11mol of methacryloyl chloride and dichloromethane by using a constant-pressure funnel, heating to room temperature after the addition is finished, reacting for 9 hours, washing the solution to be neutral by deionized water, drying, and performing rotary evaporation to obtain a polyoxyethylene ether monomer MAA-EO 23 C 12 The yield was 88%.
Example seven:
polyoxyethylene ether monomer MAA-EO 23 C 12 Synthesis of (2)
Dissolving 0.1mol of polyoxyethylene lauryl ether in dichloromethane, adding the solution into a three-neck round-bottom flask, cooling the temperature of a reaction system to be below 5 ℃ by ice-water bath, adding triethylamine according to the molar ratio of 1:1.2, slowly dropwise adding a mixed solution of 0.11mol of methacryloyl chloride and dichloromethane by using a constant-pressure funnel, heating to room temperature after the addition is finished, reacting for 10 hours, washing the solution to be neutral by deionized water, drying, and performing rotary evaporation to obtain a polyoxyethylene ether monomer MAA-EO 23 C 12 The yield was 94%, and this reaction time was the optimum reaction time.
Example eight:
synthesis of salt-responsive Hydrophobically associating Polymer HSRPM
(1) 9g of acrylamide, 3g of acrylic acid and 1.8g of 2-acrylamide were added to deionized water2-methylpropanesulfonic acid, 0.4g of amphiphilic monomer D12PAAC and 0.45g of polyoxyethylene ether monomer MAA-EO 23 C 12 To prepare an aqueous solution having a monomer concentration of 30%, and at the same time, Sodium Dodecyl Sulfate (SDS) was added in an amount of 2% of the total monomer concentration, and the mixture was stirred until a clear solution was obtained.
(2) After the solution is fully mixed evenly, nitrogen is introduced for 30min to remove dissolved oxygen in water.
(3) Taking 2, 2-azo diisobutyl amidine dihydrochloride (V50) as an initiator, wherein the initiator accounts for 0.3% of the total monomer concentration, carrying out free radical aqueous solution polymerization under the ultraviolet light photo-initiation condition, reacting for 8 hours to obtain the required polyether-containing hydrophobic association polymer, shearing the obtained hydrophobic association polymer, soaking and drying the hydrophobic association polymer in absolute ethyl alcohol, and crushing the hydrophobic association polymer into powder to obtain the salt-responsive hydrophobic association polymer HSRPM for the fracturing fluid.
Example nine:
taking HSRPM as the salt-responsive hydrophobically associating polymer in the example VIII, a 0.4 wt% water-based fracturing fluid is prepared by using a standard saline water, and the viscosity of the fracturing fluid is tested by using an HAAKE MARS III (006-1322) rheometer at the temperature of 25 ℃, and the viscosity of the fracturing fluid is lower than 100mPa & s at a higher mineralization degree, and has the characteristic of low viscosity.
Example ten:
taking HSRPM of the salt-responsive hydrophobically associating polymer in the example VIII, a 0.4 wt% water-based fracturing fluid is prepared by using standard saline water, and the viscoelasticity of the fracturing fluid is tested by using an HAAKE MARS III (006-1322) rheometer at the temperature of 25 ℃, wherein the storage modulus is always larger than the loss modulus, and the fracturing fluid has excellent viscoelasticity.
Example eleven:
taking HSRPM as the salt-responsive hydrophobically associative polymer in example eight, a 0.4 wt% water-based fracturing fluid was prepared from standard brine using HAAKE MARS III (006-1322) rheometer at 25 ℃ for 7.34s -1 To 1000s -1 The viscosity of the polymer at different degrees of mineralization is measured within 30 minutes, and the fracturing fluid is used for 1000s -1 The apparent viscosity of the resin composition is maintained at 53 mPas or more at the shear rate of (2), and the resin composition has good shear resistance.
Claims (5)
1. A salt-responsive hydrophobically associative polymer having the formula:
in the formula:
R 2 (OCH 2 CH 2 ) a o is fatty alcohol-polyoxyethylene ether, alkylphenol ethoxylates and fatty acid-polyoxyethylene ether, wherein the number a of ethoxy groups is 5-30;
x, y, z, m and n are monomer molar ratios, wherein x is 60-80%, y is 10-22%, z is 8-12%, m is 1-3%, and n is 1-3%.
2. The amphiphilic monomer D12PAAC of the salt-responsive hydrophobically associative polymer of claim 1 having the formula:
in the formula:
R 1 dodecyl, hexadecyl, octadecyl.
3. The method for preparing amphiphilic monomer D12PAAC according to claim 2, comprising the following steps in sequence:
(1) dissolving methyl piperazine in ethanol, heating to 50 ℃, adding bromododecane according to the molar ratio of 1: 1.1-1.2, refluxing and reacting at 50 ℃ for 12 hours, cooling after the reaction is finished, performing rotary evaporation by using a rotary evaporator to remove ethanol, performing suction filtration to obtain a light yellow liquid, adding ethyl acetate to soak for 1 day, cleaning a resultant, and performing vacuum drying to constant weight to finally obtain an intermediate D12 PA;
(2) and reacting the intermediate D12PA obtained in the first step with methacryloyl chloride in a molar ratio of 1: 1.1-1.2 to obtain the amphiphilic monomer D12 PAAC. Firstly, dissolving D12PA in dichloromethane, adding the solution into a three-neck round-bottom flask, cooling the temperature of a reaction system to be below 5 ℃ by using an ice-water bath, adding triethylamine according to the molar ratio of 1: 1.2-1.3, slowly dropwise adding a mixed solution of methacryloyl chloride and dichloromethane by using a constant-pressure funnel, heating to room temperature after the addition is finished, reacting for 8-11 h, washing the solution to be neutral by using deionized water, and drying and performing rotary evaporation to obtain a relatively pure hydrophobic monomer amphiphilic monomer D12PAAC containing polyether.
4. The method of claim 3, wherein bromododecane is replaced with bromohexadecane or bromooctadecane.
5. The method of claim 1, comprising the steps of:
(1) adding acrylamide, sodium acrylate, 2-acrylamide-2-methylpropanesulfonic acid, amphiphilic monomer DPAAC and polyoxyethylene ether monomer MAA-EO into deionized water 23 C 12 The mol percentage of the components is that 60 to 80 percent of acrylamide, 10 to 22 percent of sodium acrylate, 8 to 12 percent of 2-acrylamide-2-methylpropanesulfonic acid, 1 to 3 percent of amphiphilic monomer DPAAC, and 1 to 3 percent of polyoxyethylene ether monomer MAA-EO 23 C 12 Preparing an aqueous solution with the monomer concentration of 25-30%, adding Sodium Dodecyl Sulfate (SDS) accounting for 0.5-2% of the total monomer concentration, and stirring to obtain a clear solution;
(2) after the solution is fully and uniformly mixed, introducing nitrogen for 30min, and removing dissolved oxygen in water;
(3) taking 2, 2-azo diisobutyl amidine dihydrochloride (V50) as an initiator, wherein the initiator accounts for 0.1-0.3% of the total monomer concentration, carrying out free radical aqueous solution polymerization under the ultraviolet light photo-initiation condition, reacting for 6-8 hours to obtain the required polyether-containing hydrophobic association polymer, finally shearing the obtained hydrophobic association polymer, soaking and drying the hydrophobic association polymer in absolute ethyl alcohol, and crushing the hydrophobic association polymer into powder to obtain the salt-responsive hydrophobic association polymer HSRPM (hydrogen induced pressure swing velocity) used for the fracturing fluid.
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