CN112142909B - Resistance reducing agent and preparation method thereof - Google Patents
Resistance reducing agent and preparation method thereof Download PDFInfo
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- CN112142909B CN112142909B CN201910576114.3A CN201910576114A CN112142909B CN 112142909 B CN112142909 B CN 112142909B CN 201910576114 A CN201910576114 A CN 201910576114A CN 112142909 B CN112142909 B CN 112142909B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
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- C08F2/10—Aqueous solvent
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- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
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- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/84—Compositions based on water or polar solvents
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
- C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
Abstract
The invention discloses a resistance reducing agent and a preparation method thereof, and belongs to the technical field of oil and gas field fracturing. The resistance reducing agent comprises the following raw materials in parts by mass: 60-95 parts by mass of acrylamide and 1-5 parts by mass of alkyl polyethylene glycol acrylate; the raw materials for synthesizing the resistance reducing agent also comprise: at least one of acrylic acid, 2-acrylamide-2-methylpropanesulfonic acid or sodium p-styrenesulfonate, and the balance of water; the raw materials for synthesizing the resistance reducing agent are all water-soluble monomers, and the formed resistance reducing agent also has good water solubility and can be quickly dissolved in water. Therefore, the resistance reducing agent only needs to be added with water as a solvent during preparation, other oil phase, emulsifier or cosolvent is not needed, the preparation method is simple and easy to operate, and the preparation cost of the resistance reducing agent is reduced. Moreover, the resistance reducing agent has good stability and high resistance reducing rate, can improve the acid fracturing operation efficiency, and achieves the purpose of increasing the yield of the shale gas reservoir.
Description
Technical Field
The invention relates to the technical field of oil and gas field fracturing. In particular to a resistance reducing agent and a preparation method thereof.
Background
Shale gas in China is widely distributed and has huge development potential. However, shale gas reservoirs have the characteristics of low porosity, low permeability, strong heterogeneity and the like, and compared with conventional oil and gas resources, the exploitation difficulty is high. Therefore, there is a need for effective stimulation of shale gas reservoirs. At present, yield increasing measures adopted for shale gas reservoirs are mainly to pump slickwater, fracture the shale gas reservoirs through the slickwater, form large-scale complex seam networks in the reservoirs, increase the shale gas seepage area and achieve the purpose of increasing the yield. When fracturing the shale gas reservoir through the slickwater, a resistance reducing agent needs to be added, the friction resistance of the slickwater flowing in a pipeline of the mining equipment is reduced through the resistance reducing agent, and the pressure provided by the ground high-pressure equipment is transmitted to the shale gas reservoir as far as possible.
When the polymer resistance reducing agent is prepared, a hydrophobic monomer is generally introduced, and the stability of the resistance reducing agent is enhanced through the hydrophobic association of the hydrophobic monomer, so that the resistance reducing effect is enhanced. In the prior art, the hydrophobic monomer added in the preparation of the resistance reducing agent is generally alkyl acrylate or a derivative thereof, and the resistance reducing agent is obtained by copolymerizing the hydrophobic monomer and other monomers.
However, in the prior art, alkyl acrylate and derivatives thereof used in the preparation of the resistance reducing agent have poor water solubility, such as lauryl acrylate, and an appropriate oil phase and an emulsifier or a cosolvent with a certain hydrophilic-lipophilic balance (HLB) value need to be added in the reaction process to dissolve the alkyl acrylate and the derivatives thereof, so that the synthesis operation of the resistance reducing agent is complex and the cost is high.
Disclosure of Invention
The embodiment of the invention provides a resistance reducing agent and a preparation method thereof, which simplify a synthesis method and reduce production cost under the condition of not reducing the performance of the resistance reducing agent. The specific technical scheme is as follows:
in one aspect, an embodiment of the present invention provides a resistance reducing agent, where the resistance reducing agent includes the following components in parts by mass: 60-95 parts by mass of acrylamide and 1-5 parts by mass of alkyl polyethylene glycol acrylate;
the friction reducer further comprises: at least one of acrylic acid, 2-acrylamide-2-methylpropanesulfonic acid or sodium p-styrenesulfonate, and the balance of water;
the mass portion of the acrylic acid is not more than 10, the mass portion of the 2-acrylamide-2-methylpropanesulfonic acid is not more than 20, and the mass portion of the sodium p-styrenesulfonate is not more than 5.
In one possible implementation, the alkyl polyethylene glycol acrylate has the general structural formula:
wherein, R is1Is methyl or hydrogen atom, n is 2-30, R2Is benzene ring, alkyl phenyl, cyclane or straight chain alkane with 8-24 carbon atoms.
In another possible implementation, the alkylphenyl group is at least one of tert-butylphenyl, hexylphenyl, heptylphenyl, octylphenyl, isooctylphenyl, nonylphenyl, decylphenyl, dodecylphenyl, tetradecylphenyl, pentadecylphenyl, hexadecylphenyl, octadecylphenyl or a corresponding derivative thereof.
In another possible implementation, the cycloalkane is at least one of cyclohexane, cyclopentane, amantadine, a bridged cycloalkane, or a corresponding derivative thereof.
In another possible implementation manner, the mass part of the acrylamide is 75-85 mass parts, and the mass part of the alkyl polyethylene glycol acrylate is 3-5 mass parts.
In another aspect, an embodiment of the present invention provides a method for preparing a resistance reducing agent, where the method includes:
adding two monomers, namely acrylamide and alkyl polyethylene glycol acrylate, into a reactor according to the mass parts of the components, adding at least one monomer of acrylic acid, 2-acrylamide-2-methylpropanesulfonic acid or sodium p-styrenesulfonate into the reactor to obtain a mixture solution, and adjusting the hydrogen ion concentration index pH of the mixture solution to 8-9;
adding water to prepare an aqueous solution with the total monomer mass concentration of 20 percent, and introducing N 2 20～40min；
Adding an initiator, uniformly stirring, and reacting at 40-60 ℃ for 4-7 h to obtain a milky colloidal product;
and washing the milky colloidal product with ethanol, and drying and crushing to obtain the resistance reducing agent.
In one possible implementation, the initiator is at least one of ammonium persulfate-sodium bisulfite system, azobisisobutyramidine hydrochloride, azobisisobutyrimidazoline hydrochloride, or azobisisopropylimidazoline.
In another possible implementation manner, the mass ratio of ammonium persulfate to sodium bisulfite in the ammonium persulfate-sodium bisulfite system is 1-1.5: 1.
In another possible implementation, the mass of the initiator is between 0.05% and 0.5% of the total monomer mass.
In another possible implementation, the mass of the initiator is between 0.05% and 0.2% of the total monomer mass.
The technical scheme provided by the embodiment of the invention has the following beneficial effects:
the resistance reducing agent provided by the embodiment of the invention uses alkyl polyethylene glycol acrylate and acrylamide as uncharged main bodies, and at least one of acrylic acid, 2-acrylamide-2-methylpropanesulfonic acid or sodium p-styrenesulfonate as an auxiliary raw material with negative charges. The raw materials for synthesizing the resistance reducing agent are all water-soluble monomers, and the formed resistance reducing agent also has good water solubility and can be quickly dissolved in water. Therefore, the resistance reducing agent only needs to be added with water as a solvent during preparation, other oil phase, emulsifier or cosolvent is not needed, the preparation method is simple and easy to operate, and the preparation cost of the resistance reducing agent is reduced. In addition, the alkyl polyethylene glycol acrylate is an amphiphilic monomer, and the molecule of the alkyl polyethylene glycol acrylate has a hydrophobic group and a hydrophilic group, so that the stability of the resistance reducing agent can be enhanced through hydrophobic association, and good water solubility can be ensured. Acrylamide, acrylic acid, 2-acrylamide-2-methylpropanesulfonic acid and sodium p-styrenesulfonate have high polymerizability, and can perform random copolymerization reaction with alkyl polyethylene glycol acrylate under certain conditions to form the resistance reducing agent. Therefore, the resistance reducing agent has good stability and high resistance reducing rate, can improve the fracturing operation efficiency, and achieves the purpose of increasing the yield of the shale gas reservoir.
Drawings
FIG. 1 is a schematic diagram of drag reducer D1 according to an embodiment of the present invention at different flow rates;
FIG. 2 is a schematic diagram of drag reducer D2 according to an embodiment of the present invention at different flow rates;
FIG. 3 is a schematic diagram of drag reducer D3 according to an embodiment of the present invention at different flow rates;
FIG. 4 is a schematic diagram of drag reducer D4 according to an embodiment of the present invention at different flow rates;
fig. 5 is a schematic diagram of drag reducer D5 according to an embodiment of the present invention at different flow rates.
Detailed Description
In order to make the technical solutions and advantages of the present invention clearer, the following describes embodiments of the present invention in further detail.
The embodiment of the invention provides a resistance reducing agent, which comprises the following raw materials in parts by mass:
60-95 parts by mass of acrylamide and 1-5 parts by mass of alkyl polyethylene glycol acrylate;
the raw materials for synthesizing the resistance reducing agent also comprise: at least one of acrylic acid, 2-acrylamide-2-methylpropanesulfonic acid or sodium p-styrenesulfonate, and the balance of water;
the mass portion of the acrylic acid is not more than 10, the mass portion of the 2-acrylamide-2-methylpropanesulfonic acid is not more than 20, and the mass portion of the sodium p-styrenesulfonate is not more than 5.
Wherein, the acrylamide is a water-soluble monomer, has good water solubility, and can generate copolymerization reaction with other components under certain conditions to form a polymer.
The alkyl polyethylene glycol acrylate can be mixed with water in any proportion, is an amphiphilic monomer, has a hydrophobic group and a hydrophilic group, and thus not only can enhance the stability of the resistance reducing agent through hydrophobic association, but also can ensure good water solubility.
The carboxylic acid ions in the acrylic acid are anionic hydrophilic groups, so that the acrylic acid can be mixed and dissolved with water in any proportion, can be subjected to polymerization reaction with other components, and has a very high polymerization speed.
The amido and the sulfonic acid group in the 2-acrylamide-2-methylpropanesulfonic acid are anionic hydrophilic groups, so the 2-acrylamide-2-methylpropanesulfonic acid is a water-soluble monomer and has good water solubility. And, it has a polymerizable vinyl group in its molecule, and can undergo copolymerization reaction with other components under certain conditions.
The sulfonic group in the sodium p-styrene sulfonate is an anionic hydrophilic group, so the sodium p-styrene sulfonate is a water-soluble monomer and has good water solubility. And, the sulfonic acid group and vinyl group are located at para-positions of the benzene ring, so that the sulfonic acid group has high polymerizability and can undergo copolymerization reaction with other components under certain conditions.
The resistance reducing agent provided by the embodiment of the invention uses alkyl polyethylene glycol acrylate and acrylamide as uncharged main bodies, and at least one of acrylic acid, 2-acrylamide-2-methylpropanesulfonic acid or sodium p-styrenesulfonate as an auxiliary raw material with negative charges. The raw materials for synthesizing the resistance reducing agent are all water-soluble monomers, and the formed resistance reducing agent also has good water solubility and can be quickly dissolved in water. Therefore, the resistance reducing agent only needs to be added with water as a solvent during preparation, other oil phase, emulsifier or cosolvent is not needed, the preparation method is simple and easy to operate, and the preparation cost of the resistance reducing agent is reduced. In addition, the alkyl polyethylene glycol acrylate is an amphiphilic monomer, and the molecule of the alkyl polyethylene glycol acrylate has a hydrophobic group and a hydrophilic group, so that the stability of the resistance reducing agent can be enhanced through hydrophobic association, and good water solubility can be ensured. Acrylamide, acrylic acid, 2-acrylamide-2-methylpropanesulfonic acid and sodium p-styrenesulfonate have high polymerizability, and can perform random copolymerization reaction with alkyl polyethylene glycol acrylate under certain conditions to form the resistance reducing agent. Therefore, the resistance reducing agent has good stability and high resistance reducing rate, can improve the acid fracturing operation efficiency, and achieves the purpose of increasing the yield of the shale gas reservoir.
In the embodiment of the present invention, the acrylamide may be present in an amount of 60 parts, 65 parts, 68 parts, 70 parts, 73 parts, 75 parts, 80 parts, 82 parts, 85 parts, 87 parts, 90 parts, 95 parts, or the like by mass. The alkyl polyethylene glycol acrylate may be present in an amount of 1 part, 1.2 parts, 1.8 parts, 2 parts, 2.3 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 4.7 parts, 5 parts, etc. The acrylic acid may be present in an amount of 0, 0.5, 0.8, 1, 2, 2.5, 3, 3.5, 4, 5, 7, 8, 10 parts by mass. The mass parts of the 2-acrylamide-2-methylpropanesulfonic acid may be 0, 1.5, 2, 3, 5, 6, 7, 7.5, 9, 10, 12, 15, 18, 20, and the like. The mass portion of the sodium p-styrene sulfonate can be 0, 0.5, 0.8, 1, 2, 2.5, 3, 3.5, 4, 5, etc.
In a possible implementation mode, the mass part of the acrylamide is 75-85 parts, and the mass part of the alkyl polyethylene glycol acrylate is 3-5 parts.
In another possible implementation, the friction reducer includes at least one of three monomers of acrylic acid, 2-acrylamide-2-methylpropanesulfonic acid, and sodium p-styrenesulfonate.
When the friction reducer comprises one of the monomers, the monomer can be any one of acrylic acid, 2-acrylamide-2-methyl propane sulfonic acid and sodium p-styrene sulfonate. When the monomer is acrylic acid, correspondingly, the resistance reducing agent comprises the following components in parts by mass: 60-95 parts by mass of acrylamide and 1-5 parts by mass of alkyl polyethylene glycol acrylate; the resistance reducing agent also comprises: acrylic acid and the balance of water, wherein the mass part of the acrylic acid is not more than 10 parts. When the monomer is 2-acrylamide-2-methylpropanesulfonic acid, the resistance reducer comprises the following components in parts by mass: 60-95 parts by mass of acrylamide and 1-5 parts by mass of alkyl polyethylene glycol acrylate; the resistance reducing agent also comprises: 2-acrylamide-2-methylpropanesulfonic acid and the balance of water, wherein the mass part of the 2-acrylamide-2-methylpropanesulfonic acid is not more than 20 parts. When the monomer is sodium p-styrene sulfonate, the resistance reducing agent correspondingly comprises the following components in parts by mass: 60-95 parts by mass of acrylamide and 1-5 parts by mass of alkyl polyethylene glycol acrylate; the resistance reducing agent also comprises: sodium p-styrene sulfonate and the balance of water, wherein the mass part of the sodium p-styrene sulfonate is not more than 5.
When the friction reducer comprises two monomers, the two monomers can be acrylic acid and 2-acrylamide-2-methyl propane sulfonic acid, or acrylic acid and sodium p-styrene sulfonate, or 2-acrylamide-2-methyl propane sulfonic acid and sodium p-styrene sulfonate. When the two monomers are acrylic acid and 2-acrylamide-2-methylpropanesulfonic acid, the resistance reducing agent correspondingly comprises the following components in parts by mass: 60-95 parts by mass of acrylamide, 1-5 parts by mass of alkyl polyethylene glycol acrylate, and the resistance reducing agent further comprises: acrylic acid, 2-acrylamide-2-methylpropanesulfonic acid and the balance of water, wherein the mass part of the acrylic acid is not more than 10 parts, and the mass part of the 2-acrylamide-2-methylpropanesulfonic acid is not more than 20 parts. When the two monomers are 2-acrylamide-2-methylpropanesulfonic acid and sodium p-styrenesulfonate, the resistance reducing agent correspondingly comprises the following components in parts by mass: 60-95 parts by mass of acrylamide, 1-5 parts by mass of alkyl polyethylene glycol acrylate, and the resistance reducing agent further comprises: 2-acrylamide-2-methylpropanesulfonic acid, sodium p-styrenesulfonate and the balance of water, wherein the mass part of the 2-acrylamide-2-methylpropanesulfonic acid is not more than 20 parts, and the mass part of the sodium p-styrenesulfonate is not more than 5 parts. When the two monomers are acrylic acid and sodium p-styrene sulfonate, the resistance reducing agent correspondingly comprises the following components in parts by mass: 60-95 parts by mass of acrylamide, 1-5 parts by mass of alkyl polyethylene glycol acrylate, and the resistance reducing agent further comprises: acrylic acid, sodium p-styrene sulfonate and the balance of water, wherein the mass part of the acrylic acid is not more than 10 parts, and the mass part of the sodium p-styrene sulfonate is not more than 5 parts.
When the resistance reducing agent comprises the three monomers, correspondingly, the resistance reducing agent comprises the following components in parts by mass: 60-95 parts by mass of acrylamide, 1-5 parts by mass of alkyl polyethylene glycol acrylate, and the resistance reducing agent further comprises: the acrylic acid-sodium styrene sulfonate composite material comprises acrylic acid, 2-acrylamide-2-methylpropanesulfonic acid, sodium p-styrenesulfonate and the balance of water, wherein the mass part of the acrylic acid is not more than 10 parts, the mass part of the 2-acrylamide-2-methylpropanesulfonic acid is not more than 20 parts, and the mass part of the sodium p-styrenesulfonate is not more than 5 parts.
In one possible implementation, the alkyl polyethylene glycol acrylate has the general structural formula:
wherein R is1Is methyl or hydrogen atom, n is 2 to 30, R2Is benzene ring, alkyl phenyl, cyclane or straight chain alkane with 8-24 carbon atoms.
From the structural formula and R2It can be seen that R in the alkyl polyethylene glycol acrylate2Is a hydrophobic group and is a hydrophobic group,
the hydrophilic group is used, so that the alkyl polyethylene glycol acrylate can be dissolved in water, and the stability of the resistance reducing agent can be enhanced through hydrophobic association.
Wherein R is1When it is methyl, R2Can be any one of benzene ring, alkyl phenyl, cyclane or straight chain alkane with 8-24 carbon atoms. For example, when R is1When it is methyl, R2It may be an alkylphenyl group.
In another possible implementation, the alkylphenyl group is at least one of tert-butylphenyl, hexylphenyl, heptylphenyl, octylphenyl, isooctylphenyl, nonylphenyl, decylphenyl, dodecylphenyl, tetradecylphenyl, pentadecylphenyl, hexadecylphenyl, octadecylphenyl or a corresponding derivative thereof.
For example, when R is1When it is methyl, R2When the alkyl group is an octadecyl group, the alkyl polyethylene glycol acrylate obtained is octadecyl polyethylene glycol methacrylate. Wherein when R is2When the derivative is a derivative corresponding to an alkylphenyl group, the derivative may be an alkylphenol, an alkylaniline, or the like. When R is1When it is a hydrogen atom, R2Is a derivative of nonylphenyl, and when the derivative is nonylphenol, the obtained alkyl polyethylene glycol acrylate is nonylphenol polyethylene glycol acrylate.
In another possible implementation, the cycloalkane is at least one of cyclohexane, cyclopentane, amantadine, a bridged cycloalkane, or a corresponding derivative thereof.
The embodiment of the invention provides a preparation method of a resistance reducing agent, which comprises the following steps:
step 1: adding two monomers, namely acrylamide and alkyl polyethylene glycol acrylate, into a reactor according to the mass parts of the components, adding at least one monomer of acrylic acid, 2-acrylamide-2-methylpropanesulfonic acid or sodium p-styrenesulfonate into the reactor to obtain a mixture solution, and adjusting the pH value of the mixture solution to 8-9.
In the step, 60-95 parts by weight of acrylamide and 1-5 parts by weight of alkyl polyethylene glycol acrylate are added into a reactor. And, at least one of acrylic acid, 2-acrylamido-2-methylpropanesulfonic acid, or sodium p-styrenesulfonate is also added to the reactor, and then the pH of the mixture is adjusted.
Wherein the mass part of the acrylic acid is not more than 10 parts, the mass part of the 2-acrylamide-2-methylpropanesulfonic acid is not more than 20 parts, and the mass part of the sodium p-styrenesulfonate is not more than 5 parts.
In this step, the pH of the aqueous solution may be adjusted with NaOH solution. Further, when the pH of the aqueous solution is adjusted by the NaOH solution, the concentration of the NaOH solution may be set and changed as needed, for example, the concentration of the NaOH solution may be 0.1mol/L, 0.5mol/L, or 1 mol/L. In the examples of the present invention, the concentration of the NaOH solution is not particularly limited.
Step 2: adding water to prepare an aqueous solution with the total monomer mass concentration of 20 percent, and introducing N 220～40min。
In this step, N is introduced2Can eliminate oxygen dissolved in the water solution and avoid the oxygen from influencing free radicals generated by the initiator.
The total monomers are a generic name for monomers other than water in the aqueous solution. For example, when the aqueous solution includes acrylic acid monomers in addition to two monomers of acrylamide and alkyl polyethylene glycol acrylate in the preparation of the friction reducer, the total monomers are three monomers of acrylamide, alkyl polyethylene glycol acrylate and acrylic acid. When the aqueous solution includes 2-acrylamide-2-methylpropanesulfonic acid in addition to the above three monomers, the total monomers are four monomers of acrylamide, alkyl polyethylene glycol acrylate, acrylic acid, and 2-acrylamide-2-methylpropanesulfonic acid.
And step 3: adding an initiator, uniformly stirring, and reacting at 40-60 ℃ for 4-7 h to obtain a milky colloidal product.
The initiator is used for initiating each component in the aqueous solution to carry out random copolymerization reaction to obtain the polymer. In one possible implementation, the initiator may be at least one of ammonium persulfate-sodium bisulfite system, azobisisobutylamidine hydrochloride, azobisisobutylimidazoline hydrochloride, or azobisdiisopropylimidazoline.
When the initiator is an ammonium persulfate-sodium bisulfite system, the mass ratio of ammonium persulfate to sodium bisulfite is 1-1.5: 1. For example, when the initiator is an ammonium persulfate-sodium bisulfite system, the mass ratio of ammonium persulfate to sodium bisulfite is 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, or 1.5: 1.
It should be noted that the amount of initiator added is preferably not too much or too little. When the mass of the added initiator is too much, the reaction speed is too fast to control; when the mass of the added initiator is too small, the initiator is not easy to initiate, the reaction cannot be normally carried out, and the performance of the polymer is influenced. Thus, in the present examples, the mass of initiator added is between 0.05% and 0.5% of the total monomer mass. Further, the mass of the added initiator is 0.05-0.2% of the total monomer mass. For example, the mass of initiator added is 0.05%, 0.1%, 0.15% or 0.2% of the total monomer mass. Preferably, the mass of initiator added is 0.1% of the total monomer mass.
In the step, the reaction temperature is preferably 50 to 60 ℃ and the reaction time is preferably 5 to 7 hours.
And 4, step 4: washing the milky colloidal product with ethanol, drying and crushing to obtain the resistance reducing agent.
In the step, the milky colloidal product is washed by a large amount of ethanol, and impurities are removed to obtain an intermediate product. And drying and crushing the intermediate product under certain conditions to obtain the resistance reducing agent.
The drying temperature may be set and changed as required, and in the embodiment of the present invention, the drying temperature is not specifically limited. For example, the temperature for drying is 40 ℃, 45 ℃ or 50 ℃.
When the drag reducer is prepared, all the components are monomers with good water solubility, so that an oil phase, an emulsifier and any cosolvent are not required. The preparation method of the resistance reducing agent is simple and easy to prepare, and has good water solubility.
The technical solution of the present invention will be described in detail by specific examples below.
In the following examples, those whose operations are not subject to the conditions indicated, are carried out according to the conventional conditions or conditions recommended by the manufacturer. The raw materials are all conventional products which can be obtained by market without indicating manufacturers and specifications.
Wherein, the octadecyl polyethylene glycol methacrylate is purchased from the winning industrial group, and the nonyl phenol polyethylene glycol acrylate is obtained by using acryloyl chloride and nonyl phenol polyethylene glycol to carry out esterification reaction in a laboratory. Acrylamide, acrylic acid, sodium hydroxide, 2-acrylamido-2-methylpropanesulfonic acid, sodium p-styrenesulfonate, and azobisisobutyramidine hydrochloride, all available from Shanghai Maxin Biochemical technology, Inc.
Example 1
This example provides a resistance reducing agent and measures the resistance reducing rate. The preparation method of the resistance reducing agent comprises the following steps:
adding 85 parts by mass of acrylamide, 5 parts by mass of octadecyl polyethylene glycol methacrylate and 10 parts by mass of acrylic acid into a reactor according to the parts by mass of the components to obtain a mixture solution, and adjusting the pH of the mixture solution to 8-9 by using a NaOH solution; adding water to prepare an aqueous solution with the total monomer mass concentration of 20 percent, and introducing N 230 min; adding azodiisobutyramidine hydrochloride accounting for 0.1 percent of the total monomer mass, uniformly stirring, placing in a water bath at 55 ℃, and reacting for 5 hours to obtain a milky colloid product; washing the milky white colloid with ethanol, drying and crushing to obtain the resistance reducing agent. For ease of distinction, this friction reducer is designated as D1.
The method for measuring the friction reducer D1 comprises the following steps:
taking 20L of clear water, adding a certain amount of resistance reducing agent D1 into the clear water to prepare a dilute solution with the mass concentration of 0.025 percent. The resistivity reduction of clear water and D1 was measured according to the apparatus and method in patent 201320092441X "a fracturing fluid pipe friction resistance measuring apparatus". A pipeline with the pipe diameter of 8mm is selected as a test condition, friction resistance of clean water is used as a comparison experiment, and resistance reduction rate of D1 under different flow rates is calculated, and the figure 1 is shown.
As can be seen from fig. 1: as the flow rate increases, the drag reduction of D1 also increases. And when the flow rate is small, the increasing rate of the resistance reducing rate is high, and along with the increase of the flow rate, the increasing rate of the resistance reducing rate gradually becomes low. The resistance reduction rate is up to 69.1% at a flow rate of 10 m/s.
Example 2
This example provides a resistance reducing agent and measures the resistance reducing rate. The preparation method of the resistance reducing agent comprises the following steps:
according to the mass parts of the components, 85 parts of acrylamide, 3 parts of octadecyl polyethylene glycol acrylate, 7 parts of acrylic acid and 5 parts of 2-acrylamide-2-methylpropanesulfonic acidAdding acid into the reactor to obtain a mixture solution, and adjusting the pH of the mixture solution to 8-9 by using a NaOH solution; adding water to prepare an aqueous solution with the total monomer mass concentration of 20 percent, and introducing N 230 min; adding azodiisobutyramidine hydrochloride accounting for 0.1 percent of the total monomer mass, uniformly stirring, placing in a water bath at 55 ℃, and reacting for 5 hours to obtain a milky colloid product; washing the milky colloidal product with ethanol, drying and crushing to obtain the resistance reducing agent. For ease of distinction, this friction reducer is designated as D2.
The method for measuring the friction reducer D2 comprises the following steps:
taking 20L of clear water, adding a certain amount of resistance reducing agent D2 into the clear water to prepare a dilute solution with the mass concentration of 0.025 percent. The resistivity reduction of clear water and D2 was measured according to the apparatus and method in patent 201320092441X "a fracturing fluid pipe friction resistance measuring apparatus". A pipeline with the pipe diameter of 8mm is selected as a test condition, the frictional resistance of clear water is used as a comparison experiment, and the resistance reduction rate of D2 at different flow rates is calculated, and the figure 2 is shown.
As can be seen from fig. 2: as the flow rate increases, the drag reduction of D2 also increases. And when the flow rate is small, the increasing rate of the resistance reducing rate is high, and along with the increase of the flow rate, the increasing rate of the resistance reducing rate gradually becomes low. The resistance reduction rate is as high as 68.9% when the flow speed is 10 m/s.
Example 3
This example provides a resistance reducing agent and measures the resistance reducing rate. The preparation method of the resistance reducing agent comprises the following steps:
adding 85 parts by mass of acrylamide, 5 parts by mass of nonylphenol polyethylene glycol acrylate and 10 parts by mass of acrylic acid into a reactor according to the parts by mass of the components to obtain a mixture solution, and adjusting the pH of the mixture solution to 8-9 by using a NaOH solution; adding water to prepare an aqueous solution with the total monomer mass concentration of 20 percent, and introducing N 230 min; adding azodiisobutyramidine hydrochloride accounting for 0.1 percent of the total monomer mass, uniformly stirring, placing in a water bath at 55 ℃, and reacting for 5 hours to obtain a milky colloid product; washing the milky colloidal product with ethanol, drying and crushing to obtain the resistance reducing agent. To is coming toFor easy distinction, the resistance reducing agent is named as D3.
The method for measuring the friction reducer D3 comprises the following steps:
taking 20L of clear water, adding a certain amount of resistance reducing agent D3 into the clear water to prepare a dilute solution with the mass concentration of 0.025 percent. The resistivity reduction of clear water and D3 was measured according to the apparatus and method in patent 201320092441X "a fracturing fluid pipe friction resistance measuring apparatus". A pipeline with the pipe diameter of 8mm is selected as a test condition, friction resistance of clean water is used as a comparison experiment, and resistance reduction rate of D3 under different flow rates is calculated, and the figure 3 is shown.
As can be seen in fig. 3: as the flow rate increases, the drag reduction of D3 also increases. And when the flow rate is small, the increasing rate of the resistance reducing rate is high, and along with the increase of the flow rate, the increasing rate of the resistance reducing rate gradually becomes low. When the flow speed is 10m/s, the resistance reducing rate is as high as 75.3 percent.
Example 4
This example provides a resistance reducing agent and measures the resistance reducing rate. The preparation method of the resistance reducing agent comprises the following steps:
adding 75 parts by mass of acrylamide, 5 parts by mass of nonylphenol polyethylene glycol acrylate, 7.5 parts by mass of acrylic acid and 12.5 parts by mass of 2-acrylamide-2-methylpropanesulfonic acid into a reactor according to the parts by mass of the components to obtain a mixture solution, and adjusting the pH of the mixture solution to 8-9 by using a NaOH solution; adding water to prepare an aqueous solution with the total monomer mass concentration of 20 percent, and introducing N 230 min; adding azodiisobutyramidine hydrochloride accounting for 0.1 percent of the total monomer mass, uniformly stirring, placing in a water bath at 55 ℃, and reacting for 5 hours to obtain a milky colloid product; washing the milky colloidal product with ethanol, drying and crushing to obtain the resistance reducing agent. For ease of distinction, this friction reducer is designated as D4.
The method for measuring the resistance reducing agent D4 comprises the following steps:
taking 20L of clear water, adding a certain amount of resistance reducing agent D4 into the clear water to prepare a dilute solution with the mass concentration of 0.025 percent. The resistivity reduction of clear water and D4 was measured according to the apparatus and method in patent 201320092441X "a fracturing fluid pipe friction resistance measuring apparatus". A pipeline with the pipe diameter of 8mm is selected as a test condition, friction resistance of clean water is used as a comparison experiment, and resistance reduction rate of D4 under different flow rates is calculated, and the figure 4 shows that the resistance reduction rate is high.
As can be seen in fig. 4: as the flow rate increases, the drag reduction of D4 also increases. And when the flow rate is small, the increasing rate of the resistance reducing rate is high, and along with the increase of the flow rate, the increasing rate of the resistance reducing rate gradually becomes low. When the flow speed is 10m/s, the resistance reducing rate is as high as 75.1 percent.
Example 5
This example provides a resistance reducing agent and measures the resistance reducing rate. The preparation method of the resistance reducing agent comprises the following steps:
according to the mass parts of the components, 85 parts of acrylamide, 5 parts of nonylphenol polyethylene glycol acrylate, 4 parts of acrylic acid, 5 parts of 2-acrylamide-2-methylpropanesulfonic acid and 1 part of sodium p-styrenesulfonate are added into a reactor to obtain a mixture, and the pH of the mixture is adjusted to 8-9 through a NaOH solution; adding water to prepare an aqueous solution with the total monomer mass concentration of 20 percent, and introducing N 230 min; adding azodiisobutyramidine hydrochloride accounting for 0.1 percent of the total monomer mass, uniformly stirring, placing in a water bath at 55 ℃, and reacting for 5 hours to obtain a milky colloid product; washing the milky colloidal product with ethanol, drying and crushing to obtain the resistance reducing agent. For ease of distinction, this friction reducer is designated as D5.
The method for measuring the friction reducer D5 comprises the following steps:
taking 20L of clear water, adding a certain amount of resistance reducing agent D5 into the clear water to prepare a dilute solution with the mass concentration of 0.025 percent. The resistivity reduction of clear water and D5 was measured according to the apparatus and method in patent 201320092441X "a fracturing fluid pipe friction resistance measuring apparatus". A pipeline with the pipe diameter of 8mm is selected as a test condition, friction resistance of clean water is used as a comparison experiment, and resistance reduction rate of D5 under different flow rates is calculated, and the figure 5 is shown.
As can be seen from fig. 5: as the flow rate increases, the drag reduction of D5 also increases. And when the flow rate is small, the increasing rate of the resistance reducing rate is high, and along with the increase of the flow rate, the increasing rate of the resistance reducing rate gradually becomes low. At a flow rate of 10m/s, the drag reduction rate is as high as 74.7%.
As can be seen from the results of the drag reduction ratio measurements on the drag reduction agents D1-D5 in examples 1-5 above: when the mass concentration of the resistance reducing agent is 0.025%, the resistance reducing rate can reach 75.3 percent at most.
In conclusion, the drag reducer provided by the embodiment of the invention is simple in operation process and easy to prepare, has high drag reduction rate, can improve the operation efficiency, achieves the purpose of increasing the yield of the shale gas reservoir and has good application prospect.
The above description is only for facilitating the understanding of the technical solutions of the present invention by those skilled in the art, and is not intended to limit the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. The resistance reducing agent is characterized by comprising the following raw materials in parts by mass:
60-95 parts by mass of acrylamide and 1-5 parts by mass of alkyl polyethylene glycol acrylate;
the raw materials for synthesizing the resistance reducing agent also comprise: at least one of acrylic acid, 2-acrylamide-2-methylpropanesulfonic acid or sodium p-styrenesulfonate, and the balance of water;
the mass part of the acrylic acid is not more than 10 parts, the mass part of the 2-acrylamide-2-methylpropanesulfonic acid is not more than 20 parts, and the mass part of the sodium p-styrenesulfonate is not more than 5 parts;
the general structural formula of the alkyl polyethylene glycol acrylate is as follows:
wherein, R is1Is methyl or hydrogen atom, n is 2-30, R2Is phenyl, alkyl phenyl, cycloalkyl or C8-24 linear alkyl.
2. The drag reducer of claim 1, wherein said alkylphenyl group is at least one of tert-butylphenyl, hexylphenyl, heptylphenyl, octylphenyl, isooctylphenyl, nonylphenyl, decylphenyl, dodecylphenyl, tetradecylphenyl, pentadecylphenyl, hexadecylphenyl, octadecylphenyl, or a corresponding derivative thereof.
3. The drag reducer of claim 1, wherein said cycloalkyl group is at least one of a cyclohexane group, a cyclopentane group, a bridged cycloalkyl group, or their corresponding derivatives.
4. The resistance reducing agent according to claim 1, wherein the mass part of the acrylamide is 75 to 85 mass parts, and the mass part of the alkyl polyethylene glycol acrylate is 3 to 5 mass parts.
5. The method for preparing the resistance reducing agent according to any one of claims 1 to 4, wherein the method comprises the following steps:
adding two monomers, namely acrylamide and alkyl polyethylene glycol acrylate, into a reactor according to the mass parts of the components, adding at least one monomer of acrylic acid, 2-acrylamide-2-methylpropanesulfonic acid or sodium p-styrenesulfonate into the reactor to obtain a mixture solution, and adjusting the pH value of the hydrogen ion concentration index of the mixture solution to 8-9;
adding water to prepare an aqueous solution with the total monomer mass concentration of 20 percent, and introducing N2 20～40min；
Adding an initiator, uniformly stirring, and reacting at 40-60 ℃ for 4-7 h to obtain a milky colloidal product;
and washing the milky colloidal product with ethanol, and drying and crushing to obtain the resistance reducing agent.
6. The method of claim 5, wherein the initiator is at least one of ammonium persulfate-sodium bisulfite system, azobisisobutyramidine hydrochloride, azobisisobutyrimidazoline hydrochloride, or azobisisopropylimidazoline.
7. The preparation method of the resistance reducing agent according to claim 6, wherein the mass ratio of ammonium persulfate to sodium bisulfite in the ammonium persulfate-sodium bisulfite system is 1-1.5: 1.
8. The method for preparing the friction reducer according to claim 5, wherein the mass of the initiator is 0.05-0.5% of the total monomer mass.
9. The method for preparing the friction reducer according to claim 5, wherein the mass of the initiator is 0.05-0.2% of the total monomer mass.
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