CN113583652A - Clean environment-friendly high-temperature-resistant nano fracturing fluid and preparation method thereof - Google Patents
Clean environment-friendly high-temperature-resistant nano fracturing fluid and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a clean environment-friendly high-temperature-resistant nano fracturing fluid and a preparation method thereof, wherein the clean environment-friendly high-temperature-resistant nano fracturing fluid comprises the following components in parts by weight: 5-8 parts of guanidine gum, 1-3 parts of modified lignosulfonate, 1-2 parts of organic boron crosslinking agent, 0.5-1 part of nano material, 2-3 parts of clay stabilizer, 2-3 parts of cleanup additive, 0.3-0.5 part of gel breaker, 2-3 parts of phase change filler and 100 parts of water. According to the invention, through the compounding of the modified lignosulfonate, the organic boron crosslinking agent, the nano material and the phase-change filler, the long molecular chain of the guanidine gum is hybridized to form a stable network structure, the temperature resistance and the shear resistance of the guanidine gum are improved, and the guanidine gum has excellent sand carrying performance under high temperature and high shear.
Description
Technical Field
The invention relates to the technical field of oil and gas field exploitation, in particular to a clean environment-friendly high-temperature-resistant nano fracturing fluid and a preparation method thereof.
Background
In the field of petroleum, fracturing refers to a method of forming cracks in oil and gas layers by using the action of water power in the process of oil or gas production, and is also called hydraulic fracturing. Fracturing is the process of artificially cracking stratum, improving the flowing environment of oil in underground and increasing the yield of oil well, and plays an important role in improving the flowing condition of oil well bottom, slowing down the interlamination and improving the oil layer utilization condition.
With the increasing global energy demand and the increasing level of oil and gas exploration and development, a large amount of shallow oil resources are developed and reduced, the oil and gas exploration and development have to be developed towards deep strata, and the stratum temperature faced by the oil and gas reservoir development is higher and higher. Aiming at reservoirs with deep burial, compact lithology, poor permeability, low natural productivity after perforation and even no yield, artificial fractures are formed by means of yield increasing measures of hydraulic fracturing, and original low-efficiency pore seams are communicated to improve the oil gas yield.
The fracturing fluid is one of the key factors of the fracturing effect, and the main problems of the fracturing fluid in the prior art are as follows: the existing fracturing fluid basically adopts polymer materials such as polymer or guar gum and the like as important components to block micron and nanometer pores; as the polymer or guar gum is mostly cross-linked by boron when being used as the fracturing fluid, the boron element is an environment-friendly forbidden component, and the existing fracturing fluid contains heavy metal atoms, sulfides, organic chlorine, fluorine elements and the like, the flowback fluid is not environment-friendly, the treatment cost is extremely high, and the clean production is not facilitated; in addition, because the energy storage stratum and the high-salinity stratum have strong wettability, high clay expansion rate, strong water sensitivity, acid sensitivity, alkali sensitivity and salt sensitivity and more fracturing fluid residues, sensitive blockage and blockage of nano and micron pore gaps are easily caused.
Furthermore, water-based fracturing fluids are most commonly used in fracturing operations, with guar gum being the most widely used thickener. The glycosidic bond can be broken at high temperature (such as over 170 ℃), so that the viscosity of the fracturing fluid is rapidly reduced, and the sand-carrying performance is lost. How to improve the temperature resistance of the fracturing fluid to ensure the use effect of the fracturing fluid in the high-temperature deep well construction has important significance.
In summary, it is an urgent need to solve the problem of providing a clean and environment-friendly fracturing fluid which can be recycled in high-temperature deep well construction.
Disclosure of Invention
The invention aims to provide a clean environment-friendly high-temperature-resistant nano fracturing fluid aiming at the problems of poor temperature resistance and poor shearing resistance of the existing guanidine gum fracturing fluid.
The purpose of the invention is realized by the following technical scheme:
a clean environment-friendly high-temperature-resistant nano fracturing fluid comprises the following components in parts by weight: 5-8 parts of guanidine gum, 1-3 parts of modified lignosulfonate, 1-2 parts of organic boron crosslinking agent, 0.5-1 part of nano material, 2-3 parts of clay stabilizer, 2-3 parts of cleanup additive, 0.3-0.5 part of gel breaker, 2-3 parts of phase change filler and 100 parts of water.
Further, the modified lignosulfonate is prepared by the following method:
(1) weighing lignosulfonate, adding the lignosulfonate into a closed reactor, adding alkali liquor, stirring and dissolving, adding ethylene oxide and ethanol, and reacting at 60-70 ℃ for 6-8 hours to obtain hydroxyethylated lignosulfonate;
(2) adding 2-chloroethyl diethylamine, adjusting the reaction temperature to 40-50 ℃, reacting for 3-5 hours, neutralizing with hydrochloric acid until the pH value is 6 after the reaction is finished, and then centrifuging, washing and drying to obtain the modified lignosulfonate.
Further, the organic boron crosslinking agent contains boric acid, and the ligands are sodium gluconate and triethanolamine.
Further, the nano material is TiO2Nanoparticles, the nanomaterial stabilized with a polymer, a surfactant, or a combination thereof, the nanoparticles of the nanomaterial not to aggregate or agglomerate.
Further, the clay stabilizer is sodium chloride.
Further, the cleanup additive is a sodium dodecyl sulfate anionic surfactant.
Further, the gel breaker is potassium persulfate.
Further, the phase change filler comprises a graphene aerogel framework and hexadecanol filled in a network formed by the graphene aerogel framework.
Further, the phase-change filler is prepared by the following method:
(1) placing graphene oxide in water, stirring and carrying out ultrasonic treatment to obtain a uniform graphene oxide solution, carrying out hydrothermal reaction to obtain graphene hydrogel, and carrying out vacuum freeze drying to obtain a graphene aerogel framework;
(2) mixing graphene oxide and hexadecanol at a temperature higher than the melting point of the phase-change material, stirring to obtain a microcapsule emulsion, and cooling, washing and drying to obtain the phase-change filler.
A preparation method of a clean environment-friendly high-temperature-resistant nano fracturing fluid comprises the following steps:
(1) dividing water into two parts, adding guar gum into one part of water, stirring to prepare a guar gum aqueous solution, and adding modified lignosulfonate into the other part of water to prepare uniformly dispersed nano dispersion liquid;
(2) under the condition of stirring, adding the nano dispersion liquid into a guanidine gum aqueous solution, and stirring to obtain a uniform mixed solution;
(3) under the condition of stirring, the nano material, the clay stabilizer, the cleanup additive, the gel breaker and the phase change filler are sequentially added into the mixed solution, the mixed solution is uniformly stirred to prepare a base solution, and then the organic boron crosslinking agent is added into the base solution to be uniformly mixed, so that the fracturing fluid is obtained.
The molecular chain diameter of the guanidine gum is only 1-2nm, and a long chain with the diameter ranging from nanometer to micrometer is formed through the interaction of a plurality of molecular chains. If a breaking point appears on the long molecular chain of the guanidine gum, the whole long chain is broken, so that the viscosity of the guanidine gum fracturing fluid is rapidly reduced. After the modified lignosulfonate and the organic boron crosslinking agent are added, the modified lignosulfonate and the organic boron crosslinking agent can well act together with a flexible chain of a thickening agent, so that the molecular structure of the guanidine gum fracturing fluid becomes stable, and the added rigid chain can still connect long chains together even if the long chains of the guanidine gum are locally broken, thereby playing a role in thickening the fracturing fluid and achieving the purpose of enhancing the temperature resistance and the shearing resistance of the fracturing fluid.
The tackifying speed of the guanidine gum in the modified lignosulfonate solution is slow and is less than that in water. Firstly, the guar gum powder is added into water, so that the guar gum powder is quickly tackified and fully swelled. Therefore, the guanidine gum is quickly tackified in water, the prepared modified lignosulfonate aqueous solution is mixed with the guanidine gum aqueous solution, and other auxiliary additives are added to ensure that the guanidine gum achieves the effect of quick dissolution, and the shearing resistance of the guanidine gum at high temperature can be obviously improved.
According to the invention, the layered nano silicate and the guanidine gum long molecular chain are added to form a stable network structure through hybridization, so that the temperature resistance and the shear resistance of the guanidine gum are improved, and the guanidine gum still has good sand carrying performance under high temperature and high shear. The modified lignosulfonate and the guanidine gum form a non-crosslinking system with better viscoelasticity, when the nano material is stabilized by the polymer, nano particles of the nano material do not aggregate or agglomerate, a supermolecule system can be further constructed by utilizing non-covalent acting force, and the high-viscosity elastic fluid can be obtained by self-assembly under the condition of lower concentration.
In addition, the phase change filler is added, the graphene aerogel is used as a framework, the high intrinsic thermal conductivity of the graphene is utilized to provide heat conduction modification for the composite material, a packaging environment is provided for the phase change material through a complex pore structure, after the phase change material is added into the nano fracturing fluid, the high-temperature use requirement of a deep well can be met, the chemical stability and the thermal stability are excellent, and the problems of decomposition, aging, phase separation and the like do not occur in the multiple phase change heat storage/release process in the well.
Detailed Description
The present invention is described in detail below with reference to specific examples, but the present invention is not limited thereto in any way.
Example 1
A preparation method of a clean environment-friendly high-temperature-resistant nano fracturing fluid comprises the following steps:
(1) preparing materials according to the following components: 5 parts of guanidine gum, 1 part of modified lignosulfonate, 1 part of organic boron crosslinking agent, 0.5 part of nano material, 2 parts of clay stabilizer, 2 parts of cleanup additive, 0.3 part of gel breaker, 2 parts of phase change filler and 100 parts of water;
(2) dividing water into two parts, adding guar gum into one part of water, stirring to prepare a guar gum aqueous solution, and adding modified lignosulfonate into the other part of water to prepare uniformly dispersed nano dispersion liquid;
(3) under the condition of stirring, adding the nano dispersion liquid into a guanidine gum aqueous solution, and stirring to obtain a uniform mixed solution;
(4) under the condition of stirring, the nano material, the clay stabilizer, the cleanup additive, the gel breaker and the phase change filler are sequentially added into the mixed solution, the mixed solution is uniformly stirred to prepare a base solution, and then the organic boron crosslinking agent is added into the base solution to be uniformly mixed, so that the fracturing fluid is obtained.
Specifically, the organic boron crosslinking agent contains boric acid, and the ligands are sodium gluconate and triethanolamine; the nano material is TiO2Nanoparticles; the clay stabilizer is sodium chloride; the cleanup additive is sodium dodecyl sulfate anionic surfactant, and the gel breaker is potassium persulfate.
The modified lignosulfonate is modified sodium lignosulfonate and can be prepared by the following method:
(1) weighing 15g of sodium lignosulfonate, adding the sodium lignosulfonate into a closed reactor, introducing nitrogen into the reactor to remove air in an upper space, adding 150 mL1.5wt% KOH aqueous solution, and stirring to dissolve; weighing ethylene oxide, dissolving the ethylene oxide in ethanol to prepare ethanol solution containing 10 wt% of ethylene oxide, slowly adding 10mL of ethanol solution containing ethylene oxide into a reaction kettle, and reacting for 7 hours at 65 ℃; after the reaction is finished, adding 100mL of distilled water for dilution, cooling to room temperature, adjusting the pH value to 6 by using glacial acetic acid, and centrifuging to remove impurities; slowly adding the supernatant into 95% ethanol with volume of 3 times, standing for 2h, filtering to obtain filter cake, washing with anhydrous ethanol, vacuum drying at 60 deg.C for 10h, and pulverizing to obtain hydroxyethylated sodium lignosulfonate;
(2) dissolving 10g of the hydroxyethylated sodium lignosulfonate prepared in the step (1) in 100mL of water, regulating the pH value of the solution to 10, adding 1g of 2-chloroethyl diethylamine, regulating the reaction temperature to 40 ℃, reacting for 3 hours, neutralizing with hydrochloric acid after the reaction is finished until the pH value is 6, and then centrifuging, washing and drying to obtain the modified sodium lignosulfonate.
The phase change filler comprises a graphene aerogel framework and hexadecanol filled in a network formed by the graphene aerogel framework, and is prepared by the following method:
(1) placing graphene oxide in water, stirring and carrying out ultrasonic treatment to obtain a uniform graphene oxide solution, carrying out hydrothermal reaction to obtain graphene hydrogel, and carrying out vacuum freeze drying to obtain a graphene aerogel framework; the ultrasonic frequency is 40-50 kHz, the ultrasonic time is 2h, the hydrothermal reaction temperature is 160 ℃, and the hydrothermal reaction time is 12 h;
(2) mixing graphene oxide and hexadecanol at a temperature higher than the melting point of the phase-change material, stirring to obtain a microcapsule emulsion, and cooling, washing and drying to obtain the phase-change filler.
Example 2
A preparation method of a clean environment-friendly high-temperature-resistant nano fracturing fluid comprises the following steps:
(1) preparing materials according to the following components: 8 parts of guanidine gum, 3 parts of modified lignosulfonate, 2 parts of organic boron crosslinking agent, 1 part of nano material, 3 parts of clay stabilizer, 3 parts of cleanup additive, 0.5 part of gel breaker, 3 parts of phase change filler and 100 parts of water.
(2) Dividing water into two parts, adding guar gum into one part of water, stirring to prepare a guar gum aqueous solution, and adding modified lignosulfonate into the other part of water to prepare uniformly dispersed nano dispersion liquid;
(3) under the condition of stirring, adding the nano dispersion liquid into a guanidine gum aqueous solution, and stirring to obtain a uniform mixed solution;
(4) under the condition of stirring, the nano material, the clay stabilizer, the cleanup additive, the gel breaker and the phase change filler are sequentially added into the mixed solution, the mixed solution is uniformly stirred to prepare a base solution, and then the organic boron crosslinking agent is added into the base solution to be uniformly mixed, so that the fracturing fluid is obtained.
The rest is the same as in example 1.
Example 3
A preparation method of a clean environment-friendly high-temperature-resistant nano fracturing fluid comprises the following steps:
(1) preparing materials according to the following components: 6 parts of guanidine gum, 2 parts of modified lignosulfonate, 2 parts of organic boron crosslinking agent, 0.5 part of nano material, 2 parts of clay stabilizer, 2 parts of cleanup additive, 0.5 part of gel breaker, 3 parts of phase change filler and 100 parts of water.
(2) Dividing water into two parts, adding guar gum into one part of water, stirring to prepare a guar gum aqueous solution, and adding modified lignosulfonate into the other part of water to prepare uniformly dispersed nano dispersion liquid;
(3) under the condition of stirring, adding the nano dispersion liquid into a guanidine gum aqueous solution, and stirring to obtain a uniform mixed solution;
(4) under the condition of stirring, the nano material, the clay stabilizer, the cleanup additive, the gel breaker and the phase change filler are sequentially added into the mixed solution, the mixed solution is uniformly stirred to prepare a base solution, and then the organic boron crosslinking agent is added into the base solution to be uniformly mixed, so that the fracturing fluid is obtained.
The rest is the same as in example 1.
Example 4
A preparation method of a clean environment-friendly high-temperature-resistant nano fracturing fluid comprises the following steps:
(1) preparing materials according to the following components: 7 parts of guanidine gum, 2 parts of modified lignosulfonate, 1 part of organic boron crosslinking agent, 1 part of nano material, 2 parts of clay stabilizer, 2 parts of cleanup additive, 0.4 part of gel breaker, 2 parts of phase change filler and 100 parts of water.
(2) Dividing water into two parts, adding guar gum into one part of water, stirring to prepare a guar gum aqueous solution, and adding modified lignosulfonate into the other part of water to prepare uniformly dispersed nano dispersion liquid;
(3) under the condition of stirring, adding the nano dispersion liquid into a guanidine gum aqueous solution, and stirring to obtain a uniform mixed solution;
(4) under the condition of stirring, the nano material, the clay stabilizer, the cleanup additive, the gel breaker and the phase change filler are sequentially added into the mixed solution, the mixed solution is uniformly stirred to prepare a base solution, and then the organic boron crosslinking agent is added into the base solution to be uniformly mixed, so that the fracturing fluid is obtained.
The rest is the same as in example 1.
Example 5
A preparation method of a clean environment-friendly high-temperature-resistant nano fracturing fluid comprises the following steps:
(1) preparing materials according to the following components: 6 parts of guanidine gum, 2 parts of modified lignosulfonate, 1.5 parts of organic boron crosslinking agent, 0.75 part of nano material, 2.5 parts of clay stabilizer, 2.5 parts of cleanup additive, 0.4 part of gel breaker, 2.5 parts of phase change filler and 100 parts of water.
(2) Dividing water into two parts, adding guar gum into one part of water, stirring to prepare a guar gum aqueous solution, and adding modified lignosulfonate into the other part of water to prepare uniformly dispersed nano dispersion liquid;
(3) under the condition of stirring, adding the nano dispersion liquid into a guanidine gum aqueous solution, and stirring to obtain a uniform mixed solution;
(4) under the condition of stirring, the nano material, the clay stabilizer, the cleanup additive, the gel breaker and the phase change filler are sequentially added into the mixed solution, the mixed solution is uniformly stirred to prepare a base solution, and then the organic boron crosslinking agent is added into the base solution to be uniformly mixed, so that the fracturing fluid is obtained.
The rest is the same as in example 1.
Comparative example 1
The nano fracturing fluid is not added with modified lignosulfonate, and the rest is the same as the embodiment 5.
Comparative example 2
The nano fracturing fluid is not added with an organic boron crosslinking agent, and the rest is the same as the embodiment 5.
Comparative example 3
The nano fracturing fluid is not added with nano materials, and the rest is the same as the embodiment 5.
Comparative example 4
The nano fracturing fluid is not added with phase change filler, and the rest is the same as the embodiment 5.
The fracturing fluids obtained in examples 1 to 5 and comparative examples 1 to 4 were passed through a rheometer at 180 ℃ for 170 seconds-1The viscosity was measured after 60min shear and is specified in table 1.
TABLE 1 comparison of fracturing fluids Performance of examples 1-5 and comparative examples 1-4
As can be seen from Table 1, the clean environment-friendly high-temperature-resistant nano fracturing fluid in the embodiment of the invention is obviously superior to a comparative example, when a certain component is lacked in the comparative example, the viscosity of the nano fracturing fluid is reduced to a certain extent, and the nano fracturing fluid has excellent performance only after the components are compounded.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. The clean environment-friendly high-temperature-resistant nano fracturing fluid is characterized by comprising the following components in parts by weight: 5-8 parts of guanidine gum, 1-3 parts of modified lignosulfonate, 1-2 parts of organic boron crosslinking agent, 0.5-1 part of nano material, 2-3 parts of clay stabilizer, 2-3 parts of cleanup additive, 0.3-0.5 part of gel breaker, 2-3 parts of phase change filler and 100 parts of water.
2. The clean environment-friendly high-temperature-resistant nano fracturing fluid as claimed in claim 1, wherein the modified lignosulfonate is prepared by the following method:
(1) weighing lignosulfonate, adding the lignosulfonate into a closed reactor, adding alkali liquor, stirring and dissolving, adding ethylene oxide and ethanol, and reacting at 60-70 ℃ for 6-8 hours to obtain hydroxyethylated lignosulfonate;
(2) adding 2-chloroethyl diethylamine, adjusting the reaction temperature to 40-50 ℃, reacting for 3-5 hours, neutralizing with hydrochloric acid until the pH value is 6 after the reaction is finished, and then centrifuging, washing and drying to obtain the modified lignosulfonate.
3. The clean environment-friendly high-temperature-resistant nano fracturing fluid as claimed in claim 1, wherein the organic boron crosslinking agent comprises boric acid, and the ligands are sodium gluconate and triethanolamine.
4. The clean environment-friendly high-temperature-resistant nano fracturing fluid as claimed in claim 1, wherein the nano material is TiO2Nanoparticles.
5. The clean environment-friendly high-temperature-resistant nano fracturing fluid as claimed in claim 1, wherein the clay stabilizer is sodium chloride.
6. The clean environment-friendly high-temperature-resistant nano fracturing fluid as claimed in claim 1, wherein the cleanup additive is sodium dodecyl sulfate anionic surfactant.
7. The clean environment-friendly high-temperature-resistant nano fracturing fluid as claimed in claim 1, wherein the gel breaker is potassium persulfate.
8. The clean environment-friendly high-temperature-resistant nano fracturing fluid as claimed in claim 1, wherein the phase change filler comprises a graphene aerogel framework and hexadecanol filled in a network formed by the graphene aerogel framework.
9. The clean environment-friendly high-temperature-resistant nano fracturing fluid as claimed in claim 8, wherein the phase-change filler is prepared by the following method:
(1) placing graphene oxide in water, stirring and carrying out ultrasonic treatment to obtain a uniform graphene oxide solution, carrying out hydrothermal reaction to obtain graphene hydrogel, and carrying out vacuum freeze drying to obtain a graphene aerogel framework;
(2) mixing graphene oxide and hexadecanol at a temperature higher than the melting point of the phase-change material, stirring to obtain a microcapsule emulsion, and cooling, washing and drying to obtain the phase-change filler.
10. The preparation method of the clean environment-friendly high-temperature-resistant nano fracturing fluid as claimed in any one of claims 1 to 9, characterized by comprising the following steps:
(1) dividing water into two parts, adding guar gum into one part of water, stirring to prepare a guar gum aqueous solution, and adding modified lignosulfonate into the other part of water to prepare uniformly dispersed nano dispersion liquid;
(2) under the condition of stirring, adding the nano dispersion liquid into a guanidine gum aqueous solution, and stirring to obtain a uniform mixed solution;
(3) under the condition of stirring, the nano material, the clay stabilizer, the cleanup additive, the gel breaker and the phase change filler are sequentially added into the mixed solution, the mixed solution is uniformly stirred to prepare a base solution, and then the organic boron crosslinking agent is added into the base solution to be uniformly mixed, so that the fracturing fluid is obtained.
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