CN113717708B - Low-cost nanoparticle enhanced fluorocarbon cleanup additive for oil and gas well fracturing - Google Patents
Low-cost nanoparticle enhanced fluorocarbon cleanup additive for oil and gas well fracturing Download PDFInfo
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Abstract
The invention discloses a low-cost nanoparticle enhanced fluorocarbon cleanup additive for oil-gas well fracturing, and belongs to the technical field of chemical cleanup of oil-gas fields. The cleanup additive comprises 0.05-0.1% by mass of nonionic fluorocarbon surfactant and 0.02-0.04% by mass of hydrophobic SiO 2 Nano particles and the balance of deionized water. By adding the hydrophobic nano-particles with low cost, the usage amount of the fluorocarbon surfactant with higher cost is obviously reduced, and simultaneously, better surface and interface characteristics are obtained and the interface wettability is improved. The cleanup additive for fracturing has good compatibility with fracturing fluid, the self performance of the fracturing fluid cannot be influenced after the cleanup additive is compounded, the surface tension of a fracturing fluid gel breaking liquid is less than 24.4mN/m, and the interfacial tension of the fracturing fluid gel breaking liquid and kerosene is less than 1.90mN/m. In addition, the existence of the nano particles can strengthen the self drag reduction performance of the fracturing fluid, and the double-effect is achieved.
Description
Technical Field
The invention belongs to the technical field of chemical cleanup of oil and gas fields, and particularly relates to a low-cost nanoparticle enhanced fluorocarbon cleanup additive for oil and gas well fracturing.
Background
The reserves of compact oil and gas resources are very rich at home and abroad, but due to the narrow pore throat and low permeability of a reservoir matrix, the economic and efficient development of the compact oil and gas resources needs to depend on horizontal drilling and multi-stage hydraulic fracturing technology. In the hydraulic fracturing process, fracturing fluid of tens of thousands of cubic meters is pumped into a stratum at high discharge capacity to form an artificial fracture network, so that the drainage area of a compact reservoir is increased; but at the same time, the fracturing fluid inevitably enters the reservoir, causing water entrapment damage (water lock), reducing the relative permeability of the oil or gas phase and thus reducing single well productivity. It is believed that the narrow pore throats and pore structure of the tight reservoir matrix contribute to high capillary forces, and that production pressure drops are insufficient to counteract the retention of the capillary forces on the invading water phase, resulting in increased saturation of residual water in the hydrocarbon seepage pathways and water lock damage. The surface interface of the low-permeability oil-gas reservoir mostly shows hydrophilic property, so that the capillary pressure is mainly expressed as resistance in the liquid drainage and production processes, oil gas is prevented from flowing to a shaft, the driving energy of a stratum is consumed, the production pressure difference is increased, and correspondingly, the flowing pressure at the bottom of a well is greatly reduced. The special functional additive is added into the fracturing fluid, so that the surface tension of the fluid is reduced after the fracturing fluid enters a stratum, the wetting angle of a rock is increased, the permeability of fluid in a low-permeability hydrocarbon reservoir is improved, and the flowback capability of the water-lock-preventing fracturing fluid is possibly greatly improved. The key problem of solving the flowback of the fracturing fluid is the research and development of a high-efficiency cleanup additive which is suitable for the fracturing fluid and compatible with the stratum. As an important component of various cleanup additives, a surfactant is used in a large amount.
The fluorine-containing surfactant as a special surfactant has superior performance which cannot be compared with a hydrocarbon surfactant, but the cost is too high, and the fluorine-containing surfactant alone is not practical to be used for oil field production. The fluorine-containing surfactant and the hydrocarbon surfactant are compounded for use, so that the use amount of the fluorine-containing surfactant is greatly reduced, and the surface tension of the cleanup additive is lower than 25mN/m. The cleanup additive system proposed by the currently granted Chinese patent CN200510044934.6 is prepared by dissolving 4 chemical agents of dodecyl dimethyl betaine, polyoxyethylene perfluorooctyl ether-14, 2,3 epoxypropyl trimethyl ammonium chloride and methanol in water; the discharge assistant system proposed in the granted Chinese invention patent CN200910083139.6 is composed of dodecyl dimethyl benzyl ammonium chloride, fatty alcohol polyoxyethylene ether JFC-4, polyoxyethylene alkyl alcohol ether-8 JFC, fatty alcohol polyoxyethylene ether JFC-6 and fluorine-containing surfactant FN-3 (C) 16 H 17 F 17 N 2 O 2 ) 5 chemical agents are prepared in water according to a certain proportion; the discharge assistant provided by the granted Chinese invention patent CN201010588476.3 is prepared by adding 4 medicaments of fluorocarbon chain-containing Gemini surfactant G1 or G2, nonionic surfactant, micromolecular alcohol, alkyl benzyl dimethyl ammonium chloride or alkyl trimethyl ammonium chloride into water. The cleanup additive provided by the granted Chinese patent invention 201652078.1 consists of 0.1-0.25 wt% of perfluorononenoxybenzene sodium sulfonate, 10-37.5 wt% of coconut oil fatty acid diethanolamide and the balance of water. The types of the surfactants used by the cleanup additive system are more than 2, excessive organic matters enter the stratum to inevitably pollute the underground water, and the configuration is complicated and is not beneficial to popularization and use. All of the peopleIt is known that although fluorocarbon surfactants are excellent in performance, they are very expensive, and how to reduce the amount of fluorocarbon surfactants in the cleanup additive while maintaining its cleanup performance becomes a key issue.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a low-cost nanoparticle enhanced fluorocarbon cleanup additive for oil-gas well fracturing, which is prepared by selecting hydrophobic SiO with certain size and concentration 2 The nano particles are compounded with the fluorocarbon surfactant, so that the dosage of the expensive fluorocarbon surfactant is reduced by 50 percent compared with the conventional dosage, and better surface interface characteristics and fracturing fluid drainage assisting performance are obtained.
In order to achieve the purpose of the invention, the invention is realized by adopting the following technical scheme:
a low-cost nano-particle reinforced fluorocarbon cleanup additive for oil-gas well fracturing is prepared from fluorocarbon active agent with selected chain length and hydrophobic SiO with selected size 2 After the nano particles are compounded, a self-assembly structure is formed, and after the self-assembly structure is added into fracturing fluid, the flowback rate of fracturing fluid gel breaking liquid after oil and gas well fracturing can be greatly improved under the condition of the same usage amount of the nonionic fluorocarbon surfactant.
The invention is further improved in that the fluorocarbon emulsion cleanup additive is prepared by using a nonionic fluorocarbon surfactant and hydrophobic SiO 2 The nano particles and deionized water are evenly stirred and compounded to obtain the nano-particle.
The further improvement of the invention is that the surface tension of the fracturing fluid gel breaking liquid added with the cleanup additive is as low as 22.68N/m, and the interfacial tension of the fracturing fluid gel breaking liquid and kerosene reaches 1.58mN/m.
The invention has the further improvement that the invention specifically comprises the following raw materials by mass percent:
nonionic fluorocarbon surfactant: 0.05 percent to 0.1 percent;
hydrophobic SiO 2 Nano-particles: 0.02 to 0.04 percent;
deionized water: the balance;
the sum of the mass percent of the components is 100 percent.
In a further improvement of the invention, the chemical formula of the nonionic fluorocarbon surfactant is that the number of carbon atoms is between 8 and 14.
In a further improvement of the invention, the nonionic fluorocarbon surfactant contains a hydrophobic fluorocarbon linkage at one end and a hydrophilic hydroxyl group in the middle of the carbon chain.
In a further development of the invention, the hydrophobic SiO is 2 The particle diameter of the nano particles is between 20 and 50nm, and SiO is prepared by mixing 2 The nano particles are dispersed in a toluene solution and subjected to reflux treatment, so that the surface of the nano particles shows strong hydrophobic characteristics.
Compared with the prior art, the invention has at least the following beneficial technical effects:
1. the cleanup additive for fracturing only comprises two raw materials, and is simple to prepare and more environment-friendly.
2. The hydrophobic nano-particles with low cost and selected size and concentration are added, so that the dosage of the expensive fluorocarbon surfactant is obviously reduced, the dosage of the fluorocarbon surfactant in the cleanup additive for fracturing is reduced by 50 percent compared with the conventional dosage, and the cost is obviously reduced.
3. Fluorocarbon active agent and hydrophobic SiO 2 The nano particles are compounded to generate a synergistic effect, so that the cleanup additive has lower surface tension (25 ℃, less than or equal to 20.23 mN/m).
3. Fluorocarbon active agent and hydrophobic SiO 2 The nano particles are compounded to generate a synergistic effect, so that the cleanup additive has lower interfacial tension (25 ℃ and less than 1.71 mN/m).
4. The cleanup additive can improve the wettability of fracturing fluid and stratum rock (change the strong hydrophilicity of natural mica sheets into weak hydrophilicity), reduce capillary force and promote flowback.
5. The cleanup additive for fracturing has good compatibility with fracturing fluid, the self performance of the fracturing fluid cannot be influenced after the cleanup additive is compounded, the surface tension of a fracturing fluid gel breaking liquid is less than or equal to 24.4mN/m, and the interfacial tension of the fracturing fluid gel breaking liquid and kerosene is less than 1.90mN/m. The wettability of the fracturing fluid and formation rock is obviously improved, the capillary force is reduced, and the flowback of the fracturing fluid of the oil-gas well is promoted.
6. The addition of the nano particles in the cleanup additive for fracturing can improve the interface wettability and the resistance reduction performance of fracturing fluid.
Drawings
FIG. 1 is a flow chart of preparation of hydrophobic silica nano-silica spheres.
FIG. 2 is an SEM image of a silicon wafer treated with the dispersion of example 5.
Detailed Description
The invention will be described in more detail with reference to the accompanying fig. 1 and the examples, but the scope of the invention is not limited thereto.
Example 1:
adding 0.05g of nonionic fluorocarbon surfactant into 99.3g of deionized water, uniformly stirring to fully dissolve the surfactant, and stirring at the rotating speed of 800-1200r/min for 20min to obtain the blank fluorocarbon cleanup additive.
Example 2:
adding 0.05g of nonionic fluorocarbon surfactant into 99.3g of deionized water, stirring uniformly to fully dissolve the surfactant, and then adding 0.02g of hydrophobic SiO 2 Slowly adding the mixture into the solution under the stirring condition, and stirring at the rotating speed of 800-1200r/min for 20min to obtain the low-cost nanoparticle enhanced fluorocarbon cleanup additive for oil-gas well fracturing.
Example 3:
adding 0.06g of nonionic fluorocarbon surfactant into 99.2g of deionized water, stirring uniformly to fully dissolve the surfactant, and then adding 0.02g of hydrophobic SiO 2 Slowly adding the mixture into the solution under the stirring condition, and stirring at the rotating speed of 800 r/min to 1200r/min for 20min to obtain the low-cost nanoparticle enhanced fluorocarbon cleanup additive for oil and gas well fracturing.
Example 4:
adding 0.07g of nonionic fluorocarbon surfactant into 99.1g of deionized water, stirring uniformly to fully dissolve the surfactant, and adding 0.02g of hydrophobic SiO 2 Slowly adding the mixture into the solution under the stirring condition, and stirring the mixture for 20min at the rotating speed of 800-1200r/min to obtain the low-cost nanoparticle enhanced fluorocarbon for oil-gas well fracturingA cleanup additive.
Example 5
Adding 0.08g of nonionic fluorocarbon surfactant into 99.1g of deionized water, stirring uniformly to fully dissolve the surfactant, and then adding 0.02g of hydrophobic SiO 2 Slowly adding the mixture into the solution under the stirring condition, and stirring at the rotating speed of 800-1200r/min for 20min to obtain the low-cost nanoparticle enhanced fluorocarbon cleanup additive for oil-gas well fracturing.
Example 6
Adding 0.08g of nonionic fluorocarbon surfactant into 99.1g of deionized water, stirring uniformly to fully dissolve the surfactant, and then adding 0.02g of hydrophobic SiO 2 Slowly adding the mixture into the solution under the stirring condition, and stirring at the rotating speed of 800-1200r/min for 20min to obtain the low-cost nanoparticle enhanced fluorocarbon cleanup additive for oil-gas well fracturing.
Example 7
Adding 0.1g of nonionic fluorocarbon surfactant into 99.1g of deionized water, stirring uniformly to fully dissolve the surfactant, and then adding 0.02g of hydrophobic SiO 2 Slowly adding the mixture into the solution under the stirring condition, and stirring at the rotating speed of 800-1200r/min for 20min to obtain the low-cost nanoparticle enhanced fluorocarbon cleanup additive for oil-gas well fracturing.
Example 8:
adding 0.05g of non-ionic fluorocarbon surfactant into 99.2g of deionized water, stirring uniformly to fully dissolve the non-ionic fluorocarbon surfactant, and then adding 0.03g of hydrophobic SiO 2 Slowly adding the mixture into the solution under the stirring condition, and stirring at the rotating speed of 800-1200r/min for 20min to obtain the low-cost nanoparticle enhanced fluorocarbon cleanup additive for oil-gas well fracturing.
Example 9:
adding 0.05g of nonionic fluorocarbon surfactant into 99.1g of deionized water, stirring uniformly to fully dissolve the surfactant, and then adding 0.04g of hydrophobic SiO 2 Slowly adding the mixture into the solution under the stirring condition, and stirring at the rotating speed of 800-1200r/min for 20min to obtain the low-cost nanoparticle enhanced fluorocarbon cleanup additive for oil and gas well fracturing.
The surface tension, interfacial tension and contact angle of the low-cost nanoparticle-enhanced fluorocarbon cleanup additive for oil and gas well fracturing prepared in examples 1 to 9 are shown in table 1.
The temperature of the test experiment was 25 ℃ and the interfacial tension was the interfacial tension with kerosene. The surface tension of deionized water was 72.15mN/m, and its contact angle on mica sheets was 27 °.
TABLE 1
The surface tension and the interfacial tension of the fracturing fluid gel breaking liquid of the fracturing fluid prepared by the fluorine-containing cleanup additive for fracturing prepared in the embodiments 1 to 9 according to the use concentration are shown in table 2 after the fracturing fluid gel breaking is carried out for 5 hours at 70 ℃. The test temperature was 25 ℃ and the interfacial tension was the interfacial tension with kerosene.
TABLE 2
After the silicon wafer is fully soaked in the dispersion liquid (99.1 g of deionized water, 0.08g of nonionic fluorocarbon surfactant and 0.02g of hydrophobic SiO 2) in the embodiment 5 for 5 hours, the silicon wafer is treated and observed by a scanning electron microscope, the surface appearance of the silicon wafer is shown in figure 2, a layer of self-assembly structure of nano particles and surfactant is uniformly covered on the surface of the silicon wafer, the appearance of the original silicon wafer is almost covered, and the appearance and the characteristics of the surface of the silicon wafer can be changed by the self-assembly structure adsorbed on the surface, so that the wettability of the silicon wafer is changed.
The above results show that: the nano-particle enhanced fluorocarbon emulsion cleanup additive prepared by the invention can effectively reduce the surface/interface tension of the fracturing fluid gel breaking liquid, improve the wettability and is beneficial to improving the flowback rate of the fracturing fluid. Compared with the common cleanup additive, the invention has only two components and simple preparation process. Using SiO abundantly present in the formation 2 The nano-particles prepared from the components can obviously reduce the dosage of the fluorocarbon surfactant, reduce the cost of the cleanup additive and improve the environmental protection performance of the cleanup additive. In addition, using 0.2% anionic polyacrylamide solutionDrag reduction experiments show that the existence of 0.04% by mass of nano particles can improve the drag reduction rate of a polymer solution from 71.2% to 75.1%, and the double-effect is achieved.
Claims (1)
1. The low-cost nanoparticle enhanced fluorocarbon cleanup additive for oil-gas well fracturing is characterized by specifically comprising the following raw materials in percentage by mass:
nonionic fluorocarbon surfactant: 0.05% -0.1%;
hydrophobic SiO 2 Nano-particles: 0.02 to 0.04 percent;
deionized water: the balance;
the nano-particle enhanced fluorocarbon cleanup additive passes through a nonionic fluorocarbon surfactant and hydrophobic SiO 2 The nano particles and deionized water are evenly stirred and compounded to prepare the nano-particle-based water-based paint;
the chemical molecular formula of the nonionic fluorocarbon surfactant is that the number of carbon atoms is between 8 and 14;
one end of the nonionic fluorocarbon surfactant contains a hydrophobic fluorocarbon bond, and the middle part of the carbon chain contains a hydrophilic hydroxyl group;
the hydrophobic SiO 2 The particle diameter of the nano-particles is between 20 and 50nm, and SiO is added 2 The nano particles are dispersed in a toluene solution and subjected to reflux treatment, so that the surfaces of the nano particles show strong hydrophobic characteristics.
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