CN115093841A - High-stability Pickering emulsion type drilling fluid and preparation method thereof - Google Patents

High-stability Pickering emulsion type drilling fluid and preparation method thereof Download PDF

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CN115093841A
CN115093841A CN202210930721.7A CN202210930721A CN115093841A CN 115093841 A CN115093841 A CN 115093841A CN 202210930721 A CN202210930721 A CN 202210930721A CN 115093841 A CN115093841 A CN 115093841A
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drilling fluid
nano
pickering emulsion
lignin
type drilling
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李美春
刘馨月
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Nanjing Forestry University
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Nanjing Forestry University
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    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/02Well-drilling compositions
    • C09K8/04Aqueous well-drilling compositions
    • C09K8/26Oil-in-water emulsions

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Abstract

The invention discloses a high-stability Pickering emulsion drilling fluid and a preparation method thereof, wherein the Pickering emulsion drilling fluid is prepared by mixing and emulsifying a nano-cellulose suspension, a lignin nanoparticle dispersion, slurrying bentonite and biodiesel; the volume ratio of the nano-cellulose suspension, the lignin nanoparticle dispersion liquid and the biodiesel is 3:3:2, and the mass ratio of the nano-cellulose or the lignin nanoparticles to the pulping bentonite is 1 (1-2); the preparation method comprises the following steps: mixing the nano-cellulose suspension and the lignin nano-particle dispersion liquid according to the proportion; adding slurrying bentonite into the mixed solution according to the proportion for uniform mixing; and ultrasonically emulsifying the mixed solution to obtain homogeneous emulsion to obtain the Pickering emulsion type drilling fluid with the lignin nanoparticles and the nanocellulose being stable. The Pickering emulsion type drilling fluid prepared by the invention has the advantages of high stability, low filtration loss, low permeability, compact deposited filter cake structure and excellent rheological property.

Description

High-stability Pickering emulsion type drilling fluid and preparation method thereof
Technical Field
The invention belongs to the technical field of drilling fluids, and relates to a high-stability Pickering emulsion type drilling fluid and a preparation method thereof.
Background
The emulsion type drilling fluid is a multifunctional fluid formed by mixing oil, water and a surfactant, benefits from larger capacity increment, higher stability and low interfacial tension of the emulsion, and has wide application in the fields of drill chip cleaning, drill string lubrication and stuck release, oil displacement and oil extraction and the like in the oil field drilling process. However, surfactant-stabilized emulsions have two major disadvantages: (1) a large amount of surfactant is required to be added, which is not beneficial to environmental protection and sustainable development; (2) a large amount of surfactant is difficult to remove, and a complicated purification and recovery means is required. Compared with the traditional emulsion, the Pickering emulsion stabilized by the solid nano particles has higher stability. This is because the solid nanoparticles have characteristics of large specific surface area, various particle shapes, adjustable surface wettability, and the like, and also have advantages of low cost, low toxicity, low usage amount, and the like. Therefore, Pickering emulsions have attracted a great deal of attention in the oil and gas extraction industry.
In the existing Pickering emulsion drilling fluid technology, the addition of the nano particles can not only improve the rheological property of the drilling fluid and reduce the effects of filtration loss and permeability, but also stabilize the oil phase through strong adsorption and keep higher emulsion stability. Common nano materials of the Pickering emulsion drilling fluid include nano silicon dioxide, nano aluminum oxide, nano calcium carbonate, nano graphite and the like. Although the problems of large dosage, poor stability and the like of the traditional emulsion type drilling fluid surfactant can be solved by adding the nano material, the nano material has the defect of non-biodegradability. The solid particles can enter a stratum in a flowing mode in the drilling process and cause blockage, the disadvantage of non-biodegradability of the solid particles can cause irreversible damage to an oil-gas reservoir, the environment is not protected, and the application of the Pickering emulsion in the field of drilling fluid is limited to a certain extent. Therefore, in order to meet the development requirements of green ecological oil fields in China, the Pickering emulsion type drilling fluid which is biodegradable, high in performance and stable in biomass nano materials needs to be developed urgently.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide the high-stability Pickering emulsion type drilling fluid and the preparation method thereof.
In order to achieve the purpose, the invention is realized by adopting the following technical scheme:
a high-stability Pickering emulsion type drilling fluid is prepared by mixing and emulsifying a nano-cellulose suspension, a lignin nanoparticle dispersion, slurrying bentonite and biodiesel; the volume ratio of the nano-cellulose suspension, the lignin nanoparticle dispersion liquid and the biodiesel is 3:3:2, and the mass ratio of the nano-cellulose or the lignin nanoparticles to the bentonite is 1 (1-2).
Optionally, the concentration of the nano-cellulose suspension is 0.5-2 wt%.
Optionally, the method for preparing a nanocellulose suspension comprises:
dispersing absolutely dry eucalyptus fibers in deionized water, adding a TEMPO solution, a sodium bromide solution and a sodium hypochlorite solution, stirring and dropwise adding a sodium hydroxide solution to control the pH value of a reaction system to be kept between 10.0 and 10.5, and adding ethanol to finish the reaction when the pH value of the reaction system is not changed; centrifuging the mixed solution after the reaction is finished, washing the obtained product to be neutral, dispersing the product in deionized water, and performing ultrasonic treatment to a nano scale to prepare a nano cellulose suspension; the mass ratio of the eucalyptus fibers to the TEMPO solution to the sodium bromide solution to the sodium hypochlorite solution is 1:0.016:0.1:6.9, and the concentration of the sodium hypochlorite solution is 5.2 wt%.
Optionally, the surface of the nano-cellulose is provided with hydroxyl and carboxyl functional groups, the diameter is 1-50 nm, and the length is more than 1000 nm.
Optionally, the concentration of the lignin nanoparticle dispersion liquid is 0.5-2 wt%.
Optionally, the preparation method of the lignin nanoparticle dispersion liquid comprises:
using H 2 SO 4 Adjusting the pH value of waste liquid generated in the process of boiling the fiber raw material by an alkaline method to 1.5-2.0, stirring for 20-40 min at room temperature, stirring, placing in a water bath kettle at 45-55 ℃ for stirring for 80-100 min at constant temperature, standing at room temperature, and centrifuging to wash precipitates; and dispersing the product in deionized water, and performing ultrasonic treatment to obtain a nano-scale lignin nanoparticle dispersion liquid.
Optionally, the lignin nanoparticles are spherical lignin with a nanoscale size, and the diameter of the lignin nanoparticles is 1-50 nm.
Optionally, the slurrying bentonite is sodium bentonite.
Optionally, the density of the biodiesel is 0.87~0.89 g/cm 3 The content of fatty acid methyl ester is more than or equal to 99.5 percent.
A preparation method of a high-stability Pickering emulsion drilling fluid comprises the following steps:
mixing the nano-cellulose suspension and the lignin nano-particle dispersion liquid according to a ratio to prepare a mixed solution 1;
adding slurrying bentonite into the mixed solution 1 according to the proportion, and uniformly mixing to obtain a mixed solution 2;
and ultrasonically emulsifying the mixed solution 2 to obtain homogeneous emulsion, thus obtaining the Pickering emulsion type drilling fluid with the lignin nanoparticles and the nanocellulose being stable.
Compared with the prior art, the invention has the following beneficial effects:
according to the high-stability Pickering emulsion drilling fluid and the preparation method thereof, the stability of the Pickering emulsion with stable nanocellulose is improved by adopting the lignin nanoparticles as the synergistic stabilizer, and the oil-in-water (O/W) Pickering emulsion drilling fluid with high stability, low filtration loss and low permeability, which is stable by combining the lignin nanoparticles with the nanocellulose, can be obtained by adding the slurrying bentonite;
the nano-cellulose and lignin nanoparticles belong to environment-friendly renewable biomass green materials, are safe, non-toxic, biodegradable and good in biocompatibility, are beneficial to environmental protection and construction of green oil fields, and can promote efficient utilization of biomass resources;
the preparation method of the high-stability Pickering emulsion type drilling fluid provided by the invention is simple, convenient and easy, and the process is easy to regulate and control;
the high-stability Pickering emulsion drilling fluid provided by the invention has potential application value in the field of oil and gas exploitation; the entanglement network structure and the shear thinning characteristic of the nano-cellulose are beneficial to improving the carrying capacity and rheological property of drilling cuttings of a drilling fluid system, reducing the using amount of other drilling fluid additives and reducing the total solid content of the drilling fluid.
Drawings
FIG. 1 is a transmission electron microscope scan of nanocellulose;
FIG. 2 is a transmission electron microscope scan of lignin nanoparticles;
FIG. 3 is a diagram of POM of a comparative example of the present invention;
FIG. 4 is a diagram of a POM according to a first embodiment of the present invention;
FIG. 5 is a diagram of a POM according to a second embodiment of the present invention;
FIG. 6 is a graph of fluid loss performance for comparative example and examples one and two of the present invention;
FIG. 7 is a scanning electron microscope photograph of the surface of a filter cake formed in a comparative example of the present invention;
FIG. 8 is a scanning electron microscope image of the surface of a filter cake formed in accordance with one embodiment of the present invention;
FIG. 9 is a scanning electron microscope image of the surface of a filter cake formed in example two of the present invention.
Detailed Description
The invention is further described below with reference to the accompanying drawings. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
For the purposes of this specification and the appended claims, unless otherwise indicated, all numbers expressing quantities, percentages, or proportions, and other numerical values used in the specification and the appended claims, are to be understood as being modified in all instances by the term "about". Moreover, all ranges disclosed herein are inclusive of the endpoints and independently combinable.
Comparative example
As shown in fig. 1 to 3, 6 and 7, the comparative example provides a high-stability Pickering emulsion type drilling fluid, which is composed of a nano-cellulose suspension, a lignin nanoparticle dispersion and biodiesel, wherein the volume ratio of the nano-cellulose suspension, the lignin nanoparticle dispersion and the biodiesel is 3:3:2, and the concentrations of the nano-cellulose suspension and the lignin nanoparticle dispersion are both 2 wt%.
A preparation method of a high-stability Pickering emulsion drilling fluid comprises the following steps:
s1, dispersing 1 g of oven-dried eucalyptus fibers in 100mL of deionized water, adding 16 mg of TEMPO, 0.1 g of sodium bromide and 6.9g of sodium hypochlorite solution with 5.2% of available chlorine content, dropwise adding 0.5 mol/L of sodium hydroxide solution while stirring to control the pH value of a reaction system to be kept between 10.0 and 10.5, and adding a large amount of ethanol when the pH value of the reaction system is not changed any more to finish the reaction; centrifuging the mixed solution after the reaction is finished, washing the obtained product to be neutral, dispersing the product in deionized water, performing ultrasonic treatment to a nanoscale to obtain a nano-cellulose suspension, and adjusting the concentration of the suspension to be 2 wt%;
s2, using 64-72 wt% H 2 SO 4 The solution adjusts the pH value of waste liquid (black liquid) generated in the process of boiling the fiber raw material by an alkaline method to 1.5-2.0, is placed in a water bath kettle at the temperature of 45-55 ℃ to be stirred for 90 min after being stirred for 30 min at room temperature, and is placed in a room temperature to be centrifuged to wash precipitate; dispersing the product in deionized water, and performing mechanical ultrasonic treatment to obtain a nano-scale lignin dispersion liquid, and adjusting the concentration of the lignin dispersion liquid to 2 wt%;
s3, mixing 37.5mL of 2wt% lignin nanoparticle dispersion liquid and 37.5mL of 2wt% nano-cellulose suspension, and carrying out ultrasonic emulsification with 25mL biodiesel for 40min to obtain the Pickering emulsion type drilling fluid with the lignin nanoparticles and the nano-cellulose being stable.
The filtration loss of the Pickering emulsion type drilling fluid stabilized by the lignin nanoparticles and the nanocellulose is measured according to the API standard, the rheological property of the Pickering emulsion type drilling fluid is measured by a rotary rheometer, and the experimental result is shown in Table 1.
Example one
As shown in fig. 1, 2, 4, 6, and 8, this embodiment provides a high-stability Pickering emulsion-type drilling fluid, which is composed of a nanocellulose suspension, a lignin nanoparticle dispersion, natural sodium bentonite, and biodiesel, wherein a volume ratio of the nanocellulose suspension, the lignin nanoparticle dispersion, and the biodiesel is 3:3:2, concentrations of the nanocellulose suspension and the lignin nanoparticle dispersion are both 2wt%, and a mass ratio of the nanocellulose or the lignin nanoparticle to the slurried bentonite is 1: 1.
A preparation method of a high-stability Pickering emulsion drilling fluid comprises the following steps:
s1, dispersing 1 g of oven-dried eucalyptus fibers in 100mL of deionized water, adding 16 mg of TEMPO, 0.1 g of sodium bromide and 6.9g of sodium hypochlorite solution with the effective chlorine content of 5.2%, dropwise adding 0.5 mol/L of sodium hydroxide solution while stirring to control the pH value of a reaction system to be kept between 10.0 and 10.5, and adding a large amount of ethanol when the pH value of the reaction system is not changed any more to finish the reaction; centrifuging the mixed solution after the reaction is finished, washing the obtained product to be neutral, dispersing the product in deionized water, performing ultrasonic treatment to reach a nanoscale to prepare a nano-cellulose suspension, and adjusting the concentration of the suspension to be 2 wt%;
s2, using 64-72 wt% H 2 SO 4 The solution adjusts the pH value of waste liquid (black liquid) generated in the process of boiling the fiber raw material by an alkaline method to 1.5-2.0, is placed in a water bath kettle at the temperature of 45-55 ℃ to be stirred for 90 min after being stirred for 30 min at room temperature, and is placed in a room temperature to be centrifuged to wash precipitate; dispersing the product in deionized water, and performing mechanical ultrasonic treatment to obtain a nano-scale lignin dispersion liquid, and adjusting the concentration of the lignin dispersion liquid to 2 wt%;
s3, mixing 37.5mL of 2wt% lignin nanoparticle dispersion liquid and 37.5mL of 2wt% nanocellulose suspension, continuously adding 0.75g of natural sodium bentonite, uniformly dispersing, and finally ultrasonically emulsifying the mixture with 25mL biodiesel for 40min to obtain the Pickering emulsion type drilling fluid with the lignin nanoparticles and the nanocellulose stabilized.
The filtration loss of the Pickering emulsion type drilling fluid stabilized by the lignin nanoparticles and the nanocellulose is measured according to the API standard, the rheological property of the Pickering emulsion type drilling fluid is measured by a rotary rheometer, and the experimental result is shown in Table 1.
Example two
As shown in fig. 1, 2, 5, 6, and 9, this embodiment provides a high-stability Pickering emulsion-type drilling fluid, which is composed of a nanocellulose suspension, a lignin nanoparticle dispersion, natural sodium bentonite, and biodiesel, wherein a volume ratio of the nanocellulose suspension, the lignin nanoparticle dispersion, and the biodiesel is 3:3:2, concentrations of the nanocellulose suspension and the lignin nanoparticle dispersion are both 2wt%, and a mass ratio of the nanocellulose or lignin nanoparticles to slurried bentonite is 1: 2.
A preparation method of a high-stability Pickering emulsion drilling fluid comprises the following steps:
s1, dispersing 1 g of oven-dried eucalyptus fibers in 100mL of deionized water, adding 16 mg of TEMPO, 0.1 g of sodium bromide and 6.9g of sodium hypochlorite solution with 5.2% of available chlorine content, dropwise adding 0.5 mol/L of sodium hydroxide solution while stirring to control the pH value of a reaction system to be kept between 10.0 and 10.5, and adding a large amount of ethanol when the pH value of the reaction system is not changed any more to finish the reaction; centrifuging the mixed solution after the reaction is finished, washing the obtained product to be neutral, dispersing the product in deionized water, performing ultrasonic treatment to reach a nanoscale to prepare a nano-cellulose suspension, and adjusting the concentration of the suspension to be 2 wt%;
s2, using 64-72 wt% H 2 SO 4 The solution adjusts the pH value of waste liquid (black liquid) generated in the process of boiling the fiber raw material by an alkaline method to 1.5-2.0, and is placed in a water bath kettle at 45-55 ℃ for stirring for 90 min after being stirred at room temperature for 30 min, and is placed in a room temperature for centrifugal washing of sediment; dispersing the product in deionized water, and performing mechanical ultrasonic treatment to obtain a nano-scale lignin dispersion liquid, and adjusting the concentration of the lignin dispersion liquid to 2 wt%;
s3, mixing 37.5mL of 2wt% lignin nanoparticle dispersion liquid and 37.5mL of 2wt% nanocellulose suspension, continuously adding 1.5g of natural sodium bentonite, uniformly dispersing, and finally ultrasonically emulsifying the natural sodium bentonite and 25mL of biodiesel for 40min to obtain the Pickering emulsion type drilling fluid with the lignin nanoparticles and the nanocellulose stabilized.
The filtration loss of the Pickering emulsion type drilling fluid stabilized by the lignin nanoparticles and the nanocellulose is measured according to the API standard, the rheological property of the Pickering emulsion type drilling fluid is measured by a rotary rheometer, and the experimental result is shown in Table 1.
Performance test
Fluid loss performance and rheology tests were performed on the Pickering emulsion drilling fluids prepared in examples 1 and 2, and comparative example. The test results are shown in Table 1.
The following method was used for the fluid loss test:
injecting 100mL of Pickering emulsion drilling fluid into a water loss instrument, adjusting the pressure to 100 psi, opening a pressure reducing valve, starting a stopwatch, and recording the filtration time and the filtration loss. And recording the volume of the filtrate with the filtering time of 30 min by taking mL as a unit, namely the API filtration loss.
The steady state rheology test method is as follows:
and carrying out steady-state shear test on the prepared Pickering emulsion type drilling fluid by adopting a Thermo HAAKE MARS60 rotational rheometer flat plate measuring system. The test conditions for all samples were as follows: keeping the temperature at 25 ℃ and the shear rate within 0.1-1000 s -1
The Pickering emulsion type drilling fluid loss properties and viscosity test results prepared in examples 1 and 2 and comparative example are shown in table 1 below:
Figure DEST_PATH_IMAGE001
as can be seen from Table 1, in the comparative example, when the lignin nanoparticles are cooperated with the nanocellulose as the solid particle stabilizer, the prepared Pickering emulsion drilling fluid has large filtration loss (all loss within 5 min), can not effectively block filter paper, has high loss speed, reduces the viscosity along with the increase of the shear rate, and has typical shear thinning behavior. In examples 1 and 2, after the stable Pickering emulsion drilling fluid containing the lignin nanoparticles and the nanocellulose is added to the slurrying bentonite, the filtration loss of the stable Pickering emulsion drilling fluid is greatly reduced, and the filtration loss of the stable Pickering emulsion drilling fluid is gradually reduced along with the increase of the content of the slurrying bentonite. After addition of 1.5g slurried bentonite, a minimum fluid loss of 3.4mL was obtained. Meanwhile, the rheological data show that the viscosity under different shearing speeds is obviously higher than that of the Pickering emulsion type drilling fluid in the comparative example. Therefore, after the stable Pickering emulsion of the lignin nanoparticles and the nanocellulose is added into the slurrying bentonite, the rheological property and the fluid loss property of the emulsion are obviously improved.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A high-stability Pickering emulsion drilling fluid is characterized in that: the Pickering emulsion type drilling fluid is prepared by mixing and emulsifying a nano cellulose suspension, a lignin nanoparticle dispersion, slurrying bentonite and biodiesel; the volume ratio of the nano-cellulose suspension, the lignin nano-particle dispersion liquid and the biodiesel is 3:3:2, and the mass ratio of the nano-cellulose or the lignin nano-particles to the pulping bentonite is 1 (1-2).
2. The high stability Pickering emulsion type drilling fluid of claim 1, wherein: the concentration of the nano-cellulose suspension is 0.5-2 wt%.
3. The high-stability Pickering emulsion drilling fluid as claimed in claim 2, wherein the preparation method of the nanocellulose suspension comprises the following steps:
dispersing absolutely dry eucalyptus fibers in deionized water, adding TEMPO, sodium bromide and sodium hypochlorite solution, dropwise adding sodium hydroxide solution while stirring to control the pH value of a reaction system to be 10.0-10.5, and adding ethanol to finish the reaction when the pH value of the reaction system is not changed; centrifuging the mixed solution after the reaction is finished, washing the obtained product to be neutral, dispersing the product in deionized water, and performing ultrasonic treatment to the nanoscale to obtain a nano-cellulose suspension; the mass ratio of the eucalyptus fibers to the TEMPO solution to the sodium bromide solution to the sodium hypochlorite solution is 1:0.016:0.1:6.9, and the concentration of the sodium hypochlorite solution is 5.2 wt%.
4. The high-stability Pickering emulsion-type drilling fluid as claimed in claim 3, wherein: the surface of the nano-cellulose is provided with hydroxyl and carboxyl functional groups, the diameter is 1-50 nm, and the length is more than 1000 nm.
5. The high stability Pickering emulsion type drilling fluid of claim 1, wherein: the concentration of the lignin nanoparticle dispersion liquid is 0.5-2 wt%.
6. The high-stability Pickering emulsion-type drilling fluid as claimed in claim 5, wherein the preparation method of the lignin nanoparticle dispersion comprises the following steps:
using H 2 SO 4 Adjusting the pH value of waste liquid generated in the process of boiling the fiber raw material by an alkaline method to 1.5-2.0, stirring for 20-40 min at room temperature, stirring, placing in a water bath kettle at 45-55 ℃ for stirring for 80-100 min at constant temperature, standing at room temperature, and centrifuging to wash precipitates; and dispersing the product in deionized water, and performing ultrasonic treatment to obtain a nano-scale lignin nanoparticle dispersion liquid.
7. The high stability Pickering emulsion type drilling fluid of claim 6, wherein: the lignin nanoparticles are spherical lignin with a nanoscale size, and the diameter of the lignin nanoparticles is 1-50 nm.
8. The high stability Pickering emulsion type drilling fluid of claim 1, wherein: the pulping bentonite is sodium bentonite.
9. The high stability Pickering emulsion type drilling fluid of claim 1, wherein: the density of the biodiesel is 0.87-0.89 g/cm 3 The content of fatty acid methyl ester is more than or equal to 99.5 percent.
10. A method for preparing a high stability Pickering emulsion type drilling fluid according to any one of claims 2 to 9, comprising:
mixing the nano-cellulose suspension and the lignin nano-particle dispersion according to the proportion to prepare a mixed solution 1;
adding slurrying bentonite into the mixed solution 1 according to the proportion, and uniformly mixing to obtain a mixed solution 2;
and ultrasonically emulsifying the mixed solution 2 to obtain homogeneous emulsion, thus obtaining the Pickering emulsion type drilling fluid with the lignin nanoparticles and the nanocellulose being stable.
CN202210930721.7A 2022-08-04 2022-08-04 High-stability Pickering emulsion type drilling fluid and preparation method thereof Pending CN115093841A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104955848A (en) * 2012-11-30 2015-09-30 阿普艾知识产权控股有限责任公司 Processes and apparatus for producing nanocellulose, and compositions and products produced therefrom
US20200270504A1 (en) * 2017-12-19 2020-08-27 Halliburton Energy Services, Inc. Pickering Foam Drilling Fluids
CN113968978A (en) * 2021-10-12 2022-01-25 南京林业大学 Novel nano lignin and preparation method thereof
CN113980660A (en) * 2021-11-18 2022-01-28 南京林业大学 Pickering emulsion type drilling fluid with stable nanocellulose and preparation method thereof
CN114601740A (en) * 2021-12-16 2022-06-10 大连工业大学 Preparation method of multifunctional natural lignin-based Pickering emulsion

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104955848A (en) * 2012-11-30 2015-09-30 阿普艾知识产权控股有限责任公司 Processes and apparatus for producing nanocellulose, and compositions and products produced therefrom
US20200270504A1 (en) * 2017-12-19 2020-08-27 Halliburton Energy Services, Inc. Pickering Foam Drilling Fluids
CN113968978A (en) * 2021-10-12 2022-01-25 南京林业大学 Novel nano lignin and preparation method thereof
CN113980660A (en) * 2021-11-18 2022-01-28 南京林业大学 Pickering emulsion type drilling fluid with stable nanocellulose and preparation method thereof
CN114601740A (en) * 2021-12-16 2022-06-10 大连工业大学 Preparation method of multifunctional natural lignin-based Pickering emulsion

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Application publication date: 20220923