CN113355063A - Elastic graphite strong-adsorption salt-resistant plugging agent and oil-based drilling fluid - Google Patents
Elastic graphite strong-adsorption salt-resistant plugging agent and oil-based drilling fluid Download PDFInfo
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Abstract
The invention discloses an elastic graphite strong-adsorption salt-resistant plugging agent and an oil-based drilling fluid, and belongs to the technical field of oil and gas field drilling. The elastic graphite strong-adsorption salt-resistant blocking agent is mainly prepared from elastic graphite, a sulfonate-containing compound and long-chain alkyl dimethyl tertiary amine by a step method, and has a plurality of quaternary ammonium functional groups and sulfonates. Wherein, the synthetic raw materials of the blocking agent are easy to obtain, and the synthetic method is simple and reliable. The particle size distribution of the synthesized elastic graphite strong-adsorption salt-resistant plugging agent is between 0.5 and 28 mu m, and the plugging agent can effectively plug nano-sized and micron-sized pores in the shale well wall. The plugging agent can be directly added into oil-based drilling fluid, has good compatibility, can effectively prevent the drilling fluid from permeating into the stratum, further stabilizes the well wall, prevents collapse, and has good plugging and fluid loss reduction effects.
Description
Technical Field
The invention relates to the technical field of oil and gas field drilling, in particular to an elastic graphite strong-adsorption salt-resistant plugging agent and an oil-based drilling fluid containing the plugging agent.
Background
In the process of developing petroleum and natural gas resources, the exploitation of deep shale gas has been a research hotspot of researchers. For some hard brittle and fractured formations where bedding and micro-cracks develop, invasion of oil based drilling fluid filtrate can contribute to formation instability. In addition, the transmission of hydraulic pressure through the micro-apertures also causes wellbore wall instability, and therefore, the plugging of the micro-apertures by the oil-based drilling fluid must be enhanced. At present, the plugging agent of the oil-based drilling fluid is few in types, the used plugging materials are mostly bridge plugs with only hydrophilic performance while drilling leakage-proof materials, the adaptability in the oil-based drilling fluid is poor, and the particle size matching capability is insufficient. Simultaneously, the change of pit shaft pressure will arouse the change of aperture size, and aperture dynamic deformation can lead to the fact the destruction to the shutoff layer, and the shutoff layer that inelastic plugging agent formed can not adapt to the aperture and warp, and this will influence the shutoff effect, compares in conventional rigid plugging agent, and elastic plugging agent can adapt to the aperture better and warp, and the shutoff effect is stable. Meanwhile, when the drill string is lifted up, the pressure of a liquid column in the well is reduced due to the pumping action, and when the adsorbability of the plugging material to the well wall is not strong, the plugging material in the hole seams is possibly displaced out under the action of the pumping pressure, so that the plugging material-the elastic graphite hyperbranched strong-adsorption salt-resistant plugging agent suitable for the oil-based drilling fluid is researched.
The elastic graphite is a novel graphite material which has low density, can be highly compressed and can be recovered after losing pressure, can deform under the pressure to enter a micropore gap to realize a plugging function, and can be well dispersed in the drilling fluid after oleophylic modification. The elastic graphite has high temperature resistance, and the grafted sulfonic acid functional group can increase the salt resistance and keep good plugging effect in a high-salt environment; the introduction of the multi-quaternary ammonium functional group structure can enhance the adsorption capacity of the plugging agent to the stratum and improve the bridging capacity of the elastic graphite in large pores and the plugging performance of the elastic graphite in small pores; meanwhile, a filter membrane can be formed on the surface of the rock stratum, so that the invasion of liquid is reduced.
Disclosure of Invention
Aiming at the problem of borehole wall instability caused by the fact that the conventional plugging agent cannot effectively plug micropores in shale at present, the invention provides the elastic graphite strong-adsorption salt-resistant plugging agent, the particle size of the elastic graphite strong-adsorption salt-resistant plugging agent can reach the nanometer level at the minimum, and micron-level and nanometer-level pores in a shale stratum can be effectively plugged, so that the aim of stabilizing the borehole wall is fulfilled.
In order to achieve the purpose, the technical scheme of the invention is as follows: the elastic graphite strong-adsorption salt-resistant plugging agent is characterized by comprising the following preparation steps:
s1, a, weighing 2.5-3g of elastic graphite powder ground to 200nm, adding 60-80ml of concentrated sulfuric acid, stirring and reacting in an ice bath at the temperature of-2-0 ℃ for 25-35min, then adding 2-2.5g of sodium nitrate, and continuing stirring for 25-35 min; b. slowly adding 8-10g of potassium permanganate, controlling the temperature not to exceed 20 ℃, and stirring for 2-2.5 h; c. raising the temperature to 30-40 ℃, standing for 2-2.5h, then dropwise adding 150mL of deionized water, raising the temperature to 95-100 ℃, adding 18-20mL of hydrogen peroxide after golden yellow suspension appears, then adding 150mL of deionized water, and ultrasonically dispersing for 1 h; d. after the reaction is finished, putting the mixture into a centrifuge, centrifuging the mixture for 5min at 5000rpm, filtering the mixture, washing solid matters for 3 times by using deionized water and absolute ethyl alcohol, and finally, drying the solid matters for 24h in vacuum at 60 ℃ to obtain the oxidized elastic graphite;
s2, a, dispersing 0.5-0.8g of oxidized elastic graphite in 100mL of distilled water, and treating for 1h by ultrasonic to obtain a uniform solution; b. adding 6-10g of NaOH and 5-8g of chloroacetic acid into the oxidized elastic graphite solution, carrying out water bath ultrasonic treatment for 2h, and adding 150mL of 8% diluted hydrochloric acid 100-150 to obtain a uniformly dispersed aqueous solution; c. filtering the solution, washing the solid matter with deionized water for 3 times, and finally, vacuum-drying the solid matter for 24 hours at 60 ℃ to obtain carboxylated elastic graphite; d. taking 0.2-0.3g of dried solid, dispersing the solid in 100mL of N, N-dimethylformamide, carrying out ultrasonic treatment for 1h at the temperature of 25-30 ℃ under mechanical stirring, and then adding 30-45g of monomer containing sulfonate groups for reaction for 1 h; e. adding 20-30mg of coupling agent into the solution, transferring the solution into a water bath at 60 ℃, cooling and refluxing for 6h, diluting the product with 1500-1800mL of ethanol, filtering, washing the solid substance with deionized water for 3 times, and finally, drying the solid substance at 60 ℃ in vacuum for 24h to obtain modified elastic graphite;
s3, a, adding 0.1-0.15g of modified elastic graphite into 35mL of absolute ethyl alcohol, and placing the mixture into a three-neck flask; b. diluting 1mL of epichlorohydrin with 20mL of absolute ethanol, slowly adding the diluted epichlorohydrin into 80mL of absolute ethanol while stirring, and continuously stirring and reacting for 48 hours at room temperature; c. after the reaction is finished, filtering the solution, and washing the solid matter for 3 times by using deionized water and absolute ethyl alcohol; d. and adding the obtained object into 80mL of absolute ethyl alcohol, adding 2.0-2.5g of long-chain alkyl dimethyl tertiary amine, stirring and reacting for 48h at room temperature, filtering after the reaction is finished, washing the solid substance for 3 times by using deionized water, and finally vacuum-drying the solid substance for 24h at 60 ℃ to obtain the elastic graphite strong-adsorption salt-resistant blocking agent.
The sulfonic acid radical monomer in step S2 is one of taurine, 3-amino-1-propanesulfonic acid, and N- (2-acylamino) -2-aminoethanesulfonic acid.
The coupling agent in the step S2 is one of 2- (7-azobenzotriazol) -N, N-tetramethylurea hexafluorophosphate, O-benzotriazol-tetramethylurea hexafluorophosphate and 6-chlorobenzotriazole-1, 1,3, 3-tetramethylurea hexafluorophosphate.
In the step S3, the long-chain alkyl dimethyl tertiary amine is one of dodecyl dimethyl tertiary amine, dimethyl tetradecyl amine and hexadecyl dimethyl tertiary amine.
An oil-based drilling fluid, which is characterized by comprising the elastic graphite strong-adsorption salt-resistant plugging agent of claims 1-3, wherein the drilling fluid comprises the following components in parts by weight: 70-90 parts of white oil, 0.5-1 part of main emulsifier, 1-3 parts of auxiliary emulsifier, 5-10 parts of fluid loss additive, 2-5 parts of organic soil, 0.5-5 parts of quicklime and 10-30 parts of CaCl2(concentration is 20-25%) saline water, 0.5-2 parts of wetting agent, 10-30 parts of barite and 1-10 parts of elastic graphite strong adsorption salt-resistant blocking agent.
The white oil of the oil-based drilling fluid is 3# white oil, the main emulsifier is one of OME, WO-NT, HIEMUL and HW Pmul-1, the auxiliary emulsifier is one of OME-2, HICOAT and HW Smul-1, the wetting agent is HW Wet-1, the filtrate reducer is one of oxidized asphalt, YJ-2 and HWTrol-101, the organic soil is HW Gel-3, and the density of barite is 4.2g/cm3。
The pH of the oil-based drilling fluid is 8.5-12.
The density of the oil-based drilling fluid is 1.50-2.10g/cm when the elastic graphite strong adsorption salt-resistant plugging agent is not added3。
The invention has the following beneficial effects:
the particle size distribution of the elastic graphite strong-adsorption salt-resistant plugging agent prepared by the invention is 0.5-28 mu m, and micro-and nano-level pore gaps in shale strata can be effectively plugged, so that the effect of stabilizing the well wall is achieved; the long carbon chain in the structure of the oil-based drilling fluid has good oleophylic property, and can ensure that the plugging agent is uniformly dispersed in the oil-based drilling fluid; the structure of the quaternary ammonium functional group greatly enhances the adsorption performance of the plugging agent to the stratum, and the plugging agent can be well adsorbed on the surface of the stratum, so that the plugging performance of the plugging agent is enhanced; the sulfonate can enhance the salt resistance of the plugging agent, so that the plugging agent can maintain good plugging performance in a high-salinity environment. Compared with the traditional plugging agent, the plugging agent is extruded into the micropore gap under the action of pressure difference, and has good compatibility with the oil-based drilling fluid. The plugging agent participates in the formation of an inner filter cake and an outer filter cake at the same time, and can plug stratums with different porosities at high temperature, thereby effectively reducing the osmotic filtration loss and the filtration rate. In addition, the oil-based drilling fluid used by the invention has good performances in the aspects of rheological property, plugging property and the like under the condition of shale formation.
Drawings
FIG. 1 is a graph showing the distribution of particle sizes of the strongly adsorptive salt-resistant plugging agent of elastic graphite in the first example;
FIG. 2 is a particle size distribution diagram of the strongly adsorptive salt-resistant plugging agent of elastic graphite in example two.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Synthesis of elastic graphite strong-adsorption salt-resistant plugging agent
Example 1:
weighing 2.5g of elastic graphite powder ground to 200nm, adding 65ml of concentrated sulfuric acid, stirring and reacting in an ice bath at the temperature of-2 ℃ for 30min, then adding 2g of sodium nitrate, and continuing stirring for 30 min; slowly adding 8g of potassium permanganate, controlling the temperature to be 20 ℃, and stirring for 2 hours; raising the temperature to 35 ℃, standing for 2 hours, then dropwise adding 150mL of deionized water, raising the temperature to 98 ℃, adding 20mL of hydrogen peroxide after a golden yellow suspension appears, then adding 150mL of deionized water, and ultrasonically dispersing for 1 hour; and after the reaction is finished, putting the mixture into a centrifuge, centrifuging the mixture for 5min at 5000rpm, filtering the mixture, washing solid matters for 3 times by using deionized water and absolute ethyl alcohol, and finally, drying the solid matters for 24h in vacuum at 60 ℃ to obtain the oxidized elastic graphite.
Dispersing 0.5g of oxidized elastic graphite in 100mL of distilled water, and treating for 1h by using ultrasonic waves to obtain a uniform solution; adding 7g of NaOH and 6g of chloroacetic acid into the oxidized elastic graphite solution, carrying out water bath ultrasonic treatment for 2h, and adding 130mL of 8% diluted hydrochloric acid to obtain a uniformly dispersed aqueous solution; filtering the solution, washing the solid matter with deionized water for 3 times, and finally, vacuum drying the solid matter for 24 hours at 60 ℃ to obtain the carboxylated elastic graphite.
Taking 0.2g of the dried solid, dispersing the solid in 100mL of N, N-dimethylformamide, and carrying out ultrasonic treatment for 1h at the temperature of 25 ℃ under mechanical stirring; adding 35g of 3-amino-1-propanesulfonic acid to react for 1h, adding 20mg of 2- (7-azobenzotriazol) -N, N, N, N-tetramethylurea hexafluorophosphate into the solution, transferring the solution into a water bath at 60 ℃, cooling and refluxing for 6h, diluting the product with 1500mL of ethanol, filtering, washing the solid substance with deionized water for 3 times, and finally, vacuum drying the solid substance at 60 ℃ for 24h to obtain the modified elastic graphite.
Adding 0.1g of modified elastic graphite into 35mL of absolute ethyl alcohol, and placing the mixture into a three-neck flask; diluting 1mL of epichlorohydrin with 20mL of absolute ethanol, slowly adding the diluted epichlorohydrin into the absolute ethanol while stirring, and continuously stirring and reacting for 48 hours at room temperature; after the reaction is finished, filtering the solution, and washing the solid matter for 3 times by using deionized water and absolute ethyl alcohol; and adding the obtained object into 80mL of absolute ethyl alcohol, adding 2.0g of hexadecyl dimethyl tertiary amine, stirring and reacting at room temperature for 48h, filtering after the reaction is finished, washing the solid matter for 3 times by using deionized water, and finally vacuum drying the solid matter for 24h at 60 ℃ to obtain the elastic graphite strong-adsorption salt-resistant blocking agent.
Example 2:
weighing 3g of elastic graphite powder ground to 200nm, adding 80ml of concentrated sulfuric acid, stirring and reacting in an ice bath at the temperature of-2 ℃ for 35min, then adding 2.5g of sodium nitrate, and continuing stirring for 30 min; slowly adding 10g of potassium permanganate, controlling the temperature to be 20 ℃, and stirring for 2.0 h; raising the temperature to 35 ℃, and standing for 2.5 h; dropwise adding 150mL of deionized water, raising the temperature to 98 ℃, adding 20mL of hydrogen peroxide after a golden yellow suspension appears, then adding 150mL of deionized water, and performing ultrasonic dispersion for 1 h; and after the reaction is finished, putting the mixture into a centrifuge, centrifuging the mixture for 5min at 5000rpm, filtering the mixture, washing solid matters for 3 times by using deionized water and absolute ethyl alcohol, and finally, drying the solid matters for 24h in vacuum at 60 ℃ to obtain the oxidized elastic graphite.
Dispersing 0.8g of oxidized elastic graphite in 100mL of distilled water, and treating for 1h by using ultrasonic waves to obtain a uniform solution; adding 10g of NaOH and 8g of chloroacetic acid into the oxidized elastic graphite solution, carrying out water bath ultrasonic treatment for 2h, and adding 150mL of 8% diluted hydrochloric acid to obtain a uniformly dispersed aqueous solution; filtering the solution, washing the solid matter with deionized water for 3 times, and finally, vacuum drying the solid matter for 24 hours at 60 ℃ to obtain the carboxylated elastic graphite.
Taking 0.3g of dried solid, dispersing the solid in 100mL of N, N-dimethylformamide, carrying out ultrasonic treatment for 1h at 25 ℃ under mechanical stirring, then adding 40g of taurine for reaction for 1h, e, adding 30mg of 2- (7-azobenzotriazole) -N, N, N, N-tetramethylurea hexafluorophosphate into the solution, transferring the solution into a water bath at 60 ℃ for cooling and refluxing for 6h, diluting the product with 1500mL of ethanol, filtering, washing the solid with deionized water for 3 times, and finally, carrying out vacuum drying on the solid at 60 ℃ for 24h to obtain the modified elastic graphite.
Adding 0.15g of modified elastic graphite into 35mL of absolute ethyl alcohol, and placing the mixture into a three-neck flask; diluting 1mL of epichlorohydrin with 20mL of absolute ethanol, slowly adding the diluted epichlorohydrin into the absolute ethanol while stirring, and continuously stirring and reacting for 48 hours at room temperature; after the reaction is finished, filtering the solution, and washing the solid matter for 3 times by using deionized water and absolute ethyl alcohol; and adding the obtained object into 80mL of absolute ethyl alcohol, adding 2.5g of tetradecyl dimethyl tertiary amine, stirring and reacting at room temperature for 48h, filtering after the reaction is finished, washing the solid substance for 3 times by using deionized water, and finally vacuum-drying the solid substance at 60 ℃ for 24h to obtain the elastic graphite strong-adsorption salt-resistant blocking agent.
Secondly, preparing the oil-based drilling fluid:
directly weighing 1.80g of main emulsifier HW Pmul-1, 4.50g of auxiliary milk HW Smul-1 and 2.40g of wetting agent HW Wet-1 in a high stirring cup; measuring 240mL of 3# white oil, introducing the white oil into a high-speed stirring cup, placing the high-speed stirring cup on a high-speed stirring machine, stirring at a high speed of 12000rpm, and stirring for 10 min; weighing 9g of organic soil HW Gel-3 by using glass paper, slowly adding the organic soil HW Gel-3 into a high-stirring cup under the high-stirring state, preventing splashing, and stirring for 10min at high speed; measuring 60mL of CaCl with the concentration of 25 percent under the high stirring state2Adding the aqueous solution to a high agitationIn the cup, splashing is prevented, and high stirring is carried out for 10 min; slowly adding 9g of quick lime HW-pH into a high stirring cup under the high stirring state, and stirring for 10 min; slowly adding 24g of the fluid loss agent HW Trol-101 into a high stirring cup, and stirring for 10 min; slowly adding the calculated (different adding amounts) elastic graphite strong adsorption plugging agent into a high-stirring cup under a high-stirring state, stirring for 10min, and taking down the high-stirring cup to scrape the wall; slowly adding 295g of barite into the high-stirring cup under the high-stirring state, continuously stirring for 30min, and taking off the high-stirring cup to scrape the wall again in the period;
third, performance test
In order to further illustrate the effects of the elastic graphite strong-adsorption salt-resistant plugging agent and the oil-based drilling fluid, the elastic graphite strong-adsorption salt-resistant plugging agent and the oil-based drilling fluid in the embodiments 1 and 2 are subjected to performance tests.
1. Particle size test of elastic graphite strong-adsorption salt-resistant plugging agent
The particle size of the elastic graphite strong adsorption salt-resistant plugging agent prepared in example 1 is shown in figure 1, the particle size of the elastic graphite strong adsorption salt-resistant plugging agent prepared in example 2 is shown in figure 2, and as can be seen from figures 1 and 2, the particle size distribution of the elastic graphite strong adsorption salt-resistant plugging agent is between 0.5 and 28 micrometers.
2. Plugging performance test of elastic graphite strong-adsorption salt-resistant plugging agent
A ceramic module is used as a simulated stratum, based on the plugging principle of 1/2 bridging and 2/3 filling, ceramic discs of 10 micrometers and 25 micrometers are selected, and a plugging experiment is carried out on a 71-type high-capacity HTHP water loss instrument, under the condition that after oil-based drilling fluid, the oil-based drilling fluid and a plugging agent roll for 16 hours at a high temperature of 160 ℃, the filtration loss and the mud cake permeability (160 ℃/3.5MPa/30min) are measured on the HTHP water loss instrument.
According to the preparation steps of the oil-based drilling fluid, the oil-based drilling fluid which is not added with the elastic graphite strong adsorption salt-resistant blocking agent and has the density of 1.55g/cm3 is prepared to be used as base slurry, the elastic graphite strong adsorption salt-resistant blocking agents synthesized in the embodiment 1 and the embodiment 2 with different mass fractions are respectively added, and the drilling fluid mud cake permeability experiment is carried out after aging and rolling for 16 hours at 150 ℃. The results of permeability measurements for ceramic disks of different pore sizes are shown in tables 1 and 2.
TABLE 1.10 μm ceramic disks test data
| Drilling fluid formula | Permeability of 10 μm ceramic disc (10)-5mD) | Plugging Rate (%) |
| Base pulp | 11.23 | / |
| Base stock + 1% example 1 | 3.38 | 69.90 |
| Base stock + 1% example 2 | 3.43 | 69.46 |
| Base stock + 2% example 1 | 2.13 | 81.03 |
| Base stock + 2% example 2 | 1.98 | 82.37 |
| Base stock + 3% example 1 | 1.59 | 85.84 |
| Base stock + 3% example 2 | 1.56 | 86.11 |
| Base stock + 4% example 1 | 1.41 | 87.44 |
| Base stock + 4% example 2 | 1.36 | 87.89 |
| Base stock + 5% example 1 | 1.27 | 88.69 |
| Base stock + 5% example 2 | 1.30 | 88.42 |
TABLE 2.25 μm ceramic disks test data
| Drilling fluid formula | Permeability of 10 μm ceramic disc (10)-5mD) | Plugging Rate (%) |
| Base pulp | 12.16 | / |
| Base stock + 1% example 1 | 3.89 | 68.01 |
| Base stock + 1% example 2 | 3.76 | 69.08 |
| Base stock + 2% example 1 | 2.26 | 81.41 |
| Base stock + 2% example 2 | 2.34 | 80.76 |
| Base stock + 3% example 1 | 1.78 | 85.36 |
| Base stock + 3% example 2 | 1.76 | 85.53 |
| Base stock + 4% example 1 | 1.43 | 88.24 |
| Base stock + 4% example 2 | 1.41 | 88.40 |
| Base stock + 5% example 1 | 1.37 | 88.73 |
| Base stock + 5% example 2 | 1.33 | 89.06 |
As can be seen from tables 1 and 2, when the elastic graphite strong-adsorption salt-resistant plugging agent is added into the drilling fluid, the permeability is effectively reduced, and at the addition amount of 3%, the permeability of the ceramic disk with the pore diameter of 10 μm in example 1 and example 2 is reduced by 85.84% and 86.11%, respectively, and the permeability of the ceramic disk with the pore diameter of 25 μm in example 1 and example 2 is reduced by 85.36% and 85.53%, respectively. Tables 2 and 3 show that the elastic graphite strong-adsorption salt-resistant plugging agent can effectively plug micropores with different sizes, when the addition amount of the elastic graphite strong-adsorption salt-resistant plugging agent exceeds 3%, the downward trend of the permeability of a mud cake is slowed down, and the result shows that the effect of the plugging agent formula on reducing leakage is good.
3. Compatibility of elastic graphite strong-adsorption salt-resistant plugging agent and oil-based drilling fluid
The oil-based drilling fluid prepared with different amounts of the elastic graphite strong-adsorption salt-resistant plugging agent is aged for 16 hours at 160 ℃, and the rheological property and the water loss are measured, and the results are shown in table 3.
TABLE 3 oil-based drilling fluids Performance parameters with addition of different mass fractions of plugging agent
Note: AV-apparent viscosity, unit is mPa.s; PV-plastic viscosity, unit is mPa.s; YP-dynamic shear force, in Pa; API-filtration loss at normal temperature and medium pressure, the unit is mL; HTHP, namely high-temperature high-pressure filtration loss, and the unit is mL; ES-demulsification voltage in V; the HTHP had a temperature of 160 ℃ and a pressure of 3.5 MPa.
As can be seen from Table 3, the oil-based drilling fluid prepared by using the elastic graphite strong-adsorption salt-resistant plugging agent as the plugging agent in the embodiments 1 and 2 has excellent drilling fluid rheological property, the viscosity and the shear force can meet the field drilling requirement, the demulsification voltage is more than 600V, and the viscosity and the shear force of the oil-based drilling fluid are slightly increased with the increase of the addition amount of the elastic graphite strong-adsorption salt-resistant plugging agent, but the change range is small, which indicates that the plugging agent has good compatibility with the oil-based drilling fluid.
4. Salt resistance of elastic graphite strong-adsorption salt-resistant plugging agent
NaCl with different addition amounts is added into the oil-based drilling fluid with the prepared elastic graphite strong-adsorption salt-resistant plugging agent accounting for 3 percent, the oil-based drilling fluid is overtaken for 30min under a high-speed stirrer of 2000r/min, the oil-based drilling fluid is put into a high-temperature roller heating furnace with the temperature of 160 ℃ for aging for 16h, and the performance of the aged drilling fluid is measured, and the result is shown in Table 4.
TABLE 4 oil-based drilling fluid Performance parameters with addition of different mass fractions of NaCl
As can be seen from Table 4, when different amounts of NaCl are added into the oil-based drilling fluid with the elastic graphite strong-adsorption salt-resistant plugging agent being 3%, the viscosity and the shear force of the drilling fluid are increased with the increase of the amount of NaCl, but the increase is slow, the demulsification voltage of the drilling fluid is slightly reduced but still is more than 600V, and good emulsification stability is shown. Meanwhile, the water loss of the drilling fluid is increased, and the drilling fluid can still meet the construction requirements on site, so that the oil-based drilling fluid added with the elastic graphite strong-adsorption salt-resistant plugging agent has excellent salt resistance.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (8)
1. The elastic graphite strong-adsorption salt-resistant plugging agent is characterized by comprising the following preparation steps:
s1, a, weighing 2.5-3g of elastic graphite powder ground to 200nm, adding 60-80ml of concentrated sulfuric acid, stirring and reacting in an ice bath at the temperature of-2-0 ℃ for 25-35min, then adding 2-2.5g of sodium nitrate, and continuing stirring for 25-35 min; b. slowly adding 8-10g of potassium permanganate, controlling the temperature not to exceed 20 ℃, and stirring for 2-2.5 h; c. raising the temperature to 30-40 ℃, standing for 2-2.5h, then dropwise adding 150mL of deionized water, raising the temperature to 95-100 ℃, adding 18-20mL of hydrogen peroxide after golden yellow suspension appears, then adding 150mL of deionized water, and ultrasonically dispersing for 1 h; d. after the reaction is finished, putting the mixture into a centrifuge, centrifuging the mixture for 5min at 5000rpm, filtering the mixture, washing solid matters for 3 times by using deionized water and absolute ethyl alcohol, and finally, drying the solid matters for 24h in vacuum at 60 ℃ to obtain the oxidized elastic graphite;
s2, a, dispersing 0.5-0.8g of oxidized elastic graphite in 100mL of distilled water, and treating for 1h by ultrasonic to obtain a uniform solution; b. adding 6-10g of NaOH and 5-8g of chloroacetic acid into the oxidized elastic graphite solution, carrying out water bath ultrasonic treatment for 2h, and adding 150mL of 8% diluted hydrochloric acid 100-150 to obtain a uniformly dispersed aqueous solution; c. filtering the solution, washing the solid matter with deionized water for 3 times, and finally, vacuum-drying the solid matter for 24 hours at 60 ℃ to obtain carboxylated elastic graphite; d. taking 0.2-0.3g of dried solid, dispersing the solid in 100mL of N, N-dimethylformamide, carrying out ultrasonic treatment for 1h at the temperature of 25-30 ℃ under mechanical stirring, and then adding 30-45g of monomer containing sulfonate groups for reaction for 1 h; e. adding 20-30mg of coupling agent into the solution, transferring the solution into a water bath at 60 ℃, cooling and refluxing for 6h, diluting the product with 1500-1800mL of ethanol, filtering, washing the solid substance with deionized water for 3 times, and finally, drying the solid substance at 60 ℃ in vacuum for 24h to obtain modified elastic graphite;
s3, a, adding 0.1-0.15g of modified elastic graphite into 35mL of absolute ethyl alcohol, and placing the mixture into a three-neck flask; b. diluting 1mL of epichlorohydrin with 20mL of absolute ethanol, slowly adding the diluted epichlorohydrin into 80mL of absolute ethanol while stirring, and continuously stirring and reacting for 48 hours at room temperature; c. after the reaction is finished, filtering the solution, and washing solid substances for 3 times by using deionized water and absolute ethyl alcohol; d. and adding the obtained object into 80mL of absolute ethyl alcohol, adding 2.0-2.5g of long-chain alkyl dimethyl tertiary amine, stirring and reacting for 48h at room temperature, filtering after the reaction is finished, washing the solid substance for 3 times by using deionized water, and vacuum-drying the solid substance for 24h at 60 ℃ to obtain the elastic graphite strong-adsorption salt-resistant blocking agent.
2. The method for preparing the elastic graphite strong-adsorption salt-resistant plugging agent according to claim 1, wherein the sulfonic acid group-containing monomer in step S2 is one of taurine, 3-amino-1-propanesulfonic acid and N- (2-acylamino) -2-aminoethanesulfonic acid.
3. The method for preparing the elastic graphite strong-adsorption salt-resistant blocking agent according to claim 1, wherein the coupling agent in the step S2 is one of 2- (7-azobenzotriazol) -N, N, N, N-tetramethylurea hexafluorophosphate, O-benzotriazol-tetramethylurea hexafluorophosphate and 6-chlorobenzotriazole-1, 1,3, 3-tetramethylurea hexafluorophosphate.
4. The method for preparing the elastic graphite strong adsorption salt-resistant plugging agent according to claim 1, wherein the long-chain alkyl dimethyl tertiary amine in the step S3 is one of dodecyl dimethyl tertiary amine, tetradecyl dimethyl tertiary amine and hexadecyl dimethyl tertiary amine.
5. An oil-based drilling fluid, which is characterized by comprising the elastic graphite strong-adsorption salt-resistant plugging agent of claims 1-3, wherein the drilling fluid comprises the following components in parts by weight: 70-90 parts of white oil, 0.5-1 part of main emulsifier and 1-3 parts of auxiliary emulsifier5-10 parts of filtrate reducer, 2-5 parts of organic soil, 0.5-5 parts of quicklime and 10-30 parts of CaCl2(concentration is 20-25%) saline water, 0.5-2 parts of wetting agent, 10-30 parts of barite and 1-10 parts of elastic graphite strong adsorption salt-resistant blocking agent.
6. The oil-based drilling fluid of claim 5, wherein the white oil is # 3 white oil, the primary emulsifier is one of OME, WO-NT, HIEMUL and HW Pmul-1, the secondary emulsifier is one of OME-2, HICOAT and HW Smul-1, the wetting agent is HW Wet-1, the fluid loss additive is one of oxidized bitumen, YJ-2 and HWTrol-101, the organic soil is HW Gel-3, and the density of barite is 4.2g/cm3。
7. The oil-base drilling fluid of claim 5, wherein the pH of said oil-base drilling fluid is from 8.5 to 10.
8. The oil-based drilling fluid of claim 5, wherein the oil-based drilling fluid has a density of 1.50 to 2.10g/cm without the addition of the strongly-absorbing, salt-tolerant plugging agent of the elastomeric graphite type3。
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