CN113969148A - Low-density high-temperature plugging agent, preparation method and application thereof - Google Patents
Low-density high-temperature plugging agent, preparation method and application thereof Download PDFInfo
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/02—Well-drilling compositions
- C09K8/03—Specific additives for general use in well-drilling compositions
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
- C09K8/426—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells for plugging
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Abstract
The invention relates to the technical field of leak-proof and leak-stopping working fluid for drilling engineering, in particular to a low-density high-temperature plugging agent, a preparation method and application thereof; which comprises the following components in parts by volume: 20-40 parts of water glass, 5-18 parts of resin and 2-5 parts of silane coupling agent; the preparation method comprises the steps of firstly converting the water glass into silicon dioxide gel, then modifying the surface of the silicon dioxide gel by using a silane coupling agent, and combining with low-density resin to form the low-density high-temperature plugging agent. The inside of the protective agent particle has a nano porous network structure, the weight is light, the density is low, and the density is less than or equal to 1.65g/cm3(ii) a Is insensitive to the degree of mineralization and can resist the temperature of more than or equal to 200 ℃; the inorganic rigidity and the organic flexibility are blocked, and the reduction rate of the intrusion depth of the micro-foam fluid before and after the blocking agent is added is more than or equal to 65.7 percent;and the stability of the micro-foam fluid can be improved; the method can be applied to high-temperature leakage stratum, and the plugging property and stability of low-density fluid are improved.
Description
Technical Field
The invention relates to the technical field of leak-proof and leak-stopping working fluids for drilling engineering, in particular to a low-density high-temperature plugging agent, a preparation method and application thereof.
Background
The aerated foam drilling fluid and the recyclable micro-foam drilling fluid are low-density (< 1.0 g/cm) for coping with low-pressure and malignant leakage stratum3) Although the temperature resistance of the key drilling fluid technology is continuously improved by industrial workers, the problems of insufficient plugging property and pressure-bearing property are rarely involved. Particularly, the recyclable micro-foam drilling fluid has higher free water content than the foam drilling fluid, so that the permeability loss of the filtrate is larger than that of the foam drilling fluid, the problems of plugging capability and bearing capability are more prominent, and the leakage-proof plugging effect and the popularization and application prospect of the low-density drilling fluid are influenced.
Although various inorganic or organic blocking agents are developed in the drilling fluid or completion fluid industry, the blocking agents are basically 1.0g/cm3The working solution above was developed. Although the density of the plugging agent of vegetable fibers such as walnut shells, cottonseed shells and sawdust, nano emulsion and the like is lower, the plugging agent can be used as a plugging agent for low-density drilling fluid, but the temperature resistance is less than or equal to 150 ℃, and the recycling time is short; inorganic blocking agent such as superfine calcium carbonate, mica and silicon dioxide can resist high temperature more than or equal to 240 DEG CIn addition, the circulation frequency in the shaft is high, but the densities are all higher, and the density of the superfine calcium carbonate is 2.71g/cm3The mica sheet is 2.7-3.5 g/cm3The density of the nano-silica is 2.27g/cm3The high density plugging agent can increase the density of the foam surface film, cause the foam to settle and destabilize under gravity, cause the half life period of the foam to be seriously reduced, and is not used as the low density working fluid plugging agent.
An application study on inorganic low-density plugging agent for plugging a high-temperature high-pressure low-permeability oil reservoir discloses a well cementation cement slurry plugging agent formula consisting of G-grade oil well cement, silica fume, a dispersing agent, a fluid loss additive and a high-temperature retarder, and the formula is successfully applied to a high-temperature high-pressure low-permeability oil reservoir of 3-3 wells of the east league, the density is 1.2-1.5, the temperature resistance can reach 130 ℃, but the formula is a solidification type plugging agent of cement gel for well cementation and cannot be used as a low-density drilling completion fluid leak-proof plugging agent while drilling.
The article "Performance evaluation of Low Density Selective plugging agent for oil-Water interface" discloses a Low Density Mixed plugging agent comprising superfine Cement, 3% penetration enhancer, framework bridging agent, 0.1% suspending dispersant, 0.1-0.4% retarder, 0.3-0.6% Water reducer, and Density adjusting agent, although the Density is adjusted to 1.049-1.121 g/cm3But also well cementing cement, cannot be used as a low density drilling completion fluid plugging agent.
Chinese patent (CN106281265A) discloses an ultralow-density plugging agent suitable for low-pressure easily-leaked stratum. Consists of 50 to 70 percent of gel plugging agent, 0.1 to 0.3 percent of plugging fiber, 2.5 to 3.5 percent of surfactant, 2 to 6 percent of light rigid plugging additive, 1 to 2 percent of polymer and 0.5 to 2 percent of water-absorbing expansion resin, and the lowest density can reach 1.0g/cm3The density is adjustable; the temperature resistance reaches 180 ℃, the pressure bearing capacity is more than or equal to 15MPa, the plugging agent has the characteristics of large plugging depth and good plugging effect, and can plug large-size cracks, pores, cracks and other types of stratum leakage. The composition is also a consolidation plugging agent mainly based on cement gel, and is not suitable for being used as a leakage-proof plugging agent for low-density drilling completion fluid.
Therefore, the existing plugging agent used for the low-density drilling fluid has insufficient temperature resistance and low recycling rate; inorganic plug with excellent temperature resistanceThe agent has high density and reduces the foam stability; suitable for 1.0g/cm3The water-based or oil-based drilling fluid or completion fluid with the density is not suitable for the low-density consolidation plugging agent with the density of 1.0g/cm and the high temperature resistance3The following micro-foam drilling fluid or plugging agent for foam drilling fluid.
Disclosure of Invention
The invention aims to improve the plugging property of low-density drilling fluid or completion fluid at high temperature, reduce the filtration loss and improve the leakage-proof effect of working fluid, and aims to develop a special low-density inorganic-organic plugging agent for low-density working fluid, which is insensitive to mineralization degree, good in compatibility and easy to dissolve and disperse, can strengthen the plugging property of micro-foam or foam fluid and does not influence the foam stability, and the technical scheme is as follows:
a low-density high-temperature plugging agent comprises the following components in parts by volume:
20-40 parts of water glass, 5-18 parts of resin and 2-5 parts of silane coupling agent.
The modulus of the water glass is 2-3.5.
The resin is a low-density resin,
the low-density resin has a density of 0.8-1.4 g/cm3。
The low-density resin is one of natural resin and thermoplastic resin or a mixture of the natural resin and the thermoplastic resin.
Preferably, the low-density resin is one of rosin resin, acryl resin and vinyl resin or a mixture thereof.
The silane coupling agent is one or a mixture of KH-550, KH-560 or KH-570.
The silane coupling agent is KH-560.
The preparation method of the low-density high-temperature plugging agent comprises the following steps:
(1) adding water glass into a reaction container, adding 2 times of distilled water, uniformly stirring, adding 30% phosphoric acid solution while stirring, adjusting the pH to 2-3, and hydrolyzing and stirring for 0.5-1 h; adding ammonia water, adjusting the pH value to 5-6.5, continuously stirring until gel is separated out, and standing for 0.5-2 h; adding ethanol and isopropanol which are uniformly mixed while stirring for surface modification, and stirring for 1-2 h; and standing for 24 hours, then carrying out filter pressing on the gel, drying and crushing the gel at the temperature of 50-80 ℃, soaking the gel in 80% n-hexane solution for 8-16 hours, removing the solvent, and drying again to obtain the low-density nano silicon dioxide particles.
(2) Adding low-density silicon dioxide powder particles and resin powder particles into a high-speed premixer according to the volume ratio of 4: 1-3: 1, mixing and stirring for 20-30 min, spraying a 10% silane coupling agent solution on the mixed material under the high-speed stirring state, continuously mixing for 20-30 min, and drying for 1-2 h at the temperature of 100-130 ℃.
(3) And uniformly mixing the powder particles obtained by secondary drying and the rest resin to obtain the low-density high-temperature plugging agent.
The low-density high-temperature plugging agent can be applied to high-temperature leakage stratum and high-temperature low-pressure stratum.
Furthermore, the low-density high-temperature plugging agent can be applied to low-density fluid or conventional water-based working fluid in a synergistic compatibility mode.
Further, the low density fluid may be applied as a high temperature, recyclable micro-foam drilling or completion fluid, a high temperature aerated foam drilling or completion fluid.
The invention has the beneficial effects that:
the developed low-density high-temperature plugging agent has low density, light weight, multiple pores, temperature resistance, hypersalinity resistance, inorganic rigidity and organic flexible elastic plugging characteristics, and the nano-level particles can not only enhance the effects of leakage prevention, leakage penetration and plugging of the micro-foam or foam fluid on low-pressure easily-leaked strata, but also improve the service life of the micro-foam, and are environment-friendly, non-toxic and pollution-free to soil and air.
The main performance can reach the following indexes:
(1) inert material, strong compatibility, Na+，Ca2+、Cl-Is not sensitive to contamination.
(2) The dispersion and solubility are good. Difficult to form agglomerates, small particle size, narrow distribution and easy dispersion.
(3) The interior of the particle has a nano porous network structure, the light weight density is low, and the density is less than or equal to 1.65g/cm3Can increase the micro-scaleThe stability of the foamed fluid without affecting the rheology of the water-based completion fluid.
(4) High heat resistance and good plugging performance. The temperature resistance is more than or equal to 200 ℃, the invasion depth of the micro-foam fluid is reduced by 65.7 percent compared with that of the base fluid, and the invasion depth of the filtrate is reduced by 68.6 percent compared with that of the base fluid.
Detailed Description
The invention is further illustrated, but is not to be construed as being limited, by the following examples. The raw materials used are wide in source and can be industrially produced.
Example 1:
adding 40 parts of water glass and 2 times of distilled water into a reaction container, adding 30% phosphoric acid solution while stirring to adjust the pH to 3, hydrolyzing for 1h, adding ammonia water to adjust the pH to 6.5, stirring until gel is separated out, and standing for 2 h; immersing in ethanol and isopropanol solution for surface modification, standing for 24h, press filtering the gel, drying and pulverizing at 65 deg.C, immersing in 80% n-hexane solution for 16h, removing solvent, and drying again. Adding the obtained low-density silica powder particles and 7.5 parts of polypropylene resin powder particles into a high-speed premixer, mixing and stirring for 25min, spraying a 10% silane coupling agent solution on the mixed material in a high-speed stirring state, continuously mixing for 30min, and drying for 2h at the temperature of 110 ℃ to obtain the sample of the embodiment 1.
Test 1: example 1 dispersibility test.
50mL of clear water was weighed, placed on a magnetic stirrer, and 1g of example 1 was added while stirring, and the dispersibility and solubility of the sample were observed, and the results are shown in Table 1.
Table 1 example 1 dispersion solubility
Example 1 had good dispersion and dissolution properties.
And (3) testing 2: example 1 Density test
The apparent density of the free-flowing powder of example 1 was tested using GB/T13175-1991 and was 1.65g/cm3。
And (3) testing: example 1 test for the Effect on rheology
2%, 4% and 6% earth moving slurries were prepared, 3% of example 1 was added to each slurry, and the rheology and filter press loss were measured before and after the addition of example 1, with the test results shown in the following table.
Table 2 example 1 effect on base stock rheology
| Formulation of | FL/mL | ρ/g/cm3 | AV/mPa.s | PV/mPa.s |
| 2% earth moving slurry | 60.0 | 1.010 | 2.5 | 1.5 |
| 2% Carrier slurry + 3% EXAMPLE 1 | 59.6 | 1.015 | 2.5 | 1 |
| 4% soil-shifting slurry | 32.0 | 1.030 | 8.5 | 5 |
| 4% Carrier slurry + 3% EXAMPLE 1 | 31.2 | 1.042 | 8.5 | 4 |
| 6% earth moving slurry | 21.4 | 1.050 | 16 | 8.5 |
| 6% Carrier slurry + 3% EXAMPLE 1 | 19.8 | 1.062 | 18.5 | 7 |
The 3% of example 1 has no influence on the viscosity and density of 2-6% of base slurry, and slightly reduces the medium-pressure filtration loss.
Preparing 2% of soil-shifting slurry and 0.3% of DSP-II base slurry, adding 0.2% of AOS and 0.1% of SDS foaming agent while stirring by using a low-speed strong stirrer under the stirring environment with the shearing rate of 1000r/min, and stirring for 2 hours to form micro-foam base liquid; then, 1-5% of example 1 with different concentrations is added into the base solution, the stirring is continued for 1h, the rheological property of the micro-foam fluid and the filter pressing loss are tested before and after the addition of the example 1, and the test results are shown in the following table.
Table 3 example 1 effect on rheology of microfoam base fluids
| Formulation of | ρ(g/cm3) | FL(mL) | AV(mPa.s) | PV(mPa.s) |
| Base liquid | 0.66 | 12.0 | 16.5 | 10 |
| Base liquid + 1% example 1 | 0.62 | 11.6 | 28 | 17 |
| Base liquid + 3% example 1 | 0.58 | 6.8 | 33 | 19.5 |
| Base fluid + 5% example 1 | 0.61 | 7 | 30.5 | 21.5 |
Example 1 after addition of the microfoam base fluid, the density decreased first and then increased, the medium pressure filtration loss decreased gradually, and the viscosity of the base fluid increased first and then decreased.
And (3) testing: normal temperature medium pressure plugging performance test
Preparing 2% of soil-moving slurry and 0.3% of comb-shaped polymer filtrate reducer base slurry, adding 0.2% of AOS and 0.1% of SDS foaming agent while stirring by using a low-speed strong stirrer under the stirring environment with the shear rate of 1000r/min, stirring for 2h to form micro-foam base fluid, then adding 1% -5% of example 1 with different concentrations into the base fluid, continuously stirring for 1h, testing the plugging performance of the micro-foam fluid before and after the micro-foam fluid is added into the example 1 by using an FA type normal-temperature medium-pressure sand bed filtrate reducer (the longitudinal thickness of a sand bed is 20cm), and performing hot roll aging at 180 ℃/16h and 200 ℃/16 h. The test results are shown in the table below.
Table 4 example 1 medium pressure sand bed plugging performance
With increasing addition of example 1, the plugging of the microfoam fluid increased.
And (4) testing: high temperature high pressure plugging performance test
Preparing 2% of soil-shifting slurry, 0.2% of TFS, 0.3% of DSP-II and 0.2% of SPNH base slurry, adding 0.2% of AOS and 0.2% of SDS foaming agent while stirring under the stirring environment with the shearing rate of 1100r/min by using a low-speed strong stirrer, stirring for 2 hours to form a micro-foam base fluid, then adding 3% of example 1 into the base fluid, continuously stirring for 1 hour, and testing the micro-foam fluid invasion depth of the micro-foam fluid in the environment of 180 ℃/3.5MPa and 200 ℃/3.5MPa by using a high-temperature high-pressure sand bed filtration instrument (the vertical thickness of a sand bed is 500cm) before and after the micro-foam fluid is added into the example 1, wherein the test results are shown in the table below.
TABLE 5 example 1 high temperature high pressure sand bed plugging Performance
The 3% example 1 significantly improved the high temperature plugging performance of the microfoam base fluid, especially reducing the base fluid filtrate intrusion depth.
And (5) testing: effect on the Life of the microfoam fluid
Preparing 2% of soil-shifting slurry and 0.3% of DSP-II base slurry, adding 0.2% of AOS and 0.1% of SDS foaming agent while stirring by using a low-speed strong stirrer under the stirring environment with the shear rate of 1000r/min, stirring for 2h to form a micro-foam base solution, then adding 1% -5% of example 1 with different concentrations into the base solution, continuously stirring for 1h, pouring into a 500mL measuring cylinder, observing the micro-foam initial separation and half-life time, and obtaining the test results as shown in the table below.
Table 6 example 1 effect on microfoam stability
Example 1 improves the stability of the microfoam fluid.
Example 2:
adding 35 parts of water glass and 2 times of distilled water in a reaction container, adding 30% phosphoric acid solution while stirring to adjust the pH to 2.5, hydrolyzing for 1h, adding ammonia water to adjust the pH to 6, stirring until gel is separated out, and standing for 2 h; immersing in ethanol and isopropanol solution for surface modification, standing for 24h, press filtering the gel, drying and pulverizing at 65 deg.C, immersing in 80% n-hexane solution for 16h, removing solvent, and drying again. Adding the obtained low-density silicon dioxide powder particles and 6.5 parts of polypropylene resin powder particles into a high-speed premixer, mixing and stirring for 25min, spraying a 10% silane coupling agent solution on the mixed material in a high-speed stirring state, continuously mixing for 30min, and drying for 2h in an environment at 115 ℃. And (3) uniformly mixing the powder particles obtained by secondary drying and 11 parts of rosin resin to obtain the sample of the embodiment 2.
Test 1: example 2 dispersibility test.
50mL of clear water was measured and placed on a magnetic stirrer, 1g of example 1 was added while stirring, and the dispersion solubility of the sample was observed, and the results are shown in Table 7.
Table 7 example 2 dispersion solubility
| Sample (I) | Time of dispersion |
| Example 2 | 3.8min |
Example 2 had good dispersion and dissolution properties.
And (3) testing 2: example 2 Density testing
The apparent density of the free-flowing powder of example 2 was tested using GB/T13175-1991 and was 1.38g/cm3。
And (3) testing: example 2 test for the Effect on rheology
2%, 4% and 6% earth-moving slurries were prepared, 3% of example 2 was added thereto, respectively, and the rheology and medium filter press loss before and after the addition of example 2 were tested, with the test results shown in the following table.
Table 8 example 2 impact on base stock rheology
Example 2 has no effect on the viscosity and density of 2-6% base slurry, and slightly reduces the medium pressure filtration loss.
Preparing 2% of soil-shifting slurry and 0.3% of DSP-II base slurry, adding 0.2% of AOS and 0.1% of SDS foaming agent while stirring by using a low-speed strong stirrer under the stirring environment with the shearing rate of 1000r/min, and stirring for 2 hours to form micro-foam base liquid; then, the example 2 with different concentrations of 1-5% is added into the base solution, the stirring is continued for 1h, the rheological property of the micro-foam fluid and the filter pressing loss before and after the addition of the example 2 are tested, and the test results are shown in the following table.
Table 9 example 2 effect on microfoam base fluid rheology
| Formulation of | ρ(g/cm3) | FL(mL) | AV(mPa.s) | PV(mPa.s) |
| Base liquid | 0.66 | 12 | 16.5 | 10 |
| Base liquid + 1% example 2 | 0.61 | 11.4 | 28.5 | 17 |
| Base fluid + 3% example 2 | 0.57 | 7.2 | 34.5 | 20 |
| Base fluid + 5% example 2 | 0.53 | 6.8 | 36 | 22.5 |
Example 2 after addition of the microfoam base fluid, the density and fluid loss gradually decreased and the viscosity of the base fluid gradually increased.
And (3) testing: normal temperature medium pressure plugging performance test
Preparing 2% of soil-moving slurry and 0.3% of comb-shaped polymer filtrate reducer base slurry, adding 0.2% of AOS and 0.1% of SDS foaming agent while stirring by using a low-speed strong stirrer under the stirring environment with the shear rate of 1000r/min, stirring for 2h to form micro-foam base fluid, then adding 1% -5% of example 2 with different concentrations into the base fluid, continuously stirring for 1h, testing the plugging performance of the micro-foam fluid before and after the addition of the example 2 at normal temperature by using an FA type normal-temperature medium-pressure sand bed filtrate reducer (the longitudinal thickness of a sand bed is 20cm), and performing hot roll aging at 180 ℃/16h and 200 ℃/16 h. The test results are shown in the table below.
Table 10 example 2 medium pressure sand bed plugging performance
And the implementation 2 improves the plugging performance of the micro-foam fluid at normal temperature and under medium pressure.
And (4) testing: high temperature high pressure plugging performance test
Preparing 2% of soil-shifting slurry, 0.2% of TFS, 0.3% of DSP-II and 0.2% of SPNH base slurry, adding 0.2% of AOS and 0.1% of SDS foaming agent while stirring under the stirring environment with the shearing rate of 1100r/min by using a low-speed strong stirrer, stirring for 2 hours to form a micro-foam base fluid, then adding 3% of example 2 with different concentrations into the base fluid, continuously stirring for 1 hour, and testing the micro-foam fluid invasion depth within 30 minutes under the environment with 180 ℃/3.5MPa and 200 ℃/3.5MPa by using a high-temperature high-pressure sand bed filtration instrument (the vertical thickness of a sand bed is 500cm) before and after the micro-foam fluid is added into the example 2, wherein the test results are shown in the table below.
Table 11 example 2 high temperature high pressure sand bed plugging performance
Example 2 significantly improves the plugging performance of the microfoam base fluid in high temperature environments, reducing the depth of intrusion of fluid and filtrate.
And (5) testing: effect on the Life of the microfoam fluid
Preparing 2% of soil-shifting slurry and 0.3% of DSP-II base slurry, adding 0.2% of AOS and 0.1% of SDS foaming agent while stirring by using a low-speed strong stirrer under the stirring environment with the shear rate of 1000r/min, stirring for 2h to form a micro-foam base solution, then adding 1% -5% of example 2 with different concentrations into the base solution, continuously stirring for 1h, pouring into a 500mL measuring cylinder, observing the micro-foam initial analysis and half-life time, and obtaining the test results as shown in the table below.
Table 12 example 2 effect on microfoam stability
Example 2 significantly improves the stability of the microfoam fluid.
Example 3:
adding 25 parts of water glass and 2 times of distilled water into a reaction container, adding 30% phosphoric acid solution while stirring to adjust the pH to 2, hydrolyzing for 1h, adding ammonia water to adjust the pH to 5.5, stirring until gel is separated out, and standing for 2 h; immersing in ethanol and isopropanol solution for surface modification, standing for 24h, press filtering the gel, drying and pulverizing at 65 deg.C, immersing in 80% n-hexane solution for 16h, removing solvent, and drying again. Adding the obtained low-density silicon dioxide powder particles and 4.7 parts of polypropylene resin powder particles into a high-speed premixer, mixing and stirring for 25min, spraying a 10% silane coupling agent solution on the mixed material in a high-speed stirring state, continuously mixing for 20min, and drying for 2h in an environment of 120 ℃. And uniformly mixing the powder particles obtained by secondary drying and 3.6 parts of polyethylene powder particles to obtain the sample of the embodiment 3.
Test 1: example 3 dispersibility test.
50mL of clear water was measured, placed on a magnetic stirrer, and 1g of example 3 was added while stirring, and the dispersion solubility of the sample was observed, and the results are shown in Table 13.
Table 13 example 3 dispersion solubility
| Sample (I) | Time of dispersion |
| Example 3 | 4.5min |
Example 3 has good dispersion and dissolution properties.
And (3) testing 2: example 3 Density testing
The apparent density of the free-flowing powder of example 3 was tested using GB/T13175-1991 and was 1.03g/cm3。
And (3) testing: example 3 Effect on rheology
2%, 4% and 6% earth moving slurries were prepared, 3% of example 3 was added to each slurry, and the rheology and filter press loss were measured before and after the addition of example 3, with the test results shown in the following table.
Table 14 example 3 effect on base stock rheology
| Formulation of | FL/mL | ρ/g/cm3 | AV/mPa.s | PV/mPa.s |
| 2% earth moving slurry | 60 | 1.010 | 2.5 | 1.5 |
| 2% Carrier slurry + 3% EXAMPLE 3 | 56.6 | 1.011 | 3.5 | 2 |
| 4% soil-shifting slurry | 32 | 1.030 | 8.5 | 5 |
| 4% Furring slurry + 3% EXAMPLE 3 | 26.4 | 1.031 | 10.5 | 6 |
| 6% earth moving slurry | 21.4 | 1.050 | 16 | 8.5 |
| 6% Carrier slurry + 3% EXAMPLE 3 | 13.8 | 1.051 | 20 | 10.5 |
Example 3 has no effect on the viscosity and density of 2-6% base slurry, and obviously reduces medium pressure filtration loss.
Preparing 2% of soil-shifting slurry and 0.3% of DSP-II base slurry, adding 0.2% of AOS and 0.1% of SDS foaming agent while stirring by using a low-speed strong stirrer under the stirring environment with the shearing rate of 1000r/min, and stirring for 2 hours to form micro-foam base liquid; then, the example 3 with different concentrations of 1-5% is added into the base solution, the stirring is continued for 1h, the rheological property of the micro-foam fluid and the filter pressing loss before and after the addition of the example 3 are tested, and the test results are shown in the following table.
Table 15 example 3 effect on microfoam base fluid rheology
| Formulation of | ρ(g/cm3) | FL(mL) | AV(mPa.s) | PV(mPa.s) |
| Base liquid | 0.66 | 12 | 16.5 | 10 |
| Base liquid + 1% example 3 | 0.59 | 10.2 | 31.5 | 18.5 |
| Base liquid + 3% example 3 | 0.53 | 5.8 | 35 | 20 |
| Base fluid + 5% example 3 | 0.50 | 5.2 | 38.5 | 23.5 |
Example 3 after the addition of the microfoam base fluid, the density and filter press losses gradually decreased and the base fluid viscosity gradually increased.
And (3) testing: normal temperature medium pressure plugging performance test
Preparing 2% of soil-moving slurry and 0.3% of comb-shaped polymer filtrate reducer base slurry, adding 0.2% of AOS and 0.1% of SDS foaming agent while stirring by using a low-speed strong stirrer under the stirring environment with the shear rate of 1000r/min, stirring for 2h to form micro-foam base fluid, then adding 1% -5% of example 3 with different concentrations into the base fluid, continuously stirring for 1h, testing the plugging performance of the micro-foam fluid before and after the addition of the example 3 by using an FA type normal-temperature medium-pressure sand bed filtrate reducer (the longitudinal thickness of a sand bed is 20cm) at normal temperature and after hot rolling aging at 180 ℃/16h and 200 ℃/16 h. The test results are shown in the table below.
Table 16 example 3 medium pressure sand bed plugging performance
Example 3 significantly improves the plugging performance of the microfoam fluid.
And (4) testing: high temperature high pressure plugging performance test
Preparing 2% of soil-shifting slurry, 0.2% of TFS, 0.3% of DSP-II and 0.2% of SPNH base slurry, adding 0.2% of AOS and 0.1% of SDS foaming agent while stirring under the stirring environment with the shearing rate of 1100r/min by using a low-speed strong stirrer, stirring for 2 hours to form a micro-foam base fluid, then adding 3% of example 3 with different concentrations into the base fluid, continuously stirring for 1 hour, and testing the micro-foam fluid invasion depth within 30 minutes under the environment with 180 ℃/3.5MPa and 200 ℃/3.5MPa by using a high-temperature high-pressure sand bed filtration instrument (the vertical thickness of a sand bed is 500cm) before and after the micro-foam fluid is added into the example 3, wherein the test results are shown in the table below.
TABLE 17 example 3 high temperature high pressure sand bed plugging Performance
Example 3 significantly improves the plugging performance of the microfoam base fluid in high temperature environments, reducing the depth of intrusion of the base fluid and filtrate.
And (5) testing: effect on the Life of the microfoam fluid
Preparing 2% of soil-shifting slurry and 0.3% of DSP-II base slurry, adding 0.2% of AOS and 0.1% of SDS foaming agent while stirring by using a low-speed strong stirrer under the stirring environment with the shear rate of 1000r/min, stirring for 2h to form a micro-foam base solution, then adding 1% -5% of example 3 with different concentrations into the base solution, continuously stirring for 1h, pouring into a 500mL measuring cylinder, observing the micro-foam initial analysis and half-life time, and obtaining the test results as shown in the table below.
Table 18 example 3 effect on microfoam stability
Example 3 significantly improves the stability of the microfoam fluid.
Example 4:
adding 20 parts of water glass and 2 times of distilled water into a reaction container, adding 30% phosphoric acid solution while stirring to adjust the pH to 2, hydrolyzing for 1h, adding ammonia water to adjust the pH to 6.5, stirring until gel is separated out, and standing for 2 h; immersing in ethanol and isopropanol solution for surface modification, standing for 24h, press filtering the gel, drying and pulverizing at 65 deg.C, immersing in 80% n-hexane solution for 16h, removing solvent, and drying again. Adding the obtained low-density silicon dioxide powder particles and 3.75 parts of polypropylene resin powder particles into a high-speed premixer, mixing and stirring for 25min, spraying a 10% silane coupling agent solution on the mixed material in a high-speed stirring state, continuously mixing for 20min, and drying for 2h in an environment at 130 ℃. And uniformly mixing the powder particles obtained by secondary drying and 6.25 parts of polyethylene powder particles to obtain the sample of the embodiment 4.
Test 1: example 4 dispersibility test.
50mL of clear water was measured, placed on a magnetic stirrer, and 1g of example 4 was added with stirring, and the dispersion solubility of the sample was observed, and the results are shown in Table 19.
Table 19 example 4 dispersion solubility
Example 4 had good dispersion and dissolution properties.
And (3) testing 2: example 4 Density testing
The apparent density of the free-flowing powder of example 4 was tested using GB/T13175-1991,is 0.81g/cm3。
And (3) testing: example 4 testing for the Effect on rheology
2%, 4% and 6% earth moving slurries were prepared, 3% of example 4 was added to each slurry, and the rheology and filter press loss were measured before and after the addition of example 4, with the test results shown in the following table.
Table 20 example 4 effect on base stock rheology
| Formulation of | FL/mL | ρ/g/cm3 | AV/mPa.s | PV/mPa.s |
| 2% earth moving slurry | 60 | 1.01 | 2.5 | 1.5 |
| 2% Carrier slurry + 3% EXAMPLE 4 | 53.6 | 1 | 4.5 | 2.5 |
| 4% soil-shifting slurry | 32 | 1.03 | 8.5 | 5 |
| 4% Furring slurry + 3% EXAMPLE 4 | 22.8 | 1.02 | 12.5 | 7 |
| 6% earth moving slurry | 21.4 | 1.05 | 16 | 8.5 |
| 6% Furring slurry + 3% EXAMPLE 4 | 10.2 | 1.04 | 21.5 | 11 |
Example 4 has less impact on the viscosity and density of 2-6% base slurry, and the medium pressure filtration loss is obviously reduced.
Preparing 2% of soil-shifting slurry and 0.3% of DSP-II base slurry, adding 0.2% of AOS and 0.1% of SDS foaming agent while stirring by using a low-speed strong stirrer under the stirring environment with the shearing rate of 1000r/min, and stirring for 2 hours to form micro-foam base liquid; then, the example 4 with different concentrations of 1-5% is added into the base solution, the stirring is continued for 1h, the rheological property of the micro-foam fluid and the filter pressing loss before and after the addition of the example 4 are tested, and the test results are shown in the following table.
TABLE 21 rheology effects of example 4 on microfoam base fluids
| Formulation of | ρ(g/cm3) | FL(mL) | AV(mPa.s) | PV(mPa.s) |
| Base liquid | 0.66 | 12 | 16.5 | 10 |
| Base fluid + 1% example 4 | 0.57 | 8.6 | 32.5 | 18.5 |
| Base fluid + 3% example 4 | 0.47 | 4.8 | 37.5 | 21 |
| Base fluid + 5% example 4 | 0.41 | 4.2 | 41 | 23.5 |
Example 4 after addition of the microfoam base fluid, the density and filter press losses gradually decreased and the base fluid viscosity gradually increased.
And (3) testing: normal temperature medium pressure plugging performance test
Preparing 2% of soil-moving slurry and 0.3% of comb-shaped polymer filtrate reducer base slurry, adding 0.2% of AOS and 0.1% of SDS foaming agent while stirring by using a low-speed strong stirrer under the stirring environment with the shear rate of 1000r/min, stirring for 2h to form micro-foam base fluid, then adding 1% -5% of example 4 with different concentrations into the base fluid, continuously stirring for 1h, testing the plugging performance of the micro-foam fluid before and after the addition of the example 4 by using an FA type normal-temperature medium-pressure sand bed filtrate reducer (the longitudinal thickness of a sand bed is 20cm) at normal temperature and after hot rolling aging at 180 ℃/16h and 200 ℃/16 h. The test results are shown in the table below.
TABLE 22 example 4 Medium pressure sand bed plugging Performance
Example 4 significantly improves the plugging performance of the microfoam fluid.
And (4) testing: high temperature high pressure plugging performance test
Preparing 2% of soil-shifting slurry, 0.2% of TFS, 0.3% of DSP-II and 0.2% of SPNH base slurry, adding 0.2% of AOS and 0.1% of SDS foaming agent while stirring under the stirring environment with the shearing rate of 1100r/min by using a low-speed strong stirrer, stirring for 2 hours to form a micro-foam base fluid, then adding 3% of example 4 with different concentrations into the base fluid, continuously stirring for 1 hour, and testing the micro-foam fluid invasion depth within 30 minutes under the environment with 180 ℃/3.5MPa and 200 ℃/3.5MPa by using a high-temperature high-pressure sand bed filtration instrument (the vertical thickness of a sand bed is 500cm) before and after the micro-foam fluid is added into the example 4, wherein the test results are shown in the table below.
TABLE 23 example 4 high temperature high pressure sand bed plugging performance
Example 4 reduces the invasion depth of fluid and filtrate in the high-temperature environment of the micro-foam fluid, improves the high-temperature plugging performance of the low-density fluid, and compared with base fluid, the invasion depth of the fluid is reduced by 65.7%, and the invasion depth of the filtrate is reduced by 68.6%.
And (5) testing: effect on the Life of the microfoam fluid
Preparing 2% of soil-shifting slurry and 0.3% of DSP-II base slurry, adding 0.2% of AOS and 0.1% of SDS foaming agent while stirring by using a low-speed strong stirrer under the stirring environment with the shear rate of 1000r/min, stirring for 2h to form a micro-foam base solution, then adding 1% -5% of example 4 with different concentrations into the base solution, continuously stirring for 1h, pouring into a 500mL measuring cylinder, observing the micro-foam initial analysis and half-life time, and obtaining the test results as shown in the table below.
Table 24 example 4 effect on microfoam stability
Example 4 improves the stability of the microfoam fluid.
Of course, only specific data of each component is listed in examples 1 to 4, but in the specific implementation process, adaptive adjustment may be performed within the range of each component as needed, and details are not repeated here.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (12)
1. A low-density high-temperature plugging agent comprises the following components in parts by volume:
20-40 parts of water glass, 5-18 parts of resin and 2-5 parts of silane coupling agent.
2. The low-density high-temperature plugging agent according to claim 1, wherein the water glass modulus is 2-3.5.
3. The low density high temperature plugging agent according to claim 1, wherein said resin is a low density resin.
4. The low-density high-temperature plugging agent according to claim 3, wherein the density of the low-density resin is 0.8-1.4 g/cm3。
5. The low-density high-temperature plugging agent according to claim 3, wherein the low-density resin is one of natural resin, thermoplastic resin or a mixture thereof.
6. The low-density high-temperature plugging agent according to claim 5, wherein the low-density resin is one of rosin resin, acryl resin, vinyl resin or a mixture thereof.
7. The low-density high-temperature plugging agent according to claim 1, wherein the silane coupling agent is one or a mixture of KH-550, KH-560 or KH-570.
8. The low-density high-temperature plugging agent according to claim 7, wherein said silane coupling agent is KH-560.
9. The preparation method of the low-density high-temperature plugging agent is characterized by comprising the following steps of:
(1) adding water glass into a reaction container, adding 2 times of distilled water, uniformly stirring, adding 30% phosphoric acid solution while stirring, adjusting the pH to 2-3, and hydrolyzing and stirring for 0.5-1 h; adding ammonia water, adjusting the pH value to 5-7, continuously stirring until gel is separated out, and standing for 0.5-2 h; adding ethanol and isopropanol which are uniformly mixed while stirring for surface modification, and stirring for 1-2 h; standing for 24h, performing filter pressing on the gel, drying and crushing the gel at the temperature of 50-80 ℃, soaking the gel in 80% n-hexane solution for 8-16 h, removing the solvent, and drying again to obtain low-density nano silicon dioxide particles;
(2) adding low-density silicon dioxide powder particles and resin powder particles into a high-speed premixer according to the volume ratio of 4: 1-3: 1, mixing and stirring for 20-30 min, spraying a 10% silane coupling agent solution on the mixed material under the high-speed stirring state, continuously mixing for 20-30 min, and drying for 1-2 h at the temperature of 100-130 ℃;
(3) and uniformly mixing the powder particles obtained by secondary drying and the rest resin to obtain the low-density high-temperature plugging agent.
10. The low density high temperature plugging agent according to any one of claims 1 to 8, wherein the agent is used in high temperature lost circulation formations, high temperature low pressure formations.
11. The low density high temperature plugging agent according to any one of claims 1 to 8, wherein the agent is used for the synergistic compatibility of low density fluid or conventional water-based working fluid.
12. The low density high temperature plugging agent of claim 11 wherein said low density fluid is a high temperature recyclable micro-foam drilling or completion fluid, a high temperature aerated foam drilling or completion fluid.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114381253A (en) * | 2022-03-24 | 2022-04-22 | 中国石油大学(华东) | Thixotropic type reinforced foam system and preparation method thereof |
| CN118460191A (en) * | 2024-07-09 | 2024-08-09 | 成都西油华巍科技有限公司 | Oil-gas layer protective agent for drilling fluid |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004300363A (en) * | 2003-04-01 | 2004-10-28 | Shin Etsu Chem Co Ltd | Room temperature-curable organopolysiloxane composition |
| US7762329B1 (en) * | 2009-01-27 | 2010-07-27 | Halliburton Energy Services, Inc. | Methods for servicing well bores with hardenable resin compositions |
| US20100282465A1 (en) * | 2009-05-08 | 2010-11-11 | Halliburton Energy Services, Inc. | Methods of consolidating particulates using a hardenable resin and an orgaosilane coupling agent |
| CN103102876A (en) * | 2012-12-31 | 2013-05-15 | 哈尔滨工业大学 | Preparation method for inorganic-organic composite type profile control agent |
| CN106047322A (en) * | 2016-06-03 | 2016-10-26 | 唐山市金沙工贸有限公司 | Locating high-strength blocking crack deflection fracturing resin coated sand and application process technology |
| US9790415B1 (en) * | 2016-05-11 | 2017-10-17 | China University Of Petroleum (Beijing) | Modified silicon dioxide nano-particles and preparation method thereof, and drilling fluid suitable for shale gas wells |
| US20190023964A1 (en) * | 2016-04-27 | 2019-01-24 | Halliburton Energy Services, Inc. | Additive to enhance sag stability of drilling fluid |
| CN110117486A (en) * | 2019-05-06 | 2019-08-13 | 河北工业大学 | A kind of plugging material that epoxy resin/floating bead is compound |
| CN111303643A (en) * | 2020-02-22 | 2020-06-19 | 西南石油大学 | SiO of core-shell structure2@ paraffin nanoparticle and preparation method thereof |
-
2020
- 2020-07-23 CN CN202010714140.0A patent/CN113969148B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004300363A (en) * | 2003-04-01 | 2004-10-28 | Shin Etsu Chem Co Ltd | Room temperature-curable organopolysiloxane composition |
| US7762329B1 (en) * | 2009-01-27 | 2010-07-27 | Halliburton Energy Services, Inc. | Methods for servicing well bores with hardenable resin compositions |
| US20100282465A1 (en) * | 2009-05-08 | 2010-11-11 | Halliburton Energy Services, Inc. | Methods of consolidating particulates using a hardenable resin and an orgaosilane coupling agent |
| CN103102876A (en) * | 2012-12-31 | 2013-05-15 | 哈尔滨工业大学 | Preparation method for inorganic-organic composite type profile control agent |
| US20190023964A1 (en) * | 2016-04-27 | 2019-01-24 | Halliburton Energy Services, Inc. | Additive to enhance sag stability of drilling fluid |
| US9790415B1 (en) * | 2016-05-11 | 2017-10-17 | China University Of Petroleum (Beijing) | Modified silicon dioxide nano-particles and preparation method thereof, and drilling fluid suitable for shale gas wells |
| CN106047322A (en) * | 2016-06-03 | 2016-10-26 | 唐山市金沙工贸有限公司 | Locating high-strength blocking crack deflection fracturing resin coated sand and application process technology |
| CN110117486A (en) * | 2019-05-06 | 2019-08-13 | 河北工业大学 | A kind of plugging material that epoxy resin/floating bead is compound |
| CN111303643A (en) * | 2020-02-22 | 2020-06-19 | 西南石油大学 | SiO of core-shell structure2@ paraffin nanoparticle and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| TIANTIAN ZHANG等: "Engineered Nanoparticles as Harsh-Condition Emulsion and Foam Stabilizers and as Novel Sensors", 《OFFSHORE TECHNOLOGY CONFERENCE》 * |
| 苏俊霖等: "抗高温无机/有机复合纳米降滤失剂室内研究", 《断块油气田》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114381253A (en) * | 2022-03-24 | 2022-04-22 | 中国石油大学(华东) | Thixotropic type reinforced foam system and preparation method thereof |
| CN114381253B (en) * | 2022-03-24 | 2022-06-07 | 中国石油大学(华东) | Thixotropic type reinforced foam system and preparation method thereof |
| CN118460191A (en) * | 2024-07-09 | 2024-08-09 | 成都西油华巍科技有限公司 | Oil-gas layer protective agent for drilling fluid |
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