CN112646564A - Magnetic hydrophobic proppant and preparation method thereof - Google Patents
Magnetic hydrophobic proppant and preparation method thereof Download PDFInfo
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- CN112646564A CN112646564A CN201910952462.6A CN201910952462A CN112646564A CN 112646564 A CN112646564 A CN 112646564A CN 201910952462 A CN201910952462 A CN 201910952462A CN 112646564 A CN112646564 A CN 112646564A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 20
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- 229920005989 resin Polymers 0.000 claims abstract description 55
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- 238000002156 mixing Methods 0.000 claims abstract description 11
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- 239000004925 Acrylic resin Substances 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
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- 238000000034 method Methods 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- 239000006004 Quartz sand Substances 0.000 claims description 9
- 239000000696 magnetic material Substances 0.000 claims description 8
- 229920005749 polyurethane resin Polymers 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 235000009496 Juglans regia Nutrition 0.000 claims description 3
- 235000020234 walnut Nutrition 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 229920002050 silicone resin Polymers 0.000 claims description 2
- 240000007049 Juglans regia Species 0.000 claims 1
- QXJJQWWVWRCVQT-UHFFFAOYSA-K calcium;sodium;phosphate Chemical compound [Na+].[Ca+2].[O-]P([O-])([O-])=O QXJJQWWVWRCVQT-UHFFFAOYSA-K 0.000 claims 1
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- 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
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/80—Compositions for reinforcing fractures, e.g. compositions of proppants used to keep the fractures open
- C09K8/805—Coated proppants
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- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
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- Materials Engineering (AREA)
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- Hard Magnetic Materials (AREA)
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Abstract
The invention relates to a magnetic hydrophobic proppant and a preparation method thereof. And blending the proppant aggregate and liquid hydrophobic resin glue containing magnetic powder, and then curing to obtain the magnetic proppant. The invention adopts the hydrophobic resin glue solution containing magnetic powder to coat the modified proppant aggregate, has strong universality, is suitable for various conventional proppants such as raw sand, ceramsite and the like, is suitable for preparing the tonnage proppant, and has simple and easy operation. Not only the density of the magnetic hydrophobic proppant is reduced, but also the preparation cost is greatly reduced.
Description
Technical Field
The invention relates to a magnetic hydrophobic proppant and a preparation method thereof, belonging to the technical field of hydraulic fracturing in the process of oil and natural gas exploitation.
Background
The hydraulic fracturing is an important technical means for increasing the yield of oil and gas wells, plays a key role in increasing the yield of conventional low-permeability and ultra-low-permeability oil and gas reservoirs and shale and compact sandstone reservoirs of unconventional oil and gas reservoirs, and particularly plays a role in increasing the yield of unconventional reservoirs without hydraulic fracturing, so that underground oil and gas are difficult to extract. Hydraulic fracturing is to pump fracturing fluid into a stratum by using a high-pressure pump set to form one or more cracks with certain geometric dimensions in the stratum, wherein the length of the crack is generally dozens of meters to hundreds of meters, the height of the crack is dozens of meters to dozens of meters, and the width of the crack is a few millimeters. A sand-carrying fluid (a mixture of fracturing fluid and proppant) with proppant is then injected into the fracture. After fracturing, fracturing fluid gel is broken and is drained back to the ground, the propping agent is left in the fracture to play a role in propping the fracture, the fracture is kept in an open state, and pores among propping agent particles provide a flow channel for formation oil, gas and water, so that the fracturing yield increase effect is achieved. The proppant is one of the key factors for improving the yield effect, and the good proppant has higher flow conductivity (the width of a fracture is multiplied by the permeability of the fracture) and can provide a smooth flow channel for oil, gas and water.
The traditional propping agent mainly comprises three main types of natural sand, resin-coated sand and ceramsite, and generally, the strength and the flow conductivity are sequentially enhanced. Selecting different types of proppants according to the characteristics of stratum, depth and the like of a fracturing area, and mainly comprising the following steps: natural quartz sand, artificial ceramsite, glass microsphere, walnut shell, high-molecular synthetic microsphere and the like. After the proppant is pumped into the stratum, adverse factors such as backflow, embedding, dissolution, crushing and the like can occur, and the proppant has no selectivity to oil and water. One well fracturing needs from tens to hundreds of tons of proppant, and unconventional reservoir fracturing of shale and the like often needs from thousands to tens of thousands of tons of proppant.
The purpose of well fracturing is to increase the production of oil and reduce the production of water as much as possible. The conventional fracturing propping agent has no water control and oil increasing effects, so that the water content of some oil wells is too high after fracturing, the development result is high, and the yield increasing effect is not ideal.
Chinese patent document CN 106546658A discloses an apparatus for measuring proppant distribution in a rock formation and a measuring method thereof. The specific process for manufacturing the magnetic proppant is as follows: selecting a plurality of small iron particles and magnetizing the small iron particles; sieving and selecting qualified products; mixing oil shale waste, bauxite, manganese mineral powder, iron powder and a binder according to a certain proportion, attaching the mixture to the outer surface of the small iron particles, and uniformly coating a layer of resin on the outermost layer of the small iron particles to prepare the proppant. Therefore, the main solid material of the magnetic proppant is an iron material, and the magnetic proppant has higher density and higher cost than the traditional sand and ceramsite.
Chinese patent document CN105670600A discloses a water-acid-sensitive deformation magnetic tracing function self-suspending proppant and a preparation method thereof, wherein the magnetic additive used in the magnetic proppant is a magnetic rare earth material, the cost is high, the addition amount is small, the magnetic strength is low, and the main key performance is the self-suspending function generated by coating a water bloom layer.
Chinese patent document CN109423271A discloses a bulk-expanded magnetic self-suspending proppant and a preparation method thereof; chinese patent document CN109423270A discloses an adhesion-promoting type magnetic self-suspending proppant beneficial for fracture monitoring and a preparation method thereof. The aggregate of the magnetic proppant used in the two methods is Fe3O4、γ-Fe2O3、CoFe2O4、MnFe2O4And NiFe2O4At least one of the sand and the ceramsite has higher density and higher cost than the traditional sand and ceramsite.
In a word, the application of the existing magnetic proppant in the fracturing process is mostly researched, but the defects of high preparation or modification cost, high magnetic material density, complex preparation process and the like exist.
Therefore, it is necessary to develop a high magnetic force propping agent with simple operation, simple process flow and strong universality, and simultaneously reduce the cost and the harm degree to human bodies and the environment.
Disclosure of Invention
Aiming at the defects of the prior art, particularly the defects of high density and high cost caused by the fact that the existing magnetic proppant mostly takes magnetic substances as aggregates, the invention provides a magnetic hydrophobic proppant and a preparation method thereof. The proppant disclosed by the invention does not need a process of adding other chemical additives except the magnetic hydrophobic glue solution, the improved proppant has good and stronger magnetic property, is suitable for various proppants such as raw sand, ceramsite and the like, and reduces the complexity of chemical reaction and operation implementation in the traditional modification process. The method has strong universality, is suitable for different sizes and different types of proppants, can reduce the cost of hydrophobic modification of the proppants, and is suitable for large-scale industrial application.
The invention is realized by the following technical scheme:
the magnetic hydrophobic proppant comprises proppant aggregate, wherein the surface of the proppant aggregate is coated with magnetic hydrophobic resin, and the magnetic hydrophobic resin comprises a magnetic material and hydrophobic resin.
According to the invention, the proppant aggregate is preferably common proppant such as quartz sand or ceramsite or various proppant such as walnut shell and glass ball. Preferably, the particle size of the proppant aggregate is 20-140 meshes. The invention can adopt the conventional proppant as the aggregate, has wide applicability, low density and low cost, and is very beneficial to large-scale popularization and application.
According to the present invention, preferably, the magnetic material is magnetic powder, which is a hard magnetic single domain particle, and is commercially available. The magnetic powder can also be obtained by magnetizing iron powder. The particle size range of the magnetic powder is 100 nanometers to 5 micrometers.
According to the present invention, preferably, the hydrophobic resin is fluorinated acrylic resin, fluorinated dopamine resin, acrylate resin, silicone resin, polyurethane resin, epoxy resin or other resins with similar properties. The hydrophobic resin is selected, so that the magnetic proppant is endowed with a hydrophobic function, the strength of the proppant can be increased, the proppant is prevented from being embedded, the dissolution degree of the proppant under the high-temperature and high-pressure conditions of the stratum is reduced, the migration of broken proppant fragments is prevented, and the like.
According to the present invention, preferably, the mass ratio of the magnetic powder to the hydrophobic resin in the magnetic hydrophobic resin is 100: (60-90), more preferably 100: (70-80).
According to the invention, preferably, the mass ratio of the proppant aggregate to the magnetic hydrophobic resin is 100: (10-50), more preferably 100: (20-40). The magnetic material has too low specific gravity, which causes poor coating degree, uneven coating and exposed ceramsite; the excessive magnetic material is separated from the proppant material due to the overlarge specific gravity of the magnetic material, and the improvement degree of the exposed ceramsite is small.
According to the invention, the preparation method of the magnetic hydrophobic proppant comprises the following steps:
and blending the proppant aggregate and liquid hydrophobic resin glue containing magnetic powder, and then curing to obtain the magnetic proppant.
According to the invention, preferably, the curing mode is that the used proppant aggregate is preheated or is heated after being added with the liquid hydrophobic resin glue solution, so that the liquid hydrophobic resin glue solution is cured;
further preferably, the proppant aggregate and the liquid hydrophobic resin glue containing the magnetic powder are mixed and heated to 30-90 ℃ under the stirring condition for 0.2-6 hours to be cured.
According to the preparation method of the magnetic hydrophobic proppant, a preferred embodiment comprises the following steps:
(1) cleaning the proppant aggregate with water, acid liquor or alkali liquor for 0.5-3 hours to obtain the cleaned proppant aggregate;
(2) adding the magnetic powder into the liquid hydrophobic resin glue solution, and uniformly mixing to obtain a magnetic hydrophobic resin glue solution;
(3) adding the magnetic hydrophobic resin glue solution into the cleaned proppant aggregate, and stirring at a constant speed for 5-60 minutes to blend the proppant aggregate and the magnetic hydrophobic resin glue solution to obtain a blend;
(4) and heating the blend to 30-90 ℃ under the stirring condition for 0.2-6 hours, and curing to obtain the magnetic hydrophobic modified proppant.
The liquid hydrophobic resin glue solution used in the invention is a conventional hydrophobic glue solution, can be purchased or prepared in laboratories, such as acrylic acid, acrylate, dopamine, epoxy, polyurethane, organosilicon hydrophobic glue solutions and the like, and the hydrophobic time is selected according to the difference of the type and the hydrophobic effect of the glue solution. The raw materials and equipment used in the invention are the prior art unless otherwise specified.
The invention has the following beneficial effects:
1. the invention adopts the hydrophobic resin glue solution containing magnetic powder to coat the modified proppant aggregate, has strong universality, is suitable for various conventional proppants such as raw sand, ceramsite and the like, is suitable for preparing the tonnage proppant, and has simple and easy operation. Not only the density of the magnetic hydrophobic proppant is reduced, but also the preparation cost is greatly reduced.
2. The hydrophobic resin glue solution used in the invention is a conventional hydrophobic glue solution, the raw material source is wide and easy to obtain, and the modified magnetic hydrophobic proppant has good magnetism and surface hydrophobicity through tests, is beneficial to being used in high-speed channel fracturing and is beneficial to oil and gas exploitation.
3. The invention carries out surface treatment on the existing proppant, realizes new functions of magnetism and hydrophobicity, and can increase the strength of the proppant, prevent the proppant from being embedded, reduce the dissolution degree of the proppant under the conditions of high temperature and high pressure of the stratum and prevent the transportation of broken proppant fragments. The method does not need to change the components and the production process of the proppant, and has the characteristics of simple operation, low cost, short production time, suitability for large-scale industrial application and the like.
Drawings
FIG. 1 is a diagram of a magnetic hydrophobically modified ceramsite product prepared in example 2;
FIG. 2 is a drawing showing the magnetic attraction of the magnetic hydrophobic modified ceramsite prepared in example 2;
FIG. 3 is a diagram of a magnetic hydrophobically modified ceramsite product prepared in comparative example 2.
Detailed Description
The present invention is further illustrated by, but is not limited to, the following specific examples.
Example 1
The magnetic hydrophobic modified proppant is obtained by adding a magnetic hydrophobic resin glue solution into proppant aggregate, uniformly stirring to enable the magnetic hydrophobic glue solution to wet the surface of the proppant and then curing.
The preparation method comprises the following steps:
(1) the liquid hydrophobic acrylic resin pre-cured glue solution prepared by the prior art can refer to the synthesis of a von-Harden hydrophobic modified acrylic emulsion thickening agent and the rheological behavior [ D ]. university of south China's science and technology, 2011.
(2) Washing the quartz sand with different grain diameters by water, acid liquor or alkali liquor for 2 hours to obtain washed quartz sand;
(3) adding 80% by mass of magnetic powder into the liquid hydrophobic acrylic resin glue solution, and uniformly mixing to prepare a liquid magnetic resin glue solution; the magnetic powder is hard magnetic single domain particles and can be purchased in the market;
(4) taking 50 parts of liquid magnetic hydrophobic acrylic resin glue solution and 100 parts of cleaned quartz sand, adding the magnetic hydrophobic acrylic resin glue solution into the cleaned quartz sand, and stirring to uniformly mix the quartz sand and the magnetic hydrophobic acrylic resin glue solution so as to achieve the effect that the surface of the quartz sand is coated by the magnetic hydrophobic acrylic resin glue solution; and then heating to 60 ℃, discharging after 2 hours, and cooling to obtain the magnetic hydrophobic modified proppant.
Example 2
A magnetic hydrophobic modified proppant is prepared by adding a hydrophobic dopamine resin liquid solution containing magnetized iron powder into proppant aggregate, uniformly stirring to enable the hydrophobic dopamine resin liquid solution containing magnetized iron powder particles to coat the surface of the proppant aggregate, and then curing.
The preparation method comprises the following steps:
(1) hydrophobic dopamine resin gels are prepared by the prior art, as referenced by Wang X L, Ye Q A, Liu J X, et al, Low surface energy surfaces from self-assembly of a fluorinated with mechanical functional groups [ J ]. Journal of Colloid and Interface Science,2010,351(1): 261-.
(2) Cleaning the ceramsite with water, acid liquor or alkali liquor for 2 hours to obtain the cleaned ceramsite;
(3) adding 70% by mass of magnetized iron powder into the liquid hydrophobic dopamine resin glue solution, and uniformly mixing to prepare a liquid magnetic dopamine resin glue solution;
(4) taking 45 parts of magnetic hydrophobic dopamine resin glue solution and 100 parts of cleaned ceramsite, adding the magnetic hydrophobic dopamine resin glue solution into the cleaned ceramsite, and uniformly stirring for 30 minutes to uniformly mix the ceramsite and the magnetic hydrophobic dopamine resin glue solution; and then heating to 60 ℃, discharging after 2 hours, and cooling to obtain the magnetic hydrophobic modified proppant.
The photo of the magnetic hydrophobic modified proppant obtained in this example is shown in fig. 1, and the photo of the magnetic adsorption effect is shown in fig. 2. As can be seen from figures 1 and 2, the magnetic hydrophobic modified proppant disclosed by the invention is uniform in surface coating and has stronger magnetism.
Example 3
The magnetic hydrophobic modified proppant is obtained by adding a magnetic hydrophobic resin glue solution into proppant aggregate, uniformly stirring to enable the magnetic hydrophobic glue solution to wet the surface of the proppant and then curing.
The preparation method comprises the following steps:
(1) the liquid hydrophobic fluorinated acrylic resin glue solution prepared by the prior art can refer to Wuyang, soft matter interface friction drag reduction regulation and control research [ D ]. Lanzhou chemical and physical research institute of Chinese academy of sciences, 2015.
(2) Cleaning the glass balls with different particle sizes with water, acid liquor or alkali liquor for 2 hours to obtain the cleaned glass balls;
(3) adding 60% by mass of magnetic powder into the liquid hydrophobic fluorinated acrylic resin glue solution, and uniformly mixing to prepare a liquid magnetic resin glue solution; the magnetic powder is hard magnetic single domain particles and can be purchased in the market;
(4) taking 20 parts of liquid magnetic hydrophobic fluorinated acrylic resin glue solution and 100 parts of cleaned glass balls, adding the magnetic hydrophobic fluorinated acrylic resin glue solution into the cleaned glass balls, and stirring to uniformly mix the glass balls with the magnetic hydrophobic fluorinated acrylic resin glue solution so as to achieve the effect that the surfaces of the glass balls are coated by the magnetic hydrophobic fluorinated acrylic resin glue solution; and then heating to 40 ℃, discharging after 5 hours, and cooling to obtain the magnetic hydrophobic modified proppant.
Example 4
The magnetic hydrophobic modified proppant is obtained by adding a hydrophobic polyurethane resin glue solution containing magnetized iron powder into proppant aggregate, uniformly stirring to enable the hydrophobic polyurethane resin glue solution containing magnetized iron powder particles to coat the surface of the proppant aggregate, and then curing.
The preparation method comprises the following steps:
(1) the hydrophobic polyurethane resin glue solution prepared by adopting the prior art can refer to the preparation and performance research [ D ] of the Wanhao vinyl acrylic polyurethane hydrophobic anticorrosive paint, Harbin university, 2011.
(2) Cleaning the ceramsite with water, acid liquor or alkali liquor for 2 hours to obtain the cleaned ceramsite;
(3) adding 85% by mass of magnetized iron powder into the liquid hydrophobic polyurethane resin glue solution, and uniformly mixing to prepare a liquid magnetic dopamine resin glue solution;
(4) taking 30 parts of magnetic hydrophobic dopamine resin glue solution and 100 parts of cleaned ceramsite, adding the magnetic hydrophobic polyurethane resin glue solution into the cleaned ceramsite, and uniformly stirring for 30 minutes to uniformly mix the ceramsite and the magnetic hydrophobic polyurethane resin glue solution; and then heating to 70 ℃, discharging after 1 hour, and cooling to obtain the magnetic hydrophobic modified proppant.
Comparative example 1
As described in example 2, except that:
and (3) directly adding the magnetized iron powder into the hydrophobic dopamine resin glue solution, uniformly mixing, and curing to obtain the magnetic hydrophobic modified proppant.
Comparative example 2
As described in example 2, except that:
and (3) taking 70 parts of magnetic hydrophobic dopamine resin glue solution and 100 parts of cleaned ceramsite, and uniformly mixing.
The effect is shown in figure 3.
As can be seen from FIG. 3, the content of the magnetic hydrophobic dopamine resin colloidal solution is too high, so that the ceramsite cannot be completely coated, and a large amount of aggregates occur.
Test example 1
The density and aqueous suspension of the proppants obtained in example 2 and comparative example 1 were tested, and the results are shown in table 1.
TABLE 1
| Index (I) | Example 2 | Comparative example 1 |
| Density g/cm3 | 1.8 | 6.9 |
| Suspensibility in aqueous solution | Float | Precipitation of |
As can be seen from table 1, the proppant obtained in comparative example 1 in which the resin cement was directly coated with the magnetized iron powder had a large density, so that it precipitated in an aqueous solution. Compared with comparative example 1, the magnetic hydrophobic modified proppant obtained in example 2 not only has greatly reduced density, but also can float in aqueous solution. Is very beneficial to the application in high-speed channel fracturing.
Claims (10)
1. The magnetic hydrophobic proppant comprises proppant aggregate and is characterized in that the surface of the proppant aggregate is coated with magnetic hydrophobic resin, and the magnetic hydrophobic resin comprises a magnetic material and hydrophobic resin.
2. The magnetic hydrophobic proppant of claim 1, wherein the proppant aggregate is quartz sand, ceramsite, walnut shell or glass spheres.
3. The magnetic hydrophobic proppant of claim 1, wherein the proppant aggregate has a particle size of 20-140 mesh.
4. The magnetic hydrophobic proppant of claim 1, wherein the magnetic material is a magnetic powder, preferably having a particle size in the range of 100 nm to 5 microns.
5. The magnetic hydrophobic proppant according to claim 1, wherein the hydrophobic resin is fluorinated acrylic resin, fluorinated dopamine resin, acrylate resin, silicone resin, polyurethane resin, epoxy resin or other resin with similar properties.
6. The magnetic hydrophobic proppant according to claim 1, wherein the mass ratio of magnetic powder to hydrophobic resin in the magnetic hydrophobic resin is 100: (60-90).
7. The magnetic hydrophobic proppant according to claim 1, wherein the mass ratio of the proppant aggregate to the magnetic hydrophobic resin is 100: (10-50).
8. A method of making the magnetic hydrophobic proppant of claim 1, comprising the steps of:
and blending the proppant aggregate and liquid hydrophobic resin glue containing magnetic powder, and then curing to obtain the magnetic proppant.
9. The preparation method of the magnetic hydrophobic proppant as set forth in claim 8, wherein the curing mode is preheating the used proppant aggregate or heating after adding the liquid hydrophobic resin glue solution to cure the liquid hydrophobic resin glue solution.
10. The method of claim 9, wherein the proppant aggregate is blended with a liquid hydrophobic resin glue containing magnetic powder, heated to 30-90 ℃ under stirring for 0.2-6 hours, and cured.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6116342A (en) * | 1998-10-20 | 2000-09-12 | Halliburton Energy Services, Inc. | Methods of preventing well fracture proppant flow-back |
| US20080283243A1 (en) * | 2007-05-15 | 2008-11-20 | Georgia-Pacific Chemicals Llc | Reducing flow-back in well treating materials |
| CN105670600A (en) * | 2016-03-07 | 2016-06-15 | 王展旭 | Water acid-sensitivity deformation magnetic tracer function self-suspension propping agent and preparation method thereof |
| CN106883837A (en) * | 2017-02-17 | 2017-06-23 | 北京大学 | A kind of hydrophobically modified proppant and preparation method thereof |
| CN109423270A (en) * | 2017-09-01 | 2019-03-05 | 中国石油化工股份有限公司 | A kind of increasing stick type magnetism of beneficial Crack Monitoring is from suspended prop and preparation method thereof |
| CN110157405A (en) * | 2019-04-23 | 2019-08-23 | 中国石油大学(北京) | For the overlay film proppant of unconventional reservoir hydraulic fracturing and preparation and application |
-
2019
- 2019-10-09 CN CN201910952462.6A patent/CN112646564B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6116342A (en) * | 1998-10-20 | 2000-09-12 | Halliburton Energy Services, Inc. | Methods of preventing well fracture proppant flow-back |
| US20080283243A1 (en) * | 2007-05-15 | 2008-11-20 | Georgia-Pacific Chemicals Llc | Reducing flow-back in well treating materials |
| CN105670600A (en) * | 2016-03-07 | 2016-06-15 | 王展旭 | Water acid-sensitivity deformation magnetic tracer function self-suspension propping agent and preparation method thereof |
| CN106883837A (en) * | 2017-02-17 | 2017-06-23 | 北京大学 | A kind of hydrophobically modified proppant and preparation method thereof |
| CN109423270A (en) * | 2017-09-01 | 2019-03-05 | 中国石油化工股份有限公司 | A kind of increasing stick type magnetism of beneficial Crack Monitoring is from suspended prop and preparation method thereof |
| CN110157405A (en) * | 2019-04-23 | 2019-08-23 | 中国石油大学(北京) | For the overlay film proppant of unconventional reservoir hydraulic fracturing and preparation and application |
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