CN114437707B - Self-suspending proppant and preparation method thereof - Google Patents
Self-suspending proppant and preparation method thereof Download PDFInfo
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- CN114437707B CN114437707B CN202210124277.XA CN202210124277A CN114437707B CN 114437707 B CN114437707 B CN 114437707B CN 202210124277 A CN202210124277 A CN 202210124277A CN 114437707 B CN114437707 B CN 114437707B
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- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000011247 coating layer Substances 0.000 claims abstract description 66
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 37
- 239000010410 layer Substances 0.000 claims abstract description 28
- 239000000243 solution Substances 0.000 claims abstract description 27
- 239000000843 powder Substances 0.000 claims abstract description 26
- 229920006351 engineering plastic Polymers 0.000 claims abstract description 25
- 229920005989 resin Polymers 0.000 claims abstract description 25
- 239000011347 resin Substances 0.000 claims abstract description 25
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 19
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims description 58
- 238000003756 stirring Methods 0.000 claims description 49
- 239000011248 coating agent Substances 0.000 claims description 33
- 238000000576 coating method Methods 0.000 claims description 33
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- 239000004576 sand Substances 0.000 claims description 18
- 239000007822 coupling agent Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 13
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 11
- 238000005253 cladding Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 229920001568 phenolic resin Polymers 0.000 claims description 11
- 239000005011 phenolic resin Substances 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 239000004677 Nylon Substances 0.000 claims description 9
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 9
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 9
- 239000003822 epoxy resin Substances 0.000 claims description 9
- 229920001778 nylon Polymers 0.000 claims description 9
- 239000004417 polycarbonate Substances 0.000 claims description 9
- 229920000515 polycarbonate Polymers 0.000 claims description 9
- 229920000647 polyepoxide Polymers 0.000 claims description 9
- 229920002530 polyetherether ketone Polymers 0.000 claims description 9
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229920003180 amino resin Polymers 0.000 claims description 6
- 239000000839 emulsion Substances 0.000 claims description 6
- XPBBUZJBQWWFFJ-UHFFFAOYSA-N fluorosilane Chemical compound [SiH3]F XPBBUZJBQWWFFJ-UHFFFAOYSA-N 0.000 claims description 6
- -1 polytetrafluoroethylene Polymers 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 229920006337 unsaturated polyester resin Polymers 0.000 claims description 6
- 239000000853 adhesive Substances 0.000 claims description 5
- 230000001070 adhesive effect Effects 0.000 claims description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 229920002050 silicone resin Polymers 0.000 claims description 4
- 239000000725 suspension Substances 0.000 abstract description 25
- 239000002562 thickening agent Substances 0.000 abstract description 9
- 239000011148 porous material Substances 0.000 abstract description 8
- 239000011358 absorbing material Substances 0.000 abstract description 5
- 230000000903 blocking effect Effects 0.000 abstract description 4
- 230000003075 superhydrophobic effect Effects 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 20
- 239000002253 acid Substances 0.000 description 16
- 239000002245 particle Substances 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- 239000007788 liquid Substances 0.000 description 13
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 11
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000006087 Silane Coupling Agent Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000006004 Quartz sand Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000012216 screening Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000004088 foaming agent Substances 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
- 230000008961 swelling Effects 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Classifications
-
- 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
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The application discloses a self-suspending proppant and a preparation method thereof, wherein the self-suspending proppant comprises aggregate, a low-density high-strength coating layer and a hydrophobic layer, wherein the low-density high-strength coating layer is coated on the surface of the aggregate, and the hydrophobic layer is coated on the surface of the low-density high-strength coating layer; the low-density high-strength coating layer is of a light porous structure and comprises the following components in parts by weight: 2-5 parts of azoaminobenzene solution, 40-100 parts of thermosetting resin and 20-50 parts of engineering plastic powder, wherein the azoaminobenzene solution is a mixed solution of an organic solvent and 2-5% of azoaminobenzene by weight. The self-suspending proppant realizes self-suspension through high-strength light porous film and super-hydrophobic performance, does not use thickening agents or high-molecular water-absorbing materials, and can avoid damaging stratums and blocking pore canals and throats in cracks.
Description
Technical Field
The application belongs to the technical field of fracturing exploitation of oil and gas fields, and particularly relates to a self-suspending proppant and a preparation method thereof.
Background
The hydraulic fracturing is an important measure for increasing the yield and injection of the oil and gas field, and achieves a good effect in the yield increasing transformation of the oil and gas reservoir. The method comprises the steps of injecting high-viscosity liquid into a well by using a ground high-pressure pump truck group, forming high pressure at the bottom of the well, generating a fracture when the bottom pressure is greater than the fracture pressure of a stratum, continuously injecting sand-carrying liquid with a propping agent, extending the fracture forwards and filling the propping agent, closing the fracture on the propping agent after closing the well and flowback, supporting the fracture, forming a sand-filled fracture with high flow conductivity in a reservoir stratum, and finally achieving the purposes of increasing production and injection.
The proppant needs to have suspending properties due to the need to be carried in with the fracturing fluid. Currently, proppants generally comprise aggregates, low-density high-strength coating layers, water-soluble polymer materials (or swelling polymers, thickeners), curing agents and the like. Even more, in order to ensure the suspension characteristic of the proppant, aggregate with lower mass density is prepared by adopting a powder granulation technology. The thickening agent is dissolved in the sand-carrying liquid in the using process, so that the propping agent is suspended, however, the existence of the thickening agent inevitably causes formation damage, and simultaneously, incomplete gel breaking possibly causes blockage of a pore channel and a throat in a crack; the swelling polymer absorbs water to swell when in use, so that the propping agent is suspended, and although the propping agent has little damage to the stratum, the swelling polymer is easy to deform when being extruded, thereby causing the blockage of the pore canal and the throat in the crack.
For the reasons, the self-suspending proppant without adding a thickening agent (a tackifier and a swelling agent) and gel breaking into a sand carrying fluid or a proppant is urgently needed to be developed, so that the formation damage is reduced, and the exploitation efficiency is increased.
Disclosure of Invention
The embodiment of the application provides a self-suspending proppant and a preparation method thereof, the self-suspending proppant realizes self-suspension through a high-strength light porous film and super-hydrophobic property, does not use a thickening agent or a high-molecular water-absorbing material, and can avoid damaging stratums and blocking pore passages and throats in cracks.
According to a first aspect of the embodiments of the present application, a self-suspending proppant is provided, which includes aggregate, a low-density high-strength coating layer and a hydrophobic layer, wherein the low-density high-strength coating layer is coated on the surface of the aggregate, and the hydrophobic layer is coated on the surface of the low-density high-strength coating layer; the low-density high-strength coating layer is of a light porous structure and comprises the following components in parts by weight: 2-5 parts of azoaminobenzene solution, 40-100 parts of thermosetting resin and 20-50 parts of engineering plastic powder, wherein the azoaminobenzene solution is a mixed solution of an organic solvent and 2-5% of azoaminobenzene by weight ratio.
In some alternative embodiments, the thermosetting resin is selected from one of phenolic resin, epoxy resin, amino resin, unsaturated polyester resin, and silicone resin.
In some alternative embodiments, the engineering plastic powder includes at least one of polycarbonate, polyaromatic nylon, polyetheretherketone, polyphenylene sulfide, and the like.
In some alternative embodiments, the low-density, high-strength cladding layer comprises a plurality of coating films stacked from inside to outside to form the low-density, high-strength cladding layer.
In some optional embodiments, the hydrophobic layer is selected from one of polytetrafluoroethylene emulsion, fluorosilane coupling agent, fluorine-containing adhesive.
According to a second aspect of embodiments herein, there is provided a method of making a self-suspending proppant comprising:
mixing azoaminobenzene solution, thermosetting resin and engineering plastic powder according to the ratio of 2-5:40-100: uniformly mixing the components in a weight ratio of 20-50 to obtain a low-density high-strength coating material for later use; wherein the azoaminobenzene solution is a mixed solution of an organic solvent and 2-5 wt% of azoaminobenzene;
heating the ceramsite aggregate to 160-220 ℃, putting the ceramsite aggregate into a sand mixer, and cooling to 200 ℃;
adding the prepared low-density high-strength coating layer material into a sand mixer, and stirring for 20-25s to form a low-density high-strength coating layer;
adding the hydrophobic material into a sand mixer, and stirring for 10-15s to form a hydrophobic layer.
In some embodiments, the thermosetting resin is selected from one of phenolic resin, epoxy resin, amino resin, unsaturated polyester resin, and silicone resin.
In some alternative embodiments, the method further comprises the step of adding a coupling agent to the mill before the low-density, high-strength cladding material is added to the mill and before the hydrophobic material is added to the mill.
In some optional embodiments, the low-density high-strength coating layer is prepared by a layered film covering mode.
In some alternative embodiments, the method further comprises the step of adding a curing agent to the mill while the low-density, high-strength cladding material is added to the mill or after the low-density, high-strength cladding material is added to the mill.
The technical scheme of the application has the following beneficial technical effects:
the self-suspending proppant provided by the embodiment of the application has the advantages that the low-density high-strength coating layer is a light porous structure formed by materials such as azoaminobenzene solution, thermosetting resin, engineering plastic powder and the like, the structure has higher strength and lower density, so that the self-suspending proppant can realize self-suspension by matching with the hydrophobicity of the hydrophobic layer, and in addition, due to the fact that a thickening agent or a high-molecular water-absorbing material is not used any more, the formation can be prevented from being damaged, and pore canals and throat canals in cracks can be prevented from being blocked. In addition, due to the low-density characteristic of the coating material, the requirement on the mass density of the aggregate is greatly reduced, and the production cost is favorably reduced.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the present application is further described in detail with reference to the following detailed description. It should be understood that the description is intended to be exemplary only, and is not intended to limit the scope of the present application. Moreover, in the following description, descriptions of well-known structures and techniques are omitted so as to not unnecessarily obscure the concepts of the present application.
The embodiment of the application provides a self-suspending proppant, which comprises aggregate, a low-density high-strength coating layer and a hydrophobic layer, wherein the low-density high-strength coating layer is coated on the surface of the aggregate, and the hydrophobic layer is coated on the surface of the low-density high-strength coating layer; the low-density high-strength coating layer is of a light porous structure and comprises the following components in parts by weight: 2-5 parts of azoaminobenzene solution, 40-100 parts of thermosetting resin and 20-50 parts of engineering plastic powder, wherein the azoaminobenzene solution is a mixed solution of an organic solvent and 2-5% of azoaminobenzene by weight.
In the embodiment, the low-density high-strength coating layer of the self-suspending proppant comprises azoamino benzene solution, thermosetting resin, engineering plastic powder and other materials, a large number of micropores are formed inside the low-density high-strength coating layer due to resin foaming and incomplete infiltration of the engineering plastic powder in the film covering process, the proppant has a light porous structure with lower density due to the existence of the micropores, and an organic solvent in the azoamino benzene solution is used as a physical foaming agent and is evaporated in the film covering process, so that the number of the micropores inside the low-density high-strength coating layer can be increased, the surface of the low-density high-strength coating layer is roughened, the rough surface of the low-density high-strength coating layer can improve the hydrophobic effect of the hydrophobic layer, and the self-suspending proppant can realize self-suspending based on lower density and better hydrophobic effect. In addition, the engineering plastic powder is used as a framework material of the low-density high-strength coating layer, so that the light porous low-density high-strength coating layer can be effectively supported, and the low-density high-strength coating layer has enough strength when the pressure of an underground crack is met. Based on the characteristics of self-suspension and high strength, the self-suspension proppant of the embodiment can avoid damaging the stratum and blocking the pore and throat in the crack because no thickening agent or high-molecular water-absorbing material is used.
In the embodiment, based on the low density characteristic of the coating layer of the self-suspending proppant in the embodiment, the requirement on the mass density of the aggregate is greatly reduced, and the aggregate of the self-suspending proppant is selected from common aggregate, for example, the aggregate is the aggregate with the volume density of not more than 1.55g/cm 3 The light ceramsite, the quartz sand and the like, thereby being beneficial to reducing the production cost.
In some embodiments, the thermosetting resin is selected from one of phenolic resin, epoxy resin, amino resin, unsaturated polyester resin, and silicone ether resin.
In some embodiments, the engineering plastic powder includes at least one of polycarbonate, polyaromatic nylon, polyetheretherketone, polyphenylene sulfide, and the like. In the embodiment, the engineering plastic powder is used as the framework material of the low-density high-strength coating layer, so that the structure of the low-density high-strength coating layer can be effectively supported when the low-density high-strength coating layer forms a honeycomb porous structure, thereby reducing the density of the low-density high-strength coating layer and ensuring that the low-density high-strength coating layer has enough strength to deal with the pressure of underground cracks.
In some embodiments, the low-density, high-strength cladding layer comprises a plurality of coating films stacked from inside to outside to form the low-density, high-strength cladding layer. The low-density high-strength coating layer formed by the multiple layers of coating films is more uniform in thickness, and the crushing resistance and the acid solubility of the propping agent can be effectively improved. Optionally, the low-density high-strength coating layer includes two or more layers of coating films, and the thickness, material ratio, curing agent and the like of each layer of coating film may be the same or different according to specific needs. In the present embodiment, the thickness, material ratio, and curing agent used are the same for each coating film.
In some embodiments, the hydrophobic layer is selected from one of polytetrafluoroethylene emulsion, fluorosilane coupling agent, fluorine-containing adhesive. The hydrophobicity of the hydrophobic layer can prevent water from entering open pores on the surface of the proppant, and due to the fact that the tension of the surface of the proppant is low, an integral unit is formed among a certain number of proppant particles in water around the bubbles, and the integral unit is increased in buoyancy due to the bubbles, and finally self-suspension is achieved.
In order to prepare the self-suspending proppant of the previous embodiments, embodiments of the present application further provide a method of preparing a self-suspending proppant comprising the steps of:
mixing azoaminobenzene solution, thermosetting resin and engineering plastic powder according to the ratio of 2-5:40-100: uniformly mixing the components in a weight ratio of 20-50 to obtain a low-density high-strength coating layer material for later use; wherein the azoaminobenzene solution is a mixed solution of an organic solvent and 2-5 wt% of azoaminobenzene;
heating the ceramsite aggregate to 160-220 ℃, putting the ceramsite aggregate into a sand mixer, and cooling to 200 ℃;
adding the prepared low-density high-strength coating layer material into a sand mixer, and stirring for 20-25s to form a low-density high-strength coating layer;
and adding the hydrophobic material into a sand mixer, and stirring for 10-15s to form the hydrophobic layer.
In the steps, the low-density high-strength coating layer of the prepared self-suspending proppant comprises azoaminobenzene solution, thermosetting resin, engineering plastic powder and other materials, a large number of micropores are formed inside the low-density high-strength coating layer due to resin foaming and incomplete infiltration of the engineering plastic powder in the film covering process, the proppant has a light porous structure with lower density due to the existence of the micropores, and an organic solvent in the azoaminobenzene solution is used as a physical foaming agent and is evaporated in the film covering process, so that the number of the micropores inside the low-density high-strength coating layer can be increased, the surface of the low-density high-strength coating layer is roughened, the rough surface of the low-density high-strength coating layer can improve the hydrophobic effect of the hydrophobic layer, and the self-suspending proppant can realize self-suspending based on lower density and better hydrophobic effect. In addition, the engineering plastic powder is used as a framework material of the low-density high-strength coating layer, so that the light porous low-density high-strength coating layer can be effectively supported, and the low-density high-strength coating layer has enough strength when the pressure of an underground crack is met. Based on the characteristics of self-suspension and high strength, the self-suspension propping agent of the embodiment can avoid damaging the stratum and blocking the pore canal and the throat in the crack because no thickening agent or high-molecular water-absorbing material is used.
In some embodiments, the thermosetting resin is selected from one of phenolic resin, epoxy resin, amino resin, unsaturated polyester resin, and silicone ether resin.
In some embodiments, the engineering plastic powder includes at least one of polycarbonate, polyaromatic nylon, polyetheretherketone, polyphenylene sulfide, and the like. In the embodiment, the engineering plastic powder is used as the framework material of the low-density high-strength coating layer, so that the structure of the low-density high-strength coating layer can be effectively supported when the low-density high-strength coating layer forms a honeycomb porous structure, thereby reducing the density of the low-density high-strength coating layer and ensuring that the low-density high-strength coating layer has enough strength to deal with the pressure of underground cracks.
In some embodiments, the hydrophobic layer is selected from one of a polytetrafluoroethylene emulsion, a fluorosilane coupling agent, a fluorine-containing adhesive.
In some embodiments, to ensure the bonding properties of the low-density, high-strength coating to the substrate, the method further comprises the step of adding a coupling agent to the mill before the low-density, high-strength coating material is added to the mill and before the hydrophobic material is added to the mill. The coupling agent is also called a surface treatment agent, and is exemplified by one of a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, a bimetallic coupling agent, a phosphate coupling agent, a borate coupling agent, a chromium complex and other coupling agents of higher fatty acid, alcohol, ester, and the like. In the present embodiment, the coupling agent is selected from silane coupling agents.
In some embodiments, the low-density high-strength coating layer is prepared by layering a film in order to make the thickness of the low-density high-strength coating layer more uniform. Optionally, the low-density high-strength clad layer comprises two or more clad films. For example, the coating is two layers, and the preparation process of the low-density high-strength coating layer can be as follows: after the ceramsite aggregate is cooled to 200 ℃, adding part of the prepared low-density high-strength coating material into a sand mixer, and stirring for 20-25s to form a first coating; and adding part of the prepared low-density high-strength coating layer material into a sand mixer, and stirring for 20-25s to form a second coating film. The low-density high-strength coating layer formed by the multiple layers of coating films is more uniform in thickness, and the anti-crushing capacity and the acid solubility of the propping agent can be effectively improved.
In some embodiments, the method further comprises the step of adding a curing agent to the mill while the low-density, high-strength cladding material is added to the mill or after the low-density, high-strength cladding material is added to the mill. Wherein, different curing agents are selected according to the types of the low-density high-strength coating layer materials, for example, when the resin material is phenolic resin, the corresponding curing agent adopts fluosilicic acid, and when the resin material is epoxy resin, the corresponding curing agent adopts dodecyl mercaptan. In the embodiment, the resin material is phenolic resin or epoxy resin, and the curing agent is fluorosilicic acid or dodecyl mercaptan, wherein the fluorosilicic acid and the dodecyl mercaptan have curing effect and hydrophobicity, and are matched with the hydrophobic layer, so that the hydrophobicity of the proppant can be further improved.
Example 1
A method of making a self-suspending proppant, comprising the steps of:
adding 2,2,2' -azobisisobutyronitrile (azoaminobenzene) with the weight ratio of 3% (mass ratio of foaming agent to solvent) into an ethanol solution, stirring until the azoisobutyronitrile (azoaminobenzene) is completely dissolved, adding 3g of the mixed solution into the ethanol solution, uniformly mixing the mixed solution with 50g of liquid thermosetting phenolic resin, adding 25g of engineering plastic powder (one or more of polycarbonate, polyaromatic nylon, polyether ether ketone, polyphenylene sulfide and the like), and uniformly stirring to obtain a low-density high-strength coating material for later use;
heating 2kg of ceramsite aggregate (850-425 mu m) to 160-220 ℃, adding the ceramsite aggregate into a sand mixer, cooling to 200 ℃, adding a silane coupling agent accounting for 0.1 percent of the weight of the ceramsite aggregate, stirring for 10s, then adding 30g of the low-density high-strength coating material, stirring for 20-30s, adding 1g of fluosilicic acid, stirring for 10-20s, then adding 30g of the low-density high-strength coating material, stirring for 25-35s, adding 1g of fluosilicic acid, stirring for 20-25s, finally adding 25g of hydrophobic material (polytetrafluoroethylene emulsion), stirring until the particles are in a dispersed state, cooling, and screening out the particles with the particle size of 850-425 mu m. The performance of the suspension proppant obtained according to an industrial standard SY/T5108-2014 test shows that the 52MPa crushing rate is 0.23 percent, the roundness is 0.9, the sphericity is 0.9, the acid solubility is 0.34 percent, the volume density is 1.36g/cm < 3 >, the contact angle is 150 degrees, the suspension time is 5-10s, the suspension time is more than 48h, the settling time in mineralized water is more than 48h, and the liquid viscosity is 1.1MPa · s.
Example 2
A method of making a self-suspending proppant, comprising the steps of:
adding 2,2,2' -azobisisobutyronitrile (azoaminobenzene) with the weight ratio of 4% into an ethanol solution, stirring until the azoisobutyronitrile (azoaminobenzene) is completely dissolved, adding 3g of the mixed solution into 50g of liquid bisphenol A epoxy resin, uniformly mixing, adding 25g of engineering plastic powder (one or more of polycarbonate, polyaromatic nylon, polyether ether ketone, polyphenylene sulfide and the like), and uniformly stirring to obtain a low-density high-strength coating material for later use;
heating 2kg of ceramsite (850-425 mu m) aggregate to 160-220 ℃, adding the ceramsite into a sand mixer, cooling to 200 ℃, adding a silane coupling agent accounting for 0.1 percent of the weight of the ceramsite aggregate, stirring for 10s, then adding 30g of the low-density high-strength coating material, stirring for 20-30s, adding 1g of dodecyl mercaptan, stirring for 10-20s, then adding 30g of the low-density high-strength coating material, stirring for 25-35s, adding 1g of dodecyl mercaptan, stirring for 20-25s, finally adding 25g of hydrophobic material (fluorosilane coupling agent), stirring until the particles are in a dispersed state, cooling, and screening out the particles with the particle size of 850-425 mu m. The performance of the suspension proppant obtained according to an industrial standard SY/T5108-2014 test shows that the crushing rate at 52MPa is 0.67%, the roundness is 0.9, the sphericity is 0.9, the acid solubility is 0.28%, the volume density is 1.38g/cm < 3 >, the contact angle is 143 degrees, the suspension time is 8-12s, the suspension time is 6h, the sedimentation time in mineralized water is more than 48h, and the liquid viscosity is 1.03MPa · s.
Example 3
A method of making a self-suspending proppant, comprising the steps of:
adding 2,2,2' -azobisisobutyronitrile (azoaminobenzene) with the weight ratio of 2% into an ethanol solution, stirring until the azodiisobutyronitrile (azoaminobenzene) is completely dissolved, adding 3g of the mixed solution into 50g of liquid bisphenol A epoxy resin, uniformly mixing, adding 25g of engineering plastic powder (one or more of polycarbonate, polyaromatic nylon, polyether ether ketone, polyphenylene sulfide and the like), and uniformly stirring to obtain a low-density high-strength coating material for later use;
heating 2kg of ceramsite (850-425 mu m) aggregate to 160-220 ℃, adding the ceramsite into a sand mixer, cooling to 190 ℃, adding a silane coupling agent accounting for 0.1 percent of the weight of the ceramsite aggregate, stirring for 10s, then adding 30g of the low-density high-strength coating material, stirring for 25-30s, adding 1g of dodecyl mercaptan, stirring for 15-20s, then adding 30g of the low-density high-strength coating material, stirring for 28-35s, adding 1g of dodecyl mercaptan, stirring for 23-25s, finally adding 30g of hydrophobic material (fluorosilane coupling agent), stirring until the particles are in a dispersed state, cooling, and screening out the particles with the particle size of 850-425 mu m. The performance of the suspension proppant obtained according to an industrial standard SY/T5108-2014 test shows that the fracture rate at 52MPa is 0.33%, the roundness is 0.9, the sphericity is 0.9, the acid solubility is 0.32%, the volume density is 1.39g/cm < 3 >, the contact angle is 149 degrees, the suspension time is 5-10s, the suspension time is 6h, the settling time in mineralized water is more than 48h, and the liquid viscosity is 1.05MPa · s.
Example 4
A method of making a self-suspending proppant, comprising the steps of:
adding 3 wt% of 2,2,2' -azobisisobutyronitrile (azoaminobenzene) into an ethanol solution, stirring until the azoisobutyronitrile (azoaminobenzene) is completely dissolved, adding 3g of the mixed solution into 50g of liquid thermosetting phenolic resin, uniformly mixing, adding 25g of engineering plastic powder (one or more of polycarbonate, polyaromatic nylon, polyether ether ketone, polyphenylene sulfide and the like), and uniformly stirring to obtain a low-density high-strength coating material for later use;
heating 2kg of quartz sand (850-425 mu m) aggregate to 160-220 ℃, adding the quartz sand into a sand mixer, cooling to 200 ℃, adding a silane coupling agent accounting for 0.1 percent of the weight of the aggregate, stirring for 10s, then adding 30g of the low-density high-strength coating material, stirring for 20-30s, adding 1g of fluosilicic acid, stirring for 10-20s, then adding 30g of the low-density high-strength coating material, stirring for 25-35s, adding 1g of the fluosilicic acid, stirring for 20-25s, finally adding 25g of hydrophobic material (fluorocarbon adhesive), stirring until the particles are in a dispersed state, cooling, and screening out the particles with the particle size of 850-425 mu m. The performance of the suspension proppant obtained according to an industrial standard SY/T5108-2014 test shows that the 52MPa breakage rate is 1.89%, the roundness is 0.8, the sphericity is 0.8, the acid solubility is 0.34%, the volume density is 1.38g/cm < 3 >, the contact angle is 150 degrees, the suspension time is 5-10s, the suspension time is more than 48h, the sedimentation time in mineralized water is more than 48h, and the liquid viscosity is 1.09MPa · s.
Example 5
A method of making a self-suspending proppant, comprising the steps of:
adding 2,2,2' -azobisisobutyronitrile (azoaminobenzene) with the weight ratio of 3% (mass ratio of foaming agent to solvent) into an ethanol solution, stirring until the azoisobutyronitrile (azoaminobenzene) is completely dissolved, adding 3g of the mixed solution into the ethanol solution, uniformly mixing the mixed solution with 50g of liquid thermosetting phenolic resin, adding 25g of engineering plastic powder (one or more of polycarbonate, polyaromatic nylon, polyether ether ketone, polyphenylene sulfide and the like), and uniformly stirring to obtain a low-density high-strength coating material for later use;
heating 2kg of quartz sand (425-212 mu m) aggregate to 160-220 ℃, adding the quartz sand into a sand mixer, cooling to 200 ℃, adding a silane coupling agent accounting for 0.1 percent of the weight of the aggregate, stirring for 10s, then adding 20g of the low-density high-strength coating material, stirring for 20-30s, adding 0.6g of fluosilicic acid, stirring for 10-20s, then adding 20g of the low-density high-strength coating material, stirring for 25-35s, adding 0.6g of fluosilicic acid, stirring for 20-25s, finally adding 20g of hydrophobic material (polytetrafluoroethylene emulsion), stirring until the particles are in a dispersed state, cooling, and screening out the particles with the particle size of 425-212 mu m. The performance of the suspension proppant obtained according to an industrial standard SY/T5108-2014 test shows that the crushing rate at 52MPa is 0.68%, the roundness is 0.8, the sphericity is 0.8, the acid solubility is 1.37%, the volume density is 1.33g/cm < 3 >, the contact angle is 154 degrees, the suspension time is 3-8s, the suspension time is more than 48h, the sedimentation time in mineralized water is more than 48h, and the liquid viscosity is 1.17MPa · s.
Although the self-suspending proppant prepared by using different resin materials has basically the same physical structure, the self-suspending proppant prepared by using the epoxy resin and the dodecyl mercaptan curing agent has better hydrophobic property, good suspending effect and higher strength, so that the self-suspending proppant is slower in sedimentation and longer in propping fracture length in the using process, is beneficial to increasing the diversion area and improving the recovery ratio, and has high strength and can be suitable for higher stratum closing pressure. Further experiments have found that the higher the temperature is, the faster the reaction rate of the resin material is in the required temperature range, and thus the stirring time can be reduced. And as the temperature increases, the reaction rate of the azoaminobenzene increases, and a macroporous structure is formed in the low-density high-strength coating layer and on the surface of the low-density high-strength coating layer, so that the strength of the low-density high-strength coating layer is reduced, the hydrophobic property is weakened, and the suspension effect is deteriorated. In addition, the self-suspending proppant prepared by the embodiment of the application has stable structural performance, is convenient to transport and store and has long effective period.
While the present application has been described with reference to exemplary embodiments thereof, it is to be understood that the present application is not limited to the disclosed embodiments, which are presented by way of illustration rather than of limitation, and that various modifications may be made by those skilled in the art without departing from the spirit and scope of the present application as defined by the appended claims.
Claims (10)
1. The self-suspending proppant is characterized by comprising aggregate, a low-density high-strength coating layer and a hydrophobic layer, wherein the low-density high-strength coating layer is coated on the surface of the aggregate, and the hydrophobic layer is coated on the surface of the low-density high-strength coating layer; the low-density high-strength coating layer is of a light porous structure and comprises the following components in parts by weight: 2-5 parts of azoaminobenzene solution, 40-100 parts of thermosetting resin and 20-50 parts of engineering plastic powder, wherein the azoaminobenzene solution is a mixed solution of an organic solvent and 2-5% of azoaminobenzene by weight ratio.
2. The self-suspending proppant of claim 1, wherein the thermosetting resin is selected from one of phenolic resin, epoxy resin, amino resin, unsaturated polyester resin, and silicone resin.
3. The self-suspending proppant of claim 1, wherein the engineering plastic powder comprises at least one of polycarbonate, polyaromatic nylon, polyetheretherketone, and polyphenylene sulfide.
4. The self-suspending proppant of claim 1, wherein the low-density high-strength coating comprises a plurality of coating films stacked from inside to outside to form the low-density high-strength coating.
5. The self-suspending proppant of claim 1, wherein the hydrophobic layer is selected from one of a polytetrafluoroethylene emulsion, a fluorosilane coupling agent, and a fluorine-containing adhesive.
6. A method of making a self-suspending proppant, comprising:
mixing azoaminobenzene solution, thermosetting resin and engineering plastic powder according to the ratio of 2-5:40-100: uniformly mixing the components in a weight ratio of 20-50 to obtain a low-density high-strength coating layer material for later use; wherein the azoaminobenzene solution is a mixed solution of an organic solvent and 2-5 wt% of azoaminobenzene;
heating the ceramsite aggregate to 160-220 ℃, putting the ceramsite aggregate into a sand mixer, and cooling to 200 ℃;
adding the prepared low-density high-strength coating layer material into a sand mixer, and stirring for 20-25s to form a low-density high-strength coating layer;
and adding the hydrophobic material into a sand mixer, and stirring for 10-15s to form the hydrophobic layer.
7. The method according to claim 6, wherein the thermosetting resin is selected from one of phenolic resin, epoxy resin, amino resin, unsaturated polyester resin and silicone resin.
8. The method of claim 6, further comprising the step of adding a coupling agent to the mill prior to adding the low-density, high-strength cladding material to the mill and prior to adding the hydrophobic material to the mill.
9. The method according to claim 6, wherein the low-density high-strength coating layer is prepared by means of a layered film.
10. The method of claim 7, further comprising the step of adding a curing agent to the roller mill while or after the low-density, high-strength cladding material is added to the roller mill.
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