CN112282722A - Low-density organic water-control proppant and preparation method thereof - Google Patents
Low-density organic water-control proppant and preparation method thereof Download PDFInfo
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- CN112282722A CN112282722A CN202010507171.9A CN202010507171A CN112282722A CN 112282722 A CN112282722 A CN 112282722A CN 202010507171 A CN202010507171 A CN 202010507171A CN 112282722 A CN112282722 A CN 112282722A
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- water
- proppant
- density organic
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- 239000003795 chemical substances by application Substances 0.000 claims description 18
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 17
- 239000011159 matrix material Substances 0.000 claims description 16
- 239000004800 polyvinyl chloride Substances 0.000 claims description 16
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 16
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
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- -1 polypropylene Polymers 0.000 claims description 11
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- LSEWYWRTOPOTBV-UHFFFAOYSA-N 2-(oxiran-2-ylmethoxymethyl)oxirane silane Chemical compound [SiH4].C(C1CO1)OCC1CO1 LSEWYWRTOPOTBV-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000003921 oil Substances 0.000 claims description 8
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- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 6
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- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 4
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- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
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- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 2
- 229940012017 ethylenediamine Drugs 0.000 claims description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
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- 239000005056 polyisocyanate Substances 0.000 claims description 2
- 229920001228 polyisocyanate Polymers 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- 239000010903 husk Substances 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 239000003129 oil well Substances 0.000 abstract description 13
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 26
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
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Images
Classifications
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- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/25—Methods for stimulating production
- E21B43/26—Methods for stimulating production by forming crevices or fractures
- E21B43/267—Methods for stimulating production by forming crevices or fractures reinforcing fractures by propping
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
- C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D123/10—Homopolymers or copolymers of propene
- C09D123/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D157/00—Coating compositions based on unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09D157/02—Copolymers of mineral oil hydrocarbons
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
- C09D161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09D161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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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
- C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
- C09K8/44—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing organic binders only
-
- 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
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/25—Methods for stimulating production
- E21B43/26—Methods for stimulating production by forming crevices or fractures
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/04—Homopolymers or copolymers of styrene
- C08J2325/06—Polystyrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2327/06—Homopolymers or copolymers of vinyl chloride
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Abstract
The invention discloses a low-density organic water-control proppant which is prepared by the following steps: and carrying out high-temperature oxidation activation on the surface of the low-density organic proppant substrate to generate active groups on the surface, grafting a graft coating material on the surface of the activated low-density organic proppant substrate to form a graft coating, and grafting a water-controlling coating material on the surface of the graft coating to form a water-controlling coating to obtain the low-density organic water-controlling proppant. The low-density organic proppant has the density equivalent to that of water, has excellent carrying performance, and can greatly improve the filling efficiency of a shaft and a stratum in well completion filling and fracturing operations; meanwhile, the surface of the low-density organic proppant is subjected to hydrophobic modification, so that the low-density organic proppant has a water control function, and the life cycle of an oil well is prolonged; the low-density organic water-control proppant disclosed by the invention realizes the dual effects of low density and water control of the proppant in oil well completion or fracturing operation.
Description
Technical Field
The invention belongs to the technical field of petroleum and natural gas exploitation, and particularly relates to a low-density organic water-control proppant and a preparation method thereof.
Background
The proppant is a key material for generating high-flow-guide cracks in fracturing production increasing measures of oil fields, and the proppants such as quartz sand, ceramsite and the like commonly used in the fracturing operation at present have the defects of easy sedimentation, uneven distribution in the cracks and high requirements on the performance of fracturing fluid and pumping conditions. Meanwhile, the well completion propping agent is also a key material for gravel packing sand prevention operation in the well completion process of an oil well, the commonly used propping agent for the gravel packing operation at present is quartz sand series with different granularities, but the quartz sand has the defect of low packing efficiency, and the sand prevention effect of the oil well is further influenced.
In addition, in the process of oil and gas development, due to reservoir heterogeneity, natural cracks, fluid characteristic difference and the like, the edge bottom water coning phenomenon is prominent, so that the oil well is exposed to water prematurely, once the edge bottom water breaks through and enters the shaft, the water content of the oil well is rapidly increased, the energy consumption and the ground water treatment workload are increased, the recovery ratio of the oil field is greatly reduced, and the overall development benefit of the oil field is seriously influenced.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a low-density organic water-control proppant and a preparation method thereof.
The technical purpose of the invention is realized by the following technical scheme.
A low-density organic water-control proppant is prepared by the following processes: and carrying out high-temperature oxidation activation on the surface of the low-density organic proppant substrate to generate active groups on the surface, grafting a graft coating material on the surface of the activated low-density organic proppant substrate to form a graft coating, and grafting a water-controlling coating material on the surface of the graft coating to form a water-controlling coating to obtain the low-density organic water-controlling proppant.
In the low-density organic water-control proppant, the low-density organic proppant matrix is one of polystyrene pellets, polyvinyl chloride pellets, epoxy resin pellets, phenolic resin pellets, polyurethane pellets and shell particles, and the particle size of the low-density organic proppant matrix is 16-80 meshes.
In the low-density organic water-control proppant, the grafted coating material comprises one or more of the following components: water glass, urea resin, phenolic resin, polyacrylic resin, epoxy resin and glycidyl ether silane; the content of the graft coating material is 0.1-3 wt% of the mass of the low-density organic proppant substrate.
In the low-density organic water-control proppant, the glycidyl ether silane is gamma- (2, 3-glycidoxy) propyl trimethoxy silane.
Preferably, the graft coating material is epoxy resin, and the mass ratio of (1-2): 6 of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and epoxy resin or 1:3 of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and phenolic resin.
In the above low density organic water-controlling proppant, the water-controlling coating material comprises one or more of the following components: polyethylene resin, polypropylene resin, petroleum resin, silicone resin, modified polyfluoro resin; the content of the water control coating material is 0.5-5 wt% of the mass of the low-density organic proppant substrate.
The invention also discloses application of the low-density organic water-control proppant in well completion filling and fracturing operations of oil fields, and the low-density organic water-control proppant has dual effects of low density and water control in the well completion filling or fracturing operations of oil fields.
A preparation method of a low-density organic water-control proppant comprises the following steps:
step 1: heating a low-density organic proppant substrate to 200-350 ℃, keeping the temperature for more than 1min, and carrying out surface activation on the low-density organic proppant substrate;
in the step 1, keeping the temperature for 1 min-2 h to activate the surface of the low-density organic proppant substrate;
in the step 1, the low-density organic proppant matrix is one of polystyrene pellets, polyvinyl chloride pellets, epoxy resin pellets, phenolic resin pellets, polyurethane pellets and shell particles, and the particle size of the low-density organic proppant matrix is 16-70 meshes.
Step 2: adjusting the temperature of the low-density organic proppant substrate subjected to surface activation in the step (1) to 130-220 ℃, adding a graft coating material into the low-density organic proppant substrate, mixing and dispersing the mixture uniformly, and grafting the graft coating material on the surface of the low-density organic proppant substrate subjected to surface activation to form a graft coating;
in step 2, the graft coating material comprises one or more of the following components: water glass, urea resin, phenolic resin, polyacrylic resin and epoxy resin; the graft coating material further comprises a glycidyl ether silane; the addition amount of the grafting coating material is 0.1-3 wt% of the dosage of the low-density organic proppant substrate in the step 1; preferably, the graft coating material is epoxy resin, and the mass ratio of (1-2): 6 of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and epoxy resin or the gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and phenolic resin with the mass ratio of 1: 3;
in step 2, when the graft coating material comprises glycidyl ether silane, the glycidyl ether silane is added into the low-density organic proppant substrate after surface activation in step 1 and is uniformly mixed and dispersed, and then the rest components of the graft coating material are added and are uniformly mixed and dispersed.
And step 3: adjusting the temperature of the mixed material after the graft coating is formed in the step 2 to 100-200 ℃, adding a water-controlling coating material into the mixed material, and uniformly mixing, wherein the water-controlling coating material is grafted on the surface of the graft coating to form a water-controlling coating;
in the step 3, after the water control coating material is added into the mixed material with the grafted coating formed in the step 2, stirring for 30-60 s at the speed of 80-100 r/min to uniformly mix and form the water control coating;
in step 3, the water-controlling coating material comprises one or more of the following components: polyethylene resin, polypropylene resin, petroleum resin, silicone resin, modified polyfluoro resin; the addition amount of the water-control coating material is 0.5-5 wt% of the dosage of the low-density organic proppant substrate in the step 1.
And 4, step 4: adding a curing agent into the mixed material with the water-control coating formed in the step 3 for full curing to obtain the low-density organic water-control proppant;
in the step 4, adding a curing agent into the mixed material with the water-control coating formed in the step 3, stirring for 10-20 s at a speed of 80-100 r/min to fully cure, and then cooling the cured mixed material to room temperature to obtain the low-density organic water-control proppant;
in step 4, the curing agent comprises one or more of the following components: maleic anhydride, ethylenediamine, m-phenylenediamine, triethylene tetramine, polyisocyanate, phthalic anhydride and urotropine; the addition amount of the curing agent is 10-30 wt% of the sum of the addition amount of the grafted coating material in the step 2 and the addition amount of the water-control coating material in the step 3.
The low-density and water-control function is the urgent need of domestic and foreign oil fields for the proppant, the low-density organic proppant has the same density and water, has excellent carrying performance, and can greatly improve the filling efficiency of a shaft and a stratum in well completion filling and fracturing operations; meanwhile, the inert surface of the low-density organic proppant is activated to generate active groups such as hydrogen bonds on the surface of the inert surface, and then a grafted coating is formed on the surface of the activated low-density organic proppant substrate, so that more abundant active groups are introduced, the chemical connection between the water control coating and the grafted coating is stronger, namely the water control coating is more firmly combined on the low-density organic proppant, the low-density organic proppant has a water control function, and in the sand control completion of the horizontal well, the axial channeling of the shaft of formation water can be effectively inhibited by filling the low-density organic water control proppant, the water flooding speed of the bottom water horizontal well is slowed down, and the life cycle of an oil well is prolonged; in the fracturing operation process, the low-density organic water-control propping agent is introduced into the fractures, so that the flow resistance of formation water in the fractures is increased, the speed of the formation water flowing into an oil well is slowed down, the water content of the oil well is reduced, and the fracturing water control is realized; the low-density organic water-control proppant disclosed by the invention realizes the dual effects of low density and water control of the proppant in oil well completion or fracturing operation.
Drawings
FIG. 1 is a mass spectrum of the organic beads before grafting in example 5 using a Secondary Ion Mass Spectrometer (SIMS);
FIG. 2 is a mass spectrum of the grafted organic globule of example 5 analyzed by Secondary Ion Mass Spectrometer (SIMS);
FIG. 3 is a schematic diagram of a water blocking height testing apparatus for the low density organic water control proppant of the present invention;
FIG. 4 is a schematic diagram of a simulated erosion experimental apparatus for the low-density organic water-control proppant of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The relevant information of the instrument and equipment related to the embodiment of the invention is as follows:
contact angle measuring apparatus, model number Dataphysics DCA20, Dataphysics, germany;
sand mixer, model SHY, co-creation machinery ltd, jining;
time of flight secondary mass spectrometry, model tof.sims 5, lontiof corporation;
a proppant water-blocking height measurement device, self-made, as shown in fig. 3;
the proppant simulates a washing experiment device, and is prepared by self as shown in figure 4.
The relevant information of the drugs used in the specific embodiment of the present invention is as follows:
polystyrene pellets, Shanghai Yangyo electro-mechanical science and technology Limited, model PS 38300;
polyvinyl chloride pellets, Tianjin Staphylea chemical Co., Ltd., brand DG-1300;
polypropylene resin, Yanshan petrochemical company, designation B4808;
gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane, Nanjing Needed New Material technology Co., Ltd, model SCA-E87M, effective concentration 98%;
epoxy resin, Yueyangbailing petrochemical company, model CYD-134, 100% solids content;
petroleum resin, Daqing Huake, brand C9, softening point 110 ℃, solid content 100%;
phenolic resin, model 1901, shijiazhuangfeng fine chemical company ltd, 100% solids;
triethylene tetramine, Nanjing chemical reagents, Inc., with an effective concentration of 95%;
m-phenylenediamine, Nanjing chemical reagents, Inc., with an effective concentration of 98%;
modified polyfluoro resin, available from Japan Dajin Co., trademark D-310, having a solid content of 60%.
Example 1
The low-density organic water-control proppant is prepared by the following steps: and carrying out high-temperature oxidation activation on the surface of the low-density organic proppant substrate to generate active groups on the surface, grafting a graft coating material on the surface of the activated low-density organic proppant substrate to form a graft coating, and grafting a water-controlling coating material on the surface of the graft coating to form a water-controlling coating to obtain the low-density organic water-controlling proppant.
In the low-density organic water-control proppant, the matrix of the low-density organic proppant is 60-mesh/80-mesh polystyrene pellets (the volume density is 0.7 g/cm)3) (ii) a The graft coating material comprises epoxy resin and gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane, and the content of the gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane is 0.8 wt% of the mass of the low-density organic proppant substrate; the water control coating material is petroleum resin, and the content of the petroleum resin is 0.6 wt% of the low-density organic proppant matrix.
The invention discloses a preparation method of a low-density organic water-control proppant, which comprises the following steps:
step 1: 500g of 60 mesh/80 mesh polystyrene beads (volume density of 0.7 g/cm) were weighed3) Heating to 280 deg.C, maintaining the temperature for 1min, and activating the surface of the polystyrene spheresMelting;
step 2: cooling the temperature of the polystyrene spheres after surface activation in the step 1 to 220 ℃, adding the polystyrene spheres into a sand mixer, adding 1.0g of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane into the sand mixer, and stirring for 10s at a speed of 80r/min to uniformly mix and disperse the polystyrene spheres; then adding 3.0g of epoxy resin into the sand mixer, stirring for 30s at 80r/min to uniformly mix and disperse, and forming a grafted coating on the surface of the polystyrene spheres after surface activation;
and step 3: after the temperature of the mixed material with the grafted coating formed in the step 2 is reduced to 180 ℃, adding 3.0g of petroleum resin into a sand mixer, stirring for 30s at 80r/min to mix uniformly, and grafting on the surface of the grafted coating to form a water-controlling coating;
and 4, step 4: and adding 1.5g of triethylene tetramine into the sand mixer, stirring for 10s at a speed of 80r/min to fully solidify, and cooling the solidified mixed material to room temperature to obtain the low-density organic water-control proppant.
Example 2
The low-density organic water-control proppant is prepared by the following steps: and carrying out high-temperature oxidation activation on the surface of the low-density organic proppant substrate to generate active groups on the surface, grafting a graft coating material on the surface of the activated low-density organic proppant substrate to form a graft coating, and grafting a water-controlling coating material on the surface of the graft coating to form a water-controlling coating to obtain the low-density organic water-controlling proppant.
In the low-density organic water-control proppant, the matrix of the low-density organic proppant is 60-mesh/80-mesh polystyrene pellets (the volume density is 0.7 g/cm)3) (ii) a The graft coating material is epoxy resin, and the content of the graft coating material is 1.0 wt% of the mass of the low-density organic proppant substrate; the water control coating material is polypropylene resin, and the content of the polypropylene resin is 0.6 wt% of the low-density organic proppant matrix.
The invention discloses a preparation method of a low-density organic water-control proppant, which comprises the following steps:
step 1: 500g of 60 mesh/80 mesh polystyrene beads (volume density of 0.7 g/cm) were weighed3) Heating the polystyrene beads to 300 ℃, keeping the temperature for 5min, and performing surface activation on the polystyrene beads;
step 2: cooling the temperature of the polystyrene spheres after surface activation in the step 1 to 220 ℃, adding the polystyrene spheres into a sand mixer, then adding 5.0g of epoxy resin into the sand mixer, stirring for 30s at 80r/min to uniformly mix and disperse, and forming a graft coating on the surfaces of the polystyrene spheres after surface activation;
and step 3: after the temperature of the mixed material with the grafted coating formed in the step 2 is reduced to 180 ℃, 3.0g of polypropylene resin is added into a sand mixer, the mixture is stirred for 30s at a speed of 80r/min to be uniformly mixed, and the surface of the grafted coating is grafted to form a water-controlling coating;
and 4, step 4: and adding 1.2g of m-phenylenediamine into a sand mixer, stirring for 10s at a speed of 80r/min to fully solidify, and cooling the solidified mixed material to room temperature to obtain the low-density organic water-control proppant.
Example 3
The low-density organic water-control proppant is prepared by the following steps: and carrying out high-temperature oxidation activation on the surface of the low-density organic proppant substrate to generate active groups on the surface, grafting a graft coating material on the surface of the activated low-density organic proppant substrate to form a graft coating, and grafting a water-controlling coating material on the surface of the graft coating to form a water-controlling coating to obtain the low-density organic water-controlling proppant.
In the low-density organic water-control proppant, the matrix of the low-density organic proppant is 60-mesh/80-mesh polystyrene pellets (the volume density is 0.7 g/cm)3) (ii) a The graft coating material comprises phenolic resin and gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane, and the content of the gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane is 0.8 wt% of the mass of the low-density organic proppant substrate; the water control coating material is polypropylene resin, and the content of the polypropylene resin is 0.6 wt% of the low-density organic proppant matrix.
The invention discloses a preparation method of a low-density organic water-control proppant, which comprises the following steps:
step 1: 500g of 60 mesh/80 mesh polystyrene beads (volume)The density was 0.7g/cm3) Heating the polystyrene beads to 300 ℃, keeping the temperature for 10min, and carrying out surface activation on the polystyrene beads;
step 2: cooling the temperature of the polystyrene spheres after surface activation in the step 1 to 180 ℃, adding the polystyrene spheres into a sand mixer, adding 1.0g of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane into the sand mixer, and stirring for 10s at a speed of 80r/min to uniformly mix and disperse the polystyrene spheres; then adding 3.0g of phenolic resin into the sand mixer, stirring for 50s at 80r/min to uniformly mix and disperse, and forming a grafted coating on the surface of the polystyrene spheres after surface activation;
and step 3: after the temperature of the mixed material with the grafted coating formed in the step 2 is reduced to 160 ℃, adding 3.0g of polypropylene resin into a sand mixer, stirring for 30s at 80r/min to mix uniformly, and grafting on the surface of the grafted coating to form a water-controlling coating;
and 4, step 4: and adding 1.8g of triethylene tetramine into the sand mixer, stirring for 10s at a speed of 80r/min to fully solidify, and cooling the solidified mixed material to room temperature to obtain the low-density organic water-control proppant.
Example 4
The low-density organic water-control proppant is prepared by the following steps: and carrying out high-temperature oxidation activation on the surface of the low-density organic proppant substrate to generate active groups on the surface, grafting a graft coating material on the surface of the activated low-density organic proppant substrate to form a graft coating, and grafting a water-controlling coating material on the surface of the graft coating to form a water-controlling coating to obtain the low-density organic water-controlling proppant.
In the low-density organic water-control proppant, the matrix of the low-density organic proppant is polyvinyl chloride pellets with 40 meshes/70 meshes (the volume density is 0.9 g/cm)3) (ii) a The graft coating material comprises epoxy resin and gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane, and the content of the gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane is 0.7 wt% of the mass of the low-density organic proppant substrate; the water control coating material is modified polyfluoro resin, and the content of the modified polyfluoro resin is 0.6 wt% of the low-density organic proppant matrix.
The invention discloses a preparation method of a low-density organic water-control proppant, which comprises the following steps:
step 1: 500g of 40 mesh/70 mesh polyvinyl chloride pellets (volume density 0.9 g/cm) were weighed3) Heating the polyvinyl chloride pellets to 250 ℃, keeping the temperature for 1min, and carrying out surface activation on the polyvinyl chloride pellets;
step 2: cooling the temperature of the polyvinyl chloride pellets after surface activation in the step (1) to 180 ℃, adding the polyvinyl chloride pellets into a sand mixer, adding 0.5g of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane into the sand mixer, and stirring for 10s at a speed of 80r/min to uniformly mix and disperse; then adding 3.0g of epoxy resin into the sand mixer, stirring for 50s at 80r/min to uniformly mix and disperse, and forming a grafted coating on the surface of the polyvinyl chloride pellets after surface activation;
and step 3: after the temperature of the mixed material with the grafted coating formed in the step 2 is reduced to 160 ℃, adding 3g of modified polyfluoro resin into a sand mixer, stirring for 30s at 80r/min to mix uniformly, and grafting on the surface of the grafted coating to form a water-controlling coating;
and 4, step 4: and adding 2.0g of triethylene tetramine into the sand mixer, stirring for 10s at a speed of 80r/min to fully solidify, and cooling the solidified mixed material to room temperature to obtain the low-density organic water-control proppant.
Mass spectrometry was performed on the polyvinyl chloride pellets before and after the grafting in example 4 using a Secondary Ion Mass Spectrometer (SIMS), and the results are shown in fig. 1 and 2, respectively. As can be seen by comparing the mass spectrum of the polyvinyl chloride pellet before grafting in FIG. 1 with the mass spectrum of the polyvinyl chloride pellet after grafting in FIG. 2, the mass spectrum of FIG. 2 has a large number of peaks of-Cl-O-Si-group and-Cl-O-Si-O-group near the m/z values of 79 and 95, while the mass spectrum of FIG. 1 has no peak of such group, and the structural formula of the chemical raw material gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and epoxy resin of the grafted coating has no two groups, which indicates that the polyvinyl chloride pellet after grafting has a new group, wherein the-Cl bond in the new group is from the polyvinyl chloride pellet ([ CH-Cl bond)2Cl-CH2]n) And the-O-Si-O-and-O-Si-bonds are derived from gamma- (2, 3-glycidoxy) propyltrimethoxysilane, one of the graft coating materials, further indicating graftingThe dendritic coating is connected with the low-density organic globules through covalent bonds with higher bond energy.
TABLE 1 measurement results of water blocking height and contact angle of the low-density organic water-controlling proppant of the present invention
As shown in fig. 3, the manufacturing method of the proppant water-blocking height measuring device comprises the following steps: and cutting 40cm of an organic glass tube with the inner diameter of 5cm, and sealing one end of the organic glass tube by using a screen to prepare the simple instrument for measuring the water blocking height of the propping agent. The water blocking height of the low-density organic water-controlling proppant of the present invention was measured by the apparatus shown in fig. 3, as follows: adding a low-density organic water-control propping agent into a glass tube of the propping agent water-blocking height measuring device to reach the height of 5cm, and slowly pouring clear water along the wall of the organic glass tube; when water drops seep out of the bottom of the glass tube, recording the height of clear water in the organic glass tube above the end face of the propping agent as the water blocking height of the water-control propping agent; in addition, the contact angle of the low-density organic water-controlling proppant of the present invention was measured by a contact angle measuring instrument, and the measurement results are shown in table 1.
As can be seen from table 1, the low-density organic water-controlling proppant of the present invention has a certain water column height as measured by the self-made proppant water-blocking height measuring device, and compared with the low-density organic proppant, it is shown that when water passes through the low-density organic water-controlling proppant of the present invention, additional flow resistance is added, and the formation water-controlling effect under the oil well condition can be realized; meanwhile, the contact angle measurement of the low-density organic water-control proppant disclosed by the invention shows that the contact angle is positively correlated with the water-blocking height value, namely the larger the contact angle value is, the better the hydrophobic property is, and the better the water-control property of the low-density organic water-control proppant is.
Table 2 washout experiment measurement results of the low density organic water control proppant of the present invention
As shown in fig. 4, the manufacturing method of the proppant simulated washing experimental device comprises the following steps: and placing the proppant at the bottom of a 5-liter beaker, placing a layer of screen above the proppant, and placing a stirrer blade above the screen to prepare the simple device for the proppant scouring experiment. The washout resistance of the low density organic water-control proppant of the present invention was measured by the apparatus shown in fig. 4, as follows: placing a low-density organic water-controlling proppant into a beaker of a proppant washing experimental device, placing a layer of screen above the proppant, placing a stirrer blade above the screen, then adding filtered seawater into the beaker, keeping the liquid level above the stirring blade for 5cm, continuously washing for 7 days at the rotating speed of 1000 revolutions per minute, and then taking out and drying the low-density organic water-controlling proppant; then, the contact angle and the water-blocking height before and after the low-density organic water-controlling proppant washing experiment are respectively measured by a contact angle measuring instrument and a proppant water-blocking height measuring device, and the measurement results are shown in table 2.
As can be seen from table 2, the water blocking height and the contact angle of the low-density organic water-controlling proppant of the present invention were only slightly reduced after continuous multi-day flushing, as measured by the self-made proppant simulated flushing experimental apparatus, indicating that the organic water-controlling proppant can maintain a certain period of validity of formation water control under the condition of formation fluid seepage.
The low-density organic proppant has the density equivalent to that of water, has excellent carrying performance, and can greatly improve the filling efficiency of a shaft and a stratum in well completion filling and fracturing operations; meanwhile, the surface of the low-density organic proppant is subjected to hydrophobic modification, so that the low-density organic proppant has a water control function, and the life cycle of an oil well is prolonged; the low-density organic water-control proppant disclosed by the invention realizes the dual effects of low density and water control of the proppant in oil well completion or fracturing operation.
Although the methods and techniques of the present invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and/or rearrangements of the methods and techniques described herein may be made without departing from the spirit and scope of the invention. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and content of the invention.
Claims (10)
1. A low-density organic water-control proppant is characterized by being prepared by the following steps: and carrying out high-temperature oxidation activation on the surface of the low-density organic proppant substrate to generate active groups on the surface, grafting a graft coating material on the surface of the activated low-density organic proppant substrate to form a graft coating, and grafting a water-controlling coating material on the surface of the graft coating to form a water-controlling coating to obtain the low-density organic water-controlling proppant.
2. The low-density organic water-control proppant as set forth in claim 1, wherein the low-density organic proppant matrix is one of polystyrene pellets, polyvinyl chloride pellets, epoxy resin pellets, phenolic resin pellets, polyurethane pellets and husk particles, and the particle size of the low-density organic proppant matrix is 16-80 mesh.
3. The low density organic water control proppant of claim 1, wherein the graft coating material comprises one or more of the following components: water glass, urea resin, phenolic resin, polyacrylic resin, epoxy resin and glycidyl ether silane; the content of the graft coating material is 0.1-3 wt% of the mass of the low-density organic proppant substrate; the water control coating material comprises one or more of the following components: polyethylene resin, polypropylene resin, petroleum resin, silicone resin, modified polyfluoro resin; the content of the water control coating material is 0.5-5 wt% of the mass of the low-density organic proppant substrate.
4. The low density organic water control proppant of claim 3, wherein the glycidyl ether silane is γ - (2, 3-glycidoxy) propyltrimethoxysilane; the graft coating material is epoxy resin, gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and epoxy resin in a mass ratio of (1-2) to 6, or gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and phenolic resin in a mass ratio of 1 to 3.
5. A preparation method of a low-density organic water-control proppant is characterized by comprising the following steps:
step 1: heating a low-density organic proppant substrate to 200-350 ℃, keeping the temperature for more than 1min, and carrying out surface activation on the low-density organic proppant substrate;
step 2: adjusting the temperature of the low-density organic proppant substrate subjected to surface activation in the step (1) to 130-220 ℃, adding a graft coating material into the low-density organic proppant substrate, mixing and dispersing the mixture uniformly, and grafting the graft coating material on the surface of the low-density organic proppant substrate subjected to surface activation to form a graft coating;
and step 3: adjusting the temperature of the mixed material after the graft coating is formed in the step 2 to 100-200 ℃, adding a water-controlling coating material into the mixed material, and uniformly mixing, wherein the water-controlling coating material is grafted on the surface of the graft coating to form a water-controlling coating;
and 4, step 4: and (3) adding a curing agent into the mixed material with the water-control coating formed in the step (3) for full curing to obtain the low-density organic water-control propping agent.
6. The method for preparing the low-density organic water-control proppant as claimed in claim 5, wherein in the step 1, the temperature is kept for 1min to 2h to activate the surface of the low-density organic proppant matrix; wherein the particle size of the low-density organic proppant matrix is 16-80 meshes.
7. The method of claim 5, wherein in step 2, the graft coating material comprises one or more of the following components: water glass, urea resin, phenolic resin, polyacrylic resin and epoxy resin; the graft coating material further comprises a glycidyl ether silane; the addition amount of the grafting coating material is 0.1-3 wt% of the dosage of the low-density organic proppant substrate in the step 1; when the grafted coating material comprises glycidyl ether silane, firstly adding the glycidyl ether silane into the low-density organic proppant substrate subjected to surface activation in the step 1, uniformly mixing and dispersing, and then adding the rest components of the grafted coating material, uniformly mixing and dispersing.
8. The preparation method of the low-density organic water-controlling proppant as claimed in claim 5, wherein in the step 3, after the water-controlling coating material is added to the mixed material after the graft coating is formed in the step 2, the mixture is stirred for 30-60 s at a speed of 80-100 r/min to be uniformly mixed and form the water-controlling coating; wherein the water-controlling coating material comprises one or more of the following components: the water control coating material comprises polyethylene resin, polypropylene resin, petroleum resin, organic silicon resin and modified polyfluoro resin, wherein the addition amount of the water control coating material is 0.5-5 wt% of the dosage of the low-density organic proppant substrate in the step 1.
9. The preparation method of the low-density organic water-controlling proppant as claimed in claim 5, wherein in step 4, after the curing agent is added to the mixed material after the water-controlling coating is formed in step 3, the mixture is stirred for 10-20 s at a speed of 80-100 r/min to be fully cured, and then the cured mixed material is cooled to room temperature to obtain the low-density organic water-controlling proppant; wherein the curing agent comprises one or more of the following components: the curing agent is composed of maleic anhydride, ethylenediamine, m-phenylenediamine, triethylene tetramine, polyisocyanate, phthalic anhydride and urotropine, and the addition amount of the curing agent is 10-30 wt% of the sum of the addition amount of the graft coating material in the step 2 and the addition amount of the water control coating material in the step 3.
10. Use of the low density organic water control proppant of any one of claims 1 to 4 in oilfield completion packing and fracturing operations, wherein: the low-density organic water-control proppant has the dual effects of low density and water control in the well completion filling or fracturing operation of an oil field.
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