CN103849371A - Fracturing propping agent and its preparation method - Google Patents
Fracturing propping agent and its preparation method Download PDFInfo
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- CN103849371A CN103849371A CN201210504139.0A CN201210504139A CN103849371A CN 103849371 A CN103849371 A CN 103849371A CN 201210504139 A CN201210504139 A CN 201210504139A CN 103849371 A CN103849371 A CN 103849371A
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- silane coupling
- coupling agent
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- particles
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/80—Compositions for reinforcing fractures, e.g. compositions of proppants used to keep the fractures open
- C09K8/805—Coated proppants
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
- C04B26/10—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
- C04B26/10—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B26/14—Polyepoxides
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
- C04B26/10—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B26/16—Polyurethanes
Abstract
The invention provides a fracturing propping agent preparation method, and a fracturing propping agent prepared through the method. The fracturing propping agent comprises aggregate particles, and a silane coupling agent layer and a resin layer sequentially coated on the surfaces of the aggregate particles. The fracturing propping agent has the advantages of low breakage rate, good diversion capability and great industrial application prospect.
Description
Technical field
The fracturing propping agents that the present invention relates to the preparation method of a kind of fracturing propping agents, a kind of fracturing propping agents and prepared by the method.
Background technology
In the recovery process of oil, Sweet natural gas deep mining and ultra deep well, high locking pressure deposits of low permeability is after fracture treatment, Oil gas-containing rock layer is split, the passage that oil gas forms from crack, collect, fracturing propping agents enter Filling in rock crack in company with high-pressure solution, play support crack not stress discharge and closed effect, thereby keep high flow conductivity, make oil gas unimpeded, increase the output of oil and gas.Therefore, fracturing propping agents need to have certain intensity and flow conductivity, to meet the closure stress requirement on different depths stratum.
Existing fracturing propping agents are mainly haydite (generally take bauxitic clay as main raw material, and forming through 800 ℃ of above high temperature sinterings) and quartz sand.But the percentage of damage of haydite and quartz sand is high, the haydite crushing in reservoir easily moves, and flow conductivity is poor.RESIN COATING PROPPING AGENT is also widely used in recent years.This propping agent can, by regulating the type of resin to obtain the propping agent of various different performances, for example, in the time gathering oil, adopt lipophilic resin can improve recovery ratio.The existing method of preparing resin-coated sand normally mixes after fixing by the mixture that contains aggregate, resin and solidifying agent.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of new fracturing propping agents, a kind of fracturing propping agents and the fracturing propping agents that prepared by the method.
The invention provides a kind of fracturing propping agents, wherein, described fracturing propping agents comprise particles of aggregates and are coated on successively silane coupling agent layer and the resin layer on described particles of aggregates surface.
The present invention also provides a kind of preparation method of fracturing propping agents, wherein, the method comprises and particles of aggregates is mixed with silane coupling agent and react, obtain the particles of aggregates that surface is coated with silane coupling agent layer, and described surface is coated with to the particles of aggregates of silane coupling agent layer and mixed with resin evenly and solidifies.
In addition, the present invention also provides the fracturing propping agents that prepared by aforesaid method.
The normally direct resin-coated layer on particles of aggregates surface of the RESIN COATING PROPPING AGENT of prior art, but the present inventor finds, adopts the percentage of damage of the propping agent that such method obtains higher, flow conductivity is poor.And fracturing propping agents provided by the invention have added silane coupling agent layer between particles of aggregates and resin layer, the percentage of damage of the fracturing propping agents that obtain is lower, flow conductivity is better.Infer its reason, may be due to: particles of aggregates is inorganic materials, and resin is organic materials, and both compatibility are poor, easily occurs demixing phenomenon; And silane coupling agent is in fact the silane that a class has organo-functional group, in its molecule, not only there is the group (Si) that is easy to be combined with inorganic materials, also there is the group being easy to organic materials (resin etc.) combination; Be provided with silane coupling agent layer between particles of aggregates and resin layer after, can be by particles of aggregates together with resin layer mortise, thus the intensity of the fracturing propping agents that obtain is increased, and improve thus its performance stability and flow conductivity, reduce its percentage of damage.
Embodiment
Fracturing propping agents provided by the invention comprise particles of aggregates and are coated on successively silane coupling agent layer and the resin layer on described particles of aggregates surface.
According to the present invention, described particles of aggregates can be the existing various particulate materials of preparing fracturing propping agents that can be used in, and for example, described particles of aggregates can be selected from one or more in roughing sand, slag, haydite and glass microballon.Wherein, described roughing sand is also referred to as quartz sand conventionally, and its hardness is 7 left and right, and property is crisp and hard.Roughing sand Heat stability is good, starts to soften while being heated to 1500 ℃, has good acid-alkali-corrosive-resisting.The main chemical compositions of roughing sand is silicon oxide (SiO
2), contain a small amount of aluminum oxide (Al simultaneously
2o
3) and ferric oxide (Fe
2o
3).
The present invention is not particularly limited the mean diameter of described particles of aggregates, and can reasonably select according to actual needs, and for example, the mean diameter of described particles of aggregates can be 0.04-5 millimeter, is preferably 0.05-2 millimeter, more preferably 0.1-0.85mm.The mean diameter of described particles of aggregates is to adopt method of sieving to measure., particles of aggregates is measured by the sieve aperture of different size.
According to the present invention, the degree of sphericity of described particles of aggregates can be selected and change in wider scope, and as a rule, degree of sphericity is better, and the flow conductivity after fragmentation is stronger, and therefore, under preferable case, the circularity of described particles of aggregates and sphericity are preferably >=0.6.Wherein, " sphericity " refers to the degree of particle subglobular; " circularity " refers to the relative acutance of grain corner or measuring of curvature.The measuring method of sphericity and circularity is conventionally known to one of skill in the art, for example, can adopt chart method to measure.
The present invention is not particularly limited the thickness of described silane coupling agent layer, can adjust according to practical situation, as long as can improve the bonding strength between described particles of aggregates and resin layer, for example, the thickness of described silane coupling agent layer can be 0.0001-0.001mm.
According to the present invention, the silane coupling agent in described silane coupling agent layer can be the existing various silicon-containing coupling reagents with organo-functional group, and for example, its structural formula can be as shown in formula I:
formula I,
Wherein, R
1and R
2for C
1-C
5alkyl, R
3for C
1-C
5alkyl or C
1-C
5alkoxyl group, R
4for C
1-C
5alkyl, C
1-C
5alkoxyl group, C
1-C
8alkylidene amino or C
1-C
8alkylidene group epoxy group(ing), described R
4on carbon atom and/or hydrogen atom optionally replaced by heteroatoms, described heteroatoms is selected from nitrogen, oxygen, sulphur, silicon, phosphorus or halogen.
Described C
1-C
5the specific examples of alkyl can include but not limited to: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, tert-pentyl or neo-pentyl.Described C
1-C
5the specific examples of alkoxyl group can include but not limited to: methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert.-butoxy, n-pentyloxy, isopentyloxy, tertiary pentyloxy or neopentyl oxygen.
Particularly, described silane coupling agent can be selected from one or more in r-aminopropyltriethoxywerene werene, r-glycidyl ether oxygen propyl trimethoxy silicane and N-(β-aminoethyl)-r-aminopropyl methyl dimethoxysilane.The angle of the crushing strength of the fracturing propping agents that prepared by method of the present invention from further raising, described silane coupling agent is particularly preferably r-aminopropyltriethoxywerene werene and/or r-glycidyl ether oxygen propyl trimethoxy silicane.
The present invention is not particularly limited the thickness of described resin layer, and as a rule, the thickness of described resin layer is larger, and the recovery ratio of oil and natural gas is higher, but the percentage of damage of the fracturing propping agents that obtain is also higher; The thickness of described resin layer is less, the intensity of the fracturing propping agents that obtain is higher, but flow conductivity is also poorer, therefore, consider the intensity of the fracturing propping agents that obtain, with and recovery ratio and flow conductivity to oil and natural gas, the thickness of described resin layer is preferably 0.01-0.02mm.
In the present invention, the thickness of the mean diameter of described particles of aggregates, silane coupling agent layer and the thickness of resin layer can adopt electron microscope to measure.
According to the present invention, described resin layer is for to obtain resin solidification.Described resin can be various resin well known in the art, there is no particular restriction.Under normal circumstances, in described oil well or gas well, contain water, in the process of recover petroleum or Sweet natural gas, oil well or gas WIH can, along with oil gas together extraction, increase exploitation difficulty (exploitation of oil gas mainly relies on reservoir pressure) thereby a large amount of underground water can reduce reservoir pressure after being plucked out of.Therefore,, in order to make the pressure in oil well or gas well keep balance, under preferable case, described resin is hydrophobic resin.Described hydrophobic resin can be selected from one or more in hydrophobicity epoxy resin, hydrophobicity resol, hydrophobicity furane resin, hydrophobic polyurethane and unsaturated polyester.Described resin all can be commercially available.
Wherein, described hydrophobicity epoxy resin for example can be selected from bisphenol A type epoxy resin, glycidyl ether based epoxy resin, glycidyl ester based epoxy resin, Racemic glycidol amine epoxy resin, aliphatic category epoxy resin, polysulfide-rubber-modified epoxy, polyamide resin modified epoxy, the tertiary butyraldehyde modified epoxy of polyvinyl alcohol, acrylonitrile butadiene rubber modified epoxy resin, phenolic resin modified epoxy resin, vibrin modified epoxy, urea aldehyde Melamine resin modified epoxy resin, furfuryl resin modified epoxy, ethenoid resin modified epoxy, one or more in isocyanate modified epoxy resin and silicone resin modified epoxy.
According to the present invention, described hydrophobicity resol for example can be selected from one or more in dimethylbenzene modified phenolic resins, epoxy resin modification resol and Effect of Organosilicon-modified Phenol-formaldehyde Resin.
The preparation method of described fracturing propping agents provided by the invention comprises and particles of aggregates is mixed with silane coupling agent and react, obtain the particles of aggregates that surface is coated with silane coupling agent layer, and described surface is coated with to the particles of aggregates of silane coupling agent layer and mixed with resin evenly and solidifies.
The present invention is to being not particularly limited particles of aggregates with the condition that the mixture of silane coupling agent reacts, as long as can make the surface obtaining be coated with the particles of aggregates of silane coupling agent layer, as a rule, the condition of described reaction comprises temperature of reaction and reaction times.Described temperature of reaction can be selected and change in wider scope, but in order to be more conducive to the mortise between silane coupling agent layer and particles of aggregates, described temperature of reaction is preferably 100-250 ℃.The prolongation in described reaction times is conducive to silane coupling agent being evenly coated on particles of aggregates surface, but it is also not obvious that reaction times process can be coated the amplitude of degree of uniformity raising, therefore, consider efficiency and effect, the described reaction times is preferably 0.01-0.5 hour.
According to the present invention, the consumption of described silane coupling agent can be selected according to the thickness of the silane coupling agent in the actual fracturing propping agents that will obtain, as a rule, in the time that making the thickness of the silane coupling agent layer that is coated on particles of aggregates surface be 0.0001-0.001mm, the consumption of described silane coupling agent can meet the demand of use.
According to the present invention, the kind of described particles of aggregates and silane coupling agent can, according to above reasonably selecting, will repeat no more at this.
The present invention is also not particularly limited the consumption of described resin, and can select according to the thickness of the resin layer in the actual fracturing propping agents that will obtain, as mentioned above, in order to take into account the intensity of the fracturing propping agents that obtain and the recovery ratio to oil and natural gas and flow conductivity, the thickness of described resin layer is preferably 0.01-0.02mm, therefore, the consumption of described resin is 0.01-0.02mm as long as preferably make the thickness of the resin layer obtaining.
According to the present invention, as mentioned above, the kind of described resin is known to the skilled person, and is preferably selected from one or more in hydrophobicity epoxy resin, hydrophobicity resol, hydrophobicity furane resin, hydrophobic polyurethane and unsaturated polyester.Wherein, in order further to improve the curing performance of resin, the preparation method of described fracturing propping agents is preferably coated with solidifying agent and surface after the particles of aggregates of silane coupling agent layer and resin are mixed together solidifies again.The kind of described solidifying agent can reasonably be selected according to described resin.For example, for glycidyl ether based epoxy resin, glycidyl ester based epoxy resin, Racemic glycidol amine epoxy resin, aliphatic category epoxy resin, polysulfide-rubber-modified epoxy, polyamide resin modified epoxy, the tertiary butyraldehyde modified epoxy of polyvinyl alcohol, acrylonitrile butadiene rubber modified epoxy resin, phenolic resin modified epoxy resin, vibrin modified epoxy, urea aldehyde Melamine resin modified epoxy resin, furfuryl resin modified epoxy, ethenoid resin modified epoxy, isocyanate modified epoxy resin and silicone resin modified epoxy, described solidifying agent is preferably selected from aliphatic amide, aliphatic cyclic amine, aromatic amine, polymeric amide, one or more in acid anhydrides and tertiary amine.For dimethylbenzene modified phenolic resins, epoxy resin modification resol and Effect of Organosilicon-modified Phenol-formaldehyde Resin, described solidifying agent is preferably selected from hexamethylenetetramine.For described hydrophobic polyurethane resin, described solidifying agent is preferably selected from the prepolymer of affixture, TDI and hydroxy-containing component and the tripolymer of TDI of tolylene diisocyanate (TDI), Trimethoprim (TMP).For unsaturated polyester (polymkeric substance of terephthalic acid and ethylene glycol), the solidifying agent adding when normal temperature is preferably ketone peroxide and/or cobalt naphthenate, and the solidifying agent adding when heating is preferably selected from one or more in peroxidized t-butyl perbenzoate, peroxy dicarbonate, dialkyl peroxide, the tertiary own ester of peroxidation acid and bis peroxy dicarbonate.Take the described resin of 100 weight parts as benchmark, the content of described solidifying agent can be for 1-20 weight part, be preferably 5-18 weight part.
According to the present invention, described curing condition can be that the routine of this area is selected, as long as can be by described resin solidification, the resin layer that makes to obtain is coated on surface and is coated with the particles of aggregates surface of silane coupling agent layer, as a rule, described curing condition can comprise solidification value and set time.Described solidification value can be carried out appropriate selection according to the resin of selecting and the kind of solidifying agent, as a rule, in the time that described solidification value is 100-250 ℃, just can make described solidifying carry out smoothly.As a rule, the prolongation of described set time is conducive to solidify more completely, but set time, the long amplitude that state of cure is improved was also not obvious, therefore, considered effect and efficiency, was preferably 0.01-0.5 hour described set time.
According to the present invention, from the angle of avoiding mutually boning between particles of aggregates, under preferred described reaction and the curing preferred condition stirring, to carry out, the speed of described stirring can be carried out choose reasonable according to practical situation, will repeat no more at this.
In addition, the present invention also provides the fracturing propping agents that prepared by aforesaid method.
Describe the present invention in detail below in conjunction with embodiment.
In following examples and comparative example, the thickness of the mean diameter of described particles of aggregates, the thickness of silane coupling agent layer and resin layer all adopts digital Stereo microscope (purchased from Bejing Huaqi Information Digital Science & Technology Co., Ltd, trade mark DLC300) to measure.
In following examples and comparative example:
Roughing sand: purchased from blue sky, Yongdeng quartz sand company limited, circularity and sphericity are 0.7, particle diameter is 40/20 order (0.425-0.85 millimeter);
Haydite: purchased from holy well water-purifying material factory of Gongyi City, circularity and sphericity are 0.9, particle diameter is 70/40 order (0.212-0.425 millimeter).
Embodiment 1
This embodiment is used for illustrating fracturing propping agents provided by the invention and preparation method thereof.
(1) 2000g roughing sand is mixed with the r-aminopropyltriethoxywerene werene of 2g, then temperature is risen to 250 ℃ after stirring reaction 0.05 hour, obtain surface and be coated with the particles of aggregates of silane coupling agent layer;
(2) at 250 ℃, particles of aggregates and 100g epoxy resin that the surface that step (1) is obtained is coated with silane coupling agent layer (are purchased from Langfang Nore letter Chemical Co., Ltd., the trade mark is E-44, oxirane value is 0.44mol/100g, hydroxyl value is 0.088mol/100g) be uniformly mixed, then add 40g tetrahydrophthalic anhydride and 3g diethylenetriamine and continue to be uniformly mixed 0.05 hour, then temperature is reduced to 25 ℃ of room temperatures, thereby obtain comprising and be coated on successively the silane coupling agent layer on particles of aggregates surface and the fracturing propping agents Z1 of resin layer, wherein, the thickness of silane coupling agent layer is 0.0001-0.001mm, the thickness of resin layer is 0.01-0.02mm.
Embodiment 2
This embodiment is used for illustrating fracturing propping agents provided by the invention and preparation method thereof.
(1) 2000g haydite is mixed with N-(β-aminoethyl)-r-aminopropyl methyl dimethoxysilane of 2g, then temperature is risen to 100 ℃ after stirring reaction 0.5 hour, obtain surface and be coated with the particles of aggregates of silane coupling agent layer;
(2) at 100 ℃, particles of aggregates and 100g urethane resin that the surface that step (1) is obtained is coated with silane coupling agent layer (are purchased from Dongguan City Jing Ze resin company limited, the trade mark is FR-HE603) be uniformly mixed, then add 10gTDI trimer curing agent (Le Liu town, Shunde City Bo Gao coating factory, and continue to be uniformly mixed 0.5 hour BG350TB), then temperature is reduced to 25 ℃ of room temperatures, thereby obtain comprising and be coated on successively the silane coupling agent layer on particles of aggregates surface and the fracturing propping agents Z2 of resin layer, wherein, the thickness of silane coupling agent layer is 0.0001-0.001mm, the thickness of resin layer is 0.01-0.02mm.
Embodiment 3
This embodiment is used for illustrating fracturing propping agents provided by the invention and preparation method thereof.
(1) 2000g haydite is mixed with the r-glycidyl ether oxygen propyl trimethoxy silicane of 2g, then temperature is risen to 150 ℃ after stirring reaction 0.3 hour, obtain surface and be coated with the particles of aggregates of silane coupling agent layer;
(2) at 150 ℃, particles of aggregates and 100g epoxy resin that the surface that step (1) is obtained is coated with silane coupling agent layer (are purchased from Langfang Nore letter Chemical Co., Ltd., the trade mark is E-51, oxirane value is 0.51mol/100g, hydroxyl value is 0.046mol/100g) be uniformly mixed, then add 40g tetrahydrophthalic anhydride and 3g diethylenetriamine, and continue to be uniformly mixed 0.2 hour, then temperature is reduced to 25 ℃ of room temperatures, thereby obtain comprising and be coated on successively the silane coupling agent layer on particles of aggregates surface and the fracturing propping agents Z3 of resin layer, wherein, the thickness of silane coupling agent layer is 0.0001-0.001mm, the thickness of resin layer is 0.01-0.02mm.
Embodiment 4
This embodiment is used for illustrating fracturing propping agents provided by the invention and preparation method thereof.
Method according to embodiment 1 is prepared fracturing propping agents, different, and it is 0.001-0.006mm that the consumption of described epoxy resin and r-aminopropyltriethoxywerene werene makes the thickness of the silane coupling agent layer obtaining, and the thickness of resin layer is 0.02-0.04mm.
Comparative example 1
This comparative example is used for illustrating reference fracturing propping agents and preparation method thereof.
Method according to embodiment 1 is prepared fracturing propping agents, different is, described silane coupling agent (is purchased from Langfang Nore letter Chemical Co., Ltd. with the epoxy resin of identical weight part, the trade mark is E-44, oxirane value is 0.44mol/100g, hydroxyl value is 0.088mol/100g) substitute, obtain reference fracturing propping agents DZ1.
Test case 1-4
Test case 1-4 is for illustrating the test of fracturing propping agents performance provided by the invention.
According to standard SY/T5108-2006, the performance of the fracturing propping agents that prepared by embodiment 1-4 is tested, test result is as shown in table 1 below.
Contrast test example 1
This contrast test example is for illustrating the performance test of reference fracturing propping agents.
According to the method for test case 1-4, the performance of fracturing propping agents is tested, different, test be the fracturing propping agents that made by the method for comparative example 1, test result is as shown in table 1.
Table 1
Wherein, " sphericity " refers to the degree of proppant particles subglobular; " circularity " refers to the relative acutance of its corner angle or measuring of curvature, and practical measurement can be used chart method; " volume density " refers to the propping agent of unit mass and the ratio of its stacking volume; " volume density " refers to the propping agent of unit mass and the ratio of its particle volume; " turbidity " refers to add the propping agent of certain volume in the distilled water of unit volume, then stirs, and the muddy degree of liquid is called the turbidity of propping agent; " acid solubility " refers at the acid solution of regulation and in the acid-soluble time, determines that certain mass propping agent is by the per-cent of the quality of acid-soluble solution and total propping agent quality; " percentage of damage " refers to the propping agent to certain volume, carries out pressure-bearing test under rated pressure, and definite percentage of damage has characterized the ability of the anti-fragmentation of propping agent.
Can find out from the result of above-mentioned table 1, the fracturing propping agents that adopt method provided by the invention to prepare have good flow conductivity and anti-percentage of damage and good antiacid corrodibility, can reach the performance requriements of fracturing propping agents, be the stratum below 69MPa for locking pressure.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition each the concrete technical characterictic described in above-mentioned embodiment, in reconcilable situation, can combine by any suitable mode.For fear of unnecessary repetition, the present invention is to the explanation no longer separately of various possible array modes.
In addition, also can carry out arbitrary combination between various embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (10)
1. fracturing propping agents, is characterized in that, described fracturing propping agents comprise particles of aggregates and are coated on successively silane coupling agent layer and the resin layer on described particles of aggregates surface.
2. fracturing propping agents according to claim 1, wherein, the mean diameter of described particles of aggregates is 0.04-5mm, and the thickness of described silane coupling agent layer is 0.0001-0.001mm, and the thickness of described resin layer is 0.01-0.02mm.
3. fracturing propping agents according to claim 1 and 2, wherein, the structure of the silane coupling agent in described silane coupling agent layer is as shown in formula I:
formula I,
Wherein, R
1and R
2for C
1-C
5alkyl, R
3for C
1-C
5alkyl or C
1-C
5alkoxyl group, R
4for C
1-C
5alkyl, C
1-C
5alkoxyl group, C
1-C
8alkylidene amino or C
1-C
8alkylidene group epoxy group(ing), described R
4on carbon atom and/or hydrogen atom optionally replaced by heteroatoms, described heteroatoms is selected from nitrogen, oxygen, sulphur, silicon, phosphorus or halogen.
4. fracturing propping agents according to claim 3, wherein, described silane coupling agent is selected from one or more in r-aminopropyltriethoxywerene werene, r-glycidyl ether oxygen propyl trimethoxy silicane and N-(β-aminoethyl)-r-aminopropyl methyl dimethoxysilane.
5. fracturing propping agents according to claim 1 and 2, wherein, the circularity of described particles of aggregates and sphericity are all >=0.6; Preferably, described resin layer is by one or more curing the obtaining in hydrophobicity epoxy resin, hydrophobicity resol, hydrophobicity furane resin, hydrophobic polyurethane resin and unsaturated polyester.
6. the preparation method of fracturing propping agents, it is characterized in that, the method comprises and particles of aggregates is mixed with silane coupling agent and react, obtain the particles of aggregates that surface is coated with silane coupling agent layer, and described surface is coated with to the particles of aggregates of silane coupling agent layer and mixed with resin evenly and solidifies.
7. preparation method according to claim 6, wherein, the mean diameter of described particles of aggregates is 0.04-5mm, it is 0.0001-0.001mm that the consumption of described silane coupling agent makes the thickness of the silane coupling agent layer that is coated on particles of aggregates surface, and the thickness that the consumption of described resin makes to be coated on the resin layer on silane coupling agent layer is 0.01-0.02mm.
8. according to the preparation method described in claim 6 or 7, wherein, the structure of described silane coupling agent is as shown in formula I:
formula I,
Wherein, R
1and R
2for C
1-C
5alkyl, R
3for C
1-C
5alkyl or C
1-C
5alkoxyl group, R
4for C
1-C
5alkyl, C
1-C
5alkoxyl group, C
1-C
8alkylidene amino or C
1-C
8alkylidene group epoxy group(ing), described R
4on carbon atom and/or hydrogen atom optionally replaced by heteroatoms, described heteroatoms is selected from nitrogen, oxygen, sulphur, silicon, phosphorus or halogen; Preferably, described silane coupling agent is selected from one or more in r-aminopropyltriethoxywerene werene, r-glycidyl ether oxygen propyl trimethoxy silicane and N-(β-aminoethyl)-r-aminopropyl methyl dimethoxysilane.
9. according to the preparation method described in claim 6 or 7, wherein, the condition of described reaction comprises that temperature is that 100-250 ℃, time are 0.01-0.5 hour.
10. the fracturing propping agents that prepared by the method described in any one in claim 6-9.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105368441A (en) * | 2014-08-26 | 2016-03-02 | 王霆 | Spherical ceramsite petroleum propping agent coated with silicon resin and preparing method thereof |
| CN105602536A (en) * | 2015-11-09 | 2016-05-25 | 中国石油化工股份有限公司 | Non-acid solution high-strength plugging agent, and preparation method thereof |
| CN105885819A (en) * | 2014-08-26 | 2016-08-24 | 王霆 | Ultralow-density spherical silicon resin oil proppant and preparation method thereof |
| CN106987239A (en) * | 2016-01-21 | 2017-07-28 | 中国石油化工股份有限公司 | A kind of compound hollow microballoon and its preparation method and application |
| CN109705836A (en) * | 2019-01-24 | 2019-05-03 | 陕西科技大学 | A kind of preparation method of bivalve layer coated sand proppant |
| JP2019529304A (en) * | 2016-09-16 | 2019-10-17 | ダウ グローバル テクノロジーズ エルエルシー | Particles coated with adhesion promoters for polymer concrete compositions |
| CN110591686A (en) * | 2019-09-30 | 2019-12-20 | 西安摩根恩能能源科技有限公司 | Proppant for oil and gas exploitation and preparation method thereof |
| CN112680205A (en) * | 2019-10-17 | 2021-04-20 | 中国石油化工股份有限公司 | Surfactant oil displacement system and preparation method thereof |
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| CN105368441A (en) * | 2014-08-26 | 2016-03-02 | 王霆 | Spherical ceramsite petroleum propping agent coated with silicon resin and preparing method thereof |
| CN105885819A (en) * | 2014-08-26 | 2016-08-24 | 王霆 | Ultralow-density spherical silicon resin oil proppant and preparation method thereof |
| CN105602536A (en) * | 2015-11-09 | 2016-05-25 | 中国石油化工股份有限公司 | Non-acid solution high-strength plugging agent, and preparation method thereof |
| CN105602536B (en) * | 2015-11-09 | 2018-07-03 | 中国石油化工股份有限公司 | A kind of non-acid-soluble high intensity seal stoppage agent and preparation method thereof |
| CN106987239A (en) * | 2016-01-21 | 2017-07-28 | 中国石油化工股份有限公司 | A kind of compound hollow microballoon and its preparation method and application |
| CN106987239B (en) * | 2016-01-21 | 2022-07-15 | 中国石油化工股份有限公司 | Composite hollow microsphere and preparation method and application thereof |
| JP2019529304A (en) * | 2016-09-16 | 2019-10-17 | ダウ グローバル テクノロジーズ エルエルシー | Particles coated with adhesion promoters for polymer concrete compositions |
| JP7186693B2 (en) | 2016-09-16 | 2022-12-09 | ダウ グローバル テクノロジーズ エルエルシー | Adhesion promoter coated particles for polymer concrete compositions |
| CN109705836A (en) * | 2019-01-24 | 2019-05-03 | 陕西科技大学 | A kind of preparation method of bivalve layer coated sand proppant |
| CN110591686A (en) * | 2019-09-30 | 2019-12-20 | 西安摩根恩能能源科技有限公司 | Proppant for oil and gas exploitation and preparation method thereof |
| CN110591686B (en) * | 2019-09-30 | 2021-05-28 | 西安摩根恩能能源科技有限公司 | Proppant for oil and gas exploitation and preparation method thereof |
| CN112680205A (en) * | 2019-10-17 | 2021-04-20 | 中国石油化工股份有限公司 | Surfactant oil displacement system and preparation method thereof |
| CN112680209A (en) * | 2019-10-17 | 2021-04-20 | 中国石油化工股份有限公司 | Proppant and preparation method thereof |
| CN112680209B (en) * | 2019-10-17 | 2022-12-09 | 中国石油化工股份有限公司 | Proppant and preparation method thereof |
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