CN109321229A - One kind is from suspended prop - Google Patents
One kind is from suspended prop Download PDFInfo
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- CN109321229A CN109321229A CN201811159577.1A CN201811159577A CN109321229A CN 109321229 A CN109321229 A CN 109321229A CN 201811159577 A CN201811159577 A CN 201811159577A CN 109321229 A CN109321229 A CN 109321229A
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- resin
- coat
- proppant
- haydite
- suspended prop
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/80—Compositions for reinforcing fractures, e.g. compositions of proppants used to keep the fractures open
- C09K8/805—Coated proppants
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- 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
- C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
- C09D171/02—Polyalkylene oxides
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
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- General Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The present patent application belongs to the fluid minerals production technique such as petroleum, natural gas and shale gas field, it specifically discloses a kind of from suspended prop, including aggregate and coat, the coat includes resin, curing agent and additive, and the aggregate is 1.05~2.65g/cm of apparent density3Haydite, the additive be aminated compounds.Present invention is mainly used for exploitation petroleum, shale gas, solve the problems, such as that proppant causes cost to increase and cause environmental pollution using needing to add gelling agent in clear water.
Description
Technical field
The invention belongs to the fluid minerals production technique such as petroleum, natural gas and shale gas fields, specifically disclose one kind certainly
Suspended prop.
Background technique
Modern age, the conventional production technique innovation and development with unconventional oil and gas formd the hydraulic fracturing normal technology of system
Specification, basic technical features are exactly to use fracturing system, will contain various functional materials by high pressure pump truck and help
The water base mixing liquid of agent is sent into underground and produces that all size is different, crack widely distributed, that go deep into reservoir, and keeps obtaining
Reservoir fracture be in the interconnected a kind of volume increase for reaching reservoir reconstruction of non-occluded state bring reservoir and production tubing
Technical system.It is exactly to keep non-closed in the reservoir fracture of acquisition as a kind of technical method vital in the technical system
It needs to insert to have in crack when state and centainly Z can be continuously maintained the proppant that voidage will not be crushed by reservoir closed high
Material, this material are referred to as " proppant ".Due to the technology utilize be economy preferably and have incompressible characteristic
How the water that nature is easily obtained is more convenient to be easy in such liquid, is more efficient, economically will " branch as carrier
It is all that oil fracturing engineers are dedicated to the major class technical problem solved all the time that support agent ", which is sent into reservoir,.
The usual material of proppant for meeting pressing crack construction requirement is that inorganic high-strength degree material is prepared, because its apparent density is equal
It is far longer than clear water density 1g/cm3, so various glue must be added by carrying the carrying liquid of high-visual density proppant when pressing crack construction
The proppant that clear water presentation " frozen glue " state will be added will in carrying liquid in solidifying agent wraps carrying by gel and is sent into reservoir fracture,
Then the carrying liquid addition gel breaker of " frozen glue " shape is broken glue again makes " proppant being suspended " to be deposited to crack by self weight
In play the role of support crack.For this purpose, engineers can will also be propped up in searching without using " gelling agent " clear water for a long time
The technological approaches that agent is sent into reservoir is supportted, the technology of the opposite apparent density difference of inorganic material proppant and load fluid is such as reduced, makes
The absolute apparent density that proppant is reduced with organic synthesis material is combined using low-density inorganic material with organic overlay film compound
Material reduces the technology of density, and using mutual between surfactant and coated material change proppant and carrying liquid
Active force, technology of wellability etc..Although achieving certain effect, it is difficult to realize that pure clear water is taken as pressing crack construction always
The technical effect of sand liquid.
Proppant is mainly to be formed by aggregate with the resin film for being coated on aggregate surface at present, and resin film common at present has
Phenolic resin film, epoxy resin film and urethane resin film etc., but at present in the main mesh of mode of proppant surface overlay film
Be improve aggregate intensity, so what is usually solved is how to improve resin film strength, to promote the water conservancy diversion of proppant
Ability, but proppant in the prior art does not have suspendability in clear water, is not able to satisfy construction requirement, when construction, still need
The carrying liquid with vicidity is prepared again, carries the chemical gum material contained in liquid, and there is injury and meeting to subsurface reservoir
It pollutes the environment, while increasing use cost.
Summary of the invention
The purpose of the present invention is to provide one kind from suspended prop, to solve proppant in clear water using needing to add
The problem of gelling agent causes cost to increase and causes environmental pollution.
In order to achieve the above object, base case of the invention are as follows: a kind of from suspended prop, including aggregate and coating
Layer, the coat include resin, catalyst, curing agent and additive, and the aggregate is 1.05~2.65g/cm of apparent density3's
Haydite, the additive are aminated compounds.
The working principle of this base case is: after the proppant in the present invention is mixed with water, proppant can suspend or
Person half suspends in water；In pressing crack construction, mixture is pumped in the crack of lithosphere, proppant can be entered with water to be split
It plays a supporting role in seam.
The beneficial effect of this base case is:
(1) it is 1.05~2.65g/cm that the present invention, which is with apparent density,3Haydite is the proppant that aggregate is prepared into, through inventor
Test discovery uses range density for 1.05~2.65g/cm when additive is aminated compounds3The proppant energy of haydite preparation
It is uniformly suspended in clear water, the time to suspend in clear water is at least 4h, can reach construction requirement；Proppant of the invention exists
Coating layer surface contains nanoscale protrusion, these protrusions extend in the surface of proppant particles, and protrusion will increase the floating of proppant
Power, while when proppant and water contact, a kind of group reserved in surface coating resin can react rapidly with water to be released greatly
It measures gas molecules, these gas molecules or is enclosed in resin film to expand against resin membrane body stage and thicken and increases branch
The equivalent diameter of agent granule is supportted, or is attached to the extension of proppant surface stage or is gathered in proppant resin film and connect with water body
The gas blanket of one layer of package proppant particles body, this gas blanket formation stages between proppant particles body are formed on the interface of touching
Property be connected to and the result closed causes simple grain proppant to form more loose cotton wadding in water body to gather shape, thus drop significantly
The low relative density of proppant in water, so as to make proppant suspend in water.When proppant moves in water, branch
The protrusion of curved surface on support agent resin film can reduce the proppant rate of settling in water；Part is settled down to the branch of water bottom accumulation
Support agent reduces the degree of packing of proppant particles stack layer because the more protrusion of its surface resin film is attached to proppant surface,
Intergranular water body amount is more compared with conventional particle stack, and then when water body can be more easier the fluidity with very little
Ground pushes the separation of its congeries and movement, realizes that proppant preferably suspends in water；
(2) proppant is mixed into water, proppant can be made to suspend or partly suspend in water, proppant enters in rock
Gap after proppant can be made to dispersing, to ensure that proppant has preferable support effect with water flowing；
(3) after proppant is mixed with water, other thickening substances are not added, protective effect is played to environment；Use water
As suspending agent, use cost is low；
(4) the Applicable temperature range of proppant of the invention in pressing crack construction is 5 DEG C -145 DEG C, proppant Applicable temperature
Range is wide, and the stability in this temperature range is good；
(5) scheme change traditional pressing crack construction need to be added guar gum etc. thickening substance, realize clear water take sand.Thus
Pressure break cost is greatly saved, construction technology is simplified, reduces the pollution to environment, saves water resource；Use haydite as aggregate
Proppant, proppant sphericity is good, intensity is high, water conservancy diversion is good.
Compared with prior art, this proppant can use in the water of PH > 3, and alkalinity is stronger, and suspension is better, in height
The suspension of proppant is more preferable in the water of salinity, is more advantageous to pressing crack construction, is influenced by water quality smaller, and stability is good, fits
It is wide with range.
Further, the coat includes interior coat and outer coat, and the outer coat is by polyalcohols resin, different
Cyanate and catalyst are made, and in outer coat, the isocyanates accounts for polyalcohols resin for the aminated compounds addition
40-80%, the hydroxyl equivalent of the polyalcohols resin is 60-300.Applicant it is found through experiment that, using in above range
Isocyanates, urethane resin film can be formed on outer coat, polyurethane resin can be sent out under the action of amines additives
Raw reaction generates bubble, can coat layer surface when bubble is overflowed to outside film outside and form more protrusions, bump sizes are between 100
~500nm, protrusion is in coating layer surface random distribution, when protrusion is observed under scanning electron microscope on the resin membrane body of discovery deep dark
For light highlighted or white curved body, there is the random distribution of heterogencity in the surface resin film of single particle body, then be
The surface of every 100 square micron has 1~40 or so protrusion under homogeneous distribution state, increases the suspension of proppant in this way
Performance；A certain number of isocyanate-reactive groups are also reserved in the resin film body of above-mentioned proppant simultaneously, work as residue
Isocyanate groups meet water after, reacted with water and gas can be generated in the microcosmic small space body that the chain element of resin film surrounds
Body, gradually overall volume forms bubble to this small quantity gas under the promotion of reaction energy, and pushes resin film in proppant
The radial dimension of grain increases, and outer coat can be made to expand in this way, further improve the suspendability of proppant.
Further, epoxy group, phenolic hydroxyl group, carbonyl, amide are at least contained in the resinous molecular structure in the interior coat
The organic macromolecule material of base, amino, two or more groups in isocyanate group, the resin average mark in the interior coat
Son amount is greater than 100.Using above-mentioned resin, the resin film formed in interior coat can become the film of netted high intensity with precuring
Form can't discharge other so that product is contacted with fracturing fluid when being applied to oil field fracturing construction with chemical inertness height
Harmful substance.
Further, the haydite is 100 parts, and total amount of resin in interior coat and outer coat is 2-10 parts, interior coating
The curing agent that layer uses is the 10-50% of resin in interior coat, and the quality of the catalyst is the 1/ of polyalcohols resin
, the quality of the aminated compounds is the 1-20% of polyalcohols resin quality；It is more when containing in interior coat
When first alcohol resinoid and other resins, the mass ratio of polyalcohols resin and other resins is 1:1-5.It is upper when containing in proppant
When stating haydite, resin, curing agent, catalyst and the aminated compounds of ratio, proppant can have preferable suspension effect；Using more
First alcohol resinoid and isocyanates can form more protrusion in outer coat under the action of catalyst, increase proppant in this way
Buoyancy in water, enables proppant to suspend in water.
Further, range of viscosities of the polyalcohols resin at 20 DEG C is 30~60cp.It is more in above-mentioned range of viscosities
The film strength that first alcohol resinoid is formed is high, and Technological adaptability is strong, acid-fast alkali-proof.
Further, sphericity >=0.7 of the haydite, circularity >=0.7, percentage of damage≤8%, acid solubility≤5%.
Further, the aminated compounds is diethylenetriamine, triethylamine, ethamine, triethylene tetramine, one in ethylenediamine
Kind or two or more compositions.The molecule of above-mentioned amine is small, and reactivity is big.
Further, the curing agent includes organic amine, organic acid anhydride, stearic acid, dihydroxy stearic acid, oleic acid, sub- oil
The mixture of one of acid, ricinoleic acid or any component, the degree of functionality of the curing agent are 2-5.When between degree of functionality 2-5,
Curing agent reactivity is good, can accelerate the comprehensive performance performance and chemical synthesis inertia of the resin membrane body of support surface coat.
Further, the catalyst is one or more of alkyls tin compound and/or alkyls lead compound
Mixture.Use the suspending efficiency of raising proppant in water when the catalyst of alkyls tin and/or alkyl ekalead.
Further, alkyls tin compound includes dibutyl tin dilaurate, tributyl tin, the alkyls lead compound
Including lead tetraethide, isooctyl acid lead.It can accelerate the solidification rate of coat using above-mentioned catalyst and intensity shows.
Detailed description of the invention
Fig. 1 is a kind of electron-microscope scanning figure from suspended prop embodiment 1 of the present invention；
Fig. 2 is the display figure of proppant under the microscope in embodiment 1.
Specific embodiment
It is further described below by specific embodiment:
Raw material selected by the present invention is as follows:
Aggregate is haydite.The apparent density of haydite is 1.05~2.65g/cm3, granularity is 20~140 mesh, sphericity >=0.7, circle
Degree >=0.7, percentage of damage≤8%, acid solubility≤5%.
Polyalcohols resin is organic thermoplastic polymer resin, and polyalcohols resin viscosity range is 30~60cp (20
DEG C), at least contain epoxy group, phenolic hydroxyl group, carbonyl, amide groups, amino, isocyanates in the resinous molecular structure in interior coat
The organic macromolecule material of two or more groups in base, the average molecular weight of resin are greater than 100, and polyurethane resin is toluene two
Isocyanates, methylenediphenyl diisocyanates, isophorone diisocyanate, one in methyl diphenylene diisocyanate
Kind is several.
Curing agent include organic amine, organic acid anhydride, stearic acid, dihydroxy stearic acid, oleic acid, linoleic acid, in ricinoleic acid
One kind or any component mixture, the degree of functionality of curing agent is between 2-5.
Additive is aminated compounds, and aminated compounds is diethylenetriamine, triethylamine, ethamine, triethylene tetramine, second two
The composition of one or more of amine.
Catalyst be alkyls tin compound and alkyls lead compound, including dibutyl tin dilaurate, tributyl tin,
One of lead tetraethide, isooctyl acid lead or several mixtures.
Proppant of the invention has coat, and coat includes interior coat and outer coat, as shown in connection with fig. 1, real
The proppant applied in example 1 finds that bump sizes are divided between 100~500nm, protrusion in coating layer surface at random through electron-microscope scanning
White curved body is presented in cloth, protrusion, and the surface of every 100 square micron has 40 or so protrusions；Fig. 2 is propped up in embodiment 1
Support the display figure of agent under the microscope.
Particular technique or condition person are not specified in various embodiments of the present invention, it is described conventional according to the literature in the art
Technology or conditions carry out.Reagents or instruments used without specified manufacturer is that can buy the routine obtained by market
Reagent manufacture.
In the present invention from suspended prop, haydite is 100 parts, and resin is total in the resin of interior coat and outer coat
Amount is 2-10 parts, and when interior coat curing agent is epoxy resin, the curing agent of interior coat is the 10-50% of epoxy resin,
When interior coat curing agent is phenolic resin, the curing agent of interior coat is the 10-30% of phenolic resin quality；When interior coating
When resin in layer or outer coat is polyalcohols resin, isocyanates is the 40-80% of polyalcohols resin quality, catalysis
The quality of agent is the 1/1000-1/100 of polyalcohols resin, and the quality of aminated compounds is the 1- of polyalcohols resin quality
20%；When containing polyalcohols resin and other resins in interior coat, the mass ratio of polyalcohols resin and other resins
For 1:1-5.
In the present invention, it is 1.05~2.65g/cm that embodiment 1-4, which uses apparent density,3Haydite.
Embodiment 1
Taking apparent density is 1.05g/cm3, granularity be 100 parts of 20/40 haydite, be heated to 180 DEG C, the haydite of heating poured into
Inside bowl-type mulling pot and 2 parts of epoxy resin and 0.2 part of curing agent T31 stirring are added, are added after temperature reaches 170-180 DEG C
2 parts of glycol polymers and the stirring of 0.02 part of dibutyl tin dilaurate, are added 0.02 part after temperature reaches 100-130 DEG C
1.4 parts of isocyanates stirring is added in the stirring of the mixture of diethylenetriamine and ethylenediamine after temperature reaches 80-110 DEG C, to
Temperature takes the dish out of the pot after reaching 70 DEG C.
Embodiment 2
Taking apparent density is 1.5g/cm3, granularity be 100 parts of 30/50 haydite, be heated to 200 DEG C, the haydite of heating poured into
Inside bowl-type mulling pot and 5 parts of phenolic resin and 1.5 parts of hexamethylenetetramine stirrings are added, after temperature reaches 180-190 DEG C
The ethylene glycol polymer and 0.005 part of dibutyl tin dilaurate for being added 5 parts stir, and are added after temperature reaches 80-130 DEG C
3.5 parts of isocyanates is added in the stirring of the mixture of 0.75 part of triethylamine and triethylene tetramine after temperature reaches 70-110 DEG C
Stirring, takes the dish out of the pot after temperature reaches 40 DEG C.
Embodiment 3
Taking apparent density is 2.1g/cm3, granularity be 100 parts of 40/70 haydite, be heated to 190 DEG C, the haydite of heating poured into
Inside bowl-type mulling pot and 6 parts of epoxy ester resins and 1.8 parts of curing agent T31 stirrings are added, add after temperature reaches 170-180 DEG C
Enter 4 parts of ethylene glycol polymers and 0.004 part of dibutyl tin dilaurate stirring, 0.4 part is added after temperature reaches 150-160 DEG C
2.8 parts of isocyanates stirring is added after temperature reaches 110-120 DEG C, takes the dish out of the pot after temperature reaches 50 DEG C for ethamine stirring.
Embodiment 4
Taking apparent density is 2.65g/cm3, granularity be 100 parts of 70/140 haydite, be heated to 130 DEG C, the haydite of heating fallen
Enter inside bowl-type mulling pot and be added the mixture stirring of 6 parts of ethylene glycol polymers and epoxy resin, wherein epoxy resin 3
Part, 0.03 part of dibutyl tin dilaurate is added after temperature reaches 80-130 DEG C and stirs and heats, reaches 180- to temperature
3 parts of methylenediphenyl diisocyanates and 3 parts of curing agent T31 stirring are added after 190 DEG C, reach 160-170 DEG C to temperature
5 parts of ethylene glycol polymers and the stirring of 0.05 part of dibutyl tin dilaurate are added afterwards, are added after temperature reaches 120-130 DEG C
3.5 parts of isocyanates stirring is added after temperature reaches 100-110 DEG C, goes out after temperature reaches 60 DEG C for 1 part of ethylenediamine stirring
Pot.
Comparative example 1
Taking apparent density is 1.0g/cm3, granularity be 100 parts of 20/40 haydite, be heated to 180 DEG C, the haydite of heating poured into
Inside bowl-type mulling pot and 2 parts of epoxy resin and 0.2 part of curing agent T31 stirring are added, are added after temperature reaches 160-170 DEG C
2 parts of glycol polymers and the stirring of 0.02 part of dibutyl tin dilaurate, are added 0.02 part after temperature reaches 140-150 DEG C
1.4 parts of isocyanates stirring is added in the stirring of the mixture of diethylenetriamine and ethylenediamine after temperature reaches 120-130 DEG C,
It takes the dish out of the pot after temperature reaches 70 DEG C.
Comparative example 2
Taking apparent density is 2.7g/cm3, granularity be 100 parts of 70/140 haydite, be heated to 130 DEG C, the haydite of heating poured into
Inside bowl-type mulling pot and the mixture of 6 parts of ethylene glycol polymers of addition and epoxy resin stirs, wherein and epoxy resin is 3 parts,
The dibutyl tin dilaurate for being added 0.03 part after temperature reaches 80-130 DEG C is stirred and is heated, and reaches 180-190 to temperature
3 parts of methylenediphenyl diisocyanates and 3 parts of curing agent T31 stirring are added after DEG C, add after temperature reaches 160-170 DEG C
Enter 5 parts of ethylene glycol polymers and the stirring of 0.05 part of dibutyl tin dilaurate, 1 part is added after temperature reaches 120-130 DEG C
3.5 parts of isocyanates stirring is added after temperature reaches 100-110 DEG C, takes the dish out of the pot after temperature reaches 60 DEG C for ethylenediamine stirring.
Comparative example 3
Taking apparent density is 2.1g/cm3, granularity be 100 parts of 40/70 haydite, be heated to 190 DEG C, the haydite of heating poured into
Inside bowl-type mulling pot and 6 parts of epoxy ester resins and 1.8 parts of curing agent T31 stirrings are added, add after temperature reaches 170-180 DEG C
Enter 4 parts of ethylene glycol polymers and 0.004 part of dibutyl tin dilaurate stirring, 2.8 parts are added after temperature reaches 150-160 DEG C
Isocyanates stirring, take the dish out of the pot after temperature reaches 50 DEG C.
Comparative example 4
Taking apparent density is 1.05g/cm3, granularity be 100 parts of 20/40 haydite, be heated to 180 DEG C, the haydite of heating poured into
Inside bowl-type mulling pot and 2 parts of epoxy resin and 0.2 part of curing agent T31 stirring are added, are added after temperature reaches 160-170 DEG C
2 parts of glycol polymers and the stirring of 0.02 part of dibutyl tin dilaurate, are added 0.02 part after temperature reaches 140-150 DEG C
1.7 parts of isocyanates stirring is added in the stirring of the mixture of diethylenetriamine and ethylenediamine after temperature reaches 120-130 DEG C,
Reach 70 DEG C to temperature to take the dish out of the pot.
Comparative example 5
Taking apparent density is 1.05g/cm3, granularity be 100 parts of 20/40 haydite, be heated to 180 DEG C, the haydite of heating poured into
Inside bowl-type mulling pot and 2 parts of epoxy resin and 0.2 part of curing agent T31 stirring are added, are added after temperature reaches 160-170 DEG C
2 parts of glycol polymers and the stirring of 0.02 part of dibutyl tin dilaurate, are added 0.02 part after temperature reaches 140-150 DEG C
0.7 part of isocyanates stirring is added in the stirring of the mixture of diethylenetriamine and ethylenediamine after temperature reaches 120-130 DEG C,
It takes the dish out of the pot after temperature reaches 70 DEG C.
To as shown in table 1 from suspended prop test data in embodiment 1-4 and comparative example 1-5.
Table 1
" certainly outstanding composite index " is the overall target for evaluating proppant suspendability in clear water in upper table, by mattress height
Ratio codetermines with suspending, and engineering significance is practical bulk density of the proppant in clear water, and value is smaller to be equivalent in water
In relative density with regard to smaller, then the suspension of proppant is better, suspension time is longer.
(b is suspension ratio, h is mattress height)
By table 1 analysis obtain: when in proppant haydite apparent density in 1.05~2.65g/cm3Between when, proppant exists
There is preferable suspension effect in water.
Embodiment 1 is compared with comparative example 1 it is found that the apparent density when haydite is less than 1.05g/cm3When, proppant broken and
Acid is molten larger, and the proppant in comparative example 1 is not able to satisfy requirement broken and that acid is molten.
Compared with comparative example 3 it is found that when not containing amines additives in proppant, proppant suspends embodiment 3 certainly
Index is larger, and the proppant in comparative example 3 is not able to satisfy from suspending and requires.
Embodiment 4 is compared with comparative example 2 it is found that the apparent density when haydite is greater than 2.65g/cm3When, proppant suspends certainly
Index is larger, and the proppant in comparative example 2 is not able to satisfy from suspending and requires.
Embodiment l is compared with comparative example 4 as can be seen that hanging composite index certainly using proppant obtained in embodiment 1
It is significantly less than the certainly outstanding composite index of proppant obtained in comparative example 4, and embodiment l and the difference of comparative example 4 are: comparison
It is 35% that the amount of isocyanates, which accounts for the amount of polyalcohols resin, in example 4, it is seen that when the amount of isocyanates accounts for polyalcohols resin
When amount is less than 40%, the proppant that is prepared is substantially reduced from suspendability.
Embodiment l is compared with comparative example 5 it is found that using the obvious from outstanding composite index of proppant obtained in embodiment 1
Less than proppant obtained in comparative example 5 from outstanding composite index, and embodiment l and the difference of comparative example 5 are: comparative example 5
The amount that the amount of middle isocyanates accounts for polyalcohols resin is 85%, it is seen that when the amount that the amount of isocyanates accounts for polyalcohols resin is big
When 80%, the proppant that is prepared is substantially reduced from suspendability.
The suspension of proppant proppant in the water of mine high salinity in the present invention is more preferable, by water quality influenced compared with
It is small, it is more advantageous to pressing crack construction, stability is good.
The proppant of different haydite granularities is cooked into suspension time, suspend ratio, mattress high measure.
Suspension time refers to the maximum duration that can freely suspend in water.
Suspend than be evaluate proppant in water upper layer suspension amount be total proppant percentage, our uses in test
Haydite: the case where water quality ratio is 1:4 is evaluated.Experimental method is to measure 200ml with graduated cylinder in the wide-mouth bottle of 300ml
Water pours into wide-mouth bottle, and precise 50g proppant pours into the wide-mouth bottle for having filled water, closes the lid, and firmly shakes 30 up and down
It is secondary, it is static firmly to shake up and down after the same method after ten minutes for 30 times, the suspension on upper layer is filtered out after static with filter paper
Haydite, the weight that the haydite filtered out is weighed after drying is m, suspension amount X=m/50*100%.
Since laboratory can only do static suspension test, so the mattress height of lower layer is also evaluate suspendability one
Item important indicator.Mattress height definition: lower layer height of the 20g proppant in the 100ml graduated cylinder equipped with 100ml clear water.Detection
Method: with the amount of plastic wound packages 100ml water of 100ml, precise 20g proppant is poured into the graduated cylinder for having filled water, tight with the right hand
Cover graduated cylinder mouth, left hand is picked up graduated cylinder and is gently reversed 10 times up and down, it is static after ten minutes, reverse 10 up and down after the same method
It is secondary, there is vernier caliper to measure the bed height of lower layer's haydite after static.
With embodiment 1 and buying conventional coating phenolic resin haydite in the market is 20/40,30/50,40/70,70/140
Proppant compare, the purchase of proppant in comparative example 6-9 is from Luoyang Zhong Tai Industrial Co., Ltd. 20/40,30/50,40/
70, the proppant of 70/140 specification.Suspension time is done to the proppant of different haydite granularities, suspend ratio, mattress high measure knot
Fruit is as shown in table 2.
Table 2
The haydite of different size and mattress height all < 27mm of conventional proppants.It can by the experimental data of table 2
Know, proppant mattress height all > 30mm in the present invention, so proppant is suspended with a kind of half in fact in static state
State be deposited in liquid bottom, once liquid flows, the present invention in proppant can suspend.
The parameter indexes such as sphericity, bulk density, apparent density of different size haydite are as shown in table 3 in above-described embodiment.
Table 3
What has been described above is only an embodiment of the present invention, and the common sense such as well known specific structure and characteristic are not made herein in scheme
Excessive description.It, without departing from the structure of the invention, can be with it should be pointed out that for those skilled in the art
Several modifications and improvements are made, these also should be considered as protection scope of the present invention, these all will not influence what the present invention was implemented
Effect and patent practicability.
Claims (10)
1. one kind is from suspended prop, including aggregate and coat, the coat includes resin, catalyst, curing agent and adds
Add agent, which is characterized in that the aggregate is 1.05~2.65g/cm of apparent density3Haydite, the additive be aminated compounds.
2. according to claim 1 a kind of from suspended prop, which is characterized in that the coat include interior coat and
Outer coat, the outer coat are made of polyalcohols resin, isocyanates and catalyst, and the aminated compounds addition exists
In outer coat, the isocyanates accounts for the 40-80% of polyalcohols resin, and the hydroxyl equivalent of the polyalcohols resin is
60-300。
3. according to claim 2 a kind of from suspended prop, which is characterized in that the molecular resin in the interior coat
At least containing the organic of the two or more groups in epoxy group, phenolic hydroxyl group, carbonyl, amide groups, amino, isocyanate group in structure
Macromolecular substances, the resin average molecular weight in the interior coat are greater than 100.
4. according to claim 3 a kind of from suspended prop, which is characterized in that the haydite is 100 parts, interior coat
It is 2-10 parts with total amount of resin in outer coat, the curing agent that interior coat uses is the 10-50% of resin in interior coat,
The quality of the catalyst is the 1/1000-1/100 of polyalcohols resin, and the quality of the aminated compounds is polyalcohols tree
The 1-20% of lipid amount；When containing polyalcohols resin and other resins in interior coat, polyalcohols resin and other trees
The mass ratio of rouge is 1:1-5.
5. according to claim 4 a kind of from suspended prop, which is characterized in that the polyalcohols resin is at 20 DEG C
Range of viscosities be 30~60cp.
6. according to claim 1 a kind of from suspended prop, which is characterized in that sphericity >=0.7 of the haydite, circularity
>=0.7, percentage of damage≤8%, acid solubility≤5%.
7. according to claim 1 a kind of from suspended prop, which is characterized in that the aminated compounds is divinyl three
The composition of one or more of amine, triethylamine, ethamine, triethylene tetramine, ethylenediamine.
8. according to claim 1 a kind of from suspended prop, which is characterized in that the curing agent include organic amine,
The mixture of one of organic acid anhydride, stearic acid, dihydroxy stearic acid, oleic acid, linoleic acid, ricinoleic acid or any component, institute
The degree of functionality for stating curing agent is 2-5.
9. according to claim 1 a kind of from suspended prop, which is characterized in that the catalyst is alkyls tin chemical combination
The mixture of one or more of object and/or alkyls lead compound.
10. according to claim 9 a kind of from suspended prop, which is characterized in that alkyls tin compound includes February
Dilaurylate, tributyl tin, the alkyls lead compound include lead tetraethide, isooctyl acid lead.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811159577.1A CN109321229A (en) | 2018-09-30 | 2018-09-30 | One kind is from suspended prop |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811159577.1A CN109321229A (en) | 2018-09-30 | 2018-09-30 | One kind is from suspended prop |
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| Publication Number | Publication Date |
|---|---|
| CN109321229A true CN109321229A (en) | 2019-02-12 |
Family
ID=65266303
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811159577.1A Withdrawn CN109321229A (en) | 2018-09-30 | 2018-09-30 | One kind is from suspended prop |
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Application publication date: 20190212 |