CN109021961A - A kind of preparation method of suspended prop - Google Patents
A kind of preparation method of suspended prop Download PDFInfo
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- CN109021961A CN109021961A CN201811161763.9A CN201811161763A CN109021961A CN 109021961 A CN109021961 A CN 109021961A CN 201811161763 A CN201811161763 A CN 201811161763A CN 109021961 A CN109021961 A CN 109021961A
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- 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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Abstract
The present patent application belongs to exploitation of oil-gas field technical field, specifically discloses a kind of preparation method of suspended prop, comprising the following steps: (1) quartz sand is heated to 80-230 DEG C, and stirred in 70-100r/min revolving speed;(2) reach to temperature and resin, curing agent are added in the quartz sand obtained in 150-230 DEG C to step (1) and stirs to form interior coat;(3) reach to temperature and polyalcohols resin, catalyst, isocyanates and amines additives are added in the mixture that 80-130 DEG C obtains to step (2) again and stir to form outer coat;(4) it takes the dish out of the pot to obtain from suspended prop after temperature reaches 40-90 DEG C.Present invention is mainly used for preparations from suspended prop, solves 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 exploitation of oil-gas field technical fields, specifically disclose a kind of preparation method of 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 a kind of preparation methods of suspended prop, to solve proppant in clear water using need
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 preparation method of suspended prop, including it is following
Step:
(1) quartz sand is heated to 80-230 DEG C, and is stirred in 70-100r/min revolving speed;
(2) reach to temperature and resin, curing agent are added in the quartz sand obtained in 150-230 DEG C to step (1) and stirs
Coat in being formed;
(3) reach to temperature and polyalcohols resin, catalysis is added in the mixture that 80-130 DEG C obtains to step (2) again
Agent, isocyanates and amines additives simultaneously stir to form outer coat;
(4) it takes the dish out of the pot to obtain from suspended prop after temperature reaches 40-90 DEG C.
The beneficial effect of this base case is:
(1) proppant coated temperature of the invention is low, and the process time is short, and yield is high, lower to equipment and energy consumption.It covers
Product index after film is such as: bulk density, apparent density, acid solubility, percentage of damage are able to satisfy the basic demand of industry.And
Also there is the characteristic to suspend in clear water from suspended prop, the substance of the thickeninies such as addition guar gum is not needed in fracturing process,
Cost is greatly reduced, fracturing unit and technique have been simplified, reduces the pollution to environment;
(2) proppant of the invention realizes riverfrac treatment, using clear water as fracturing fluid, reduces matching for fracturing fluid complexity
Process is set, equipment has been simplified, reduces manpower waste.Proppant suspend in clear water it is natural suspension, in fracturing process with
Clear water enter stratum, the local proppant of the arrival such as water can reach, at the same decrease brokenly glue this part.Return drain only
Need to be i.e. reusable by simple processing, riverfrac treatment proppant also reduces cost while increasing fracturing effect;
(3) proppant containing the polyurethane resin present invention to be with quartz sand be aggregate in the proppant of this method preparation,
It tests and finds through inventor, proppant of the invention contains nanoscale protrusion in coating layer surface, these protrusions extend in support
The surface of agent particle, protrusion will increase the buoyancy of proppant, while when proppant and water contact, and reserve in surface coating resin
A kind of group can be reacted rapidly with water and release bulk gas small molecule, these gas molecules or be enclosed in swollen in resin film
Swollen promotion resin membrane body stage, which thickens, increases the equivalent diameter of proppant particles body, or is attached to proppant surface stage
The gas blanket that one layer of package proppant particles body is formed on the interface that proppant resin film is contacted with water body is extended or is gathered in, this
Kind of gas blanket formation stages between proppant particles body are connected to and the result closed cause simple grain proppant formed in water body compared with
Gather shape for loose cotton wadding, is greatly lowered the relative density of proppant in water, in this way so as to make proppant exist
It suspends in water.When proppant moves in water, the protrusion of the curved surface on proppant resin film can reduce proppant in water
The rate of settling;Part is settled down to the proppant of water bottom accumulation because the more protrusion of its surface resin film reduces proppant
The degree of packing of grain stack layer, intergranular water body amount is more compared with conventional particle stack, and then when water body has very little in time
Fluidity also can more easily push the separation of its congeries and movement, realize that proppant preferably suspends in water;
(4) interior coat can be formed by step (2) in the present invention, outer coat, interior coating can be formed by step (3)
The resin film precuring of layer becomes the film form of netted high intensity, and product connects when being applied to oil field fracturing construction with fracturing fluid
Touching has chemical inertness high, can't discharge other harmful substances;
(5) present invention controls temperature within the above range, has convenient for the protrusion that outer coating layer surface is formed biggish
Intensity will not be damaged in whipping process protrusions, proppant is made to have preferable suspension.
Further, in step (3) isocyanates be polyalcohols resin 40-70%, the polyalcohols resin works as
Amount is 60-300.Applicant it is found through experiment that, using the isocyanates in above range, polyurethane can be formed on outer coat
Resin film, polyurethane resin can react under the action of amines additives and generate bubble, can be when bubble is overflowed to outside film
Outer coating layer surface forms more protrusions, and for bump sizes between 100~500nm, protrusion is coating layer surface random distribution, convex
Rising when observing under scanning electron microscope is light highlighted or white curved body on the resin membrane body of discovery deep dark, in single particle body
Surface resin film have heterogencity random distribution, then calculate be homogeneous distribution state under every 100 square micron surface tool
There is 1~40 or so protrusion, increases the suspendability of proppant in this way;In the resin film body of above-mentioned proppant also simultaneously
A certain number of isocyanate-reactive groups are reserved with, after remaining isocyanate groups meet water, are reacted with water and can be
Generate gas in microcosmic small space body that the chain element of resin film surrounds, this small quantity gas reaction can promotion under by
Gradually overall volume forms bubble, and resin film is pushed to increase in the radial dimension of proppant particles, and outer coat can in this way sent out
Raw expansion, further improves the suspendability of proppant.
Further, in the resinous molecular structure in step (2) in interior coat at least containing epoxy group, phenolic hydroxyl group, carbonyl,
The organic macromolecule material of amide groups, amino, two or more groups in isocyanate group, the resin in the interior coat are flat
Average molecular weight is greater than 100.Proppant surface can be made quickly to form protrusion under amine chemical combination using polyurethane resin, in this way
Suspended state can be in after proppant can be made to contact water.
Further, the quartz sand is 100 parts, and the resin of the outer coat of the resin of interior coat is 0.5-8 parts, interior painting
The curing agent that coating uses is the 20-40% of resin quality in interior coat, and the quality of the catalyst is polyalcohols resin
1/1000-1/100, the quality of the aminated compounds is the 1-20% of polyalcohols resin quality;When interior coat includes
When having polyalcohols resin and other resins, the mass ratio of polyalcohols resin and other resins is 1:1-5.When containing in proppant
When having quartz sand, resin, curing agent, catalyst and the aminated compounds of aforementioned proportion, proppant can have preferable suspension effect;
More protrusion can be formed in outer coat under the action of catalyst using polyalcohols resin and isocyanates, is increased in this way
The buoyancy of proppant in water, enables proppant to suspend in water.
Further, range of viscosities of the polyalcohols resin at 20 DEG C is 10~60cp.
Further, sphericity >=0.7 of the quartz sand, circularity >=0.7, percentage of damage≤8%, acid solubility≤5%.It uses
The proppant of the quartz sand preparation of above-mentioned specification meets suspension and requires.
Further, the aminated compounds is diethylenetriamine, triethylamine, ethamine, triethylene tetramine, one in ethylenediamine
Kind or two or more compositions.It can accelerate resin using above-mentioned several amines to react with water, proppant is made to be less likely to occur to sink
Drop.
Further, curing agent used includes organic amine, organic acid anhydride, isocyanates in step (2), stearic acid,
The mixture of one of dihydroxy stearic acid, oleic acid, linoleic acid, ricinoleic acid or any component, the degree of functionality of the curing agent are
2-5.Using the curing agent of mentioned kind, comprehensive performance performance and the chemistry that can accelerate the resin membrane body of support surface coat are comprehensive
Close inertia.
Further, the catalyst is the organo-metallic compound 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 1 electron-microscope scanning figure of proppant embodiment of the preparation method preparation of suspended prop of the present invention;
Fig. 2 is the display figure in embodiment 1 under the microscope of proppant.
Specific embodiment
It is further described below by specific embodiment:
Raw material selected by the present invention is as follows:
Aggregate is quartz sand.The apparent density of quartz sand is 2.55g/cm3, granularity is 20~140 mesh, sphericity >=0.7, circularity
>=0.7, percentage of damage≤8%, acid solubility≤5%.
Polyalcohols resin is organic thermoplastic polymer resin, and polyalcohols resin viscosity range is 10-60cp (20
DEG C), epoxy group, phenolic hydroxyl group, carbonyl, amide groups, amino, isocyanate group are at least contained in the resinous molecular structure of interior coat
In two or more groups organic macromolecule material, the average molecular weight of resin is greater than 100;Isocyanates is polyalcohols tree
The 40-70% of rouge, the hydroxyl equivalent of the polyalcohols resin are 60-300.Isocyanates include as toluene di-isocyanate(TDI),
One of methylenediphenyl diisocyanates, isophorone diisocyanate, methyl diphenylene diisocyanate are several
Kind.
Curing agent includes organic amine, organic acid anhydride, isocyanates, 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 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 is the organo-metallic compound of alkyls tin and alkyl ekalead, including dibutyl tin dilaurate, three fourths
One of Ji Xi, lead tetraethide, isooctyl acid lead or several mixtures.
Proppant of the invention has coat, and coat includes interior coat and outer coat, contains in outer coat
Polyurethane resin, polyurethane resin and additive in outer coat can form more nanoscales protrusions, knot after contacting with water
It closes shown in Fig. 1, the proppant in embodiment 1 is found through electron-microscope scanning, and bump sizes are between 100~500nm, and protrusion is in coat
White curved body is presented in surface random distribution, protrusion, and the surface of every 100 square micron has 40 or so protrusions;Fig. 2 is real
Apply the display figure in example 1 under the microscope of proppant.
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, quartz sand is 100 parts, and the resin in interior coat and outer coat is
0.5-8 parts, the curing agent in interior coat is the 20-40% of resin, and the quality of catalyst is the 1/1000- of polyalcohols resin
1/100, the quality of aminated compounds is the 1-20% of polyalcohols resin quality;When in interior coat contain polyalcohols resin
When with other resins, the mass ratio of polyalcohols resin and other resins is 1:1-5.
Quartz sand apparent density of the invention is 2.55g/cm3, all embodiments follow the steps below.
(1) quartz sand is heated to 80-230 DEG C, and is stirred in 70-100r/min revolving speed;
(2) reach to temperature and resin, curing agent are added in the quartz sand obtained in 150-230 DEG C to step (1) and stirs
Coat in being formed;
(3) reach to temperature and polyalcohols resin, catalysis is added in the mixture that 80-130 DEG C obtains to step (2) again
Agent, isocyanates and amines additives simultaneously stir to form outer coat;
(4) it takes the dish out of the pot to obtain from suspended prop after temperature reaches 40-90 DEG C.
Embodiment 1
Taking granularity is 100 parts of quartz sand of 20/40, is heated to 180 DEG C, the quartz sand of heating is poured into bowl-type mulling pot
Simultaneously 0.5 part of epoxy resin and 0.05 part and 0.1 curing agent T31 stirring is added in face, and 5 parts are added after temperature reaches 160-170 DEG C
Glycol polymers and the stirring of 0.05 part of dibutyl tin dilaurate, are added 0.005 part two after temperature reaches 140-150 DEG C
3.5 parts of toluene di-isocyanate(TDI) is added after temperature reaches 100-120 DEG C and stirs for the stirring of the mixture of ethylene triamine and ethylenediamine
It mixes, takes the dish out of the pot after temperature reaches 80 DEG C.
Embodiment 2
Taking granularity is 100 parts of quartz sand of 30/50, is heated to 230 DEG C, the quartz sand of heating is poured into bowl-type mulling pot
Simultaneously 5 parts of phenolic resin and 1.5 parts of hexamethylenetetramine stirrings are added in face, and 3 parts of second two is added after temperature reaches 190-200 DEG C
Alkoxide polymer and the stirring of 0.003 part of dibutyl tin dilaurate, be added after temperature reaches 160-170 DEG C 0.45 part of triethylamine and
The mixture of triethylene tetramine stirs, and 2.1 parts of methylenediphenyl diisocyanates are added after temperature reaches 140-150 DEG C
Stirring, takes the dish out of the pot after temperature reaches 90 DEG C.
Embodiment 3
Taking granularity is 100 parts of quartz sand of 40/70, is heated to 190 DEG C, the quartz sand of heating is poured into bowl-type mulling pot
Simultaneously 6 parts of epoxy ester resins and 2.5 parts of stirrings of curing agent 31 are added in face, and it is poly- that 2 parts of ethylene glycol are added after temperature reaches 160-170 DEG C
Object and 0.02 part of dibutyl tin dilaurate stirring are closed, 0.2 part of ethamine stirring is added after temperature reaches 140-150 DEG C, to temperature
1.4 parts of isophorone diisocyanate stirring is added in degree after reaching 110-120 DEG C, take the dish out of the pot after temperature reaches 80 DEG C.
Embodiment 4
Taking granularity is 100 parts of quartz sand of 70/140, is heated to 130 DEG C, the quartz sand of heating is poured into bowl-type mulling pot
The inside and the mixture that 6 parts of ethylene glycol polymers and epoxy resin are added, wherein epoxy resin is 3 parts, reaches 80- to temperature
The mixture that both 0.03 part dibutyl tin dilaurate, lead tetraethides are added after 130 DEG C is stirred and is heated, and is reached to temperature
3 parts of methylenediphenyl diisocyanates and 1.2 parts of curing agent T31 stirring are added after 200-210 DEG C;Reach 160- to temperature
The mixing of both 2 parts of ethylene glycol polymers and 0.02 part of dibutyl tin dilaurate, lead tetraethide is added after 170 DEG C,
0.4 part of ethylenediamine stirring is added after temperature reaches 140-160 DEG C, 1.4 parts of hexichol is added after temperature reaches 110-120 DEG C
Dicyclohexylmethane diisocyanate stirring, takes the dish out of the pot after temperature reaches 80 DEG C.
Comparative example 1
Taking granularity is 100 parts of quartz sand of 20/40, is heated to 180 DEG C, the quartz sand of heating is poured into bowl-type mulling pot
Simultaneously 0.5 part of epoxy resin and 0.05 part and 0.1 curing agent T31 stirring is added in face, and 5 parts are added after temperature reaches 160-170 DEG C
Epoxy resin and the stirring of 0.05 part of dibutyl tin dilaurate, are added 0.005 part of divinyl after temperature reaches 140-150 DEG C
3.5 parts of toluene di-isocyanate(TDI) stirring is added in the stirring of the mixture of triamine and ethylenediamine after temperature reaches 100-120 DEG C,
It takes the dish out of the pot after temperature reaches 80 DEG C.
Comparative example 2
Taking granularity is 100 parts of quartz sand of 30/50, is heated to 230 DEG C, the quartz sand of heating is poured into bowl-type mulling pot
Simultaneously 5 parts of phenolic resin and 1.5 parts of hexamethylenetetramine stirrings are added in face, and 3 parts of phenolic aldehyde is added after temperature reaches 190-200 DEG C
Resin and 0.003 part of dibutyl tin dilaurate stirring, are added 0.45 part of triethylamine and three second after temperature reaches 160-170 DEG C
The mixture of alkene tetramine stirs, and 2.1 parts of methylenediphenyl diisocyanates are added after temperature reaches 140-150 DEG C and stir
It mixes, reaches 90 DEG C to temperature and take the dish out of the pot.
Comparative example 3
Taking granularity is 100 parts of quartz sand of 40/70, is heated to 190 DEG C, the quartz sand of heating is poured into bowl-type mulling pot
Simultaneously 6 parts of epoxy ester resins and 2.5 parts of stirrings of curing agent 31 are added in face, and it is poly- that 2 parts of ethylene glycol are added after temperature reaches 160-170 DEG C
Object and 0.02 part of dibutyl tin dilaurate stirring are closed, it is different that 1.4 parts of isophorone two is added after temperature reaches 140-150 DEG C
Cyanate stirring, takes the dish out of the pot after temperature reaches 80 DEG C.
Comparative example 4
Taking granularity is 100 parts of quartz sand of 20/40, is heated to 180 DEG C, the quartz sand of heating is poured into bowl-type mulling pot
Simultaneously 0.5 part of epoxy resin and 0.05 part and 0.1 curing agent T31 stirring is added in face, and 5 parts are added after temperature reaches 160-170 DEG C
Glycol polymers and the stirring of 0.05 part of dibutyl tin dilaurate, are added 0.005 part two after temperature reaches 140-150 DEG C
1.75 parts of toluene di-isocyanate(TDI) is added in the stirring of the mixture of ethylene triamine and ethylenediamine after temperature reaches 100-120 DEG C
Stirring, takes the dish out of the pot after temperature reaches 80 DEG C.
Comparative example 5
Taking granularity is 100 parts of quartz sand of 20/40, is heated to 180 DEG C, the quartz sand of heating is poured into bowl-type mulling pot
Simultaneously 0.5 part of epoxy resin and 0.05 part and 0.1 curing agent T31 stirring is added in face, and 5 parts are added after temperature reaches 160-170 DEG C
Glycol polymers and the stirring of 0.05 part of dibutyl tin dilaurate, are added 0.005 part two after temperature reaches 140-150 DEG C
3.75 parts of toluene di-isocyanate(TDI) is added in the stirring of the mixture of ethylene triamine and ethylenediamine after temperature reaches 100-120 DEG C
Stirring, takes the dish out of the pot after temperature reaches 80 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.
Obtained by the analysis of table 1: the proppant in embodiment 1-4 is all satisfied construction requirement, this is because in outer coat
Containing polyalcohols resin and isocyanates, polyalcohols resin and isocyanates reaction generate polyurethane resin, polyurethane tree
Adipose membrane can react rapidly a large amount of gas molecules of generation after meeting water, these gas molecules are attached to the table of proppant particles
Face forms the bubble of micro/nano level in proppant surface, while the bubble generated can cause the coat on surface to expand, and a large amount of
Proppant clustering together when, formed cotton it is cotton-shaped, be greatly lowered the relative density of proppant in water in this way, thus
Proppant can be made to suspend in water, realization uses clear water as liquid is carried and (carries liquid certainly and be also not only limited to clear water, can also be
Added with the carrying liquid of thickener), while making the proppant in this programme meet the basic pressure break of industry to require, in fracturing process
In do not need the addition thickeners such as guar gum, greatly reduce cost, simplified fracturing unit and technique, reduce the dirt to environment
Dye, and huge discharge operation may be implemented using clear water as liquid is carried, improve working efficiency.
Embodiment 1 is compared with comparative example 1 it is found that using the obvious from outstanding composite index of proppant obtained in embodiment 1
Less than proppant obtained in comparative example 1 from outstanding composite index, and embodiment l and the difference of comparative example 1 are: comparative example 1
In resin in interior coat and outer coat be epoxy resin, the proppant that comparative example 1 is prepared from suspendability
It is substantially reduced.
Embodiment 2 is compared with comparative example 2 it is found that using the obvious from outstanding composite index of proppant obtained in embodiment 2
Less than proppant obtained in comparative example 2 from outstanding composite index, and embodiment 2 and the difference of comparative example 2 are: comparative example 2
In resin in interior coat and outer coat be phenolic resin, the proppant that comparative example 2 is prepared from suspendability
It is substantially reduced.
Embodiment 3 is compared with comparative example 3 it is found that using the obvious from outstanding composite index of proppant obtained in embodiment 3
Less than proppant obtained in comparative example 3 from outstanding composite index, and embodiment 3 and the difference of comparative example 3 are: comparative example 3
Aminated compounds is free of in China and foreign countries' coat, the proppant being prepared is substantially reduced from suspendability.When in proppant not
When containing amines additives, proppant it is larger from suspension index, the proppant in comparative example 3 be not able to satisfy from suspend require.
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 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 5, and embodiment l and the difference of comparative example 5 are: comparison
It is 75% that the amount of isocyanates, which accounts for the amount of polyalcohols resin, in example 5, it is seen that when the amount of isocyanates accounts for polyalcohols resin
When amount is greater than 70%, 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 quartz sand sizes 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
Quartz sand: the case where water quality ratio is 1:4 is evaluated.Experimental method is to be measured in the wide-mouth bottle of 300ml with graduated cylinder
200ml 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 up and down
It is dynamic 30 times, static firmly to shake 30 times up and down after the same method after ten minutes, with filter paper the outstanding of upper layer is filtered out after static
Floating quartz sand, the weight that the quartz sand 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 quartz sand after static.
Proppant purchase for the proppant in comparative example 6-9 bought by embodiment 1 and in the market, in comparative example 4-7
Buy the proppant from 20/40,30/50,40/70,70/140 specification of Luoyang Zhong Tai Industrial Co., Ltd..To different quartz sand sizes
Proppant do suspension time, suspend ratio, the results are shown in Table 2 for mattress high measure.
Table 2
The quartz sand of different size and mattress height all < 28mm 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 index of different quartz sand sizes is 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. a kind of preparation method of suspended prop, which comprises the following steps:
(1) quartz sand is heated to 80-230 DEG C, and is stirred in 70-100r/min revolving speed;
(2) reach to temperature and resin, curing agent are added in the quartz sand obtained in 150-230 DEG C to step (1) and stirs to be formed
Interior coat;
(3) reach to temperature be added again in the mixture that 80-130 DEG C obtains to step (2) polyalcohols resin, catalyst,
Isocyanates and amines additives simultaneously stir to form outer coat;
(4) it takes the dish out of the pot to obtain from suspended prop after temperature reaches 40-90 DEG C.
2. according to claim 1 a kind of from suspended prop, which is characterized in that isocyanates is polynary in step (3)
The 40-70% of alcohol resinoid, the hydroxyl equivalent of the polyalcohols resin are 60-300.
3. according to claim 1 a kind of from suspended prop, which is characterized in that the tree in step (2) in interior coat
At least containing the two or more groups in epoxy group, phenolic hydroxyl group, carbonyl, amide groups, amino, isocyanate group in rouge molecular structure
Organic macromolecule material, the resin average molecular weight in the interior coat is greater than 100.
4. according to claim 3 a kind of from suspended prop, which is characterized in that the quartz sand is 100 parts, interior coating
The resin of the outer coat of the resin of layer is 0.5-8 parts, and the curing agent that interior coat uses is resin quality in interior coat
20-40%, the quality of the catalyst are the 1/1000-1/100 of polyalcohols resin, and the quality of the aminated compounds is more
The 1-20% of first alcohols resin quality;When containing polyalcohols resin and other resins in interior coat, polyalcohols resin
Mass ratio with other resins 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 10~60cp.
6. according to claim 1 a kind of from suspended prop, which is characterized in that sphericity >=0.7 of the quartz sand, circle
Degree >=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 curing agent used includes in step (2)
Organic amine, organic acid anhydride, isocyanates, one of stearic acid, dihydroxy stearic acid, oleic acid, linoleic acid, ricinoleic acid or
The mixture of any component, the degree of functionality of the curing agent are 2-5.
9. according to claim 1 a kind of from suspended prop, which is characterized in that the catalyst be alkyls tin and/
Or the organo-metallic compound of alkyl ekalead.
10. a kind of preparation method of suspended prop according to claim 9, which is characterized in that alkyls tin compound
Including dibutyl tin dilaurate, tributyl tin, the alkyls lead compound includes lead tetraethide, isooctyl acid lead.
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Cited By (1)
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Application publication date: 20181218 |