CN109233796A - A kind of certainly outstanding proppant - Google Patents
A kind of certainly outstanding proppant Download PDFInfo
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- CN109233796A CN109233796A CN201811162062.7A CN201811162062A CN109233796A CN 109233796 A CN109233796 A CN 109233796A CN 201811162062 A CN201811162062 A CN 201811162062A CN 109233796 A CN109233796 A CN 109233796A
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- proppant
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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
Abstract
The invention belongs to the fluid minerals production technique such as petroleum, natural gas and shale gas fields, specifically disclose a kind of certainly outstanding proppant, including aggregate and the coating layer being wrapped in outside aggregate, coating layer is generated by resin, curing agent and catalyst；Certainly after the outstanding proppant is impregnated with organic solvent, filtering takes filtering solution to test, the content of the isocyano in solution accounts for the one thousandth of solid content or more.Certainly the outstanding proppant of the present patent application, not only actual requirement is all satisfied in indexs such as intensity, drag reduction efficiency, broken material, acid solubilities, it can also be in water from suspension, it is easy to be carried in well, it is not required to the substance of the thickeninies such as addition guar gum, cost is greatly reduced, fracturing unit and technique have been simplified, reduces the pollution to environment.
Description
Technical field
The invention belongs to the fluid minerals production technique fields such as petroleum, natural gas and shale gas more particularly to a kind of from outstanding
Proppant.
Background technique
Proppant, which refers to, brings crack into fracturing fluid, after pressure is released to support the liquid adjuvants in oil field crack, energy
Enough provide to crack supports and guarantees that its is unimpeded, flows into liquid in drilling by crack, prevents from causing hole oily due to crack
The collapsing and leakage of field drilling well.
Ideal fracturing propping agent for oil gas well requires have high carrying capacity and high sand ratio, it is therefore desirable to alap
Density and intensity as high as possible.Traditional fracturing propping agents have quartz sand and haydite and their coated products, outer layer to cover
Film is solidified at high temperature with phenolic aldehyde or epoxy resin, and generally in the 5-50% of amount of resin, coated temperature exists the amount of curing agent
230 degree or so, traditional fracturing propping agents intensity is big, but density is also high, and suspension is poor, is easy precipitating, it is not easy to be taken
It is brought into well.There are also coating urethane resin films other than coating epoxy resin, phenolic resin film for existing proppant product
, polyurethane resin is a great system, passes through the raw material of strict control selection, dosage, the condition of reaction of raw material etc.
It can make polyurethane resin that there is entirely different substance physical property, the existing polyurethane resin for being used to support agent is to have height hard
Spend the polyurethane resin of substance physical property, it is ensured that resin film has high-caliber hardness and good resistance to crushing, finally to support
Agent has good resistant to breakage ability.But the proppant product of the existing urethane resin film of coating is still only to meet by force
Degree, hardness requirement, not can solve suspension it is poor, be easy precipitate the problem of.
In order to more effectively make fracturing propping agents reach the target position of well, need to prepare carrying liquid during pressure break.
Carrying liquid is to add water soluble polymer and other additive using water as main carriers to increase the viscosity for carrying liquid,
The frictional resistance for carrying liquid is reduced simultaneously.Fracturing propping agents and carrying liquid mixing in the construction process, in highly viscous carrying liquid,
Fracturing propping agents suspend wherein, thus can pump farther.But it carries macromolecule frozen glue material used in liquid and exists
It is at high cost, serious to reservoir damage, cause serious pollution to the environment, complicated construction technique the disadvantages of.
Also occur some proppants that can be suspended certainly in water, the existing proppant master that can be suspended certainly in water at present
There are two class technologies, first is that in aggregate quartz sand or haydite surface coating layer of material, this material is mainly some water-soluble
Property high molecular material, such as polyacrylamide, carboxymethyl cellulose, polyacrylic acid, guar gum, natural plant gum.These materials meet water
It can expand rapidly, and the viscosity that can dissolve into increase water in water achievees the purpose that suspension.This technology from suspended prop not
There is the technology for fundamentally changing suspension, thickener overlay film is not only solved environmental issue on aggregate, without real
Realization reduce cost, increase production and improve productivity.Another technology is to change the apparent density of aggregate, makes the haydite of extremely-low density, or
Resin beads.Such product is able to achieve really half to suspend in water, reduces the rate of settling of proppant in water, but due to wanting
Apparent density is greatly lowered, production cost greatly increases, and the performance of proppant, such as broken, sour molten, water conservancy diversion performance meeting
It is substantially reduced.And the production efficiency of resin beads is low, it is at high cost the defects of, also limit its popularization and use.
Summary of the invention
The purpose of the present invention is to provide a kind of certainly outstanding proppants, and environmentally protective, production cost is relatively low, passes meeting
While fracturing propping agents index of uniting, it can be easy to be carried in water from suspending.
In order to achieve the above object, base case of the invention are as follows: it is a kind of from outstanding proppant, including aggregate and it is wrapped in bone
Coating layer outside material, coating layer are generated by resin, curing agent and catalyst；Certainly after the outstanding proppant is impregnated with organic solvent,
Filtering, takes filtering solution to test, the content of the isocyano in solution accounts for the one thousandth of solid content or more.
The beneficial effect of this base case is:
1, applicant studies for a long period of time discovery, after being impregnated with organic solvent from outstanding proppant, takes filtering solution to test, works as solution
In the content of isocyano when accounting for the one thousandth of solid content or more, proppant can suspend in clear water, and when suspending
Between be greater than 4 hours, suspend than be greater than 10%, the effect of suspension is preferable.
2, the proppant of the present patent application can suspend in water, therefore directly achieve that height takes sand energy using clear water
Power, without changing the density of water.During exploiting oil gas, traditional fracturing propping agents are replaced using riverfrac treatment proppant,
Traditional fracturing fluid is replaced using clear water, realizes zero addition of load fluid thickener in fracturing work, and then save conventional pressure break
With liquid process and equipment.Meanwhile the removal of thickener also reduces injury and pressure break cost of the pressure break to reservoir.
3, using the proppant of the present patent application, fracturing fluid of constructing not only can be used clear water, water flooding and connection also can be used
Close station sewage, recycling can be recycled after instead arrange in fracturing fluid, and Saline Water is more advantageous to the use of the product, reduction fracturing fluid at
This.
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, using effect is good.
Further, coating layer includes theca interna and theca externa, and theca externa is solidified by outermost resin, outer layer catalyst and outer layer
Agent generates；Theca interna is generated by the first resin and the first curing agent or by the life of the second resin, the second curing agent and internal layer catalyst
At.Two layers of overlay film is set, can make different overlay films that there is different characteristics, theca interna is mainly used for improving the whole strong of proppant
Degree, and theca externa be used to improve proppant material from suspension.
Further, the outer layer curing agent, the second curing agent are isocyanates.Select isocyanates as solidification
Agent, resin cured effect of being heated are preferable.
Further, the outer layer catalyst, internal layer catalyst are the organo-metallic compound and/or alkyl of alkyls tin
One or more of organo-metallic compound of ekalead.The organo-metallic compound conduct catalysis of alkyls tin, alkyl ekalead
Agent, the effect for being catalyzed reaction are preferable.
Further, the outermost resin, the second resin are polyalcohols resin；The equivalent of outermost resin hydroxyl is 60-
300, the mass fraction of outer layer curing agent is the 40-80% of outermost resin mass fraction.Polyalcohols resin energy and isocyanates
Reaction generate polyurethane resin, we application in by the dosage of strict control outer layer curing agent make isocyanates with it is more
First alcohols resin reaction still has residue after generating polyurethane resin.Proppant is put into water, when proppant and water contact, table
The isocyanates in face can react rapidly with water releases gas molecules, these gas molecules or is enclosed in swollen in theca externa
It is swollen, it pushes theca externa stage to thicken and increases the equivalent diameter of proppant particles body, or be attached to proppant surface stage
The gas blanket that one layer of package proppant particles body is formed on the interface that proppant coating layer 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, the suspension of proppant can be made
Performance is more preferably.
Further, according to the mass fraction, resin quality number is the 2-10% of aggregate quality number, and outermost resin accounts for resin
The 10-90% of total amount；Outer layer catalyst mass fraction is the 0.1-1% of outermost resin mass fraction.Catalyst in the range,
It is not only able to achieve outermost resin to solidify well, and is conducive to generate protuberance, both can increase the resistant to breakage ability of proppant in this way,
It can increase suspension again.Applicant is by repeatedly the study found that make proppant, preparation using the raw material of above-mentioned mass fraction
Obtained proppant suspension effect and other better performances.
Further, theca externa further includes aminated compounds, and theca externa is by outermost resin, outer layer curing agent, outer layer catalyst
It is prepared with aminated compounds；Aminated compounds mass fraction is the 1-20% of the mass fraction of outermost resin.Polyalcohols
Resin reacts the isocyanates for having some residual with isocyanates, and remaining isocyanates is reacted with aminated compounds, this
In the process, the gases such as nitrogen, nitric oxide, carbon monoxide can be generated, portion gas is closed in not yet fully hardened poly- ammonia
In ester resin film, a large amount of protuberance is formed, the diameter of protuberance is 100-500nm, swells quantity at every square millimeter 4 × 107It is a
Left and right, these protuberances facilitate proppant and suspend.The amount that strict control aminated compounds is added, it is ensured that produced in reaction process
Raw suitable gas guarantees that the protuberance size generated controls in suitable range, not too big and stomata is worn in formation.Amine
The isocyanates that there remains part after object is reacted with isocyanates is closed, it is remaining different in proppant after proppant is put into water
Cyanate radical can act on water and generate gas, and portion gas evolution, portion gas is closed in protuberance, and the volume of protuberance is further
Expand, makes resin membrane swelling, the suspendability of proppant can be made more preferably.
Further, the first curing agent mass fraction is the 10-50% of the first resin quality number.
Further, the second curing agent mass fraction is the 40-80% of the second resin quality number, internal layer catalyst mass parts
Number is the 0.1-1% of the second resin quality number.
Further, polyalcohols resin selects one of polymer such as ethyl alcohol, ethylene glycol, propylene glycol, glycerine, propyl alcohol
Or it is several.Application experiment discovery, selects above-mentioned specific resin, the proppant material resultant effect being prepared is preferable.
Further, isocyanates selects toluene di-isocyanate(TDI), methylenediphenyl diisocyanates, isophorone two
One of isocyanates, methyl diphenylene diisocyanate are several.By applicant's the study found that selecting above-mentioned
For raw material as curing agent, resin cured effect of being heated is preferable.
Further, the organo-metallic compound of alkyls tin specifically selects dibutyl tin dilaurate, tributyl tin, alkyl
The organo-metallic compound of ekalead specifically selects lead tetraethide, isooctyl acid lead.By applicant's the study found that selecting above-mentioned
For raw material as catalyst, the effect for being catalyzed reaction is preferable.
Further, the aminated compounds is diethylenetriamine, triethylamine, ethamine, triethylene tetramine, one in ethylenediamine
Kind is several.Applicant has found by test of many times, selects above-mentioned raw material as aminated compounds, can make proppant material
The effect for generating protuberance is more preferable.
Further, in first resinous molecular structure at least containing epoxy group, phenolic hydroxyl group, carbonyl, amide groups, amino,
The average molecular weight of the organic macromolecule material of two or more groups in isocyanate group, the first resin is greater than 100.Applicant
It is found by test of many times, selects above-mentioned material as the first resin, the theca interna intensity being prepared is preferable.
Further, the aggregate selects quartz sand, haydite, Artificial Ceramic matter sand, organic synthesis sand or organo-mineral complexing
Material sand.The aggregate of proppant material need to meet index in certain performances, and above-mentioned aggregate can preferably meet use demand.
Detailed description of the invention
Fig. 1 is the electron-microscope scanning figure from outstanding proppant being prepared in embodiment 1.
Specific embodiment
Raw material selection is illustrated below, and the present invention is described in further detail by specific embodiment:
Outer layer curing agent, the second curing agent in the present embodiment are isocyanates, select toluene di-isocyanate(TDI), methylene
One of base diphenyl diisocyanate, isophorone diisocyanate, methyl diphenylene diisocyanate are several.
Aminated compounds in the present embodiment is diethylenetriamine, in triethylamine, ethamine, triethylene tetramine, ethylenediamine
It is one or several kinds of.
Outer layer catalyst, internal layer catalyst in the present embodiment are the organo-metallic compound and/or alkane of alkyls tin
One or more of the organo-metallic compound of base class lead, the organo-metallic compound of alkyls tin specifically select tin dilaurate
Dibutyl tin, tributyl tin, the organo-metallic compound of alkyl ekalead specifically select lead tetraethide, isooctyl acid lead.
Outermost resin, the second resin in the present embodiment are polyalcohols resin, select ethyl alcohol, ethylene glycol, propylene glycol,
One of polymer such as glycerine, propyl alcohol are several.
Organic solvent selects acetone, ethyl alcohol, ethyl acetate, any one in isopropanol in the present embodiment.
At least containing in epoxy group, phenolic hydroxyl group, carbonyl, amide groups, amino, isocyanate group in first resinous molecular structure
Two or more groups organic macromolecule material, the average molecular weight of the first resin is greater than 100.
Embodiment 1
A kind of certainly outstanding proppant, including aggregate and the coating layer being wrapped in outside aggregate, coating layer includes theca interna and outer membrane
Layer, theca externa are generated by outermost resin, outer layer catalyst, outer layer curing agent, and theca interna is raw by the first resin and the first curing agent
At.The specifically used mass fraction of above-mentioned raw materials is as follows: 100 parts of aggregate, 1.8 parts of outermost resin, 2 parts of the first resin, first are consolidated
0.8 part of agent, 1.3 parts of outer layer curing agent, 0.005 part of outer layer catalyst, 0.2 part of aminated compounds.Wherein aggregate selects 20/40
Quartz sand, outermost resin select alcohol polymer, the first resin to select epoxy resin, and the first curing agent selects T31, outer layer solidification
Isophorone diisocyanate is selected in agent, and outer layer catalyst selects isooctyl acid lead, and aminated compounds selects triethylamine.The present embodiment
In, by this from after outstanding proppant acetone soak, filtering takes filtering solution to test, and the content of the isocyano in solution accounts for solid
The 1/900 of content.Wherein, solid content refers to solvent and water are removed in filtering solution after remaining organic component gross mass.
It should be prepared from outstanding proppant using following methods:
(1) aggregate is heated to be put into sand mixer after 140 DEG C, the first resin is added, stirred, 50 revs/min of sand mixer revolving speed；
(2) temperature drops to 110 DEG C, and the first curing agent is added, and stirs, 50 revs/min of sand mixer revolving speed；
(3) temperature drops to 95 DEG C, and outermost resin and outer layer catalyst is added, and stirs, 50 revs/min of sand mixer revolving speed；
(4) temperature drops to 85 DEG C, and aminated compounds is added, and stirs 10 seconds, 55 revs/min of sand mixer revolving speed；
(5) temperature drops to 75 DEG C, and outer layer curing agent is added, and stirs, 55 revs/min of sand mixer revolving speed；Temperature drops to 55 DEG C,
It takes the dish out of the pot, obtains from outstanding proppant.
Embodiment 2
A kind of certainly outstanding proppant, including aggregate and the coating layer being wrapped in outside aggregate, coating layer includes theca interna and outer membrane
Layer, theca externa are generated by outermost resin, outer layer catalyst, outer layer curing agent and aminated compounds, theca interna by the first resin and
First curing agent generates.The specifically used mass fraction of above-mentioned raw materials is as follows: 100 parts of aggregate, 1 part of outermost resin, the first resin 1
Part, 0.6 part of the first curing agent, 0.8 part of outer layer curing agent, 0.008 part of outer layer catalyst, 0.3 part of aminated compounds.Wherein aggregate
30/50 quartz sand is selected, outermost resin selects glycerine polymer, the first resin to select epoxy resin, and the first curing agent is selected
113D, outer layer curing agent select methylenediphenyl diisocyanates, and outer layer catalyst selects tributyl tin, aminated compounds choosing
Use ethylenediamine.In the present embodiment, after which is impregnated with ethyl alcohol, filtering takes filtering solution to test, different in solution
The content of cyanate radical accounts for the 1/680 of solid content.
It should be prepared from outstanding proppant using following methods:
(1) aggregate is heated to be put into sand mixer after 120 DEG C, the first resin is added, stirred 15 seconds, sand mixer revolving speed 55
Rev/min；
(2) temperature drops to 100 DEG C, and the first curing agent is added, and stirs, 55 revs/min of sand mixer revolving speed；
(3) temperature drops to 90 DEG C, and outermost resin and outer layer catalyst is added, and stirs 15s, and 55 revs/min of sand mixer revolving speed；
(4) temperature drops to 80 DEG C, and aminated compounds is added, and stirs, 55 revs/min of sand mixer revolving speed；
(5) temperature drops to 70 DEG C, and outer layer curing agent is added, and stirs, 55 revs/min of sand mixer revolving speed；Temperature drops to 50 DEG C, out
Pot is obtained from outstanding proppant.
Embodiment 3
A kind of certainly outstanding proppant, including aggregate and the coating layer being wrapped in outside aggregate, coating layer includes theca interna and outer membrane
Layer, theca externa are generated by outermost resin, outer layer catalyst, outer layer curing agent and aminated compounds, theca interna by the first resin and
First curing agent generates.The specifically used mass fraction of above-mentioned raw materials is as follows: 100 parts of aggregate, 1.2 parts of outermost resin, the first tree
1.5 parts of rouge, 0.5 part of the first curing agent, 0.8 part of outer layer curing agent, 0.01 part of outer layer catalyst, 0.3 part of aminated compounds.Wherein
Aggregate selects 40/70 quartz sand, and outermost resin selects ethylene glycol polymer, the first resin to select phenolic resin, the first curing agent
Hexamethylenetetramine, outer layer curing agent is selected to select toluene di-isocyanate(TDI), outer layer catalyst selects tributyl tin, amine chemical combination
Object selects triethylene tetramine.In the present embodiment, after which is impregnated with ethyl acetate, filtering takes filtering solution to survey
It tries, the content of the isocyano in solution accounts for the 1/860 of solid content.
It should be prepared from outstanding proppant using following methods:
(1) aggregate is heated to be put into sand mixer after 150 DEG C, the first resin is added, stirred, 60 revs/min of sand mixer revolving speed；
(2) temperature drops to 130 DEG C, and the first curing agent is added, and stirs, 60 revs/min of sand mixer revolving speed；
(3) temperature drops to 110 DEG C, and outermost resin and outer layer catalyst is added, and stirs, 60 revs/min of sand mixer revolving speed；
(4) temperature drops to 95 DEG C, and aminated compounds is added, and stirs, 60 revs/min of sand mixer revolving speed；
(5) temperature drops to 80 DEG C, and outer layer curing agent is added, and stirs, 60 revs/min of sand mixer revolving speed；Temperature drops to 50 DEG C, out
Pot is obtained from outstanding proppant.
Embodiment 4
A kind of certainly outstanding proppant, including aggregate and the coating layer being wrapped in outside aggregate, coating layer includes theca interna and outer membrane
Layer, theca externa are generated by outermost resin, outer layer catalyst, outer layer curing agent and aminated compounds, theca interna by the first resin and
First curing agent generates.The specifically used mass fraction of above-mentioned raw materials is as follows: 100 parts of aggregate, 2 parts of outermost resin, the first resin
1.5 parts, 0.7 part of the first curing agent, 1.5 parts of outer layer curing agent, 0.015 part of outer layer catalyst, 0.2 part of aminated compounds.Wherein
Aggregate selects 40/70 quartz sand, and outermost resin selects ethyl alcohol polymer, the first resin to select phenolic resin, the choosing of the first curing agent
Toluene di-isocyanate(TDI) is selected with hexamethylenetetramine, outer layer curing agent, outer layer catalyst selects dibutyl tin dilaurate, amine
Class compound selects triethylamine.In the present embodiment, after which is impregnated with isopropanol, filtering takes filtering solution to survey
It tries, the content of the isocyano in solution accounts for the 1/750 of solid content.
It should be prepared from outstanding proppant using following methods:
(1) aggregate is heated to be put into sand mixer after 130 DEG C, the first resin is added, stirred, 58 revs/min of sand mixer revolving speed；
(2) temperature drops to 110 DEG C, and the first curing agent is added, and stirs, 58 revs/min of sand mixer revolving speed；
(3) temperature drops to 90 DEG C, and outermost resin and outer layer catalyst is added, and stirs, 58 revs/min of sand mixer revolving speed；
(4) temperature drops to 80 DEG C, and aminated compounds is added, and stirs, 58 revs/min of sand mixer revolving speed；
(5) temperature drops to 70 DEG C, and outer layer curing agent is added, and stirs, 58 revs/min of sand mixer revolving speed；Temperature drops to 45 DEG C, out
Pot is obtained from outstanding proppant.
Comparative example 1
Comparative example 1 the difference from embodiment 1 is that: in this comparative example outer layer catalyst be added amount be 0.05 part.It should
After being impregnated with organic solvent from outstanding proppant, filtering takes filtering solution to test, the content of the isocyano in solution accounts for solid content
1/1660.
Comparative example 2
Comparative example 2 the difference from embodiment 1 is that: in this comparative example outer layer curing agent be added amount be 0.5 part (for outer layer
The 28% of resin quality number).After the outstanding proppant is impregnated with organic solvent, filtering solution is taken to test certainly, it is different in solution
The content of cyanate radical accounts for the 1/2880 of solid content.
Riverfrac treatment proppant in embodiment 1-4, comparative example 1-2 is tested, the performance of this proppant measured
Index is as shown in table 1:
Table 1
It illustrates:
1, suspension time refers to the maximum duration that proppant can freely suspend in water.
2, it suspends than being that suspension amount in upper layer accounts for the percentage of total proppant to evaluation proppant in water.
We use the mass ratio of proppant and water to evaluate for the case where 1:4 in test.Experimental method is in 300ml
Wide-mouth bottle in, with graduated cylinder measure 200ml water pour into wide-mouth bottle, precise 50g proppant pours into the wide-mouth bottle for having filled water
In, it closes the lid, firmly shakes 30 times up and down, it is static firmly to shake 30 times up and down after the same method after ten minutes, it is static
The proppant for filtering out upper layer suspension with filter paper afterwards, the quality that the proppant filtered out is weighed after drying is m (g), and b is compared in suspension
=m/50*100%.
3, mattress height is lower layer height of the 20g proppant in the 100ml graduated cylinder equipped with 100ml clear water.
Since laboratory can only do static suspension test, so the mattress height of lower layer is also evaluate suspendability one
Item important indicator.The amount of plastic wound packages 100ml water of 100ml is used in experiment, precise 20g proppant pours into the graduated cylinder for having filled water
In, tightly cover graduated cylinder mouth with the right hand, left hand is picked up graduated cylinder and is gently reversed 10 times up and down, it is static after ten minutes, according to same side
Method is reversed 10 times up and down, has vernier caliper to measure the bed height of lower layer support agent after static.
It 4, is to evaluate the overall target of proppant suspendability in clear water from outstanding composite index, by mattress height and suspension
Than codetermining, engineering significance is practical bulk density of the proppant in clear water, is worth the smaller phase being equivalent in water
To density with regard to smaller, then the suspension of proppant is better, suspension time is longer.
5, the test of apparent density, bulk density, percentage of damage and acid solubility is according to " SY/T 5108-2014 hydraulic fracturing
With gravel packing operations proppant performance test methods " it is tested.
Conclusion:
(1) come as can be seen from Table 1, after being impregnated from outstanding proppant with organic solvent, filtering solution is taken to test, it is molten
When the content of isocyano in liquid accounts for 1/1000 of solid content or more, the suspension ratio from outstanding proppant being prepared is all larger than
10%, suspension time is both greater than 4 hours, and suspendability is good, can preferably meet the pressure break requirement of deep-well.
(2) it can be seen that come from the data in table 1, when static, the certainly outstanding proppant in embodiment 1-4 is on upper layer
There is a certain amount of proppant that left floating.
(3) in general, the roughing sand of different size, original pottery and their mattress height all < from outstanding proppant
30mm；And in embodiment 1-4, the mattress height of proppant all > 30mm, therefore in static state, in fact from outstanding proppant
It is that the state to suspend with a kind of half is deposited in liquid bottom, once liquid flows, these proppants can suspend.
(4) as can be seen from Table 1, existing pressure break branch can be met or exceeded from outstanding proppant in embodiment 1-4
The indices for supportting agent, can meet use demand.
(5) embodiment 1 and comparative example 1, comparative example 2 are compared, it was therefore concluded that: it is soaked from outstanding proppant with organic solvent
After bubble, filtering solution is taken to test, when the content of the isocyano in solution accounts for 1/1000 or less solid content, the suspension of proppant
It is substantially reduced than, suspension time, the suspendability decline of proppant.
Claims (15)
1. a kind of from outstanding proppant, it is characterised in that: including aggregate and the coating layer being wrapped in outside aggregate, coating layer by resin,
Curing agent and catalyst generate；Certainly after the outstanding proppant is impregnated with organic solvent, filtering takes filtering solution to test, in solution
The content of isocyano account for the one thousandth of solid content or more.
2. according to claim 1 a kind of from outstanding proppant, it is characterised in that: coating layer includes theca interna and theca externa,
Theca externa is generated by outermost resin, outer layer catalyst and outer layer curing agent；Theca interna is generated by the first resin and the first curing agent
Or it is generated by the second resin, the second curing agent and internal layer catalyst.
3. according to claim 2 a kind of from outstanding proppant, it is characterised in that: the outer layer curing agent, the second curing agent
For isocyanates.
4. according to claim 3 a kind of from outstanding proppant, it is characterised in that: the outer layer catalyst, internal layer catalyst
It is one or more of organo-metallic compound and/or the organo-metallic compound of alkyl ekalead of alkyls tin.
5. according to claim 4 a kind of from outstanding proppant, it is characterised in that: the outermost resin, the second resin are
Polyalcohols resin；The equivalent of outermost resin hydroxyl is 60-300, and the mass fraction of outer layer curing agent is outermost resin mass parts
Several 40-80%.
6. according to claim 5 a kind of from outstanding proppant, it is characterised in that: according to the mass fraction, resin quality number
For the 2-10% of aggregate quality number, outermost resin accounts for the 10-90% of resin total amount；Outer layer catalyst mass fraction is outer layer tree
The 0.1-1% of rouge mass fraction.
7. according to claim 6 a kind of from outstanding proppant, it is characterised in that: theca externa further includes aminated compounds, outside
Film layer is prepared by outermost resin, outer layer curing agent, outer layer catalyst and aminated compounds；Aminated compounds mass fraction is
The 1-20% of the mass fraction of outermost resin.
8. described in any item a kind of from outstanding proppant according to claim 2-7, it is characterised in that: the first curing agent mass fraction
For the 10-50% of the first resin quality number.
9. described in any item a kind of from outstanding proppant according to claim 2-7, it is characterised in that: the second curing agent mass fraction
For the 40-80% of the second resin quality number, internal layer catalyst mass fraction is the 0.1-1% of the second resin quality number.
10. according to claim 5 a kind of from outstanding proppant, it is characterised in that: polyalcohols resin selects ethyl alcohol, second two
One of polymer such as alcohol, propylene glycol, glycerine, propyl alcohol are several.
11. according to claim 3 a kind of from outstanding proppant, it is characterised in that: isocyanates selects toluene diisocyanate
One of acid esters, methylenediphenyl diisocyanates, isophorone diisocyanate, methyl diphenylene diisocyanate or
Person is several.
12. according to claim 4 a kind of from outstanding proppant, it is characterised in that: the organo-metallic compound of alkyls tin
Specific to select dibutyl tin dilaurate, tributyl tin, the organo-metallic compound of alkyl ekalead specifically selects lead tetraethide, different
Lead octoate.
13. according to claim 7 a kind of from outstanding proppant, it is characterised in that: the aminated compounds is divinyl three
One of amine, triethylamine, ethamine, triethylene tetramine, ethylenediamine are several.
14. described in any item a kind of from outstanding proppant according to claim 2-7, it is characterised in that: first molecular resin
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
The average molecular weight of macromolecular substances, the first resin is greater than 100.
15. according to claim 1-7 a kind of from outstanding proppant, it is characterised in that: the aggregate selects quartz
Sand, haydite, Artificial Ceramic matter sand, organic synthesis sand or organo-mineral complexing material sand.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811162062.7A CN109233796A (en) | 2018-09-30 | 2018-09-30 | A kind of certainly outstanding proppant |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811162062.7A CN109233796A (en) | 2018-09-30 | 2018-09-30 | A kind of certainly outstanding proppant |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115822546A (en) * | 2022-12-16 | 2023-03-21 | 中国矿业大学(北京) | Construction method for directionally embedding time-limited dissolution backflow-prevention proppant into fracturing crack |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104797681A (en) * | 2012-09-25 | 2015-07-22 | 优选技术有限责任公司 | Coated and cured proppants |
| US20160333259A1 (en) * | 2015-05-13 | 2016-11-17 | Preferred Technology, Llc | High performance proppants |
| US20170058190A1 (en) * | 2009-10-20 | 2017-03-02 | Self-Suspending Proppant Llc | Proppants for hydraulic fracturing technologies |
-
2018
- 2018-09-30 CN CN201811162062.7A patent/CN109233796A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170058190A1 (en) * | 2009-10-20 | 2017-03-02 | Self-Suspending Proppant Llc | Proppants for hydraulic fracturing technologies |
| CN104797681A (en) * | 2012-09-25 | 2015-07-22 | 优选技术有限责任公司 | Coated and cured proppants |
| US20160333259A1 (en) * | 2015-05-13 | 2016-11-17 | Preferred Technology, Llc | High performance proppants |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115822546A (en) * | 2022-12-16 | 2023-03-21 | 中国矿业大学(北京) | Construction method for directionally embedding time-limited dissolution backflow-prevention proppant into fracturing crack |
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Application publication date: 20190118 |