CN109233790A - A kind of proppant material - Google Patents
A kind of proppant material Download PDFInfo
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- CN109233790A CN109233790A CN201811159656.2A CN201811159656A CN109233790A CN 109233790 A CN109233790 A CN 109233790A CN 201811159656 A CN201811159656 A CN 201811159656A CN 109233790 A CN109233790 A CN 109233790A
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- resin
- proppant
- curing agent
- proppant material
- outer layer
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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 compositions fields for reinforcing rupturing, specifically disclose a kind of proppant material, and including aggregate and the coating layer being wrapped in outside aggregate, coating layer is generated by resin, curing agent, catalyst and aminated compounds；The volume density of the proppant material: 1.35-1.60g/cm3, apparent density: 2.35-2.60g/cm3, 52Mpa percentage of damage :≤8%, acid solubility :≤5%, turbidity :≤50, the certainly outstanding composite index of clear water: 0.6-1.3g/cm3.The proppant material 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 compositions fields more particularly to a kind of proppant material for reinforcing rupturing.
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
Environmentally protective the purpose of the present invention is to provide a kind of proppant material, 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: a kind of proppant material, including aggregate and it is wrapped in bone
Coating layer outside material, coating layer are generated by resin, curing agent, catalyst and aminated compounds；The body of the proppant material is close
Degree: 1.35-1.60g/cm3, apparent density: 2.35-2.60g/cm3, 52Mpa percentage of damage :≤8%, acid solubility :≤5%, turbidity:
≤ 50, the certainly outstanding composite index of clear water: 0.6-1.3g/cm3。
The beneficial effect of this base case is:
1, applicant studies for a long period of time discovery, when the apparent density range of proppant material is in 2.35-2.60g/cm3, volume density
In 1.35-1.60g/cm3, proppant material can form solid-liquid mixing in clear water, apply to the solid-liquid mixing certain
When mechanical stirring is impacted, proppant material can be more evenly distributed in clear water, when the mixed liquor of proppant material and water reaches
When to certain flow rate proppant in mixed liquor can be split with carrying out the reservoir under long distance delivery to recovery well from suspended state
In gap, and slot height distribution support of totally cleaving can be reached compared to conventional proppants, improve yield.And by proppant material
52Mpa percentage of damage Kong ≤8%, acid solubility Kong ≤5%, ≤50 turbidity Kong can make proppant material effective
Support crack is played, high flow conductivity is kept, makes the smooth effect of oil gas.
It 2, is by the height of bed and to suspend than codetermining from outstanding composite index, engineering significance is reality of the proppant in clear water
Border bulk density.Applicant has found by long-term research, when the certainly outstanding composite index of the clear water of backing material is in 0.6-1.3g/
cm3When, the suspension of backing material is preferable, can occur from suspension in clear water, therefore directly achieve that height takes sand using clear water
Ability, without changing the density of water.During exploiting oil gas, traditional fracturing propping agents, benefit are replaced using proppant material
Traditional fracturing fluid is replaced with clear water, realizes zero addition of load fluid thickener in fracturing work, and then save matching for conventional pressure break
Liquid process and equipment；Meanwhile the removal of thickener also reduces injury and pressure break cost of the pressure break to reservoir.
3, during resin is reacted with curing agent, under the action of aminated compounds, the surface of the material of proppant
A large amount of protuberance can be generated, a large amount of proppant material flocks together, and formation cotton is cotton-shaped, is greatly lowered support in this way
The relative density of agent material in water, so as to make proppant material suspend in water.
Further, coating layer includes theca interna and theca externa, and theca externa is solidified by outermost resin, outer layer catalyst, outer layer
Agent and aminated compounds generate；Theca interna generated by the first resin and the first curing agent or by the second resin, the second curing agent and
Internal layer catalyst generates.Coating layer includes theca interna and theca externa, and the benefit of two layers of cladding is adequately to wrap up aggregate,
Even property is more preferable.And two layers of overlay film of setting, it can make different overlay films that there is different characteristics, theca interna is mainly used for improving support
The integral strength of agent, 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 of alkyls tin and alkyl ekalead is as catalysis
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.Applicant has found in long-term test,
The dosage of polyalcohols resin and Isocyanates curing agent is controlled in above range, can be generated with current material performance completely not
Same performance.Polyalcohols resin can be reacted with isocyanates generates polyurethane resin, passes through strict control in we's application
The dosage of outer layer curing agent make isocyanate curing agent with polyalcohols resin reaction generate polyurethane resin after still have it is surplus
Remaining, remaining isocyanates is reacted with aminated compounds, during this, can generate the gas such as nitrogen, nitric oxide, carbon monoxide
Body, these gases can generate a large amount of protuberance on the surface of not yet fully hardened urethane resin film, and protuberance quantity is put down often
Square millimeter 4 × 107A or so, these protuberances facilitate proppant and suspend.When proppant material moves in water, proppant
Surface 4 × 107A or so protuberance can reduce the proppant rate of settling in water；Part is settled down to the support of water bottom accumulation
The agent protuberance more because its surface has reduces the degree of packing of proppant particles stack layer, more conventional of intergranular water body amount
Grain accumulation body it is more, and then when water body even if with very little fluidity can more easily push proppant congeries separation and
It is mobile, realize that proppant preferably suspends in water.Simultaneously as the strict control dosage of raw material, the size of these protuberances
Control in suitable range, it is not too big and formed wear stomata.Isocyanates there remains part after reacting with aminated compounds
Isocyanates, proppant is put into water, when proppant and water contact, the isocyanates on surface can react rapidly with water to be released
Gas molecules are released, these gas molecules or be enclosed in theca externa expand, and push theca externa stage to thicken and increase
The equivalent diameter of proppant particles body, or be attached to the extension of proppant surface stage or be gathered in proppant theca externa and water body
The gas blanket of one layer of package proppant particles body is formed on the interface of contact, this gas blanket forms rank between proppant particles body
Section property be connected to and the result closed causes simple grain proppant to form more loose cotton in water body and wad a quilt with cotton to gather shape, thus significantly
The relative density of proppant in water is reduced, the suspendability of proppant can be made more preferably.
Further, the aminated compounds mass fraction is the 1-20% of the mass fraction of outermost resin.Strict control amine
The dosage of class additive, in addition to ensuring that amines additives react and different completely when amines additives are reacted with isocyanate curing agent
There are also remaining outer, the yields of the gases such as nitrogen, carbon monoxide in control reaction process, it is ensured that can support for cyanate curing agent
Agent surface formed fixed quantity protuberance, and guarantee protuberance diameter be 100-500nm, will not it is too small will not be excessive and formed
Wear stomata.
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,
Not only resin can be made to realize solidification well, and be conducive to generate protuberance, not only can increase the resistant to breakage ability of proppant in this way, but also
It can increase suspension.And applicant is by repeatedly the study found that the raw material using above-mentioned mass fraction make proppant material
Material, the proppant material suspension effect being prepared and other better performances.
Further, the first curing agent mass fraction is the 10-50% of the first resin quality number；Second curing agent mass parts
Number is the 40-80% of the second resin quality number, and internal layer catalyst mass fraction is the 0.1-1% of the second resin quality number.
The dosage strict control of the various raw materials of theca interna is improved into proppant material so that theca interna has high intensity and hardness
Resistance to crushing.
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 raw materials preferably meet use demand.
Detailed description of the invention
Fig. 1 is the electron-microscope scanning figure for the proppant material 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.
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 proppant material, 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, 1.5 parts of outermost resin, the first tree
2 parts of rouge, 0.8 part of the first curing agent, 1 part of outer layer curing agent, 0.01 part of outer layer catalyst, 0.2 part of aminated compounds.Wherein aggregate
20/40 quartz sand is selected, outermost resin selects glycol polymers, the first resin to select epoxy resin, and the first curing agent is selected
Curing agent T31, outer layer curing agent select methylenediphenyl diisocyanates, and outer layer catalyst selects di lauric dibutyl
Tin, aminated compounds select ethamine.In the present embodiment, the volume density of proppant material: 1.47g/cm3, apparent density: 2.49g/
cm3, 52Mpa percentage of damage: 6.2%, acid solubility: 3.9%, turbidity :≤50, the certainly outstanding composite index of clear water: 1.13g/cm3。
The proppant material is prepared using following methods:
(1) after aggregate being heated to 190-220 DEG C, the first resin and the first curing agent is added, is stirred；
(2) 150-180 DEG C is dropped to temperature, outermost resin and outer layer catalyst is added, is stirred；
(3) 120-150 DEG C is dropped to temperature, aminated compounds is added, is stirred；
(4) 80-110 DEG C is dropped to temperature, outer layer curing agent is added, is stirred；Temperature drops to 50-80 DEG C, takes the dish out of the pot, and obtains
To proppant material.
Embodiment 2
A kind of proppant material, 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 2
Part, 1 part of the first curing agent, 1 part of outer layer curing agent, 0.015 part of outer layer catalyst, 0.3 part of aminated compounds.Wherein aggregate is selected
30/50 quartz sand, outermost resin select glycerine polymer, the first resin to select epoxy resin, and the first curing agent selects solidification
Agent T31, outer layer curing agent select isophorone diisocyanate, and outer layer catalyst selects tributyl tin, and aminated compounds is selected
Triethylene tetramine.In the present embodiment, the volume density of proppant material: 1.45g/cm3, apparent density: 2.44g/cm3, 52Mpa is broken
Rate: 5.4%, acid solubility: 4.1%, turbidity :≤50, the certainly outstanding composite index of clear water: 1.02g/cm3。
The proppant material is prepared using following methods:
(1) after aggregate being heated to 175-185 DEG C, the first resin and the first curing agent is added, is stirred；
(2) 150-160 DEG C is dropped to temperature, outermost resin and outer layer catalyst is added, is stirred；
(3) 120-130 DEG C is dropped to temperature, aminated compounds is added, is stirred；
(4) 100-110 DEG C is dropped to temperature, outer layer curing agent is added, is stirred；Temperature drops to 60-80 DEG C, takes the dish out of the pot,
Be supported agent material.
Embodiment 3
A kind of proppant material, 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, 3 parts of outermost resin, the first resin 2
Part, 1 part of the first curing agent, 2 parts of outer layer curing agent, 0.015 part of outer layer catalyst, 0.4 part of aminated compounds.Wherein aggregate is selected
40/70 quartz sand, outermost resin select ethylene glycol polymer, the first resin to select phenolic resin, and the first curing agent is selected six times
Tetramine, outer layer curing agent select toluene di-isocyanate(TDI), and outer layer catalyst selects isooctyl acid lead, and aminated compounds selects three
Ethamine.In the present embodiment, the volume density of proppant material: 1.44g/cm3, apparent density: 2.42g/cm3, 52Mpa percentage of damage
4.9%, acid solubility: 3.8%, turbidity :≤50, the certainly outstanding composite index of clear water: 0.72g/cm3。
The proppant material is prepared using following methods:
(1) after aggregate being heated to 180-190 DEG C, the first resin and the first curing agent is added, is stirred；
(2) 150-160 DEG C is dropped to temperature, outermost resin and outer layer catalyst is added, is stirred；
(3) 120-130 DEG C is dropped to temperature, aminated compounds is added, is stirred；
(4) 90-100 DEG C is dropped to temperature, outer layer curing agent is added, is stirred；Temperature drops to 50-70 DEG C, takes the dish out of the pot, and obtains
To proppant material.
Embodiment 4
A kind of proppant material, 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, and theca interna is by the second resin, the
Two curing agent and internal layer catalyst generate.The specifically used mass fraction of above-mentioned raw materials is as follows: 100 parts of aggregate, outermost resin 2
Part, 2 parts of the second resin, 1 part of the second curing agent, 1.5 parts of outer layer curing agent, 0.015 part of internal layer catalyst, outer layer catalyst
0.015 part, 0.3 part of aminated compounds.Wherein aggregate selects 40/70 quartz sand, and outermost resin selects ethylene glycol polymer, first
Resin selects phenolic resin, and the second curing agent selects methyl diphenylene diisocyanate, and outer layer curing agent selects toluene diisocyanate
Acid esters, outer layer catalyst select isooctyl acid lead, and internal layer catalyst selects dibutyl tin dilaurate, and aminated compounds selects diethyl
Alkene triamine.In the present embodiment, the volume density of proppant material: 1.46g/cm3, apparent density: 2.44g/cm3, 52Mpa percentage of damage
4.5%, acid solubility: 4.1%, turbidity :≤50, the certainly outstanding composite index of clear water: 0.69g/cm3。
The proppant material is prepared using following methods:
(1) after aggregate being heated to 115-125 DEG C, the second resin and internal layer catalyst is added, is stirred；
(2) 100-110 DEG C is dropped to temperature, internal layer curing agent is added, is stirred；
(3) 95-105 DEG C is dropped to temperature, outermost resin and outer layer catalyst is added, is stirred；
(4) 85-95 DEG C is dropped to temperature, aminated compounds is added, is stirred；
(5) 80-90 DEG C is dropped to temperature, outer layer curing agent is added, is stirred；Temperature drops to 50-60 DEG C, takes the dish out of the pot, and obtains
To proppant material.
Comparative example 1
Comparative example 1 the difference from embodiment 1 is that: aminated compounds is added without in this comparative example.In the comparative example, support
The volume density of agent material: 1.53g/cm3, apparent density: 2.56g/cm3, 52Mpa percentage of damage 6.2%, acid solubility: 3.8%, it is turbid
Spend :≤50, the certainly outstanding composite index of clear water: 1.44g/cm3。
Comparative example 2
Comparative example 2 the difference from embodiment 1 is that: in this comparative example outermost resin select phenolic resin.In the comparative example,
The volume density of proppant material: 1.51g/cm3, apparent density: 2.54g/cm3, 52Mpa percentage of damage 5.4%, acid solubility: 3.9%,
Turbidity :≤50, the certainly outstanding composite index of clear water: 1.38g/cm3。
Comparative example 3
Comparative example 3 the difference from embodiment 1 is that: in this comparative example outer layer curing agent be added 0.5 part (for outermost resin matter
Measure the 33.3% of number).In the comparative example, the volume density of proppant material: 1.48g/cm3, apparent density: 2.44g/cm3, 52Mpa
Percentage of damage 5.9%, acid solubility: 3.8%, turbidity :≤50, the certainly outstanding composite index of clear water: 1.37g/cm3。
Comparative example 4
Comparative example 4 the difference from embodiment 1 is that: in this comparative example outer layer curing agent be added 0.2 part (for outermost resin matter
Measure the 13.3% of number).In the comparative example, the volume density of proppant material: 1.53g/cm3, apparent density: 2.56g/cm3, 52Mpa
Percentage of damage 6.2%, acid solubility: 3.8%, turbidity :≤50, the certainly outstanding composite index of clear water: 1.45g/cm3。
Comparative example 5
Comparative example 5 the difference from embodiment 1 is that: in this comparative example outer layer curing agent be added 2 parts (for outermost resin quality
The 133% of number).In the comparative example, the volume density of proppant material: 1.51g/cm3, apparent density: 2.52g/cm3, 52Mpa is broken
Broken rate 5.4%, acid solubility: 3.8%, turbidity :≤50, the certainly outstanding composite index of clear water: 1.39g/cm3。
It illustrates: being to evaluate the overall target of proppant suspendability in clear water from outstanding composite index, by mattress height
Degree and the ratio that suspends codetermine, and engineering significance is practical bulk density of the proppant in clear water, and value is smaller to be equivalent to
Relative density in water is with regard to smaller, then the suspension of proppant is better, suspension time is longer.
(b is suspension ratio, h is mattress height)
The proppant material being prepared in embodiment 1-4, comparative example 1-5 is tested, this proppant measured
Performance indicator such as table 1:
Table 1
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.
Conclusion:
(1) as can be seen from Table 1, it is small that the suspension time for the proppant material that embodiment 1-4 is prepared is both greater than 4
When, the pressure break requirement of deep-well can be fully met, and the ratio that suspends is all larger than 10%, the proppant material being prepared has on upper layer
A certain amount of proppant that left floating.And the proppant material in comparative example 1-5, it cannot suspend or suspension time is extremely short, suspend
Property is very poor.Proppant material volume density in embodiment 1-4 is in 1.35-1.60g/cm3, apparent density is in 2.35-2.60g/cm3, clearly
Water is from outstanding composite index in 0.6-1.3g/cm3, and the volume density of the proppant material in comparative example 1-2, apparent density, clear water are certainly
Equal no longer above range in the indexs such as outstanding composite index, this illustrates the volume density of proppant material in 1.35-1.60g/cm3,
Apparent density is in 2.35-2.60g/cm3, clear water is from outstanding composite index in 0.6-1.3g/cm3When, proppant material just has good
Suspension.
(2) in general, the roughing sand of different size, the mattress height of original pottery and their traditional overlay film proppant is all
< 30mm；And in embodiment 1-4, the mattress height of proppant all > 30mm, therefore in static state, proppant material its
It is that the state to suspend with a kind of half is deposited in liquid bottom in fact, once liquid flows, these proppants can suspend.
(3) in comparative example 1,3,4,5, outer layer curing agent, the dosage of aminated compounds addition are against regulation, and proppant produces
Raw protuberance lazy weight is so that proppant suspends, therefore suspension time is extremely short or even does not suspend.Analyze comparative example 3-5 it is found that
The mass fraction of outer layer curing agent is necessary for the 40-80% of outermost resin mass fraction in the present invention program, outer layer curing agent
Dosage is very few cannot to be generated the protuberance for needing quantity or cannot generate protuberance, and outer layer hardener dose is excessive, can make grand
The volume risen is excessive, leads to swell being easy to rupture, finally can proppant be made not have suspendability.
(4) in comparative example 2, outermost resin selects phenolic resin, is not had according to the proppant of 1 data comparative example 2 of table
Thus suspension it can be inferred that, only selects polyalcohols resin, Isocyanates curing agent, the amine chemical combination of special ratios
Theca externa is made in object, outer layer catalyst, and proppant can just be made to have suspension.
Claims (14)
1. a kind of proppant material, it is characterised in that: including aggregate and the coating layer that is wrapped in outside aggregate, coating layer by resin,
Curing agent, catalyst and aminated compounds generate；The volume density of the proppant material: 1.35-1.60g/cm3, apparent density:
2.35-2.60g/cm3, 52Mpa percentage of damage :≤8%, acid solubility :≤5%, turbidity :≤50, the certainly outstanding composite index of clear water:
0.6-1.3g/cm3。
2. a kind of proppant material according to claim 1, it is characterised in that: coating layer includes theca interna and theca externa,
Theca externa is generated by outermost resin, outer layer catalyst, outer layer curing agent and aminated compounds；Theca interna is by the first resin and first
Curing agent is generated or is generated by the second resin, the second curing agent and internal layer catalyst.
3. a kind of proppant material according to claim 2, it is characterised in that: the outer layer curing agent, the second curing agent
For isocyanates.
4. a kind of proppant material according to claim 3, 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. a kind of proppant material according to claim 4, 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. a kind of proppant material according to claim 5, it is characterised in that: the aminated compounds mass fraction is outer
The 1-20% of the mass fraction of layer resin.
7. a kind of proppant material according to claim 6, 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.
8. a kind of proppant material according to claim 7, it is characterised in that: the first curing agent mass fraction is the first tree
The 10-50% of rouge mass fraction；Second curing agent mass fraction is 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.
9. according to a kind of described in any item proppant materials of claim 5-8, it is characterised in that: polyalcohols resin selects second
One of polymer such as alcohol, ethylene glycol, propylene glycol, glycerine, propyl alcohol are several.
10. according to a kind of described in any item proppant materials of claim 3-8, it is characterised in that: isocyanates selects first
Phenylene diisocyanate, methylenediphenyl diisocyanates, isophorone diisocyanate, in methyl diphenylene diisocyanate
One or several kinds.
11. according to a kind of described in any item proppant materials of claim 4-8, it is characterised in that: organic gold of alkyls tin
Belong to compound and specifically select dibutyl tin dilaurate, tributyl tin, the organo-metallic compound of alkyl ekalead specifically selects four
Lead ethyl, isooctyl acid lead.
12. a kind of proppant material according to claim 1-8, it is characterised in that: the aminated compounds is
One of diethylenetriamine, triethylamine, ethamine, triethylene tetramine, ethylenediamine are several.
13. a kind of proppant material according to claim 12, it is characterised in that: in first resinous molecular structure extremely
Few organic macromolecule object containing the two or more groups in epoxy group, phenolic hydroxyl group, carbonyl, amide groups, amino, isocyanate group
The average molecular weight of matter, the first resin is greater than 100.
14. a kind of riverfrac treatment proppant according to claim 1-8, feature are being: the aggregate choosing
With quartz sand, haydite, Artificial Ceramic matter sand, organic synthesis sand or organo-mineral complexing material sand.
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| CN201811159656.2A CN109233790A (en) | 2018-09-30 | 2018-09-30 | A kind of proppant material |
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| CN201811159656.2A CN109233790A (en) | 2018-09-30 | 2018-09-30 | A kind of proppant material |
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Application publication date: 20190118 |