CN109456752A - A kind of preparation method of proppant material - Google Patents
A kind of preparation method of proppant material Download PDFInfo
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- CN109456752A CN109456752A CN201811159615.3A CN201811159615A CN109456752A CN 109456752 A CN109456752 A CN 109456752A CN 201811159615 A CN201811159615 A CN 201811159615A CN 109456752 A CN109456752 A CN 109456752A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/80—Compositions for reinforcing fractures, e.g. compositions of proppants used to keep the fractures open
- C09K8/805—Coated proppants
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/58—Epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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- Engineering & Computer Science (AREA)
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- Polyurethanes Or Polyureas (AREA)
Abstract
The invention belongs to the compositions fields for reinforcing rupturing, specifically disclose a kind of preparation method of proppant material, the volume density of 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 preparation of proppant material is the following steps are included: (1) prepares aggregate, inner membrance material and outer membrane material；(2) aggregate is heated to 80-230 DEG C, inner membrance material is added, is stirred；(3) 75-200 DEG C is dropped to temperature, outermost resin and outer layer catalyst is added, is stirred；(4) 55-130 DEG C is dropped to temperature, aminated compounds is added, is stirred；(5) 45-110 DEG C is dropped to temperature, outer layer curing agent is added, be mixed；Temperature drops to 30-80 DEG C, takes the dish out of the pot, and obtains riverfrac treatment proppant.The proppant material suspension being prepared using the method for the present invention is good, is easy to be carried into well.
Description
Technical field
The invention belongs to for reinforcing rupturing compositions field more particularly to a kind of preparation side of proppant material
Method.
Background technique
In order to develop deep-seated oil, gas well, yield is improved, hydraulic fracturing technology is widely used.Hydraulic fracturing technology is benefit
With the high pressure pump group on ground, the fracturing fluid with viscosity higher is injected constantly into oil well by pit shaft, so that oil well lower part shape
At a kind of technology of high pressure.With the continuous injection of fracturing fluid, pressure is also constantly increased, the formation rock anti-tensile near the borehole wall
When intensity and reservoir stress are less than the pressure that fracturing fluid is formed, the stratum near shaft bottom will just generate crack.When carrying proppant
Fracturing fluid continue injection when, formation fractures can extend forward and be supported agent filling, stop the agent of fracturing work rear support
Play a part of equilibrium strata pressure, make rock seam keep split and have certain flow conductivity, thus reach make oil gas field volume increase,
Extend the purpose of the oil/gas well length of service.
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.The fracturing propping agents that conventional method is prepared have quartz sand and haydite and their overlay film
Product, outer film coating are solidified at high temperature with phenolic aldehyde or epoxy resin, the amount of curing agent generally in the 5-50% of amount of resin,
Coated temperature is at 230 degree or so, and 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 carried into well.The proppant product of existing method preparation is gone back other than coating epoxy resin, phenolic resin film
There is coating urethane resin film, polyurethane resin is a great system, the raw material selected by strict control, raw material
Dosage, condition of reaction etc. can make polyurethane resin have entirely different substance physical property, the existing poly- ammonia for being used to support agent
Ester resin is the polyurethane resin with high rigidity substance physical property, it is ensured that resin film has high-caliber hardness and good resistance to compression
Fragility finally makes proppant have good resistant to breakage ability.But the proppant of the existing urethane resin film of coating produces
Product are still only to meet intensity, hardness requirement, not can solve proppant suspension it is poor, be easy precipitating 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 preparation method of proppant material, it is prepared with to solve conventional method
Fracturing propping agents density is high, suspension is poor, it is not easy to be carried into the problems in well.
In order to achieve the above object, base case of the invention are as follows: a kind of preparation method of proppant material, proppant material
The volume density of 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 preparation of the proppant material the following steps are included:
(1) prepare aggregate, inner membrance material and outer membrane material, outer membrane material includes that outermost resin, outer layer catalyst, outer layer are solid
Agent and aminated compounds；
(2) aggregate is heated to 120-230 DEG C, inner membrance material is added, be mixed 10-30 seconds；
(3) outermost resin and outer layer catalyst is added, 15s is mixed；
(4) aminated compounds is added, is stirred 15 seconds；
(5) outer layer curing agent is added, is mixed 40 seconds and takes the dish out of the pot, obtain riverfrac treatment proppant.
The beneficial effect of this base case is:
1, the volume density for the proppant material being prepared using this method: 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.Applicant studies for a long period of time discovery, when the apparent density range of proppant material is in 2.40-2.45g/cm3, volume density exists
1.35-1.60g/cm3, proppant material can form comprehensive bulk density in 0.6-1.3g/cm in clear water3Solid-liquid mixing
State, when applying certain mechanical stirring impact to the solid-liquid mixing, proppant material can be more evenly distributed in clear water,
The proppant in mixed liquor can be made to be grown from suspended state when the mixed liquor of proppant material and water reaches certain flow rate
Distance is delivered in the reservoir fracture under recovery well, and can reach slot height distribution support of totally cleaving compared to conventional proppants,
Improve yield.And by proppant material 52Mpa percentage of damage Kong ≤8%, acid solubility Kong ≤5%, turbidity, which controls, to exist
≤ 50, proppant material can be made to effectively play support crack, high flow conductivity is kept, make the smooth effect of oil gas.
2, it is the index of applicant oneself definition from outstanding composite index, by the height of bed and suspends than codetermining, engineering meaning
Justice is practical bulk density of the proppant in clear water.Applicant has found by long-term research, when backing material clear water from
Composite index is hanged in 0.6-1.3g/cm3When, the suspension of backing material is preferable, can occur from suspension in clear water, therefore directly make
High prop-carrying capacity is achieved that with clear water, without changing the density of water.During exploiting oil gas, using proppant material generation
For traditional fracturing propping agents, traditional fracturing fluid is replaced using clear water, realizes zero addition of load fluid thickener in fracturing work, into
And save conventional pressure break with liquid process and equipment；Meanwhile the removal of thickener also reduce pressure break to the injury of reservoir and
Pressure break cost.
3, the coating layer on proppant material surface contains resin and amines additives, amines additives energy catalytic resin and water
Reaction generates a large amount of gas molecules rapidly, these gas molecules are attached to the surface of proppant material and covering for surface
Film layer acts on the gas wrapping hydrated sheath to form micro/nano level, while can cause the resin membrane swelling on surface, a large amount of proppant
Material flocks together, and formation cotton is cotton-shaped, is greatly lowered the relative density of proppant material in water in this way, so as to
Proppant material is set to suspend in water.
4, during preparing proppant material, it is separately added into resin in section in different times, it can be in aggregate surface
Two layers of resin film is formed, two layers of resin film can more fully wrap up internal layer aggregate, and uniformity is more preferable.
Further, inner membrance material includes the first resin and the first curing agent, and the first resin quality number is aggregate quality part
Several 0.5-9%, the first curing agent mass fraction are the 10-50% of the first resin quality number；In step (2), by aggregate plus
Heat arrives 160-230 DEG C, and the first resin and the first curing agent is added, and is mixed 10-20 seconds.
Further, inner membrance material includes the second resin, the second curing agent and internal layer catalyst, and the second resin quality number is
The 0.5-9% of aggregate quality number, the second curing agent mass fraction are the 40-80% of the second resin quality number, internal layer catalysis
Agent mass fraction is the 0.1-1% of the second resin quality number；In step (2), aggregate is heated to 120-160 DEG C, is added the
One resin and internal layer catalyst are mixed 10-20 seconds；The second curing agent is added, is mixed 10-20 seconds.
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, outermost resin mass fraction is the 0.5-9% of aggregate quality number, outer layer catalysis
Agent mass fraction is the 0.1-1% of outermost resin mass fraction.Applicant is by repeatedly the study found that using above-mentioned mass fraction
Raw material, the proppant material suspension effect being finally prepared and other better performances.
Further, the polyalcohols resin is selected in the polymer such as ethyl alcohol, ethylene glycol, propylene glycol, glycerine, propyl alcohol
It is one or several kinds of.Applicant has found by test of many times, selects above-mentioned raw material as aminated compounds, can make proppant material
The effect that material generates protuberance is more preferable.
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, 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
Found by test of many times, select above-mentioned material as the first resin, the proppant material comprehensive performance that is finally prepared compared with
It is good.
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 kind, 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 preparation method, comprising the following steps:
(1) prepare the raw material of following mass fraction: 100 parts of aggregate, 1.5 parts of outermost resin, 2 parts of the first resin, first are consolidated
0.8 part of agent, 1 part of outer layer curing agent, 0.01 part of outer layer catalyst, 0.2 part of aminated compounds.Wherein aggregate selects 20/40 stone
Sand, outermost resin select glycol polymers, the first resin to select epoxy resin, and the first curing agent selects T31, outer layer solidification
Methylenediphenyl diisocyanates are selected in agent, and outer layer catalyst selects dibutyl tin dilaurate, and aminated compounds selects second
Amine.
(2) after aggregate being heated to 190-220 DEG C, the first resin and the first curing agent is added, is stirred；
(3) 150-180 DEG C is dropped to temperature, outermost resin and outer layer catalyst is added, is stirred；
(4) 120-150 DEG C is dropped to temperature, aminated compounds is added, is stirred；
(5) 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.
Use the volume density for the proppant material that this method is prepared: 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。
Embodiment 2
One kind is from suspended prop material preparation method, comprising the following steps:
(1) prepare the raw material of following mass fraction: 100 parts of aggregate, 2 parts of outermost resin, 2 parts of the first resin, the first solidification
1 part of agent, 1 part of outer layer curing agent, 0.015 part of outer layer catalyst, 0.3 part of aminated compounds.Wherein aggregate selects 30/50 quartz
Sand, outermost resin select glycerine polymer, the first resin to select epoxy resin, and the first curing agent selects 113D, outer layer solidification
Isophorone diisocyanate is selected in agent, and outer layer catalyst selects tributyl tin, and aminated compounds selects triethylene tetramine.
(2) after aggregate being heated to 175-185 DEG C, the first resin and the first curing agent is added, is stirred；
(3) 150-160 DEG C is dropped to temperature, outermost resin and outer layer catalyst is added, is stirred；
(4) 120-130 DEG C is dropped to temperature, aminated compounds is added, is stirred；
(5) 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.
Use the volume density for the proppant material that this method is prepared: 1.45g/cm3, apparent density: 2.44g/cm3,
52Mpa percentage of damage: 5.4%, acid solubility: 4.1%, turbidity :≤50, the certainly outstanding composite index of clear water: 1.02g/cm3。
Embodiment 3
One kind is from suspended prop material preparation method, comprising the following steps:
(1) prepare the raw material of following mass fraction: 100 parts of aggregate, 3 parts of outermost resin, 2 parts of the first resin, the first solidification
1 part of agent, 2 parts of outer layer curing agent, 0.015 part of outer layer catalyst, 0.4 part of aminated compounds.Wherein aggregate selects 40/70 quartz
Sand, outermost resin selection ethylene glycol polymer, the first resin selection phenolic resin, the first curing agent selection hexamethylenetetramine,
Outer layer curing agent selects toluene di-isocyanate(TDI), and outer layer catalyst selects isooctyl acid lead, and aminated compounds selects triethylamine.
(2) after aggregate being heated to 180-190 DEG C, the first resin and the first curing agent is added, is stirred；
(3) 150-160 DEG C is dropped to temperature, outermost resin and outer layer catalyst is added, is stirred；
(4) 120-130 DEG C is dropped to temperature, aminated compounds is added, is stirred；
(5) 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.
Use the volume density for the proppant material that this method is prepared: 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。
Embodiment 4
One kind is from suspended prop material preparation method, comprising the following steps:
(1) prepare the raw material of following mass fraction: 100 parts of aggregate, 2 parts of outermost resin, 2 parts of the second resin, the second solidification
1 part of agent, 1.5 parts of outer layer curing agent, 0.015 part of internal layer catalyst, 0.015 part of outer layer catalyst, 0.3 part of aminated compounds.Its
Middle aggregate selects 40/70 quartz sand, and outermost resin selects ethylene glycol polymer, the first resin to select phenolic resin, the second solidification
Methyl diphenylene diisocyanate is selected in agent, and outer layer curing agent selects toluene di-isocyanate(TDI), and outer layer catalyst selects isooctyl acid
Lead, internal layer catalyst select dibutyl tin dilaurate, and aminated compounds selects diethylenetriamine.
(2) after aggregate being heated to 115-125 DEG C, the second resin and internal layer catalyst is added, is stirred；
(3) 100-110 DEG C is dropped to temperature, internal layer curing agent is added, is stirred；
(4) 95-105 DEG C is dropped to temperature, outermost resin and outer layer catalyst is added, is stirred；
(5) 85-95 DEG C is dropped to temperature, aminated compounds is added, is stirred；
(6) 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.
Use the volume density for the proppant material that this method is prepared: 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: 0.81g/cm3。
Comparative example 1
Comparative example 1 the difference from embodiment 1 is that: amines additives are 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/cm33, apparent density: 2.54g/cm3, 52Mpa percentage of damage 6.2%, 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 polyalcohols tree
The 13.3% of rouge mass fraction).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.
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, suspend than be evaluation proppant upper layer suspension amount Zhan total proppant in water percentage.
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%, shows the proppant material being prepared on upper layer
There is a certain amount of proppant that left floating.And the proppant material in comparative example 1-2, it cannot suspend or suspension time is extremely short,
Suspension is very poor.In 1.35-1.60g/cm3, apparent density exists the proppant material volume density being prepared in embodiment 1-4
2.35-2.60g/cm3, clear water is from outstanding composite index in 0.6-1.3g/cm3, and the proppant material being prepared in comparative example 1-2
For the indexs such as the certainly outstanding composite index of the volume density of material, apparent density, clear water not in above range, this illustrates the body of proppant material
Density is in 1.35-1.60g/cm3, and 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 material all > 30mm, therefore in static state, proppant material
Material 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
Get up.
(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 discrepancy of quantity, which closes, to be required, therefore suspension time is extremely short or even does not suspend.Comparative example 3-5 is analyzed it is found that side of the present invention
The mass fraction of outer layer curing agent is necessary for the 40-80% of outermost resin mass fraction in case, and the dosage of outer layer curing agent is very few
The protuberance for needing quantity cannot be generated or protuberance cannot be generated, and outer layer hardener dose is excessive, can make the volume of protuberance
It is excessive, lead 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 preparation method of proppant material, it is characterised in that: the volume density of proppant material: 1.35-1.60g/cm3, depending on
Density: 2.35-2.60g/cm3, 52Mpa percentage of damage :≤8%, acid solubility :≤5%, turbidity :≤50, outstanding integrate refers to clear water certainly
Number: 0.6-1.3g/cm3；The preparation of the proppant material the following steps are included:
(1) preparing aggregate, inner membrance material and outer membrane material, outer membrane material includes outermost resin, outer layer catalyst, outer layer curing agent
And aminated compounds；
(2) aggregate is heated to 80-230 DEG C, inner membrance material is added, is stirred；
(3) 70-200 DEG C is dropped to temperature, outermost resin and outer layer catalyst is added, is stirred；
(4) 55-130 DEG C is dropped to temperature, aminated compounds is added, is stirred；
(5) 45-110 DEG C is dropped to temperature, outer layer curing agent is added, be mixed；Temperature drops to 30-80 DEG C, takes the dish out of the pot, and obtains clear
Water fracturing propping agents.
2. a kind of preparation method of proppant material according to claim 1, it is characterised in that: inner membrance material includes first
Resin and the first curing agent, the first resin quality number are the 0.5-9% of aggregate quality number, and the first curing agent mass fraction is
The 10-50% of first resin quality number；In step (2), aggregate is heated to 80-230 DEG C, the first resin and first is added and consolidates
Agent is mixed 10-20 seconds.
3. a kind of preparation method of proppant material according to claim 1, it is characterised in that: inner membrance material includes second
Resin, the second curing agent and internal layer catalyst, the second resin quality number are the 0.5-9% of aggregate quality number, the second solidification
Agent mass fraction is the 40-80% of the second resin quality number, and internal layer catalyst mass fraction is the second resin quality number
0.1-1%；In step (2), aggregate is heated to 80-230 DEG C, the second resin and internal layer catalyst is added, is stirred；To temperature
Degree drops to 75-210 DEG C, and the second curing agent is added, and is mixed.
4. a kind of preparation method of proppant material according to claim 3, it is characterised in that: the outer layer curing agent,
Second curing agent is isocyanates.
5. a kind of preparation method of proppant material according to claim 3, it is characterised in that: the outer layer catalyst,
Internal layer catalyst be one of the organo-metallic compound of alkyls tin and/or the organo-metallic compound of alkyl ekalead or
It is several.
6. a kind of preparation method of proppant material according to claim 3, it is characterised in that: the outermost resin,
Two resins are polyalcohols resin；The equivalent of outermost resin hydroxyl is 60-300, and the mass fraction of outer layer curing agent is outer layer
The 40-80% of resin quality number.
7. a kind of preparation method of proppant material according to claim 1-6, it is characterised in that: the amine
Compound quality number is the 1-20% of the mass fraction of outermost resin.
8. a kind of preparation method of proppant material according to claim 7, it is characterised in that: according to the mass fraction, outside
Layer resin quality number is the 0.5-9% of aggregate quality number, and outer layer catalyst mass fraction is outermost resin mass fraction
0.1-1%.
9. a kind of preparation method of proppant material according to claim 6, it is characterised in that: the polyalcohols resin
Select one of polymer such as ethyl alcohol, ethylene glycol, propylene glycol, glycerine, propyl alcohol or several.
10. a kind of preparation method of proppant material according to claim 4, it is characterised in that: isocyanates is selected
Toluene di-isocyanate(TDI), methylenediphenyl diisocyanates, isophorone diisocyanate, methyl diphenylene diisocyanate
One of or it is several.
11. a kind of preparation method of proppant material according to claim 5, it is characterised in that: alkyls tin it is organic
Metallic compound specifically selects dibutyl tin dilaurate, tributyl tin, and the organo-metallic compound of alkyl ekalead is specifically selected
Lead tetraethide, isooctyl acid lead.
12. a kind of preparation method of proppant material according to claim 1-6, it is characterised in that: the amine
Class compound is one of diethylenetriamine, triethylamine, ethamine, triethylene tetramine, ethylenediamine or several.
13. a kind of preparation method of proppant material according to claim 2, it is characterised in that: first resin point
At least having containing the two or more groups in epoxy group, phenolic hydroxyl group, carbonyl, amide groups, amino, isocyanate group in minor structure
The average molecular weight of machine macromolecular substances, the first resin is greater than 100.
14. a kind of preparation method of proppant material according to claim 1-6, it is characterised in that: the bone
Material selects quartz sand, haydite, Artificial Ceramic matter sand, organic synthesis sand or organo-mineral complexing material sand.
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Application publication date: 20190312 |