CN109233789A - One kind is from suspension overlay film backing material - Google Patents
One kind is from suspension overlay film backing material Download PDFInfo
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- CN109233789A CN109233789A CN201811159527.3A CN201811159527A CN109233789A CN 109233789 A CN109233789 A CN 109233789A CN 201811159527 A CN201811159527 A CN 201811159527A CN 109233789 A CN109233789 A CN 109233789A
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- Prior art keywords
- resin film
- backing material
- overlay film
- suspension
- film backing
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Classifications
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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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3228—Polyamines acyclic
Abstract
The invention belongs to petroleum, the fluid minerals production technique such as natural gas and shale gas field, it specifically discloses a kind of from suspension overlay film backing material, including aggregate and the coat being coated on aggregate, the coat includes inner layer resin film and outermost resin film, drag reducer is added in the outermost resin film and inner layer resin film, the outermost resin film includes amines additives, the drag reducer quality is the 0.7-1.8% of aggregate, the drag reducer of outermost resin film accounts for the 40-60% of drag reducer total amount, the apparent density from suspension overlay film backing material is 1.05-2.60g/cm3.This programme can suspend from suspension overlay film backing material in clear water, while meeting industry basic demand, the substance of the thickeninies such as addition guar gum is not needed in fracturing process, greatly reduce cost, fracturing unit and technique are simplified, the pollution to environment, while good guide performance are reduced, construction efficiency is improved.
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
Floating overlay film backing material.
Background technique
Hydraulic fracturing technology at home and abroad comparative maturity, petroleum fracturing propping agent is as essential in fracturing process
One of article, performance superiority and inferiority will directly influence fracturing effect, and apparent density is to evaluate the important finger of proppant performance
One of mark, apparent density is lower, and it is lower relative to the relative density of fracturing fluid, after proppant is mixed with pressure break carrying liquid, depending on
The lower density the easier to suspend in fracturing fluid, to greatly reduce the rate of settling.It will pump farther in pumping procedure.
High pumping pressure pumps fluid into well, while rock stratum of splitting is to allow hydrocarbons preferably to pass through.However, removing non-pressure
It keeps, the aperture otherwise newly formed is closed.In order to open and keep path, support is injected simultaneously during pumping fluid
Agent, support needed for keeping aperture with generation.When forming crack, biography when proppant passes through release hydraulic pressure in the slurry
It passs, proppant forms the filling or support for staying open crack herein.
With the development that domestic petroleum fracturing propping agents produce, miscellaneous proppant emerges one after another, such as covers
Film proppant.And for domestic fracturing technology mainly based on quartz sand and haydite, quartz sand is mainly used in the low closure of shallow-layer at present
The fracturing work of pressure well, haydite is mainly used in middle-deep well fracturing technology, but the resistant to breakage ability of quartz sand and haydite is equal
It is limited, it is difficult to adapt to hyperbaric environment.And overlay film proppant is by enhancing the intensity of proppant in aggregate surface overlay film, to improve
Proppant resists broken ability.Currently, the coating film of overlay film proppant common are phenolic resin film, epoxy resin film at present
With urethane resin film etc..
Present aggregate surface cladding phenolic resin film, epoxy resin film and urethane resin film etc. are primarily to improve branch
The intensity of agent is supportted, so substantially to consider how that improving resin film (covers phenolic resin film, epoxy resin film and poly- ammonia at present
Ester resin film etc.) intensity, but the suspendability of proppant is not improved, is applied using this kind of overlay film proppant pressure break
Working hour usually requires preparing the carrying liquid with viscoelasticity, and traditional carrying liquid making method is that a large amount of increase is added in water
The viscoelasticity that thick dose (substances such as guar gum) increase its own enables overlay film proppant to suspend in carrying liquid, but its disadvantage
It is that will lead to that pressure break higher cost, reservoir damage are serious, pollute the environment after addition thickener, therefore be badly in need of one now
The proppant that kind can suspend in clear water.
Existing proppant can be in water from there are two main classes the technology of suspension, first is that on aggregate quartz sand or haydite surface
Overlay film layer of material, this material are mainly some water-soluble high-molecular materials, such as polyacrylamide, carboxymethyl cellulose, are gathered
Acrylic acid, guar gum, natural plant gum etc..These materials are met water energy and are expanded rapidly, and the viscosity that can dissolve into increase water in water reaches outstanding
Floating purpose.The technology for not changing suspension fundamentally from suspended prop of this technology, only thickener overlay film
On aggregate, environmental issue is not solved, cost is reduced without really realizing, increases production and improves productivity.Another technology is to change
The apparent density of aggregate makes the haydite or resin beads of extremely-low density.Such product is able to achieve really half to suspend in water,
The rate of settling of proppant in water is reduced, but since apparent density to be greatly lowered, production cost is greatly increased, and
The performance of proppant, such as broken, sour molten, water conservancy diversion performance can be substantially reduced.And the production efficiency of resin beads is low, it is at high cost etc.
Defect also limits its popularization and use.And although above-mentioned proppant can be realized from suspension in water, but carry the frictional resistance of liquid
It is enhanced, so that proppant could be pumped into corresponding position by applying the higher pump pressure of man-hour requirement, improves
Construction cost.
Summary of the invention
It is good, good from suspension overlay film backing material from suspendability that the purpose of the present invention is to provide a kind of drag-reduction effects.
In order to achieve the above object, base case of the invention are as follows: it is a kind of from suspension overlay film backing material, including aggregate and
The coat being coated on aggregate, the coat include inner layer resin film and outermost resin film, the outermost resin film with it is interior
It is added with drag reducer in layer resin film, the outermost resin film includes amines additives, and the drag reducer quality is aggregate
0.7-1.8%, the drag reducer of outermost resin film account for the 40-60% of drag reducer total amount, the view from suspension overlay film backing material
Density is 1.05-2.60g/cm3。
The beneficial effect of this base case is:
Drag reducer is added in internal layer resin film and outermost resin film, makes to contain in inner layer resin film and outermost resin film
There is draft reduction material, in the drag reduction from suspension overlay film backing material and clear water mixed process in inner layer resin film and outermost resin film
Material can dissolve into load fluid rapidly, make also have good guide performance in clear water from suspension overlay film backing material, reach
Corresponding technical requirements, compared with the existing technology for this programme eliminate the auxiliary additives such as slippery water, reduce and be constructed into
This, simplifies construction technology, reduces equipment requirement.Since drag reducer addition is in internal layer resin film and outermost resin film,
Drag reducer of the middle addition in outer layer resin film is 40-60%, so will not to the influence from the performances such as suspendability and sphericity
It is too big, and in order to ensure the drag reducing efficiency from suspension overlay film backing material, control drag reducer quality is the 0.7-1.8% of aggregate, is subtracted
The quality of resist addition is reduced compared with only adding in outer layer resin film, enables to follow from suspension overlay film backing material
Carrying liquid, to reach the rate of dissolution from suspension overlay film backing material in corresponding destination this programme fast, can in 3-15s
It is dissolved in clear water, is quickly dissolved in clear water from suspension overlay film backing material in construction, huge discharge operation may be implemented, significantly
Improve work efficiency.
In this programme includes internal layer and outer layer two layers of resin film from suspension overlay film backing material, keeps aggregate complete
Full cladding, inner layer resin film can guarantee the integral strength from suspension overlay film backing material, guarantee from suspension overlay film backing material
Resistant to breakage rate.
In work progress, the reserved group in outermost resin film can react rapidly a large amount of small point of gas of generation after meeting water
Son, these gas molecules or is enclosed in resin film to expand against resin membrane body stage and thicken and increases overlay film backing material
The equivalent diameter of granule, or be attached to the extension of overlay film backing material surface stage or be gathered in overlay film backing material resin film
The gas blanket of one layer of package overlay film backing material granule is formed on the interface contacted with water body, this gas blanket is supported in overlay film
Formation stages are connected between material granule body and the result closed causes simple grain overlay film backing material to be formed in water body more loosely
Cotton wadding gather shape, be greatly lowered the relative density of overlay film backing material in water, in this way so as to support overlay film
Material suspends in water, and realization uses clear water as liquid is carried and (carries liquid certainly and be also not only limited to clear water, can also be added with increasing
Thick dose of carrying liquid).When overlay film backing material moves in water, the protrusion of the curved surface on overlay film backing material resin film can reduce
The overlay film backing material rate of settling in water；Part is settled down to the overlay film backing material of water bottom accumulation because of its surface resin film
More protrusion reduces the degree of packing of overlay film backing material settled layer, the more conventional particle packing of intergranular water body amount
Body is more, and then when water body can more easily push the separation of its congeries and mobile, realization the fluidity with very little
Overlay film backing material preferably suspends in water, and the overlay film backing material in this programme is made to meet what the basic pressure break of industry required
Meanwhile the thickeners such as addition guar gum are not needed in fracturing process, cost is greatly reduced, fracturing unit and work have been simplified
Skill reduces the pollution to environment, and huge discharge operation may be implemented using clear water as liquid is carried, and improves working efficiency.
Apparent density range is 1.05-2.60g/cm3Synthesis can be formed in pure clear water from suspension overlay film backing material
Bulk density is in 0.6~1.3g/cm3Solid-liquid mixing, when such solid-liquid mixing is applied certain mechanical stirring punching
When amount, it can more be evenly distributed in clear water from suspension overlay film backing material, can make when mixed liquor reaches certain flow rate
In mixed liquor from suspension overlay film backing material with from suspended state carry out long distance delivery to recovery well under reservoir fracture in,
And slot height distribution support of totally cleaving can be reached from suspension overlay film backing material compared to tradition, improve the rate of growth of petroleum etc..
Further, the drag reducer preparation step is as follows, as mass fraction the water of addition 85-93%, and the third of 5-10%
Acrylamide and acrylamide derivative, the acrylic acid and methacrylic acid of 0.5-2%, the 2- acrylamide -2- methyl-prop of 1-5%
The methylpropene sodium sulfonate of sulfonic acid and 0.5-3% stirs 150-220rpm, and is warming up to 40-70 DEG C, and above-mentioned gross mass is added
The initiator of 0.3-2%, reacts through 3-40min, is down to room temperature.
Further, the outermost resin film is urethane resin film, and the inner layer resin film is urethane resin film, epoxy
Resin film and phenolic resin film it is one or more.Urethane resin film can generate several nanometers under the action of amines additives
Grade protrusion reduces volume density and apparent density from suspension overlay film backing material on surface, while urethane resin film is when meeting water
It is capable of forming bubble, to can be improved to a certain extent from suspension overlay film backing material from suspendability, inner layer resin film
It can guarantee the intensity from suspension overlay film backing material with urethane resin film, epoxy resin film or phenolic resin film cladding.
Further, the amines additives are diethylenetriamine, triethylamine, ethamine, diethylamine, one in triethylene tetramine
Kind is a variety of.Cheap, the excellent catalytic effect of these types of amines additives is conducive to the formation of protrusion.
Further, the initiator is azo diisobutyl amidine hydrochloride, two isobutyl imidazoline hydrochloride of azo, azo two
The one or more of cyanopentanoic acid, azo dicyclohexyl formonitrile HCN.
Further, it is described from suspension overlay film backing material include following mass fraction material, 100 parts of aggregate, internal layer tree
0.25-5 parts of adipose membrane, 0.25-5 parts of outermost resin film, the amines additives quality is the 1/100-20/ of outermost resin film quality
100。
Further, the outermost resin film is synthesized by polyalcohols resin, catalyst and Isocyanates curing agent, polynary
The equivalent of alcohol resinoid hydroxyl is 60-300, and Isocyanates curing agent quality is polyalcohols resin quality in outermost resin film
40-80%, catalyst quality be outermost resin film in polyalcohols resin quality 1/1000-1/100.Applicant is long-term
Practice in find, polyalcohols resin, isocyanates control in above range, produce entirely different with current material performance
Performance, firstly, polyalcohols resin reacted with isocyanate groups generate have micro protrusion urethane resin film, due to
It further include amines additives, amines additives can be to isocyanate group in polyalcohols resin and isocyanate groups reaction process
Facilitation is played in the reaction of group, makes to generate a large amount of mutually isolated bubbles inside urethane resin film, bubble is closed in poly-
Inside urethane resin film, so that bubble forms a large amount of protrusion in polyurethane resin film surface, bump sizes between 100~
500nm, protrusion have random point of heterogencity in coating layer surface random distribution, in the surface resin film of single particle body
Cloth, converting has 1~40 or so protrusion for the surface of 100 square micron every under homogeneous distribution state, reduce apparent density and
Volume density improves it from suspendability.Simultaneously because the equivalent of polyalcohols resin hydroxyl is 60-300, isocyanate is extremely
It is less the 40% of polyalcohols resin, after isocyanates and whole polyalcohols resin reaction generation urethane resin films, also
Remain part isocyanate groups not reacted, so that there is also isocyanate groups in urethane resin film at this time, when
Remaining isocyanate groups are reacted with water and can be enclosed in the chain element of resin film when the overlay film backing material of this programme meets water
At microcosmic small space body in generate gas, this small quantity gas reaction can promotion under be gradually increased volume and form gas
Bubble, and resin film is pushed to increase in the radial dimension of overlay film backing material particle, reach the dilation for coating layer surface most preferably,
To further reduced the apparent density and volume density of overlay film backing material, while isocyanate is at most polyalcohols tree
The 80% of rouge makes the volume of the bubble generated be unlikely to too big and bubble is caused to be easy breakage etc., and makes the bubble generated
Quantity will not be excessive, makes all to be mutually isolated between a large amount of bubbles, leads to air bubble intensity without contacting with each other there are bubble
The problem of reduction.
Further, the catalyst is one or more of alkyls tin compound and/or alkyls lead compound
Mixture.
Further, alkyls tin compound is one of dibutyl tin dilaurate, tributyl tin or several mixed
Object is closed, alkyls lead compound is one of lead tetraethide, isooctyl acid lead or several mixtures.Above-mentioned several catalyst
Cost performance it is high, catalysis time is short, can accelerate solidification rate and the intensity performance of coat.
Further, Isocyanates curing agent is toluene di-isocyanate(TDI), methylenediphenyl diisocyanates, different Fo Er
One or more of ketone diisocyanate, methyl diphenylene diisocyanate.Select above-mentioned several isocyanates solidifications
Agent can accelerate the formation of coat, improve working efficiency.
Detailed description of the invention
Fig. 1 is in embodiment 1 from the electron-microscope scanning figure of suspension overlay film backing material.
Specific embodiment
Below by specific embodiment, the present invention is described in further detail:
Raw material is selected:
Aggregate selects the one or more of haydite, quartz sand, selects haydite as an example, haydite in present embodiment
Apparent density is 1.05~2.65g/cm3, circularity >=0.7, sphericity >=0.7, resistant to breakage rate≤3% (86mpa), acid solubility≤
5%, granularity is 20~140 mesh.
Outermost resin film is urethane resin film, and inner layer resin film is urethane resin film, epoxy resin film and phenolic aldehyde tree
Adipose membrane it is one or more.
Polyol resin is the polymer one or several kinds of ethylene glycol, propylene glycol, glycerine, polyalcohols resin hydroxyl
Equivalent be 60-300.
Isocyanates curing agent, toluene di-isocyanate(TDI), methylenediphenyl diisocyanates, two isocyanide of isophorone
One or more of acid esters, methyl diphenylene diisocyanate.
Catalyst is alkyls tin compound and alkyls lead compound, preferably dibutyl tin dilaurate, tributyl
One of tin, lead tetraethide, isooctyl acid lead or several mixtures.
Amines additives select one of diethylenetriamine, triethylamine, ethamine, triethylene tetramine, ethylenediamine or more
Kind.
It include the material of following mass fraction from suspension overlay film backing material, 100 parts of aggregate, inner layer resin film 0.25-5
Part, 0.25-5 parts of outermost resin film, the drag reducer quality is the 0.7-1.8% of aggregate, and the amines additives quality is more
The 1/100-20/100 of first alcohols resin quality, the drag reducer of outermost resin film account for the 40-60% of drag reducer total amount, isocyanates
Class curing agent quality is the 40-80% of polyalcohols resin quality in outermost resin film, and catalyst quality is polyalcohols resin
The 1/1000-1/100 of quality.
Drag reducer, as mass fraction be added 85-93% water, the acrylamide and acrylamide derivative of 5-10%,
The acrylic acid and methacrylic acid of 0.5-2%, the 2- acrylamide-2-methyl propane sulfonic of 1-5% and the metering system of 0.5-3%
Sodium sulfonate stirs 150-220rpm, and is warming up to 40-70 DEG C, the initiator of above-mentioned gross mass 0.3-2% is added, through 3-40min
Reaction, is down to room temperature and obtains required drag reducer.Wherein initiator includes azo diisobutyl amidine hydrochloride, two isobutyl imidazoles of azo
Quinoline hydrochloride, azo dicyano valeric acid, azo dicyclohexyl formonitrile HCN one or more.
Embodiment 1
Taking apparent density is 1.05g/cm3, granularity be 100 parts of haydite of 20/40,180-190 DEG C is heated to, by the pottery of heating
Grain pours into inside bowl-type mulling pot, and 2 parts of epoxy resin stirrings are then added；Temperature is down to 150-160 DEG C, and 0.2 part of modification is added
Aromatic amine curing agent (T31) simultaneously stirs；Temperature is down to 140-150 DEG C, adds 0.3 part of drag reducer mixing；Temperature is down to 80-
90 DEG C, 2 parts of propylene glycol and the stirring of 0.02 part of dibutyl tin dilaurate are added；Temperature is down to 70-80 DEG C, and 0.2 part of second is added
Diamines stirring；Temperature is down to 60-70 DEG C, and 0.8 part of toluene di-isocyanate(TDI) stirring is added；Temperature is down to 50-60 DEG C, adds
0.4 part of drag reducer mixing；Temperature is down to 40-50 DEG C and takes the dish out of the pot.Epoxy resin and modified aromatic amine curing agent generate inner layer resin
Film, inner layer resin film are epoxy resin film；Glycerine, dibutyl tin dilaurate, diethylenetriamine and toluene di-isocyanate(TDI)
Outermost resin film is generated, outermost resin film is urethane resin film, as shown in Figure 1, from suspension overlay film backing material appearance mask
There is nanoscale raised.
Embodiment 2
Taking apparent density is 1.65g/cm3, granularity be 100 parts of haydite of 30/50,220-230 DEG C is heated to, by the pottery of heating
Grain pours into inside bowl-type mulling pot, and 3 parts of phenolic resin stirrings are then added；Temperature is down to 190-200 DEG C, be added 0.6 part six times
Tetramine simultaneously stirs；Temperature is down to 180-190 DEG C, then 0.6 part of addition drag reducer mixing；Temperature is down to 120-130 DEG C, is added
4 parts of glycerine and the stirring of 0.02 part of isooctyl acid lead；Temperature is down to 100-110 DEG C, and 0.2 part of triethylamine stirring is added；Temperature drop
To 90-100 DEG C, 1 part of methylenediphenyl diisocyanates stirring is added；Temperature is down to 70-80 DEG C, adds 0.6 part of drag reduction
Agent mixing；Temperature is down to 60-70 DEG C and takes the dish out of the pot.
Embodiment 3
Taking apparent density is 2.05g/cm3, granularity be 100 parts of haydite of 40/70,80-90 DEG C is heated to, by the haydite of heating
It pours into inside bowl-type mulling pot, 2 parts of ethylene glycol and the stirring of 0.02 part of tributyl tin is then added；Temperature is down to 70-80 DEG C, adds
Enter 0.6 part of isophorone diisocyanate and stirs；Temperature is down to 60-70 DEG C, adds 0.7 part of drag reducer mixing；Temperature drop
To 50-60 DEG C, 4 parts of glycerine and the stirring of 0.02 part of isooctyl acid lead are added；Temperature is down to 40-50 DEG C, and 0.2 part of triethylamine is added
Stirring；Temperature is down to 35-45 DEG C, and 1 part of methylenediphenyl diisocyanates stirring is added；Temperature is down to 30-40 DEG C, adds
0.8 part of drag reducer mixing；Temperature is down to 30-35 DEG C and takes the dish out of the pot.
Embodiment 4
Taking apparent density is 2.65g/cm3, granularity be 100 parts of haydite of 70/140,150-160 DEG C is heated to, by heating
Haydite pours into inside bowl-type mulling pot, and 2 parts of ethylene glycol and the stirring of 0.02 part of tributyl tin are then added；Temperature is down to 130-
140 DEG C, 0.6 part of isophorone diisocyanate is added and stirs；Temperature is down to 120-130 DEG C, and it is mixed to add 0.8 portion of drag reducer
It closes；Temperature is down to 100-110 DEG C, and 4 parts of glycerine and the stirring of 0.02 part of isooctyl acid lead are added；Temperature is down to 90-100 DEG C, adds
Enter 0.2 part of triethylamine stirring；Temperature is down to 80-90 DEG C, and 1 part of methylenediphenyl diisocyanates stirring is added；Temperature is down to
70-80 DEG C, add 1 part of drag reducer mixing；Temperature is down to 50-60 DEG C and takes the dish out of the pot.
Comparative example 1
Taking apparent density is 1.05g/cm3, granularity be 100 parts of haydite of 20/40,180-190 DEG C is heated to, by the pottery of heating
Grain pours into inside bowl-type mulling pot, and 2 parts of epoxy resin stirrings are then added；Temperature is down to 150-160 DEG C, and 0.2 part of modification is added
Aromatic amine curing agent (T31) simultaneously stirs；Temperature is down to 140-150 DEG C, adds 0.3 part of drag reducer mixing；Temperature is down to 80-
90 DEG C, 2 parts of epoxy resin stirrings are added；Temperature is down to 70-80 DEG C, and 0.2 part of ethylenediamine stirring is added；Temperature is down to 60-70 DEG C,
0.2 part of modified aromatic amine curing agent (T31) stirring is added；Temperature is down to 50-60 DEG C, adds 0.4 part of drag reducer mixing；Temperature
Degree is down to 40-50 DEG C and takes the dish out of the pot that (obtaining from the inner layer resin film and outermost resin film of suspension overlay film backing material is asphalt mixtures modified by epoxy resin
Adipose membrane).
Comparative example 2
Taking apparent density is 1.65g/cm3, granularity be 100 parts of haydite of 30/50,220-230 DEG C is heated to, by the pottery of heating
Grain pours into inside bowl-type mulling pot, and 3 parts of phenolic resin stirrings are then added；Temperature is down to 190-200 DEG C, be added 0.6 part six times
Tetramine simultaneously stirs；Temperature is down to 180-190 DEG C, adds 0.6 part of drag reducer mixing；Temperature is down to 120-130 DEG C, is added
4 parts of phenolic resin stirrings；Temperature is down to 100-110 DEG C, and 0.2 part of triethylamine stirring is added；Temperature is down to 90-100 DEG C, is added
0.8 part of hexamethylenetetramine simultaneously stirs；Temperature is down to 70-80 DEG C, adds 0.6 part of drag reducer mixing；Temperature is down to 60-70 DEG C
Take the dish out of the pot (obtaining from the inner layer resin film and outermost resin film of suspension overlay film backing material is phenolic resin film).
Comparative example 3
The difference of this comparative example and embodiment 1, which is only that, is added without ethylenediamine (amines additives).
Comparative example 4
The difference of this comparative example and embodiment 1, which is only that, is added without drag reducer.
Comparative example 5
The difference of this comparative example and embodiment 1 is only that the mass fraction of the drag reducer added twice is 0.26, drag reducer
Total number be 0.5.
Comparative example 6
The difference of this comparative example and embodiment 1 is only that the mass fraction of the drag reducer added twice is 1, the matter of drag reducer
Measuring number is 2.
Comparative example 7
It buys from the ceramsite propping agent of 20/40 specification of Luoyang Zhong Tai Industrial Co., Ltd. and is tested for the property.
Comparative example 8
The difference of this comparative example and embodiment 1 is only that the mass fraction of toluene di-isocyanate(TDI) is 0.7 part.
Comparative example 9
The difference of this comparative example and embodiment 4 is only that the mass fraction of methylenediphenyl diisocyanates is 3.4 parts.
Raw material parts is mass fraction in above embodiments and comparative example.
Above-mentioned main performance index and measuring method from suspension overlay film backing material:
Examination criteria: molten about apparent density, bulk density, circle/sphericity, percentage of damage and acid in above-described embodiment and comparative example
The test of Xie Du according to " SY/T 5108-2014 hydraulic fracturing and gravel packing operations proppant performance test methods " into
Row test.
Simultaneously by above-described embodiment and when doing mattress height, suspension ratio from suspension overlay film backing material and suspend of comparative example
Between test.
1. suspension ratio
Suspend than be evaluate from suspension overlay film backing material in water upper layer suspension amount account for it is total from suspension overlay film fid
The percentage of material.
We use from the mass ratio of suspension overlay film backing material and water and evaluate for the case where 1:4 in test.Experiment
Method is to measure 200ml water in the wide-mouth bottle of 300ml with graduated cylinder and pour into wide-mouth bottle, precise 50g is from suspension overlay film branch
Timbering material pours into the wide-mouth bottle for having filled water, closes the lid, up and down firmly shake 30 times, it is static after ten minutes, according to same
Method up and down firmly shake 30 times, it is static after with filter paper filter out upper layer suspension from suspension overlay film backing material, claim after drying
Measuring the quality from suspension overlay film backing material filtered out is m (g), and b=m/50*100% is compared in suspension.
2. mattress height
Mattress height is 20g high from lower layer of the suspension overlay film backing material in the 100ml graduated cylinder equipped with 100ml clear water
Degree.
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 pours into dress from suspension overlay film backing material
In the graduated cylinder of water, graduated cylinder mouth is tightly covered with the right hand, left hand is picked up graduated cylinder and is gently reversed for 10 times up and down, it is static after ten minutes, press
It is reversed 10 times up and down according to same method, the bed for having vernier caliper to measure lower layer from suspension overlay film backing material after static is high
Degree.
3. suspension time
Suspension time refers to the maximum duration that can freely suspend in water.
We use from the mass ratio of suspension overlay film backing material and water and evaluate for the case where 1:4 in test.Experiment
Method is to measure 200ml water in the wide-mouth bottle of 300ml with graduated cylinder and pour into wide-mouth bottle, precise 50g is from suspension overlay film branch
Timbering material pours into the wide-mouth bottle for having filled water, closes the lid, up and down firmly shake 30 times, it is static after ten minutes, according to same
Method is firmly shaken 30 times up and down, then by the static placement of wide-mouth bottle, timing measuring from suspension overlay film backing material in water from
By the maximum duration to suspend.
Embodiment 1- embodiment 4, the Example Test Data of comparative example 1- comparative example 9 are as follows:
It is to evaluate that the synthesis of suspendability refers in clear water from suspension overlay film backing material " from outstanding composite index " in upper table
Mark by mattress height and suspends than codetermining, and engineering significance is the true reactor from suspension overlay film backing material in clear water
Product density, is worth the smaller relative density being equivalent in water with regard to smaller, then just from the suspension of suspension overlay film backing material
Better, suspension time is longer.
(b is suspension ratio, h is mattress height)
Embodiment 1 and comparative example 1 are compared, embodiment 2 and comparative example 2 compare, and wherein embodiment 1 and embodiment 2 is outer
Layer resin film is urethane resin film, and the outermost resin film of comparative example 1 and comparative example 2 is not urethane resin film, root
According to upper table, can release, the suspension time of embodiment 1 and embodiment 2 is respectively higher than the suspension time of comparative example 1 and comparative example 2,
The certainly outstanding composite index of embodiment 1 and embodiment 2 is respectively smaller than comparative example 1 and comparative example 2, that is, embodiment 1 and 1 phase of comparative example
More preferable than from suspendability, embodiment 2 is more preferable from suspendability compared with comparative example 2, it can be seen that, urethane resin film can
It improves from suspension overlay film backing material from suspendability, specifically in preparation process, polyurethane resin film surface can be generated
Several protrusions, the isocyanates root (Isocyanates curing agent offer) when meeting water in urethane resin film can also occur anti-with water
Bubble should be generated, and then reduces the volume density and apparent density from suspension overlay film backing material.
According to upper table, embodiment 1 suspension time and the ratio that suspends compared with comparative example 7 are significantly increased, i.e., this programme is compared
It is greatly improved for conventional proppants from suspendability.
Embodiment 1 is only in outermost resin film compared with comparative example 3 containing ethylenediamine (amines additives), according to upper table,
Conclude that made from embodiment 1 that suspension time and suspension ratio are significant from suspension overlay film backing material compared with comparative example 3
It improves, i.e. significantly improving from suspendability from suspension overlay film backing material, illustrates that embodiment 1 is obtained and supported from suspension overlay film
Material surface has more protrusions, can release amines additives for the formation from suspension overlay film backing material surface bulge
With preferable facilitation, make greatly improving from suspendability from suspension overlay film backing material by amines additives.
Embodiment 1 and comparative example 4 are compared, it was therefore concluded that: after being added to drag reducer from suspension overlay film fid
The drag reducing efficiency of material is substantially better than the drag reducing efficiency from suspension overlay film backing material for being not added with drag reducer, can be with by addition drag reducer
The frictional resistance from suspension overlay film backing material is substantially reduced, its guide performance is promoted.
Embodiment 1 and comparative example 5 are compared, it was therefore concluded that: when the total mass fraction of drag reducer is less than 0.7 from outstanding
The drag reducing efficiency of floating overlay film backing material substantially reduces, and corresponding technique requirement is not achieved.
Embodiment 1 and comparative example 6 are compared, it was therefore concluded that: when the mass fraction of drag reducer is greater than 1.8 from suspension
The resistant to breakage of overlay film backing material, which is filtered, and acid is molten is all increased, and reduces the performance from suspension overlay film backing material product, simultaneously
Suspension can also be deteriorated, and reduce from suspension overlay film backing material from suspendability.
Comparative example 8 is distinguished compared with Example 1 is that the mass fraction of toluene di-isocyanate(TDI) is 0.7 part, in comparative example 8
Toluene di-isocyanate(TDI) (isocyanates) and the quality accounting of glycerine polymer (polyalcohols resin) areThe quality accounting of isocyanates and polyalcohols resin in embodiment 1 is
The quality of isocyanates is less than the 40% of polyalcohols resin quality i.e. in comparative example 8, according to upper table, it can be deduced that comparative example 8
The suspension time of backing material and suspension are decreased obviously than, are significantly improved from outstanding composite index, i.e., comparative example 8 compares embodiment
It is substantially reduced for 1 from suspendability, when illustrating that the quality of isocyanates is less than the 40% of polyalcohols resin quality, fid
Material is substantially reduced from suspendability.
Comparative example 9 is distinguished compared with Example 4 is that the mass fraction of toluene di-isocyanate(TDI) is 3.4 parts, in comparative example 9
Methylenediphenyl diisocyanates (isocyanates) and the quality accounting of glycerine polymer (polyalcohols resin) areThe quality accounting of isocyanates and polyalcohols resin in embodiment 4 is
The quality of isocyanates is greater than the 80% of polyalcohols resin quality i.e. in comparative example 9, according to upper table, it can be deduced that comparative example 9
The suspension time of backing material and suspension are decreased obviously than, are significantly improved from outstanding composite index, i.e., comparative example 9 compares embodiment
It is substantially reduced for 4 from suspendability, when illustrating that the quality of isocyanates is greater than the 80% of polyalcohols resin quality, fid
Material is substantially reduced from suspendability.
To sum up, the quality of isocyanates is controlled in the range of polyalcohols resin quality 40%-80% in this programme
When, overlay film backing material all has preferably from suspendability, meets overlay film backing material in clear water from the requirement to suspend.And
When the quality of isocyanates is lower than polyalcohols resin quality less than 40% or greater than 80%, overlay film backing material suspends certainly
Performance is decreased obviously, it is difficult to meet the requirement to suspend in clear water.
What has been described above is only an embodiment of the present invention, and the common sense such as well known specific structure and characteristic are not made herein in scheme
Excessive description.It, without departing from the structure of the invention, can be with it should be pointed out that for those skilled in the art
Several modifications and improvements are made, these also should be considered as protection scope of the present invention, these all will not influence what the present invention was implemented
Effect and patent practicability.The scope of protection required by this application should be based on the content of the claims, in specification
The records such as specific embodiment can be used for explaining the content of claim.
Claims (10)
1. it is a kind of from suspension overlay film backing material, including aggregate and the coat being coated on aggregate, it is characterised in that: the painting
Coating includes inner layer resin film and outermost resin film, is added with drag reducer, institute in the outermost resin film and inner layer resin film
Stating outermost resin film includes amines additives, and the drag reducer quality is the 0.7-1.8% of aggregate, the drag reducer of outermost resin film
The 40-60% of drag reducer total amount is accounted for, the apparent density from suspension overlay film backing material is 1.05-2.60g/cm3。
2. according to claim 1 a kind of from suspension overlay film backing material, it is characterised in that: the drag reducer preparation step
It is as follows, as mass fraction be added 85-93% water, the acrylamide and acrylamide derivative of 5-10%, the third of 0.5-2%
Olefin(e) acid and methacrylic acid, the 2- acrylamide-2-methyl propane sulfonic of 1-5% and the methylpropene sodium sulfonate of 0.5-3%, stirring
150-220rpm, and it is warming up to 40-70 DEG C, the initiator of above-mentioned gross mass 0.3-2% is added, is reacted through 3-40min, is down to often
Temperature.
3. according to claim 1 a kind of from suspension overlay film backing material, it is characterised in that: the outermost resin film is poly-
Urethane resin film, the inner layer resin film are the one or more of urethane resin film, epoxy resin film and phenolic resin film.
4. according to claim 1 a kind of from suspension overlay film backing material, it is characterised in that: the amines additives are two
One or more of ethylene triamine, triethylamine, ethamine, diethylamine, triethylene tetramine.
5. according to claim 2 a kind of from suspension overlay film backing material, it is characterised in that: the initiator is azo two
Isobutyl amidine hydrochloride, two isobutyl imidazoline hydrochloride of azo, azo dicyano valeric acid, azo dicyclohexyl formonitrile HCN one kind
Or it is two or more.
6. according to claim 1 a kind of from suspension overlay film backing material, it is characterised in that: described to be supported from suspension overlay film
Material includes the material of following mass fraction, and 100 parts of aggregate, 0.25-5 parts of inner layer resin film, 0.25-5 parts of outermost resin film, institute
State the 1/100-20/100 that amines additives quality is outermost resin film quality.
7. according to claim 1 a kind of from suspension overlay film backing material, it is characterised in that: the outermost resin film is by more
First alcohol resinoid, catalyst and Isocyanates curing agent synthesis, the equivalent of polyalcohols resin hydroxyl are 60-300, isocyanic acid
Esters curing agent quality is the 40-80% of polyalcohols resin quality in outermost resin film, and catalyst quality is outermost resin film
The 1/1000-1/100 of middle polyalcohols resin quality.
8. according to claim 7 a kind of from suspension overlay film backing material, it is characterised in that: the catalyst is alkyls
The mixture of one or more of tin compound and/or alkyls lead compound.
9. according to claim 8 a kind of from suspension overlay film backing material, it is characterised in that: alkyls tin compound is two
One of dibutyl tin laurate, tributyl tin or several mixtures, alkyls lead compound are lead tetraethide, different pungent
One of lead plumbate or several mixtures.
10. according to claim 8 a kind of from suspension overlay film backing material, it is characterised in that: Isocyanates curing agent
For toluene di-isocyanate(TDI), methylenediphenyl diisocyanates, isophorone diisocyanate, diphenylmethane diisocyanate
One or more of ester.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201811159527.3A CN109233789A (en) | 2018-09-30 | 2018-09-30 | One kind is from suspension overlay film backing material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811159527.3A CN109233789A (en) | 2018-09-30 | 2018-09-30 | One kind is from suspension overlay film backing material |
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Family
ID=65054842
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Cited By (1)
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| WO2021087658A1 (en) * | 2019-11-04 | 2021-05-14 | 中国石油大学(北京) | Self-suspension hydraulic fracturing coated proppant having targeting function, and preparation and application |
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