CN109135720A - A kind of low-density propping agent - Google Patents
A kind of low-density propping agent Download PDFInfo
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- CN109135720A CN109135720A CN201811159637.XA CN201811159637A CN109135720A CN 109135720 A CN109135720 A CN 109135720A CN 201811159637 A CN201811159637 A CN 201811159637A CN 109135720 A CN109135720 A CN 109135720A
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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
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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
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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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
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
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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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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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Abstract
The invention belongs to the fluid minerals production technique such as petroleum, natural gas and shale gas fields, specifically disclose a kind of low-density propping agent, including aggregate and the coat being coated on aggregate, the aggregate is composite Nano bead, the coat is made of resin, curing agent, catalyst and amines additives, and the apparent density range of the low-density propping agent is 1.08-1.25g/cm3.The low-density propping agent of this programme can suspend in water, while meeting industry basic demand, the substance of the thickeninies such as addition guar gum is not needed in fracturing process, greatly reduces cost, has simplified fracturing unit and technique, reduces the pollution to environment.
Description
Technical field
The invention belongs to the fluid minerals production technique such as petroleum, natural gas and shale gas field, more particularly to one kind are low close
Spend proppant.
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 and gather
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 low-density propping agent 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.
Summary of the invention
The purpose of the present invention is to provide a kind of low-density propping agents at low cost, environmental pollution is small.
In order to achieve the above object, base case of the invention are as follows: a kind of low-density propping agent, including aggregate and be coated on
Coat on aggregate, the aggregate are composite Nano bead, and the coat is added by resin, curing agent, catalyst and amine
Agent is added to be made, the apparent density range of the low-density propping agent is 1.08-1.25g/cm3。
The working principle of this base case is: in actual use, low-density propping agent can suspend or half suspends
In clear water, in pressing crack construction, mixture is pumped in the crack of lithosphere, proppant can be entered in crack with water and be risen
To supporting role.
The beneficial effect of this base case is: resin, catalyst and curing agent in the proppant coat of this programme
Reaction generates resin film and is coated on aggregate surface, and the surface resin film of generation has nanoscale protrusion, these protrusions extend in branch
The surface of agent particle is supportted, protrusion will increase the buoyancy of proppant, reduce the volume density and apparent density of proppant entirety, improve
Proppant from suspendability.
In work progress, the reserved group in the resin film of proppant surface can react rapidly a large amount of gas of generation after meeting water
Body small molecule, these gas molecules or is enclosed in resin film to expand against resin membrane body stage and thicken and increases proppant
The equivalent diameter of granule, or be attached to the extension of proppant surface stage or be gathered in what proppant resin film was contacted with water body
The gas blanket of one layer of package proppant particles body is formed on interface, this gas blanket formation stages between proppant particles body connect
Lead to and the result closed causes simple grain proppant to form more loose cotton wadding in water body to gather shape, be greatly lowered in this way
The relative density of proppant in water, so as to make proppant suspend in water, realization uses clear water (certain as liquid is carried
It carries liquid and is also not only limited to clear water, can also be the carrying liquid added with thickener).When proppant moves in water, proppant resin
The protrusion of curved surface on film can reduce the proppant rate of settling in water；Part is settled down to the proppant of water bottom accumulation because of it
The more protrusion of surface resin film reduces the degree of packing of proppant particles stack layer, the more conventional particle of intergranular water body amount
Accumulation body is more, and then working as water body can more easily push its congeries to separate and move the fluidity with very little,
Realize that proppant preferably suspends in water, while making the proppant in this programme meet the basic pressure break of industry to require,
The thickeners such as addition guar gum are not needed in fracturing process, greatly reduce cost, have simplified fracturing unit and technique, reduction pair
The pollution of environment, and huge discharge operation may be implemented using clear water as liquid is carried, improve working efficiency.
Apparent density range is 1.08-1.25g/cm3Proppant can form practical bulk density in pure clear water and exist
0.6-1.3g/cm3Solid-liquid mixing, when such solid-liquid mixing is applied certain mechanical stirring momentum, proppant
It can make the support in mixed liquor when mixed liquor reaches certain flow rate in clear water in the state for suspending or partly suspending
Agent is and can reach complete compared to conventional proppants from the reservoir fracture that suspended state carries out under long distance delivery to recovery well
Crack seam height distribution support, improves the rate of growth of petroleum etc..
Further, the resin is polyalcohols resin, and the curing agent is isocyanates, polyalcohols resin hydroxyl
Equivalent is 60-300, and isocyanate is the 40-80% of polyalcohols resin.Applicant has found in long-term practice, more
First alcohol resinoid, isocyanates control produce the performance entirely different with current material performance, firstly, more in above range
First alcohol resinoid reacts the urethane resin film for generating and having micro protrusion with isocyanate groups, due to further including amine addition
Agent, polyalcohols resin can play rush to reacting for isocyanate groups with amines additives in isocyanate groups reaction process
Into effect, making to generate a large amount of mutually isolated bubbles inside urethane resin film, bubble is closed in inside urethane resin film,
To which bubble forms a large amount of protrusion in polyurethane resin film surface, bump sizes are between 100~500nm, and protrusion is in coat
Surface random distribution has the random distribution of heterogencity in the surface resin film of single particle body, converts as homogeneous distribution shape
The surface of every 100 square micron has 1~40 or so protrusion under state, and apparent density and the body for reducing low-density propping agent are close
Degree, improves it from suspendability.Simultaneously because the equivalent of polyalcohols resin hydroxyl is 60-300, isocyanate is at least
The 40% of polyalcohols resin also remains after isocyanates and whole polyalcohols resin reaction generation urethane resin films
There are part isocyanate groups not reacted, so that there is also isocyanate groups in urethane resin film at this time, works as we
Remaining isocyanate groups are reacted with water and can be surrounded in the chain element of resin film when the low-density propping agent of case meets water
Gas is generated in microcosmic small space body, this small quantity gas is gradually increased volume under the promotion of reaction energy and forms bubble, and
It pushes resin film to increase in the radial dimension of proppant particles, reaches the dilation for coating layer surface most preferably, thus further
The apparent density and volume density of proppant are reduced, while isocyanate is at most the 80% of polyalcohols resin, makes to generate
The volume of bubble be unlikely to too big and bubble caused to be easy breakage etc., and make the quantity of the bubble generated will not be excessive, make
It being all mutually isolated between a large amount of bubbles, causing air bubble intensity to reduce without there are problems that bubble contacts with each other.
Further, the low-density propping agent includes the raw material of following mass fraction, 100 parts of composite Nano bead, resin
0.1-1 parts；Catalyst quality is the 1/1000-1/100 of resin quality, and the amines additives quality is the 1/ of resin quality
100-20/100.Keep the suspendability of manufactured low-density propping agent preferable using the raw material of aforementioned proportion.
Further, the composite Nano bead apparent density is 1.05~1.35g/cm3, circularity >=0.7, sphericity >=0.7 resists
Percentage of damage≤1%, acid solubility≤0.5%, granularity are 20~140 mesh.This kind of composite Nano bead is selected to make obtained low close
Spending proppant has preferable guide performance, reduces the friction between proppant, it may have preferable crush resistance energy.
Further, the polyalcohols resin is the polymer one or several kinds of ethylene glycol, propylene glycol, glycerine.
Further, the isocyanates is toluene di-isocyanate(TDI), methylenediphenyl diisocyanates, isophorone two
One or more of isocyanates, methyl diphenylene diisocyanate.Select above-mentioned several curing agent that can accelerate to coat
The formation of layer improves working efficiency.
Further, the amines additives are diethylenetriamine, triethylamine, ethamine, triethylene tetramine, one in ethylenediamine
Kind is a variety of.These types of amines additives facilitation effect is good, is conducive to the formation of bubble.
Further, the catalyst is one or more of alkyls tin compound and/or alkyls lead compound
Mixture.
Further, alkyls tin compound is one or more of dibutyl tin dilaurate, tributyl tin, alkyl
Class lead compound is one or more of lead tetraethide, isooctyl acid lead.It can accelerate consolidating for coat using above-mentioned catalyst
Change rate and intensity performance.
Detailed description of the invention
Fig. 1 is the microscopy figure of low-density propping agent made from embodiment 1；
Fig. 2 is the electron-microscope scanning figure of low-density propping agent in embodiment 1.
Specific embodiment
Below by specific embodiment, the present invention is described in further detail:
Raw material is selected:
Composite Nano bead, apparent density are 1.05~1.35g/cm3, circularity >=0.7, sphericity >=0.7, resistant to breakage rate≤
1% (86mpa), acid solubility≤0.5%, granularity are 20~140 mesh.Composite Nano bead selects applicant's application in embodiment
Another patent in (application number: nano combined aggregate 2018104695900).
Polyalcohols resin, ethylene glycol, propylene glycol, the polymer of glycerine are one or several kinds of, polyalcohols resin hydroxyl
The equivalent of base is 60-300.
Curing agent is isocyanates, preferably toluene di-isocyanate(TDI), methylenediphenyl diisocyanates, different Fo Er
One or more of ketone diisocyanate, methyl diphenylene diisocyanate.
One of catalyst, including dibutyl tin dilaurate, tributyl tin, lead tetraethide, isooctyl acid lead are several
The mixture of kind.
Amines additives select one of diethylenetriamine, triethylamine, ethamine, triethylene tetramine, ethylenediamine or more
Kind.
Low-density propping agent includes the raw material of following mass fraction, 100 parts of composite Nano bead, polyalcohols resin 0.1-
1 part, the 40-80% that isocyanate is polyalcohols resin；Catalyst quality is the 1/1000-1/100 of resin quality, amine
Class additive quality is the 1/100-20/100 of resin quality.
Embodiment 1
Claim 20~40 100 parts of mesh composite Nano beads, is heated to 60-85 DEG C, the composite Nano bead of heating is poured into bowl
Inside type mulling pot, 0.2 part of glycerine polymer and 0.001 part of dibutyl tin dilaurate stirring is then added, temperature is down to
55-75 DEG C, 0.3 part of diethylenetriamine stirring is added, temperature is down to 50-65 DEG C, 0.08 part of toluene di-isocyanate(TDI) stirring is added,
Temperature is down to 40-50 DEG C and takes the dish out of the pot.Glycerine polymer (resin), dibutyl tin dilaurate (catalyst), diethylenetriamine (amine
Class additive) and toluene di-isocyanate(TDI) (curing agent) reaction generate and urethane resin film and be coated on composite Nano bead table
Face, as shown in Figure 1 and Figure 2, low-density propping agent surface obtained have nanoscale protrusion.
Embodiment 2
Claim 30~50 100 parts of mesh composite Nano beads, is heated to 60-85 DEG C, the composite Nano bead of heating is poured into bowl
Inside type mulling pot, 0.4 part of glycol polymers and 0.002 part of isooctyl acid lead stirring are then added, temperature is down to 55-75 DEG C,
0.3 part of ethylenediamine stirring is added, temperature is down to 50-65 DEG C, and 0.2 part of methylenediphenyl diisocyanates stirring, temperature is added
40-50 DEG C is down to take the dish out of the pot.
Embodiment 3
Claim 40~70 100 parts of mesh composite Nano beads, is heated to 60-85 DEG C, the composite Nano bead of heating is poured into bowl
Inside type mulling pot, 0.7 part of ethylene glycol polymer and 0.003 part of tributyl tin stirring is then added, temperature is down to 55-75 DEG C,
0.3 part of triethylamine stirring is added, temperature is down to 50-65 DEG C, and 0.5 part of isophorone diisocyanate stirring is added, and temperature is down to
40-50 DEG C takes the dish out of the pot.
Embodiment 4
Claim 70~140 100 parts of mesh composite Nano beads, is heated to 60-85 DEG C, the composite Nano bead of heating is poured into bowl
Inside type mulling pot, polymeric blends and 0.01 part of isooctyl acid lead and two laurels of 1 part of ethylene glycol and glycerine are then added
The mixture of sour dibutyl tin stirs, and temperature is down to 55-75 DEG C, and 0.3 part of ethylenediamine stirring is added, and temperature is down to 50-65 DEG C, is added
Enter 0.8 part of methyl diphenylene diisocyanate stirring, temperature is down to 40-50 DEG C and takes the dish out of the pot.
Comparative example 1
This comparative example and the difference of embodiment 1 are only that and do not add diethylenetriamine (amines additives).
Comparative example 2
This comparative example and the difference of embodiment 1 are only that with 1 part of epoxy resin instead of 1 part of glycerine polymer and 0.01 part
Dibutyl tin dilaurate replaces 0.04 part of toluene two different with 0.1 part of modified aromatic amine curing agent (epoxy curing agent)
Cyanate stirring (the proppant surface resin film obtained is epoxy resin film).
Comparative example 3
It directly selects composite Nano bead as proppant, (surface does not contain resin film) is tested for the property to it.
Comparative example 4
This comparative example is the difference from embodiment 1 is that the mass fraction of toluene di-isocyanate(TDI) is 0.07 part.
Comparative example 5
The difference of the present embodiment and embodiment 4 is only that the mass fraction of methyl diphenylene diisocyanate is 0.85 part.
Raw material parts is mass fraction in above embodiments and comparative example.
The main performance index and measuring method of above-mentioned proppant:
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.
The proppant of above-described embodiment and comparative example is cooked to the test of mattress height, suspend ratio and suspension time simultaneously.
1. suspension ratio
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%.
2. mattress height
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,
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, after the same method on
It is lower to reverse 10 times, there is vernier caliper to measure the bed height of lower layer support agent after static.
3. suspension time
Suspension time refers to the maximum duration that can freely suspend 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, close the lid, up and down firmly shake 30 times, it is static after ten minutes, after the same method up and down firmly shake 30 times, then
By the static placement of wide-mouth bottle, the maximum duration that timing measuring proppant freely suspends in water.
Embodiment 1- embodiment 4, the Example Test Data of comparative example 1- comparative example 5 are as follows:
" certainly outstanding composite index " is the overall target for evaluating proppant suspendability in clear water in upper table, by mattress height
Ratio codetermines with suspending, and engineering significance is practical bulk density of the proppant in clear water, and value is smaller to be equivalent in water
In relative density with regard to smaller, then the suspension of proppant is better, suspension time is longer.
Embodiment 1 is only in resin film compared with comparative example 1 containing diethylenetriamine (amines additives), according to upper table,
Conclude that bulk density and apparent density are remarkably decreased proppant made from comparative example 1 compared with Example 1, suspension time
Ratio is significantly increased with suspending, i.e. proppant is significantly improved from suspendability, illustrates the tool of proppant surface made from embodiment 1
There are more protrusions, can release amines additives has preferable catalytic action for the formation of proppant surface protrusion, leads to
Crossing amines additives makes greatly improving from suspendability for proppant.
It is epoxy resin film that the embodiment 1 of comparative example 2, which is comparably proppant surface resin film, does not have polyurethane resin
Film.According to upper table, it was therefore concluded that: comparative example 2 compare the bulk density and apparent density of proppant for embodiment 1 it is significant on
It rises, suspension time and suspending is significantly reduced than, i.e. proppant is substantially reduced from suspendability, illustrates urethane resin film phase
Compared with can be improved for epoxy resin film proppant from suspendability.
According to upper table, embodiment 1 bulk density and apparent density compared with comparative example 3 are remarkably decreased, suspension time and outstanding
Floating ratio is significantly increased, i.e., this programme greatly improves for the composite Nano bead of not overlay film from suspendability.
Comparative example 4 is distinguished compared with Example 1 and is that the mass fraction of toluene di-isocyanate(TDI) is 0.07 part, at this time first
Phenylene diisocyanate (isocyanates) and the quality accounting of glycerine polymer (polyalcohols resin) areThe accounting of isocyanates and polyalcohols resin is in embodiment 1Comparison
The quality of 4 isocyanates of example is less than the 40% of polyalcohols resin quality, according to upper table, it can be deduced that 4 proppant of comparative example
Suspension time is decreased obviously with suspension than, is significantly improved from outstanding composite index, i.e., comparative example 4 is compared and hanged certainly for embodiment 1
Buoyancy can substantially reduce, and when illustrating that the quality of isocyanates is less than the 40% of polyalcohols resin quality, proppant suspends certainly
Performance is substantially reduced.
Comparative example 5 is distinguished compared with Example 4 and is only that the mass fraction of methyl diphenylene diisocyanate is 0.85
Part, polymeric blends (polyalcohols of methyl diphenylene diisocyanate (isocyanates) and ethylene glycol and glycerine at this time
Resin) quality accounting beThe accounting of isocyanates and polyalcohols resin is in embodiment 4The quality of isocyanates is greater than the 80% of polyalcohols resin quality in comparative example 5, can according to upper table
It is decreased obviously, is significantly improved from outstanding composite index, i.e. comparative example than with obtaining the suspension time of 5 proppant of comparative example and suspending
5 for embodiment 4 from suspendability compared to substantially reducing, and illustrates that the quality of isocyanates is greater than polyalcohols resin quality
When 80%, proppant 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, proppant all has preferably from suspendability, meets proppant in clear water from the requirement to suspend.And when isocyanates
Lower than polyalcohols resin quality less than 40% or when being greater than 80%, proppant is decreased obviously quality from suspendability, 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 (9)
1. a kind of low-density propping agent, including aggregate and the coat being coated on aggregate, it is characterised in that: the aggregate is multiple
Nanometer bead is closed, the coat is made of resin, curing agent, catalyst and amines additives, the low-density propping agent
Apparent density range is 1.08-1.25g/cm3。
2. a kind of low-density propping agent according to claim 1, it is characterised in that: the resin is polyalcohols resin,
The curing agent is isocyanates, and the equivalent of polyalcohols resin hydroxyl is 60-300, and isocyanate is polyalcohols tree
The 40-80% of rouge.
3. a kind of low-density propping agent according to claim 1, it is characterised in that: the low-density propping agent includes following
The raw material of mass fraction, 100 parts of composite Nano bead, 0.1-1 parts of resin；Catalyst quality is the 1/1000-1/ of resin quality
100, the amines additives quality is the 1/100-20/100 of resin quality.
4. a kind of low-density propping agent according to claim 1, it is characterised in that: the composite Nano bead apparent density is
1.05~1.35g/cm3, circularity >=0.7, sphericity >=0.7, resistant to breakage rate≤1%, acid solubility≤0.5%, granularity be 20~
140 mesh.
5. a kind of low-density propping agent according to claim 2, it is characterised in that: the polyalcohols resin is second two
Alcohol, propylene glycol, the polymer of glycerine are one or several kinds of.
6. a kind of low-density propping agent according to claim 2, it is characterised in that: the isocyanates is toluene diisocyanate
One of acid esters, methylenediphenyl diisocyanates, isophorone diisocyanate, methyl diphenylene diisocyanate or
Person is a variety of.
7. a kind of low-density propping agent according to claim 1, it is characterised in that: the amines additives are divinyl three
One or more of amine, triethylamine, ethamine, triethylene tetramine, ethylenediamine.
8. a kind of low-density propping agent according to claim 1, it is characterised in that: the catalyst is alkyls tin chemical combination
The mixture of one or more of object and/or alkyls lead compound.
9. a kind of low-density propping agent according to claim 8, it is characterised in that: alkyls tin compound is tin dilaurate
One or more of dibutyl tin, tributyl tin, alkyls lead compound be one of lead tetraethide, isooctyl acid lead or
Person is a variety of.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811159637.XA CN109135720A (en) | 2018-09-30 | 2018-09-30 | A kind of low-density propping agent |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811159637.XA CN109135720A (en) | 2018-09-30 | 2018-09-30 | A kind of low-density propping agent |
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ID=64814212
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Cited By (1)
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| CN113025303A (en) * | 2021-03-18 | 2021-06-25 | 中国石油大学(华东) | Supramolecular elastomer-based self-polymerization fracturing sand modifier and preparation method thereof |
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