CN108949140A - One kind is from suspension type support agent - Google Patents
One kind is from suspension type support agent Download PDFInfo
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- CN108949140A CN108949140A CN201811159599.8A CN201811159599A CN108949140A CN 108949140 A CN108949140 A CN 108949140A CN 201811159599 A CN201811159599 A CN 201811159599A CN 108949140 A CN108949140 A CN 108949140A
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- type support
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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
- 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
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
-
- 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
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
-
- 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
- C08G18/54—Polycondensates of aldehydes
- C08G18/542—Polycondensates of aldehydes with phenols
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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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The present patent application belongs to the fluid minerals production technique such as petroleum, natural gas and shale gas field, it specifically discloses a kind of from suspension type support agent, including aggregate and coat, the coat includes resin, curing agent and additive, and the aggregate is 1.1~2.65g/cm of apparent density3Haydite and quartz sand, the additive be aminated compounds.Present invention is mainly used for exploitation petroleum, shale gas, solve the problems, such as that proppant causes cost to increase and cause environmental pollution using needing to add gelling agent in clear water.
Description
Technical field
The invention belongs to the fluid minerals production technique such as petroleum, natural gas and shale gas fields, specifically disclose one kind certainly
Suspension type support agent.
Background technique
Modern age, the conventional production technique innovation and development with unconventional oil and gas formd the hydraulic fracturing normal technology of system
Specification, basic technical features are exactly to use fracturing system, will contain various functional materials by high pressure pump truck and help
The water base mixing liquid of agent is sent into underground and produces that all size is different, crack widely distributed, that go deep into reservoir, and keeps obtaining
Reservoir fracture be in the interconnected a kind of volume increase for reaching reservoir reconstruction of non-occluded state bring reservoir and production tubing
Technical system.It is exactly to keep non-closed in the reservoir fracture of acquisition as a kind of technical method vital in the technical system
It needs to insert to have in crack when state and centainly Z can be continuously maintained the proppant that voidage will not be crushed by reservoir closed high
Material, this material are referred to as " proppant ".Due to the technology utilize be economy preferably and have incompressible characteristic
How the water that nature is easily obtained is more convenient to be easy in such liquid, is more efficient, economically will " branch as carrier
It is all that oil fracturing engineers are dedicated to the major class technical problem solved all the time that support agent ", which is sent into reservoir,.
The usual material of proppant for meeting pressing crack construction requirement is that inorganic high-strength degree material is prepared, because its apparent density is equal
It is far longer than clear water density 1g/cm3, so various glue must be added by carrying the carrying liquid of high-visual density proppant when pressing crack construction
The proppant that clear water presentation " frozen glue " state will be added will in carrying liquid in solidifying agent wraps carrying by gel and is sent into reservoir fracture,
Then the carrying liquid addition gel breaker of " frozen glue " shape is broken glue again makes " proppant being suspended " to be deposited to crack by self weight
In play the role of support crack.For this purpose, engineers can will also be propped up in searching without using " gelling agent " clear water for a long time
The technological approaches that agent is sent into reservoir is supportted, the technology of the opposite apparent density difference of inorganic material proppant and load fluid is such as reduced, makes
The absolute apparent density that proppant is reduced with organic synthesis material is combined using low-density inorganic material with organic overlay film compound
Material reduces the technology of density, and using mutual between surfactant and coated material change proppant and carrying liquid
Active force, technology of wellability etc..Although achieving certain effect, it is difficult to realize that pure clear water is taken as pressing crack construction always
The technical effect of sand liquid.
Proppant is mainly to be formed by aggregate with the resin film for being coated on aggregate surface at present, and resin film common at present has
Phenolic resin film, epoxy resin film and urethane resin film etc., but at present in the main mesh of mode of proppant surface overlay film
Be improve aggregate intensity, so what is usually solved is how to improve resin film strength, to promote the water conservancy diversion of proppant
Ability, but proppant in the prior art does not have suspendability in clear water, is not able to satisfy construction requirement, when construction, still need
The carrying liquid with vicidity is prepared again, carries the chemical gum material contained in liquid, and there is injury and meeting to subsurface reservoir
It pollutes the environment, while increasing use cost.
Summary of the invention
The purpose of the present invention is to provide one kind from suspension type support agent, is added with solving proppant in clear water using needs
The problem of adding gelling agent that cost is caused to increase.
In order to achieve the above object, base case of the invention are as follows: a kind of from suspension type support agent, including aggregate and cladding
Coat on aggregate, the coat include resin, catalyst, curing agent and additive, and the aggregate is apparent density 1.1
~2.65g/cm3Haydite and quartz sand, the additive be aminated compounds.
The working principle of this base case is: after the proppant in the present invention is mixed with water, proppant can suspend or
Person half suspends in water；In pressing crack construction, mixture is pumped in the crack of lithosphere, proppant can be entered with water to be split
It plays a supporting role in seam.
The beneficial effect of this base case is:
(1) proppant of the present invention to be with the mixture of haydite and quartz sand be aggregate, tests through inventor and finds, when outer
When resin in coat is isocyanates, proppant can be uniformly suspended in clear water, and the time to suspend in clear water is at least
For 4h, construction requirement can be reached；Proppant surface of the invention has nanoscale protrusion, these protrusions extend in proppant
The surface of grain, protrusion will increase the buoyancy of proppant, while when proppant and water contact, one reserved in surface coating resin
Kind of group can react rapidly with water releases bulk gas small molecule, these gas molecules or is enclosed in expand in resin film and pushes away
Dynamic resin membrane body stage, which thickens, increases the equivalent diameter of proppant particles body, or is attached to the extension of proppant surface stage
Or it is gathered in the gas blanket that one layer of package proppant particles body is formed on the interface that proppant resin film is contacted with water body, this gas
Body layer formation stages between proppant particles body are connected to and the result closed causes simple grain proppant to form more pine in water body
Scattered cotton wadding gathers shape, is greatly lowered the relative density of proppant in water, in this way so as to make proppant in water
Suspension is got up.When proppant moves in water, the protrusion of the curved surface on proppant resin film can reduce proppant and settle in water
Rate；Part is settled down to the proppant of water bottom accumulation because the more protrusion of its surface resin film reduces proppant particles heap
The degree of packing of lamination, intergranular water body amount is more compared with conventional particle stack, even and if then when water body has the flowing of very little
Degree also can more easily push the separation of its congeries and movement, realize that proppant preferably suspends in water；
(2) proppant is mixed into water, proppant can be made to suspend or partly suspend in water, proppant enters in rock
Gap after proppant can be made to dispersing, to ensure that proppant has preferable support effect with water flowing；
(3) after proppant is mixed with water, other thickening substances are not added, protective effect is played to environment；Use water
As suspending agent, use cost is low；
(4) the Applicable temperature range of proppant of the invention in pressing crack construction is 5-145 DEG C, proppant Applicable temperature model
It encloses extensively, the stability in this temperature range is good；
(5) scheme change traditional pressing crack construction need to be added guar gum etc. thickening substance, realize clear water take sand.Thus
Pressure break cost is greatly saved, construction technology is simplified, reduces the pollution to environment, saves water resource；Use haydite and quartz sand
As the proppant of aggregate, proppant sphericity is good, intensity is high, water conservancy diversion is good.
Compared with prior art, this proppant can use in the water in PH > 3, and alkalinity is stronger, and suspension is better,
The suspension of proppant is more preferable in the water of high salinity, is more advantageous to pressing crack construction, is influenced by water quality smaller, and stability is good,
It is applied widely.
Further, the coat includes interior coat and outer coat, and the outer coat is by polyalcohols resin, different
Cyanate and catalyst are made, and in outer coat, the isocyanates is polyalcohols resin for the aminated compounds addition
45-75%, the hydroxyl equivalent of the polyalcohols resin is 60-300.It tests and finds through applicant, using in above range
Isocyanates, urethane resin film can be formed on outer coat, polyurethane resin can be sent out under the action of amines additives
Raw reaction generates bubble, can coat layer surface when bubble is overflowed to outside film outside and form more protrusions, bump sizes are between 100
~500nm, protrusion is in coating layer surface random distribution, when protrusion is observed under scanning electron microscope on the resin membrane body of discovery deep dark
For light highlighted or white curved body, there is the random distribution of heterogencity in the surface resin film of single particle body, then be
The surface of every 100 square micron has 1~40 or so protrusion under homogeneous distribution state, increases the suspension of proppant in this way
Performance；A certain number of isocyanate-reactive groups are also reserved in the resin film body of above-mentioned proppant simultaneously, work as residue
Isocyanate groups meet water after, reacted with water and gas can be generated in the microcosmic small space body that the chain element of resin film surrounds
Body, gradually overall volume forms bubble to this small quantity gas under the promotion of reaction energy, and pushes resin film in proppant
The radial dimension of grain increases, and outer coat can be made to expand in this way, further improve the suspendability of proppant.
Further, epoxy group, phenolic hydroxyl group, carbonyl, amide are at least contained in the resinous molecular structure in the interior coat
The organic macromolecule material of base, amino, two or more groups in isocyanate group, the resin average mark in the interior coat
Son amount is greater than 100.Using mentioned kind resin when, the resin film of interior coat can precuring become the film shape of netted high intensity
State, obtained product are contacted with fracturing fluid when being applied to oil field fracturing construction with chemical inertness height, can't discharge other
Harmful substance.
Further, the haydite and quartz sand are 100 parts, and the resin in interior coat and outer coat is 1-9 parts, interior painting
The curing agent that coating uses is the 25-45% of resin in interior coat, and the quality of the catalyst is the 1/ of polyalcohols resin
, the quality of the aminated compounds is the 1-20% of polyalcohols resin quality；It is more when containing in interior coat
When first alcohol resinoid and other resins, the mass ratio of polyalcohols resin and other resins is 1:1-5.It is upper when containing in proppant
When stating the haydite and quartz sand, resin, curing agent, catalyst and aminated compounds of ratio, proppant can have the preferable effect that suspends
Fruit.
Further, range of viscosities of the polyalcohols resin at 20 DEG C is 20~60cp.Such thermoplastic resin
Intensity is high, and Technological adaptability is strong, acid-fast alkali-proof.
Further, the sphericity of the haydite and quartz sand >=0.7, circularity >=0.7, percentage of damage≤8%, acid solubility≤
5%.When the sphericity of haydite in proppant and quartz sand >=0.7, proppant has preferably from suspension effect.
Further, the aminated compounds is diethylenetriamine, triethylamine, ethamine, triethylene tetramine, one in ethylenediamine
Kind or two or more compositions.The molecule of above-mentioned amine is small, and reactivity is big.
Further, the curing agent includes organic amine, organic acid anhydride, isocyanates, and stearic acid, dihydroxy are stearic
The mixture of one of acid, oleic acid, linoleic acid, ricinoleic acid or any component, the degree of functionality of the curing agent are 2-5.Function
When spending between 2-5, curing agent reactivity is good, can accelerate the comprehensive performance performance of the resin membrane body of support surface coat and change
Learn comprehensive inertia.
Further, the catalyst is the mixture of one or more of alkyls tin and/or alkyls lead compound.
It can make to improve the suspending efficiency of proppant in water using the catalyst of alkyls tin and/or alkyl ekalead.
Further, alkyls tin compound includes dibutyl tin dilaurate, tributyl tin, the alkyls lead compound
Including lead tetraethide, isooctyl acid lead.It can accelerate the solidification rate of outer coat using above-mentioned catalyst and intensity shows.
Detailed description of the invention
Fig. 1 is a kind of electron-microscope scanning figure from suspension type support agent embodiment 1 of the present invention；
Fig. 2 is the display figure of proppant under the microscope in embodiment 1.
Specific embodiment
It is further described below by specific embodiment:
Raw material selected by the present invention is as follows:
Aggregate is haydite and quartz sand.The apparent density of haydite and quartz sand is 1.1~2.65g/cm3, granularity be 20~
140 mesh, sphericity >=0.7, circularity >=0.7, percentage of damage≤8%, acid solubility≤5%.
Resin is organic thermoplastic polymer resin, and resin viscosity range is 20~60cp (20 DEG C), resinous molecular structure
In organic big point at least containing the two or more groups in epoxy group, phenolic hydroxyl group, carbonyl, amide groups, amino, isocyanate group
The average molecular weight of sub- substance, resin is greater than 100, such as toluene di-isocyanate(TDI), methylenediphenyl diisocyanates, different Fo Er
One of ketone diisocyanate, methyl diphenylene diisocyanate are several.
Curing agent includes organic amine, organic acid anhydride, isocyanates, stearic acid, dihydroxy stearic acid, oleic acid, sub- oil
The mixture of one of acid, ricinoleic acid or any component, the degree of functionality of curing agent is between 2-5.
Additive is aminated compounds, and aminated compounds is diethylenetriamine, triethylamine, ethamine, triethylene tetramine, second two
The composition of one or more of amine.
Catalyst be alkyls tin compound and alkyls lead compound, including dibutyl tin dilaurate, tributyl tin,
One of lead tetraethide, isooctyl acid lead or several mixtures.
Proppant of the invention has coat, and coat includes interior coat and outer coat, and outer coat connects with water
More nanoscale protrusions can be formed after touch, and as shown in connection with fig. 1, the proppant in embodiment 1 is found through electron-microscope scanning, raised ruler
Very little between 100~500nm, protrusion is coating layer surface random distribution, raised that white curved body is presented, every 100 square micron
Surface has 40 or so protrusions；Fig. 2 is the display figure of proppant under the microscope in embodiment 1.
Particular technique or condition person are not specified in various embodiments of the present invention, it is described conventional according to the literature in the art
Technology or conditions carry out.Reagents or instruments used without specified manufacturer is that can buy the routine obtained by market
Reagent manufacture.
In the present invention from suspended prop, haydite and quartz sand are 100 parts, the resin in interior coat and outer coat
Total amount is 1-9 parts, and the curing agent that interior coat uses is the 25-45% of interior coat resin quality, and isocyanates is polyalcohol
The 45-75% of resinoid, the hydroxyl equivalent of polyalcohols resin are 60-300.The quality of catalyst is the 1/1000-1/ of resin
100, the quality of aminated compounds is the 1-20% of polyalcohols resin quality；When in interior coat contain polyalcohols resin and
When other resins, the mass ratio of polyalcohols resin and other resins is 1:1-5.
The apparent density of haydite used in the embodiment of the present invention 1-4 and quartz sand is in 1.1~2.65g/cm3Between.
Embodiment 1
Taking apparent density is 1.1g/cm3, granularity be 20/40 haydite and totally 100 parts of quartz sand, be heated to 180 DEG C, will heat
Haydite and quartz sand pour into bowl-type mulling pot and stir, after temperature reaches 170-180 DEG C be added 1 part of epoxy resin and 0.25
Part curing agent T31 stirring, is added 5 parts of glycol polymers and 0.01 part of tin dilaurate two after temperature reaches 110-130 DEG C
The mixture stirring of 0.005 part of diethylenetriamine and ethylenediamine is added, to temperature in butyl tin stirring after temperature reaches 80-110 DEG C
3.5 parts of isocyanates stirring is added in degree after reaching 80-110 DEG C, take the dish out of the pot when temperature reaches between 40-70 DEG C.
Embodiment 2
Taking apparent density is 1.6g/cm3, granularity be 30/50 haydite and totally 100 parts of quartz sand, by the mixed of haydite and quartz sand
It closes to pour into bowl-type mulling pot after object is heated to 200 DEG C and stir, reach 5 parts of phenolic resin of addition between 180-190 DEG C to temperature
Stirring reaches to temperature and 1.5 parts of hexamethylenetetramine stirrings is added between 160-170 DEG C, reaches between 100-120 DEG C to temperature
4 parts of ethylene glycol polymer stirring is added, the dibutyl tin dilaurate of 0.04 part of addition between 80-100 DEG C is reached to temperature
Stirring reaches the isocyanates stirring of 2.3 parts of addition between 80-100 DEG C to temperature, reaches to temperature and take the dish out of the pot between 40-70 DEG C.
Embodiment 3
Taking apparent density is 2.2g/cm3, granularity be 40/70 haydite and totally 100 parts of quartz sand, by the mixed of haydite and quartz sand
It closes to pour into bowl-type mulling pot after object is heated to 230 DEG C and stir, 6 parts of epoxy ester resins are added after temperature reaches 190-230 DEG C
Stirring, to temperature to 2.7 parts of curing agent T31 stirrings are added between 160-170 DEG C, to temperature to 3 parts of addition between 160-170 DEG C
Ethylene glycol polymer stirring is stirred to 0.03 part of dibutyl tin dilaurate is added between 100-110 DEG C to temperature, is arrived to temperature
0.6 part of ethamine stirring is added between 100-110 DEG C, 2 parts of diphenyl diisocyanate is added after temperature reaches 80-100 DEG C
Stirring, to temperature to taking the dish out of the pot between 40-70 DEG C.
Embodiment 4
Taking apparent density is 2.65g/cm3, granularity be 70/140 haydite and totally 100 parts of quartz sand, by the haydite and stone of heating
The mixture heat of sand is stirred to pouring into bowl-type mulling pot after 180 DEG C, and 6 parts of ethylene glycol are added after temperature reaches 80-160 DEG C
The mixture of polymer and epoxy resin is stirred and is heated, wherein epoxy resin is 3 parts, is added after temperature reaches 160-170 DEG C
The mixture stirring for entering both 0.03 part dibutyl tin dilaurate, lead tetraethides, is added after temperature reaches 100-110 DEG C
2.5 parts of methylenediphenyl diisocyanates stirrings；3 parts of ethylene glycol polymers and 0.05 are added after temperature reaches 90-100 DEG C
The dibutyl tin dilaurate stirring of part reaches the isocyanates stirring of 1.3 parts of addition between 80-90 DEG C to temperature, to temperature
Reach and takes the dish out of the pot between 40-70 DEG C.
Comparative example 1
Taking apparent density is 1.0g/cm3, granularity be 20/40 haydite and totally 100 parts of quartz sand, be heated to 180 DEG C, will heat
Haydite and quartz sand pour into bowl-type mulling pot and stir, after temperature reaches 170-180 DEG C be added 1 part of epoxy resin and 0.25
Part curing agent T31 stirring, is added 5 parts of glycol polymers and 0.01 part of tin dilaurate two after temperature reaches 110-130 DEG C
The mixture stirring of 0.005 part of diethylenetriamine and ethylenediamine is added, to temperature in butyl tin stirring after temperature reaches 80-110 DEG C
3.5 parts of isocyanates stirring is added in degree after reaching 80-110 DEG C, take the dish out of the pot when temperature reaches between 40-70 DEG C.
Comparative example 2
Taking apparent density is 2.7g/cm3, granularity be 70/140 haydite and totally 100 parts of quartz sand, wherein 50 parts of haydite, stone
50 parts of sand, the mixture heat of the haydite of heating and quartz sand is stirred to pouring into bowl-type mulling pot after 180 DEG C, is reached to temperature
6 parts of ethylene glycol polymers are added after to 80-160 DEG C and the mixture of epoxy resin is stirred and heated, wherein epoxy resin 3
Part, the mixture that both 0.03 part dibutyl tin dilaurate, lead tetraethides are added after temperature reaches 160-170 DEG C stirs
It mixes, 2.5 parts of methylenediphenyl diisocyanates stirrings is added after temperature reaches 100-110 DEG C；Reach 90-100 to temperature
3 parts of ethylene glycol polymers and the stirring of 0.05 part of dibutyl tin dilaurate are added after DEG C, reaches to temperature and adds between 80-90 DEG C
The isocyanates stirring for entering 1.3 parts, reaches to temperature and takes the dish out of the pot between 40-70 DEG C.
Comparative example 3
Taking apparent density is 1.6g/cm3, granularity be 40/70 haydite and 100 parts of quartz sand, by the mixing of haydite and quartz sand
Object is poured into bowl-type mulling pot after being heated to 230 DEG C and is stirred, and 6 parts of epoxy ester resins are added after temperature reaches 190-230 DEG C and stir
It mixes, to temperature to 2.7 parts of curing agent T31 stirrings are added between 160-170 DEG C, to temperature to 3 parts of second of addition between 160-170 DEG C
Diol polymer stirring is stirred to 0.03 part of dibutyl tin dilaurate is added between 100-110 DEG C to temperature, is reached to temperature
2 parts of diphenyl diisocyanate stirring is added after 80-100 DEG C, to temperature to taking the dish out of the pot between 40-70 DEG C.
Comparative example 4
Taking apparent density is 1.1g/cm3, granularity be 20/40 haydite and totally 100 parts of quartz sand, be heated to 180 DEG C, will heat
Haydite and quartz sand pour into bowl-type mulling pot and stir, after temperature reaches 170-180 DEG C be added 1 part of epoxy resin and 0.25
Part curing agent T31 stirring, is added 5 parts of glycol polymers and 0.01 part of tin dilaurate two after temperature reaches 110-130 DEG C
The mixture stirring of 0.005 part of diethylenetriamine and ethylenediamine is added, to temperature in butyl tin stirring after temperature reaches 80-110 DEG C
2 parts of isocyanates stirring is added in degree after reaching 80-110 DEG C, take the dish out of the pot when temperature reaches between 40-70 DEG C.
Comparative example 5
Taking apparent density is 1.1g/cm3, granularity be 20/40 haydite and totally 100 parts of quartz sand, be heated to 180 DEG C, will heat
Haydite and quartz sand pour into bowl-type mulling pot and stir, after temperature reaches 170-180 DEG C be added 1 part of epoxy resin and 0.25
Part curing agent T31 stirring, is added 5 parts of glycol polymers and 0.01 part of tin dilaurate two after temperature reaches 110-130 DEG C
The mixture stirring of 0.005 part of diethylenetriamine and ethylenediamine is added, to temperature in butyl tin stirring after temperature reaches 80-110 DEG C
4 parts of isocyanates stirring is added in degree after reaching 80-110 DEG C, take the dish out of the pot when temperature reaches between 40-70 DEG C.
To as shown in table 1 from suspended prop test data in embodiment 1-4 and comparative example 1-5.
Table 1
" 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.
(b is suspension ratio, h is mattress height)
It is obtained by the analysis of table 1: when haydite in proppant and quartz sand apparent density are in 1.1~2.65g/cm3Between when, branch
Support agent has preferable suspension effect in water.
Embodiment 1 is compared with comparative example 1 it is found that using the obvious from outstanding composite index of proppant obtained in embodiment 1
Less than proppant obtained in comparative example 1 from outstanding composite index, and embodiment l and the difference of comparative example 1 are: comparative example 1
In used in the apparent density of haydite and quartz sand be less than 1.1g/cm3, it is seen that when the apparent density of quartz sand and haydite is less than
1.1g/cm3When, the proppant that is prepared is substantially reduced from suspendability, and the percentage of damage and acid of proppant are molten higher, comparison
Proppant in example 1 is not able to satisfy percentage of damage and sour molten requirement.
Embodiment 3 is compared with comparative example 3 it is found that using the obvious from outstanding composite index of proppant obtained in embodiment 3
Less than proppant obtained in comparative example 3 from outstanding composite index, and embodiment 3 and the difference of comparative example 3 are: comparative example 3
Contain aminated compounds inside China and foreign countries' coat, it is seen that when containing aminated compounds inside outer coat, comparative example 3 is prepared into
To proppant be substantially reduced from suspendability.
Embodiment 4 is compared with comparative example 2 it is found that using the obvious from outstanding composite index of proppant obtained in embodiment 4
Less than proppant obtained in comparative example 2 from outstanding composite index, and embodiment 4 and the difference of comparative example 1 are: comparative example 2
In used in the apparent density of haydite and quartz sand be greater than 2.65g/cm3, it is seen that when the apparent density of quartz sand and haydite is greater than
2.65g/cm3When, the proppant that is prepared is substantially reduced from suspendability, the comparison larger from suspension index of proppant
Proppant in example 2 is not able to satisfy from suspending and requires.
Embodiment l is compared with comparative example 4 as can be seen that hanging composite index certainly using proppant obtained in embodiment 1
It is significantly less than the certainly outstanding composite index of proppant obtained in comparative example 4, and embodiment l and the difference of comparative example 4 are: comparison
It is 40% that the amount of isocyanates, which accounts for the amount of polyalcohols resin, in example 4, it is seen that when the amount of isocyanates accounts for polyalcohols resin
When amount is less than 45%, the proppant that is prepared is substantially reduced from suspendability.
Embodiment l is compared with comparative example 5 it is found that using the obvious from outstanding composite index of proppant obtained in embodiment 1
Less than proppant obtained in comparative example 5 from outstanding composite index, and embodiment l and the difference of comparative example 5 are: comparative example 5
The amount that the amount of middle isocyanates accounts for polyalcohols resin is 80%, it is seen that when the amount that the amount of isocyanates accounts for polyalcohols resin is big
When 75%, the proppant that is prepared is substantially reduced from suspendability.
The suspension of proppant proppant in the water of mine high salinity in the present invention is more preferable, by water quality influenced compared with
It is small, it is more advantageous to pressing crack construction, stability is good.
The proppant of different haydites and quartz sand size is cooked into suspension time, suspend ratio, mattress high measure.
Suspension time refers to the maximum duration that can freely suspend in water.
Suspend than be evaluate proppant in water upper layer suspension amount be total proppant percentage, our uses in test
Haydite and quartz sand: the case where water quality ratio is 1:4 is evaluated.Experimental method is in the wide-mouth bottle of 300ml, with graduated cylinder amount
200ml water is taken to pour into wide-mouth bottle, precise 50g proppant pours into the wide-mouth bottle for having filled water, closes the lid, exerts oneself up and down
It shakes 30 times, it is static firmly to shake 30 times up and down after the same method after ten minutes, with filter paper upper layer is filtered out after static
The haydite and quartz sand of suspension, the weight that the haydite and quartz sand that filter out are weighed after drying is m, suspension amount X=m/50*
100%.
Since laboratory can only do static suspension test, so the mattress height of lower layer is also evaluate suspendability one
Item important indicator.Mattress height definition: lower layer height of the 20g proppant in the 100ml graduated cylinder equipped with 100ml clear water.Detection
Method: with the amount of plastic wound packages 100ml water of 100ml, precise 20g proppant is poured into the graduated cylinder for having filled water, tight with the right hand
Cover graduated cylinder mouth, left hand is picked up graduated cylinder and is gently reversed 10 times up and down, it is static after ten minutes, reverse 10 up and down after the same method
It is secondary, there is vernier caliper to measure the bed height of lower layer's haydite and quartz sand after static.
By taking the proppant in embodiment 1 and comparative example 6-9 as an example, the proppant of different haydites and quartz sand size is cooked outstanding
The floating time, the ratio that suspends, the results are shown in Table 2 for mattress high measure, and the proppant in comparative example 6-9 buys the safe industry from Luoyang
The proppant of 20/40,30/50,40/70,70/140 specification of Co., Ltd.
Table 2
The haydite and quartz sand of different size and mattress height all < 30mm of conventional proppants.Pass through the experiment of table 2
Data are it is found that proppant mattress height all > 30mm in the present invention, so proppant is with one kind in fact in static state
Half state to suspend is deposited in liquid bottom, once liquid flows, the proppant in the present invention can suspend.
The parameter index of different haydites and quartz sand size is as shown in table 3 in above-described embodiment.
Table 3
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.
Claims (10)
1. a kind of from suspension type support agent, including aggregate and the coat being coated on aggregate, the coat includes resin, urges
Agent, curing agent and additive, which is characterized in that the aggregate is 1.1~2.65g/cm of apparent density3Haydite and quartz sand,
The additive is aminated compounds.
2. according to claim 1 a kind of from suspension type support agent, which is characterized in that the coat includes interior coat
With outer coat, the outer coat is made of polyalcohols resin, isocyanates and catalyst, the aminated compounds addition
In outer coat, the isocyanates is the 45-75% of polyalcohols resin, and the hydroxyl equivalent of the polyalcohols resin is
60-300。
3. according to claim 2 a kind of from suspension type support agent, which is characterized in that the resin point in the interior coat
At least having containing the two or more groups in epoxy group, phenolic hydroxyl group, carbonyl, amide groups, amino, isocyanate group in minor structure
Machine macromolecular substances, the resin average molecular weight in the interior coat are greater than 100.
4. according to claim 3 a kind of from suspension type support agent, which is characterized in that the haydite and quartz sand are 100
Part, the resin in interior coat and outer coat is 1-9 parts, and the curing agent that interior coat uses is resin in interior coat
25-45%, the quality of the catalyst are the 1/1000-1/100 of polyalcohols resin, and the quality of the aminated compounds is more
The 1-20% of first alcohols resin quality；When containing polyalcohols resin and other resins in interior coat, polyalcohols resin
Mass ratio with other resins is 1:1-5.
5. according to claim 4 a kind of from suspension type support agent, which is characterized in that the polyalcohols resin is at 20 DEG C
When range of viscosities be 20~60cp.
6. according to claim 1 a kind of from suspension type support agent, which is characterized in that the sphericity of the haydite and quartz sand
>=0.7, circularity >=0.7, percentage of damage≤8%, acid solubility≤5%.
7. according to claim 1 a kind of from suspension type support agent, which is characterized in that the aminated compounds is divinyl
The composition of one or more of triamine, triethylamine, ethamine, triethylene tetramine, ethylenediamine.
8. according to claim 1 a kind of from suspension type support agent, which is characterized in that the curing agent includes organic amine
Class, organic acid anhydride, isocyanates, one of stearic acid, dihydroxy stearic acid, oleic acid, linoleic acid, ricinoleic acid or any group
The mixture divided, the degree of functionality of the curing agent are 2-5.
9. according to claim 1 a kind of from suspension type support agent, which is characterized in that the catalyst is alkyls tin
And/or the mixture of one or more of alkyls lead compound.
10. according to claim 9 a kind of from suspension type support agent, which is characterized in that alkyls tin compound includes two
Dibutyl tin laurate, tributyl tin, the alkyls lead compound include lead tetraethide, isooctyl acid lead.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110317602A (en) * | 2019-06-28 | 2019-10-11 | 辽宁石油化工大学 | A kind of preparation method of aqueous fracturing fluid proppant |
| CN114891492A (en) * | 2022-05-24 | 2022-08-12 | 中国地质科学院勘探技术研究所 | Low-temperature self-suspension solidified sand and preparation method thereof |
| CN116751578A (en) * | 2023-08-23 | 2023-09-15 | 山东鼎维石油科技有限公司 | Self-suspension propping agent and preparation method thereof |
Citations (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006023172A2 (en) * | 2004-08-16 | 2006-03-02 | Fairmount Minerals, Ltd. | Control of particulate flowback in subterranean formations using elastomeric resin coated proppants |
| CN102203211A (en) * | 2008-10-29 | 2011-09-28 | 巴斯夫欧洲公司 | A proppant |
| CN103003386A (en) * | 2010-07-21 | 2013-03-27 | 巴斯夫欧洲公司 | A proppant |
| CN103608427A (en) * | 2011-05-03 | 2014-02-26 | 优选技术有限责任公司 | Coated and cured proppants |
| CN103889706A (en) * | 2011-07-22 | 2014-06-25 | 优选技术有限责任公司 | Coated and cured proppants |
| CN104039920A (en) * | 2011-12-15 | 2014-09-10 | 阿什兰南方化学科恩弗斯特有限公司 | Method for producing coated proppants |
| CN104379697A (en) * | 2012-04-19 | 2015-02-25 | 自悬浮支撑有限公司 | Self-suspending proppants for hydraulic fracturing |
| CN104520530A (en) * | 2012-01-23 | 2015-04-15 | 优选技术有限责任公司 | Manufacture of polymer coated proppants |
| CN104797681A (en) * | 2012-09-25 | 2015-07-22 | 优选技术有限责任公司 | Coated and cured proppants |
| CN104946234A (en) * | 2014-03-28 | 2015-09-30 | 北京仁创科技集团有限公司 | Self-suspended propping agent and preparation method thereof |
| CN104944840A (en) * | 2014-03-28 | 2015-09-30 | 北京仁创科技集团有限公司 | Preparation method of self-suspension proppant for natural hydrofracturing construction |
| CN105408444A (en) * | 2013-05-17 | 2016-03-16 | 优选技术有限责任公司 | Proppant with enhanced interparticle bonding |
| CN105670600A (en) * | 2016-03-07 | 2016-06-15 | 王展旭 | Water acid-sensitivity deformation magnetic tracer function self-suspension propping agent and preparation method thereof |
| CN105934495A (en) * | 2013-11-26 | 2016-09-07 | 巴斯夫欧洲公司 | Proppant |
| US20160333259A1 (en) * | 2015-05-13 | 2016-11-17 | Preferred Technology, Llc | High performance proppants |
| CN106281299A (en) * | 2016-08-05 | 2017-01-04 | 重庆长江造型材料（集团）股份有限公司 | Low-density film-coated ceramisite proppant and preparation method thereof |
| US20170058190A1 (en) * | 2009-10-20 | 2017-03-02 | Self-Suspending Proppant Llc | Proppants for hydraulic fracturing technologies |
| CN106675549A (en) * | 2016-12-05 | 2017-05-17 | 北京奇想达新材料有限公司 | Water suspensible propping agent for oil and gas well fracturing and preparation method thereof |
| CN106928990A (en) * | 2015-12-30 | 2017-07-07 | 北京仁创科技集团有限公司 | Expanding material composition and from suspended prop and preparation method and application |
| CN107438652A (en) * | 2015-03-30 | 2017-12-05 | 陶氏环球技术有限责任公司 | Proppant coating with preforming isocyanuric acid ester |
| US20180148636A1 (en) * | 2016-11-28 | 2018-05-31 | Preferred Technology, Llc | Durable coatings and uses thereof |
-
2018
- 2018-09-30 CN CN201811159599.8A patent/CN108949140A/en active Pending
Patent Citations (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006023172A2 (en) * | 2004-08-16 | 2006-03-02 | Fairmount Minerals, Ltd. | Control of particulate flowback in subterranean formations using elastomeric resin coated proppants |
| CN102203211A (en) * | 2008-10-29 | 2011-09-28 | 巴斯夫欧洲公司 | A proppant |
| US20170058190A1 (en) * | 2009-10-20 | 2017-03-02 | Self-Suspending Proppant Llc | Proppants for hydraulic fracturing technologies |
| CN103003386A (en) * | 2010-07-21 | 2013-03-27 | 巴斯夫欧洲公司 | A proppant |
| US20150203745A1 (en) * | 2011-05-03 | 2015-07-23 | Preferred Technology, Llc | Coated and cured proppants |
| CN103608427A (en) * | 2011-05-03 | 2014-02-26 | 优选技术有限责任公司 | Coated and cured proppants |
| CN103889706A (en) * | 2011-07-22 | 2014-06-25 | 优选技术有限责任公司 | Coated and cured proppants |
| CN104039920A (en) * | 2011-12-15 | 2014-09-10 | 阿什兰南方化学科恩弗斯特有限公司 | Method for producing coated proppants |
| CN104520530A (en) * | 2012-01-23 | 2015-04-15 | 优选技术有限责任公司 | Manufacture of polymer coated proppants |
| CN104379697A (en) * | 2012-04-19 | 2015-02-25 | 自悬浮支撑有限公司 | Self-suspending proppants for hydraulic fracturing |
| CN104797681A (en) * | 2012-09-25 | 2015-07-22 | 优选技术有限责任公司 | Coated and cured proppants |
| CN105408444A (en) * | 2013-05-17 | 2016-03-16 | 优选技术有限责任公司 | Proppant with enhanced interparticle bonding |
| CN105934495A (en) * | 2013-11-26 | 2016-09-07 | 巴斯夫欧洲公司 | Proppant |
| CN104946234A (en) * | 2014-03-28 | 2015-09-30 | 北京仁创科技集团有限公司 | Self-suspended propping agent and preparation method thereof |
| CN104944840A (en) * | 2014-03-28 | 2015-09-30 | 北京仁创科技集团有限公司 | Preparation method of self-suspension proppant for natural hydrofracturing construction |
| CN107438652A (en) * | 2015-03-30 | 2017-12-05 | 陶氏环球技术有限责任公司 | Proppant coating with preforming isocyanuric acid ester |
| US20160333259A1 (en) * | 2015-05-13 | 2016-11-17 | Preferred Technology, Llc | High performance proppants |
| WO2016183313A1 (en) * | 2015-05-13 | 2016-11-17 | Preferred Technology, Llc | High performance proppants |
| CN106928990A (en) * | 2015-12-30 | 2017-07-07 | 北京仁创科技集团有限公司 | Expanding material composition and from suspended prop and preparation method and application |
| CN105670600A (en) * | 2016-03-07 | 2016-06-15 | 王展旭 | Water acid-sensitivity deformation magnetic tracer function self-suspension propping agent and preparation method thereof |
| CN106281299A (en) * | 2016-08-05 | 2017-01-04 | 重庆长江造型材料（集团）股份有限公司 | Low-density film-coated ceramisite proppant and preparation method thereof |
| US20180148636A1 (en) * | 2016-11-28 | 2018-05-31 | Preferred Technology, Llc | Durable coatings and uses thereof |
| CN106675549A (en) * | 2016-12-05 | 2017-05-17 | 北京奇想达新材料有限公司 | Water suspensible propping agent for oil and gas well fracturing and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110317602A (en) * | 2019-06-28 | 2019-10-11 | 辽宁石油化工大学 | A kind of preparation method of aqueous fracturing fluid proppant |
| CN114891492A (en) * | 2022-05-24 | 2022-08-12 | 中国地质科学院勘探技术研究所 | Low-temperature self-suspension solidified sand and preparation method thereof |
| CN114891492B (en) * | 2022-05-24 | 2023-10-27 | 中国地质科学院勘探技术研究所 | Low-temperature self-suspension curing sand and preparation method thereof |
| CN116751578A (en) * | 2023-08-23 | 2023-09-15 | 山东鼎维石油科技有限公司 | Self-suspension propping agent and preparation method thereof |
| CN116751578B (en) * | 2023-08-23 | 2023-11-24 | 北京化工大学 | Self-suspension propping agent and preparation method thereof |
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