CN106928987A - Expanding material composition containing polyvinylpyrrolidone and from suspended prop and its application and preparation method - Google Patents
Expanding material composition containing polyvinylpyrrolidone and from suspended prop and its application and preparation method Download PDFInfo
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- CN106928987A CN106928987A CN201511024882.6A CN201511024882A CN106928987A CN 106928987 A CN106928987 A CN 106928987A CN 201511024882 A CN201511024882 A CN 201511024882A CN 106928987 A CN106928987 A CN 106928987A
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- China
- Prior art keywords
- suspended prop
- material composition
- proppant
- expanding material
- polyvinylpyrrolidone
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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
- 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
- C09K8/84—Compositions based on water or polar solvents
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
- C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/882—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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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
- C09K8/84—Compositions based on water or polar solvents
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
- C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/90—Compositions based on water or polar solvents containing organic compounds macromolecular compounds of natural origin, e.g. polysaccharides, cellulose
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- E—FIXED CONSTRUCTIONS
- E21—EARTH DRILLING; MINING
- E21B—EARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/25—Methods for stimulating production
- E21B43/26—Methods for stimulating production by forming crevices or fractures
- E21B43/267—Methods for stimulating production by forming crevices or fractures reinforcing fractures by propping
Abstract
The invention discloses a kind of expanding material composition, said composition includes polyvinylpyrrolidone and natural macromolecular material, wherein, the mass ratio of polyvinylpyrrolidone and natural macromolecular material is (50-1200)：1, natural macromolecular material is natural plant gum family macromolecule material and/or animal glue family macromolecule material.Also disclose using expanding material composition preparation from suspended prop and its preparation method and application.Suspended state is can be at after prepared by expanding material composition of the invention mix from suspended prop with water, and suspension time is long, it is flow conductivity good, sand plug can be effectively reduced during filling crack, the distance of conveying is farther, and fuel-displaced/tolerance is bigger.
Description
Technical field
The present invention relates to exploitation of mineral resources field, in particular it relates to a kind of expanding material composition and certainly suspension
Proppant and its preparation method and application.
Background technology
Oil and gas occupy critical role, the oil gas money on China land in Chinese national economy development
Source by over half a century exploitation, many oil wells have started to aging or even exhaustion, for having for oil field
Effect exploitation and volume increase become more and more important.
The major measure of current well production increment is hydraulic fracturing technology, and the high pressure pump group using ground is isobaric
Equipment is split constantly to be injected beyond its absorbability, the fracturing fluid with hyperviscosity to oil reservoir by pit shaft
And cause to form pressure higher on oil reservoir, with the continuous injection of fracturing fluid, pressure is also constantly raised,
When this pressure is higher than strata pressure near the borehole wall and formation rock tensile strength, oil reservoir will be opened by pressure break
And the different crack of not of uniform size, length is formed, then will be propped up in proppant transport to crack by load fluid
Crack seam so that a fluid passage is formed between oil reservoir and pit shaft, the effect of volume increase is reached.Fracturing fluid
Flow at high speed, using turbulent suspension proppant, but after proppant reaches crack, due to rate of flow of fluid
Decline to a great extent, proppant rapid subsidence is in Slit bottom (A of patent CN 102159797).To reduce
Leak-off, and prop-carrying capacity is improved, generally addition organic high molecular compound makees thickener in fracturing fluid, and
These organic high molecular compounds can enter stratum with fracturing fluid, be partially left at the macromolecule chemical combination of underground
Thing blocks the hole on stratum, cause oil pump capacity decline, underground water pollution the problems such as.Additionally, fracturing fluid viscosity
Increase so that the pump power consumed during the row of returning is larger, and it is unfavorable for all rows of returning.
The content of the invention
It is an object of the invention to provide a kind of expanding material composition and from suspended prop and proppant
Preparation method and application, with overcome need in the prior art in fracturing fluid add thickener with complete to branch
Thickener blocks oil outlet and pollutes the defect of environment caused by supportting the conveying of agent.
To achieve these goals, first aspect present invention, there is provided a kind of expanding material composition, the group
Compound includes polyvinylpyrrolidone and natural macromolecular material, wherein, polyvinylpyrrolidone and natural
The mass ratio of macromolecular material is (50-1200)：1, the natural macromolecular material is that natural plant gum class is high
Molecular material and/or animal glue family macromolecule material.
Preferably, the weight average molecular weight of polyvinylpyrrolidone is 5000-1500000.
Preferably, polyvinylpyrrolidone is selected from anionic polyvinylpyrrolidone, cationic poly
At least one in vinylpyrrolidone and nonionic polyvinyl pyrrolidones.
It is further preferred that polyvinylpyrrolidone is anionic polyvinylpyrrolidone.
Preferably, natural plant gum macromolecular material is selected from Arabic gum, tragacanth, locust bean gum and rubber made from soybean cake
In at least one.
Preferably, animal glue family macromolecule material is selected from least one in gelatine, gelatin and casein.
Second aspect present invention, there is provided one kind should include proppant from suspended prop from suspended prop
Body and cladding or part are coated on the intumescent material of proppant body surface, and the intumescent material is by this
The expanding material composition of invention first aspect is bonded through binding agent and curing agent and coated or part cladding
Formed on the proppant body；Wherein, expanding material composition is with the mass ratio of proppant body
1：(50-1500)；The weight ratio of proppant body, binding agent and curing agent is 1：(0.001-0.5)：
(0.001-0.5)。
Preferably, proppant body is aggregate and/or pre-coated membrane bone material.
Preferably, aggregate is selected from quartz sand, haydite, metallic particles, globular glass particle, sintered aluminium
At least one in the shell particle of Tu Kuang, sintered alumina, sintered zirconia, synthetic resin and crushing；
The particle diameter of the aggregate is 6-200 mesh.
Preferably, pre-coated membrane bone material is to include that aggregate and cladding or part are coated on the pre- overlay film of aggregate surface
Resin bed.
Preferably, pre- film covered resin layer is resin material obtained by the coated treatment of aggregate surface, wherein,
Resin material is selected from least one in phenolic resin, furane resins and epoxy resin.
Preferably, binding agent is high selected from phenolic resin, epoxy resin, unsaturated polyester resin and heterocycle
At least one in molecular binder.
Preferably, curing agent be selected from aliphatic amine and its addition product, tertiary amine and its salt, aromatic amine and
Its modified body, imidazoles, acid anhydrides, acyl peroxide, lipid peroxidation, paraformaldehyde, phenolic aldehyde amine, divinyl
At least one in triamine, triethylene tetramine and hexamethylenetetramine.
Third aspect present invention, there is provided the preparation method from suspended prop of second aspect present invention, should
Method includes：(1) by proppant body and binding agent and curing agent, dispersion mixing is uniform at the first temperature,
Wherein, the weight ratio of proppant body, binding agent and curing agent is 1：(0.001-0.5)：(0.001-0.5)；
(2) make the proppant body and expanding material composition at the second temperature dispersion mixing it is uniform so that
Expanding material composition is coated or part is coated on proppant body, obtains granular from suspension support
Agent, wherein, expanding material composition is 1 with the mass ratio of the proppant body：(50-1500).
Preferably, the first temperature is 100-300 DEG C；Second temperature is 50-200 DEG C.
Fourth aspect present invention, there is provided second aspect present invention from suspended prop in fluid ore deposit exploitation side
The application in face.
Preferably, fluid ore deposit is including in natural gas, oil, shale gas, shale oil, fresh water and salt solution
It is at least one.
By above-mentioned technical proposal, expanding material composition low cost of the invention, environmental pollution is small.
By expanding material composition of the invention be coated on aggregate it is obtained from suspended prop without using adding
Plus organic polymer and costly fracturing fluid carries out pressure break, directly use natural water, and and water
Suspended state is can be at after mixing, suspension time is long, flow conductivity good, the energy during crack is filled
Enough effectively to reduce sand plug, the distance of conveying is farther, and fuel-displaced/tolerance is bigger.Further, since of the invention swollen
The swollen material compositions characteristics of itself, can reduce the frictional resistance of fracturing fluid, easily conveying, the easily row of returning, and the row of returning
Energy consumption reduction, does not have macromolecular material to remain, and is conducive to environmental protection, can better meet oil recovery
Need.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific embodiment
Specific embodiment of the invention is described in detail below.It should be appreciated that this place is retouched
The specific embodiment stated is merely to illustrate and explain the present invention, and is not intended to limit the invention.
First aspect present invention：A kind of expanding material composition is provided, the composition includes polyethylene pyrrole
Pyrrolidone and natural macromolecular material.
According to the first aspect of the invention, the mass ratio of polyvinylpyrrolidone and natural macromolecular material exists
It is interior in a big way to realize the purpose of the present invention, for example, polyvinylpyrrolidone and natural polymer
The mass ratio of material can be (50-1200)：1.
According to the first aspect of the invention, the implication of polyvinylpyrrolidone is ripe for those skilled in the art
Know, be water-soluble polymer, with the structural formula as shown in formula (1), wherein, n can be 1-107
Between arbitrary integer.Lactams in polyvinylpyrrolidonemolecules molecules is highly polar group, with hydrophily.
Expanding material composition of the invention includes polyvinylpyrrolidone, makes expanding material composition energy in water
Enough Fast-swellings.
According to the first aspect of the invention, the weight average molecular weight of polyvinylpyrrolidone can be in very wide range
Interior change, under preferable case, it is adaptable to which the weight for forming the polyvinylpyrrolidone of expanding material composition is equal
Molecular weight can be 5000-1500000.
According to the present invention, the species of polyvinylpyrrolidone is not required particularly, can be this area skill
Can be selected from anionic polyvinylpyrrolidone, cationic polyethylene pyrrole known to art personnel
At least one in pyrrolidone and nonionic polyvinyl pyrrolidones.Under preferable case, polyvinyl pyrrole
Alkanone can be anionic polyvinylpyrrolidone.Anionic polyvinylpyrrolidone can be preferably
It is swelling in water, the dissolubility of expanding material composition is improve, can cause to use expanding material composition
What is prepared possesses preferably from suspending power from suspended prop.The polyvinyl pyrrole of commercially available mentioned kind
Alkanone can meet the purpose of the present invention, for example, the trade mark of commercial polyethylene pyrrolidones can be but
It is not limited to：PVP-K series and PVP-C series etc..
According to the first aspect of the invention, the implication of natural macromolecular material is ripe for those skilled in the art
Know, it is preferable that natural macromolecular material can be natural plant gum family macromolecule material and/or animal glue class high score
Sub- material.Wherein, natural plant gum family macromolecule material can be selected from Arabic gum, tragacanth, locust bean gum
With at least one in rubber made from soybean cake；Animal glue family macromolecule material can be selected from gelatine, gelatin and cheese
At least one in element.The natural macromolecular material product of commercially available mentioned kind can be as the present invention
Natural macromolecular material used, for example, the natural macromolecular material of mentioned kind can purchased from south
Jing Senbeijia bio tech ltd, Zhejiang oasis Bioisystech Co., Ltd, Xi'an Yuhua biology section
Skill Co., Ltd, the Central-South bio tech ltd in Anhui and Zhengzhou Qi Huadun chemical products Co., Ltd
Deng.The water-soluble expansion suspension material for using above-mentioned natural macromolecular material to be formed with polyvinyl alcohol can be with fast
It is instantly dissolved in water and then expands, can for a long time be in suspended state, while there is low cost, polluting small
Advantage.
Second aspect present invention, there is provided one kind should include proppant from suspended prop from suspended prop
Body and cladding or part are coated on the intumescent material of proppant body surface.By first aspect present invention
Expanding material composition stick in proppant body surface after, it is resulting from suspended prop in normal temperature
Can dissolve and expand in water after mixing with water down so that the sinking speed from suspended prop is slack-off,
With suspending power.
According to the second aspect of the invention, in order to reach the purpose of the present invention, expanding material composition is at least
Part is coated on proppant body surface, it is preferable that the quality of expanding material composition and proppant body
Than that can be 1：(50-1500), what is obtained under said ratio is easier in water from suspended prop
Suspend for a long time.
According to the second aspect of the invention, proppant body is mechanical enough with crack closure stress is born
The natural hard particle of intensity or the artificial hard particles fired, can be aggregate and/or pre-coated membrane bone material.
Aggregate can be the existing various aggregates that can be used in preparing fracturing propping agents, for example, aggregate can be
Selected from quartz sand, haydite, metallic particles, globular glass particle, sintered bauxite, sintered alumina,
At least one in the shell particle of sintered zirconia, synthetic resin and crushing；The aggregate of metal material is excellent
The material that hardness is high is selected, for example, the material of metallic particles can be stainless steel, aluminium alloy, carbon steel, iron nickel
At least one in alloy or ferromanganese.The average grain diameter of aggregate can be in interior change in a big way, can
To be selected according to actual needs, for example, the particle diameter of skeletal grain can be 6-200 mesh.Using above-mentioned kind
The aggregate of class is made proppant body and is had from suspended prop with obtained in expanding material composition of the invention
Standby resistant to breakage ability higher.
According to the second aspect of the invention, one layer of pre- film covered resin layer can also be coated in above-mentioned aggregate surface
Pre-coated membrane bone material is formed so as to further improve the resistant to breakage ability of aggregate, improves circularity and sphericity, improved
Flow conductivity.Therefore, the proppant body is additionally may included in above-mentioned aggregate surface and coats pre- overlay film tree
The pre-coated membrane bone material that lipid layer is formed, for example, can be precoated sand and film-coated ceramisite；It is coated on aggregate surface
Resin material can be selected from least one in phenolic resin, furane resins and epoxy resin.
According to the second aspect of the invention, intumescent material is coated on the process of proppant body surface
In, binding agent and curing agent can also be added, so that intumescent material is more easy to stick in proppant body
On.The species of binding agent and curing agent can be well known to those skilled in the art for fracturing propping agents
Preparation field conventional binding agent and curing agent, for example, binding agent can be selected from phenolic resin, epoxy
At least one in resin, unsaturated polyester resin and heterocyclic polymer binding agent.It is further preferred that
Phenolic resin can be thermoplastic phenolic resin or thermosetting phenolic resin；Epoxy resin can use epoxy
Equivalent is the epoxy resin of 0.09-0.14mol/100g；Preferably bisphenol A type epoxy resin, more preferably
Be selected from epoxy resin E-55 (616), E-51 (618), E-44 (6101), E-42 (634), E-35 (637),
At least one in E-20 (601), E-12 (604), E-06 (607) and E-03 (609)；Unsaturated polyester (UP) tree
Fat can be unsaturated for m-phthalate unsaturated polyester resin, metaphenylene unsaturated polyester resin, xylol type
Polyester resin, Bisphenol a unsaturated polyester resin, halo unsaturated polyester resin and vinyl ester resin
In at least one；It is preferred that m-phthalate unsaturated polyester resin, model can be 191 or 196；Isophthalic
Type unsaturated polyester resin model can be 199；Xylol type unsaturated polyester resin model can be
2608th, at least one in 902A3, Xm-1 and Xm-2；Bisphenol a unsaturated polyester resin type
Number can be 197,3301 and 323 at least one；Heterocyclic polymer bonding agent can be selected from polyamides
At least one in imines, polybenzimidazoles, polyphenylene sulfide and polydiphenyl ether.Curing agent can be selected from
Aliphatic amine and its addition product, tertiary amine and its salt, aromatic amine and its modified body, imidazoles, acid anhydrides, mistake
Oxidation acyl, lipid peroxidation, paraformaldehyde, phenolic aldehyde amine, diethylenetriamine, triethylene tetramine and six first
At least one in urotropine.Using the binding agent and curing agent of mentioned kind may be such that intumescent material with
Proppant body adhesion effect more preferably, and will not make proppant particles reunite and influence fracturing propping agents
Particle size and dispersiveness.
According to the second aspect of the invention, binding agent can be according to intumescent material with the inventory of curing agent
Selected in the cladding degree of proppant body surface, under preferable case, proppant body, binding agent
Can be 1 with the weight ratio of curing agent：(0.001-0.5)：(0.001-0.5).
Third aspect present invention, there is provided the preparation method from suspended prop of second aspect present invention, should
Method includes：(1) by proppant body and binding agent and curing agent, dispersion mixing is uniform at the first temperature,
Wherein, the weight ratio of proppant body, binding agent and curing agent is 1：(0.001-0.5)：(0.001-0.5)；
(2) make the proppant body and expanding material composition at the second temperature dispersion mixing it is uniform so that
Expanding material composition is coated or part is coated on proppant body, obtains granular from suspension support
Agent, wherein, expanding material composition is 1 with the mass ratio of the proppant body：(50-1500).
Preparation method from suspended prop of the invention can be in proppant body surface cladding expansion material
Feed composition, obtain from suspended prop can using water as fracturing fluid, meanwhile, from suspended prop
The expanding material composition on surface is rapid swelling in water, forms the hydrated sheath of expansion, reduces proppant
The relative density of grain, makes it be suspended on the water surface, consequently facilitating the conveying of fracturing fluid.
In the preparation method from suspended prop of the invention, in order to improve proppant body cladding
The covered effect of expanding material composition, can pre-process to proppant body, and processing method is this
Known to art personnel, for example, it is preferred to the steps such as scouring, drying, screening can be first passed through,
To remove the moisture in aggregate, it is easy to aggregate preferably to be combined with expanding material composition.
In the preparation method from suspended prop of the invention, the first Contact Temperature and second is contacted
Temperature do not require particularly, as long as meet above-mentioned binding agent and curing agent can be with the first Contact Temperature
Melt to be coated on proppant body surface；Above-mentioned expanding material composition can be with the second Contact Temperature
It is further bonded.Under preferable case, the first temperature can be 100-300 DEG C；Second temperature can be with
It is 50-200 DEG C.At the temperature disclosed above, can obtain expanding material composition cladding or part cladding from
Suspended proppant particles.The obtained step that cooling and screening are can further include from suspended prop
Suddenly.
Fourth aspect present invention, there is provided second aspect present invention from suspended prop in fluid ore deposit exploitation side
The application in face.Wherein, fluid ore deposit includes natural gas, oil, shale gas, shale oil, fresh water and salt solution
In at least one.
The present invention is further illustrated below by embodiment, but therefore the present invention is not subject to any limit
System.
Embodiment 1
The present embodiment is used to illustrate expanding material composition of the invention and by expanding material composition system
It is standby from suspended prop and preparation method thereof.
Take the polyvinylpyrrolidone that the 10g trades mark are PVP K-25 (limited purchased from Beijing Suo Laibao science and technology
Company, weight average molecular weight is 24500) with 0.05g Arabic gums (purchased from Nanjing Sen Beijia biotechnologies
Co., Ltd) mixed as expanding material composition.
1kg quartz sands that average particle diameter is 20-40 mesh are taken as aggregate, 220 DEG C are heated to, 10g is added
Epoxy resin E-35 (637) and 5g curing agent phthalic anhydrides, stirring add after being cooled to 150 DEG C
Enter expanding material composition obtained above, stir.Cooling, screening, obtain the present embodiment from
Suspended prop.
Embodiment 2
The present embodiment is used to illustrate expanding material composition of the invention and by expanding material composition system
It is standby from suspended prop and preparation method thereof.
Take the polyvinylpyrrolidone that the 10g trades mark are PVP K-30 (limited purchased from Beijing Suo Laibao science and technology
Company, weight average molecular weight is 49000) with 0.2g tragacanths (purchased from the Zhejiang limited public affairs of oasis biotechnology
Department) mixed as expanding material composition.
2kg haydites that average particle diameter is 50-100 mesh are taken as aggregate, 180 DEG C are heated to, 50g is added
Bisphenol a unsaturated polyester resin 197 and 2g curing agent benzoyl peroxides, after being cooled to 130 DEG C
Expanding material composition obtained above is added, is stirred.Cooling, screening, obtain the present embodiment
From suspended prop.
Embodiment 3
The present embodiment is used to illustrate expanding material composition of the invention and by expanding material composition system
It is standby from suspended prop and preparation method thereof.
Take the polyvinylpyrrolidone that the 5g trades mark are PVP K-15 and (be purchased from Beijing Suo Laibao limited public affairs of science and technology
Department, weight average molecular weight be 7680) with 0.01g locust bean gums (purchased from Xi'an Yuhua bio tech ltd)
Mixed as expanding material composition.
7kg glass microspheres that average particle diameter is 70-140 mesh are taken as aggregate, 200 DEG C are heated to, added
7g neighbour's benzene-type unsaturated polyester (UP) 191 and 14g curing agent diethylenetriamines, add after being cooled to 120 DEG C
The expanding material composition for obtaining is stated, is stirred.Cooling, screening, obtain suspending certainly for the present embodiment
Proppant.
Embodiment 4
The present embodiment is used to illustrate expanding material composition of the invention and by expanding material composition system
It is standby from suspended prop and preparation method thereof.
Take the polyvinylpyrrolidone that the 6g trades mark are PVP K-90 and (be purchased from Beijing Suo Laibao limited public affairs of science and technology
Department, weight average molecular weight is 1100000) (limited purchased from Xi'an Yuhua biotechnology with 0.01g rubber made from soybean cakes
Company) mixed as expanding material composition.
Take average particle diameter be 50-100 mesh 4kg precoated sands (according to patent CN1274626A embodiments 1
Method manufacture) as aggregate, be heated to 260 DEG C, add 400g epoxy resin E12 (604) and 400g
Curing agent HPMA, adds expanding material composition obtained above after being cooled to 160 DEG C, stirring
Uniformly.Cooling, screening, obtain of the invention from suspended prop.
Embodiment 5
The present embodiment is used to illustrate expanding material composition of the invention and by expanding material composition system
It is standby from suspended prop and preparation method thereof.
Take the polyvinylpyrrolidone that the 24g trades mark are PVP K-60 (limited purchased from Beijing Suo Laibao science and technology
Company, weight average molecular weight is 216000) with 0.02g gelatine (purchased from the Anhui limited public affairs of Central-South biotechnology
Department) mixed as expanding material composition.
Take 2kg precoated sands (the scientific and technological group production of benevolence wound, model that average particle diameter is 30-50 mesh
ZFS-KGD) as aggregate, 240 DEG C are heated to, add 800g metaphenylene unsaturated polyester resins 199
With 800g curing agent chitosan quaternary ammonium salts, expanding material obtained above is added to combine after being cooled to 80 DEG C
Thing, stirs.Cooling, screening, obtain of the invention from suspended prop.
Embodiment 6
The present embodiment is used to illustrate expanding material composition of the invention and by expanding material composition system
It is standby from suspended prop and preparation method thereof.
Take the polyvinylpyrrolidone that the 8g trades mark are PVP K-17 and (be purchased from Beijing Suo Laibao limited public affairs of science and technology
Department, weight average molecular weight be 9500) with 0.01g gelatin (purchased from Zhengzhou Qi Huadun chemical products Co., Ltd)
Mixed as expanding material composition.
Take 4kg precoated sands (the scientific and technological group production of benevolence wound, model that average particle diameter is 20-40 mesh
ZFS-KGM) as aggregate, 250 DEG C are heated to, add 200g Bisphenol a unsaturated polyester resins
3301 and 100g curing agent chitosan quaternary ammonium salts, add expansion material obtained above after being cooled to 120 DEG C
Feed composition, stirs.Cooling, screening, obtain of the invention from suspended prop.
Embodiment 7
The present embodiment is used to illustrate expanding material composition of the invention and by expanding material composition system
It is standby from suspended prop and preparation method thereof.
Take the polyvinylpyrrolidone that the 100g trades mark are PVP C-30 (limited purchased from Beijing Suo Laibao science and technology
Company, weight average molecular weight is 49000) to enter with 1g casein (purchased from Shanghai Bang Jing Industrial Co., Ltd.s)
Row mixing is used as expanding material composition.
5kg sintered aluminas that average particle diameter is 50-100 mesh are taken as aggregate, 280 DEG C are heated to, plus
Enter 100g epoxy resin E-55 (616) and 100g curing agent triethylene tetramines, after being cooled to 140 DEG C
Expanding material composition obtained above is added, is stirred.Cooling, screening, obtain it is of the invention from
Suspended prop.
Embodiment 8
The present embodiment is used to illustrate expanding material composition of the invention and by expanding material composition system
It is standby from suspended prop and preparation method thereof.
Take the polyvinylpyrrolidone that the 10g trades mark are PVP K-29 (limited purchased from Beijing Suo Laibao science and technology
Company, weight average molecular weight is 34900) with 0.03g Arabic gums (purchased from Nanjing Sen Beijia biotechnologies
Co., Ltd) mixed as expanding material composition.
Stainless steel particles of 1kg that average particle diameter is 30-50 mesh are taken as aggregate, 280 DEG C are heated to, plus
Enter 3g xylol types unsaturated polyester resin 2608 and 6g curing agent hexamethylenetetramines, be cooled to
Expanding material composition obtained above is added after 100 DEG C, is stirred.Cooling, screening, obtain this
Invention from suspended prop.
Comparative example 1
It is the quartz sand of 20-40 mesh as proppant to use particle mean size.
Comparative example 2
1kg quartz sands that average particle diameter is 20-40 mesh are taken as aggregate, 220 DEG C are heated to, 10g is added
Epoxy resin E-35 (637) and 5g curing agent phthalic anhydrides, stir.Cooling, screening,
Obtain this comparative example from suspended prop.
Comparative example 3
1kg quartz sands that average particle diameter is 20-40 mesh are taken as aggregate, 220 DEG C are heated to, 10g is added
Epoxy resin E-35 (637) and 5g curing agent phthalic anhydrides, stirring add after being cooled to 150 DEG C
Enter 0.05g Arabic gums (purchased from Nanjing Sen Beijia bio tech ltd), stir.Cooling,
Screening, obtain this comparative example from suspended prop.
Comparative example 4
1kg quartz sands that average particle diameter is 20-40 mesh are taken as aggregate, 220 DEG C are heated to, 10g is added
Epoxy resin E-35 (637) and 5g curing agent phthalic anhydrides, stirring add after being cooled to 150 DEG C
Enter polyvinylpyrrolidone that the 10g trades mark are PVP K-25 (purchased from Beijing Suo Laibao Science and Technology Ltd,
Weight average molecular weight is 24500), to stir.Cooling, screening, obtain this comparative example from suspension support
Agent.
Comparative example 5
1kg quartz sands that average particle diameter is 20-40 mesh are taken as aggregate, 220 DEG C are heated to, 10g is added
Epoxy resin E-35 (637) and 5g curing agent phthalic anhydrides, stirring add after being cooled to 150 DEG C
Enter 10g PPOXs (purchased from Shanghai Zhen Zhun bio tech ltd) and (purchase of 0.05g Arabic gums
From Nanjing Sen Beijia bio tech ltd), stir.Cooling, screening, obtain this comparative example
From suspended prop.
Testing example 1
The preparation of active water：By the PAMA of 0.25g, (weight average molecular weight is 3 × 106)
It is dissolved in the water of 488.65g, is well mixed, obtains viscous water；The OP-10 of 1g is dissolved in acquisition
In viscous water, it is well mixed；10g potassium chloride is added, is stirred；Add 0.1g formaldehyde, stirring
Uniformly.
Test method：By embodiment 1-8, comparative example 1-5 from suspended prop respectively in active water
Liquid viscosity, solid-carrying performance and frictional resistance parameter testing are carried out, viscosity determining procedure is referring to standard
(SYT5107-2005)；Sinking speed is determined and uses 0.5m lucite tubes, loads 45cm work high
Property water and sand than the proppant for 30%, shake up the sinking speed of test proppant；Frictional resistance uses DV-III
Viscosimeter, configuration 30% sand than pressure break system, rotating speed is 100rpm, and the moment of torsion for determining them carrys out table
Levy the frictional resistance of proppant.Test result is as shown in table 1 below：
Table 1
From table 1 data can be seen that prepared by expanding material composition of the invention from suspended prop
Possess excellent prop-carrying capacity and drop frictional resistance ability in active water.From embodiment 1-8 and comparative example 1-5
Data Comparison can be seen that prepared by expanding material composition of the invention from suspended prop with do not make
The proppant aggregate of any cladding and only coat binding agent and compared with the proppant aggregate of curing agent, its
Sinking speed and frictional resistance are lower, and the viscosity of the active water for obtaining is also smaller, illustrate expanding material of the invention
Prepared by composition possesses more excellent prop-carrying capacity and drop frictional resistance ability from suspended prop；It is of the invention
Be applied in combination for polyvinylpyrrolidone and natural macromolecular material by expanding material composition, than being used alone
Polyvinylpyrrolidone is used alone natural macromolecular material all with more preferable effect；And use other
The resulting effect that water soluble polymer substitutes polyvinylpyrrolidone is poor.From the number of embodiment 4-6
According to it can also be seen that when doing aggregate using precoated sand, by expanding material composition of the invention prepare from
The prop-carrying capacity and drop frictional resistance ability of suspended prop are more prominent.
Testing example 2
The proppant of embodiment 1-8, comparative example 1-5 is carried out into liquid viscosity in clear water respectively, sand is taken
Performance and frictional resistance parameter testing, viscosity determining procedure is referring to standard (SYT5107-2005)；Sedimentation speed
Degree is determined and uses 0.5m lucite tubes, loads 45cm active waters high and sand than the support for 30%
Agent, shakes up the sinking speed of test proppant；Frictional resistance use DV-III viscosimeters, configuration 30% sand than
Pressure break system, fixed rotating speed and rotor, determine their moment of torsion to characterize.Test result is as shown in table 2：
Table 2
Data can be seen that existing from suspended prop for water-soluble composition preparation of the invention from table 2
Possess excellent prop-carrying capacity and drop frictional resistance ability in riverfrac treatment system.
Testing example 3：
Liaohe Oil Field, certain horizontal well, well depth 1900m.Degassing viscosity of thickened oil 5620mPas (50 DEG C),
Initial reservoir pressure 10MPa.38 DEG C of the temperature of the original reservoir.
Natural water used is the clear water of crawl discharge, estimates no solid particle.Proppant used is real
Apply example 5 from suspended prop.
, used as prepad fluid, frozen glue used is the aqueous solution of 0.4% hydroxypropyl guar gum for step one, configuration frozen glue
It is crosslinked through borax and is obtained.
Step 2, connection pressing crack construction pipeline, using prepad fluid frozen glue pressure testing, and press off target reservoir.
Step 3, in the state of continuously stirring, with 2.38m3Clear water is pumped into fracturing blender truck by the flow of/min,
Simultaneously with 1.02m3The speed of/min is well mixed fracturing blender truck is conveyed into from suspended prop.
Step 4, well mixed suspension, mesh is pumped into via pressure break pump truck with mulling identical speed
Mark Reservoir Fracture.
Work progress pressure is steady, whole process 1.5 hours, and construction finishes the closing well row of returning after 3 hours.
Return discharge opeing limpid, 10 hours rows of returning are thoroughly.Initial stage daily output liquid 2.8m3/ d, oil-producing 1.7m3/ d, and faces
Well routine guar gum frozen glue pressure break is compared, output increased 13%.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality
The detail in mode is applied, in range of the technology design of the invention, can be to technical side of the invention
Case carries out various simple variants, and these simple variants belong to protection scope of the present invention.
It is further to note that each particular technique described in above-mentioned specific embodiment is special
Levy, in the case of reconcilable, can be combined by any suitable means.In order to avoid need not
The repetition wanted, the present invention is no longer separately illustrated to various possible combinations.
Additionally, can also be combined between a variety of implementation methods of the invention, as long as its
Without prejudice to thought of the invention, it should equally be considered as content disclosed in this invention.
Claims (16)
1. a kind of expanding material composition, it is characterised in that the composition includes polyvinylpyrrolidine
The mass ratio of ketone and natural macromolecular material, the polyvinylpyrrolidone and the natural macromolecular material
It is (50-1200)：1, the natural macromolecular material is natural plant gum family macromolecule material and/or animal glue
Family macromolecule material.
2. composition according to claim 1, it is characterised in that the polyvinylpyrrolidone
Weight average molecular weight be 5000-1500000.
3. composition according to claim 1, it is characterised in that the polyvinylpyrrolidone
It is selected from anionic polyvinylpyrrolidone, cationic polyvinylpyrrolidone and the poly- second of nonionic
At least one in alkene pyrrolidone.
4. according to the composition described in claim 1 or 3, it is characterised in that the polyvinylpyrrolidine
Ketone is anionic polyvinylpyrrolidone.
5. composition according to claim 1, it is characterised in that the natural plant gum macromolecule material
Material is selected from least one in Arabic gum, tragacanth, locust bean gum and rubber made from soybean cake.
6. composition according to claim 1, it is characterised in that the animal glue family macromolecule
Material is selected from least one in gelatine, gelatin and casein.
7. one kind is from suspended prop, it is characterised in that described to include proppant sheet from suspended prop
Body and cladding or part are coated on the intumescent material of proppant body surface, and the intumescent material is by right
It is required that the expanding material composition in 1-6 described in any one bonded through binding agent and curing agent and coat or
Part is coated on the proppant body and is formed；The expanding material composition and the proppant body
Mass ratio be 1：(50-1500)；The weight ratio of the proppant body, binding agent and curing agent is 1：
(0.001-0.5)：(0.001-0.5).
8. it is according to claim 7 from suspended prop, it is characterised in that the proppant sheet
Body is aggregate and/or pre-coated membrane bone material.
9. it is according to claim 8 from suspended prop, it is characterised in that the aggregate is choosing
From quartz sand, haydite, metallic particles, globular glass particle, sintered bauxite, sintered alumina, burning
At least one in the shell particle of knot zirconium oxide, synthetic resin and crushing；The particle diameter of the aggregate is
6-200 mesh.
10. it is according to claim 8 from suspended prop, it is characterised in that the pre-coated membrane bone
Material is to include that aggregate and cladding or part are coated on the pre- film covered resin layer of aggregate surface.
11. is according to claim 10 from suspended prop, it is characterised in that the pre- overlay film
Resin bed be resin material obtained by the coated treatment of aggregate surface, the resin material is selected from phenolic aldehyde tree
At least one in fat, furane resins and epoxy resin.
12. is according to claim 7 from suspended prop, it is characterised in that the binding agent is
Selected from least in phenolic resin, epoxy resin, unsaturated polyester resin and heterocyclic polymer binding agent
Kind；The curing agent is selected from aliphatic amine and its addition product, tertiary amine and its salt, aromatic amine and its changes
Gonosome, imidazoles, acid anhydrides, acyl peroxide, lipid peroxidation, paraformaldehyde, phenolic aldehyde amine, diethylenetriamine,
At least one in triethylene tetramine and hexamethylenetetramine.
The preparation method from suspended prop in 13. claim 7-12 described in any one, it is special
Levy and be, the method is comprised the following steps：
(1) by proppant body and binding agent and curing agent, dispersion mixing is uniform at the first temperature, its
In, the weight ratio of the proppant body, binding agent and curing agent is 1：(0.001-0.5)：(0.001-0.5)；
(2) dispersion mixing is uniform at the second temperature to make the proppant body and expanding material composition
So that the expanding material composition cladding or part are coated on the proppant body, graininess is obtained
From suspended prop, wherein, the expanding material composition is with the mass ratio of the proppant body
1：(50-1500).
14. preparation methods according to claim 13, it is characterised in that first temperature is
100-300℃；The second temperature is 50-200 DEG C.
In 15. claim 7-12 described in any one from suspended prop in terms of fluid ore deposit exploitation
Application.
16. applications according to claim 15, it is characterised in that the fluid ore deposit includes natural
At least one in gas, oil, shale gas, shale oil, fresh water and salt solution.
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