CN106928991A - Expanding material composition containing polyethylene glycol and the application from suspended prop and proppant and preparation method - Google Patents
Expanding material composition containing polyethylene glycol and the application from suspended prop and proppant and preparation method Download PDFInfo
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- CN106928991A CN106928991A CN201511025457.9A CN201511025457A CN106928991A CN 106928991 A CN106928991 A CN 106928991A CN 201511025457 A CN201511025457 A CN 201511025457A CN 106928991 A CN106928991 A CN 106928991A
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- material composition
- proppant
- expanding material
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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
- 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
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/66—Compositions based on water or polar solvents
- C09K8/68—Compositions based on water or polar solvents containing organic compounds
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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
- C09K8/885—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained otherwise than 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
Abstract
The invention discloses a kind of expanding material composition containing polyethylene glycol and the application from suspended prop and proppant and preparation method.Expanding material composition of the invention is coated on proppant body, expanding material composition can be with Fast-swelling in water, firm hydrated sheath is formed in proppant particles outer surface, reduce the relative density of proppant particles, a small amount of organic molecule in composition can be stretched in water, increase the viscosity of water, this is also beneficial to suspension of the proppant particles in water.Simultaneously, it is of the invention can be easy to operate without configuring fracturing fluid using water as fracturing fluid from suspended prop, equipment is simple, avoid and use organic solvent, it is also possible to reduce the viscosity of fracturing fluid, reduce the conveying difficulty of fracturing fluid, and without additionally adding macromolecular compound in fracturing fluid, macromolecular compound is avoided as fracturing fluid enters underground, oil-gas mining hole is blocked, pollution of the macromolecular compound to ground environment is decreased.
Description
Technical field
The present invention relates to fluid ore deposit exploitation field, in particular it relates to a kind of expanding material composition containing polyethylene glycol and
Application and preparation method from suspended prop and proppant.
Background technology
Often needed by fracturing technique in the recovery process of the fluid ore deposit such as oil, natural gas, i.e., using hydraulic action, made
Oil-gas Layer forms a kind of method in crack, so also known as hydraulic fracturing.Hydraulic fracturing is exactly using ground high-pressure pump, by pit shaft
To oil reservoir fracturing fluid of the squeezing with viscosity higher.When the speed for injecting fracturing fluid exceedes the absorbability of oil reservoir, then in well
Pressure very high is formed on base oil layer, when this pressure exceedes the shaft bottom fracture pressure of reservoir rock nearby, oil reservoir will be pressed
Open and produce crack.At this moment, fracturing fluid on and on is squeezed to oil reservoir, crack will continue to oil reservoir interior expansion.In order to
The crack that holding is pressed off is in open configuration, then clamp-ons the load fluid with proppant particles to oil reservoir, and load fluid entrance is split
After seam, crack on the one hand can be made to continue to extend forward, on the other hand can support the crack for having pressed off, be not it
Closure.Followed by injection displacement fluid, the load fluid of pit shaft is all replaced and enters crack, fracture support is got up with proppant.
Finally, outside the high viscosity fracturing fluid of injection can automatically degrade discharge pit shaft, one or more length is left in oil reservoir
The crack do not waited, makes to set up a new fluid passage between oil reservoir and pit shaft.After pressure break, oil gas well yield typically can
Increase substantially.
In existing proppant-fracturing fluid system, in order to prevent proppant particles from settling, it usually needs high viscosity pressure break stream
Body makes particle suspend, and this fracturing fluid generally increases as thickener the viscous of fluid by adding water miscible polymer
Degree.But needed in this fracturing work it is special with liquid operation and equipment, while by high-viscosity fracturing fluid feeding underground
The pump power consumed when specified location and the row of returning is larger, and the macromolecular compound used in fracturing fluid enters in company with fracturing fluid
Stratum, being partially left at the macromolecular compound of underground can block the hole on stratum, cause oil pump capacity to decline and can cause stratum
Pollution.
The content of the invention
It is an object of the invention to provide a kind of expanding material composition containing polyethylene glycol and from suspended prop and support
The application of agent and preparation method, by the expanding material composition can apply to prepare relative density it is low, can be in clear water
Suspend from suspended prop, to solve to need high viscosity fracturing fluid to carry out suspended proppant particles in the prior art, and high viscous
The fracturing fluid of degree causes the technical problem of fracturing fluid difficulty of transportation, while the macromolecular compound added in can solving fracturing fluid
Block fuel-displaced hole and the technical problem polluted to stratum.
To achieve these goals, the present invention provides a kind of expanding material composition containing polyethylene glycol, the expanding material
Composition contains polyethylene glycol and semi-synthetic macromolecular material, wherein, it is described hemizygous relative to the polyethylene glycol of 100 weight portions
Content into macromolecular material is 50-300 weight portions, and the semi-synthetic macromolecular material is modified starch.
The present invention also provides one kind from suspended prop, should include proppant body and cladding or part from suspended prop
The water-soluble intumescent material on the proppant body is coated on, the water-soluble intumescent material passes through binding agent and solidification
Agent makes above-mentioned expanding material composition bond and coat or part is coated on the proppant body, relative to 100 weight
The proppant body of part, the consumption of the binding agent is 2-80 weight portions, and the consumption of the curing agent is 0.02-8 weight portions, institute
The consumption for stating expanding material composition is 2-80 weight portions.
The present invention also provides the above-mentioned preparation method from suspended prop, and 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, obtains being stained with viscous
Knot agent and/or the granular aggregates of curing agent, relative to the proppant body of 100 weight portions, the consumption of the binding agent is 2-
80 weight portions, the consumption of the curing agent is 0.02-8 weight portions；
(2) dispersion mixing is uniform so that described swollen at the second temperature to make the granular aggregates and expanding material composition
Swollen material compositions are coated in the granular aggregates, obtain granular from suspended prop, wherein, relative to 100 weights
The proppant body of part is measured, the consumption of the expanding material composition is 2-80 weight portions.
The present invention also provides the above-mentioned application from suspended prop in terms of fluid ore deposit exploitation.
By above-mentioned technical proposal, expanding material composition is coated on proppant body surface, expanding material composition
Firm hydrated sheath can be formed in proppant particles outer surface with Fast-swelling in water, reduced from suspended proppant particles
Relative density, a small amount of organic molecule in expanding material composition can be stretched in water, increase the viscosity of water, and this is also favourable
In the suspension from suspended proppant particles in water.Meanwhile, it is of the invention can be using water as fracturing fluid, nothing from suspended prop
Fracturing fluid need to be configured, easy to operate, equipment is simple, it is to avoid use organic solvent, it is also possible to reduce the viscosity of fracturing fluid, reduced
The conveying difficulty of fracturing fluid, and without additionally adding macromolecular compound in fracturing fluid, it is to avoid macromolecular compound with
Fracturing fluid enters underground, blocks oil-gas mining hole, decreases pollution of the macromolecular compound to ground environment.
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 described herein specific
Implementation method is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The present invention provides a kind of expanding material composition containing polyethylene glycol, and the expanding material composition contains polyethylene glycol
With semi-synthetic macromolecular material, wherein, relative to the polyethylene glycol of 100 weight portions, the content of the semi-synthetic macromolecular material
It is 50-300 weight portions, and the semi-synthetic macromolecular material is modified starch.By expanding material composition of the invention cladding
In proppant body surface, expanding material composition can form firm with Fast-swelling in water in proppant particles outer surface
Hydrated sheath, reduce the relative density from suspended proppant particles, a small amount of organic molecule in expanding material composition can be with
It is stretched in water, increases the viscosity of water, this is also beneficial to the suspension in water from suspended proppant particles.Meanwhile, it is of the invention
From suspended prop can be using water as fracturing fluid, easy to operate without configuring fracturing fluid, equipment is simple, it is to avoid using having
Machine solvent, it is also possible to reduce the viscosity of fracturing fluid, reduces the conveying difficulty of fracturing fluid, and without additionally adding high in fracturing fluid
Molecular compound, it is to avoid macromolecular compound enters underground with fracturing fluid, blocks oil-gas mining hole, decreases high score
Pollution of the sub- compound to ground environment.
According to the present invention, the implication of polyethylene glycol is well known to those skilled in the art, and is water-soluble polymer, with such as
Structural formula shown in formula (1), wherein, the value of n is not required particularly, can be well known to those skilled in the art, example
If n can be 1-103Integer.Containing a large amount of hydrophilic polar groups in the molecule of polyethylene glycol, solubility property is good in water,
In being conducive to polar group of the expanding material composition in water in Fast-swelling, and polyethylene glycol and can extending water, side
The hydrated sheath of stabilization formation is helped, further to make proppant particles suspend in water.
According to the present invention, the weight average molecular weight of polyethylene glycol can change in very large range, for example, can be 50-
20000, under preferable case, the weight average molecular weight of polyethylene glycol can be 200-8000, and weight average molecular weight is within the above range
Polyethylene glycol has suitable dissolubility in water so that the expanding material composition of composition has suitable swelling character,
The hydrated sheath with Suitable Density can be formed in water, so as to reduce the global density of proppant particles, it is suspended in the water surface
On.The polyethylene glycol for meeting above-mentioned condition can be commercially available, for example, the PEG 200, PEG of Dow Chemical production
300th, PEG400, PEG 600, PEG 1000, PEG 1450, PEG 3350, PEG 4000, polyethylene glycol of PEG 8000 etc..
According to the present invention, semi-synthetic macromolecular material can be modified starch.Wherein, specifically, modified starch can be with excellent
Elect as selected from CMS, HES, cyanoethyl starch, acetate starch, phosphate ester starch, cationic starch and gather
Close one or more in starch, more preferably CMS.The semi-synthetic macromolecular material of mentioned kind can with it is poly-
Acrylamide constitutes expanding material composition, and can make the swelling behavior of expanding material composition increases, meanwhile, relative to artificial
The macromolecular material of synthesis, degradable semi-synthetic macromolecular material can reduce the pollution to environment.Meet above-mentioned condition
Semi-synthetic macromolecular material can be commercially available, for example, the CMS of Renqiu City Hao Chun Chemical Co., Ltd.s；It is purchased from
Hetastarch 200/0.5 of Xi'an Kang Nuo Chemical Co., Ltd.s；Formed sediment purchased from the acetic acid of Zhengzhou Kang Yuan chemical products Co., Ltd
Powder, starch phosphate；Purchased from Dongguan Dongmei Food Co., Ltd. cationic starch DM933c.
The present invention also provides one kind from suspended prop, should include proppant body and cladding or part from suspended prop
The water-soluble intumescent material on the proppant body is coated on, the water-soluble intumescent material passes through binding agent and solidification
Agent makes above-mentioned expanding material composition bond and coat or part is coated on the proppant body, relative to 100 weight portions
Proppant body, the consumption of the binding agent is 2-80 weight portions, and the consumption of the curing agent is 0.02-8 weight portions, described
The consumption of expanding material composition is 2-80 weight portions.It is of the invention that expanding material composition is coated on branch from suspended prop
Support agent body outer surface forms the proppant particles for having coated water-soluble expanding material, and the proppant particles enter when in water, table
The expanding material composition in face can be dissolved rapidly or swelling, and one layer of hydrated sheath of expansion is formed on proppant particles surface, be made
The density for obtaining proppant particles is substantially reduced, so as to be suspended on the water surface.
According to the present invention, above-mentioned proppant body can be aggregate and/or pre-coated membrane bone material.
Wherein, aggregate can be that existing various can be used in preparing from the aggregate of suspended prop, under preferable case, bone
Material can be selected from quartz sand, haydite, metallic particles, globular glass particle, sintered bauxite, sintered alumina, sintering oxidation
Zirconium, synthetic resin, precoated sand, crush shell particle in one or more.The aggregate density of mentioned kind is suitable, thermally-stabilised
Property it is good and intensity is higher, it is possessed into good power with expanding material composition of the invention is prepared from suspended prop
Learn performance.
According to the present invention, pre-coated membrane bone material can be coated on the pre- of aggregate surface including above-mentioned aggregate and cladding or part
Film covered resin layer.Wherein, pre- film covered resin layer is preferably and contains phenolic resin, epoxy resin, furane resins, polyester resin and not
One or more in saturated polyester resin.Specifically, above-mentioned pre- film covered resin can be selected from well known to those skilled in the art
Species, for example can be bisphenol A type epoxy resin, bisphenol f type epoxy resin, thermoplastic phenolic resin, thermosetting phenolic tree
Fat, 3301 unsaturated polyester resins, dimethylbenzene unsaturated polyester resin or furfuryl alcohol resin.
According to the present invention, the average particulate diameter of proppant body can change in very large range, it is possible to according to reality
Border needs reasonably to be selected, for example, the particle diameter of proppant body can be 6-200 mesh, preferably can be 10-100 mesh.
According to the present invention, the species of above-mentioned binding agent can be well known to those skilled in the art for from suspension support
The conventional binding agent of agent preparation field, it is preferable that binding agent can be selected from phenolic resin, epoxy resin, unsaturated polyester (UP) tree
One or more in fat, heterocyclic polymer bonding agent.The binding agent of mentioned kind is for expanding material composition and graininess
The bond effect of aggregate more preferably, and will not make to reunite and influence the particle size from suspended prop from suspended proppant particles
And dispersiveness.
Preferably, phenolic resin can be thermoplastic phenolic resin or thermosetting phenolic resin；Epoxy resin can be used
Epoxide equivalent is the epoxy resin of 0.09-0.14mol/100g；Preferably bisphenol A type epoxy resin, more preferably epoxy resin E-
55(616)、E-51(618)、E-44(6101)、E-42(634)、E-35(637)、E-20(601)、E-12(604)、E-06
(607)、E-03(609)；Unsaturated polyester resin can be m-phthalate unsaturated polyester resin, metaphenylene unsaturated polyester (UP) tree
Fat, xylol type unsaturated polyester resin, Bisphenol a unsaturated polyester resin, halo unsaturated polyester resin, vinyl esters tree
One or more in fat；It is preferred that m-phthalate unsaturated polyester resin model can be 191 or 196；Metaphenylene unsaturated polyester (UP)
Resin model can be that 199, xylol type unsaturated polyester resin resin model can be in 2608,902A3, Xm-1, Xm-2
One or more；Bisphenol a unsaturated polyester resin model can be one or more in 197,3301,323；Heterocycle is high
Molecular adhesion agent can be selected from one or more in polyimides, polybenzimidazoles, polyphenylene sulfide, polydiphenyl ether.
It is above-mentioned also from suspended prop under preferable case in order to improve the covering property of binding agent according to the present invention
Can be well known to those skilled in the art with the species including curing agent, curing agent, for example can for 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, six
One kind in methine tetramine, phenolic aldehyde amine, diethylenetriamine, triethylene tetramine, the consumption of curing agent can be art technology
Known to personnel, preferably hardener dose can be the 0.5-10% of weight of binder.
The present invention also provides the above-mentioned preparation method from suspended prop, and 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, obtains being stained with viscous
Knot agent and/or the granular aggregates of curing agent, wherein, relative to the proppant body of 100 weight portions, the consumption of the binding agent
It is 2-80 weight portions, the consumption of the curing agent is 0.02-8 weight portions；
(2) dispersion mixing is uniform so that described swollen at the second temperature to make the granular aggregates and expanding material composition
Swollen material compositions are coated in the granular aggregates, obtain granular from suspended prop, wherein, relative to 100 weights
The proppant body of part is measured, the consumption of the expanding material composition is 2-80 weight portions.
Preparation method from suspended prop of the invention can proppant body surface coat binding agent, curing agent and
Expanding material composition, the water-soluble expanding material of the cladding for obtaining can be using water as fracturing fluid, together from suspended prop
When, the expanding material composition from suspended prop surface is rapid swelling in water, forms the hydrated sheath of expansion, reduces and suspends certainly
The relative density of proppant particles, 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, bonded to improve water-soluble expanding material cladding
The covered effect of agent, granular aggregates may be pretreated, and processing method is well known to those skilled in the art, for example, excellent
Selection of land can first pass through the steps such as scouring, drying, screening, to remove the moisture in aggregate, be easy to aggregate preferably with binding agent
With reference to.
In the preparation method from suspended prop of the invention, the first Contact Temperature and the second Contact Temperature do not have
It is special to require, as long as meet above-mentioned binding agent can melt to be coated on water-soluble expanding material under the first Contact Temperature
Grain surface；Above-mentioned expanding material composition can be bonded under the second Contact Temperature with binding agent.Under preferable case, first
Temperature can be 150-240 DEG C；Second temperature can be 100-190 DEG C.At the temperature disclosed above, binding agent can be uniformly wrapped on
Aggregate surface, expanding material composition can be adhere closely on binding agent, obtain what expanding material composition was uniformly coated
From suspended proppant particles.
The present invention also provides the above-mentioned application from suspended prop in terms of fluid ore deposit exploitation.
According to the present invention, the exploitation of fluid ore deposit can specifically include natural gas, oil, shale oil, shale gas, fresh water, salt
The exploitation of water, hot water.Preferably, fluid ore deposit can be one or more in oil, natural gas, shale oil and shale gas.
The present invention is further illustrated below by embodiment, but the present invention is not therefore subject to any restriction.At this
In following embodiments of invention, quartz sand, globular glass particle and haydite are purchased from Hebei Jing Hang mineral products Co., Ltd；Sintering oxygen
Change aluminium and sintered zirconia is purchased from Jiaxing Jie Naier hard alloy Co., Ltd；Polyethylene glycol is purchased from Dow Chemical, remaining
Reagent is commercially available prod.
Embodiment 1
The present embodiment is used to illustrate expanding material composition of the invention and is prepared from suspension by expanding material composition
The preparation method of proppant and from suspended prop.
The expanding material composition of the present embodiment is the polyethylene glycol (weight average molecular weight 200) and 50 weight of 100 weight portions
The CMS (Renqiu City Hao Chun Chemical Co., Ltd.s) of part.
(1) with quartz sand (particle diameter is 6-10 mesh) as raw material, after scouring, 120 DEG C of drying 5h, the quartz of screening 6-40 mesh
Sand is aggregate；
(2) quartz sand of 100 weight portions screening is taken, 240 DEG C are heated to, the weight portions of epoxy resin E-51 (618) 2 are added,
The weight portion of curing agent phthalic anhydride 0.02, is uniformly mixed the granular aggregates for obtaining binding agent cladding；
(3) when the temperature of the granular aggregates of above-mentioned binding agent cladding is down to 190 DEG C, the above-mentioned expansion material of 2 weight portions is added
Feed composition, is uniformly mixed.
(4) cool down, broken, screening, the present embodiment for obtaining from suspended prop.
Embodiment 2
The present embodiment is used to illustrate expanding material composition of the invention and is prepared from suspension by expanding material composition
The preparation method of proppant and from suspended prop.
The expanding material composition of the present embodiment is the polyethylene glycol (weight average molecular weight 8000) and 300 weights of 100 weight portions
Measure the HES (Xi'an Kang Nuo Chemical Co., Ltd.s, 200/0.5) of part.
(1) 100 weight portion haydites (particle diameter is 100-200 mesh) are taken, 190 DEG C are heated to, adds 80 parts by weight binder double
Phenol A types unsaturated polyester (UP) 3301, adds the weight portion of curing agent phthalic anhydride 8, is uniformly mixed and obtains binding agent cladding
Granular aggregates；
(2) when the temperature of the granular aggregates of above-mentioned binding agent cladding is down to 100 DEG C, the above-mentioned expansion of 80 weight portions is added
Material compositions, are uniformly mixed.
(3) cool down, broken, screening, the present embodiment for obtaining from suspended prop.
Embodiment 3
The present embodiment is used to illustrate expanding material composition of the invention and is prepared from suspension by expanding material composition
The preparation method of proppant and from suspended prop.
The expanding material composition of the present embodiment is the polyethylene glycol (weight average molecular weight 400) and 85 weight of 100 weight portions
The acetic starch (Zhengzhou Kang Yuan chemical products Co., Ltd) of part.
(1) 100 weight portion globular glass particles (particle diameter is 10-50 mesh) are taken, 210 DEG C are heated to, adds 14 weight portions to glue
Knot agent epoxy resin E-44, stirring adds the weight portion of curing agent diethylenetriamine 2.2, is uniformly mixed and obtains binding agent bag
The granular aggregates covered；
(2) when the temperature of the granular aggregates of above-mentioned binding agent cladding is down to 150 DEG C, the above-mentioned expansion of 14 weight portions is added
Material compositions, are uniformly mixed.
(3) cool down, broken, screening, the present embodiment for obtaining from suspended prop.
Embodiment 4
The present embodiment is used to illustrate expanding material composition of the invention and is prepared from suspension by expanding material composition
The preparation method of proppant and from suspended prop.
The expanding material composition of the present embodiment is the polyethylene glycol (weight average molecular weight 600) and 270 weight of 100 weight portions
The starch phosphate (Zhengzhou Kang Yuan chemical products Co., Ltd) of part.
(1) 100 weight portion sintered aluminas (particle diameter is 10-50 mesh) are taken, 150 DEG C are heated to, adds 64 weight portions to bond
Agent thermoplastic phenolic resin, adds the weight portion of curing agent phthalic anhydride 5, be uniformly mixed obtain binding agent cladding
Granular aggregate；
(2) when the temperature of the granular aggregates of above-mentioned binding agent cladding is down to 110 DEG C, the above-mentioned expansion of 55 weight portions is added
Material compositions, are uniformly mixed.
(3) cool down, broken, screening, the present embodiment for obtaining from suspended prop.
Embodiment 5
The present embodiment is used to illustrate expanding material composition of the invention and is prepared from suspension by expanding material composition
The preparation method of proppant and from suspended prop.
The expanding material composition of the present embodiment is the polyethylene glycol (weight average molecular weight 1000) and 70 weight of 100 weight portions
The starch phosphate (Zhengzhou Kang Yuan chemical products Co., Ltd) of part and the cationic starch of 50 weight portions are (purchased from Dongguan east tasteable
Co., Ltd, DM933c).
(1) 100 weight portion sintered zirconias (particle diameter is 10-100 mesh) are taken, 160 DEG C are heated to, adds 35 weight portions to bond
Agent polyimides, adds the weight portion of curing agent triethylamine 4, is uniformly mixed the granular aggregates for obtaining binding agent cladding；
(2) when the temperature of the granular aggregates of above-mentioned binding agent cladding is down to 125 DEG C, the above-mentioned expansion of 40 weight portions is added
Material compositions, are uniformly mixed.
(3) cool down, broken, screening, the present embodiment for obtaining from suspended prop.
Embodiment 6
The present embodiment is used to illustrate expanding material composition of the invention and is prepared from suspension by expanding material composition
The preparation method of proppant and from suspended prop.
Prepared from suspended prop using expanding material composition same as Example 1 and preparation method, it is different
It is that CMS is replaced with etc. the cationic starch (purchased from Dongguan Dongmei Food Co., Ltd., DM933c) of weight.
Embodiment 7
The present embodiment is used to illustrate expanding material composition of the invention and is prepared from suspension by expanding material composition
The preparation method of proppant and from suspended prop.
Prepared from suspended prop using expanding material composition same as Example 1 and preparation method, it is different
It is that the weight average molecular weight of polyethylene glycol is 100.
Embodiment 8
The present embodiment is used to illustrate expanding material composition of the invention and is prepared from suspension by expanding material composition
The preparation method of proppant and from suspended prop.
Prepared from suspended prop using expanding material composition same as Example 1 and preparation method, it is different
It is that the particle diameter of quartz sand is 300 mesh.
Comparative example 1
This comparative example is used to illustrating different from suspended prop and preparation method with of the invention.
This comparative example from suspended prop be the quartz sand that does not do any treatment.
Comparative example 2
(1) with quartz sand (particle diameter is 6-10 mesh) as raw material, after scouring, 120 DEG C of drying 5h, the quartz of screening 6-40 mesh
Sand is aggregate；
(2) quartz sand of 100 weight portions screening is taken, 240 DEG C are heated to, the weight portions of epoxy resin E-51 (618) 2 are added,
Add the weight portion of curing agent phthalic anhydride 0.02, be uniformly mixed obtain this comparative example from suspended prop.
Comparative example 3
Prepared from suspended prop using expanding material composition same as Example 1 and preparation method, it is different
It is to be added without CMS in expanding material composition.
Comparative example 4
Prepared from suspended prop using expanding material composition same as Example 1 and preparation method, it is different
It is to be added without polyethylene glycol in expanding material composition.
Comparative example 5
Prepared from suspended prop using expanding material composition same as Example 1 and preparation method, it is different
It is that polyethylene glycol is replaced with etc. the PPOX (purchased from Jiangsu Hai'an Petrochemical Plant, PPG8000) of weight
Testing example 1
The preparation of active water：The PAMA (3,000,000) of 0.25g is dissolved in the water of 488.65g, mixing is equal
It is even, obtain viscous water；The OP-10 of 1g is dissolved in the viscous water of acquisition, is well mixed；10g potassium chloride is added, stirring is equal
It is even；0.1g formaldehyde is added, is stirred.
Test method：Embodiment 1-8, comparative example 1-5 are carried out liquid in active water and glue respectively from suspended prop
Degree, solid-carrying performance and frictional resistance parameter testing, viscosity determining procedure is referring to standard (SYT5107-2005)；Sinking speed is determined and adopted
0.5m lucite tubes are used, loads 45cm active waters high and sand than the proppant for 30%, shake up the sedimentation of test proppant
Speed；Frictional resistance use DV-III viscosimeters, configuration 30% sand than pressure break system, rotating speed is 100rpm, determines their moment of torsion
To characterize the frictional resistance of proppant.Test result is as shown in table 1 below：
Table 1
| Active water viscosity/mpas | Sinking speed/cmmin-1 | Moment of torsion/% | |
| Embodiment 1 | 1.09 | 0.07 | 19 |
| Embodiment 2 | 1.09 | 0.08 | 19 |
| Embodiment 3 | 1.14 | 0.07 | 20 |
| Embodiment 4 | 1.08 | 0.07 | 22 |
| Embodiment 5 | 1.15 | 0.16 | 25 |
| Embodiment 6 | 1.16 | 0.15 | 25 |
| Embodiment 7 | 1.21 | 1.32 | 33 |
| Embodiment 8 | 1.17 | 1.29 | 34 |
| Comparative example 1 | 3.99 | 80 | 41 |
| Comparative example 2 | 2.98 | 50 | 35 |
| Comparative example 3 | 1.78 | 24 | 32 |
| Comparative example 4 | 1.99 | 27 | 36 |
| Comparative example 5 | 2.67 | 39 | 37 |
From table 1 data can be seen that prepared by expanding material composition of the invention from suspended prop in active water
In possess excellent prop-carrying capacity and drop frictional resistance ability.Expanding material composition of the invention is coated on proppant this body surface
Face, expanding material composition can form firm hydrated sheath with Fast-swelling in water in proppant particles outer surface, reduce
From the relative density of suspended proppant particles, a small amount of organic molecule in expanding material composition can be stretched in water, increased
The viscosity of water, this is also beneficial to the suspension in water from suspended proppant particles.Without additionally adding producing high-molecular in fracturing fluid
Compound, reduces the viscosity of fracturing fluid, reduce the conveying difficulty of fracturing fluid, it is to avoid macromolecular compound enters with fracturing fluid
Underground, blocks oil-gas mining hole, decreases pollution of the macromolecular compound to ground environment.
Oneself of expanding material composition preparation of the invention is can be seen that from the Data Comparison of embodiment 1 and comparative example 1-2
Compared with the proppant particles do not made the proppant aggregate of any cladding and only coated binding agent, it is settled suspended prop
Speed and frictional resistance are lower, and the viscosity of the active water for obtaining is also smaller, illustrate prepared by expanding material composition of the invention certainly outstanding
Floating proppant possesses more excellent prop-carrying capacity and drop frictional resistance ability.
Be can be seen that relative to poly- second two is used alone in comparative example 3 from the Data Comparison of embodiment 1 and comparative example 3-4
It is used alone semi-synthetic macromolecular material CMS in alcohol and comparative example 4, expanding material composition of the invention is by poly- second
Glycol and semi-synthetic macromolecular material are applied in combination with more preferable effect.Embodiment 1 can be seen with the Data Comparison of comparative example 5
Go out, proppant particles are coated relative to using other polymers, the proppant coated using expanding material composition of the invention
Particle has preferably from suspending power and drop frictional resistance ability.
From embodiment 1 dividing equally again in currently preferred polyethylene glycol is can be seen that with the Data Comparison of embodiment 7-8
Son amount is the particle diameter of the aggregate of 200-8000 and proppant in the case of 6-200 purposes, by expanding material composition of the invention
The prop-carrying capacity from suspended prop for preparing is more prominent with drop frictional resistance ability.
Testing example 2
The proppant of embodiment 1-8, comparative example 1-5 is carried out into liquid viscosity, solid-carrying performance in clear water respectively and is rubbed
Resistance parameter testing, viscosity determining procedure is referring to standard (SYT5107-2005)；Sinking speed is determined and uses 0.5m lucite tubes,
Load 45cm active waters high and sand than the proppant for 30%, shake up the sinking speed of test proppant；Frictional resistance uses DV-
III viscosimeters, 30% sand of configuration than pressure break system, fixed rotating speed and rotor determine their moment of torsion to characterize.Test result
As shown in table 2：
Table 2
| Clear water viscosity/mpas | Sinking speed/cmmin-1 | Moment of torsion/% | |
| Embodiment 1 | 1.09 | 0.05 | 20 |
| Embodiment 2 | 1.11 | 0.06 | 22 |
| Embodiment 3 | 1.17 | 0.09 | 22 |
| Embodiment 4 | 1.16 | 0.09 | 27 |
| Embodiment 5 | 1.15 | 0.12 | 25 |
| Embodiment 6 | 1.14 | 0.13 | 27 |
| Embodiment 7 | 1.16 | 3.9 | 33 |
| Embodiment 8 | 1.19 | 2.5 | 35 |
| Comparative example 1 | 3.01 | 270 | 59 |
| Comparative example 2 | 2.46 | 95 | 52 |
| Comparative example 3 | 1.59 | 21 | 38 |
| Comparative example 4 | 1.68 | 24 | 39 |
| Comparative example 5 | 1.92 | 46 | 43 |
From table 2 data can be seen that prepared by expanding material composition of the invention from suspended prop in clear water pressure
Split in system and possess excellent prop-carrying capacity and drop frictional resistance ability.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned implementation method
Detail, in range of the technology design of the invention, various simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned specific embodiment, in not lance
In the case of shield, can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy is no longer separately illustrated.
Additionally, can also be combined between a variety of implementation methods of the invention, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (15)
1. a kind of expanding material composition containing polyethylene glycol, it is characterised in that the expanding material composition contains polyethylene glycol
With semi-synthetic macromolecular material, wherein, relative to the polyethylene glycol of 100 weight portions, the content of the semi-synthetic macromolecular material
It is 50-300 weight portions, and the semi-synthetic macromolecular material is modified starch.
2. composition according to claim 1, it is characterised in that the weight average molecular weight of the polyethylene glycol is 200-
8000。
3. composition according to claim 1, it is characterised in that the modified starch is selected from CMS, hydroxyl
One or more in hydroxyethyl starch, cyanoethyl starch, acetic starch, starch phosphate, cationic starch and polymerization starch.
4. composition according to claim 3, it is characterised in that the modified starch is CMS.
5. one kind is from suspended prop, it is characterised in that should include that proppant body and cladding or part were wrapped from suspended prop
The water-soluble intumescent material on the proppant body is overlayed on, the water-soluble intumescent material passes through binding agent and curing agent
The expanding material composition in claim 1-4 described in any one is bonded and is coated or part is coated on the proppant sheet
On body, relative to the proppant body of 100 weight portions, the consumption of the binding agent is 2-80 weight portions, the use of the curing agent
It is 0.02-8 weight portions to measure, and the consumption of the expanding material composition is 2-80 weight portions.
6. it is according to claim 5 from suspended prop, it is characterised in that the proppant body is for aggregate and/or in advance
Overlay film aggregate.
7. according to claim 6 from suspended prop, wherein, the aggregate is selected from quartz sand, haydite, metal
In the shell particle of grain, globular glass particle, sintered bauxite, sintered alumina, sintered zirconia, synthetic resin and crushing
One or more.
8. according to claim 6 from suspended prop, wherein, the pre-coated membrane bone material is included described in claim 7
Aggregate and cladding or part are coated on the pre- film covered resin layer of aggregate surface.
9. according to claim 8 from suspended prop, wherein, the pre- film covered resin layer contains phenolic resin, epoxy
One or more in resin, furane resins, polyester resin and unsaturated polyester resin.
10. according to claim 5 or 6 from suspended prop, it is characterised in that the particle diameter of the proppant body is 6-
200 mesh.
11. is according to claim 5 from suspended prop, it is characterised in that the bonding agent is selected from phenolic resin, ring
One or more in oxygen tree fat, unsaturated polyester resin and heterocyclic polymer bonding agent；The curing agent be 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,
One or more in hexamethylenetetramine, phenolic aldehyde amine, diethylenetriamine and triethylene tetramine.
The preparation method from suspended prop described in 12. claims 5, it is characterised in that 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, obtains being stained with binding agent
And/or the granular aggregates of curing agent, relative to the proppant body of 100 weight portions, the consumption of the binding agent is 2-80 weights
Amount part, the consumption of the curing agent is 0.02-8 weight portions；
(2) dispersion mixing is uniform so that the expansion material at the second temperature to make the granular aggregates and expanding material composition
Feed composition is coated in the granular aggregates, obtains granular from suspended prop, wherein, relative to 100 weight portions
Proppant body, the consumption of the expanding material composition is 2-80 weight portions.
13. preparation methods according to claim 12, it is characterised in that first temperature is 150-240 DEG C；Described
Two temperature are 100-190 DEG C.
The application from suspended prop in terms of fluid ore deposit exploitation in 14. claim 5-11 described in any one.
15. applications according to claim 14, it is characterised in that the fluid ore deposit is selected from oil, natural gas, shale oil
With one or more in shale gas.
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