CN109321227A - A kind of thermosetting epoxy resin fracturing propping agents - Google Patents
A kind of thermosetting epoxy resin fracturing propping agents Download PDFInfo
- Publication number
- CN109321227A CN109321227A CN201710639675.4A CN201710639675A CN109321227A CN 109321227 A CN109321227 A CN 109321227A CN 201710639675 A CN201710639675 A CN 201710639675A CN 109321227 A CN109321227 A CN 109321227A
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- CN
- China
- Prior art keywords
- epoxy resin
- propping agents
- fracturing propping
- parts
- thermosetting
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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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
Abstract
The invention discloses a kind of thermosetting epoxy resin fracturing propping agents, belong to technical field of petroleum extraction.Thermosetting epoxy resin fracturing propping agents of the invention include following raw material according to the mass fraction: thermosetting epoxy resin is 100-200 parts；Foam microspheres or hollow glass microballoon are 1-10 parts；Methyl-silicone oil is 200-600 parts.Thermoset epoxy fracturing propping agents intensity height of the invention is non-breakable；The density of existing fracturing propping agents is dropped into 1.0 g/cm3Left and right；Use fracturing propping agents of the present invention that water can be directly used as fracturing fluid and meets environmental requirement, application value with higher using simple process.
Description
Technical field
The invention belongs to oil and gas exploration technology fields more particularly to a kind of thermosetting epoxy resin pressure break to support
Agent.
Background technique
With the needs of Chinese national economy fast development, the consumption of petroleum increases year by year.Petroleum resources is short at present
It lacks and coefficient of mining lowly causes waste, the problem of environmental pollution etc. during oil exploitation, so that cost of winning increases year by year
Add.
Fracturing technique is to improve the major measure of oil well output.During oil exploitation, high clossing pressure hyposmosis mine
Bed after frac treatment, split by oil gas rock stratum, and fracturing propping agents enter stratum in company with high-pressure solution and are filled in crack, plays
Supporting crack not stress release and be closed effect, keep high flow conductivity, increase the yield of petroleum gas.
Fracturing propping agents need the following to require:
1. proppant will have enough compression strength and antiwear property, it is resistant to crunch and frictional force when injection, and
Effectively support man-made fracture.
2. proppant particles relative density wants low, convenient for being pumped into underground.
3. in underground higher temperature conditions, with fracturing fluid and reservoir fluid chemical action does not occur for proppant particles, acid is molten
Solution degree maximum permissible value should be less than 7%.
Existing fracturing propping agents are mainly quartz sand and ceramic particle.But its common disadvantage be resistant to breakage ability compared with
Difference, density are big, it is necessary to and it is pressed into and is exported using fracturing fluid, used fracturing fluid causes serious pollution to the environment, complex process, if
Standby to require height, difficulty of construction is big.Currently, being badly in need of exploitation low-density, high-intensitive petroleum fracturing propping agent.
State Intellectual Property Office discloses on October 05th, 2016 application No. is CN201510058502.4, entitled branch
The patent of invention for supportting agent and preparation method thereof discloses a kind of proppant and preparation method thereof, belongs to oil-gas mining technical field.
The proppant includes aggregate and at least 2 layers of resin coating film for being coated on aggregate, and stating aggregate is quartz sand, haydite, glass
Microballoon, sintered alumina, burns the weight ratio of the aggregate and resin coating film for 100:3-100:13 at sintered bauxite；It is tied
The one or more of zirconium oxide, synthetic resin.
The above-mentioned prior art has the following problems: above-mentioned fracturing propping agents on aggregate using wrapping up thermosetting resin
Form, aggregate is generally adopted by the big substance of quartz sand, ceramic isodensity, cause the density of fracturing propping agents still compared with
Greatly, it need to be pressed into and be exported using fracturing fluid, prior art construction is difficult, is not easy to be pumped into underground.
Summary of the invention
The present invention is intended to provide a kind of thermosetting epoxy resin fracturing propping agents, the present invention is by directly selecting thermosetting property ring
Oxygen resin forming fracturing propping agents, and by adding a certain proportion of material for reducing density, solve prior art resistant to breakage energy
The problem of power is poor, density is big, uses fracturing fluid pollution environment and complex process；Fracturing propping agents in the present invention are that figure is high
Molecular material, intensity height are non-breakable；Percentage of damage is dropped to 11% or less；By the density of existing fracturing propping agents from 2-3 g/cm3
Drop to 1.0 g/cm3Left and right.
In order to achieve the above-mentioned object of the invention, technical scheme is as follows:
A kind of thermosetting epoxy resin fracturing propping agents, including following raw material according to the mass fraction:
Epoxy resin: 100-200 parts；
Expended microsphere or hollow glass microballoon: 1-10 parts；
Methyl-silicone oil: 200-600 parts.
Further, the invention also includes 3-90 parts of curing agent, 0-5 parts of promotor.
Further, the methyl-silicone oil that the present invention uses is one or more kinds of group of molecular weight 300-200000
It closes；Its viscosity is 10000-500000mPas.
Further, epoxy resin of the invention be selected from bisphenol A type epoxy resin E-51, bisphenol A type epoxy resin E-44,
Bisphenol A type epoxy resin E-20, bisphenol f type epoxy resin NPEF170, phenol aldehyde type epoxy resin F-44, phenol aldehyde type epoxy resin
One of F-51 and multifunction group epoxy AG-80 or two or more combinations.
Further, curing agent of the invention is selected from the one or more of dicyandiamide slurry, imidazoles, acid anhydrides or phenolic resin
Any combination；When using dicyandiamide slurry, dicyandiamide slurry is mixed to be made of the epoxy resin of 70wt%, the dicyandiamide of 30wt%
Close object.
Further, promotor of the invention is phenyl dimethylurea, 2, the modified ureas such as double dimethyl ureas of 4 toluene；DMP-30, N,
N- dimethyl benzylamine, the tertiary amines such as triethanolamine；2 methylimidazoles, 2-ethyl-4-methylimidazole, one kind of modified imidazole etc. or several
Kind.
Further, the density of expended microsphere of the invention is 0.01-1 g/cm3。
Further, the density of hollow glass microballoon of the invention is 0.3-1 g/cm3。
Compared with prior art, beneficial effects of the present invention are as follows:
(1) present invention directlys adopt thermosetting epoxy resin and prepares fracturing propping agents, utilizes methyl-silicone oil and thermoset epoxy tree
The big principle of rouge polarity spectrum, can allow epoxy resin straight forming at graininess.Epoxy resin has intensity high, and density is low,
The advantages that temperature tolerance is good improves the resistant to breakage ability of fracturing propping agents
(3) joined hollow glass microballoon or expended microsphere reduces its density to the present invention simultaneously.Fracturing propping agents are come
It says, density is easier to be pumped into underground closer to water, convenient for completing fracturing technology.Fracturing propping agents of the present invention are by density
It controls to 1.0 g/cm3Left and right is 2-3 g/cm relative to existing density3Fracturing propping agents, density greatly reduces.
(4) fracturing propping agents of the present invention can use water to convey as fracturing fluid, and transporting resistance is small, conveying distance
Far, support effect is good, is conducive to petroleum gas output, improves yield.Meet environmental requirement simultaneously.
(5) applying for methyl-silicone oil can make thermosetting epoxy resin mold to reach and think in range of the present invention
The requirement of the circularity and sphericity wanted.
To sum up, fracturing propping agents of the invention have resistant to breakage ability strong relative to existing fracturing propping agents, and density is low,
Using simple process, it is environmentally friendly the advantages that.
Specific embodiment
Below with reference to embodiment, the invention will be further described.
Embodiment 1
A kind of thermosetting epoxy resin fracturing propping agents, the raw material including following parts by weight meter:
E-51:100 parts of epoxy resin；
Curing agent dicyandiamide: 20 parts；
Promotor phenyl dimethylurea: 1 part；
Methyl-silicone oil: 600 parts.
Compressive strength 109MPa, density can reach 1.23/cm3, glass transition temperature can reach 142 DEG C.
Embodiment 2
A kind of thermosetting epoxy resin fracturing propping agents, the raw material including following parts by weight meter:
E-51:100 parts of epoxy resin；
Curing agent dicyandiamide: 20 parts；
Promotor phenyl dimethylurea: 1 part；
Methyl-silicone oil: 600 parts；
Hollow glass microballoon: 5 parts.
Compressive strength 101MPa, density can reach 1.09/cm3, glass transition temperature can reach 141 DEG C.
Embodiment 3
A kind of thermosetting epoxy resin fracturing propping agents, the raw material including following parts by weight meter:
E-51:100 parts of epoxy resin；
Curing agent dicyandiamide: 20 parts；
Promotor phenyl dimethylurea: 1 part；
Methyl-silicone oil: 600 parts；
Expended microsphere: 1 part.
Compressive strength 103MPa, density can reach 1.02/cm3, glass transition temperature can reach 141 DEG C.
Embodiment 4
A kind of thermosetting epoxy resin fracturing propping agents, the raw material including following parts by weight meter:
E-51/F-44:100 parts of epoxy resin；
Curing agent acid anhydrides: 85 parts；
P-30:3 parts of altax；
Methyl-silicone oil: 600 parts.
Compressive strength 112MPa, density can reach 1.18/cm3, glass transition temperature can reach 148 DEG C.
Embodiment 5
A kind of thermosetting epoxy resin fracturing propping agents, the raw material including following parts by weight meter:
E-51/F-44:100 parts of epoxy resin；
Curing agent acid anhydrides: 85 parts；
P-30:3 parts of altax；
Methyl-silicone oil: 600 parts；
Hollow glass microballoon: 10 parts.
Compressive strength 107MPa, density can reach 1.08/cm3, glass transition temperature can reach 146 DEG C.
Embodiment 6
A kind of thermosetting epoxy resin fracturing propping agents, the raw material including following parts by weight meter:
E-51/F-44:100 parts of epoxy resin；
Curing agent acid anhydrides: 85 parts；
P-30:3 parts of altax；
Methyl-silicone oil: 600 parts；
Expended microsphere: 1 part.
Compressive strength 105MPa, density can reach 0.99/cm3, glass transition temperature can reach 147 DEG C.
Embodiment 7
A kind of thermosetting epoxy resin fracturing propping agents, the raw material including following parts by weight meter:
F-44:100 parts of epoxy resin；
Curing agent imidazoles: 6 parts；
Methyl-silicone oil: 600 parts；
Compressive strength 105MPa, density can reach 1.25/cm3, glass transition temperature can reach 141 DEG C.
Embodiment 8
A kind of thermosetting epoxy resin fracturing propping agents, the raw material including following parts by weight meter:
F-44:100 parts of epoxy resin；
Curing agent imidazoles: 6 parts；
Methyl-silicone oil: 600 parts；
Hollow glass microballoon: 5 parts.
Compressive strength 98MPa, density can reach 1.12/cm3, glass transition temperature can reach 141 DEG C.
Embodiment 9
A kind of thermosetting epoxy resin fracturing propping agents, the raw material including following parts by weight meter:
F-44:100 parts of epoxy resin；
Curing agent imidazoles: 6 parts；
Expended microsphere: 1 part.
Compressive strength 100MPa, density can reach 1.08/cm3, glass transition temperature can reach 140 DEG C.
Embodiment 10
A kind of thermosetting epoxy resin fracturing propping agents, the raw material including following parts by weight meter:
E-51/AG-80:100 parts of epoxy resin；
Curing agent acid anhydrides: 85 parts；
Promotor modified imidazole: 3 parts；
Methyl-silicone oil: 600 parts；
Compressive strength 113MPa, density can reach 1.02/cm3, glass transition temperature can reach 158 DEG C.
From the above data, it can be seen that intensity is high, and density is obvious using the fracturing propping agents of formula preparation of the present invention
Reduce, glass transition temperature increases.Simultaneously because density reduces, water is able to use as pressure break and supports liquid, reduces environmental pollution.
Claims (8)
1. a kind of thermosetting epoxy resin fracturing propping agents, it is characterised in that: including following raw material according to the mass fraction:
Epoxy resin: 100-200 parts；
Expended microsphere or hollow glass microballoon: 1-10 parts；
Methyl-silicone oil: 200-600 parts.
2. thermosetting epoxy resin fracturing propping agents according to claim 1, it is characterised in that: further include curing agent 3-90
Part, 0-5 parts of promotor.
3. thermosetting epoxy resin fracturing propping agents according to claim 1, it is characterised in that: the methyl-silicone oil is point
One or more kinds of combinations of son amount 300-200000, viscosity 10000-500000mPas.
4. thermosetting epoxy resin fracturing propping agents according to claim 1, it is characterised in that: the epoxy resin is selected from
Bisphenol A type epoxy resin E-51, bisphenol A type epoxy resin E-44, bisphenol A type epoxy resin E-20, bisphenol f type epoxy resin
One of NPEF170, phenol aldehyde type epoxy resin F-44, phenol aldehyde type epoxy resin F-51 and multifunction group epoxy AG-80 or several
Kind.
5. thermosetting epoxy resin fracturing propping agents according to claim 1, it is characterised in that: the curing agent is selected from double
One or more of any combination of cyanamide slurry, imidazoles, acid anhydrides or phenolic resin；When using dicyandiamide slurry, dicyandiamide slurry
For the mixture being made of the epoxy resin of 70wt%, the dicyandiamide of 30wt%.
6. thermosetting epoxy resin fracturing propping agents according to claim 1, it is characterised in that: the promotor is phenyl
Dimethyl urea, 2, the modified ureas such as double dimethyl ureas of 4 toluene；DMP-30, N, N- dimethyl benzylamine, the tertiary amines such as triethanolamine；2 methyl miaows
Azoles, 2-ethyl-4-methylimidazole, the one or more of modified imidazole etc..
7. thermosetting resin fracturing propping agents according to claim 1, it is characterised in that: the density of the expended microsphere
For 0.01-1 g/cm3。
8. thermosetting resin fracturing propping agents according to claim 1, it is characterised in that: the hollow glass microballoon it is close
Degree is 0.3-1 g/cm3。
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710639675.4A CN109321227A (en) | 2017-07-31 | 2017-07-31 | A kind of thermosetting epoxy resin fracturing propping agents |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710639675.4A CN109321227A (en) | 2017-07-31 | 2017-07-31 | A kind of thermosetting epoxy resin fracturing propping agents |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111718703A (en) * | 2020-07-22 | 2020-09-29 | 青岛大地新能源技术研究院 | Liquid self-supporting high-speed channel fracturing fluid and experimental method |
| CN112048294A (en) * | 2019-06-06 | 2020-12-08 | 中蓝晨光化工研究设计院有限公司 | Epoxy resin fracturing propping agent and preparation method thereof |
| CN117050743A (en) * | 2023-10-08 | 2023-11-14 | 中蓝晨光化工研究设计院有限公司 | Preparation process, system and control system of low-density epoxy resin fracturing propping agent |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112048294A (en) * | 2019-06-06 | 2020-12-08 | 中蓝晨光化工研究设计院有限公司 | Epoxy resin fracturing propping agent and preparation method thereof |
| CN111718703A (en) * | 2020-07-22 | 2020-09-29 | 青岛大地新能源技术研究院 | Liquid self-supporting high-speed channel fracturing fluid and experimental method |
| CN111718703B (en) * | 2020-07-22 | 2022-10-14 | 青岛大地新能源技术研究院 | Liquid self-supporting high-speed channel fracturing fluid and experimental method |
| CN117050743A (en) * | 2023-10-08 | 2023-11-14 | 中蓝晨光化工研究设计院有限公司 | Preparation process, system and control system of low-density epoxy resin fracturing propping agent |
| CN117050743B (en) * | 2023-10-08 | 2023-12-26 | 中蓝晨光化工研究设计院有限公司 | Preparation process, system and control system of low-density epoxy resin fracturing propping agent |
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