CN103204756A - High temperature-resistant solid propellant for oilfield fracturing - Google Patents
High temperature-resistant solid propellant for oilfield fracturing Download PDFInfo
- Publication number
- CN103204756A CN103204756A CN2012103901918A CN201210390191A CN103204756A CN 103204756 A CN103204756 A CN 103204756A CN 2012103901918 A CN2012103901918 A CN 2012103901918A CN 201210390191 A CN201210390191 A CN 201210390191A CN 103204756 A CN103204756 A CN 103204756A
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- China
- Prior art keywords
- solid propellant
- high temperature
- oil field
- temperature resistant
- compression fracture
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Abstract
The invention provides a solid propellant for oilfield fracturing. The solid propellant uses an epoxy resin as an adhesive and comprises 7 to 21% of a bisphenol A diglycidyl ether type epoxy resin, 4 to 15% of a curing agent, 60 to 85% of an oxidizing agent, 0 to 20% of a cooling agent and 0 to 1% of a curing accelerator. The solid propellant provided by the invention has good corrosion resistance; a phenyl ring in the structure of the solid propellant enables the solid propellant to have good heat resistance and rigidity; meanwhile, through addition of the acid anhydride curing agent with a rigid structure, heat resistance of a curing system is further improved. The invention has the following advantages: the solid propellant has good heat resistance and resistance to a high temperature of 200 DEG C for 48 h, is non-combustible and non-explosive and completely meets requirements on usage in a deep well oilfield; a formula for the solid propellant contains a few components, a technology is simple and practicable, a production process is stable and produces a product with reliable quality, and compatibility of the components in the formula is good, which enables no chemical action occurs during long-term storage of the solid propellant and under the conditions of high temperature and high pressure; raw materials are widely available and cheap, so production cost is low.
Description
Technical field
The present invention relates to oil field compression fracture solid propellant prescription, particularly is the propellant formulation of tackiness agent with the Resins, epoxy resin.
Background technology
In the oil field compression fracture technical field, domestic pressure break gunpowder is mainly Dan Ji, double-base propellant and compositepropellent.At present, the nitro-cottons that adopt in Dan Ji and the double-base propellant more, but owing to be the restriction that the pressure break medicine of main component is subjected to the performance of nitro-cotton own with the nitro-cotton, be limited to 135 ℃ on its long-term heatproof, far can not satisfy the requirement of most of oil wells (the well temperature is at 120 ℃~200 ℃).And the compositepropellent prescription adopts hydroxy-terminated polybutadienes (HTPB) as tackiness agent more, and its heatproof upper limit can not satisfy deep well oilfield to the service requirements (more than 170 ℃) of perforating and fracturing gunpowder also less than 160 ℃.
Summary of the invention
The objective of the invention is to overcome disadvantages of background technology, design that a kind of recipe ingredient is few, technology good, cost is low and be applicable to the oil field compression fracture solid propellant of oil field deep well.
The present invention also aims to provide the preparation method of above-mentioned oil field compression fracture with solid propellant.
Technical scheme of the present invention comprises the component of following mass percent:
Bisphenol-A diglycidyl ether type epoxy resin: 7%~21%
Solidifying agent: 4% ~ 15%
Oxygenant: 60~85%
Cooling agent: 0%~20%
Curing catalyst: 0%~1%.
Preferred version of the present invention comprises the component of following mass percent:
Bisphenol-A diglycidyl ether type epoxy resin: 8% ~ 19%
Solidifying agent: 5.5% ~ 14.1%
Oxygenant: 60% ~ 85%
Cooling agent: 10% ~ 15%
Curing catalyst: 1%
Described bisphenol-A diglycidyl ether type epoxy resin is liquid bisphenol-A diglycidyl ether type during for normal temperature.
Described solidifying agent is a kind of or above several combination in methyl tetrahydrophthalic anhydride (MeTHPA), methylhexahydrophthalic anhydride (MeHHPA), the Pyroglutaric acid.
Described oxygenant is ammoniumper chlorate (AP).
Described cooling agent is calcium carbonate (CaCO
3).
Described curing catalyst is a kind of in 2,4,6-three (dimethylamino methyl) phenol (DMP-30) or 1,8-diaza-dicyclo [ 5.4.0 ] hendecene-7(DBU).
Preparation method of the present invention is as follows:
(1) with the bisphenol-A diglycidyl ether type epoxy resin of liquid state, solidifying agent, oxygenant, cooling agent, curing catalyst according to described ratio weighing;
(2) each starting material is put into vertical mixer and is mixed after the weighing, and 50 ℃~70 ℃ of mixing temperatures about mixing time 60min~100min, make slip;
(3) slime vacuum spray is poured into mould or is poured in the engine, be placed on then in the oil bath baking oven about 50 ℃~70 ℃ and solidified 7 days.
Design of the present invention is to adopt bisphenol A type epoxy resin with low cost as tackiness agent, bisphenol A type epoxy resin is a kind of tackiness agent of excellent property, ehter bond in the structure makes its cured product have good anti-corrosion, and the phenyl ring in its structure makes cured product have good thermotolerance and rigidity, the acid anhydride type curing agent that has rigid structure simultaneously by interpolation further improves the resistance toheat of curing system.
Advantage of the present invention is as follows.
1. resistance toheat is good.High temperature resistant property is 200 ℃, and 48h does not fire not quick-friedly, satisfies the service requirements of deep well oilfield fully.
2. recipe ingredient is few, and is simple for process, stable processing technique, and reliable in quality, the recipe ingredient consistency is good, guarantees under standing storage and the High Temperature High Pressure chemical action not to take place.
3. raw material sources are extensive, low price, and production cost is low.
Embodiment
Embodiment 1
Implement with reference to following percentage mass component
Bisphenol-A diglycidyl ether type epoxy resin E-42 16.1%
Methyl tetrahydrophthalic anhydride: 13.8%
Ammoniumper chlorate: 70%
2,4,6-three (dimethylamino methyl) phenol: 0.1%
5L powder charge propellant performance is as follows:
High thermal resistance: judge resistance toheat and roadholding with reference to WJ9016-94, (Φ 20mm * 20mm powder column) 200 ± 2 ℃, 48h, do not fire not quick-fried indeformable, hot decrement 2.31%
Combustion speed: r
10MPa=7.212mm/s
Ultimate compression strength: σ
m=42.62MPa, rate of compression ε
m=5.0%
Impact sensitivity: H
50=18.6cm, I
50=9.11J.
Embodiment 2
Implement with reference to following percentage mass component
Bisphenol-A diglycidyl ether type epoxy resin E-44:10.27%
MeHHPA: 9.23%
AP: 65%
CaCO
3: 15%
DBU 1%
5L powder charge propellant performance is as follows:
High thermal resistance: judge resistance toheat and roadholding with reference to WJ9016-94, (Φ 20mm * 20mm powder column) 200 ℃, 48h does not fire not quick-fried; Hot decrement 2.16%
Combustion speed: r
10MPa=5.13mm/s
Ultimate compression strength: σ
m=40.73MPa, rate of compression ε
m=5.7%
Impact sensitivity: H
50=25.7cm, I
50=25.1J.
Embodiment 3
Implement with reference to following percentage mass component
Bisphenol-A diglycidyl ether type epoxy resin E-51 11.8%
MeHHPA: 8.14%
AP: 80%
5L powder charge propellant performance is as follows:
High thermal resistance: judge resistance toheat and roadholding with reference to WJ9016-94, (Φ 20mm * 20mm powder column) 200 ℃, 48h does not fire not quick-fried; Hot decrement 4.56%
Combustion speed: r
10MPa=7.13mm/s
Ultimate compression strength: σ
m=40.11MPa, rate of compression ε
m=6.7%
Impact sensitivity: H
50=21.7cm, I
50=22.1J
The unspecified part of the present invention belongs to general knowledge as well known to those skilled in the art.
Claims (7)
1. oil field compression fracture high temperature resistant type solid propellant is characterized in that: the component that comprises following mass percent:
Bisphenol-A diglycidyl ether type epoxy resin: 7%~21%
Solidifying agent: 4% ~ 15%
Oxygenant: 60~85%
Cooling agent: 0%~20%
Curing catalyst: 0%~1%.
2. according to the described oil field compression fracture of claim 1 high temperature resistant type solid propellant, it is characterized in that comprising the component of following mass percent:
Bisphenol-A diglycidyl ether type epoxy resin: 8% ~ 19%
Solidifying agent: 5.5% ~ 14.1%
Oxygenant: 60% ~ 85%
Cooling agent: 10% ~ 15%
Curing catalyst: 1%.
3. according to the described oil field compression fracture of claim 1 high temperature resistant type solid propellant, it is characterized in that: described solidifying agent is a kind of or above several combination in methyl tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, the Pyroglutaric acid.
4. according to the described oil field compression fracture of claim 1 high temperature resistant type solid propellant, it is characterized in that: oxygenant is ammoniumper chlorate.
5. according to the described oil field compression fracture of claim 1 high temperature resistant type solid propellant, it is characterized in that: cooling agent is calcium carbonate.
6. according to the described oil field compression fracture of claim 1 high temperature resistant type solid propellant, it is characterized in that: described curing catalyst is 2, a kind of in 4,6-three (dimethylamino methyl) phenol (DMP-30) or 1,8-diaza-dicyclo [ 5.4.0 ] hendecene-7(DBU).
7. the described oil field compression fracture of a claim 1 is characterized in that comprising following operation with the preparation method of high temperature resistant type solid propellant:
(1) with the bisphenol-A diglycidyl ether type epoxy resin of liquid state, solidifying agent, oxygenant, cooling agent, curing catalyst according to described ratio weighing;
(2) each component is put into vertical mixer and is mixed after the weighing, and 50 ℃~70 ℃ of mixing temperatures about mixing time 60min~100min, make slip;
(3) slime vacuum spray is poured into mould or is poured in the engine, be placed on then in the oil bath baking oven about 50 ℃~70 ℃ and solidified 7 days.
Priority Applications (1)
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CN2012103901918A CN103204756A (en) | 2012-10-16 | 2012-10-16 | High temperature-resistant solid propellant for oilfield fracturing |
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CN2012103901918A CN103204756A (en) | 2012-10-16 | 2012-10-16 | High temperature-resistant solid propellant for oilfield fracturing |
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Publication Number | Publication Date |
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CN103204756A true CN103204756A (en) | 2013-07-17 |
Family
ID=48752193
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CN2012103901918A Pending CN103204756A (en) | 2012-10-16 | 2012-10-16 | High temperature-resistant solid propellant for oilfield fracturing |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105315115A (en) * | 2015-04-15 | 2016-02-10 | 湖北三沃力源航天科技有限公司 | High-temperature-resistant type solid propellant with calcium carbonate as cooling agent and preparation method of high-temperature-resistant type solid propellant |
RU2603373C1 (en) * | 2015-05-13 | 2016-11-27 | Акционерное общество "Научно-исследовательский институт полимерных материалов" | Heat-resistant gas-generating acid-producing high-strength fuel for downhole devices |
CN110982228A (en) * | 2019-11-28 | 2020-04-10 | 北方斯伦贝谢油田技术(西安)有限公司 | Power source for oil field bridge plug seat sealing and preparation method thereof |
CN113914843A (en) * | 2021-10-11 | 2022-01-11 | 中国矿业大学 | Multi-detonation-point multi-stage detonation fracturing method for horizontal well of shale gas reservoir |
CN115947641A (en) * | 2022-12-29 | 2023-04-11 | 西安石油大油气科技有限公司 | Preparation method of gunpowder propellant for deflagration fracturing of low-permeability oil field small casing |
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US3567530A (en) * | 1962-07-02 | 1971-03-02 | Monsanto Res Corp | Polymeric propellant composition containing lithium perchlorate/ammonium perchlorate eutectics |
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2012
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US3567530A (en) * | 1962-07-02 | 1971-03-02 | Monsanto Res Corp | Polymeric propellant composition containing lithium perchlorate/ammonium perchlorate eutectics |
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CN101659893A (en) * | 2009-09-28 | 2010-03-03 | 浙江大学 | Poly (methyl) acrylic acid ferrocene acyloxy ethyl ester burning-rate accelerator and propellant containing same and preparation method thereof |
CN102604046A (en) * | 2012-03-13 | 2012-07-25 | 烟台德邦科技有限公司 | DMP-30 (dimethyl phthalate-30) closing method and application of DMP-30 in epoxy adhesive |
Non-Patent Citations (2)
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戴李宗等: "高聚物在混合炸药中的应用", 《材料导报》, no. 2, 31 January 1993 (1993-01-31) * |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105315115A (en) * | 2015-04-15 | 2016-02-10 | 湖北三沃力源航天科技有限公司 | High-temperature-resistant type solid propellant with calcium carbonate as cooling agent and preparation method of high-temperature-resistant type solid propellant |
RU2603373C1 (en) * | 2015-05-13 | 2016-11-27 | Акционерное общество "Научно-исследовательский институт полимерных материалов" | Heat-resistant gas-generating acid-producing high-strength fuel for downhole devices |
CN110982228A (en) * | 2019-11-28 | 2020-04-10 | 北方斯伦贝谢油田技术(西安)有限公司 | Power source for oil field bridge plug seat sealing and preparation method thereof |
CN113914843A (en) * | 2021-10-11 | 2022-01-11 | 中国矿业大学 | Multi-detonation-point multi-stage detonation fracturing method for horizontal well of shale gas reservoir |
CN115947641A (en) * | 2022-12-29 | 2023-04-11 | 西安石油大油气科技有限公司 | Preparation method of gunpowder propellant for deflagration fracturing of low-permeability oil field small casing |
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Application publication date: 20130717 |