CN103304354A - High-temperature-resistant solid propellant for deep oil-gas well and preparation method thereof - Google Patents
High-temperature-resistant solid propellant for deep oil-gas well and preparation method thereof Download PDFInfo
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- CN103304354A CN103304354A CN2013102069859A CN201310206985A CN103304354A CN 103304354 A CN103304354 A CN 103304354A CN 2013102069859 A CN2013102069859 A CN 2013102069859A CN 201310206985 A CN201310206985 A CN 201310206985A CN 103304354 A CN103304354 A CN 103304354A
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Abstract
The invention provides a high-temperature-resistant solid propellant for a deep oil-gas well. The solid propellant is prepared from the following raw materials in percentage by weight: 55.00-73.00% of potassium perchlorate, 10.00-43.37% of high-temperature-resistant epoxy resin, 0-11.40% of bisphenol A epoxy resin, 0-12.77% of epoxy-resin reactive diluent, 0.03% of defoamer and 0.98-1.60% of 2-ethyl-4-methylimidazole, wherein the sum of the weight percent of the raw materials is 100%; and the raw materials of the propellant are subjected to premixing and remixing and are finally poured into a mold for molding so as to prepare a finished product. The solid propellant has excellent hydrolysis resistance; when the solid propellant is soaked in clean water and 3.5% brine for 24-48 hours, the loss of weight is lower than 3%, and the volume change is lower than 2%; and the temperature resistance is better, the temperature resisting level reaches 180 DEG C in 48 hours, and the spontaneous combustion does not occur, thus the solid propellant can be used in high-temperature watery environment.
Description
Technical field
The invention belongs to the heat-resisting Pressure breaking bullet powder charge of oil/gas deep well field, relate to a kind of propelling agent, be specifically related to a kind of oil/gas deep well with high temperature resistant solid propellant and preparation method thereof.
Background technology
The detonation pressure break of utilizing powder charge is existing nearly 40 years developing history at home and abroad, the box hat formula, is used widely in the oil field without the multiple Pressure breaking bullet product such as shell-type or technology, has obtained preferably increasing yield and injection effect.The detonation fracturing technique is to utilize specific propellant charge in the pay sand high velocity combustion of Oil/gas Well, produce the High Temperature High Pressure pulse gas, fracturing stratum forms many from the radial radial fissure of well, remove hydrocarbon contamination and tamper, effectively reduce the stratum skin factor, thereby reach the purpose of well production increment.
Because during oil well operation, the residing subsurface environment of Pressure breaking bullet is many water surroundings of high temperature (180 ℃), common fourth hydroxyl propelling agent heat resistance is relatively poor, and heatproof is at 150 ℃; And fourth hydroxyl propelling agent contains a large amount of ammoniumper chlorate, and the solubleness of ammoniumper chlorate in water is larger.Therefore, such propelling agent can't meet the demands.
Chinese patent (publication number CN1275556A) " hot hole with composition and the synergistic perforator of high temperature resistant solid propellant " discloses a kind of high temperature resistant solid propellant, comprises 45～60% oxygenants, 35～50% reductive agents and 2～15% sensitizing agents.Oxygenant is the oxysalt (such as saltpetre) of inorganic high-temperature resistant in this high temperature resistant solid propellant, reductive agent is resistant to elevated temperatures organic polymer material (such as polyurethane elastomer, rubber, high-temperature adhesives etc.), sensitizing agent is metal-powder, can be more active metal-powder such as magnesium powder or aluminium powder or aluminum magnesium alloy etc., granularity 50～200 orders.Saltpetre solubleness in water is larger, and 20 ℃ of solubleness are 31.6 grams, and 50 ℃ of solubleness are 85.5 grams, and temperature more high-dissolvability is larger, therefore can not in many water surroundings of high temperature (greater than 150 ℃), use.
Summary of the invention
For the deficiencies in the prior art, the object of the invention is to the high temperature resistant solid propellant of oil/gas deep well that provides a kind of detonation Pressure breaking bullet powder charge field that is applicable to oil field deep well in the many water surroundings of high temperature, to use.
In order to realize above-mentioned task, the present invention adopts following technical scheme to be achieved:
The high temperature resistant solid propellant of a kind of oil/gas deep well, by weight percentage, be comprised of following raw material: potassium perchlorate is 55.00%～73.00%, high-temperature-resistant epoxy resin is 10.00%～43.37%, and bisphenol A epoxide resin is 0～11.40%, and epoxide resin reactive diluent is 0～12.77%, defoamer is 0.03%, 2-ethyl-4-methylimidazole is 0.98%～1.60%, and raw material weight percentage ratio summation is 100%, wherein:
Described bisphenol A epoxide resin is Resins, epoxy E-51;
Described high-temperature-resistant epoxy resin is 4,4 '-diaminodiphenylmethane, four glycidyl amine type epoxy resins, 3,4 '-diaminodiphenyl oxide, four glycidyl amine type epoxy resins or 4,4 '-diaminodiphenyl oxide, four glycidyl amine type epoxy resins;
Described epoxide resin reactive diluent is o-tolyl glycidyl ether or polyethyleneglycol diglycidylether;
Described defoamer is silicone resin.
The preferred high temperature resistant solid propellant of oil/gas deep well, by weight percentage, be comprised of following raw material: potassium perchlorate is 60.00%, 4,4 '-diaminodiphenylmethane, four glycidyl amine type epoxy resins are 14.40%, and Resins, epoxy E-51 is 11.40%, and the o-tolyl glycidyl ether is 12.77%, silicone resin is 0.03%, and 2-ethyl-4-methylimidazole is 1.40%.
Above-mentioned oil/gas deep well carries out according to following steps with the preparation method of high temperature resistant solid propellant, the method:
Step 1 is according to formula rate, by weight percentage, be 10.00%～43.37% with high-temperature-resistant epoxy resin, bisphenol A epoxide resin is 0～11.40%, epoxide resin reactive diluent be 0～12.77% and defoamer be 0.03% to add in the mixing kettle premix 10 minutes;
Step 2, by weight percentage, adding potassium perchlorate in the system of step 1 is 55.00%～73.00%, mixes after 50 minutes, adding 2-ethyl-4-methylimidazole is 0.98%～1.60% again, mixes to stop mixing after 15 minutes, obtains medicine and starches;
Step 3, the medicine slurry that step 2 is obtained is poured in the mould, puts into 70 ℃ of baking ovens and solidifies 24 hours, moves back mould, obtains high temperature resistant solid propellant finished product.
The present invention compared with prior art, useful technique effect is:
(1) solid propellant excellent hydrolysis resistance of the present invention, the medicine piece of 50mm * 50mm * 20mm soak in clear water and 3.5% salt solution respectively and reach 24～48 hours, and weightless less than 3%, volume change less than 2% considerable change does not occur.And the anti-tap water of existing solid propellant and 3.5% salt solution poor-performing.
(2) heat resistance of solid propellant of the present invention is better, the heatproof rank reach 180 ℃ 48 hours, spontaneous combustion does not occur, can in the many water surroundings of high temperature, use.
Embodiment
Defer to technique scheme, following embodiment provides the high temperature resistant solid propellant of a kind of oil/gas deep well, by weight percentage, be comprised of following raw material: potassium perchlorate is 55.00%～73.00%, and high-temperature-resistant epoxy resin is 10.00%～43.37%, bisphenol A epoxide resin is 0～11.40%, epoxide resin reactive diluent is 0～12.77%, and defoamer is 0.03%, and 2-ethyl-4-methylimidazole is 0.98%～1.60%, raw material weight percentage ratio summation is 100%, wherein:
Described bisphenol A epoxide resin is Resins, epoxy E-51;
Described high-temperature-resistant epoxy resin is 4,4 '-diaminodiphenylmethane, four glycidyl amine type epoxy resins, 3,4 '-diaminodiphenyl oxide, four glycidyl amine type epoxy resins or 4,4 '-diaminodiphenyl oxide, four glycidyl amine type epoxy resins;
Described epoxide resin reactive diluent is o-tolyl glycidyl ether or polyethyleneglycol diglycidylether;
Described defoamer is silicone resin.
The preferred high temperature resistant solid propellant of oil/gas deep well, by weight percentage, be comprised of following raw material: potassium perchlorate is 60.00%, 4,4 '-diaminodiphenylmethane, four glycidyl amine type epoxy resins are 14.40%, and Resins, epoxy E-51 is 11.40%, and the o-tolyl glycidyl ether is 12.77%, silicone resin is 0.03%, and 2-ethyl-4-methylimidazole is 1.40%.
The specification requirement of above-mentioned raw materials is as follows:
Potassium perchlorate is industrial goods.
4,4 '-diaminodiphenylmethane, four glycidyl amine type epoxy resins (being abbreviated as TGDDM), reddish-brown is to amber thick liquid, oxirane value 〉=0.8 equivalent/100g, viscosity 3.0～7.0Pas(50 ℃).The structural formula of TGDDM is as follows:
The oxirane value of Resins, epoxy E-51 is 0.48～0.54, viscosity 6.0～10.0Pas(25 ℃), polymerization degree n=0.1～0.28, relative molecular mass is 307～420.The molecular formula of Resins, epoxy E-51 is as follows:
O-tolyl glycidyl ether outward appearance is colourless to light yellow transparent liquid, and oxirane value is 0.50～0.54 equivalent/100g, and 25 ℃ of viscositys are 5～10mPas.
The polyethyleneglycol diglycidylether outward appearance is colourless to light yellow transparent liquid, and oxirane value is 0.30～0.36 equivalent/100g, and 25 ℃ of viscositys are 50～70mPas.
The viscosity of silicone resin is (100～1100) * 10
-6m
2/ s, refractive index n
D 251.400～1.410.
Above-mentioned oil/gas deep well carries out according to following steps with the preparation method of high temperature resistant solid propellant, the method:
Step 1 is according to formula rate, by weight percentage, be 10.00%～43.37% with high-temperature-resistant epoxy resin, bisphenol A epoxide resin is 0～11.40%, epoxide resin reactive diluent be 0～12.77% and defoamer be 0.03% to add in the mixing kettle premix 10 minutes;
Step 2, by weight percentage, adding potassium perchlorate in the system of step 1 is 55.00%～73.00%, mixes after 50 minutes, adding 2-ethyl-4-methylimidazole is 0.98%～1.60% again, mixes to stop mixing after 15 minutes, obtains medicine and starches;
Step 3, the medicine slurry that step 2 is obtained is poured in the mould, puts into 70 ℃ of baking ovens and solidifies 24 hours, moves back mould, obtains high temperature resistant solid propellant finished product.
Below provide specific embodiments of the invention, need to prove that the present invention is not limited to following specific embodiment, all equivalents of doing on present techniques scheme basis all fall into protection scope of the present invention.
Embodiment 1:
The high temperature resistant solid propellant of the oil/gas deep well of the present embodiment, by weight percentage, be comprised of following raw material: potassium perchlorate is 60.00%, TGDDM is 14.40%, Resins, epoxy E-51 is 11.40%, the o-tolyl glycidyl ether is 12.77%, and silicone resin is 0.03%, and 2-ethyl-4-methylimidazole is 1.40%.
Performance test:
Quick-fried heat presses GJB770B-2005 method 701.2 quick-fried heat and combustion heat constant temperature method is measured.
Specific volume is pressed GJB770B-2005 method 702.1 specific volume pressure transmitter methods and is measured.
Impact sensitivity, characteristic drop height H
50Pressing GJB772A-97 method 601.2 measures.
Friction sensitivity, explosion probability P presses GJB772A-97 method 602.1 and measures.
The high thermal resistance testing method is: Ф 20mm * (1) 3 ℃/min of 20mm powder column rises to 180 ℃, insulation 48h; (2) temperature controlling point: thermopair is suspended from directly over the sample, does not contact with sample.The sample thermal weight loss is not more than 3%, does not fire not quick-fried being by test.The DSC exothermic peak temperature, 10 ℃/min heating rate.
The water-fast testing method of propelling agent is: 50mm * 50mm * 20mm medicine piece submergence 48h in tap water, weightless less than 3%, volume change is by test less than 2%.
The oil/gas deep well of the present embodiment sees Table 1 with the properties test result of high temperature resistant solid propellant.
Table 1 embodiment 1 properties test result
Can draw from table 1, the quick-fried heat of this propelling agent (being energy) is moderate, and specific volume is very high, and resistance to elevated temperatures, water resistance and salt water resistance performance all reach performance requriements.Friction sensitivity and impact sensitivity performance are also very good simultaneously.Being fit to the heat-resisting Pressure breaking bullet powder charge of oil/gas deep well uses.
Embodiment 2:
The high temperature resistant solid propellant of the oil/gas deep well of the present embodiment by weight percentage, is comprised of following raw material: potassium perchlorate is that 55.00%, TGDDM is 43.37%, and silicone resin is 0.03%, and 2-ethyl-4-methylimidazole is 1.60%.
The oil/gas deep well of the present embodiment is identical with embodiment 1 with the performance test methods of high temperature resistant solid propellant, and the properties test result sees Table 2.
Table 2 embodiment 2 properties test results
Can draw from table 2, the quick-fried heat of this propelling agent (being energy) is moderate, and specific volume is very high, and resistance to elevated temperatures, water resistance and salt water resistance performance all reach performance requriements.Friction sensitivity and impact sensitivity performance are also very good simultaneously.Being fit to the heat-resisting Pressure breaking bullet powder charge of oil/gas deep well uses.
Embodiment 3:
The high temperature resistant solid propellant of the oil/gas deep well of the present embodiment, by weight percentage, be comprised of following raw material: potassium perchlorate is 73.00%, TGDDM is 10.00%, Resins, epoxy E-51 is 4.79%, the o-tolyl glycidyl ether is 11.20%, and silicone resin is 0.03%, and 2-ethyl-4-methylimidazole is 0.98%.
The oil/gas deep well of the present embodiment is identical with embodiment 1 with the performance test methods of high temperature resistant solid propellant, and the properties test result sees Table 3.
Table 3 embodiment 3 properties test results
Can draw from table 3, the quick-fried heat of this propelling agent (being energy) is very high, and still, specific volume is lower, and resistance to elevated temperatures, water resistance and salt water resistance performance also all reach performance requriements.Friction sensitivity and impact sensitivity performance are also very good simultaneously.Also being fit to the heat-resisting Pressure breaking bullet powder charge of oil/gas deep well uses.
Among above all embodiment, raw material o-tolyl glycidyl ether can be replaced with polyethyleneglycol diglycidylether, raw material 4,4 '-diaminodiphenylmethane, four glycidyl amine type epoxy resins (being abbreviated as TGDDM) can be with 3,4 '-diaminodiphenyl oxide, four glycidyl amine type epoxy resins (are abbreviated as 3,4 '-TGDDE) or 4,4 '-diaminodiphenyl oxide, four glycidyl amine type epoxy resins (are abbreviated as 4,4 '-TGDDE) replaces, technique effect is identical, in view of length, will provide no longer one by one corresponding embodiment.
Claims (3)
1. high temperature resistant solid propellant of oil/gas deep well, it is characterized in that, by weight percentage, be comprised of following raw material: potassium perchlorate is 55.00%～73.00%, and high-temperature-resistant epoxy resin is 10.00%～43.37%, bisphenol A epoxide resin is 0～11.40%, epoxide resin reactive diluent is 0～12.77%, and defoamer is 0.03%, and 2-ethyl-4-methylimidazole is 0.98%～1.60%, raw material weight percentage ratio summation is 100%, wherein:
Described bisphenol A epoxide resin is Resins, epoxy E-51;
Described high-temperature-resistant epoxy resin is 4,4 '-diaminodiphenylmethane, four glycidyl amine type epoxy resins, 3,4 '-diaminodiphenyl oxide, four glycidyl amine type epoxy resins or 4,4 '-diaminodiphenyl oxide, four glycidyl amine type epoxy resins;
Described epoxide resin reactive diluent is o-tolyl glycidyl ether or polyethyleneglycol diglycidylether;
Described defoamer is silicone resin.
2. the high temperature resistant solid propellant of oil/gas deep well as claimed in claim 1, it is characterized in that, by weight percentage, be comprised of following raw material: potassium perchlorate is 60.00%, 4, and 4 '-diaminodiphenylmethane, four glycidyl amine type epoxy resins are 14.40%, Resins, epoxy E-51 is 11.40%, the o-tolyl glycidyl ether is 12.77%, and silicone resin is 0.03%, and 2-ethyl-4-methylimidazole is 1.40%.
3. oil/gas deep well as claimed in claim 1 is characterized in that with the preparation method of high temperature resistant solid propellant, and the method is carried out according to following steps:
Step 1 is according to formula rate, by weight percentage, be 10.00%～43.37% with high-temperature-resistant epoxy resin, bisphenol A epoxide resin is 0～11.40%, epoxide resin reactive diluent be 0～12.77% and defoamer be 0.03% to add in the mixing kettle premix 10 minutes;
Step 2, by weight percentage, adding potassium perchlorate in the system of step 1 is 55.00%～73.00%, mixes after 50 minutes, adding 2-ethyl-4-methylimidazole is 0.98%～1.60% again, mixes to stop mixing after 15 minutes, obtains medicine and starches;
Step 3, the medicine slurry that step 2 is obtained is poured in the mould, puts into 70 ℃ of baking ovens and solidifies 24 hours, moves back mould, obtains high temperature resistant solid propellant finished product.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109761731A (en) * | 2018-09-11 | 2019-05-17 | 湖北航天化学技术研究所 | The manufacturing method of the round tube and round tube of composite solidpropellant and its production |
| CN112694372A (en) * | 2020-12-25 | 2021-04-23 | 石仲仑 | Epoxy composite propellant, preparation method and application thereof |
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| CN1082706A (en) * | 1993-07-16 | 1994-02-23 | 江西钢丝厂 | A kind of combustable-shell hail-proof rain-increasing rocket shell |
| US5854442A (en) * | 1995-03-31 | 1998-12-29 | Atlantic Research Corporation | Gas generator compositions |
| CN1275556A (en) * | 1999-06-01 | 2000-12-06 | 北京石油化工学院石光技术公司 | Composition of high temp. resistant propellant for high tmep. well and synergistic perforator |
| CN101173603A (en) * | 2006-04-13 | 2008-05-07 | 施蓝姆伯格技术公司 | Sub-surface coalbed methane well enhancement through rapid oxidation |
-
2013
- 2013-05-29 CN CN201310206985.9A patent/CN103304354B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1082706A (en) * | 1993-07-16 | 1994-02-23 | 江西钢丝厂 | A kind of combustable-shell hail-proof rain-increasing rocket shell |
| US5854442A (en) * | 1995-03-31 | 1998-12-29 | Atlantic Research Corporation | Gas generator compositions |
| CN1275556A (en) * | 1999-06-01 | 2000-12-06 | 北京石油化工学院石光技术公司 | Composition of high temp. resistant propellant for high tmep. well and synergistic perforator |
| CN101173603A (en) * | 2006-04-13 | 2008-05-07 | 施蓝姆伯格技术公司 | Sub-surface coalbed methane well enhancement through rapid oxidation |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109761731A (en) * | 2018-09-11 | 2019-05-17 | 湖北航天化学技术研究所 | The manufacturing method of the round tube and round tube of composite solidpropellant and its production |
| CN112694372A (en) * | 2020-12-25 | 2021-04-23 | 石仲仑 | Epoxy composite propellant, preparation method and application thereof |
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