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CN104591934B - High-temperature-resistant propellant for deep oil-gas well and preparation method thereof - Google Patents

High-temperature-resistant propellant for deep oil-gas well and preparation method thereof Download PDF

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Publication number
CN104591934B
CN104591934B CN201510075729.XA CN201510075729A CN104591934B CN 104591934 B CN104591934 B CN 104591934B CN 201510075729 A CN201510075729 A CN 201510075729A CN 104591934 B CN104591934 B CN 104591934B
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percent
epoxy resin
propellant
high temperature
temperature
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CN104591934A (en
Inventor
王国强
强皆兵
孟玲玲
冉秀伦
李勇宏
刘春�
邓重清
屈蓓
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Xian Modern Chemistry Research Institute
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Xian Modern Chemistry Research Institute
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Abstract

The invention provides a high-temperature-resistant propellant for a deep oil-gas well, and solves the problem that the prior art cannot be used in a high-temperature washy environment. The high-temperature-resistant propellant consists of 35-50 percent of potassium perchlorate, 10-25 percent of 1,1-diamido-2,2-diamino-dinitroethylene, 10-20.90 percent of high-temperature-resistant epoxy resin, 0-16.58 percent of bisphenol A epoxy resin, 4.75-13.03 percent of an epoxy resin active diluting agent, 0.50 percent of a promoting agent, 0.03 percent of a defoaming agent and 6.57-8.14 percent of diaminodiphenyl sulfone. The solid propellant is immersed in clean water and salty water with the concentration of 3.5 percent, so that the weight loss is smaller than 3 percent, and the volume change is smaller than 2 percent; the temperature-resistant grade reaches 200 DEG C for 48 hours, and spontaneous combustion and explosion are avoided; the propellant can be used in the high-temperature washy environment.

Description

Oil/gas deep well high temperature resistant propellant and preparation method thereof
Technical field
The invention belongs to the heat-resisting Pressure breaking bullet powder charge field of oil/gas deep well, is related to a kind of propellant.
Background technology
Using the explosion fracturing at home and abroad developing history of existing nearly 40 years of powder charge, box hat formula, without shell-type etc. Various Pressure breaking bullet products or technology are used widely in oil field, achieve preferable increasing yield and injection effect.Explosion fracturing technology It is the oil-producing formation high-velocity combustion using specific propellant loading in Oil/gas Well, produces High Temperature High Pressure pulse gas, fracturing stratum Form a plurality of from the radial radial fissure of well, remove hydrocarbon contamination and tamper, be effectively reduced stratum epidermis system Number, so as to reach the purpose of well production increment.
During due to oil well operation, many water environments of the subsurface environment residing for Pressure breaking bullet for high temperature (200 DEG C), common fourth hydroxyl are pushed away Enter agent heat resistance poor, heatproof is at 150 DEG C;And HTPB propellant contains substantial amounts of ammonium perchlorate, and ammonium perchlorate is in water Dissolubility it is larger.Therefore, such propellant cannot meet requirement.
Chinese patent (publication number CN 1275556A) " composition and synergistic perforating of the high temperature well with high temperature resistant solid propellant Device " discloses a kind of high temperature resistant solid propellant, including 45~60% oxidants, 35~50% reducing agents and 2~15% are quick Agent.Oxysalt (such as potassium nitrate) of the oxidant for inorganic high-temperature resistant in the high temperature resistant solid propellant, reducing agent are resistance to height The high-molecular organic material (such as polyurethane elastomer, rubber, high-temperature adhesives etc.) of temperature, sensitizer is metal dust, Ke Yishi The more active metal dust such as magnesium powder or aluminium powder or almag, 50~200 mesh of granularity.Potassium nitrate dissolubility in water is larger, 20 DEG C of dissolubility are 31.6 grams, and 50 DEG C of dissolubility are 85.5 grams, and temperature more high-dissolvability is bigger, therefore can not be (big in high temperature In 150 DEG C) many water environments used in.
The content of the invention
For the deficiencies in the prior art, it is an object of the present invention to provide a kind of suitable for the quick-fried of oil field deep well Fire the oil/gas deep well high temperature resistant solid propellant that Pressure breaking bullet powder charge field can be used in many water environments of high temperature.
In order to realize above-mentioned task, the present invention is adopted the following technical scheme that and is achieved:
A kind of oil/gas deep well high temperature resistant propellant, by weight percentage:Potassium hyperchlorate is 35%~50%, 1,1- Diaminourea -2,2- dinitros ethylene are 10%~25%, and high-temperature-resistant epoxy resin is 10%~20.9%, bisphenol-A epoxy tree Fat is 0~16.58%, and epoxide resin reactive diluent is 4.75%~13.03%, and accelerator boron trifluoride-amine complex is 0.5%, defoamer is 0.03%, and DADPS is 6.57%~8.14%, and raw material weight percent summation is 100%, Wherein:
Described bisphenol A epoxide resin is epoxy resin E-51;
Described high-temperature-resistant epoxy resin be 4,4 '-MDA, four glycidyl amine type epoxy resin, 3,4 '- Four glycidyl amine type epoxy resin of four glycidyl amine type epoxy resin of diaminodiphenyl ether or 4,4 '-diaminodiphenyl ether;
Described epoxide resin reactive diluent is o-tolyl glycidyl ether or polyethyleneglycol diglycidylether;
Described defoamer is silicone resin.
Preferred oil/gas deep well high temperature resistant propellant, by weight percentage:Potassium hyperchlorate is 35%, 1,1- diamino Base -2,2- dinitros ethylene are 25%, 4, and 4 '-MDA, four glycidyl amine type epoxy resin is 14.4%, Epoxy resin E-51 is 5.47%, and o-tolyl glycidyl ether is 13.03%, and accelerator boron trifluoride-amine complex is 0.5%, silicone resin is 0.03%, and DADPS is 6.57%.
Preparation method of the above-mentioned oil/gas deep well with high temperature resistant propellant, the method are followed the steps below:
Step one, according to formula proportion, by high-temperature-resistant epoxy resin, bisphenol A epoxide resin, epoxide resin reactive dilution Agent, boron trifluoride-amine complex, defoamer are added in mixing kettle, are premixed 10 minutes;
Step 2, adds potassium hyperchlorate, 1,1- diaminourea -2,2- dinitro ethylene to mix in mixing kettle 50 minutes Afterwards, DADPS is added, mixing stops mixing after 15 minutes, obtains medicine slurry;
Step 3, medicine slurry is poured in mould, be put into 130 DEG C it is oven for curing 72 hours, move back mould, obtain high temperature resistant solid Body propellant finished product.
Compared with prior art, beneficial has the technical effect that the present invention:
(1) solid propellant excellent hydrolysis resistance of the invention, the medicine block of 50mm × 50mm × 20mm in clear water and Soak in 3.5% saline up to 24~48 hours, weightless to be less than 3%, change in volume is less than 2%, and significant change does not occur.And it is existing Solid propellant be not resistant to tap water and 3.5% saline.
(2) preferably, heatproof rank reaches 200 DEG C 48 hours to the heat resistance of solid propellant of the invention, does not occur certainly Combustion, can be used in many water environments of high temperature.
Specific embodiment
Above-mentioned technical proposal is deferred to, following embodiments provide a kind of oil/gas deep well high temperature resistant solid propellant, with weight Percent meter, is made up of following raw material:Potassium hyperchlorate is 35%~50%, 1,1- diaminourea -2, and 2- dinitro ethylene is 10%~25%, high-temperature-resistant epoxy resin is 10%~20.9%, and bisphenol A epoxide resin is 0~16.58%, and epoxy resin is lived Property diluent be 4.75%~13.03%, accelerator boron trifluoride-amine complex be 0.5%, defoamer is 0.03%, diamino Base diphenyl sulphone (DPS) is 6.57%~8.14%, and raw material weight percent summation is 100%, wherein:
Described bisphenol A epoxide resin is epoxy resin E-51;
Described high-temperature-resistant epoxy resin be 4,4 '-MDA, four glycidyl amine type epoxy resin, 3,4 '- Four glycidyl amine type epoxy resin of four glycidyl amine type epoxy resin of diaminodiphenyl ether or 4,4 '-diaminodiphenyl ether;
Described epoxide resin reactive diluent is o-tolyl glycidyl ether or polyethyleneglycol diglycidylether;
Described defoamer is silicone resin.
Described accelerator is boron trifluoride-amine complex.
Preferred oil/gas deep well high temperature resistant solid propellant, by weight percentage, is made up of following raw material:Perchloric acid Potassium is 35%, 1,1- diaminourea -2, and 2- dinitros ethylene is 25%, 4,4 '-MDA, four glycidic amine type Epoxy resin is 14.40%, and epoxy resin E-51 is 5.47%, and o-tolyl glycidyl ether is 13.03%, accelerator trifluoro It is 0.50% to change boron-amine complex, and silicone resin is 0.03%, and DADPS is 6.57%.
The specification requirement of above-mentioned raw materials is as follows:
Potassium hyperchlorate is industrial goods.
1,1- diaminourea -2,2- dinitro ethylene, hereinafter referred to as FOX-7, density 1.885g/cm3, bright yellow solid Powder.The structural formula of FOX-7 is as follows:
4,4 '-MDA, four glycidyl amine type epoxy resins (being abbreviated as TGDDM), rufous is to amber Thick liquid, epoxide number >=0.8 equivalent/100g, 3.0~7.0Pas of viscosity (50 DEG C).The structural formula of TGDDM is as follows:
The epoxide number of epoxy resin E-51 is 0.48~0.54,6.0~10.0Pas of viscosity (25 DEG C), polymerization degree n= 0.1~0.28, relative molecular mass is 307~420.The molecular formula of epoxy resin E-51 is as follows:
O-tolyl glycidyl ether outward appearance for colourless to light yellow transparent liquid, epoxide number be 0.50~0.54 equivalent/ 100g, 25 DEG C of viscositys are 5~10mPas.
Polyethyleneglycol diglycidylether outward appearance for colourless to light yellow transparent liquid, work as 0.30~0.36 by epoxide number Amount/100g, 25 DEG C of viscositys are 50~70mPas.
The viscosity of silicone resin is (100~1100) × 10-6m2/ s, refractive index nD 251.400~1.410.
Preparation method of the above-mentioned oil/gas deep well with high temperature resistant solid propellant, the method are followed the steps below:
Step one, according to formula proportion, by weight percentage, is 10%~20.90% by high-temperature-resistant epoxy resin, double Phenol A epoxy resin is 0~16.58%, and epoxide resin reactive diluent is 4.75%~13.03%, accelerator boron trifluoride-amine Complex is 0.50%, and defoamer is 0.03%, adds in mixing kettle, premixes 10 minutes;
Step 2, by weight percentage, adds potassium hyperchlorate to be 35%~50%, 1,1- in the system of step one Diaminourea -2,2- dinitros ethylene are 10%~25%, after mixing 50 minutes, add DADPS for 6.57%~ 8.14%, mixing stopped mixing after 15 minutes, obtained medicine slurry;
Step 3, the medicine slurry that step 2 is obtained is poured in mould, be put into 130 DEG C it is oven for curing 72 hours, move back mould, Obtain high temperature resistant solid propellant finished product.
The specific embodiment of the present invention given below, implement it should be noted that is the invention is not limited in detail below Example, all equivalents done on the basis of technical scheme each fall within protection scope of the present invention.
Embodiment 1:
The oil/gas deep well of the present embodiment high temperature resistant solid propellant, by weight percentage, is made up of following raw material:It is high Potassium chlorate is 35%, 1,1- diaminourea -2, and 2- dinitros ethylene is 25%, 4,4 '-MDA, four (+)-2,3-Epoxy-1-propanol Amine type epoxy resin is 14.40%, and epoxy resin E-51 is 5.47%, and o-tolyl glycidyl ether is 13.03%, accelerator Boron trifluoride-amine complex is 0.50%, and silicone resin is 0.03%, and DADPS is 6.57%.
Performance test:
Quick-fried heat presses 701.2 quick-fried heat of GJB770B-2005 methods and combustion heat constant temperature method is determined.
Specific volume presses 702.1 specific volume pressure transducer method of GJB770B-2005 methods measure.
Heat-resisting quantity method of testing is:(1) 3 DEG C/min of Ф 20mm × 20mm powder columns rises to 200 DEG C, is incubated 48h;(2) control Warm spot:Thermocouple is suspended from directly over sample, is not contacted with sample.Sample thermal weight loss is not more than 3%, does not fire not quick-fried as by examination Test.
Propellant is water-fast, and method of testing is:50mm × 50mm × 20mm medicine blocks submergence 48h in tap water, weightlessness are less than 3%, change in volume is less than 2%, as by test.
The properties test result of the oil/gas deep well high temperature resistant solid propellant of the present embodiment is shown in Table 1.
1 embodiment of table, 1 properties test result
As can be drawn from Table 1, quick-fried heat (i.e. energy) comparison of the propellant is high, and specific volume is moderate, and resistance to elevated temperatures, resistance to Aqueouss can reach performance requirement with resistance to salt water.The heat-resisting Pressure breaking bullet powder charge of suitable oil/gas deep well is used.
Embodiment 2:
The oil/gas deep well of the present embodiment high temperature resistant solid propellant, by weight percentage, is made up of following raw material:It is high Potassium chlorate be 40%, FOX-7 be 20%, TGDDM be 20.90%, o-tolyl glycidyl ether be 11.25%, accelerator three Boron fluoride-amine complex is 0.50%, and silicone resin is 0.03%, and DADPS is 7.32%.
The oil/gas deep well of the present embodiment is same as Example 1 with the performance test methods of high temperature resistant solid propellant, every The performance test results are shown in Table 2.
2 embodiment of table, 2 properties test result
As can be drawn from Table 2, the quick-fried heat (i.e. energy) of the propellant is slightly higher, and specific volume is moderate, and resistance to elevated temperatures, water-fast Performance and resistance to salt water can reach performance requirement.The heat-resisting Pressure breaking bullet powder charge of suitable oil/gas deep well is used.
Embodiment 3:
The oil/gas deep well of the present embodiment high temperature resistant solid propellant, by weight percentage, is made up of following raw material:It is high Potassium chlorate be 50%, FOX-7 be 10%, TGDDM be 10%, epoxy resin E-51 be 16.58%, o-tolyl glycidyl ether For 4.75%, accelerator boron trifluoride-amine complex is 0.50%, and silicone resin is 0.03%, and DADPS is 8.14%.
The oil/gas deep well of the present embodiment is same as Example 1 with the performance test methods of high temperature resistant solid propellant, every The performance test results are shown in Table 3.
3 embodiment of table, 3 properties test result
As can be drawn from Table 3, the quick-fried heat (i.e. energy) of the propellant is moderate, and specific volume is moderate, and resistance to elevated temperatures, water-fast Performance and resistance to salt water can reach performance requirement.It also is adapted for the heat-resisting Pressure breaking bullet powder charge of oil/gas deep well to use.
In all of above embodiment, raw material o-tolyl glycidyl ether can be replaced with polyethyleneglycol diglycidylether Change, raw material 4,4 '-MDA, four glycidyl amine type epoxy resins (being abbreviated as TGDDM) can be with 3,4 '-diamino Four (+)-2,3-Epoxy-1-propanol of four glycidyl amine type epoxy resins of yl diphenyl ether (being abbreviated as 3,4 '-TGDDE) or 4,4 '-diaminodiphenyl ether Amine type epoxy resin (being abbreviated as 4,4 '-TGDDE) is replaced, and technique effect is identical, in view of length, no longer will provide corresponding one by one Embodiment.

Claims (2)

1. a kind of oil/gas deep well high temperature resistant propellant, it is characterised in that weight percent is constituted:Potassium hyperchlorate is 35%, 1,1- Diaminourea -2,2- dinitros ethylene are 25%, 4, and 4 '-MDA, four glycidyl amine type epoxy resin is 14.40%, epoxy resin E-51 are 5.47%, and o-tolyl glycidyl ether is 13.03%, and boron trifluoride-amine complex is 0.50%, silicone resin is 0.03%, and DADPS is 6.57%;
Obtained oil/gas deep well high temperature resistant propellant carries out heat-resisting quantity test at 200 DEG C, is incubated 48h, the heat mistake of sample Weight is 0.066%.
2. preparation method of the oil/gas deep well as claimed in claim 1 with high temperature resistant propellant, the method are entered according to following steps OK:
Step one, according to formula proportion, by 4,4 '-MDA, four glycidyl amine type epoxy resin, epoxy resin E-51, o-tolyl glycidyl ether, boron trifluoride-amine complex, silicone resin are added in mixing kettle, are premixed 10 minutes;
Step 2, addition potassium hyperchlorate, 1,1- diaminourea -2 in mixing kettle, 2- dinitro ethylene, after mixing 50 minutes, DADPS is added, mixing stops mixing after 15 minutes, obtains medicine slurry;
Step 3, medicine slurry is poured in mould, be put into 130 DEG C it is oven for curing 72 hours, move back mould, obtain high temperature resistant solid and push away Enter agent finished product.
CN201510075729.XA 2015-02-12 2015-02-12 High-temperature-resistant propellant for deep oil-gas well and preparation method thereof Expired - Fee Related CN104591934B (en)

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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

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CN103304351A (en) * 2013-05-29 2013-09-18 西安近代化学研究所 High-temperature-resistant solid propellant for deep oil-gas well and preparation method thereof

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CN103045143A (en) * 2012-11-14 2013-04-17 浙江华正新材料股份有限公司 Halogen-free epoxy adhesive and cover film prepared by using halogen-free epoxy adhesive
CN103304351A (en) * 2013-05-29 2013-09-18 西安近代化学研究所 High-temperature-resistant solid propellant for deep oil-gas well and preparation method thereof

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