EP4165006A1 - Method for extracting ammonium perchlorate from a solid composite propellant - Google Patents
Method for extracting ammonium perchlorate from a solid composite propellantInfo
- Publication number
- EP4165006A1 EP4165006A1 EP21737723.3A EP21737723A EP4165006A1 EP 4165006 A1 EP4165006 A1 EP 4165006A1 EP 21737723 A EP21737723 A EP 21737723A EP 4165006 A1 EP4165006 A1 EP 4165006A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- aqueous solution
- solid composite
- composite propellant
- water
- pieces
- Prior art date
- 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.)
- Granted
Links
- 239000003380 propellant Substances 0.000 title claims abstract description 102
- 239000002131 composite material Substances 0.000 title claims abstract description 91
- 239000007787 solid Substances 0.000 title claims abstract description 90
- 238000000034 method Methods 0.000 title claims abstract description 66
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000007900 aqueous suspension Substances 0.000 claims abstract description 21
- 239000012634 fragment Substances 0.000 claims abstract description 18
- 239000007864 aqueous solution Substances 0.000 claims description 76
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 48
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- 239000000725 suspension Substances 0.000 claims description 19
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 14
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- YQEMORVAKMFKLG-UHFFFAOYSA-N glycerine monostearate Natural products CCCCCCCCCCCCCCCCCC(=O)OC(CO)CO YQEMORVAKMFKLG-UHFFFAOYSA-N 0.000 claims description 6
- SVUQHVRAGMNPLW-UHFFFAOYSA-N glycerol monostearate Natural products CCCCCCCCCCCCCCCCC(=O)OCC(O)CO SVUQHVRAGMNPLW-UHFFFAOYSA-N 0.000 claims description 6
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 239000002280 amphoteric surfactant Substances 0.000 claims description 5
- 239000003945 anionic surfactant Substances 0.000 claims description 5
- 238000013467 fragmentation Methods 0.000 claims description 5
- 238000006062 fragmentation reaction Methods 0.000 claims description 5
- 239000002736 nonionic surfactant Substances 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 230000007928 solubilization Effects 0.000 claims description 4
- 238000005063 solubilization Methods 0.000 claims description 4
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 235000010216 calcium carbonate Nutrition 0.000 claims description 3
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 3
- 229940075614 colloidal silicon dioxide Drugs 0.000 claims description 3
- GXGAKHNRMVGRPK-UHFFFAOYSA-N dimagnesium;dioxido-bis[[oxido(oxo)silyl]oxy]silane Chemical compound [Mg+2].[Mg+2].[O-][Si](=O)O[Si]([O-])([O-])O[Si]([O-])=O GXGAKHNRMVGRPK-UHFFFAOYSA-N 0.000 claims description 3
- 239000008172 hydrogenated vegetable oil Substances 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000391 magnesium silicate Substances 0.000 claims description 3
- 235000019359 magnesium stearate Nutrition 0.000 claims description 3
- 235000019793 magnesium trisilicate Nutrition 0.000 claims description 3
- 229940099273 magnesium trisilicate Drugs 0.000 claims description 3
- 229910000386 magnesium trisilicate Inorganic materials 0.000 claims description 3
- 239000000454 talc Substances 0.000 claims description 3
- 229910052623 talc Inorganic materials 0.000 claims description 3
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 238000002803 maceration Methods 0.000 abstract description 3
- 239000012071 phase Substances 0.000 description 30
- 238000000605 extraction Methods 0.000 description 14
- 239000003638 chemical reducing agent Substances 0.000 description 9
- 239000002699 waste material Substances 0.000 description 8
- 238000000227 grinding Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 6
- 230000006378 damage Effects 0.000 description 5
- 239000007800 oxidant agent Substances 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- 239000005062 Polybutadiene Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920005596 polymer binder Polymers 0.000 description 3
- 239000002491 polymer binding agent Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- -1 Na + Chemical class 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 238000003915 air pollution Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- CMCBDXRRFKYBDG-UHFFFAOYSA-N 1-dodecoxydodecane Chemical compound CCCCCCCCCCCCOCCCCCCCCCCCC CMCBDXRRFKYBDG-UHFFFAOYSA-N 0.000 description 1
- DDGPBVIAYDDWDH-UHFFFAOYSA-N 3-[dodecyl(dimethyl)azaniumyl]-2-hydroxypropane-1-sulfonate Chemical compound CCCCCCCCCCCC[N+](C)(C)CC(O)CS([O-])(=O)=O DDGPBVIAYDDWDH-UHFFFAOYSA-N 0.000 description 1
- QKFFSWPNFCXGIQ-UHFFFAOYSA-M 4-methylbenzenesulfonate;tetraethylazanium Chemical compound CC[N+](CC)(CC)CC.CC1=CC=C(S([O-])(=O)=O)C=C1 QKFFSWPNFCXGIQ-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 235000015842 Hesperis Nutrition 0.000 description 1
- 235000012633 Iberis amara Nutrition 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920003006 Polybutadiene acrylonitrile Polymers 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000005228 aryl sulfonate group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 229940079881 disodium lauroamphodiacetate Drugs 0.000 description 1
- QKQCPXJIOJLHAL-UHFFFAOYSA-L disodium;2-[2-(carboxylatomethoxy)ethyl-[2-(dodecanoylamino)ethyl]amino]acetate Chemical compound [Na+].[Na+].CCCCCCCCCCCC(=O)NCCN(CC([O-])=O)CCOCC([O-])=O QKQCPXJIOJLHAL-UHFFFAOYSA-L 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- XDRMBCMMABGNMM-UHFFFAOYSA-N ethyl benzenesulfonate Chemical compound CCOS(=O)(=O)C1=CC=CC=C1 XDRMBCMMABGNMM-UHFFFAOYSA-N 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- DBQHRENFKZKVRW-BTVCFUMJSA-N hexanoic acid;(2r,3s,4r,5r)-2,3,4,5,6-pentahydroxyhexanal Chemical compound CCCCCC(O)=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O DBQHRENFKZKVRW-BTVCFUMJSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- CZXGXYBOQYQXQD-UHFFFAOYSA-N methyl benzenesulfonate Chemical compound COS(=O)(=O)C1=CC=CC=C1 CZXGXYBOQYQXQD-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000012255 powdered metal Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 229940083575 sodium dodecyl sulfate Drugs 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 229940045845 sodium myristate Drugs 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- 229940045870 sodium palmitate Drugs 0.000 description 1
- 229940080350 sodium stearate Drugs 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- GGXKEBACDBNFAF-UHFFFAOYSA-M sodium;hexadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCC([O-])=O GGXKEBACDBNFAF-UHFFFAOYSA-M 0.000 description 1
- JUQGWKYSEXPRGL-UHFFFAOYSA-M sodium;tetradecanoate Chemical compound [Na+].CCCCCCCCCCCCCC([O-])=O JUQGWKYSEXPRGL-UHFFFAOYSA-M 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
- C06B21/0091—Elimination of undesirable or temporary components of an intermediate or finished product, e.g. making porous or low density products, purifying, stabilising, drying; Deactivating; Reclaiming
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B29/00—Compositions containing an inorganic oxygen-halogen salt, e.g. chlorate, perchlorate
- C06B29/22—Compositions containing an inorganic oxygen-halogen salt, e.g. chlorate, perchlorate the salt being ammonium perchlorate
Definitions
- the present invention relates to the field of the treatment and inerting of solid composite propellants.
- the present invention aims to provide a simple process, easy to implement, respectful of the environment and allowing the total extraction of ammonium perchlorate from composite propellants.
- Solid composite propellants are energetic compositions made up of a macromolecular matrix of combustible polymer, called a binder, loaded with an oxidant and a reducing agent.
- this oxidant and this reducing agent are present, respectively, in powdered solid form and in the form of a powdered metal.
- Solid composite propellants are widely used in astronautics in boosters for take-off from space launchers or in retro-rockets from space probes. They are also used in devices of the “airbag” type for automobile safety.
- a second method commonly used to dispose of waste from the production of solid composite propellants is to burn them in the open. Open combustion is limited by weather conditions and generates combustion products which are a source of air pollution. Until now, the destruction of the propellant by burning was authorized.
- patent application FR 2931814 proposes a process for purifying, before their discharge, aqueous solutions containing ammonium perchlorate and optionally nitrates, obtained following this grinding.
- the grinding under water of the waste based on solid composite propellants did not make it possible to extract all of the ammonium perchlorate.
- the inventors have therefore set themselves the goal of proposing an easy method of implementation and making it possible to extract all of the ammonium perchlorate initially contained in the waste based on solid composite propellant and thus to outsource the waste of composite propellant.
- solid inert in a conventional incineration process with flue gas treatment are examples of solid inert in a conventional incineration process with flue gas treatment.
- the present invention provides a process for recovering the ammonium perchlorate contained in a solid composite propellant, said process comprising the steps of: i) contacting, with a first aqueous solution, the solid composite propellant in the form of pieces; ii) subjecting said pieces of solid composite propellant present in said first aqueous solution to fragmentation so as to obtain fragments of solid composite propellant, the largest dimension of which does not exceed 10 mm; iii) add, to the mixture obtained in step ii), a second aqueous solution in which the quantity of water is such that the weight ratio W / P is between 2.5 and 6.8 with E representing the sum of the mass of water in the first aqueous solution and the mass of water in the second aqueous solution and P representing the mass of solid composite propellant in the form of pieces and stirring the whole whereby an aqueous suspension is obtained; iv) maintaining said stirring for a time sufficient for the ammonium perchlorate to dissolve in the continuous phase of said suspension, said so
- the method according to the invention has at least one of the following optional characteristics, taken individually or in combination.
- the largest dimension of the pieces of solid composite propellant used during step i) does not exceed 50 mm.
- the dimensions of the pieces of solid composite propellant used during step i) are less than or equal to the dimensions of a rectangular parallelepiped of 25 mm x 25 mm x 50 mm.
- the mass ratio E / P is equal to 4.
- Steps (i) to (iv) of the process are carried out at an identical or different temperature of between 30 ° C and 40 ° C.
- the first aqueous solution, the second aqueous solution and / or the third aqueous solution comprises an anti-sticking agent.
- the first aqueous solution consists of water and an anti-sticking agent
- the second aqueous solution consists of water and / or the third aqueous solution consists of water.
- the anti-sticking agent is chosen from the group consisting of talc, glycerol monostearate, kaolin, calcium carbonate, magnesium trisilicate, stearic acid, calcium stearate, magnesium stearate, zinc stearate, glycerol monostearate, glycerol palmitostearate, polyethylene glycol, ester of glycerol benenic acid, colloidal silicon dioxide, finely divided silicon dioxide, aluminum hydroxide, a hydrogenated vegetable oil, anionic surfactants, nonionic surfactants and amphoteric surfactants.
- Figure 1 is a schematic diagram of the process for recovering ammonium perchlorate from solid composite propellant according to the present invention.
- FIG. 2 is a schematic flow diagram of the complete solid composite propellant treatment line in which the “extraction by maceration” block corresponds to the process for recovering ammonium perchlorate according to the present invention.
- the present invention provides a process for treating solid composite propellant making it possible to extract and recover at least 95%, at least 97%, at least 98%, at least 99%, at least 99.5% by mass and ideally the all of the ammonium perchlorate (NH4CIO4) it contains.
- the inventors have shown that from a reasoned combination of the parameters used during the step of extracting ammonium perchlorate from a solid composite propellant, namely the size of the pieces and fragments of solid composite propellant at the start of the process, the mass ratio between the water and the propellant and the extraction temperature, it is possible to ensure complete extraction of the ammonium perchlorate initially contained in the solid composite propellant.
- the process for recovering ammonium perchlorate from solid composite propellant according to the invention is included in a waste treatment route based on solid composite propellant which respects the environment.
- the invention makes it possible to inert the solid composite propellant by a process for extracting ammonium perchlorate and thus to externalize the inert solid composite propellant waste in a conventional incineration process with a treatment of the fumes.
- the process for recovering ammonium perchlorate from solid composite propellant according to the invention takes place entirely under water, allowing the propellant to be cut while minimizing the risks.
- the operating conditions implemented within the framework of the process according to the invention namely little heating, simple mechanics and a large proportion of water, have the advantage of being a simple process with operating conditions with limited risks. , this process being considered as non-pyrotechnic after loading the reactor with the extractant.
- the control of the temperature during the process according to the invention makes it possible to minimize the reaction of the reducing agent such as the powdered aluminum contained. in the solid composite propellant with the water contained in the various aqueous solutions used.
- the process for recovering ammonium perchlorate from solid composite propellant according to the invention makes it possible to obtain not only an aqueous solution containing all of the ammonium perchlorate but also a polymeric residue containing reducing agent and exhibiting a potential calorific value for the incineration process in which the extraction residues are treated.
- the present invention relates to a process for recovering the ammonium perchlorate contained in a solid composite propellant, said process comprising the steps of: i) bringing into contact, with a first aqueous solution, the solid composite propellant in the form of of pieces; ii) subjecting said pieces of solid composite propellant present in said first aqueous solution to fragmentation so as to obtain fragments of solid composite propellant, the largest dimension of which does not exceed 10 mm; iii) add, to the mixture obtained in step ii), a second aqueous solution in which the quantity of water is such that the weight ratio W / P is between 2.5 and 6.8 with E representing the sum of the mass of water in the first aqueous solution and the mass of water in the second aqueous solution and P representing the mass of solid composite propellant in the form of pieces and stirring the whole whereby an aqueous suspension is obtained; iv) maintaining said stirring for a time sufficient for the ammonium perchlorate to dissolve in the continuous phase of said suspension
- solid composite propellant is meant, in the context of the present invention, an energetic composition comprising a polymer binder, a reducing agent and an oxidant, said oxidant comprising or consisting of ammonium perchlorate.
- the present invention applies to any solid composite propellant, the oxidant of which comprises or consists of ammonium perchlorate, regardless of the nature of the polymer binder and that of the reducing agent.
- the polymer binder present in the solid composite propellant treated in the context of the present invention is a polyurethane or a polybutadiene such as, for example, a hydroxytelechelic polybutadiene (PBHT), a polybutadiene - acrylic acid - acrylonitrile (PBAN) terpolymer or a carboxytelechelic polybutadiene (PBCT).
- PBHT hydroxytelechelic polybutadiene
- PBAN polybutadiene - acrylic acid - acrylonitrile
- PBCT carboxytelechelic polybutadiene
- the reducing agent present in the solid composite propellant treated in the context of the present invention is powdered aluminum or powdered magnesium.
- the solid composite propellant treated in the context of the present invention comes essentially from workshops for the production of solid composite propellant or from workshops for emptying the propellants in return for supply. Solid composite propellant therefore comes in various sizes and shapes. Usually, the maximum size of the solid composite propellant is 80cm.
- one of the parameters favoring the total extraction of ammonium perchlorate is the size of the pieces of solid composite propellant at the start of the process. Thus, the largest dimension of these pieces does not exceed 50 mm.
- the solid composite propellant may be subjected to one or more grinding stages, prior to the implementation of the process according to the invention.
- the solid composite propellant is subjected to two stages grinding prerequisites carried out by means of knife mills. These two grinding stages make it possible to obtain pieces of composite propellant, the largest dimension of which is less than or equal to 50 mm and, in particular, the dimensions of which are less than or equal to the dimensions of a rectangular parallelepiped of 25 mm x 25 mm x 50 mm.
- the solution implemented during step i) of the process according to the invention comprises, as solvent, water, thus justifying the designation of aqueous solution.
- water is meant, in the context of the present invention, tap water, deionized water, distilled water or even ultra-pure water (18.2 MW).
- the solution used during step i) of the process according to the invention can be a neutral, acidic or basic aqueous solution.
- the solution used during step i) is an aqueous solution whose pH is between 4 and 9.
- the aqueous solution used during step i) only comprises water, i.e. it consists of water.
- it can comprise at least one other element in addition to the solvent, which is water. This other element is in particular an anti-sticking agent.
- anti-sticking agent means a compound capable of limiting the stickiness of the pieces and subsequently of the fragments of solid composite propellant and therefore of preventing the pieces and subsequently the fragments of solid composite propellant from aggregating together. and re-agglomerate. It should be noted that the temperature of steps (i) to (iv) below 50 ° C and in particular between 30 ° C and 40 ° C also makes it possible to control the re-agglomeration of pieces or fragments of solid composite propellant. Any anti-tackifying agent known to those skilled in the art can be used within the framework of the present invention.
- the anti-sticking agent used in the context of the present invention is chosen from the group consisting of talc, glycerol monostearate, kaolin, calcium carbonate, magnesium trisilicate, stearic acid , calcium stearate, magnesium stearate, zinc stearate, glycerol monostearate, glycerol palmitostearate, a polyethylene glycol, the ester of glycerol benenic acid, colloidal silicon dioxide, finely divided silicon, aluminum hydroxide, hydrogenated vegetable oil, agents anionic surfactants, nonionic surfactants and amphoteric surfactants.
- a surfactant is a molecule comprising a lipophilic (nonpolar) part and a hydrophilic (polar) part.
- anionic surfactants exhibit a negatively charged hydrophilic part such as alkyl or aryl sulfonates, sulfates, phosphates, or sulfosuccinates associated with a counterion such as an ammonium ion (NH 4+ ), a quaternary ammonium such as tetrabutylammonium, and alkali cations such as Na + , Li + and K + .
- a counterion such as an ammonium ion (NH 4+ )
- a quaternary ammonium such as tetrabutylammonium
- alkali cations such as Na + , Li + and K + .
- anionic surfactants it is, for example, possible to use tetraethylammonium paratoluenesulfonate, sodium dodecylsulfate, sodium palmitate, sodium stearate, sodium myristate, di (2-ethylhexyl) sodium sulfosuccinate, methylbenzene sulfonate and ethylbenzene sulfonate.
- nonionic surfactants and, in particular hydrophilicity, are provided by uncharged functional groups such as an alcohol, an ether, an ester or even an amide, containing heteroatoms such as l. nitrogen or oxygen; due to the low hydrophilic contribution of these functions, the nonionic surfactant compounds are most often polyfunctional.
- nonionic surfactants it is possible to use polyethers such as polyethoxylated surfactants such as, for example, polyethylene glycol lauryl ether (POE23 or Brij ® 35), polyols (surfactants derived from sugars) in particular alkylates glucose, such as, for example, glucose hexanate.
- Amphoteric surfactants are compounds which behave both as an acid or as a base depending on the medium in which they are placed. As amphoteric surfactants, it is possible to use disodium lauroamphodiacetate, betaines such as alkylamidopropyl betaine or laurylhydroxysulfobetaine.
- the anti-sticking agent is used in an amount less than or equal to 5% by mass relative to the mass of propellant treated and in particular in an amount between 1% and 3% by mass relative to the mass of propellant treated.
- the contacting during step i) is carried out in a reactor whose dimensions will be adapted to the quantity of solid composite propellant to be treated.
- first aqueous solution optionally containing, in addition to water, an additional element such as an anti-sticking agent.
- an additional element such as an anti-sticking agent
- the latter can be placed in the reactor before or after the first aqueous solution or before or after the pieces. of solid composite propellant or else be mixed beforehand with the first aqueous solution before the latter is introduced into the reactor.
- Figure 1 illustrates the particular embodiment in which the water is introduced into the reactor and then the anti-sticking agent is added to this water whereby a first aqueous solution consisting of water and an anti-sticking agent is obtained then the pieces of solid composite propellant are introduced into the reactor filled with this first aqueous solution.
- step i) is variable and essentially depends on the quantity of pieces of solid composite propellant to be introduced into the reactor.
- step i) can last between 30 min and 2 h.
- step i) can last approximately 1 h (ie 1 h ⁇ 15 min) and this, in particular for 1.5 10 3 kg of pieces of solid composite propellant, as illustrated in FIG. 1.
- Step i) is carried out at a temperature less than or equal to 50 ° C and in particular at a temperature between 30 ° C and 40 ° C. To do this, step i) is carried out in a thermostatically controlled reactor.
- Step ii) of the process according to the invention is a step consisting in fragmenting the pieces of solid composite propellant so as to obtain fragments of solid composite propellant of smaller size, ie fragments of which the largest dimension is less than or equal to 10 mm and, in particular, the dimensions of which are less than or equal to the dimensions of a cube of 10 mm x 10 mm x 10 mm.
- This fragmentation is obtained by means of means usually used in reactors for fragmenting, dispersing and / or crushing elements such as a dispersion / fragmentation turbine or a rotor-stator system. These means advantageously have a peripheral speed greater than or equal to 10 m / s.
- step ii) is variable and essentially depends on the quantity of pieces of solid composite propellant to be fragmented in the reactor. Typically, step ii) can last between 15 min and 2.5 h. By way of example, step ii) can last between 30 min and 90 min, in particular for 1.5 10 3 kg of pieces of solid composite propellant to be fragmented, as illustrated in FIG. 1.
- Step ii) is carried out at a temperature less than or equal to 50 ° C and in particular at a temperature between 30 ° C and 40 ° C. To do this, step ii) is carried out in a thermostatically controlled reactor. Step ii) is carried out in the same thermostatted reactor as that implemented for step i).
- step iii) a second aqueous solution is added, in the thermostatted reactor used during steps i) and ii), to the mixture obtained at the end of step ii).
- This mixture consists of fragments of solid composite propellant dispersed in the first aqueous solution, part of the ammonium perchlorate initially present in the pieces of solid composite propellant possibly already being in solubilized form in this first aqueous solution.
- the second aqueous solution used during step iii) of the process according to the invention comprises, as solvent, water, thus justifying the designation of aqueous solution.
- the second aqueous solution used during step iii) only comprises water, ie it consists of water.
- it can comprise at least one other element in addition to the solvent, which is water.
- This other element is in particular an anti-sticking agent as defined above.
- the anti-sticking agent is used in an amount less than or equal to 5% by mass relative to the mass of propellant treated and in particular in an amount between 1% and 3% by mass per relative to the mass of propellant treated.
- the composition of the second aqueous solution may be the same or different from the composition of the first aqueous solution.
- Figure 1 illustrates the embodiment in which the second aqueous solution comprises only water i.e. consists of water.
- one of the parameters influencing the total extraction of the ammonium perchlorate initially contained in the pieces of solid composite propellant is the mass ratio between the mass of water contained in the first aqueous solution and in the second aqueous solution designated "E" and the mass of solid composite propellant to be treated designated "P".
- This mass corresponds, in fact, to the mass of the pieces of solid composite propellant used during step i) of the process according to the invention. It is obvious that the mass of water and the mass of propellant must be expressed in the same unit of mass.
- This W / P mass ratio is between 2.5 and 6.8, in particular between 3 and 6, in particular between 3.5 and 5 and, more particularly, the W / P mass ratio is equal to 4.
- the amount of second aqueous solution used during step ii) will depend on the amount of water it contains, on the amount of water contained in the first aqueous solution and on the target W / P mass ratio.
- step iii) and following the addition of the second aqueous solution the whole is stirred and an aqueous suspension is obtained.
- This aqueous suspension initially comprises a dispersed phase corresponding to the solid composite propellant fragments and a continuous phase comprising the mixture of the first aqueous solution and the second aqueous solution and optionally a part of the ammonium perchlorate already solubilized.
- Step iii) carried out in the thermostatted reactor used during steps i) and ii) is carried out at a temperature less than or equal to 50 ° C and in particular at a temperature between 30 ° C and 40 ° C.
- Step iv) of the process according to the invention is the step of extracting the ammonium perchlorate itself.
- the solid composite propellant fragments are kept in suspension and the solubilization of the perchlorate in the continuous phase of the suspension is promoted.
- the chemical composition of the aqueous suspension changes during step iv), the solid composite propellant fragments losing over time the pulverulent ammonium perchlorate that they initially contained, while in parallel, the phase continues to the aqueous suspension is enriched in dissolved ammonium perchlorate.
- Step iv) is carried out in the same thermostatically controlled reactor as that implemented during steps i) to iii) of the process according to the present invention. Consequently, step iv) is carried out at a temperature less than or equal to 50 ° C and in particular at a temperature between 30 ° C and 40 ° C.
- the thermostatted reactor is equipped with means suitable for stirring and maintaining in suspension the fragments of solid composite propellant. Any means known to those skilled in the art for this purpose can be used within the framework of the present invention.
- the means suitable for stirring and keeping the solid composite propellant fragments in suspension are in particular a three-bladed propeller possibly associated with a counter-rotating anchor.
- the dimensions of the three-bladed propeller are defined by the target fluidization speed as a function of the characteristics of the solid composite propellant fragments dispersed in the suspension.
- the counter-rotating anchor serves, for its part, to limit the dead zones and to reduce the vortex to avoid cavitation of the dispersion means.
- the thermostatted reactor is also equipped with means suitable for measuring the ionic conductivity of the suspension contained in said reactor. Any means known to those skilled in the art for measuring an ionic conductivity can be used within the framework of the present invention.
- the thermostatically controlled reactor is equipped with a conductivity meter designed to measure the ionic conductivity of the suspension which it contains.
- the measurement of the ionic conductivity can be carried out continuously or on an ad hoc basis, the time interval between two successive measurements being able to be regular or irregular.
- step iv) is variable and essentially depends on the quantity of composite propellant fragments.
- step iv) can last between 6 h and 15 h.
- step iv) can last less than 10 h and in particular between 8 h and 9.5 h, in particular for 1.5 10 3 kg of pieces of solid composite propellant initially used, as illustrated in Figure 1.
- Step v) of the process according to the invention is the step at which the end of the extraction is authorized, from the moment when the ionic conductivity in the suspension reaches a stabilized value, less than 60 mS / cm .
- stabilized value is meant a value of the ionic conductivity measured in the suspension which does not vary by more than 1 mS / cm upwards or downwards, during a period of more than 60 seconds.
- This stabilization phase can be more or less long depending on the products, which can vary from 1 h to 6 h.
- the stability of the signal is studied by the automatic device after an incompressible time of 1 h to ensure total extraction on products with little load.
- step v) of the process according to the present invention the dispersed phase and the continuous phase are separated from the aqueous suspension obtained at the end of the extraction.
- the dispersed phase essentially comprises the polymer playing the role of binder in the solid composite propellant, this polymer containing the reducing agent of the solid composite propellant such as aluminum or magnesium.
- This residue is therefore no longer a pyrotechnic product. It can be treated by conventional methods of incineration or recovery of the reducing agent such as aluminum.
- the continuous phase of the aqueous suspension obtained at the end of the extraction is an aqueous solution containing ammonium perchlorate.
- This solution usually called “brine” can be treated biologically, as proposed in patent application FR 2931814, before its rejection.
- step v) of the process is carried out by emptying the reactor in which steps i) to iv) have been implemented.
- the two phases are extracted and a solid liquid separation makes it possible to recover the continuous phase in order to direct it to the biological treatment; and recovering the solid phase with a view to an optional dewatering phase before upgrading to incineration.
- step v) of the process according to the present invention be carried out at a temperature between 30 ° C and 40 ° C.
- This step v) can be carried out at room temperature.
- ambient temperature is meant a temperature of the order of 23 ° C (ie 23 ° C ⁇ 5 ° C).
- the dispersed phase thus recovered can be drained so as to extract therefrom as much as possible of the continuous phase.
- Any spin-drying technique known to those skilled in the art can be used within the framework of the present invention.
- the ionic conductivity of the aqueous suspension it is possible for the ionic conductivity of the aqueous suspension to have a stabilized value greater than or equal to 60 mS / cm.
- a stabilized value does not mean that the extraction of the ammonium perchlorate is finished but, on the contrary, that it is necessary to renew the continuous phase of the suspension to ensure the inert nature of the residues at the end of the process and complete the extraction of the ammonium perchlorate still present in the dispersed phase.
- part of the continuous phase of the suspension is replaced by a third aqueous solution.
- part of the continuous phase of the suspension is drained from the thermostatted reactor in which step iv) is carried out and a third aqueous solution is introduced into this reactor.
- the volume of third aqueous solution introduced is identical to the volume of continuous phase drained. In a particular embodiment, half of the continuous phase contained in the reactor is drained.
- the third aqueous solution used during the process according to the invention comprises, as solvent, water, thus justifying the designation of aqueous solution.
- the third aqueous solution used only comprises water, ie it consists of water.
- it can comprise at least one other element in addition to the solvent, which is water.
- This other element is in particular an anti-tackifying agent as defined above.
- the anti-sticking agent is used in an amount less than or equal to 5% by mass relative to the mass of propellant treated and in particular in an amount between 1% and 3% by mass relative to the mass of propellant treated.
- composition of the third aqueous solution may be the same or different from the composition of the first aqueous solution and may be the same or different from the composition of the second aqueous solution.
- Figure 1 illustrates the embodiment in which the third aqueous solution comprises only water ie consists of water.
- step iv) is continued ie stirring of the resulting suspension is continued until a stabilized value of the conductivity. ionic is again obtained.
- step v) will be implemented (value less than 60 mS / cm), or a new emptying of the reactor and a supply of a new aqueous solution ( value greater than or equal to 60 mS / cm).
- FIG. 2 shows all the steps of the process for treating a solid composite propellant, among which the process for recovering ammonium perchlorate according to the invention corresponds to the “extraction by maceration” block.
- steps prior to or subsequent to the process according to the invention previously described, such as the steps of grinding and dewatering.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
- Extraction Or Liquid Replacement (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Molecular Biology (AREA)
- Dispersion Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Sustainable Development (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Cosmetics (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR2006254A FR3111276B1 (en) | 2020-06-16 | 2020-06-16 | METHOD FOR EXTRACTION OF AMMONIUM PERCHLORATE CONTAINED IN A SOLID COMPOSITE PROPELLANT |
PCT/FR2021/051066 WO2021255377A1 (en) | 2020-06-16 | 2021-06-15 | Method for extracting ammonium perchlorate from a solid composite propellant |
Publications (2)
Publication Number | Publication Date |
---|---|
EP4165006A1 true EP4165006A1 (en) | 2023-04-19 |
EP4165006B1 EP4165006B1 (en) | 2024-07-03 |
Family
ID=73013536
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP21737723.3A Active EP4165006B1 (en) | 2020-06-16 | 2021-06-15 | Method for extracting ammonium perchlorate from a solid composite propellant |
Country Status (6)
Country | Link |
---|---|
US (1) | US20230219865A1 (en) |
EP (1) | EP4165006B1 (en) |
KR (1) | KR20230042692A (en) |
FR (1) | FR3111276B1 (en) |
IL (1) | IL299050A (en) |
WO (1) | WO2021255377A1 (en) |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5314550A (en) * | 1992-03-27 | 1994-05-24 | Aerojet-General Corporation | Recovery of aluminum and hydrocarbon values from composite energetic compositions |
US5346512A (en) * | 1993-08-05 | 1994-09-13 | Thiokol Corporation | Carbon treatment of reclaimed ammonium perchlorate |
FR2931814B1 (en) | 2008-06-03 | 2011-07-15 | Snpe Materiaux Energetiques | PROCESS FOR THE BIOLOGICAL PURIFICATION OF AQUEOUS SOLUTION CONTAINING AMMONIUM PERCHLORATE AND POSSIBLY NITRATES |
FR2980373B1 (en) * | 2011-09-26 | 2014-03-07 | Sme | PROCESS FOR EXTRACTING SOLUBLE LOADS CONTAINED IN A PASTE |
CZ307218B6 (en) * | 2014-01-21 | 2018-04-04 | Eruca Technologies S.R.O. | A method of processing expired solid rocket fuel |
-
2020
- 2020-06-16 FR FR2006254A patent/FR3111276B1/en active Active
-
2021
- 2021-06-15 WO PCT/FR2021/051066 patent/WO2021255377A1/en unknown
- 2021-06-15 IL IL299050A patent/IL299050A/en unknown
- 2021-06-15 US US18/001,644 patent/US20230219865A1/en active Pending
- 2021-06-15 EP EP21737723.3A patent/EP4165006B1/en active Active
- 2021-06-15 KR KR1020237001685A patent/KR20230042692A/en active Search and Examination
Also Published As
Publication number | Publication date |
---|---|
WO2021255377A1 (en) | 2021-12-23 |
EP4165006B1 (en) | 2024-07-03 |
US20230219865A1 (en) | 2023-07-13 |
IL299050A (en) | 2023-02-01 |
FR3111276B1 (en) | 2022-05-13 |
KR20230042692A (en) | 2023-03-29 |
FR3111276A1 (en) | 2021-12-17 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
FR2463110A1 (en) | EXPLOSIVE EMULSION TYPE COMPOSITION AND PROCESS FOR PREPARING THE SAME | |
CA2025693C (en) | Extraction and recovery of plasticizers from solid propellants and munitions | |
US4854982A (en) | Method to dimilitarize extract, and recover ammonium perchlorate from composite propellants using liquid ammonia | |
EP2014631A1 (en) | Hydrogen generating solid compounds and hydrogen generation method | |
EP4165006B1 (en) | Method for extracting ammonium perchlorate from a solid composite propellant | |
FR2612177A1 (en) | ELECTRICALLY IGNITIONABLE IGNITION COMPOSITIONS, WITHOUT CASE AND PROPULSIVE CARTRIDGES | |
EP0823883B1 (en) | Intercalation compounds, method for preparing them and use thereof, particularly in pyrotechnics | |
EP2483222B1 (en) | Suspensions of hexanitrohexaazaisowurtzitane crystals, production of said suspensions and production of pyrotechnic objects | |
EP0123008B1 (en) | Compositions of the "emulsion explosive" type, process for their manufacture and use of these compositions | |
EP3212593A1 (en) | Composite pyrotechnic product with adn and rdx charges in a gpa binder and preparation of same | |
EP3966257A1 (en) | Organic peroxide emulsion with ethanol | |
EP3515881B1 (en) | Composite pyrotechnic product containing an anti-gleam agent of potassium salt type | |
USRE34419E (en) | Method to demilitarize, extract, and recover ammonium perchlorate from composite propellants using liquid ammonia | |
FR2490628A1 (en) | Smokeless crosslinked double-base propellant - comprising nitrocellulose, energetic plasticiser, polyester-di:isocyanate prepolymer, lead salt and carbon black | |
WO2008017764A1 (en) | Method of radium stabilization in solid effluent or effluent containing substances in suspension | |
EP0113617A1 (en) | Inert nitrate-fuel type slurry, explosive obtained by incorporating air, and manufacturing processes | |
FR2699544A1 (en) | Process for removing low molecular weight pollutants from elastomeric gaskets and plastics | |
EP4098642A1 (en) | Meltable/castable explosive composition and method for manufacturing same | |
CA2187686A1 (en) | Broken-emulsions and process for recycling emulsion explosives | |
EP1767574A1 (en) | Process for the manufacture of energetic compositions comprising nanoparticles of an element or chemical compound dispersed in an organic matrix | |
BE1008468A4 (en) | Method for extracting heavy metals from used oils | |
EP3941595A1 (en) | Process for treating energetic materials by hydrothermal oxidation | |
KR101764195B1 (en) | Method for treating solid propellant obsolete ammunition | |
US5268046A (en) | Surfactant stabilized nitroglycerin emulsion | |
EP3802416A1 (en) | Method for producing ammonium dinitramide (adn) crystals, adn crystals and energetic composites containing same |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: UNKNOWN |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE |
|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
17P | Request for examination filed |
Effective date: 20221220 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
P01 | Opt-out of the competence of the unified patent court (upc) registered |
Effective date: 20230612 |
|
DAV | Request for validation of the european patent (deleted) | ||
DAX | Request for extension of the european patent (deleted) | ||
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: GRANT OF PATENT IS INTENDED |
|
INTG | Intention to grant announced |
Effective date: 20240222 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE PATENT HAS BEEN GRANTED |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602021015219 Country of ref document: DE |
|
U01 | Request for unitary effect filed |
Effective date: 20240709 |