CN1068415A - The recovery and treatment method of the detonator of compound containing mercury, potassium chlorate and antimony trisulphide is housed - Google Patents
The recovery and treatment method of the detonator of compound containing mercury, potassium chlorate and antimony trisulphide is housed Download PDFInfo
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- CN1068415A CN1068415A CN92105677A CN92105677A CN1068415A CN 1068415 A CN1068415 A CN 1068415A CN 92105677 A CN92105677 A CN 92105677A CN 92105677 A CN92105677 A CN 92105677A CN 1068415 A CN1068415 A CN 1068415A
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- Prior art keywords
- detonator
- iron
- mercury
- potassium chlorate
- cartridge case
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- 238000000034 method Methods 0.000 title claims abstract description 41
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 title claims abstract description 19
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 title claims abstract description 12
- NVWBARWTDVQPJD-UHFFFAOYSA-N antimony(3+);trisulfide Chemical compound [S-2].[S-2].[S-2].[Sb+3].[Sb+3] NVWBARWTDVQPJD-UHFFFAOYSA-N 0.000 title claims abstract description 8
- 150000001875 compounds Chemical class 0.000 title claims abstract description 8
- 229910052753 mercury Inorganic materials 0.000 title claims abstract description 6
- 238000011084 recovery Methods 0.000 title claims abstract description 5
- 239000000843 powder Substances 0.000 claims abstract description 21
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 14
- 239000001103 potassium chloride Substances 0.000 claims abstract description 7
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 59
- 229910052742 iron Inorganic materials 0.000 claims description 27
- MHWLNQBTOIYJJP-UHFFFAOYSA-N mercury difulminate Chemical compound [O-][N+]#C[Hg]C#[N+][O-] MHWLNQBTOIYJJP-UHFFFAOYSA-N 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 229940100892 mercury compound Drugs 0.000 claims description 6
- 150000002731 mercury compounds Chemical class 0.000 claims description 6
- 238000004064 recycling Methods 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- -1 iron ion Chemical class 0.000 claims description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 238000004939 coking Methods 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 238000012805 post-processing Methods 0.000 claims description 3
- 239000000344 soap Substances 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 238000007885 magnetic separation Methods 0.000 claims description 2
- 239000012466 permeate Substances 0.000 claims description 2
- 239000010949 copper Substances 0.000 abstract description 15
- 238000005474 detonation Methods 0.000 abstract description 12
- 239000002360 explosive Substances 0.000 abstract description 11
- 229910052802 copper Inorganic materials 0.000 abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 6
- 238000012545 processing Methods 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 239000012752 auxiliary agent Substances 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 230000037452 priming Effects 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000002161 passivation Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910000497 Amalgam Inorganic materials 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 230000009172 bursting Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 description 2
- 229940005991 chloric acid Drugs 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- USXDFAGDIOXNML-UHFFFAOYSA-N Fulminate Chemical compound [O-][N+]#[C-] USXDFAGDIOXNML-UHFFFAOYSA-N 0.000 description 1
- 241000406668 Loxodonta cyclotis Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 238000004200 deflagration Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000003721 gunpowder Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000008149 soap solution Substances 0.000 description 1
- 238000003900 soil pollution Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010891 toxic waste Substances 0.000 description 1
- 238000013519 translation Methods 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
- A62D3/37—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by reduction, e.g. hydrogenation
-
- 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
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/06—Explosives, propellants or pyrotechnics, e.g. rocket fuel or napalm
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/40—Inorganic substances
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/40—Inorganic substances
- A62D2101/43—Inorganic substances containing heavy metals, in the bonded or free state
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/40—Inorganic substances
- A62D2101/47—Inorganic substances containing oxygen, sulfur, selenium or tellurium, i.e. chalcogen
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/40—Inorganic substances
- A62D2101/49—Inorganic substances containing halogen
Landscapes
- Chemical & Material Sciences (AREA)
- Business, Economics & Management (AREA)
- Organic Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Emergency Management (AREA)
- Toxicology (AREA)
- Processing Of Solid Wastes (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Fire-Extinguishing Compositions (AREA)
- Catalysts (AREA)
- Paints Or Removers (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The present invention relates to be equipped with in cartridge case and/or the arms supply recovery and treatment method of the detonator of compound containing mercury, potassium chlorate and antimony trisulphide, wherein priming is changed into can not detonation inert compound or material, and the potassium chlorate as the carrier of oxygen in the powder charge changed into potassium chloride.The advantage of the inventive method has: 1. a large amount of explosives that reclaim in the ground that can be perfectly safe, 2. be widely used in the technology of various dismounting munitions, 3. all available all over the world, 4. do not use any auxiliary agent or additive that causes environmental pollution, 5. processing step is few, 6. easy operating 7. can obtain the copper shell case of metallic state.
Description
The method of the detonator (detonating cap) of compound containing mercury, potassium chlorate and antimony trisulphide is housed in the arms supply that the present invention relates to recycle cartridge case (cartridge) and/or assemble.This method the detonating agent in detonator and/or the destructor can be changed into can not detonation inert compound or material, and the potassium chlorate as the carrier of oxygen in the powder charge changed into potassium chloride, thereby makes the powder charge in detonator and/or the destructor lose its detonation activity.
Therefore, the present invention is main relevant with military industrial technology.Involved in the present invention is to make such as powder charge in detonator, the fire in a stove before fuel is added (detonating bolt), the fuze mechanism and the chemical detonator insensitivenessization in various ammunition, safeties and the demolition set, with the safety dismounting that guarantees these class military supplies, guarantee to be equipped with the transporting safely of device of this class powder charge and the safety recycling of these mixtures or device and goods and materials.
German patent specification the 4th, 010 is introduced the method that a kind of water is removed the device that explosive is housed No. 757.The feature of this method be with water under high pressure by nozzle ejection to explosive, wherein the temperature of water is lower than the fusing point of explosive.
German patent specification the 3rd, 913 has been introduced the method and system of dismantling poisonous and/or explosive means No. 479.For safety also recycles poisonous and/or volatile device effectively, this class device is splitted into separated components separately at a kind of equipment that is used for this type of dismounting.Mask work carries out in a kind of liquid.This article requires with the high pressure water jets injection device this class hazardous device to be taken apart in this case.
British patent specification the 1st, 262 has been introduced a kind of method that reclaims gunpowder No. 831.
Powder charge in making detonator and/or device subtracts in quick and this technical field of passivation, and following method is known:
-under the condition that has safety measure to ensure, with explosion, destroy by fire or the mode of burning is destroyed detonator and apparatus to cause bursting.This method causes air pollution.
-partly subtract the parts of scrapping in the production process quick with oil or similar mediums, steadily carry out so that burn.
-powder charge is stirred in hypo solution or hydrolysis in strongly basic medium under 100 ℃ of temperature conditions, it is decomposed under uninflated condition.
Under all these situations, the catabolite that is produced all must send the toxic waste soot to handle, or the user will be owing to discharging a large amount of waste water or making environmental hazard that problems such as ammunition fragment, soil pollution cause and the back white elephant.
Make powder charge subtract quick and passivation with known method and mainly contain following shortcoming:
-to handle a large amount of relatively detonator and the powder charge required time in the similar device oversize,
-can produce and not wish the chemical by-product that produces originally,
-with meet detonating agent and explosive composition can being changed into fully inert compound and the method that potassium chlorate contained in the powder charge changes into potassium chloride being compared of people's needs, known all methods can not provide enough safety guarantee.
Ammunition before destruction in member state of the council of Mutual Economic Assistance arm store has comprised the problem of disposing mercurous detonator and apparatus to cause bursting in the work of the especially preceding East Germany People's Army's ammunition.
The objective of the invention is to find a kind of eliminate detonator and the device of similar applications is arranged or goods and materials in the viable economically and reliable replacement scheme of detonation activity of powder charge, thereby guarantee that it transports safely and effectively recycling.
The purpose that the present invention will reach is to find a kind of make detonator that contains mercury fulminate in its a large amount of relatively powder charges and/or simple, the safe and efficient method of installing passivation, thereby can dispose these owing to destroying the mercurous waste material that ammunition produces, but can not cause environmental pollution simultaneously.
For the processing method that makes mercurous detonator conforms to environmental requirement, matter of utmost importance is to make explosive wherein lose the detonation activity by chemical conversion.Next step available common method is with resulting mercurous waste material demercuration.
But inventor of the present invention is surprised to find that under the condition that has iron to exist water or a kind ofly subtracts quick aqueous solution initiated oxidation reduction reaction, in this reaction, subtracts quick solution and be not subjected to block with contacting of powder charge.This reaction make the mercury fulminate detonating agent in the powder charge change into rapidly can not detonation inertia mercury compound and/or mercury metal.Because this reaction has changed into potassium chloride to potassium chlorate simultaneously, but it also make simultaneously potassium chlorate/antimony trisulphide mixture formation of remaining detonation and ignition can not detonation mixture.
Following method of the present invention has realized goal of the invention of the present invention:
A) with the detonator in the water-bath preliminary treatment cartridge case, wherein temperature and time can choose at random, for example under 70 to 100 ℃ of temperature conditions, carried out 30 minutes to 4 hours,
B) to heating post processing, so that the residual water evaporation through this pretreated cartridge case; Treatment temperature for example can be carried out 30 to 60 minutes from 80 ℃ extremely the highest 142 ℃; Mercury fulminate begins to transform coking good fortune bright (pyrofulmin) when temperature is higher than 110 ℃,
C) at above-mentioned b) within step 3 to 12 hours after finishing, the detonator and the cartridge case that are pressed in the cartridge case bottom are separated with mechanical means,
D) subsequently, detonator and homodisperse iron/or corrodible ferrous material mix mutually, on it, inject water then or subtract the quick aqueous solution, the consumption of solution should make it not have detonator and iron,
E) material is left standstill, the powder charge in detonator is subtracted fully, and quick solution permeates, dissolved potassium chlorate has made the iron oxidation and changed into potassium chloride, and iron ion changed into mercury compound inertia mercury compound and/or mercury metal, and
F) the mercurous residue that will obtain recycles with known method.
The Jiao Fuming that mentions in the literary composition (pyrofulmin) is the burnt mercury fulminate of a kind of non-explosive of generating when being heated to more than 80 ℃ of mercury fulminate.
Especially the good embodiment of the inventive method has following feature:
-the anvil that takes off when pulling down detonator is used as iron material,
-demercuration step (so-called demercuration step comprises step e) and f)) use the method for magnetic separation to reclaim iron afterwards, and can be used as the reducing agent repeated use through the iron that this recovery obtains,
-with solution, the especially soap and the sodium hydroxide solution that contain water other composition active, as subtracting quick solution with alkalescence is arranged.
Need to contain 25% mercury fulminate in the powder charge of detonator of recycling as priming, and 37.5% potassium chlorate and antimony trisulphide as the starting mix of propellant powder separately.In order to prevent penetrating of moisture content, coating special paper, lacquer or tinfoil paper on the detonator.In order to carry out chemical reaction, at first must make clad lose its protective effect.At this, favourable factor is in the process that cartridge case is installed originally and in unloading process, and clad has been subjected to obvious impairment.In addition, before pulling down detonator, cartridge case is handled so that powder charge temporarily subtracts quick with hot water.The inventor studies the conversion of explosive from following three aspects:
A) place the neutral aqueous solution long period,
B) place the alkaline aqueous solution long period and
C) effect of various reducing agents in the aqueous solution.
Research project conclusion a)
Water carries out simple process to detonator, also gets nowhere even carry out several weeks.This be because, though KClO
3Be dissolved out and make the oxidation of copper shell in powder charge gradually, mercury fulminate does not but change, and in case just has explosivity after dry again.
Research project b) conclusion
In alkaline aqueous solution, the mercury fulminate hydrolysis resolved into HgO and various gaseous products (CO
2, N
2, NH
3) (wherein some is water miscible) be successful.While KClO
3Therefore dissolved and the copper shell is corroded.The potassium chlorate that transforms does not fully cause deflagration in heat-treatment process subsequently, and HgO makes recycling complicated.
Research project c) conclusion
It seems that the phenomenon explanation of the passiveness of introducing above should be used reducing agent.Though but mercury fulminate and potassium chlorate electroreduction, this will increase the technology and the engineering cost of the facility of dismounting arms supply.
For fear of increase handling with the difficulty on the waste liquid of the consumption of solution and the relevant therewith final discharge of disposal, the inventor tests the hydrazine compound and the metallic iron that are in neutrality and the alkaline aqueous medium.
Use hydrazine or hydrazine compound to fail to obtain compellent positive result separately.In neutral and alkaline aqueous solution, use iron to obtain unexpected success.Though use Fe that the amount of the material that needs disposal is significantly increased, yet, when disposing explosive, can access the safety guarantee this point and stipulate to have conclusive importance for satisfying national relevant laws.
The advantage that adds iron or corrodible this technological contribution of ferrous material is when pulling down detonator bottom cartridge case, and so-called anvil is also simultaneously split to get off.Common way is with the method that magnetic separates this steel part to be separated, and now, this step can be saved.When cartridge case is copper cartridge, be to add Fe's by the method for sneaking into homodisperse iron.
It is very complicated that the present invention is used for eliminating the chemical reaction of method of blasting cap detonation activity.By reference initial reactant and the end product of being tested, these react available following reaction equation and represent:
Initial reactant:
Water, brass CuZn30, potassium chlorate, antimony trisulphide, mercury fulminate, iron also have tin sometimes
End product:
Metal Hg, amalgam, Fe
2O
3, copper ion, zinc ion, chlorion, Cu, Cu, CuZn30, unreacted Fe, CuO, the Sb sticking mutually with Fe.
Also play oxidant in the potassium chlorate pass into solution, it at first reacts with metallic iron, generates ferric iron (Fe(III)) oxide:
Next, generation is as the Fe(II of intermediate product) ion
The Fe(II) the ion pair mercury fulminate has reduction, and it and mercury fulminate react, and generate mercury metal
Analysis result shows that the Cu ion is not corresponding with the ratio and the ratio of these two kinds of metals in the CuZn30 alloy of Zn ion in the aqueous solution, but a large amount of excessive Cu ions are arranged.Can infer mercury metal thus and preferentially generate zinc amalgam, the homodisperse copper of generation is oxidized to Cu by chloric acid
+:
Reaction (6) is only containing Cu
+/ ClO
- 3Solution and reducing agent Fe after separating just be observed, therefore, Fe or Fe
++Existence hindered Cu
+Be oxidized to Cu
++Sb
2S
3Being reduced into Sb must be to realize under the help of chloric acid to the oxidation of sulphur:
After potassium chlorate all transforms, the timely dominate of the reduction of excessive Fe.This can be proved by the decline of the concentration of Cu in the solution:
Though the concentration of Hg solution ion is very low, also As time goes on descending really.
As a whole, we can say that adding metallic iron in the detonator in neutrality or alkaline aqueous solution has proved that total processing procedure is had positive role.Except can eliminating the blast activity safely, as the main purpose of recycling, mercury is converted to and is easy to the further metallic state of processing, has also stoped electropositivity to be higher than the dissolving of other metal of Fe simultaneously.
Major part changes into the iron of ionic condition all with Fe
2O
3Form precipitate.
These results guaranteed final discharge waste material processing easily and expense not high.
Method of the present invention has following advantage:
-can recycle explosive in large quantities with being perfectly safe,
-to the dismounting munitions the widest applicability of technology,
All can use in-the world wide,
-do not use any meeting to cause the auxiliary agent or the additive of environmental pollution,
-processing step seldom,
-easy operating, and
-can obtain the copper shell case of metallic state.
Embodiment with illustrative is described in further detail the present invention below.
Embodiment
With the detonator in 90 ℃ the water-bath preliminary treatment cartridge case two hours.
In ensuing heating last handling process, the remaining moisture content that is attached on the parts is evaporated.
Evaporating temperature maintains 110 ℃.It is loosening that interface between cartridge case and the detonator takes place the long duration of action of about 100 steam.It is bright that high temperature (about 130 ℃) effect and simultaneous steam make mercury fulminate begin to transform the coking good fortune.Meanwhile, the granular boundary of quadrature fulminate crystal is by partial destruction, so reactive surfaces has enlarged.
Be separated within 3 to 12 hours through this detonator that still is pressed in the cartridge case of handling, and handle as follows:
8 kilograms of iron (anvil) are joined in 10 kilograms of detonators (be as the criterion) with the charging that contains mercury fulminate.In this material, inject a kind of alkalescent soap solution (pH7.5 to 8.5; Per 400 premium on currency are with 1 kilogram of industrial soap) be higher than 5 centimetres of solids to liquid level.After the mixing, all materials must leave standstill the powder charge of pressing and subtracted quick solution by this fully and soak in detonator, and mercury fulminate changes into inertia mercury compound or mercury metal and potassium chlorate with the iron ion reaction and changed into potassium chloride.
Annotation of translation: the detonator of implication on ordinary meaning of detonator in the literary composition (detonating cap) speech, also comprise detonation elements such as detonation cap, the fire in a stove before fuel is added, detonation pipe.
Claims (7)
1, the recovery and treatment method of the detonator of compound containing mercury, potassium chlorate and antimony trisulphide is housed in the arms supply of cartridge case and/or assembling, the method is characterized in that:
A) with the detonator in the water-bath preliminary treatment cartridge, wherein temperature and time can choose at random,
B) to heating post processing through this pretreated cartridge case that has detonator, so that the residual water evaporation, and make the crystal structure of mercury fulminate loosening,
C) at above-mentioned b) within step 3 to 12 hours after finishing, the detonator and the cartridge case that are pressed in the cartridge bottom are separated with mechanical means,
D) subsequently, detonator is mixed mutually with homodisperse iron and/or corrodible ferrous material, inject water then or subtract the quick aqueous solution on it, the consumption of medium should make it not have detonator and iron,
E) material is left standstill, the powder charge in detonator is subtracted fully, and quick solution permeates, dissolved potassium chlorate has made the iron oxidation and changed into potassium chloride, and iron ion changed into mercury compound inertia mercury compound and/or mercury metal, and
F) with the resulting thus mercurous residue of known method recycling.
2, method according to claim 1 is characterized in that being used in and tears anvil that detonator takes off simultaneously open as iron material.
3, method according to claim 1 and 2 it is characterized in that using the method for magnetic separation to reclaim iron after the demercuration step, and the iron that reclaims can be used as the reducing agent repeated use.
4, method according to claim 1 is characterized in that in step a), and the preliminary treatment of detonator was carried out under 70 to 100 ℃ temperature conditions 30 minutes to 4 hours.
5, method according to claim 1 is characterized in that in step b), and the heating post processing was carried out 30 to 60 minutes to the highest 142 ℃ temperature conditions at 80 ℃.
6, method according to claim 5, it is bright to it is characterized in that mercury fulminate begins to transform the coking good fortune when temperature is higher than 110 ℃.
7, method according to claim 1 is characterized in that in step d), and other composition, particularly soap that water is active with alkalescence is arranged and sodium hydroxide solution are as subtracting the quick aqueous solution.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4123225A DE4123225C1 (en) | 1991-07-11 | 1991-07-11 | |
| DEP4123225.9 | 1991-07-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1068415A true CN1068415A (en) | 1993-01-27 |
Family
ID=6436055
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN92105677A Pending CN1068415A (en) | 1991-07-11 | 1992-07-11 | The recovery and treatment method of the detonator of compound containing mercury, potassium chlorate and antimony trisulphide is housed |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0526956B1 (en) |
| CN (1) | CN1068415A (en) |
| AT (1) | ATE130203T1 (en) |
| DE (2) | DE4123225C1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4243337C1 (en) * | 1992-12-21 | 1993-12-16 | Buck Chem Tech Werke | Explosive material disposal - uses water with deactivated material to give a soln. of potassium nitrate for further use |
| US6011193A (en) * | 1997-06-20 | 2000-01-04 | Battelle Memorial Institute | Munitions treatment by acid digestion |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE757442A (en) * | 1969-10-14 | 1971-03-16 | France Etat | PROCESS FOR THE TREATMENT OF OLD WAR POWDERS, WITH A VIEW TO RECOVERING NITROCELLULOSE |
| CH633497A5 (en) * | 1977-03-30 | 1982-12-15 | Kernforschungsanlage Juelich | METHOD FOR REDUCING REDUCABLE POLLUTANTS IN AQUEOUS SOLUTIONS. |
| DE3913479C1 (en) * | 1989-04-24 | 1990-08-23 | Dr. Ing. Koehler Gmbh Ingenieurbuero, 3150 Peine, De | Disarming toxic and/or explosive objects - involves dismantling based on investigation on measuring after transport in plastics jacket |
| DE3920487A1 (en) * | 1989-06-22 | 1991-01-03 | Wacker Chemie Gmbh | Removing mercury ion from aq. solns. - by pptn. with formamidine:sulphinic acid followed by filtration |
| DE4010757C1 (en) * | 1990-04-04 | 1991-08-01 | Rheinmetall Gmbh, 4000 Duesseldorf, De |
-
1991
- 1991-07-11 DE DE4123225A patent/DE4123225C1/de not_active Expired - Fee Related
-
1992
- 1992-06-10 EP EP92250144A patent/EP0526956B1/en not_active Expired - Lifetime
- 1992-06-10 AT AT92250144T patent/ATE130203T1/en not_active IP Right Cessation
- 1992-06-10 DE DE59204321T patent/DE59204321D1/en not_active Expired - Fee Related
- 1992-07-11 CN CN92105677A patent/CN1068415A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| DE59204321D1 (en) | 1995-12-21 |
| EP0526956B1 (en) | 1995-11-15 |
| ATE130203T1 (en) | 1995-12-15 |
| DE4123225C1 (en) | 1992-11-05 |
| EP0526956A3 (en) | 1993-03-03 |
| EP0526956A2 (en) | 1993-02-10 |
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| SE01 | Entry into force of request for substantive examination | ||
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| PB01 | Publication | ||
| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |