CN103467154A - Safety disposal and resource utilization method of lead-containing energetic material - Google Patents
Safety disposal and resource utilization method of lead-containing energetic material Download PDFInfo
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- CN103467154A CN103467154A CN2013103534843A CN201310353484A CN103467154A CN 103467154 A CN103467154 A CN 103467154A CN 2013103534843 A CN2013103534843 A CN 2013103534843A CN 201310353484 A CN201310353484 A CN 201310353484A CN 103467154 A CN103467154 A CN 103467154A
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Abstract
The invention belongs to the field of energetic material processing technology, concretely relates to a safety disposal and resource utilization method of the energetic material, and also relates to a system special for the method. The safety disposal and resource utilization method of the energetic material comprises the following steps: (1) preparing a reaction material; (2) charging; (3) deenergizing, hydrolyzing and removing lead; (4) preparing fertilizer; the system comprises a reaction apparatus and a fertilizer preparing apparatus, and deenergizing and lead removing reactions can be carried out by the system, which eliminates the harm caused by high-lead content in the reaction solution; in the fertilizer preparing process, decomposed microorganisms are supplemented, thereby microorganisms of various species can be used for decomposing insoluble phosphor or the like, and enhancing the ability of the fertilizer to decompose elements for various crops, and promoting the ability of crop to absorb and use various elements, and improving fertilizer efficiency of soil.
Description
Technical field
the invention belongs to the processing technology field of energetic material, be specifically related to a kind of safe disposal and resource utilization method of leaded energetic material, also relate to the system of the method special use.
Background technology
The energetic material used in ammunition mainly contains the kinds such as propelling charge, propelling agent and explosive, and propelling charge mainly is comprised of as softening agent, stablizer etc. energy ingredient and some additives; Propelling agent, except containing energy ingredient, softening agent, stablizer etc., also contains impact modifying agent, contains a large amount of lead in impact modifying agent.Most propelling charge, propelling agent and explosives are usually used in military field, to complete the purposes of operation such as impelling, propelling and blast, are the energy of the weapons such as personal defence, land, sea and air and aviation aerospace.Propelling charge, propelling agent and explosive all have certain work-ing life, and to the propelling charge in life-span, propelling agent and explosive, its unstable and insecurity can sharply increase, and become discarded propelling charge, propelling agent and explosive.Simultaneously, due to most propelling charge, propelling agent and explosive are all poisonous, so discarded propelling charge, propelling agent and explosive are also the source of pollution larger to environmental hazard, with life, with industrial refuse, compare, although discarded propelling charge, propelling agent is relative with explosive quantity less, but due to its burning, blast and toxic characteristic, its storage in addition, very easily spontaneous combustion or self-destruction in during Destruction, still to society, environment structure larger threat, when creating a climate of fear and there is very large potentially dangerous, become a kind of worldwide public hazards, therefore, rationally process discarded propelling charge, propelling agent and explosive have become the difficult problem that each military power of the world needs solution badly.
Expired gun propellant, propelling agent and explosive treatment process are divided into following several:
1. traditional treatment process
The open incineration method, discarded propelling charge, propelling agent and explosive are transported to away from the place in city and burn, the shortcoming of the method is, the uncontrollable pollution level to environment, after discarded propelling charge, propelling agent and explosive burn, can generate a large amount of high density carcinogenic substances, and generate more nitrogen oxide; When burning, also likely generate as halogenide and oxide compound and other solid-state products of combustion such as barium, selenium, they can be with air or the soil erosion infringement mankind and environment; Bury method, propelling charge, propelling agent and explosive are processed into to pulpous state and inject deep-well, the shortcoming of the method is to produce and to pollute soil; Biological degradation method, the food using discarded propelling charge, propelling agent and explosive as bacterium, at certain temperature and pH, with degradation by bacteria expired gun propellant and explosive, shortcoming is that the efficiency of the method is not high;
2. incinerator burns
The difference of the method and open incineration is, this method is will propelling charge, propelling agent and explosive drop in incinerator and destroy, and the shortcoming of the method is, fund expends larger, and maintenance of equipment and fuel consumption all need certain funds;
3. expired gun propellant, propelling agent and explosive are changed into non-containing the energy material
For example alkaline hydrolysis method, melting salt destroy method, supercritical water oxidation method; Its principle of alkaline hydrolysis method is by propelling charge, propelling agent and explosive and alkali generation hydrolysis reaction, produces organic salt and inorganic salt; Melting salt destroys ratio juris, melting salt is carbonate and the halogenide of alkali or alkaline-earth metal, they are heat transfer material and reaction medium, oxidizing reaction is played to katalysis, and by forming in stable salt and sour gas, although the destruction blast waste of the energy effective and safe of the method, its processing efficiency is low, but also has certain potential safety hazard;
Supercritical water oxidation method for destroy expired with scrap propelling charge, propelling agent and explosive, reaction is carried out in overcritical water oxidization reactor, destroy the expired purpose with scrapping propelling charge, propelling agent and explosive to reach, the shortcoming of the method is, complex process, facility investment is large, and it is limited to process the amount of discarding explosive, can not take full advantage of its energy;
4. discard the insensitiveness of propelling charge, propelling agent and explosive
Discarded propelling charge, propelling agent and explosive are mixed with thinner or filler and can reduce its energy or combustion speed, be correlated with again afterwards and store and process.
One of feature of propelling charge, propelling agent and explosive is that self chemical reaction occurs and gives off energy, and the best method of therefore processing discarded propelling charge, propelling agent and explosive is that it is turned waste into wealth, by the mankind are utilized.
The common recycling method of expired gun propellant, propelling agent and explosive is:
(1) make the auxiliary fuel of boiler: send into boiler after expired gun propellant, propelling agent and explosive are dissolved with solution, or with spray into again boiler after oil fuel mixes;
(2) as civil explosive: the direct utilization of discarded propelling charge, propelling agent and explosive, as after yellow explosive tritonal takes out from bullet, through purifying in flakes, be introduced directly in industrial powder explosive, propelling charge, propelling agent and explosive that some are comparatively responsive, for example Cyclotrimethylene trinitramine (RDX), will make insensitiveness and process recycling afterwards; The extraordinary mixture explosive of making, other purposes is processed and done to these propelling charge, propelling agent and explosive for metal, for example: metallic explosive is compound, cutting, explosion forming, explosive strengthening and explosion hardening, blast riveted joint and welding, elimination by explosion stress explode, and Explosive powder compaction etc., the price of such explosive is higher, but consumption is less, it is not the extensive expired effective way with scrapping propelling charge, propelling agent and explosive of processing.
In above method, change propelling charge, propelling agent and explosive into the non-method containing the energy material, if further utilized containing the energy material non-, turn waste into wealth, can not only eliminate the expired potential hazard with scrapping propelling charge, propelling agent and explosive and bringing to the mankind and environment, and can make its recycling, for the mankind benefit.Therefore, for this purpose, need for further study.
Propelling charge, propelling agent and explosive are prepared as to fertilizer, can effectively solve above-mentioned technical problem, but in the fertilizer prepared by propelling agent, contain a large amount of lead elements, and it is plumbous very large to the harm of human body, lead is transferred in crop by fertilizer, and human body affects HUMAN HEALTH by the crop of edible various high lead contents.
The plumbous harm to human body is mainly manifested in: lead and compound thereof can enter human body through digestive tube, respiratory tract, and lead alkylide can also absorb by skin, and lead long half time in vivo all produces harm to many tracts and physiological action.
Neural system is the target tissue of lead poisoning effect, and lead has neurobehavioral toxicity, and the lead in invasion body is along with blood flow as cerebral tissue, and damage cerebellum and brain cortex cell, disturb Metabolic activity, causes anaemia and cerebral edema.
Anaemia is one of saturnine early symptom, the plumbous activity that can resist many enzymes in the protoheme building-up process, lead poisoning causes vasospasm, angina abdominis, and retina arteriolospasm and hypertension may be all that arteriolospasm causes, often cause tiny arteriosclerosis.
Plumbous renal impairment often shows as the pathologies such as interstitial nephritis or atrophic ephritis, the reabsorption function reduction is early stage symptom, and Effects of Lead Exposure also may affect reproductive function, contacts plumbous woman worker's Infertility, miscarriage and stillborn foetus have generation more, and lead poisoning can be transferred to fetus by placenta.
One of per os lead poisoning person liver is main damaged organ, can cause hepatomegaly, present jaundice, even liver cirrhosis or hepatic necrosis, hepatic injury may be also that in liver, arteriolospasm causes due to local asphyxia, lead causes that arteriolospasm is due to the Porphyrin Metabolism obstacle, suppresses containing the sulfydryl enzyme, disturbs vegetative nerve.
The plumbous main aspect on children's harm is the impact on children's brain development, research both domestic and external all has been found that, the more serious place at Environmental Lead Exposure, the sickness rate of children mental retardation is higher, the every rising 100 μ g/L of children's Pb-B, its IQ will descend 6～8 minutes, research is also found, children blood lead is too high to be gone back and hyperkinetic syndrome, absent minded, difficulty of learning, Aggression, and the criminal offence after growing up has substantial connection, children's Physique growth also is subject to plumbous impact, according to research both domestic and external, the children of high blood lead, its possibility of short and small stature increases, high blood lead children's stature is subnormal children often, in addition, serious children ' s lead poisoning also causes anaemia etc.
Ammunition particularly contains a large amount of lead in propelling agent, for plumbous removal method, mainly concentrate at present following several upper: the precipitator method, coacervation, absorption method, ion exchange method, in recent years, relevant for the method that adopts pyrrhotite absorption, respond well, but have a deficiency, in the natural sulphur iron ore pyrrhotite and pyritous sepn process more loaded down with trivial details, workload is large, limited practical application, but rarely seen have above method be applied to propelling agent deenergize in composting in plumbous the removal.Therefore, need to, for the removal method of above-mentioned a kind of lead of Process Design, alleviate the plumbous harm to human body.
Summary of the invention
In order to solve above-mentioned technical problem, the invention provides a kind of safe disposal and resource utilization method of leaded energetic material, adopt the method to be processed leaded energetic material, can not only effectively process energetic material, but also energetic material is hydrolyzed to and can be the fertilizer that the mankind utilize, realize the purpose of recycling, remove the lead in energetic material in the process of reaction, remove the lead in the resulting fertilizer of reaction, and then eliminate the lead brought to soil because of fertilizer, avoid human body to take in the plumbous harm brought by diet.
Safe disposal and the special-purpose system of resource utilization method of leaded energetic material provided by the present invention, waste residue, the waste water that utilizes this system can be easily leaded energetic material or production and the leaded energetic material of destruction to be produced is hydrolyzed, to the solution deleading after hydrolysis, to the solution composting after deleading, reach the effect of processing and recycling.
The safe disposal of leaded energetic material and resource utilization method comprise following step:
(1) reaction mass is prepared:
Comprise the preparation of leaded energetic material, transforming agent, hydrolyzed solution, sulfide;
Prepare energetic material: it is 20～80 orders that energetic material is crushed to its fineness;
The preparation hydrolyzed solution: the preparation hydrolyzed solution, hydrolyzed solution is alkali lye, alkali lye comprises KOH, NaOH, NH
3h
2any in O; The concentration of alkali lye is 5～30%, and during preparation alkali lye, stir on preparation limit, limit, and the control stirring velocity is 20～150rpm;
The formulating vulcanization thing: sulfide is any of potassium sulphide, S-WAT, sodium sulphite, and the concentration that makes sulfide is 0.5～2.0mmol/L;
Prepare transforming agent: transforming agent is humic acid or humate, and the concentration of transforming agent is: 10～20%;
(2) reinforced
By the energetic material of preparing in step (1), at the uniform velocity join in retort;
The hydrolyzed solution of preparation in step (1) is transferred in retort, and keeping the concentration of energetic material is 1～30%;
(3) reaction
During reaction, open temp test automatic control device, the temperature of temperature test automatic control device is arranged on to the interval of 40～150 ℃, temperature in retort is remained in above-mentioned design temperature interval, temperature in retort is prescribed a time limit lower than the lower of this interval, and this temperature test automatic control device starts heating unit and heats up; Temperature in retort is prescribed a time limit higher than the upper of this interval, and this temperature test automatic control device starts freezing unit cooling;
Open the whipping appts in retort, stirring velocity is controlled at 80～300 rpm;
Open ultrasonic generator, regulate its power; Concrete control method is:
When the reaction soln volume is no more than 800L, ultrasonic power is 1000W,
When the reaction soln volume, during at 800～1600L, ultrasonic power is 1500W,
When the reaction soln volume, during at 1600～3200L, ultrasonic power is 2000W,
When the reaction soln volume is greater than 3200L, ultrasonic power is 3000W;
Hyperacoustic frequency is: 15～60KHz;
Start gas-detecting device, NO in the monitoring reactant gases
x, CO
2, CO, N
2the content of O; While monitoring reaction liquid ionic concn; Monitoring reaction gas pressure, make reaction pressure at 0.05～0.15Mpa;
When recording NH
3≤ 6200000ug/ m
3, NOx≤1ppm, CO
2≤ 0.05%, CO≤10ppm, N
2during O≤250ppm, stopped reaction;
Reacted material carries out the deleading reaction, the steps include: to regulate pH value to 8～10; Add 0.5～2mmol/L sulfide; The pH value to 7 of regulator solution～9 again; Throw out is removed, and remaining material enters the composting step; The termination reaction when lead concentration in solution is 0.35～0.5ppm;
(4) composting
The transforming agent that adds preparation in step (1) in solution after the deleading that deenergizes, start reaction, starts whipping appts in reaction process, NO in detection reaction solution
3 -, NO
2 -ionic concn, according to the NO detected
2 -ionic concn add the oxygenant of respective amount, described oxygenant is H
2o
2or ozone;
In reaction, if the oxygenant added is H
2o
2, the pH value is controlled to 5～7;
In solution, add: NH
4nO
3, KCl, (NH
4)
3pO
4, K
3pO
4, KNO
3, K
2sO
4, NaNO
3, K
2cO
3, (NH
4)
2sO
4, Ca (NO
3)
2, NH
4at least one in Cl, water-soluble molysite, water-soluble boron salt, water-soluble magnesium salt, water-soluble mantoquita, water-soluble zinc salt, water-soluble molybdenum salt, water soluble selenium salt;
The parts by weight of above component are as follows:
NH
4NO
3 0～5 、KCl 0～5、(NH
4)
3PO
4 0～5、
K
3PO
4 0～5、KNO
3 0～5、K
2SO
4 0～5、
NaNO
3 0～5、K2CO
3 0～5、(NH
4)
2SO
4 0～5、
Ca (NO
3)
20～5, NH
4c
l0～5, water-soluble molysite 0～5,
Water-soluble boron salt 0～5, water-soluble magnesium salt 0～5, water-soluble mantoquita 0～5,
Water-soluble zinc salt 0～5, water-soluble molybdenum salt 0～5, water soluble selenium salt 0～5;
Add microbial strains in organic matter decomposing inoculant, mix with above-mentioned solution phase after becoming thoroughly decomposed,
The control stirring velocity is: 20～200 rpm; The control reaction times is 1～30h.
Above-mentioned microbial strains is vinelandii, phosphate solubilizing bacteria, potassium solubilizing bacteria, Plant hormones regulators,gibberellins, root nodule bacterium, bacillus polymyxa, subtilis, acetobacter, bacillus megaterium, trichoderma harzianum, Pseudomonas aureofaciens, silicate bacteria, yellowish-brown pseudomonas, lactobacillus delbruckii, Pseudomonas stutzeri, Bacillus licheniformis, side born of the same parents' bacillus brevis, at least one.
Preferably, in step (4): add the transforming agent of preparation in step (1) in the solution after the deleading that deenergizes, start reaction, start whipping appts in reaction process, NO in the solution after monitoring is deenergized
3 -, NO
2 -ionic concn, according to the NO detected
2 -ionic concn add the oxygenant H of respective amount
2o
2, the pH value is controlled between 6～7;
Add vinelandii, phosphate solubilizing bacteria and potassium solubilizing bacteria in organic matter decomposing inoculant, Plant hormones regulators,gibberellins, root nodule bacterium, bacillus polymyxa, subtilis, contain vinelandii 10 in every g organic matter decomposing inoculant
6cfu, phosphate solubilizing bacteria 10
6cfu, potassium solubilizing bacteria 10
6cfu, Plant hormones regulators,gibberellins 10
4cfu, root nodule bacterium 10
5cfu, bacillus polymyxa 10
6cfu, subtilis 10
6cfu;
Organic matter decomposing inoculant is agricultural crop straw, methane-generating pit refuse or human and animal excreta;
The above material through becoming thoroughly decomposed after processing is mixed with solution phase; The ratio of its mixing is: add 1～2L material that becomes thoroughly decomposed in every 10L solution; After mixing, the control stirring velocity is: 20～200 rpm; The control reaction times is 25h.
When energetic material is two stone-2 propelling agent, its safe disposal and resource utilization method comprise following step:
(1) reaction mass is prepared:
Comprise the preparation of two stone-2 propelling agents, transforming agent, hydrolyzed solution, sulfide;
Prepare two stone-2 propelling agents: it is 20～80 orders that two stone-2 propelling agent is crushed to its fineness;
The preparation hydrolyzed solution: the preparation hydrolyzed solution, described hydrolyzed solution is alkali lye, described alkali lye comprises KOH, NaOH, NH
3h
2any in O; The concentration of alkali lye is 5～30%, and during preparation alkali lye, stir on preparation limit, limit, and the control stirring velocity is 20～150rpm;
The formulating vulcanization thing: sulfide is potassium sulphide, and concentration is 1mmol/L;
Prepare transforming agent: transforming agent is sodium humate, and its concentration is: 15%;
(2) reinforced
By the energetic material of preparing in step (1), at the uniform velocity join in retort;
The hydrolyzed solution of preparation in step (1) is transferred in retort, and keeping the concentration of energetic material is 8%;
(3) reaction
During reaction, open temp test automatic control device, the temperature of temperature test automatic control device is arranged on to the interval of 60～90 ℃, temperature in retort is remained in above-mentioned design temperature interval, temperature in retort is prescribed a time limit lower than the lower of this interval, and this temperature test automatic control device starts heating unit and heats up; Temperature in retort is prescribed a time limit higher than the upper of this interval, and this temperature test automatic control device starts freezing unit cooling;
Open the whipping appts in retort, stirring velocity is controlled at 100 rpm;
Open ultrasonic generator, regulate its power; Concrete control method is:
When the reaction soln volume is 700L, ultrasonic power is 1000W;
Start gas-detecting device, NO in the monitoring reactant gases
x, CO
2, CO, N
2the content of O; While monitoring reaction liquid ionic concn; Monitoring reaction gas pressure, make reaction pressure in about 0.1Mpa;
When recording NH
3≤ 300000ug/ m
3, CO
2≤ 0.05%, NO
x≤ 2.5ppm, N
2when O≤300ppm, CO≤100ppm, stopped reaction;
Owing to containing a large amount of lead in two stone-2, therefore, reacted material carries out the deleading reaction, the steps include: to regulate pH value to 9; Add the 1mmol/L potassium sulphide; The pH value to 8 of regulator solution again; Throw out is removed, and remaining material enters the composting step; The termination reaction when lead concentration in solution is 0.4ppm;
(4) composting
The transforming agent potassium humate that adds preparation in step (1) in step (3) in the solution obtained, detect NO in the solution after deenergizing
3 -, NO
2 -ionic concn, according to the NO detected
2 -ionic concn add the oxygenant of respective amount, oxygenant is H
2o
2, the pH value is controlled to 6 left and right;
Add vinelandii, phosphate solubilizing bacteria and potassium solubilizing bacteria in organic matter decomposing inoculant, Plant hormones regulators,gibberellins, root nodule bacterium, bacillus polymyxa, subtilis, contain vinelandii 10 in every g organic matter decomposing inoculant
6cfu, phosphate solubilizing bacteria 10
6cfu, potassium solubilizing bacteria 10
6cfu, Plant hormones regulators,gibberellins 10
4cfu, root nodule bacterium 10
5cfu, bacillus polymyxa 10
6cfu, subtilis 10
6cfu;
Organic matter decomposing inoculant is agricultural crop straw, methane-generating pit refuse or human and animal excreta;
The above material through becoming thoroughly decomposed after processing is mixed with solution phase; The ratio of its mixing is: add the 1L material that becomes thoroughly decomposed in every 10L solution;
The control stirring velocity is: 100 rpm; The control reaction times is 5～20h.
Leaded energetic material can be any in Ledate-1, Ledate-2, two stone-2,161,671-3, PT-12, two acetaldehyde, two cobalt-1, two cobalt-2, casting double-basis platform, ZNP-20, KPT, two second cobalt, two copper aldehyde-35, diamine calcium-35, the leaded propelling agents such as SDP-10, SWP-11; or produce or destroy waste residue, the waste water that leaded energetic material produces; can be also other leaded energetic material, within similarly all dropping on protection scope of the present invention.
Special-purpose system in energetic material safe disposal of the present invention and resource utilization method, this system comprises following device: gas-detecting device, material-compound tank, retort, feed supplement tank, overflow back closed cans, gas recovery tank, compressor unit, heating unit, freezing unit, condensation of gas device, ultrasonic generator, the whipping appts by driven by motor, temperature test automatic control device, pressure test device, pH test automatic control device, ionic concn proofing unit;
Material-compound tank has opening for feed, inlet mouth, air outlet, discharge port; Between the discharge port of material-compound tank and retort, by pipeline, be connected;
The feed supplement tank is at least one, and each feed supplement tank has respectively opening for feed, air outlet, inlet mouth, discharge port, and the discharge port of feed supplement tank is connected by pipeline with retort respectively;
Overflow back closed cans opening for feed, inlet mouth, air outlet, overflow port, discharge port are arranged; The overflow port that overflows back closed cans is connected with overflow spout, between this overflow spout and retort, is connected; The described discharge port that overflows back closed cans is connected by pipeline with the discharge port of retort; Weir tank guarantees the security of whole reaction process;
Retort has opening for feed, inlet mouth, air outlet, overflow port, discharge port; The tank body of retort has insulation jacket; Described heating unit is connected by pipeline with the insulation jacket of retort respectively with the refrigerator group; Temperature in retort is during lower than the required temperature of reaction, and heating unit passes into heat recirculated water in chuck, to retort, heats up; Temperature in retort is during higher than the required temperature of reaction, and freezing unit passes into cooling circulating water in chuck, to retort, lowers the temperature; Reaction is carried out in the temperature range of setting;
Retort also is connected with ultrasonic generator, and the horn of ultrasonic generator is positioned at retort inside;
The retort air outlet is connected with gas-detecting device, condensation of gas device and gas withdrawing can, and gas-detecting device is mainly NO in the gas produced in the detection reaction process
x, CO
2, CO, N
2the content of O, to determine the terminal of reaction; The condensation of gas device is connected with cooling unit, and condensing works can cooling reactant gases, after the portion gas dewfall, turns back to again in retort; The gas recovery tank can reclaim the gas produced in reaction by various ways of recycling;
Retort also is connected with temperature test automatic control device, pressure test device, pH test automatic control device, ionic concn proofing unit, by above-mentioned device, but temperature, pressure, pH value, the ionic concn parameter of Real-Time Monitoring reaction, can also be regulated and controled temperature of reaction and pH value simultaneously;
Compressor unit and feed supplement tank, retort, material-compound tank, the inlet mouth that overflows back closed cans are connected by pipeline respectively, by gas, control pneumavalve, and material between each tank body can be carried smoothly;
Whipping appts by driven by motor is arranged respectively at feed supplement tank, material-compound tank, retort top, and the agitator arm of whipping appts and agitating vane lay respectively at the inside of above-mentioned feed supplement tank, material-compound tank, retort; The material component of whipping appts in can more uniform dispersion tank;
Junction at each tank body and pipeline, be provided with valve, and for controlling the conveying of material, this valve can be operated pneumatic valve, can be also manually-operated gate;
The horn of ultrasonic generator has one at least, and preferred, horn is 4, and ultrasonic amplitude transformer not only can disperse the composition that deenergizes and react uniformly, also can shorten the time of deenergize reaction and deleading reaction;
Retort, feed supplement tank, overflow back the connecting tube between each tank body in closed cans, material-compound tank, system and be stainless steel 022Cr17Ni12MO2, above-mentioned inner tank wall body inner-walls of duct has respectively corrosion protection coating, and corrosion protection coating is any in polytetrafluoroethylene PTFE, ethylene-tetrafluoroethylene copolymer ETFE, perfluoroethylene-propylene FEP, epoxy resin.
Above system can also be following structure:
In this system, special material-compound tank is not set, batching and reaction are carried out simultaneously in retort; Concrete structure is as follows:
Energetic material safe disposal and resource utilization system comprise: gas-detecting device, retort, feed supplement tank, overflow back closed cans, gas recovery tank, compressor unit, heating unit, freezing unit, condensation of gas device, ultrasonic generator, the whipping appts by driven by motor, temperature test automatic control device, pressure test device, pH test automatic control device, ionic concn proofing unit;
The feed supplement tank has three, and these three feed supplement tanks are for holding acid solution, alkali lye, sulfide, and each feed supplement tank has respectively opening for feed, air outlet, inlet mouth, discharge port, and the discharge port of feed supplement tank is connected by pipeline with retort respectively; The number of feed supplement tank can be set according to concrete needs;
Overflow back closed cans opening for feed, inlet mouth, air outlet, overflow port, discharge port are arranged; The overflow port that overflows back closed cans is connected with overflow spout, between this overflow spout and retort, is connected; The described discharge port that overflows back closed cans is connected by pipeline with the discharge port of retort;
Retort has opening for feed, inlet mouth, air outlet, overflow port, discharge port; The tank body of retort has insulation jacket; Described heating unit is connected by pipeline with the insulation jacket of retort respectively with the refrigerator group; Temperature in retort is during lower than the required temperature of reaction, and heating unit passes into heat recirculated water in chuck, to retort, heats up; Temperature in retort is during higher than the required temperature of reaction, and freezing unit passes into cooling circulating water in chuck, to retort, lowers the temperature;
Retort also is connected with ultrasonic generator, and the horn of ultrasonic generator is positioned at retort inside;
The retort air outlet is connected with gas-detecting device, condensation of gas device and gas withdrawing can;
Retort also is connected with temperature test automatic control device, pressure test device, pH test automatic control device, ionic concn proofing unit, by above-mentioned device, but temperature, pressure, pH value, the ionic concn parameter of Real-Time Monitoring reaction;
Compressor unit and feed supplement tank, retort, the inlet mouth that overflows back closed cans are connected by pipeline respectively;
Whipping appts by driven by motor is arranged respectively at feed supplement tank, retort top, and the agitator arm of whipping appts and agitating vane lay respectively at above-mentioned feed supplement tank, the inside of retort; Whipping appts can disperse the material component in tank body more uniformly;
Junction at each tank body and pipeline, be provided with valve, for controlling the conveying of material.
The horn of ultrasonic generator has 4, and these 4 horn are symmetric;
Retort, feed supplement tank, overflow back closed cans and be stainless steel 022Cr17Ni12M0
2, inner tank wall has respectively the corrosion protection coating polytetrafluoroethylene PTFE, and its thickness is 1.2mm; Prevent that tank body is corroded in the process of reaction;
Connecting tube in system between each tank body is also all made by stainless steel 022Cr17Ni12M02, and the inwall of connecting tube has the corrosion protection coating polytetrafluoroethylene PTFE equally, and its thickness is 1.2mm.
The thickness of corrosion protection coating is 0.5～2.5mm.
Corrosion protection coating is perfluoroethylene-propylene FEP, and its thickness is 0.7～1mm.
Beneficial effect of the present invention is, adopt above-mentioned method and system to be processed energetic material, solved the environmental hazard problem of for a long time discarded energetic material burning, landfill being brought, discarded energetic material is focused on, and turn waste into wealth, will discard energetic material and change fertilizer into, for agriculture production, not only eliminated due to the problem of environmental pollution burned or the discarded energetic material of landfill brings, and brought huge economic benefit for agriculture production;
In the process of the present invention's reaction, remove the lead in leaded energetic material, remove lead in the process of composting, and then eliminate the lead harm brought to soil because of fertilizer, avoid human body to take in the plumbous harm caused to health by diet.
In reaction process of the present invention, the hydrolysis later solution that deenergizes is combined with organic decomposing agent and various microbial strains, utilize microbial strains to decompose insoluble phosphorus etc., strengthen absorption and the utilization of crop to various elements.
The accompanying drawing explanation
The structural representation that Fig. 1 is embodiments of the invention 1;
The structural representation that Fig. 2 is embodiments of the invention 2;
In figure, 1-compressor unit, 2-feed supplement tank, the 3-material-compound tank, the freezing unit of 4-, 5-whipping appts, 6-condensation of gas device, 7-retort, 8-gas-detecting device, 9-gas recovery tank, the 10-ultrasonic generator, 11-overflows back closed cans, 12-temperature test automatic control device, 13-pH tests automatic control device, 14-pressure test device, 15-ionic concn proofing unit, the 16-heating unit.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is further described, so that those skilled in the art more understands the present invention, but with this, does not limit the present invention.
Embodiment 1
Energetic material safe disposal and resource utilization system comprise: gas-detecting device 8, material-compound tank 3, retort 7, feed supplement tank 2, overflow back closed cans 11, gas recovery tank 9, compressor unit 1, heating unit 16, freezing unit 4, condensation of gas device 6, ultrasonic generator 10, the whipping appts 5 by driven by motor, temperature test automatic control device 12, pressure test device 14, pH test automatic control device 13, ionic concn proofing unit 15;
Material-compound tank 3 has opening for feed, inlet mouth, air outlet, discharge port; Between the discharge port of material-compound tank 3 and retort 7, by pipeline, be connected;
Overflow back closed cans 11 opening for feed, inlet mouth, air outlet, overflow port, discharge port are arranged; The overflow port that overflows back closed cans 11 is connected with overflow spout, between this overflow spout and retort 7, is connected; The discharge port that overflows back closed cans 11 is connected by pipeline with the discharge port of retort 7;
Compressor unit 1 and feed supplement tank 2, retort 7, material-compound tank 3, the inlet mouth that overflows back closed cans 11 are connected by pipeline respectively;
Whipping appts 5 by driven by motor is arranged respectively at feed supplement tank 2, material-compound tank 3, retort 7 tops, and the agitator arm of whipping appts 5 and agitating vane lay respectively at the inside of above-mentioned feed supplement tank 2, material-compound tank 3, retort 7; The material component of whipping appts 5 in can more uniform dispersion tank;
Junction at each tank body and pipeline, be provided with valve, for controlling inputing or outputing of material.
The horn of ultrasonic generator 10 has 4, and these 4 horn are symmetric, and ultrasonic amplitude transformer not only can disperse the composition that deenergizes and react uniformly, also can shorten the time of deenergize reaction and deleading reaction;
Also have the transparent observing window on retort 7, this window is made by high temperature resistant chilled glass, and by this window, operator can grasp the response situation in retort 7.
Connecting tube in system between each tank body is also all made by stainless steel 022Cr17Ni12M02, and the inwall of connecting tube has corrosion protection coating perfluoroethylene-propylene FEP equally, and its thickness is 0.8mm.
Above system dynamic process in use is:
In material-compound tank 3, the preparation of the material of question response is ready to, then by compressor unit 1 provide power gas source by the mass transport in material-compound tank 3 to retort 7, whether by heating unit 16 or cooling unit, regulate and control the temperature in retort 7 according to concrete need to select of reaction;
During material spill-over in retort 7, by the overflow spout on retort 7 tops by mass transport to reclaiming weir tank; Material in retort 7 is no longer during overflow, by compressor unit 1, provides the aerodynamic force source of the gas will overflow back material in closed cans 11 and returns to retort 7 and continue reaction;
After question response completes, carry out the deleading reaction in retort 7; After going out plumbous the reaction, mass transport is to overflowing back in closed cans 11;
The effect that overflows back closed cans 11 is: the weir tank that serves as retort 7 overflow raw materials; Reclaim reacted material and carry out the composting process;
In reaction process, react required alkali lye or acid solution or unclassified stores and be transported in retort 7 in feed supplement tank 2;
In the process of reaction, the gas of generation enters gas recovery tank 9 after gas-detecting device 8, condensation of gas device 6.
Be with the difference of embodiment 1, in embodiment 2, special material-compound tank 3 be not set, batching and reaction are carried out simultaneously in retort 7; Concrete structure is as follows:
Energetic material safe disposal and resource utilization system comprise: gas-detecting device 8, retort 7, feed supplement tank 2, overflow back closed cans 11, gas recovery tank 9, compressor unit 1, heating unit 16, freezing unit 4, condensation of gas device 6, ultrasonic generator 10, the whipping appts 5 by driven by motor, temperature test automatic control device 12, pressure test device 14, pH test automatic control device 13, ionic concn proofing unit 15;
Overflow back closed cans 11 opening for feed, inlet mouth, air outlet, overflow port, discharge port are arranged; The overflow port that overflows back closed cans 11 is connected with overflow spout, between this overflow spout and retort 7, is connected; The described discharge port that overflows back closed cans 11 is connected by pipeline with the discharge port of retort 7;
Compressor unit 1 and feed supplement tank 2, retort 7, the inlet mouth that overflows back closed cans 11 are connected by pipeline respectively;
Whipping appts 5 by driven by motor is arranged respectively at feed supplement tank 2, retort 7 tops, and the agitator arm of whipping appts 5 and agitating vane lay respectively at above-mentioned feed supplement tank 2, the inside of retort 7; Whipping appts 5 can disperse the material component in tank body more uniformly;
Junction at each tank body and pipeline, be provided with valve, for controlling the conveying of material.
The horn of ultrasonic generator 10 has 4, and these 4 horn are symmetric;
Connecting tube in system between each tank body is also all made by stainless steel 022Cr17Ni12M02, and the inwall of connecting tube has the corrosion protection coating polytetrafluoroethylene PTFE equally, and its thickness is 1.2mm.
Embodiment 3
In following embodiment, as relate to material-compound tank, the system in the embodiment 1 adopted is reacted, as does not relate to material-compound tank, and the system in the embodiment 2 adopted is reacted;
When energetic material is two stone-2 propelling agent, adopt the equipment in embodiment 1 to react, the implementation method of safe disposal and resource utilization system comprises following step:
(1) reaction mass is prepared:
Comprise the preparation of two stone-2 propelling agents, transforming agent, hydrolyzed solution, sulfide;
Prepare two stone-2 propelling agents: it is 40 orders that two stone-2 propelling agent is crushed to its fineness;
The preparation hydrolyzed solution: preparation hydrolyzed solution alkali lye in material-compound tank 3, alkali lye is NaOH; The concentration of alkali lye is 15%, and during preparation alkali lye, stir on preparation limit, limit, and the control stirring velocity is 80rpm;
The formulating vulcanization thing: sulfide is potassium sulphide, and concentration is 1mmol/L;
Prepare transforming agent: transforming agent is sodium humate, and its concentration is: 15%;
(2) reinforced
Two stone-2 propelling agents of the energetic material of preparing in step (1) are at the uniform velocity joined in retort 7;
The hydrolyzed solution of preparation in step (1) is transferred in retort 7 from material-compound tank 3, and keeping the concentration of energetic material is 8%;
(3) reaction
During reaction, open temp test automatic control device 12, the temperature of temperature test automatic control device 12 is arranged on to the interval of 60～90 ℃, temperature in retort 7 is remained in above-mentioned design temperature interval, temperature in retort 7 is prescribed a time limit lower than the lower of this interval, and this temperature test automatic control device 12 starts heating units 16 and heats up; Temperature in retort 7 is prescribed a time limit higher than the upper of this interval, and this temperature test automatic control device 12 starts freezing unit 4 coolings;
Open the whipping appts 5 in retort 7, stirring velocity is controlled at 100 rpm;
Open ultrasonic generator 10, regulate its power; Concrete control method is:
When the reaction soln volume is 700L, ultrasonic power is 1000W;
Start gas-detecting device 8, NO in the monitoring reactant gases
x, CO
2, CO, N
2the content of O; While monitoring reaction liquid ionic concn; The pressure of monitoring reaction gas
,make reaction pressure in the 0.1Mpa left and right;
When recording NH
3≤ 300000ug/ m
3, CO
2≤ 0.05%, NO
x≤ 2.5ppm, N
2when O≤300ppm, CO≤100ppm, stopped reaction;
Reacted material carries out the deleading reaction, the steps include: to regulate pH value to 9; Add the 1mmol/L potassium sulphide; The pH value to 8 of regulator solution again; Throw out is removed, and remaining material enters the composting step; The termination reaction when lead concentration in solution is 0.4ppm;
(4) composting
The transforming agent sodium humate that adds preparation in step (1) in solution after the deleading that deenergizes, start reaction, starts whipping appts 5, NO in detection reaction solution in reaction process
3 -, NO
2 -ionic concn, according to the NO detected
2 -ionic concn add the oxygenant H of respective amount
2o
2; The pH value is controlled to 6 left and right;
In solution, add: NH
4nO
3, KCl, (NH4)
3pO
4, K
3pO
4, KNO
3, K
2sO
4, NaNO
3, K
2cO
3, (NH4)
2sO
4, Ca (NO
3)
2, NH
4cl;
The ratio of each above component is: 100 parts of solution, NH
4nO
3, KCl, (NH4)
3pO
4, K
3pO
4, KNO
3, K
2sO
4, NaNO
3, K
2cO
3, (NH
4)
2sO
4, Ca (NO
3)
2, NH
4each 2 parts of Cl;
The control stirring velocity is: 100 rpm; The control reaction times is 8h, and the solution obtained after reaction obtains liquid fertilizer.
Embodiment 4
When energetic material is two stone-2 propelling agent, adopt the equipment in embodiment 1, the implementation method of safe disposal and resource utilization system comprises following step:
(1) reaction mass is prepared:
Comprise the preparation of two stone-2 propelling agents, transforming agent, hydrolyzed solution, sulfide;
Prepare two stone-2 propelling agents: it is 60 orders that two stone-2 propelling agent is crushed to its fineness;
The preparation hydrolyzed solution: preparation hydrolyzed solution alkali lye in material-compound tank 3, described alkali lye is NH
3h
2o; The concentration of alkali lye is 20%, and during preparation alkali lye, stir on preparation limit, limit, and the control stirring velocity is 120rpm;
The formulating vulcanization thing: sulfide is potassium sulphide, and concentration is 1mmol/L;
Prepare transforming agent: transforming agent is sodium humate, and its concentration is: 15%;
(2) reinforced
The energetic material of preparing in step (1) is at the uniform velocity joined in retort 7;
The hydrolyzed solution of preparation in step (1) is transferred in retort 7 from material-compound tank 3, and keeping the concentration of energetic material is 8%;
(3) reaction
During reaction, open temp test automatic control device 12, the temperature of temperature test automatic control device 12 is arranged on to the interval of 60～90 ℃, temperature in retort 7 is remained in above-mentioned design temperature interval, temperature in retort 7 is prescribed a time limit lower than the lower of this interval, and this temperature test automatic control device 12 starts heating units 16 and heats up; Temperature in retort 7 is prescribed a time limit higher than the upper of this interval, and this temperature test automatic control device 12 starts freezing unit 4 coolings;
Open the whipping appts 5 in retort 7, stirring velocity is controlled at 100 rpm;
Open ultrasonic generator 10, regulate its power; Concrete control method is:
When the reaction soln volume is 700L, ultrasonic power is 1000W;
Start gas-detecting device 8, NO in the monitoring reactant gases
x, CO
2, CO, N
2the content of O; While monitoring reaction liquid ionic concn; Monitoring reaction gas pressure, make reaction pressure in about 0.1Mpa;
When recording NH
3≤ 300000ug/ m
3, CO
2≤ 0.05%, NO
x≤ 2.5ppm, N
2when O≤300ppm, CO≤100ppm, stopped reaction;
Owing to containing a large amount of lead in two stone-2, therefore, reacted material carries out the deleading reaction, the steps include: to regulate pH value to 9; Add the 1mmol/L potassium sulphide; The pH value to 8 of regulator solution again; Throw out is removed, and remaining material enters the composting step; The termination reaction when lead concentration in solution is 0.4ppm;
(4) composting
The transforming agent sodium humate that adds preparation in step (1) in solution in step (3), start reaction, starts whipping appts 5 in reaction process, detects NO in the solution after deenergizing
3 -, NO
2 -ionic concn, according to the NO detected
2 -ionic concn add the oxygenant of respective amount, oxygenant is H
2o
2, the pH value is controlled to 6 left and right;
Add vinelandii, phosphate solubilizing bacteria and potassium solubilizing bacteria in organic matter decomposing inoculant, Plant hormones regulators,gibberellins, root nodule bacterium, bacillus polymyxa, subtilis, contain vinelandii 10 in every g organic matter decomposing inoculant
6cfu, phosphate solubilizing bacteria 10
6cfu, potassium solubilizing bacteria 10
6cfu, Plant hormones regulators,gibberellins 10
4cfu, root nodule bacterium 10
5cfu, bacillus polymyxa 10
6cfu, subtilis 10
6cfu;
Phosphate solubilizing bacteria, potassium solubilizing bacteria have the ability of phosphorus decomposing, potassium decomposing, and insoluble phosphorus, potassium are decomposed into to titanium pigment, potassium;
Organic matter decomposing inoculant is agricultural crop straw, methane-generating pit refuse or human and animal excreta;
Microbial fertilizer is live body fertilizer, its effect is mainly to contain a large amount of beneficial microorganism vital movements by it to complete, only have when these beneficial microorganisms in vigorous breeding and metabolic situation, Substance Transformation and useful meta-bolites could constantly form, therefore, beneficial microorganism kind in microbial fertilizer, whether vital movement is vigorous is the basis of its validity, and is to take the form of the principal elements such as nitrogen, phosphorus, potassium and how many for basic unlike other fertilizer.Just because of microbial fertilizer is the preparation of living, so its fertilizer and number of viable, intensity and ambient environmental conditions are closely related, comprise temperature, water, potential of hydrogen, nutritional condition and formerly live in indigenous microorganism repulsive interaction in soil certain influence is arranged.Above-mentioned energetic material is decomposed into and contains nitrogen through humic acid, phosphorus, after the material of the elements such as potassium, supplement corresponding salt, regulating its pH value is 6～7, this liquid fertilizer is basically in neutral state, its condition is applicable to the existence of part viable bacteria class, viable bacteria is put into to this liquid fertilizer, impose on again in soil, not only to soil, increased as nitrogen, phosphorus, the fertilizer such as potassium, but also owing to containing viable bacteria in Liquid Fertilizer, viable bacteria acts on soil, as vinelandii act on soil, strengthen the fertilizer efficiency in soil, with the single nitrogen that contains, phosphorus, the fertilizer of potassium element is compared, its fertilizer efficiency of the fertilizer that contains various mushrooms is good.Liquid Fertilizer can be used as carrier, and various microorganism live bacterias are applied to soil, improves the soil property of soil, strengthens its fertilizer efficiency.
In addition, the part viable bacteria combines with above-mentioned liquid fertilizer, also strengthened the harmful microbe preventive and therapeutic effect, due to effect root microbe inoculation fertility, microorganism, at the crop root growth and breeding, at the dominant bacteria that is crop rhizosphere, has been limited the breeding chance of other pathogenic micro-organism, the microorganism simultaneously had also has antagonistic action to pathogenic micro-organism, has played the effect that alleviates crop pest.
The above material through becoming thoroughly decomposed after processing is mixed with solution phase; The ratio of its mixing is: add the 1L material that becomes thoroughly decomposed in every 10L solution;
The control stirring velocity is: 100 rpm; The control reaction times is 15h.
Manure trial
Select same piece of land, same farm crop on kind, divide this ground into 4 deciles, does 4 kinds of processing simultaneously, is respectively to use embodiment 10, the fertilizer of Comparative Examples 1 urea ammonium phosphate potassium, Comparative Examples 2 ammonium phosphate sulfate potassium, Comparative Examples 3 chlorine ammonium potassium phosphates, and its amount of application is:
During results, use the farm crop of the fertilizer of embodiment 10, its output is higher by 20% than Comparative Examples 1, higher by 24%, higher by 26% than Comparative Examples 3 than Comparative Examples 2; The sickness rate of farm crop is than the average attack rate of Comparative Examples 1,2,3 low 20%;
From above data, can find out, fertilizer amount in embodiment 10 is few, but the crop yield of using embodiment 10 is high, its fertilizer efficiency is better than other Comparative Examples, this fertilizer has the function of improving soil, and the sickness rate of crop will be lower than other Comparative Examples, the fertilizer of this explanation embodiment 10 has the effect that other disease occurs that suppresses.
When energetic material is two stone-2 propelling agent, adopt the equipment in embodiment 2, the implementation method of safe disposal and resource utilization system comprises following step:
(1) reaction mass is prepared:
Comprise the preparation of two stone-2 propelling agents, transforming agent, hydrolyzed solution, sulfide;
Prepare two stone-2 propelling agents: it is 60 orders that two stone-2 propelling agent is crushed to its fineness;
The preparation hydrolyzed solution: the preparation hydrolyzed solution, described hydrolyzed solution is alkali lye, alkali lye is KOH; The concentration of alkali lye is 20%, and during preparation alkali lye, stir on preparation limit, limit, and the control stirring velocity is 100rpm;
The formulating vulcanization thing: sulfide is potassium sulphide, and concentration is 1mmol/L;
Prepare transforming agent: transforming agent is sodium humate, and its concentration is: 15%;
(2) reinforced
Two stone-2 propelling agents of the energetic material of preparing in step (1), sodium humate are at the uniform velocity joined in retort 7;
The hydrolyzed solution of preparation in step (1) is transferred in retort 7, and keeping the concentration of energetic material is 8%;
(3) reaction
During reaction, open temp test automatic control device 12, the temperature of temperature test automatic control device 12 is arranged on to the interval of 60～90 ℃, temperature in retort 7 is remained in above-mentioned design temperature interval, temperature in retort 7 is prescribed a time limit lower than the lower of this interval, and this temperature test automatic control device 12 starts heating units 16 and heats up; Temperature in retort 7 is prescribed a time limit higher than the upper of this interval, and this temperature test automatic control device 12 starts freezing unit 4 coolings;
Open the whipping appts 5 in retort 7, stirring velocity is controlled at 100 rpm;
Open ultrasonic generator 10, regulate its power; Concrete control method is:
When the reaction soln volume is 700L, ultrasonic power is 1000W;
Start gas-detecting device 8, NO in the monitoring reactant gases
x, CO
2, CO, N
2the content of O; While monitoring reaction liquid ionic concn; The pressure of monitoring reaction gas, make reaction pressure in the 0.1Mpa left and right;
When recording NH
3≤ 300000ug/ m
3, CO
2≤ 0.05%, NO
x≤ 2.5ppm, N
2when O≤300ppm, CO≤100ppm, stopped reaction;
Owing to containing a large amount of lead in two stone-2, therefore, reacted material carries out the deleading reaction, the steps include: to regulate pH value to 9; Add the 1mmol/L potassium sulphide; The pH value to 8 of regulator solution again; Throw out is removed, and remaining material enters the composting step; The termination reaction when lead concentration in solution is 0.4ppm;
(4) composting
NO in solution after detection is deenergized
3 -, NO
2 -ionic concn, according to the NO detected
2 -ionic concn add the oxygenant of respective amount, oxygenant is H
2o
2, the pH value is controlled to 6 left and right;
Add vinelandii, phosphate solubilizing bacteria, potassium solubilizing bacteria in organic matter decomposing inoculant, silicate bacteria, root nodule bacterium, bacillus polymyxa, subtilis, trichoderma harzianum, Bacillus licheniformis, contain vinelandii 10 in every g organic matter decomposing inoculant
6cfu, phosphate solubilizing bacteria 10
6cfu, potassium solubilizing bacteria 10
6cfu, silicate bacteria 10
4cfu, root nodule bacterium 10
5cfu, bacillus polymyxa 10
6cfu, subtilis 10
6cfu, trichoderma harzianum 10
5cfu, Bacillus licheniformis 10
6cfu;
Phosphate solubilizing bacteria, potassium solubilizing bacteria have the ability of phosphorus decomposing, potassium decomposing, and insoluble phosphorus, potassium are decomposed into to titanium pigment, potassium;
Silicate bacteria can secrete organic acid, thus by indissoluble state inorganic phosphorus in soil as FePO
4, AlPO
4deng in PO
4discharge, this bacterium can secrete the Phosphoric acid esterase decomposition and utilize organophosphorus, can secrete organic acid again, makes the inorganic phosphorus of indissoluble state be converted into titanium pigment;
Organic matter decomposing inoculant is agricultural crop straw, methane-generating pit refuse or human and animal excreta;
The above material through becoming thoroughly decomposed after processing is mixed with solution phase; The ratio of its mixing is: add the 1L material that becomes thoroughly decomposed in every 10L solution;
The control stirring velocity is: 100 rpm; The control reaction times is 20h, and reaction gained solution obtains liquid fertilizer.
Claims (10)
1. the safe disposal of leaded energetic material and resource utilization method comprise following step:
(1) reaction mass is prepared:
Comprise the preparation of leaded energetic material, transforming agent, hydrolyzed solution, sulfide;
Prepare leaded energetic material: it is 20～80 orders that leaded energetic material is crushed to its fineness;
The preparation hydrolyzed solution: the preparation hydrolyzed solution, described hydrolyzed solution is alkali lye, alkali lye comprises KOH, NaOH, NH
3h
2any in O; The concentration of alkali lye is 5～30%, and during preparation alkali lye, stir on preparation limit, limit, and the control stirring velocity is 20～150rpm;
The formulating vulcanization thing: sulfide is any of potassium sulphide, S-WAT, sodium sulphite, and the concentration that makes sulfide is 0.5～2.0mmol/L;
Prepare transforming agent: described transforming agent is humic acid or humate, and the concentration of transforming agent is: 10～20%;
(2) reinforced
By the leaded energetic material of preparing in step (1), at the uniform velocity join in retort;
The hydrolyzed solution of preparation in step (1) is transferred in retort, and keeping the concentration of energetic material is 1～30%;
(3) reaction
During reaction, open temp test automatic control device, the temperature of temperature test automatic control device is arranged on to the interval of 40～150 ℃, temperature in retort is remained in above-mentioned design temperature interval, temperature in retort is prescribed a time limit lower than the lower of this interval, and this temperature test automatic control device starts heating unit and heats up; Temperature in retort is prescribed a time limit higher than the upper of this interval, and this temperature test automatic control device starts freezing unit cooling;
Open the whipping appts in retort, stirring velocity is controlled at 80～300rpm;
Open ultrasonic generator, regulate its power; Concrete control method is:
When the reaction soln volume is no more than 800L, ultrasonic power is 1000W,
When the reaction soln volume 800
~during 1600L, ultrasonic power is 1500W,
When the reaction soln volume 1600
~during 3200L, ultrasonic power is 2000W,
When the reaction soln volume is greater than 3200L, ultrasonic power is 3000W;
Hyperacoustic frequency is: 15～60KHz;
Start gas-detecting device, NO in the monitoring reactant gases
x, CO
2, CO, N
2the content of O; While monitoring reaction liquid ionic concn; The pressure of monitoring reaction gas, make reaction pressure at 0.05～0.15Mpa;
When recording NH
3≤ 40000000ug/m
3, CO
2≤ 0.1%, NO
x≤ 150ppm, N
2when O≤10000ppm, CO≤150ppm, stopped reaction;
Reacted material carries out the deleading reaction, the steps include: to regulate pH value to 8～10; Add 0.5～2mmol/L sulfide; The pH value to 7 of regulator solution～9 again; Throw out is removed, and remaining material enters the composting step; The termination reaction when lead concentration in solution is 0.35～0.5ppm;
(4) composting
The transforming agent that adds preparation in step (1) in solution after the deleading that deenergizes, start reaction, starts whipping appts in reaction process, simultaneously NO in monitoring reaction solution
3 -, NO
2 -ionic concn, according to the NO detected
2 -ionic concn add the oxygenant of respective amount, described oxygenant is H
2o
2or ozone;
In reaction, if the oxygenant added is H
2o
2, the pH value is controlled to 5～7;
In solution, add: NH
4nO
3, KCl, (NH
4)
3pO
4, K
3pO
4, KNO
3, K
2sO
4, NaNO
3, K
2cO
3, (NH
4)
2sO
4, Ca (NO
3)
2, NH
4at least one in Cl, water-soluble molysite, water-soluble boron salt, water-soluble magnesium salt, water-soluble mantoquita, water-soluble zinc salt, water-soluble molybdenum salt, water soluble selenium salt;
The parts by weight of above component are as follows:
NH
4NO
3 0～5 、KCl 0～5、(NH
4)
3PO
4 0～5、
K
3PO
4 0～5、KNO
3 0～5、K
2SO
4 0～5、
NaNO
3 0～5、K
2CO
3 0～5、(NH
4)
2SO
4 0～5、
Ca (NO
3)
20～5, NH
4cl 0～5, water-soluble molysite 0～5,
Water-soluble boron salt 0～5, water-soluble magnesium salt 0～5, water-soluble mantoquita 0～5,
Water-soluble zinc salt 0～5, water-soluble molybdenum salt 0～5, water soluble selenium salt 0～5;
Add microbial strains in organic matter decomposing inoculant, mix with above-mentioned solution phase after becoming thoroughly decomposed,
The control stirring velocity is: 20～200 rpm; The control reaction times is 1～30h.
2. safe disposal and the resource utilization method of a kind of leaded energetic material as claimed in claim 1, it is characterized in that, described microbial strains is vinelandii, phosphate solubilizing bacteria, potassium solubilizing bacteria, at least one in Plant hormones regulators,gibberellins, root nodule bacterium, bacillus polymyxa, subtilis, acetobacter, bacillus megaterium, trichoderma harzianum, Pseudomonas aureofaciens, silicate bacteria, yellowish-brown pseudomonas, lactobacillus delbruckii, Pseudomonas stutzeri, Bacillus licheniformis, side born of the same parents' bacillus brevis.
3. safe disposal and the resource utilization method of a kind of leaded energetic material as claimed in claim 1, it is characterized in that, in described step (4): the transforming agent that adds preparation in step (1) in the solution after the deleading that deenergizes, start reaction, start whipping appts in reaction process, NO in the solution after monitoring is deenergized
3 -, NO
2 -ionic concn, according to the NO detected
2 -ionic concn add the oxygenant H of respective amount
2o
2, the pH value is controlled between 6～7;
Add vinelandii, phosphate solubilizing bacteria and potassium solubilizing bacteria in organic matter decomposing inoculant, Plant hormones regulators,gibberellins, root nodule bacterium, bacillus polymyxa, subtilis, contain vinelandii 10 in every g organic matter decomposing inoculant
6cfu, phosphate solubilizing bacteria 10
6cfu, potassium solubilizing bacteria 10
6cfu, Plant hormones regulators,gibberellins 10
4cfu, root nodule bacterium 10
5cfu, bacillus polymyxa 10
6cfu, subtilis 10
6cfu;
Organic matter decomposing inoculant is agricultural crop straw, methane-generating pit refuse or human and animal excreta;
The above material through becoming thoroughly decomposed after processing is mixed with solution phase; The ratio of its mixing is: add 1～2L material that becomes thoroughly decomposed in every 10L solution; After mixing, the control stirring velocity is: 20～200 rpm; The control reaction times is 25h.
4. safe disposal and the resource utilization method of a kind of leaded energetic material as claimed in claim 1, is characterized in that, described leaded energetic material is two stone-2 propelling agents, and its safe disposal and resource utilization method comprise following step:
(1) reaction mass is prepared:
Comprise the preparation of two stone-2 propelling agents, transforming agent, hydrolyzed solution, sulfide;
Prepare two stone-2 propelling agents: it is 20～80 orders that two stone-2 propelling agent is crushed to its fineness;
The preparation hydrolyzed solution: the preparation hydrolyzed solution, described hydrolyzed solution is alkali lye, described alkali lye comprises KOH, NaOH, NH
3h
2any in O; The concentration of alkali lye is 5～30%, and during preparation alkali lye, stir on preparation limit, limit, and the control stirring velocity is 20～150rpm;
The formulating vulcanization thing: sulfide is potassium sulphide, and concentration is 1mmol/L;
Prepare transforming agent: transforming agent is potassium humate, and its concentration is: 15%;
(2) reinforced
By the energetic material of preparing in step (1), at the uniform velocity join in retort;
The hydrolyzed solution of preparation in step (1) is transferred in retort, and keeping the concentration of energetic material is 8%;
(3) reaction
During reaction, open temp test automatic control device, the temperature of temperature test automatic control device is arranged on to the interval of 60～90 ℃, temperature in retort is remained in above-mentioned design temperature interval, temperature in retort is prescribed a time limit lower than the lower of this interval, and this temperature test automatic control device starts heating unit and heats up; Temperature in retort is prescribed a time limit higher than the upper of this interval, and this temperature test automatic control device starts freezing unit cooling;
Open the whipping appts in retort, stirring velocity is controlled at 100rpm;
Open ultrasonic generator, regulate its power; The reaction soln volume is 700L, and ultrasonic power is 1000W;
Start gas-detecting device, NO in the monitoring reactant gases
x, CO
2, CO, N
2the content of O; While monitoring reaction liquid ionic concn; Monitoring reaction gas pressure, make reaction pressure in about 0.1Mpa;
When recording NH
3≤ 300000ug/ m
3, CO
2≤ 0.05%, NO
x≤ 2.5ppm, N
2when O≤300ppm, CO≤100ppm, stopped reaction;
Reacted material carries out the deleading reaction, the steps include: to regulate pH value to 9; Add the 1mmol potassium sulphide; The pH value to 8 of regulator solution again; Throw out is removed, and remaining material enters the composting step; The termination reaction when lead concentration in solution is 0.4ppm;
(4) composting
The transforming agent potassium humate that adds preparation in step (1) in step (3) in the solution obtained, detect NO in the solution after deenergizing
3 -, NO
2 -ionic concn, according to the NO detected
2 -ionic concn add the oxygenant of respective amount, oxygenant is H
2o
2, the pH value is controlled to 6 left and right;
Add vinelandii, phosphate solubilizing bacteria and potassium solubilizing bacteria in organic matter decomposing inoculant, Plant hormones regulators,gibberellins, root nodule bacterium, bacillus polymyxa, subtilis, contain vinelandii 10 in every g organic matter decomposing inoculant
6cfu, phosphate solubilizing bacteria 10
6cfu, potassium solubilizing bacteria 10
6cfu, Plant hormones regulators,gibberellins 10
4cfu, root nodule bacterium 10
5cfu, bacillus polymyxa 10
6cfu, subtilis 10
6cfu;
Organic matter decomposing inoculant is agricultural crop straw, methane-generating pit refuse or human and animal excreta;
The above material through becoming thoroughly decomposed after processing is mixed with solution phase; The ratio of its mixing is: add the 1L material that becomes thoroughly decomposed in every 10L solution;
The control stirring velocity is: 100 rpm; The control reaction times is 20h.
5. a kind of leaded energetic material safe disposal and resource utilization method as described in claim 1, it is characterized in that, described leaded energetic material is any in Ledate-1, Ledate-2, two stone-2,161,671-3, PT-12, two acetaldehyde, two cobalt-1, two cobalt-2, casting double-basis platform, ZNP-20, KPT, two second cobalt, two copper aldehyde-35, diamine calcium-35, the leaded propelling agents such as SDP-10, SWP-11, or produces or destroy waste residue, the waste water that leaded energetic material produces.
6. special-purpose system in the safe disposal of a kind of leaded energetic material as claimed in claim 1 and resource utilization method, it is characterized in that, described system comprises following device: material-compound tank, retort, feed supplement tank, overflow back closed cans, gas recovery tank, compressor unit, heating unit, freezing unit, gas-detecting device, condensation of gas device, ultrasonic generator, the whipping appts by driven by motor, temperature test automatic control device, pressure test device, pH test automatic control device, ionic concn proofing unit;
Described material-compound tank has opening for feed, inlet mouth, air outlet, discharge port; Between the discharge port of material-compound tank and retort, by pipeline, be connected;
Described feed supplement tank is at least one, and each feed supplement tank has respectively opening for feed, air outlet, inlet mouth, discharge port, and the discharge port of feed supplement tank is connected by pipeline with retort respectively;
The described closed cans that overflows back has opening for feed, inlet mouth, air outlet, overflow port, discharge port; The overflow port that overflows back closed cans is connected with overflow spout, between this overflow spout and retort, is connected; The described discharge port that overflows back closed cans is connected by pipeline with the discharge port of retort;
Described retort has opening for feed, inlet mouth, air outlet, overflow port, discharge port; The tank body of retort has insulation jacket; Described heating unit is connected by pipeline with the insulation jacket of retort respectively with the refrigerator group;
Described retort also is connected with ultrasonic generator, and the horn of ultrasonic generator is positioned at retort inside;
Described retort air outlet is connected with gas-detecting device, condensation of gas device and gas withdrawing can;
Described retort also is connected with temperature test automatic control device, pressure test device, pH test automatic control device, ionic concn proofing unit;
Described compressor unit and feed supplement tank, retort, material-compound tank, the inlet mouth that overflows back closed cans are connected by pipeline respectively;
Whipping appts by driven by motor is arranged respectively at described feed supplement tank, material-compound tank, retort top, and the agitator arm of whipping appts and agitating vane lay respectively at the inside of above-mentioned feed supplement tank, material-compound tank, retort.
7. special-purpose system in the safe disposal of a kind of leaded energetic material as claimed in claim 6 and resource utilization method, it is characterized in that, described retort, feed supplement tank, overflow back closed cans, material-compound tank is stainless steel 022Cr17Ni12M02, above-mentioned inner tank wall has respectively corrosion protection coating, and described corrosion protection coating is any in polytetrafluoroethylene PTFE, ethene～TFE copolymer ETFE, perfluoroethylene-propylene FEP, epoxy resin.
8. special-purpose system in the safe disposal of a kind of leaded energetic material as described as claim 6 or 7 and resource utilization method, it is characterized in that, connecting tube in described system between each tank body is stainless steel 022Cr17Ni12M02, the inwall of connecting tube has corrosion protection coating, and described corrosion protection coating is any in polytetrafluoroethylene PTFE, ethene～TFE copolymer ETFE, perfluoroethylene-propylene FEP, epoxy resin.
9. special-purpose system in the safe disposal of a kind of leaded energetic material as claimed in claim 8 and resource utilization method, is characterized in that, the thickness of described corrosion protection coating is 0.5～2.5mm.
10. special-purpose system in the safe disposal of a kind of leaded energetic material as claimed in claim 9 and resource utilization method, is characterized in that, described corrosion protection coating is perfluoroethylene-propylene FEP, and its thickness is 0.7～1mm.
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