CN102887771A - Fertilizer prepared by hydrolysis of bulk propellant powder and/or explosives and preparation method thereof - Google Patents
Fertilizer prepared by hydrolysis of bulk propellant powder and/or explosives and preparation method thereof Download PDFInfo
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- CN102887771A CN102887771A CN2012103663021A CN201210366302A CN102887771A CN 102887771 A CN102887771 A CN 102887771A CN 2012103663021 A CN2012103663021 A CN 2012103663021A CN 201210366302 A CN201210366302 A CN 201210366302A CN 102887771 A CN102887771 A CN 102887771A
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Abstract
The invention belongs to the field of processing methods of energy-containing materials, in particular to a fertilizer prepared by hydrolysis of bulk propellant powder and/or explosives and a preparation method of the fertilizer. The method disclosed by the invention comprises the following specific steps of: crushing the propellant powder and/or the explosives, then adding an alkaline solution and sodium/potassium humate, reacting in a reaction kettle, and supplementing P2O5, H3PO4, HCl, HNO3 or of K2SO4, Na2SO4, KNO3, (NH4)3PO4 or selenium salt according to the content of each element in the solution after the end of the reaction to get the fertilizer. The method disclosed by the invention has the beneficial effects that, by adopting the method, the propellant powder and/or the explosives can be processed for hydrolysis and then further manufactured into the fertilizer which can be utilized by humankind, so that the problem that the propellant powder and/or the explosives can cause harm to the humankind and a survival environment of the humankind can be solved, and the wastes can be turned into useful things and further become the fertilizer with economic value.
Description
Technical field
The invention belongs to the treatment process field of energetic material, be specifically related to a kind of fertilizer that propelling charge in bulk and/or explosive substance make that is hydrolyzed, also relate to the preparation method of this fertilizer.
Background technology
Most propelling charge or explosive are usually used in military field, to finish the purposes of operation such as propelling, demolition, impelling, are the energy of the weapons such as personal defence, land, sea and air and aviation aerospace.Propelling charge or explosive all have certain work-ing life, and to propelling charge or the explosive in life-span, its unstable and insecurity can sharply increase, and become expired gun propellant or explosive.Simultaneously, because most propelling charge or explosive all are poisonous, so discarded propelling charge or explosive also are the source of pollution larger to environmental hazard, compare with industrial refuse with life, although expired gun propellant or explosive quantity are relatively less, but because its burning, blast and toxic characteristic, in addition its storage, very easily spontaneous combustion or self-destruction in the during Destruction, still to environment structure larger threat, when creating a climate of fear and have the danger of hiding, become a kind of worldwide public hazards, therefore, rationally processing discarded propelling charge or explosive has become the difficult problem that each military power of the world needs solution badly.
Expired gun propellant or explosive treatment process are divided into following several:
1. traditional treatment process
The open incineration method is transported to discarded propelling charge or explosive away from the place in city and burns, and the shortcoming of the method is, uncontrollable pollution level to environment, discarded propelling charge or explosive can generate a large amount of high density carcinogenic substances, and generate more nitrogen oxide after burning; When burning, also might generate such 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 or explosive are processed into pulpous state injection deep-well, the shortcoming of the method is can produce soil to pollute; Biological degradation method, with discarding propelling charge or the explosive food as bacterium, under certain temperature and pH, with degradation by bacteria expired gun propellant and explosive, shortcoming is that the efficient of the method is not high;
2. incinerator burns
The difference of the method and open incineration is, this method be will propelling charge or explosive drop in the incinerator and destroy, the shortcoming of the method is, fund expends larger, maintenance of equipment and fuel consumption all need certain funds;
3. change expired gun propellant or explosive into the non-energy material that contains
For example alkaline hydrolysis method, melting salt destroy method, supercritical water oxidation method; Its principle of alkaline hydrolysis method is by propelling charge or 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 katalysis, and by forming in the 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 is used for destroying expired and scrapping propelling charge or explosive, reaction is carried out in overcritical water oxidization reactor, destroy expired purpose with scrapping propelling charge or 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 or explosive
Discarded propelling charge or explosive mixed with thinner or filler can reduce its energy or combustion speed, be correlated with again afterwards storage and processing.
One of feature of propelling charge or explosive is chemical reaction occurs self and to give off energy, and the best method of therefore processing discarded propelling charge or explosive is that it is turned waste into wealth, and is utilized by human.The common recycling method of expired gun propellant or explosive is:
(1) make the auxiliary fuel of boiler: with expired gun propellant or explosive with sending into boiler after the solution dissolving, or with spray into again boiler after oil fuel mixes;
(2) as civil explosive: the direct utilization of discarded propelling charge or explosive, after taking out from bullet such as the explosive tritonal of yellow, through purifying in flakes, be introduced directly in the industrial powder explosive, propelling charge or explosive that some are comparatively responsive, for example Cyclotrimethylene trinitramine (RDX) then will be made insensitiveness and process afterwards recycling; The extraordinary mixture explosive of making, these propelling charge or explosive are used for metal processing and make other purposes, 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 be not extensive process expired with scrap propelling charge or explosive use the effect approach.
In the above method, change propelling charge or explosive into the non-method that contains the energy material, if further to utilizing by material non-containing, turn waste into wealth, can not only eliminate expired potential hazard with scrapping propelling charge or explosive and bringing to human and environment, and can make its recycling, for the mankind benefit.Therefore, for this purpose, need for further study.
Summary of the invention
In order to solve above-mentioned technical problem, the invention provides a kind of fertilizer that propelling charge in bulk and/or explosive substance make that is hydrolyzed, the preparation method of this fertilizer also is provided.
Be hydrolyzed the fertilizer that propelling charge in bulk and/or explosive substance make, the major ingredient of this fertilizer is: the hydrolyzate by the hydrolysis of propelling charge in bulk and explosive substance obtains is specially: this hydrolyzate is reacted with alkaline solution, humate by propelling charge in bulk and/or explosive substance and makes; Auxiliary material comprises at least a in the following component:
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.
Preferably, above-mentioned major ingredient hydrolyzate is 60-95 part; Auxiliary material is 10-40 part, and the parts by weight of each component are as follows in the auxiliary material:
Water-soluble molysite 0-10 part, water-soluble boron salt 0-10 part, water-soluble magnesium salt 0-10 part, water-soluble mantoquita 0-10 part, water-soluble zinc salt 0-10 part, water-soluble molybdenum salt 0-10 part, water soluble selenium salt 0-10 part.
Above-mentioned water-soluble molysite is Fe
2(SO
4)
3, water-soluble boron salt is Na
2B
8O
134H
2O, water-soluble magnesium salt are MgSO
4, water-soluble mantoquita is CuSO
4, water-soluble zinc salt is ZnSO
4, water-soluble molybdenum salt is Na
2MoO
42H
2O, water soluble selenium salt are Na
2SeO
410H
2O.
Be hydrolyzed the method that propelling charge in bulk and/or explosive substance prepare fertilizer, comprise following step:
A. obtain solution: the preparation mass concentration is the KOH of 5-45% or the NH of 5-30%
4The Sodium salts humic acids of the NaOH of OH or 5-40%, 1-10% potassium humate or 1-10%; Concentration is the H of 20-40%
2O
2
B. raw materials pretreatment: it is the 10-40 order that propelling charge in bulk and/or explosive substance are crushed to its fineness, adopts recirculated water to add wet method during pulverizing, makes the water ratio of propelling charge in bulk and explosive substance at 4-6%; The heavy 2-8 of adding material water doubly in raw material after pulverizing propelling charge in bulk and/or the explosive substance, add again microbiological deterioration, microorganism is: Trichodermareesei, viride, koning trichoderma, trichoderma pseudokiningii, tiny mould, Penicllium notatum, penicillium funiculosum, Penicillium decumbens, aspergillus niger, terreus, bread mould, lacquer spot are mould, wart spore lacquer spot is mould, at least a in mould of black ball lacquer spot, regulate the pH value to 6-9, degraded 24-48h stops, and degradation temperature is 30 ℃-60 ℃;
C. reaction: will send into reaction kettle for reaction through propelling charge in bulk and/or explosive substance after the microbiological deterioration, temperature in the control reactor is at 80-150 ℃, in reactor, add alkali lye and the potassium humate/Sodium salts humic acids for preparing among the step a, strength of solution in keeping reacting is between 20-50%, reaction pressure is 0.05-0.15MPa, constantly stir in reaction process, the speed of stirring is 80-120rpm; Keep the pH of material in the reactor at 9-11, in reaction, adding concentration is the H of 20-40%
2O
2And catalyzer, catalyzer is that Di's Grindelwald alloy, Cd, Cd-Hg are neat, at least a in the aluminium, zinc, Arndt alloy, Pd, Cu, and the add-on of catalyzer accounts for the heavy 1-10% of reaction mass, in reaction, start waste gas collecting system, question response carries out beginning later on to monitor in 3-9 hour NH
3, NO
x, CO
2, CO, N
2The content of O; When recording NH
3≤ 300000-80000000ug/m
3, NO
x≤ 1-150ppm, CO
2≤ 0.05%-0.1%, CO≤10-150ppm, N
2During O≤250-10000ppm, stopped reaction;
D. composting: after the reaction in step c is finished, solution filter is removed slag, collect the filtrate after removing slag, i.e. the hydrolyzate of gained; Adjusting the pH value of solution to 7-9, is that 60-95 weight part, auxiliary material are the ratio mixing of 10-40 weight part in solution, and described auxiliary material is: NH
4NO
30-25 part, KCl 0-10 part, (NH
4)
3PO
40-20 part, K
3PO
40-10 part, KNO
30-20 part, K
2SO
40-10 part, NaNO
30-15 part, K
2CO
30-10 part, (NH
4)
2SO
40-15 part, Ca (NO
3)
20-15 part, NH
4Cl 0-15 part, water-soluble molysite Fe
2(SO
4)
30-10 part, water-soluble boron salt Na
2B
8O
134H
2O 0-10 part, water-soluble magnesium salt MgSO
40-10 part, water-soluble mantoquita CuSO
40-10 part, water-soluble zinc salt ZnSO
40-10 part, water-soluble molybdenum salt Na
2MoO
42H
2O 0-10 part, water soluble selenium salt Na
2SeO
410H
2O 0-10 part, gains are fertilizer.
Above-mentioned propelling charge in bulk and/or explosive substance are that single-base gun propellant class, double-base propellant class, propelling agent class, triple-base propellant class, nitro compound system explosive class, nitramine are that explosive class, nitric ether are that explosive class, amine nitrate are any in explosive class, pyrotechnic composition class, organic polymer bonded explosive class, the extraordinary pyrotechnic composition class.
Its concrete preparation method of fertilizer of the hydrolyzate that the hydrolysis of single-base gun propellant class obtains is as follows:
A. obtain solution: the preparation mass concentration is NaOH, the 1-10% potassium humate/Sodium salts humic acids of 10-30%; Concentration is the H of 20-40%
2O
2
B. raw materials pretreatment: it is the 10-40 order that single-base gun propellant is crushed to its fineness, adopts recirculated water to add wet method during pulverizing, makes the water ratio of single-base gun propellant at 4-6%; The heavy 2-8 of adding material water doubly in the single-base gun propellant after pulverizing, add microbiological deterioration, microorganism is again: at least a during Trichodermareesei, terreus, bread mould, lacquer spot are mould, regulate the pH value to 6-8,40 ℃-50 ℃ of degradation temperatures, degraded 24-36h stops;
C. reaction: will send into reaction kettle for reaction through the single-base gun propellant after the microbiological deterioration, temperature in the control reactor is at 80-150 ℃, in reactor, add alkali lye and the potassium humate/Sodium salts humic acids for preparing among the step a, strength of solution in keeping reacting is between 20-50%, reaction pressure is 0.05-0.15MPa, constantly stir in reaction process, the speed of stirring is 80-120rpm; Keep the pH of material in the reactor between 9-11, in reaction, adding concentration is the H of 20-40%
2O
2And catalyzer, catalyzer is that Di's Grindelwald alloy, Cd, Cd-Hg are neat, at least a in the aluminium, zinc, Arndt alloy, Pd, Cu, and the add-on of catalyzer accounts for the heavy 1-10% of reaction mass, in reaction, start waste gas collecting system, begin to monitor NH after question response 2-5 hour
3, NO
x, CO
2, CO, N
2The content of O; When recording NH
3≤ 6200000ug/m
3, NO
x≤ 1ppm, CO
2≤ 0.05%, CO≤10ppm, N
2During O≤250ppm, stopped reaction;
D. composting: after the reaction in step e is finished, solution filter is removed slag, collect the filtrate after removing slag; Adjust the pH value of solution to 7-8, in filtrate according to hydrolyzate with the 60-90 weight part, the ratio of auxiliary material 10-25 weight part is mixed, auxiliary material is specially: NH
4NO
30-25 part, KCl 0-10 part, (NH
4)
3PO
40-20 part, K
3PO
40-10 part, KNO
30-20 part, K
2SO
40-10 part, NaNO
30-15 part, K
2CO
30-10 part, (NH
4)
2SO
40-15 part, Ca (NO
3)
20-15 part, NH
4Cl 0-15 part, water-soluble molysite Fe
2(SO
4)
30-10 part, water-soluble boron salt Na
2B
8O
134H
2O 0-10 part, water-soluble magnesium salt MgSO
40-10 part, water-soluble mantoquita CuSO
40-10 part, water-soluble zinc salt ZnSO
40-10 part, water-soluble molybdenum salt Na
2MoO
42H
2O 0-10 part, water soluble selenium salt Na
2SeO
410H
2O 0-10 part, gains are fertilizer.
The hydrolysis of double-base propellant class goes its concrete preparation method of fertilizer of getable hydrolyzate as follows:
A. obtain solution: the preparation mass concentration is the NaOH of 10-35%, potassium humate/Sodium salts humic acids of 1-10%; Concentration is the H of 20-40%
2O
2
B. raw materials pretreatment: it is the 10-40 order that double-base propellant is crushed to its fineness, adopts recirculated water to add wet method during pulverizing, makes the water ratio of double-base propellant at 4-6%; The ratio that doubly weighs according to material 2-8 in the double-base propellant after pulverizing adds water, regulate the pH value, add again microbiological deterioration, microorganism is: at least a in koning trichoderma, trichoderma pseudokiningii, tiny mould, the Penicllium notatum, regulate the pH value to 7-8,30 ℃-40 ℃ of degradation temperatures, degraded 30-42h stops;
C. reaction: will send into reaction kettle for reaction through the double-base propellant after the microbiological deterioration, temperature in the control reactor is at 80-150 ℃, in reactor, add alkali lye and the potassium humate/Sodium salts humic acids for preparing among the step a, strength of solution in keeping reacting is between 20-50%, reaction pressure is 0.05-0.15MPa, in reaction process, constantly stir, the speed that stirs is 80-120rpm, keep the pH of material in the reactor between 9-11, in reaction, adding concentration is the H of 20-40%
2O
2And catalyzer, catalyzer is that Di's Grindelwald alloy, Cd, Cd-Hg are neat, at least a in the aluminium, zinc, Arndt alloy, Pd, Cu, and the add-on of catalyzer accounts for the heavy 1-10% of reaction mass, in reaction, start waste gas collecting system, begin to monitor NH behind the question response 5-7h
3, NO
x, CO
2, CO, N
2The content of O; When recording NH
3≤ 1200000ug/m
3, NO
x≤ 2ppm, CO
2≤ 0.1%, CO≤50ppm, N
2During O≤1000ppm, stopped reaction;
D. composting: after the reaction in step c is finished, solution filter is removed slag, collect the filtrate after removing slag; Adjust the pH7-9 of solution, the ratio according to hydrolyzate 80-90 weight part, auxiliary material 10-20 weight part in filtrate is mixed, and is specially: NH
4NO
30-25 part, KCl 0-10 part, (NH
4)
3PO
40-20 part, K
3PO
40-10 part, KNO
30-20 part, K
2SO
40-10 part, NaNO
30-15 part, K
2CO
30-10 part, (NH
4)
2SO
40-15 part, Ca (NO
3)
20-15 part, NH
4Cl 0-15 part, water-soluble molysite Fe
2(SO
4)
30-10 part, water-soluble boron salt Na
2B
8O
134H
2O 0-10 part, water-soluble magnesium salt MgSO
40-10 part, water-soluble mantoquita CuSO
40-10 part, water-soluble zinc salt ZnSO
40-10 part, water-soluble molybdenum salt Na
2MoO
42H
2O 0-10 part, water soluble selenium salt Na
2SeO
410H
2O 0-10 part, gains are fertilizer.
The hydrolysis of propelling agent class goes its concrete preparation method of fertilizer of getable hydrolyzate as follows:
A. obtain solution: the preparation mass concentration is the Sodium salts humic acids of NaOH, 1-10% potassium humate or the 1-10% of 10-30%; Concentration is the H of 20-40%
2O
2
B. raw materials pretreatment: it is the 10-40 order that propelling agent is crushed to its fineness, adopts recirculated water to add wet method during pulverizing, makes the water ratio of propelling agent about 4-6%; Raw material propelling agent after pulverizing adds water in the ratio of 5 times of weights of material, regulates the pH value, adds microbiological deterioration again, microorganism is: aspergillus niger, terreus, bread mould, lacquer spot are mould, at least a in the Penicillium decumbens, regulate the pH value to 8-9,50 ℃-60 ℃ of degradation temperatures, degraded 24-32h stops;
C. reaction: will send into reaction kettle for reaction through the propelling agent after the microbiological deterioration, temperature in the control reactor is at 80-150 ℃, in reactor, add alkali lye and the potassium humate/Sodium salts humic acids for preparing among the step a, strength of solution in keeping reacting is between 20-50%, and reaction pressure is 0.05-0.15MPa, constantly stirs in reaction process, the speed that stirs is 80-120rpm, keep the pH of material in the reactor between 9-11, in reaction, adding concentration is the H of 20-40%
2O
2And catalyzer, catalyzer is that Di's Grindelwald alloy, Cd, Cd-Hg are neat, at least a in the aluminium, zinc, Arndt alloy, Pd, Cu, and the add-on of catalyzer accounts for the heavy 1-10% of reaction mass, in the time of reaction, start waste gas collecting system, react and begin to monitor NH after 7-9 hour
3, NO
x, CO
2, N
2The content of O; When recording NH
3≤ 300000ug/m
3, NO
x≤ 2.5ppm, CO
2≤ 0.05%, N
2During O≤300ppm, stopped reaction;
D. composting: after the reaction in step c is finished, solution filter is removed slag, collect the filtrate after removing slag; Adjust the pH value of solution to 7-8, according to hydrolyzate 70-85 weight part, the ratio of auxiliary material 10-20 weight part is mixed, and is specially: NH in filtrate
4NO
30-25 part, KCl 0-10 part, (NH
4)
3PO
40-20 part, K
3PO
40-10 part, KNO
30-20 part, K
2SO
40-10 part, NaNO
30-15 part, K
2CO
30-10 part, (NH
4)
2SO
40-15 part, Ca (NO
3)
20-15 part, NH
4Cl 0-15 part, water-soluble molysite Fe
2(SO
4)
30-10 part, water-soluble boron salt Na
2B
8O
134H
2O 0-10 part, water-soluble magnesium salt MgSO
40-10 part, water-soluble mantoquita CuSO
40-10 part, water-soluble zinc salt ZnSO
40-10 part, water-soluble molybdenum salt Na
2MoO
42H
2O 0-10 part, water soluble selenium salt Na
2SeO
410H
2O 0-10 part, gains are fertilizer.
The hydrolysis of nitro-compound class explosive goes its concrete preparation method of fertilizer of getable hydrolyzate as follows:
A. obtain solution: the preparation mass concentration is NaOH, the 1-10% potassium humate/Sodium salts humic acids of 5-30%; Concentration is the H of 20-40%
2O
2
B. raw materials pretreatment: it is the 10-40 order that nitro-compound class explosive powder is broken to its fineness, adopts recirculated water to add wet method during pulverizing, makes the water ratio of nitro-compound class explosive about 4-6%; The ratio that doubly weighs according to material 2-8 in the nitro-compound class explosive after pulverizing adds entry, regulate the pH value, add again microbiological deterioration, microorganism is: at least a in Trichodermareesei, koning trichoderma, Penicillium decumbens, aspergillus niger, the bread mould, regulate the pH value to 8-9,40 ℃-50 ℃ of degradation temperatures, degraded 36-48h stops;
C. reaction: will send into reaction kettle for reaction through the nitro-compound class explosive after the microbiological deterioration, temperature in the control reactor is at 80-150 ℃, in reactor, add alkali lye and the potassium humate/Sodium salts humic acids for preparing among the step a, strength of solution in keeping reacting is between 20-50%, reaction pressure is 0.05-0.15MPa, constantly stir in reaction process, the speed of stirring is 80-120rpm; Keep the pH of material in the reactor between 9-11, in reaction, adding concentration is the H of 20-40%
2O
2And catalyzer, catalyzer is that Di's Grindelwald alloy, Cd, Cd-Hg are neat, at least a in the aluminium, zinc, Arndt alloy, Pd, Cu, and the add-on of catalyzer accounts for the heavy 1-10% of reaction mass, in reaction, start waste gas collecting system, begin to monitor NH after question response 4-6 hour
3, NO
x, CO
2, CO, N
2The content of O; When recording NH3≤80000000ug/m
3, NO
x≤ 150ppm, CO
2≤ 0.1%, CO≤150ppm, N
2During O≤10000ppm, stopped reaction;
D. composting: after the reaction in step c is finished, solution filter is removed slag, collect the filtrate after removing slag; Adjust the pH8-9 of solution, according to hydrolyzate 80-90 weight part, the ratio of auxiliary material 10-20 weight part is mixed, and is specially: NH in filtrate
4NO
30-25 part, KCl 0-10 part, (NH
4)
3PO
40-20 part, K
3PO
40-10 part, KNO
30-20 part, K
2SO
40-10 part, NaNO
30-15 part, K
2CO
30-10 part, (NH
4)
2SO
40-15 part, Ca (NO
3)
20-15 part, NH
4Cl 0-15 part, water-soluble molysite Fe
2(SO
4)
30-10 part, water-soluble boron salt Na
2B
8O
134H
2O 0-10 part, water-soluble magnesium salt MgSO
40-10 part, water-soluble mantoquita CuSO
40-10 part, water-soluble zinc salt ZnSO
40-10 part, water-soluble molybdenum salt Na
2MoO
42H
2O 0-10 part, water soluble selenium salt Na
2SeO
410H
2O 0-10 part, gains are fertilizer.
Beneficial effect of the present invention is, adopt above method to be hydrolyzed propelling charge in bulk and/or explosive substance, then be made into the fertilizer that can utilize for the mankind, not only solved the harm problem that propelling charge in bulk and/or explosive substance bring to the environment of the mankind and human survival, and turn waste into wealth, become the fertilizer with economic worth.
Embodiment
Below in conjunction with specific embodiment the present invention is further described, so that those skilled in the art more understands the present invention, but does not therefore limit the present invention.
Embodiment 1
Be hydrolyzed the method that propelling charge in bulk and/or explosive substance prepare fertilizer, comprise following step:
A. obtain solution: the preparation mass concentration is the KOH of 5-45% or the NH of 5-30%
4The Sodium salts humic acids of the NaOH of OH or 5-40%, 1-10% potassium humate or 1-10%; Concentration is the H of 20-40%
2O
2
B. raw materials pretreatment: it is the 10-40 order that propelling charge in bulk and/or explosive substance are crushed to its fineness, adopts recirculated water to add wet method during pulverizing, makes the water ratio of propelling charge in bulk and explosive substance at 4-6%; The heavy 2-8 of adding material water doubly in raw material after pulverizing propelling charge in bulk and/or the explosive substance, add again microbiological deterioration, microorganism is: Trichodermareesei, viride, koning trichoderma, trichoderma pseudokiningii, tiny mould, Penicllium notatum, penicillium funiculosum, Penicillium decumbens, aspergillus niger, terreus, bread mould, lacquer spot are mould, wart spore lacquer spot is mould, at least a in mould of black ball lacquer spot, regulate the pH value to 6-9, degraded 24-48h stops, and degradation temperature is 30 ℃-60 ℃;
C. reaction: will send into reaction kettle for reaction through propelling charge in bulk and/or explosive substance after the microbiological deterioration, temperature in the control reactor is at 80-150 ℃, in reactor, add alkali lye and the potassium humate/Sodium salts humic acids for preparing among the step a, strength of solution in keeping reacting is between 20-50%, reaction pressure is 0.05-0.15MPa, constantly stirs in reaction process, and the speed of stirring is 80-120rpm, reaction times 10-30h; Keep the pH of material in the reactor at 9-11, in reaction, adding concentration is the H of 20-40%
2O
2And catalyzer, catalyzer is that Di's Grindelwald alloy, Cd, Cd-Hg are neat, at least a in the aluminium, zinc, Arndt alloy, Pd, Cu, and the add-on of catalyzer accounts for the heavy 1-10% of reaction mass, in reaction, start waste gas collecting system, question response carries out beginning later on to monitor in 3-9 hour NH
3, NO
x, CO
2, CO, N
2The content of O; When recording NH
3≤ 300000-80000000ug/m
3, NO
x≤ 1-150ppm, CO
2≤ 0.05%-0.1%, CO≤10-150ppm, N
2During O≤250-10000ppm, stopped reaction;
D. composting: after the reaction in step c is finished, solution filter is removed slag, collect the filtrate after removing slag, i.e. the hydrolyzate of gained; Adjusting the pH to 7-9 of solution, is that 60-95 weight part, auxiliary material are the ratio mixing of 10-40 weight part in solution, and described auxiliary material is: NH
4NO
30-25 part, KCl 0-10 part, (NH
4)
3PO
40-20 part, K
3PO
40-10 part, KNO
30-20 part, K
2SO
40-10 part, NaNO
30-15 part, K
2CO
30-10 part, (NH
4)
2SO
40-15 part, Ca (NO
3)
20-15 part, NH
4Cl0-15 part, water-soluble molysite Fe
2(SO
4)
30-10 part, water-soluble boron salt Na
2B
8O
134H
2O 0-10 part, water-soluble magnesium salt MgSO
40-10 part, water-soluble mantoquita CuSO
40-10 part, water-soluble zinc salt ZnSO
40-10 part, water-soluble molybdenum salt Na
2MoO
42H
2O 0-10 part, water soluble selenium salt Na
2SeO
410H
2O 0-10 part, gains are fertilizer.
Above-mentioned propelling charge in bulk and/or explosive substance are that single-base gun propellant class, double-base propellant class, propelling agent class, triple-base propellant class, nitro compound system explosive class, nitramine are that explosive class, nitric ether are that explosive class, amine nitrate are any in explosive class, pyrotechnic composition class, organic polymer bonded explosive class, the extraordinary pyrotechnic composition class.
Embodiment 2
Its concrete preparation method of fertilizer of the hydrolyzate that the hydrolysis of single-base gun propellant class obtains is as follows:
A. obtain solution: the preparation mass concentration is NaOH, the 1-10% potassium humate/Sodium salts humic acids of 10-30%; Concentration is the H of 20-40%
2O
2
B. raw materials pretreatment: it is the 10-40 order that single-base gun propellant is crushed to its fineness, adopts recirculated water to add wet method during pulverizing, makes the water ratio of single-base gun propellant at 4-6%; The heavy 2-8 of adding material water doubly in the single-base gun propellant after pulverizing, add microbiological deterioration, microorganism is again: at least a during Trichodermareesei, terreus, bread mould, lacquer spot are mould, regulate the pH value to 6-8,40 ℃-50 ℃ of degradation temperatures, degraded 24-36h stops;
C. reaction: will send into reaction kettle for reaction through the single-base gun propellant after the microbiological deterioration, temperature in the control reactor is at 80-150 ℃, in reactor, add alkali lye and the potassium humate/Sodium salts humic acids for preparing among the step a, strength of solution in keeping reacting is between 20-50%, reaction pressure is 0.05-0.15MPa, constantly stir in reaction process, the speed of stirring is 80-120rpm; Keep the pH of material in the reactor between 9-11, in reaction, adding concentration is the H of 20-40%
2O
2And catalyzer, catalyzer is that Di's Grindelwald alloy, Cd, Cd-Hg are neat, at least a in the aluminium, zinc, Arndt alloy, Pd, Cu, and the add-on of catalyzer accounts for the heavy 1-10% of reaction mass, in reaction, start waste gas collecting system, begin to monitor NH after question response 3-5 hour
3, NO
x, CO
2, CO, N
2The content of O; When recording NH3≤6200000ug/m
3, NO
x≤ 1ppm, CO
2≤ 0.05%, CO≤10ppm, N
2During O≤250ppm, stopped reaction;
D. composting: after the reaction in step c is finished, solution filter is removed slag, collect the filtrate after removing slag; Adjust the pH7-8 of solution, mix with the ratio of 60-90 weight part, auxiliary material 10-25 weight part according to hydrolyzate in filtrate, auxiliary material is specially: NH
4NO
30-25 part, KCl 0-10 part, (NH
4)
3PO
40-20 part, K
3PO
40-10 part, KNO
30-20 part, K
2SO
40-10 part, NaNO
30-15 part, K
2CO
30-10 part, (NH
4)
2SO
40-15 part, Ca (NO
3)
20-15 part, NH
4Cl 0-15 part, water-soluble molysite Fe
2(SO
4)
30-10 part, water-soluble boron salt Na
2B
8O
134H
2O 0-10 part, water-soluble magnesium salt MgSO
40-10 part, water-soluble mantoquita CuSO
40-10 part, water-soluble zinc salt ZnSO
40-10 part, water-soluble molybdenum salt Na
2MoO
42H
2O 0-10 part, water soluble selenium salt Na
2SeO
410H
2O 0-10 part, gains are fertilizer.
Embodiment 3
The hydrolysis of double-base propellant class goes its concrete preparation method of fertilizer of getable hydrolyzate as follows:
A. obtain solution: the preparation mass concentration is the NaOH of 10-35%, potassium humate/Sodium salts humic acids of 1-10%; Concentration is the H of 20-40%
2O
2
B. raw materials pretreatment: it is the 10-40 order that double-base propellant is crushed to its fineness, adopts recirculated water to add wet method during pulverizing, makes the water ratio of double-base propellant at 4-6%; The ratio that doubly weighs according to material 2-8 in the double-base propellant after pulverizing adds water, regulate the pH value, add again microbiological deterioration, microorganism is: at least a in koning trichoderma, trichoderma pseudokiningii, tiny mould, the Penicllium notatum, regulate the pH value to 7-8,30 ℃-40 ℃ of degradation temperatures, degraded 30-42h stops;
C. reaction: will send into reaction kettle for reaction through the double-base propellant after the microbiological deterioration, temperature in the control reactor is at 80-150 ℃, in reactor, add alkali lye and the potassium humate/Sodium salts humic acids for preparing among the step a, strength of solution in keeping reacting is between 20-50%, reaction pressure is 0.05-0.15MPa, in reaction process, constantly stir, the speed that stirs is 80-120rpm, keep the pH of material in the reactor between 9-11, in reaction, adding concentration is the H of 20-40%
2O
2And catalyzer, catalyzer is that Di's Grindelwald alloy, Cd, Cd-Hg are neat, at least a in the aluminium, zinc, Arndt alloy, Pd, Cu, and the add-on of catalyzer accounts for the heavy 1-10% of reaction mass, in reaction, start waste gas collecting system, begin to monitor NH behind the question response 5-7h
3, NO
x, CO
2, CO, N
2The content of O; When recording NH
3≤ 1200000ug/m
3, NO
x≤ 2ppm, CO
2≤ 0.1%, CO≤50ppm, N
2During O≤1000ppm, stopped reaction;
D. composting: after the reaction in step c is finished, solution filter is removed slag, collect the filtrate after removing slag; Adjust the pH value of solution to 7-9, the ratio according to hydrolyzate 80-90 weight part, auxiliary material 10-20 weight part in filtrate is mixed, and is specially: NH
4NO
30-25 part, KCl 0-10 part, (NH
4)
3PO
40-20 part, K
3PO
40-10 part, KNO
30-20 part, K
2SO
40-10 part, NaNO
30-15 part, K
2CO
30-10 part, (NH
4)
2SO
40-15 part, Ca (NO
3)
20-15 part, NH
4Cl 0-15 part, water-soluble molysite Fe
2(SO
4)
30-10 part, water-soluble boron salt Na
2B
8O
134H
2O 0-10 part, water-soluble magnesium salt MgSO
40-10 part, water-soluble mantoquita CuSO
40-10 part, water-soluble zinc salt ZnSO
40-10 part, water-soluble molybdenum salt Na
2MoO
42H
2O 0-10 part, water soluble selenium salt Na
2SeO
410H
2O 0-10 part, gains are fertilizer.
Embodiment 4
The hydrolysis of propelling agent class goes its concrete preparation method of fertilizer of getable hydrolyzate as follows:
A. obtain solution: the preparation mass concentration is the Sodium salts humic acids of NaOH, 1-10% potassium humate or the 1-10% of 10-30%; Concentration is the H of 20-40%
2O
2
B. raw materials pretreatment: it is the 10-40 order that propelling agent is crushed to its fineness, adopts recirculated water to add wet method during pulverizing, makes the water ratio of propelling agent about 4-6%; Raw material propelling agent after pulverizing adds water in the ratio of 5 times of weights of material, regulates the pH value, adds microbiological deterioration again, microorganism is: aspergillus niger, terreus, bread mould, lacquer spot are mould, at least a in the Penicillium decumbens, regulate the pH value to 8-9,50 ℃-60 ℃ of degradation temperatures, degraded 24-32h stops;
C. reaction: will send into reaction kettle for reaction through the propelling agent after the microbiological deterioration, temperature in the control reactor is at 80-150 ℃, in reactor, add alkali lye and the potassium humate/Sodium salts humic acids for preparing among the step a, strength of solution in keeping reacting is between 20-50%, and reaction pressure is 0.05-0.15MPa, constantly stirs in reaction process, the speed that stirs is 80-120rpm, keep the pH of material in the reactor between 9-11, in reaction, adding concentration is the H of 20-40%
2O
2With and catalyzer, catalyzer is that Di's Grindelwald alloy, Cd, Cd-Hg are neat, at least a in the aluminium, zinc, Arndt alloy, Pd, Cu, and the add-on of catalyzer accounts for the heavy 1-10% of reaction mass, in the time of reaction, start waste gas collecting system, react and begin to monitor NH after 7-9 hour
3, NO
x, CO
2, N
2The content of O; When recording NH
3≤ 300000ug/m
3, NO
x≤ 2.5ppm, CO
2≤ 0.05%, N
2During O≤300ppm, stopped reaction;
D. composting: after the reaction in step c is finished, solution filter is removed slag, collect the filtrate after removing slag; Adjust the pH7-8 of solution, according to hydrolyzate 70-85 weight part, the ratio of auxiliary material 10-20 weight part is mixed, and is specially: NH in filtrate
4NO
30-25 part, KCl 0-10 part, (NH
4)
3PO
40-20 part, K
3PO
40-10 part, KNO
30-20 part, K
2SO
40-10 part, NaNO
30-15 part, K
2CO
30-10 part, (NH
4)
2SO
40-15 part, Ca (NO
3)
20-15 part, NH
4Cl 0-15 part, water-soluble molysite Fe
2(SO
4)
30-10 part, water-soluble boron salt Na
2B
8O
134H
2O 0-10 part, water-soluble magnesium salt MgSO
40-10 part, water-soluble mantoquita CuSO
40-10 part, water-soluble zinc salt ZnSO
40-10 part, water-soluble molybdenum salt Na
2MoO
42H
2O 0-10 part, water soluble selenium salt Na
2SeO
410H
2O 0-10 part, gains are fertilizer.
Embodiment 5
The hydrolysis of nitro-compound class explosive goes its concrete preparation method of fertilizer of getable hydrolyzate as follows:
A. obtain solution: the preparation mass concentration is NaOH, the 1-10% potassium humate/Sodium salts humic acids of 5-30%; Concentration is the H of 20-40%
2O
2
B. raw materials pretreatment: it is the 10-40 order that nitro-compound class explosive powder is broken to its fineness, adopts recirculated water to add wet method during pulverizing, makes the water ratio of nitro-compound class explosive about 4-6%; The ratio that doubly weighs according to material 2-8 in the nitro-compound class explosive after pulverizing adds entry, regulate the pH value, add again microbiological deterioration, microorganism is: at least a in Trichodermareesei, koning trichoderma, Penicillium decumbens, aspergillus niger, the bread mould, regulate the pH value to 8-9,40 ℃-50 ℃ degradeds of degradation temperature 36-48h stops;
C. reaction: will send into reaction kettle for reaction through the nitro-compound class explosive after the microbiological deterioration, temperature in the control reactor is at 80-150 ℃, in reactor, add alkali lye and the potassium humate/Sodium salts humic acids for preparing among the step a, strength of solution in keeping reacting is between 20-50%, reaction pressure is 0.05-0.15MPa, constantly stir in reaction process, the speed of stirring is 80-120rpm; Keep the pH of material in the reactor between 9-11, in reaction, adding concentration is the H of 20-40%
2O
2And catalyzer, catalyzer is that Di's Grindelwald alloy, Cd, Cd-Hg are neat, at least a in the aluminium, zinc, Arndt alloy, Pd, Cu, and the add-on of catalyzer accounts for the heavy 1-10% of reaction mass, in reaction, start waste gas collecting system, begin to monitor NH after question response 4-6 hour
3, NO
x, CO
2, CO, N
2The content of O; When recording NH
3≤ 80000000ug/m
3, NO
x≤ 150ppm, CO
2≤ 0.1%, CO≤150ppm, N
2During O≤10000ppm, stopped reaction;
D. composting: after the reaction in step c is finished, solution filter is removed slag, collect the filtrate after removing slag; Adjust the pH value of solution to 8-9, according to hydrolyzate 80-90 weight part, the ratio of auxiliary material 1-20 weight part is mixed, and is specially: NH in filtrate
4NO
30-25 part, KCl 0-10 part, (NH
4)
3PO
40-20 part, K
3PO
40-10 part, KNO
30-20 part, K
2SO
40-10 part, NaNO
30-15 part, K
2CO
30-10 part, (NH
4)
2SO
40-15 part, Ca (NO
3)
20-15 part, NH
4Cl 0-15 part, water-soluble molysite Fe
2(SO
4)
30-10 part, water-soluble boron salt Na
2B
8O
134H
2O 0-10 part, water-soluble magnesium salt MgSO
40-10 part, water-soluble mantoquita CuSO
40-10 part, water-soluble zinc salt ZnSO
40-10 part, water-soluble molybdenum salt Na
2MoO
42H
2O 0-10 part, water soluble selenium salt Na
2SeO
410H
2O 0-10 part, gains are fertilizer.
Embodiment 6
9/7 propelling charge hydrolysis in the single-base gun propellant class goes its concrete preparation method of fertilizer of getable hydrolyzate as follows:
A. obtain solution: the preparation mass concentration is 15% NaOH, 8% potassium humate; Concentration is 20% H
2O
2
B. raw materials pretreatment: it is 30 orders that 9/7 propelling charge is crushed to its fineness, adopts recirculated water to add wet method during pulverizing, makes the water ratio of 9/7 propelling charge about 4-6%; Ratio according to 6 times of weights of material in 9/7 propelling charge after pulverizing adds entry, adds microbial hydrolytic, and added microorganism is: Trichodermareesei and terreus, regulate pH value to 8, and 45 ℃ of degradation temperatures, degraded 28h stops;
C. reaction: will send into reaction kettle for reaction through 9/7 propelling charge after the microbiological deterioration, temperature in the control reactor is at 110 ℃, in reactor, add alkali lye and the potassium humate for preparing among the step a, strength of solution in keeping reacting is 40%, reaction pressure is 0.1MPa, constantly stir in reaction process, the speed of stirring is 80-120rpm; Keep the pH value of material in the reactor 9, in reaction, adding concentration is 20% H
2O
2With catalyzer Di Grindelwald alloy, the add-on of catalyzer account for material heavy 5%, in reaction, start waste gas collecting system, question response begins to monitor NH after 3 hours
3, NO
x, CO
2, CO, N
2The content of O; When recording NH
3≤ 6200000ug/m
3, NO
x≤ 1ppm, CO
2≤ 0.05%, CO≤10ppm, N
2During O≤250ppm, stopped reaction, total reaction times is about 7 hours;
D. composting: after the reaction in step c is finished, solution filter is removed slag, collect the filtrate after removing slag; Adjust the pH value to 8 of solution, in filtrate according to hydrolyzate 80 weight parts, (NH
4)
3PO
410 weight parts, water-soluble molysite Fe
2(SO
4)
35 parts, water-soluble mantoquita CuSO
45 parts of ratios are mixed, and gains are fertilizer.
Embodiment 7
Two virtues in the double-base propellant class-3-16/1 propelling charge hydrolysis goes its concrete preparation method of fertilizer of getable hydrolyzate as follows:
A. obtain solution: the preparation mass concentration is 20% NaOH, 10% Sodium salts humic acids; Concentration is 20% H
2O
2
B. raw materials pretreatment: it is 40 orders that two virtues-3-16/1 propelling charge is crushed to its fineness, adopts recirculated water to add wet method during pulverizing, makes the water ratio of two virtues-3-16/1 propelling charge at 4-6%; Ratio according to 4 times of weights of material in two virtues after pulverizing-3-16/1 propelling charge adds entry, regulates the pH value, adds microbiological deterioration again, and added microorganism is: koning trichoderma, trichoderma pseudokiningii, regulate pH value to 8, and 40 ℃ of degradation temperatures, degraded 32h stops;
C. reaction: will send into reaction kettle for reaction through the two virtues after the microbiological deterioration-3-16/1 propelling charge, temperature in the control reactor is at 100 ℃, in reactor, add alkali lye and the Sodium salts humic acids for preparing among the step a, strength of solution in keeping reacting is 40%, reaction pressure is 0.1MPa, constantly stir in reaction process, the speed of stirring is 80-120rpm; Keep the pH value of material in the reactor 9, in reaction, adding concentration is 20% H
2O
2With catalyzer Di Grindelwald alloy, the add-on of catalyzer accounts for 7% of weight of material, in reaction, starts waste gas collecting system, and question response begins to monitor NH after 5 hours
3, NO
x, CO
2, CO, N
2The content of O; When recording NH
3≤ 1200000ug/m
3, NO
x≤ 2ppm, CO
2≤ 0.1%, CO≤50ppm, N
2During O≤1000ppm, stopped reaction, total reaction times is about 10 hours;
D. composting: after the reaction in step c is finished, solution filter is removed slag, collect the filtrate after removing slag; Adjust the pH value to 8 of solution, in filtrate according to hydrolyzate 85 weight parts, K
3PO
45 weight parts, water-soluble boron salt Na
2B
8O
134H
2O 5 weight parts, water-soluble magnesium salt MgSO
4The ratio of 5 weight parts is mixed, and gains are fertilizer.
Embodiment 8
Two stones-2 propelling agent hydrolysis in the propelling agent class goes its concrete preparation method of fertilizer of getable hydrolyzate as follows:
A. obtain solution: the preparation mass concentration is 20% NaOH, 10% potassium humate; Concentration is 25% H
2O
2
B. raw materials pretreatment: it is the 10-40 order that two stones-2 propelling agent is crushed to its fineness, adopts recirculated water to add wet method during pulverizing, makes the water ratio of two stone-2 propelling agents at 4-6%; Two stones-2 propelling agent after pulverizing adds entry according to the ratio of 4 times of weights of material, regulates the pH value, adds microbiological deterioration again, and added microorganism is: aspergillus niger, terreus, regulate pH value to 8, and 50 ℃ of degradation temperatures, degraded 24h stops;
C. reaction: will send into reaction kettle for reaction through two stones-2 propelling agent after the microbiological deterioration, temperature in the control reactor is at 120 ℃, in reactor, add alkali lye and the potassium humate for preparing among the step a, strength of solution in keeping reacting is 40%, reaction pressure is 0.1MPa, constantly stir in reaction process, the speed of stirring is 80-120rpm; Keep the pH value of material in the reactor 10, in reaction, adding concentration is 25% H
2O
2With with catalyst Z n, the add-on of catalyzer accounts for 10% of weight of material, in reaction, starts waste gas collecting system, question response begins to monitor NH after 9 hours
3, NO
x, CO
2, N
2The content of O; When recording NH
3≤ 300000ug/m
3, NO
x≤ 2.5ppm, CO
2≤ 0.05%, N
2During O≤300ppm, stopped reaction, total reaction times is about 12 hours;
D. composting: after the reaction in step c is finished, solution filter is removed slag, collect the filtrate after removing slag; Adjust the pH value to 8 of solution, in filtrate according to hydrolyzate 85 weight parts, NH
4NO
35 weight parts, water-soluble zinc salt ZnSO
45 weight parts, water soluble selenium salt Na
2SeO
410H
2The ratio of O 5 weight parts is mixed, and gains are fertilizer.
Embodiment 9
Trinitrotoluene hydrolysis in the nitro-compound class explosive goes its concrete preparation method of fertilizer of getable hydrolyzate as follows:
A. obtain solution: the preparation mass concentration is 15% NaOH, 10% potassium humate; Concentration is 20% H
2O
2
B. raw materials pretreatment: it is 40 orders that tritonal is crushed to its fineness, adopts recirculated water to add wet method during pulverizing, makes the water ratio of tritonal about 4-6%; Tritonal propelling charge after pulverizing adds entry according to the ratio of 4 times of weights of material, regulates the pH value, adds microbiological deterioration again, and added microorganism is: Trichodermareesei and koning trichoderma, regulate pH value to 8, and 45 ℃ of degradation temperatures, degraded 40h stops;
C. reaction: will send into reaction kettle for reaction through the tritonal after the microbiological deterioration, temperature in the control reactor is at 90 ℃, in reactor, add alkali lye and the potassium humate for preparing among the step a, strength of solution in keeping reacting is between 20-50%, reaction pressure is 0.1MPa, constantly stir in reaction process, the speed of stirring is 80-120rpm; Keep the pH value of material in the reactor 9, in reaction, adding concentration is 20% H
2O
2With catalyzer zinc, the add-on of catalyzer account for reaction mass heavy 10%, in reaction, start waste gas collecting system, question response begins to monitor NH after 6 hours
3, NO
x, CO
2, CO, N
2The content of O; When recording NH
3≤ 80000000ug/m
3, NO
x≤ 150ppm, CO
2≤ 0.1%, CO≤150ppm, N
2During O＜10000ppm, stopped reaction, total reaction times is about 9 hours;
D. composting: after the reaction in step c is finished, solution filter is removed slag, collect the filtrate after removing slag; Adjust the pH value to 8 of solution, in filtrate according to hydrolyzate 80 weight parts, (NH
4)
3PO
410 weight parts, water-soluble molysite Fe
2(SO
4)
35 weight parts, water-soluble boron salt Na
2B
8O
134H
2The ratio of O 5 weight parts is mixed, and gains are fertilizer.
Claims (9)
1. be hydrolyzed the fertilizer that propelling charge in bulk and/or explosive substance make, it is characterized in that, the major ingredient of described fertilizer is: the hydrolyzate by the hydrolysis of propelling charge in bulk and/or explosive substance obtains is specially: this hydrolyzate is reacted with alkaline solution, humate by propelling charge in bulk and/or explosive substance and makes; Auxiliary material comprises at least a in the following component:
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.
2. the fertilizer that makes of hydrolysis as claimed in claim 1 propelling charge in bulk and/or explosive substance is characterized in that, described major ingredient hydrolyzate is 60-95 part; Auxiliary material is 10-40 part, and the parts by weight of each component are as follows in the described auxiliary material:
Water-soluble molysite 0-10 part, water-soluble boron salt 0-10 part, water-soluble magnesium salt 0-10 part, water-soluble mantoquita 0-10 part, water-soluble zinc salt 0-10 part, water-soluble molybdenum salt 0-10 part, water soluble selenium salt 0-10 part.
3. the fertilizer that makes of hydrolysis as claimed in claim 2 propelling charge in bulk and/or explosive substance is characterized in that, described water-soluble molysite is Fe
2(SO
4)
3, water-soluble boron salt is Na
2B
8O
134H
2O, water-soluble magnesium salt are MgSO
4, water-soluble mantoquita is CuSO
4, water-soluble zinc salt is ZnSO
4, water-soluble molybdenum salt is Na
2MoO
42H
2O, water soluble selenium salt are Na
2SeO
410H
2O.
4. prepare the method for fertilizer such as each described hydrolysis propelling charge in bulk and/or explosive substance in the claims 1 to 3, comprise following step:
A. obtain solution: the preparation mass concentration is the KOH of 5-45% or the NH of 5-30%
4The Sodium salts humic acids of the NaOH of OH or 5-40%, 1-10% potassium humate or 1-10%; Concentration is the H of 20-40%
2O
2
B. raw materials pretreatment: it is the 10-40 order that propelling charge in bulk and/or explosive substance are crushed to its fineness, adopts recirculated water to add wet method during pulverizing, makes the water ratio of propelling charge in bulk and explosive substance at 4-6%; The heavy 2-8 of adding material water doubly in raw material after pulverizing propelling charge in bulk and/or the explosive substance, add again microbiological deterioration, described microorganism is: Trichodermareesei, viride, koning trichoderma, trichoderma pseudokiningii, tiny mould, Penicllium notatum, penicillium funiculosum, Penicillium decumbens, aspergillus niger, terreus, bread mould, lacquer spot are mould, wart spore lacquer spot is mould, at least a in mould of black ball lacquer spot, regulate the pH value to 6-9, degraded 24-48h stops, and degradation temperature is 30 ℃-60 ℃;
C. reaction: will send into reaction kettle for reaction through propelling charge in bulk and/or explosive substance after the microbiological deterioration, temperature in the control reactor is at 80-150 ℃, in reactor, add alkali lye and the potassium humate/Sodium salts humic acids for preparing among the step a, strength of solution in the maintenance reactor is between 20-50%, reaction pressure is 0.05-0.15MPa, constantly stir in reaction process, the speed of stirring is 80-120rpm; Keep the pH value of material in the reactor at 9-11, in reaction, adding concentration is the H of 20-40%
2O
2And catalyzer, described catalyzer is that Di's Grindelwald alloy, Cd, Cd-Hg are neat, at least a in the aluminium, zinc, Arndt alloy, Pd, Cu, the add-on of described catalyzer accounts for the heavy 1-10% of reaction mass, in reaction, start waste gas collecting system, question response carries out beginning later on to monitor in 3-9 hour NH
3, NO
x, CO
2, CO, N
2The content of O; When recording NH
3≤ 300000-80000000ug/m
3, NO
x≤ 1-150ppm, CO
2≤ 0.05%-0.1%, CO≤10-150ppm, N
2During O≤250-10000ppm, stopped reaction;
D. composting: after the reaction in step c is finished, solution filter is removed slag, collect the filtrate after removing slag, i.e. the hydrolyzate of gained; Adjusting the pH value of solution to 7-9, is that 60-95 weight part, auxiliary material are the ratio mixing of 10-40 weight part in solution, and described auxiliary material is: NH
4NO
30-25 part, KCl 0-10 part, (NH
4)
3PO
40-20 part, K
3PO
40-10 part, KNO
30-20 part, K
2SO
40-10 part, NaNO
30-15 part, K
2CO
30-10 part, (NH
4)
2SO
40-15 part, Ca (NO
3)
20-15 part, NH
4Cl0-15 part, water-soluble molysite Fe
2(SO
4)
30-10 part, water-soluble boron salt Na
2B
8O
134H
2O 0-10 part, water-soluble magnesium salt MgSO
40-10 part, water-soluble mantoquita CuSO
40-10 part, water-soluble zinc salt ZnSO
40-10 part, water-soluble molybdenum salt Na
2MoO
42H
2O 0-10 part, water soluble selenium salt Na
2SeO
410H
2O 0-10 part, gains are fertilizer.
5. hydrolysis as claimed in claim 4 propelling charge in bulk and/or explosive substance prepare the method for fertilizer, it is characterized in that, described propelling charge in bulk and/or explosive substance are that single-base gun propellant class, double-base propellant class, propelling agent class, triple-base propellant class, nitro compound system explosive class, nitramine are that explosive class, nitric ether are that explosive class, amine nitrate are any in explosive class, pyrotechnic composition class, organic polymer bonded explosive class, the extraordinary pyrotechnic composition class.
6. hydrolysis as claimed in claim 5 propelling charge in bulk and/or explosive substance prepare the method for fertilizer, it is characterized in that, its concrete preparation method of fertilizer of the hydrolyzate that the single-base gun propellant hydrolysis of being gone back obtains is as follows:
A. obtain solution: the preparation mass concentration is NaOH, the 1-10% potassium humate/Sodium salts humic acids of 10-30%; Concentration is the H of 20-40%
2O
2
B. raw materials pretreatment: it is the 10-40 order that single-base gun propellant is crushed to its fineness, adopts recirculated water to add wet method during pulverizing, makes the water ratio of single-base gun propellant at 4-6%; The heavy 2-8 of adding material water doubly in the single-base gun propellant after pulverizing, add microbiological deterioration, described microorganism is again: at least a during Trichodermareesei, terreus, bread mould, lacquer spot are mould, regulate the pH value to 6-8,40 ℃-50 ℃ of degradation temperatures, degraded 24-36h stops;
C. reaction: will send into reaction kettle for reaction through the single-base gun propellant after the microbiological deterioration, temperature in the control reactor is at 80-150 ℃, in reactor, add alkali lye and the potassium humate/Sodium salts humic acids for preparing among the step a, solution speed in keeping reacting is between 20-50%, reaction pressure is 0.05-0.15MPa, constantly stir in reaction process, the speed of stirring is 80-120rpm; Keep the pH of material in the reactor between 9-11, in reaction, adding concentration is the H of 20-40%
2O
2And catalyzer, described catalyzer is that Di's Grindelwald alloy, Cd, Cd-Hg are neat, at least a in the aluminium, zinc, Arndt alloy, Pd, Cu, the add-on of described catalyzer accounts for the heavy 1-10% of reaction mass, in reaction, start waste gas collecting system, begin to monitor NH after question response 3-5 hour
3, NO
x, CO
2, CO, N
2The content of O; When recording NH
3≤ 6200000ug/m
3, NO
x≤ 1ppm, CO
2≤ 0.05%, CO≤10ppm, N
2During O≤250ppm, stopped reaction;
D. composting: after the reaction in step c is finished, solution filter is removed slag, collect the filtrate after removing slag; Adjust the pH value of solution to 7-8, in filtrate according to hydrolyzate with the 60-90 weight part, the ratio of auxiliary material 10-25 weight part is mixed, auxiliary material is specially: NH
4NO
30-25 part, KCl 0-10 part, (NH
4)
3PO
40-20 part, K
3PO
40-10 part, KNO
30-20 part, K
2SO
41-10 part, NaNO
30-15 part, K
2CO
30-10 part, (NH
4)
2SO
40-15 part, Ca (NO
3)
20-15 part, NH
4Cl 0-15 part, water-soluble molysite Fe
2(SO
4)
30-10 part, water-soluble boron salt Na
2B
8O
134H
2O 0-10 part, water-soluble magnesium salt MgSO
40-10 part, water-soluble mantoquita CuSO
40-10 part, water-soluble zinc salt ZnSO
40-10 part, water-soluble molybdenum salt Na
2MoO
42H
2O 0-10 part, water soluble selenium salt Na
2SeO
410H
2O 0-10 part, gains are fertilizer.
7. hydrolysis as claimed in claim 5 propelling charge in bulk and/or explosive substance prepare the method for fertilizer, it is characterized in that, described double-base propellant hydrolysis goes its concrete preparation method of getable hydrolyzate fertilizer as follows:
A. obtain solution: the preparation mass concentration is the NaOH of 10-35%, potassium humate/Sodium salts humic acids of 1-10%; Concentration is the H of 20-40%
2O
2
B. raw materials pretreatment: it is the 10-40 order that double-base propellant is crushed to its fineness, adopts recirculated water to add wet method during pulverizing, makes the water ratio of double-base propellant at 4-6%; The ratio that doubly weighs according to material 2-8 in the double-base propellant after pulverizing adds water, regulate the pH value, add again microbiological deterioration, described microorganism is: at least a in koning trichoderma, trichoderma pseudokiningii, tiny mould, the Penicllium notatum, regulate the pH value to 7-8,30 ℃-40 ℃ of degradation temperatures, degraded 30-42h stops;
C. reaction: will send into reaction kettle for reaction through the double-base propellant after the microbiological deterioration, temperature in the control reactor is at 80-150 ℃, in reactor, add alkali lye and the potassium humate/Sodium salts humic acids for preparing among the step a, strength of solution in keeping reacting is between 20-50%, reaction pressure is 0.05-0.15MPa, in reaction process, constantly stir, the speed that stirs is 80-120rpm, keep the pH of material in the reactor between 9-11, in reaction, adding concentration is the H of 20-40%
2O
2And catalyzer, described catalyzer is that Di's Grindelwald alloy, Cd, Cd-Hg are neat, at least a in the aluminium, zinc, Arndt alloy, Pd, Cu, and the add-on of described catalyzer accounts for the heavy 1-10% of reaction mass, in reaction, start waste gas collecting system, begin to monitor NH behind the question response 5-7h
3, NO
x, CO
2, CO, N
2The content of O; When recording NH3≤1200000ug/m
3, NO
x≤ 2ppm, CO
2≤ 0.1%, CO≤50ppm, N
2During O≤1000ppm, stopped reaction;
D. composting: after the reaction in step c is finished, solution filter is removed slag, collect the filtrate after removing slag; Adjust the pH value of solution to 7-9, the ratio according to hydrolyzate 80-90 weight part, auxiliary material 10-20 weight part in filtrate is mixed, and is specially: NH
4NO
30-25 part, KCl 0-10 part, (NH
4)
3PO
40-20 part, K
3P
3O
40-10 part, KNO
30-20 part, K
2SO
40-10 part, NaNO
30-15 part, K
2CO
30-10 part, (NH
4)
2SO
40-15 part, Ca (NO
3)
20-15 part, NH
4Cl 0-15 part, water-soluble molysite Fe
2(SO
4)
30-10 part, water-soluble boron salt Na
2B
8O
134H
2O 0-10 part, water-soluble magnesium salt MgSO
40-10 part, water-soluble mantoquita CuSO
40-10 part, water-soluble zinc salt ZnSO
40-10 part, water-soluble molybdenum salt Na
2MoO
42H
2O 0-10 part, water soluble selenium salt Na
2SeO
410H
2O 0-10 part, gains are fertilizer.
8. hydrolysis as claimed in claim 5 propelling charge in bulk and/or explosive substance prepare the method for fertilizer, it is characterized in that, described propelling agent hydrolysis goes its concrete preparation method of fertilizer of getable hydrolyzate as follows:
A. obtain solution: the preparation mass concentration is the Sodium salts humic acids of NaOH, 1-10% potassium humate or the 1-10% of 10-30%; Concentration is the H of 20-40%
2O
2
B. raw materials pretreatment: it is the 10-40 order that propelling agent is crushed to its fineness, adopts recirculated water to add wet method during pulverizing, makes the water ratio of propelling agent about 4-6%; Raw material propelling agent after pulverizing adds water in the ratio of 5 times of weights of material, regulate the pH value, add again microbiological deterioration, described microorganism is: aspergillus niger, terreus, bread mould, lacquer spot are mould, at least a in the Penicillium decumbens, regulate the pH value to 8-9,50 ℃-60 ℃ of degradation temperatures, degraded 24-32h stops;
C. reaction: will send into reaction kettle for reaction through the propelling agent after the microbiological deterioration, temperature in the control reactor is at 80-150 ℃, in reactor, add alkali lye and the potassium humate/Sodium salts humic acids for preparing among the step a, strength of solution in keeping reacting is between 20-50%, and reaction pressure is 0.05-0.15MPa, constantly stirs in reaction process, the speed that stirs is 80-120rpm, keep the pH of material in the reactor between 9-11, in reaction, adding concentration is the H of 20-40%
2O
2And catalyzer, described catalyzer is that Di's Grindelwald alloy, Cd, Cd-Hg are neat, at least a in the aluminium, zinc, Arndt alloy, Pd, Cu, and the add-on of described catalyzer accounts for the heavy 1-10% of reaction mass, in the time of reaction, start waste gas collecting system, react and begin to monitor NH after 7-9 hour
3, NO
x, CO
2, N
2The content of O; When recording NH
3≤ 300000ug/m
3, NO
x≤ 2.5ppm, CO
2≤ 0.05%, N
2During O≤300ppm, stopped reaction;
D. composting: after the reaction in step c is finished, solution filter is removed slag, collect the filtrate after removing slag; Adjust the pH value of solution to 7-8, according to hydrolyzate 70-85 weight part, the ratio of auxiliary material 10-20 weight part is mixed, and is specially: NH in filtrate
4NO
30-25 part, KCl 0-10 part, (NH
4)
3PO
40-20 part, K
3PO
40-10 part, KNO
30-20 part, K
2SO
40-10 part, NaNO
30-15 part, K
2CO
30-10 part, (NH
4)
2SO
40-15 part, Ca (NO
3)
20-15 part, NH
4Cl 0-15 part, water-soluble molysite Fe
2(SO
4)
30-10 part, water-soluble boron salt Na
2B
8O
134H
2O 0-10 part, water-soluble magnesium salt MgSO
40-10 part, water-soluble mantoquita CuSO
40-10 part, water-soluble zinc salt ZnSO
40-10 part, water-soluble molybdenum salt Na
2MoO
42H
2O 0-10 part, water soluble selenium salt Na
2SeO
410H
2O 0-10 part, gains are fertilizer.
9. hydrolysis as claimed in claim 5 propelling charge in bulk and/or explosive substance prepare the method for fertilizer, it is characterized in that, described nitro-compound class explosive hydrolysis goes its concrete preparation method of fertilizer of getable hydrolyzate as follows:
A. obtain solution: the preparation mass concentration is NaOH, the 1-10% potassium humate/Sodium salts humic acids of 5-30%; Concentration is the H of 20-40%
2O
2
B. raw materials pretreatment: it is the 10-40 order that nitro-compound class explosive powder is broken to its fineness, adopts recirculated water to add wet method during pulverizing, makes the water ratio of nitro-compound class explosive about 4-6%; The ratio that doubly weighs according to material 2-8 in the nitro-compound class explosive after pulverizing adds entry, regulate the pH value, add again microbiological deterioration, described microorganism is: at least a in Trichodermareesei, koning trichoderma, Penicillium decumbens, aspergillus niger, the bread mould, regulate the pH value to 8-9,40 ℃-50 ℃ degradeds of degradation temperature 36-48h stops;
C. reaction: will send into reaction kettle for reaction through the nitro-compound class explosive after the microbiological deterioration, temperature in the control reactor is at 80-150 ℃, in reactor, add alkali lye and the potassium humate/Sodium salts humic acids for preparing among the step a, strength of solution in keeping reacting is between 20-50%, reaction pressure is 0.05-0.15MPa, constantly stir in reaction process, the speed of stirring is 80-120rpm; Keep the pH of material in the reactor between 9-11, in reaction, adding concentration is the H of 20-40%
2O
2And catalyzer, described catalyzer is that Di's Grindelwald alloy, Cd, Cd-Hg are neat, at least a in the aluminium, zinc, Arndt alloy, Pd, Cu, the add-on of described catalyzer accounts for the heavy 1-10% of reaction mass, in reaction, start waste gas and receive assembling system, begin to monitor NH after question response 4-6 hour
3, NO
x, CO
2, CO, N
2The content of O; When recording NH
3≤ 80000000ug/m
3, NO
x≤ 150ppm, CO
2≤ 0.1%, CO≤150ppm, N
2During O≤10000ppm, stopped reaction;
D. composting: after the reaction in step c is finished, solution filter is removed slag, collect the filtrate after removing slag; Adjust the pH value of solution to 8-9, according to hydrolyzate 80-90 weight part, the ratio of auxiliary material 10-20 weight part is mixed, and is specially: NH in filtrate
4NO
30-25 part, KCl 0-10 part, (NH
4)
3PO
40-20 part, K
3PO
40-10 part, KNO
30-20 part, K
2SO
40-10 part, NaNO
30-15 part, K
2CO
30-10 part, (NH
4)
2SO
40-15 part, Ca (NO
3)
20-15 part, NH
4Cl 0-15 part, water-soluble molysite Fe
2(SO
4)
30-10 part, water-soluble boron salt Na
2B
8O
134H
2O 0-10 part, water-soluble magnesium salt MgSO
40-10 part, water-soluble mantoquita CuSO
40-10 part, water-soluble zinc salt ZnSO
40-10 part, water-soluble molybdenum salt Na
2MoO
42H
2O 0-10 part, water soluble selenium salt Na
2SeO
410H
2O 0-10 part, gains are fertilizer.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103408341A (en) * | 2013-08-14 | 2013-11-27 | 中国人民解放军济南军区72465部队 | Energy-containing material safe disposal and resource utilization method and system |
| CN103408342A (en) * | 2013-08-14 | 2013-11-27 | 中国人民解放军济南军区72465部队 | Safe disposal and resourceful utilization system for energetic material and implementation method |
| CN103467154A (en) * | 2013-08-14 | 2013-12-25 | 中国人民解放军济南军区72465部队 | Safety disposal and resource utilization method of lead-containing energetic material |
| CN104108964A (en) * | 2014-07-08 | 2014-10-22 | 山东大学 | Preparation method and application of total nutrient microorganism biocontrol organic fertilizer |
| CN104446988A (en) * | 2014-12-03 | 2015-03-25 | 山东省农业科学院农业资源与环境研究所 | Special leaf fertilizer prepared from expired incapacitating single-base propellant for wheat and preparation method of special leaf fertilizer |
| CN104446994A (en) * | 2014-12-03 | 2015-03-25 | 林海涛 | Special water-soluble fertilizer for cucumber under protected cultivation prepared from obsolete disabled single-base propellant and preparation method of water-soluble fertilizer |
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| RU2215720C2 (en) * | 2001-06-29 | 2003-11-10 | Пасешник Георгий Викторович | Method of reusing gun powders and solid rocket fuels based on nitroesters of cellulose and polyatomic alcohols |
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|---|---|---|---|---|
| CN103467154B (en) * | 2013-08-14 | 2015-04-22 | 中国人民解放军济南军区72465部队 | Safety disposal and resource utilization method and system of lead-containing energetic material |
| CN103408342A (en) * | 2013-08-14 | 2013-11-27 | 中国人民解放军济南军区72465部队 | Safe disposal and resourceful utilization system for energetic material and implementation method |
| CN103467154A (en) * | 2013-08-14 | 2013-12-25 | 中国人民解放军济南军区72465部队 | Safety disposal and resource utilization method of lead-containing energetic material |
| CN103408341A (en) * | 2013-08-14 | 2013-11-27 | 中国人民解放军济南军区72465部队 | Energy-containing material safe disposal and resource utilization method and system |
| CN103408342B (en) * | 2013-08-14 | 2014-12-03 | 中国人民解放军济南军区72465部队 | Safe disposal and resourceful utilization system for energetic material and implementation method |
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| CN104108964B (en) * | 2014-07-08 | 2016-06-15 | 山东大学 | The preparation method of a kind of full vegetative microorganism biological and ecological methods to prevent plant disease, pests, and erosion fertilizer and application |
| CN104108964A (en) * | 2014-07-08 | 2014-10-22 | 山东大学 | Preparation method and application of total nutrient microorganism biocontrol organic fertilizer |
| CN104446994A (en) * | 2014-12-03 | 2015-03-25 | 林海涛 | Special water-soluble fertilizer for cucumber under protected cultivation prepared from obsolete disabled single-base propellant and preparation method of water-soluble fertilizer |
| CN104446988A (en) * | 2014-12-03 | 2015-03-25 | 山东省农业科学院农业资源与环境研究所 | Special leaf fertilizer prepared from expired incapacitating single-base propellant for wheat and preparation method of special leaf fertilizer |
| CN104446988B (en) * | 2014-12-03 | 2017-05-31 | 山东省农业科学院农业资源与环境研究所 | A kind of Special foliage fertilizer for wheat using retired disability single-base powder and preparation method thereof |
| CN107855090A (en) * | 2017-11-30 | 2018-03-30 | 西安交通大学 | A kind of vertical tubular reactor for basic hydrolysis of being deenergized for TNT |
| CN108613604A (en) * | 2018-05-10 | 2018-10-02 | 西安交通大学 | One kind scrapping ammunition thermal energy recovery process |
| CN108613604B (en) * | 2018-05-10 | 2019-04-23 | 西安交通大学 | One kind scrapping ammunition thermal energy recovery process |
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