CN111112289A - Treatment method of waste energetic material - Google Patents

Treatment method of waste energetic material Download PDF

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Publication number
CN111112289A
CN111112289A CN201911320588.8A CN201911320588A CN111112289A CN 111112289 A CN111112289 A CN 111112289A CN 201911320588 A CN201911320588 A CN 201911320588A CN 111112289 A CN111112289 A CN 111112289A
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pyrolysis
waste
energetic materials
stage
energetic
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CN111112289B (en
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高宁博
段一航
全翠
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Xian Jiaotong University
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Xian Jiaotong University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B5/00—Operations not covered by a single other subclass or by a single other group in this subclass
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C10B53/02—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of cellulose-containing material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C10B53/07—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of solid raw materials consisting of synthetic polymeric materials, e.g. tyres
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/10—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal from rubber or rubber waste
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/002—Removal of contaminants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/002—Removal of contaminants
    • C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/04—Purifying combustible gases containing carbon monoxide by cooling to condense non-gaseous materials
    • C10K1/046—Reducing the tar content
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
    • C10K3/02—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
    • C10K3/02—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
    • C10K3/023—Reducing the tar content
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B21/00—Obtaining aluminium
    • C22B21/0038—Obtaining aluminium by other processes
    • C22B21/0069—Obtaining aluminium by other processes from scrap, skimmings or any secondary source aluminium, e.g. recovery of alloy constituents
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1003—Waste materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock
    • Y02P20/143—Feedstock the feedstock being recycled material, e.g. plastics
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/20—Waste processing or separation

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Environmental & Geological Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Manufacturing & Machinery (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

The invention discloses a method for treating waste energetic materials, which comprises the following steps: a pretreatment stage, a co-pyrolysis reaction stage, a pyrolysis solid product treatment stage and a pyrolysis gaseous product treatment stage; wherein, the pretreatment stage comprises three processes of cutting and grinding, controllable cleaning and mixing granulation of energetic materials; the co-pyrolysis reaction stage comprises a co-pyrolysis reaction process; the pyrolysis solid product treatment stage comprises a water washing separation process, and main products in the stage are active coke and aluminum; the pyrolysis gaseous product treatment stage mainly comprises catalytic reforming, cooling separation and water washing upgrading processes, and the products of the stage are high-quality pyrolysis oil and pyrolysis gas. The method has simple process and good treatment effect, and can recover the energy in the waste energetic materials.

Description

Treatment method of waste energetic material
Technical Field
The invention belongs to the technical field of waste energetic material treatment, and particularly relates to a treatment method of a waste energetic material.
Background
The solid rocket occupies an important position in the military field, and the use of the solid energetic material can improve the maneuvering performance and the operational use performance of weapons.
The solid energetic material can go through a series of physical and chemical processes along with the prolonging of time in the storage period, the performance of the solid energetic material is reduced, the danger in storage is increased, and therefore the solid energetic material needs to be retired after being in service for a certain period of time; in addition, unqualified products produced by manufacturers in the production process and the replacement of military weapons can also generate scrapped energetic materials which need to be destroyed. If the scrapped solid energetic materials cannot be timely and effectively treated and destroyed, the scrapped solid energetic materials become great explosion hazard sources and pollution sources, and safety and environmental problems are caused.
At present, the traditional treatment methods of waste energetic materials mainly comprise methods of deep soil burying, open sea dumping, open air incineration, explosion and the like, the methods bring great safety and environmental problems, the whole ecological system can be damaged to a certain degree by the landfill and the dumping, certain potential safety hazards still exist, and the incineration method and the explosion method can cause the generation of particles, nitrogen oxides and chlorine-containing gases in the combustion process and damage to the atmospheric environment to different degrees.
In view of the above, it is necessary to find an economical and efficient treatment method to solve the problem of the waste energetic materials.
Disclosure of Invention
The invention aims to provide a method for treating waste energetic materials, so as to solve one or more technical problems. The treatment method disclosed by the invention is simple in process and good in treatment effect, and can be used for recovering energy in the waste energetic materials.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention relates to a method for treating waste energetic materials, which comprises the following steps:
(1) a pre-treatment stage comprising:
(1.1) cutting, stripping and grinding to separate the waste energetic materials into particles meeting the requirement of a preset particle size;
(1.2) controllably cleaning, namely quantitatively removing the oxidant on the surface of the waste energetic material treated in the step (1.1) and reducing the concentration of the oxidant in the energetic material;
(1.3) mixing and granulating, wherein the waste energetic materials treated in the step (1.2) and the organic solid wastes are subjected to uniform energy density mixing and granulating to obtain a mixed and granulated product;
(2) a co-pyrolysis reaction stage comprising:
a co-pyrolysis reaction, wherein a pyrolysis solid product and a pyrolysis gaseous product are obtained through the co-pyrolysis reaction;
(3) a pyrolysis solid product treatment stage comprising:
water washing separation for separating the pyrolysis solid product into coke and aluminum according to density difference between different substances; hydrogen chloride used for removing the surface of the pyrolysis solid product;
(4) a pyrolysis gaseous product treatment stage comprising:
(4.1) catalytic reforming for achieving an improvement in the quality of the pyrolysis gaseous product;
(4.2) cooling and separating to separate normal-temperature liquid components and normal-temperature gaseous components in the pyrolysis gaseous product treated in the step (4.1) to obtain a product liquid oil product;
and (4.3) water washing upgrading is carried out, and the hydrogen chloride gas mixed with the normal-temperature gaseous components obtained in the step (4.2) is removed, so that upgraded pyrolysis gas is obtained.
Further, in the step (1.1), cutting and peeling grinding is used for separating the waste energetic materials into particles with the particle size of less than or equal to 100 microns.
Further, after the step (1.2) of controllable cleaning, the energy component of the energetic material is kept between 0 and 40 percent.
Further, in the step (1.3), the particle sizes of the waste energetic materials and the organic solid wastes are kept consistent, and the energy density per unit length is kept consistent.
Further, in the step (1.3), when the waste energetic materials are mixed with the organic solid waste, the waste energetic materials are mechanically mixed according to the mass percent of 1-50%.
Further, in the step (2), the pyrolysis temperature exceeds 160 ℃, and the waste energetic materials generate exothermic reaction to release heat.
Further, the step (4.1) specifically includes: the pyrolysis gaseous product and the reformed gas are subjected to chemical reaction under the catalysis of the catalyst at high temperature, so that the quality of the pyrolysis gaseous product is improved.
Further, in the step (4.1),
the reformed gas is steam or hydrogen;
the catalyst is Ni, Co or Pd;
the high temperature is 400-800 deg.c.
Further, in the step (4.3), a water washing and spraying technology is adopted to remove hydrogen chloride gas mixed with the normal-temperature gaseous components obtained in the step (4.2); the obtained upgraded pyrolysis gas comprises CO and CO2And CH4。
Further, the organic solid waste is biomass, oil-containing waste or waste rubber.
Compared with the prior art, the invention has the following beneficial effects:
the method comprises four stages, namely a pretreatment stage of the waste energetic material, a co-pyrolysis stage, a treatment stage of pyrolysis solid products and a treatment stage of pyrolysis gaseous products, has simple process and good treatment effect, and can recover energy in the waste energetic material; the main products of the treatment stage of the pyrolysis solid product are active coke and aluminum; the main products of the treatment stage of the pyrolysis gaseous products are high-quality pyrolysis oil and pyrolysis gas. In the invention, the waste energetic materials and the organic wastes are subjected to co-pyrolysis, so that the energy consumption can be reduced, and the pyrolysis product has higher economic value.
According to the invention, the surface area of the waste energetic material after the cutting, stripping and grinding process is increased, and after the waste energetic material is controllably cleaned by liquid ammonia, water and other liquids, the oxidant on the surface of the energetic material can be quantitatively removed, so that the concentration of the oxidant in the energetic material is remarkably reduced.
In the invention, the energy component of the energetic material is kept between 0 and 40 percent, which is beneficial to the subsequent co-pyrolysis reaction.
According to the invention, the mixed particles are subjected to a co-pyrolysis reaction in the pyrolysis reactor, the oxidant contained in the waste energetic materials can release a large amount of heat at the temperature of above 160 ℃, once the pyrolysis temperature exceeds 160 ℃, the waste energetic materials can generate a heating reaction to release a large amount of heat, and the energy consumption in the co-pyrolysis process is reduced.
In the invention, after the solid product obtained after the co-pyrolysis reaction stage is washed and separated, the solid product is separated into coke and aluminum due to the density difference among different substances; in addition, the pyrolysis solid product can remove hydrogen chloride on the surface of the solid after being washed, separated and washed, so that the quality of the product is improved.
In the invention, after the hydrogen chloride gas mixed in the gas is washed by water and sprayed, the hydrogen chloride gas is very soluble in water, so that the hydrogen chloride in the pyrolysis gas is dissolved in water and removed, and finally the high-quality pyrolysis gas is obtained.
In the invention, the treatment rate of the energetic material can reach more than 95 percent.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art are briefly introduced below; it is obvious that the drawings in the following description are some embodiments of the invention, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.
Fig. 1 is a schematic flow chart of a method for processing waste energetic materials according to an embodiment of the present invention.
Detailed Description
In order to make the purpose, technical effect and technical solution of the embodiments of the present invention clearer, the following clearly and completely describes the technical solution of the embodiments of the present invention with reference to the drawings in the embodiments of the present invention; it is to be understood that the described embodiments are only some of the embodiments of the present invention. Other embodiments, which can be derived by one of ordinary skill in the art from the disclosed embodiments without inventive faculty, are intended to be within the scope of the invention.
Referring to fig. 1, a method for processing waste energetic materials according to an embodiment of the present invention includes: a pretreatment stage for the waste energetic material, a co-pyrolysis stage, a pyrolysis solid product treatment stage, and a pyrolysis gaseous product treatment stage.
In particular, the method comprises the following steps of,
1. the pretreatment stage of the waste energetic materials mainly comprises three processes of (1) cutting and grinding, (2) controllable cleaning and (3) mixing and granulating of the energetic materials;
2. the co-pyrolysis reaction stage mainly comprises (4) a co-pyrolysis reaction process;
3. the pyrolysis solid product treatment stage mainly comprises (8) a water washing separation process, wherein the main products in the stage are coke and aluminum;
4. the pyrolysis gaseous product treatment stage mainly comprises (5) catalytic reforming, (6) cooling separation and (7) water washing upgrading process.
Optionally, the waste energetic material is subjected to a pretreatment stage of the waste energetic material, and the waste energetic material is divided into particles with the particle size of less than or equal to 100 μm after being subjected to a cutting and peeling grinding process such as cutting, freezing cutting and grinding.
The energy-containing materials with the particle size of less than or equal to 100 microns are divided into energy-containing materials, the energy-containing materials enter a controllable cleaning process, the surface area of the waste energy-containing materials after the cutting, peeling and grinding process is increased, after the waste energy-containing materials are controllably cleaned by liquid ammonia, water and other liquids, the oxidant on the surface of the energy-containing materials can be quantitatively removed, the concentration of the oxidant in the energy-containing materials is remarkably reduced, the energy components of the energy-containing materials are kept between 0% and 40%, and the subsequent co-pyrolysis reaction is facilitated.
Enabling energetic material particles subjected to the controllable cleaning process to enter a mixing granulation process with uniform energy density, and mechanically mixing the waste energetic materials with organic solid waste according to the mass fraction of 1-50% of the energetic materials; wherein the particle size of the organic solid waste is consistent with that of the waste energetic material subjected to the cutting, stripping and grinding process, so that the energy density of the waste energetic material per unit length is consistent; the organic solid waste used may be biomass, oil-containing waste and waste rubber, but is not limited to these three.
After the energetic material particles and the organic solid waste are subjected to a mixing granulation process with uniform energy density, the energetic material particles and the organic solid waste enter a co-pyrolysis reaction stage. The mixed particles are subjected to co-pyrolysis reaction in the pyrolysis reactor, the waste energetic materials contain oxidant which can release a large amount of heat at the temperature of over 160 ℃, once the pyrolysis temperature exceeds 160 ℃, the waste energetic materials can generate heating reaction to release a large amount of heat, and the energy consumption of the co-pyrolysis process is reduced. And respectively enabling pyrolysis solid products and pyrolysis gas products generated after the co-pyrolysis reaction of the mixed particles to enter a pyrolysis solid product treatment stage and a pyrolysis gaseous product treatment stage.
And (3) enabling a solid product obtained after the waste energetic materials are subjected to a co-pyrolysis reaction stage to enter a pyrolysis solid product treatment stage, wherein the pyrolysis solid product treatment stage mainly comprises a water washing separation process.
After the solid product obtained after the co-pyrolysis reaction stage is washed and separated, the solid product is separated into coke and aluminum due to the density difference among different substances; in addition, the pyrolysis solid product can remove hydrogen chloride on the surface of the solid after being washed, separated and washed, so that the quality of the product is improved.
And (3) enabling a gas product obtained after the waste energetic materials pass through a co-pyrolysis reaction stage to enter a pyrolysis gaseous product treatment stage, wherein the pyrolysis gaseous product treatment stage mainly comprises three processes of catalytic reforming, cooling separation and water washing quality improvement.
Waste energetic materialThe gaseous product obtained after the Co-pyrolysis reaction stage is firstly upgraded by catalytic reforming, and the pyrolysis gaseous product and steam or hydrogen and other reformed gases are subjected to chemical reaction under the conditions of high temperature and high pressure under the catalysis of catalysts such as Ni, Co, Pd and the like, so that the quality of the pyrolysis gaseous product is improved; the pyrolysis gaseous product is subjected to catalytic reforming quality improvement and then is subjected to a cooling separation process, the process aims at separating components which are liquid at normal temperature in pyrolysis gas to cool the components into liquid, and the main product is a liquid oil product with higher quality; after the catalytic reforming pyrolysis gaseous product is cooled and separated, substances in the pyrolysis gas, which are gaseous at normal temperature, enter a washing and upgrading process, hydrogen chloride gas mixed in the gas is washed and sprayed, and the hydrogen chloride gas is very soluble in water, so that the hydrogen chloride in the pyrolysis gas is dissolved in water and removed, and finally high-quality pyrolysis gas is obtained, wherein the main components of the pyrolysis gas are CO and CO2And CH4And the like.
In summary, the embodiments of the present invention provide a method for processing an energetic material, including: a pretreatment stage, a co-pyrolysis reaction stage, a pyrolysis solid product treatment stage and a pyrolysis gaseous product treatment stage; wherein, the pretreatment stage comprises three processes of cutting and grinding, controllable cleaning and mixing granulation of energetic materials; the co-pyrolysis reaction stage comprises a co-pyrolysis reaction process; the pyrolysis solid product treatment stage comprises a water washing separation process, and main products in the stage are active coke and aluminum; the pyrolysis gaseous product treatment stage mainly comprises catalytic reforming, cooling separation and water washing upgrading processes, and the products of the stage are high-quality pyrolysis oil and pyrolysis gas.
In the invention, the treatment rate of the energetic material can reach more than 95 percent, and the energy in the energetic material can be efficiently recovered. The existing treatment processes such as incineration and landfill easily cause soil and atmospheric pollution, and cause energy waste; the dissolution method uses a large amount of solvent in the treatment process, generates a large amount of waste liquid, and causes difficulty in subsequent treatment, and the residue after solvent extraction needs another method for treatment.
Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art can make modifications and equivalents to the embodiments of the present invention without departing from the spirit and scope of the present invention, which is set forth in the claims of the present application.

Claims (10)

1. A method of processing waste energetic materials, comprising:
(1) a pre-treatment stage comprising:
(1.1) cutting, stripping and grinding to separate the waste energetic materials into particles meeting the requirement of a preset particle size;
(1.2) controllably cleaning, namely quantitatively removing the oxidant on the surface of the waste energetic material treated in the step (1.1) and reducing the concentration of the oxidant in the energetic material;
(1.3) mixing and granulating, wherein the waste energetic materials treated in the step (1.2) and the organic solid wastes are subjected to uniform energy density mixing and granulating to obtain a mixed and granulated product;
(2) a co-pyrolysis reaction stage comprising:
a co-pyrolysis reaction, wherein a pyrolysis solid product and a pyrolysis gaseous product are obtained through the co-pyrolysis reaction;
(3) a pyrolysis solid product treatment stage comprising:
water washing separation for separating the pyrolysis solid product into coke and aluminum according to density difference between different substances; hydrogen chloride used for removing the surface of the pyrolysis solid product;
(4) a pyrolysis gaseous product treatment stage comprising:
(4.1) catalytic reforming for achieving an improvement in the quality of the pyrolysis gaseous product;
(4.2) cooling and separating to separate normal-temperature liquid components and normal-temperature gaseous components in the pyrolysis gaseous product treated in the step (4.1) to obtain a product liquid oil product;
and (4.3) water washing upgrading is carried out, and the hydrogen chloride gas mixed with the normal-temperature gaseous components obtained in the step (4.2) is removed, so that upgraded pyrolysis gas is obtained.
2. The method for treating the waste energetic materials as claimed in the claim 1, wherein in the step (1.1), the cutting and peeling grinding is used for separating the waste energetic materials into particles with the particle size of 100 μm or less.
3. The method for treating the waste energetic materials as claimed in claim 1, wherein the energy component of the energetic materials is kept between 0 and 40 percent after the controllable cleaning in the step (1.2).
4. The method for treating the waste energetic materials according to the claim 1, wherein in the step (1.3), the particle sizes of the waste energetic materials and the organic solid wastes are kept consistent, and the energy density per unit length is kept consistent.
5. The method for treating the waste energetic materials according to the claim 1, wherein in the step (1.3), when the waste energetic materials are mixed with the organic solid wastes, the mechanical mixing is carried out according to the mass percent of the waste energetic materials being 1-50%.
6. The method for treating the waste energetic materials as claimed in the claim 1, wherein in the step (2), the pyrolysis temperature exceeds 160 ℃, and the waste energetic materials generate exothermic reaction to release heat.
7. The method for treating the waste energetic materials according to claim 1, wherein the step (4.1) comprises: the pyrolysis gaseous product and the reformed gas are subjected to chemical reaction under the catalysis of the catalyst under the high-temperature condition, so that the quality of the pyrolysis gaseous product is improved.
8. The method for treating the waste energetic materials according to the claim 7, wherein, in the step (4.1),
the reformed gas is steam or hydrogen;
the catalyst is Ni, Co or Pd;
the high temperature is 400-800 deg.c.
9. The method for treating the waste energetic materials as claimed in claim 1, wherein in the step (4.3), the hydrogen chloride gas mixed with the normal-temperature gaseous components obtained in the step (4.2) is removed by adopting a water washing and spraying technology;
the obtained upgraded pyrolysis gas comprises CO and CO2And CH4。
10. The method of claim 1, wherein the organic solid waste is biomass, oil-containing waste or waste rubber.
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