CN112871949A - Heavy metal recovery method based on waste incineration fly ash - Google Patents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B5/00—Operations not covered by a single other subclass or by a single other group in this subclass
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- 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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/16—Sintering; Agglomerating
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- 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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
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- 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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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- 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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/02—Working-up flue dust
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- 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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/04—Working-up slag
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B2101/00—Type of solid waste
- B09B2101/02—Gases or liquids enclosed in discarded articles, e.g. aerosol cans or cooling systems of refrigerators
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- 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
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
The invention discloses a heavy metal recovery method based on waste incineration fly ash, and particularly relates to the technical field of environmental protection treatment, which comprises the following steps: mixing garbage containing heavy metals and pulverized coal, adding the mixture into a roasting kiln for combustion, sending cold air to an air preheater by using a fan to exchange heat with combustion flue gas for heating, and feeding preheated hot air into the roasting kiln; and step two, collecting the fly ash and the slag generated in the combustion process, and mixing by using a stirrer. According to the invention, the iron slurry method is adopted for treatment, the mixed product is stirred by using a NaCl solution, the pH value is adjusted to acidity, and high-purity iron powder is added for mixing, so that heavy metals and NaCl can form various different complexes under the acidic condition, the dissolution of the heavy metals is enhanced, the recovery and reaction of the heavy metals are facilitated, no pollutant is generated in the whole process, and the method is environment-friendly and green.
Description
Technical Field
The invention relates to the technical field of environmental protection treatment, in particular to a heavy metal recovery method based on waste incineration fly ash.
Background
Along with the rapid development of social economy in China, the acceleration of the urbanization process and the continuous improvement of the living standard of people, the problem of urban garbage is increasingly prominent. Garbage disposal has become one of the major problems restricting the sustainable development of cities in China.
The basic treatment modes of municipal solid waste are landfill, incineration and composting. The incineration treatment has the advantages of small occupied area, short treatment time, remarkable reduction (weight reduction reaches 70 percent and volume reduction reaches 90 percent), capability of killing all pathogenic microorganisms and parasitic ova, capability of recycling heat energy generated in the incineration process, contribution to recycling of municipal waste and the like. The proportion of incineration disposal in developed countries is high, e.g. 80% in switzerland, 73% in japan and 70% in denmark. The municipal waste treatment in China still takes landfill as the main part, but the landfill and the composting treatment need to occupy a large amount of land, and with the rapid increase of the waste amount, the site selection of landfill sites in large and medium cities in China with the shortage of land resources is increasingly difficult. Therefore, the garbage incineration treatment technology becomes the preferred scheme for treating urban domestic garbage in China, the development is very fast in recent years, and the incineration proportion is rapidly increased from 1-2% to 15% in the last five or six years. Incineration will be one of the main treatment modes of municipal solid waste in China without any doubt.
However, the waste incineration fly ash contains heavy metals and dioxin-like organic pollutants, and both of them need to be detoxified, and it is desirable that the detoxified incineration fly ash be recycled so as to reduce the increasing burden on landfills. However, a large amount of fly ash and fly ash are generated in the waste incineration, and the phenomena of high content of heavy metals in dioxin and incineration products generated in the incineration process cannot be well treated, and various harmful reactants are generated in the recovery process in the existing waste incineration heavy metal recovery method, so that secondary pollution is caused, and the recovery efficiency is low.
Disclosure of Invention
In order to overcome the above defects of the prior art, embodiments of the present invention provide a method for recovering heavy metals based on fly ash from waste incineration, which includes collecting fly ash and slag generated during the combustion of heavy metal waste, granulating, sintering the granulated recovered material obtained by granulation at high temperature, so as to effectively decompose dioxin, solidify a part of heavy metals in Si-O grids, save energy, recover the other part of heavy metals and fly ash mixture by using a bag-type dust collector, collect and mix the solid residue collected by a flue gas purification system, treat the mixture by using an iron slurry method, stir the mixed product by using a NaCl solution, adjust the pH value to acidity, add high-purity iron powder for mixing, and form various complexes with NaCl under acidic conditions, the dissolution of the heavy metal is enhanced, the recovery and the reaction of the heavy metal are facilitated, the recovery efficiency is high, no pollutant is generated in the whole process, and the method is environment-friendly and green.
In order to achieve the purpose, the invention provides the following technical scheme: a heavy metal recovery method based on waste incineration fly ash comprises the following steps:
step one, collecting fly ash and slag generated in the combustion process, mixing the fly ash and the slag by using a stirrer, adding the mixture into a granulator to be processed into granular recycled materials with uniform size, ball-milling the granular recycled materials into granules with the diameter of 250-mesh and 300-mesh by using a ball mill, adding the granular recycled materials into a rotary furnace, and sequentially adding SiO into the rotary furnace2、AL2O3And Ti2O3The mixed powder is sintered at the temperature of 1000-1200 ℃ to decompose dioxin, part of heavy metal in the fly ash is solidified to form oxide, the other part of heavy metal is combined with flying dust and is captured by a bag-type dust collector, and the oxide is filtered and collected;
step two, after fly ash is treated, recovering fly ash collected by a bag-type dust collector, then collecting solid residues collected by a flue gas purification system, stirring and mixing the collected solid residues and the fly ash, removing large particles by using a mesh screen, and then drying at the temperature of 100-110 ℃ for 20-24 hours to obtain a fly ash mixture;
adding 100ml of NaCl solution into the stirring container, adjusting the pH value of the solution to 2-4, adding a certain amount of fly ash mixture into the solution, then adding iron powder, stirring for 2-6 hours, standing for 2-4 hours in a normal temperature environment after stirring is finished, and sucking the iron powder out of the solution by using a magnet;
step four, separating iron powder from the magnet, drying and weighing, standing the solution at 5 ℃, performing centrifugal separation by using a solid-liquid separator to obtain filtrate and solution residues, digesting the solution residues by using microwaves, and mixing the solution residues with the oxide obtained in the step two to obtain a heavy metal recovery mixture;
and step five, measuring the mixture of the filtrate and the heavy metal recovery mixture by using AAS (anaerobic-anoxic-oxic) to obtain the parameters of heavy metal recovery, and finishing the recovery of the heavy metal in the fly ash.
In a preferred embodiment, the iron powder added in the fourth step has an Fe content of not less than 98%.
In a preferred embodiment, the concentration of the NaCl solution added in the fourth step is 0.2-0.5 mol/L.
In a preferred embodiment, the SiO2、AL2O3And Ti2O3The mixing ratio in the mixed powder of (1: 1: 2).
In a preferred embodiment, the mass ratio of the quantitative fly ash mixture to the NaCl solution added in the fourth step is 1:10, the stirring speed after adding the iron powder is 100-120 r/min, and the normal temperature environment is 10-15 ℃.
In a preferred embodiment, the mesh number of the net in the third step is 20-50 meshes, and the mixing ratio of the solid residue to the fly ash is 3: 1.
In a preferred embodiment, in the fifth step, the solution is allowed to stand for 3 to 5 hours.
In a preferred embodiment, in the fifth step, the particle size of the fly ash mixture is 200-250 mesh.
The invention has the technical effects and advantages that:
1. fly ash and slag generated in the combustion process of heavy metal garbage are collected and granulated, and then the granulated recovered material obtained by granulation is sintered at high temperature, so that dioxin can be effectively decomposed, part of heavy metal is solidified in Si-O grids, and energy is saved;
2. the other part of the mixture of the heavy metal and the flying dust is recycled by using a bag-type dust collector, the solid residues collected by the flue gas purification system are collected and mixed with the mixture, the mixture is treated by adopting an iron slurry method, the mixed product is stirred by using a NaCl solution, the pH value is adjusted to be acidic, and high-purity iron powder is added for mixing, so that the heavy metal and the NaCl can form various different complexes under the acidic condition, the dissolution of the heavy metal is enhanced, the recovery and the reaction of the heavy metal are facilitated, no pollutant is generated in the whole process, and the environment-friendly and green effects are achieved;
3. the method has the advantages of simple process, low equipment requirement, strong operability and good social popularization and application.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
the implementation provides a heavy metal recovery method based on waste incineration fly ash, which comprises the following steps:
step one, collecting fly ash and slag generated in the combustion process, mixing the fly ash and the slag by using a stirrer, adding the mixture into a granulator to be processed into granular recycled materials with uniform size, ball-milling the granular recycled materials into granules with the diameter of 250-mesh and 300-mesh by using a ball mill, adding the granular recycled materials into a rotary furnace, and sequentially adding SiO into the rotary furnace2、AL2O3And Ti2O3The mixed powder of (a) and (b),the mixing ratio is 1:1:2, high-temperature sintering is carried out at 1000-1200 ℃, dioxin is decomposed, part of heavy metal in the fly ash is solidified to form oxide, the other part of heavy metal is combined with flying dust and is captured by a bag-type dust collector, and the oxide is filtered and collected;
step two, after fly ash is treated, recovering fly ash collected by a bag-type dust collector, then collecting solid residues collected by a flue gas purification system, stirring and mixing the collected solid residues and the fly ash according to the mixing ratio of 3:1, removing large particles by using a mesh screen with the mesh number of 20-50, and then drying at the temperature of 100-110 ℃ for 20-24 hours to obtain a fly ash mixture with the mesh number of 200;
adding 100ml of NaCl solution with the concentration of 0.2-0.5mol/L into a stirring container, adjusting the pH value of the solution to 2-4, adding a fly ash mixture with the mass ratio of 1:10 to the solution into the solution, then adding iron powder with the Fe content of not less than 98% into the solution, stirring for 2-6 hours at the stirring speed of 100 revolutions per minute and 120 revolutions per minute, standing for 2-4 hours at the temperature of 10-15 ℃ after stirring is finished, and sucking the iron powder out of the solution by using a magnet;
step four, separating iron powder from the magnet, drying, weighing, standing the solution at 5 ℃ for 3 hours, performing centrifugal separation by using a solid-liquid separator to obtain filtrate and solution residues, digesting the solution residues by using microwaves, and mixing the solution residues with the oxide obtained in the step two to obtain a heavy metal recovery mixture;
and step five, measuring the mixture of the filtrate and the heavy metal recovery mixture by using AAS (anaerobic-anoxic-oxic) to obtain the parameters of heavy metal recovery, and finishing the recovery of the heavy metal in the fly ash.
In this embodiment, the dioxin content in the exhaust gas generated by incineration was 0.053%, wherein the recovery rates of heavy metals were respectively: the Zn recovery rate is 90.5 percent, the Cu recovery rate is 83.9 percent, the Cd recovery rate is 80.3 percent, and the Pb recovery rate is 88.7 percent.
Example 2:
the implementation provides a heavy metal recovery method based on waste incineration fly ash, which comprises the following steps:
step oneCollecting fly ash and slag generated in the combustion process, mixing the fly ash and the slag by using a stirrer, adding the mixture into a granulator to be processed into granular recycled materials with uniform size, ball-milling the granular recycled materials into granules with the diameter of 250-300 meshes by using a ball mill, adding the granular recycled materials into a rotary furnace, and sequentially adding SiO into the rotary furnace2、AL2O3And Ti2O3The mixed powder is sintered at the temperature of 1000-1200 ℃ at the mixing ratio of 1:1:2, so that dioxin is decomposed, part of heavy metal in the fly ash is solidified to form oxide, the other part of heavy metal is combined with fly ash and captured by a bag-type dust collector, and the oxide is filtered and collected;
step two, after fly ash is treated, recovering fly ash collected by a bag-type dust collector, then collecting solid residues collected by a flue gas purification system, stirring and mixing the collected solid residues and the fly ash according to the mixing ratio of 3:1, removing large particles by using a mesh screen with the mesh number of 20-50, and then drying at the temperature of 100-;
adding 100ml of NaCl solution with the concentration of 0.2-0.5mol/L into a stirring container, adjusting the pH value of the solution to 2-4, adding a fly ash mixture with the mass ratio of 1:10 to the solution into the solution, then adding iron powder with the Fe content of not less than 98% into the solution, stirring for 2-6 hours at the stirring speed of 100 revolutions per minute and 120 revolutions per minute, standing for 2-4 hours at the temperature of 10-15 ℃ after stirring is finished, and sucking the iron powder out of the solution by using a magnet;
step four, separating iron powder from the magnet, drying, weighing, standing the solution at 5 ℃ for 4 hours, performing centrifugal separation by using a solid-liquid separator to obtain filtrate and solution residues, digesting the solution residues by using microwaves, and mixing the solution residues with the oxide obtained in the step two to obtain a heavy metal recovery mixture;
and step five, measuring the mixture of the filtrate and the heavy metal recovery mixture by using AAS (anaerobic-anoxic-oxic) to obtain the parameters of heavy metal recovery, and finishing the recovery of the heavy metal in the fly ash.
In this embodiment, the dioxin content in the exhaust gas generated by incineration is 0.045%, wherein the recovery rates of the heavy metals are respectively: the Zn recovery rate is 87.2 percent, the Cu recovery rate is 81.4 percent, the Cd recovery rate is 81.2 percent, and the Pb recovery rate is 86.9 percent
Example 3:
the implementation provides a heavy metal recovery method based on waste incineration fly ash, which comprises the following steps:
step one, collecting fly ash and slag generated in the combustion process, mixing the fly ash and the slag by using a stirrer, adding the mixture into a granulator to be processed into granular recycled materials with uniform size, ball-milling the granular recycled materials into granules with the diameter of 250-mesh and 300-mesh by using a ball mill, adding the granular recycled materials into a rotary furnace, and sequentially adding SiO into the rotary furnace2、AL2O3And Ti2O3The mixed powder is sintered at the temperature of 1000-1200 ℃ at the mixing ratio of 1:1:2, so that dioxin is decomposed, part of heavy metal in the fly ash is solidified to form oxide, the other part of heavy metal is combined with fly ash and captured by a bag-type dust collector, and the oxide is filtered and collected;
step two, after fly ash is treated, recovering fly ash collected by a bag-type dust collector, then collecting solid residues collected by a flue gas purification system, stirring and mixing the collected solid residues and the fly ash according to the mixing ratio of 3:1, removing large particles by using a mesh screen with the mesh number of 20-50, and then drying at the temperature of 100-;
adding 100ml of NaCl solution with the concentration of 0.2-0.5mol/L into a stirring container, adjusting the pH value of the solution to 2-4, adding a fly ash mixture with the mass ratio of 1:10 to the solution into the solution, then adding iron powder with the Fe content of not less than 98% into the solution, stirring for 2-6 hours at the stirring speed of 100 revolutions per minute and 120 revolutions per minute, standing for 2-4 hours at the temperature of 10-15 ℃ after stirring is finished, and sucking the iron powder out of the solution by using a magnet;
step four, separating iron powder from the magnet, drying, weighing, standing the solution at 5 ℃ for 5 hours, performing centrifugal separation by using a solid-liquid separator to obtain filtrate and solution residues, digesting the solution residues by using microwaves, and mixing the solution residues with the oxide obtained in the step two to obtain a heavy metal recovery mixture;
and step five, measuring the mixture of the filtrate and the heavy metal recovery mixture by using AAS (anaerobic-anoxic-oxic) to obtain the parameters of heavy metal recovery, and finishing the recovery of the heavy metal in the fly ash.
In this embodiment, the dioxin content in the exhaust gas generated by incineration is 0.062%, wherein the recovery rates of heavy metals are respectively: the Zn recovery rate is 91.5 percent, the Cu recovery rate is 82.3 percent, the Cd recovery rate is 79.7 percent, and the Pb recovery rate is 86.5 percent.
Three heavy metal recovery methods based on waste incineration fly ash can be obtained through the three groups of embodiments, the three heavy metal recovery methods based on waste incineration fly ash are respectively subjected to experimental inspection, heavy metal-containing garbage with the same composition and the same quality is selected, the three groups of embodiments are adopted for carrying out experiments, and heavy metal recovery parameters obtained by the experiments are counted to obtain the following table:
according to the data, the problem of heavy metal recovery can be effectively solved in the process of waste incineration, the fly ash and the slag generated in the combustion process of the heavy metal waste are collected and granulated, and then the granulated recovery object obtained through granulation is sintered at high temperature, so that dioxin can be effectively decomposed, part of heavy metal is solidified in the Si-O grid, and energy is saved;
utilize the sack cleaner to retrieve the mixture of another part heavy metal and flying dust, and collect the solid residue that gas cleaning system collected and mix with it, adopt the iron slurry method to handle, the product after will mixing utilizes NaCl solution stirring and adjusts pH value to acidity, and add high-purity iron powder and mix, under the acidic condition, heavy metal can form various different complexes with NaCl, the dissolution of heavy metal has been strengthened, be favorable to the recovery and the reaction of heavy metal, and can not produce the pollutant among the whole technological process, environmental protection and green.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments or portions thereof without departing from the spirit and scope of the invention.
Claims (8)
1. A heavy metal recovery method based on waste incineration fly ash is characterized by comprising the following steps:
step one, collecting fly ash and slag generated in the combustion process, mixing the fly ash and the slag by using a stirrer, adding the mixture into a granulator to be processed into granular recycled materials with uniform size, ball-milling the granular recycled materials into granules with the diameter of 250-mesh and 300-mesh by using a ball mill, adding the granular recycled materials into a rotary furnace, and sequentially adding SiO into the rotary furnace2、AL2O3And Ti2O3The mixed powder is sintered at the temperature of 1000-1200 ℃ to decompose dioxin, part of heavy metal in the fly ash is solidified to form oxide, the other part of heavy metal is combined with flying dust and is captured by a bag-type dust collector, and the oxide is filtered and collected;
step two, after fly ash is treated, recovering fly ash collected by a bag-type dust collector, then collecting solid residues collected by a flue gas purification system, stirring and mixing the collected solid residues and the fly ash, removing large particles by using a mesh screen, and then drying at the temperature of 100-110 ℃ for 20-24 hours to obtain a fly ash mixture;
adding 100ml of NaCl solution into the stirring container, adjusting the pH value of the solution to 2-4, adding a certain amount of fly ash mixture into the solution, then adding iron powder, stirring for 2-6 hours, standing for 2-4 hours in a normal temperature environment after stirring is finished, and sucking the iron powder out of the solution by using a magnet;
step four, separating iron powder from the magnet, drying and weighing, standing the solution at 5 ℃, performing centrifugal separation by using a solid-liquid separator to obtain filtrate and solution residues, digesting the solution residues by using microwaves, and mixing the solution residues with the oxide obtained in the step two to obtain a heavy metal recovery mixture;
and step five, measuring the mixture of the filtrate and the heavy metal recovery mixture by using AAS (anaerobic-anoxic-oxic) to obtain the parameters of heavy metal recovery, and finishing the recovery of the heavy metal in the fly ash.
2. The method for recovering heavy metal based on fly ash from waste incineration as claimed in claim 1, wherein: and the Fe content in the iron powder added in the fourth step is not lower than 98%.
3. The method for recovering heavy metal based on fly ash from waste incineration as claimed in claim 1, wherein: and the concentration of the NaCl solution added in the fourth step is 0.2-0.5 mol/L.
4. The method for recovering heavy metal based on fly ash from waste incineration as claimed in claim 1, wherein: the SiO2、AL2O3And Ti2O3The mixing ratio in the mixed powder of (1: 1: 2).
5. The method for recovering heavy metal based on fly ash from waste incineration as claimed in claim 1, wherein: the mass ratio of the quantitative fly ash mixture added in the fourth step to the NaCl solution is 1:10, the stirring speed after the iron powder is added is 100-120 r/min, and the normal temperature environment is 10-15 ℃.
6. The method for recovering heavy metal based on fly ash from waste incineration as claimed in claim 1, wherein: the mesh number of the net in the third step is 20-50 meshes, and the mixing ratio of the solid residue to the fly ash is 3: 1.
7. The method for recovering heavy metal based on fly ash from waste incineration as claimed in claim 1, wherein: in the fifth step, the standing time of the solution is 3-5 hours.
8. The method for recovering heavy metal based on fly ash from waste incineration as claimed in claim 1, wherein: the particle mesh number of the fly ash mixture is 200-250 meshes.
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