CN110734082B - Method for recycling waste aluminum - Google Patents
Method for recycling waste aluminum Download PDFInfo
- Publication number
- CN110734082B CN110734082B CN201911027577.0A CN201911027577A CN110734082B CN 110734082 B CN110734082 B CN 110734082B CN 201911027577 A CN201911027577 A CN 201911027577A CN 110734082 B CN110734082 B CN 110734082B
- Authority
- CN
- China
- Prior art keywords
- aluminum
- reaction
- recycling
- scrap
- waste aluminum
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/04—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom
- C01F7/043—Lithium aluminates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/40—Carbon monoxide
-
- 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
- C22B7/001—Dry processes
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Geology (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a method for recycling waste aluminum, which comprises the following steps: pretreating the waste aluminum; mixing the pretreated waste aluminum with lithium carbonate molten salt, then placing the mixture into a crucible, placing the crucible into a reaction furnace, and introducing inert gas to exhaust air in the reaction furnace; heating to a reaction temperature and introducing carbon dioxide for reaction; collecting the tail gas and the solid products after the reaction. The method for recycling the waste aluminum comprises the steps of firstly, generating a solid product of gamma-LiAlO2，γ‑LiAlO2The material has good thermal stability and molten carbonate corrosion resistance, and can be used as an electrolyte substrate material of MCFC. And gamma-LiAlO prepared by the method for recycling aluminum scrap2The material utilizes waste aluminum to replace original aluminum, and can greatly reduce gamma-LiAlO2The production cost of the material can be promoted and applied in a large scale. And secondly, carbon dioxide is consumed in the reaction process, and the carbon dioxide is converted into carbon monoxide fuel, so that carbon emission reduction and cyclic utilization are realized.
Description
Technical Field
The invention belongs to the technical field of waste aluminum recovery, and relates to a method for recycling waste aluminum.
Background
During the production and processing of metallic aluminum and the distribution and use of related aluminum products, a large amount of scrap aluminum is produced each year. The waste aluminum pop-top can is taken as an example for explanation, and the yield of the waste aluminum pop-top can is about 16-20 ten thousand tons every year in China; although most of the waste aluminum ring-pull cans are recycled, the recovery rate can reach more than 85%, the recycling difficulty of the recycled waste aluminum ring-pull cans is high, most of the waste aluminum ring-pull cans are degraded and used, and the utilization added value of aluminum resources is greatly reduced.
The traditional treatment method of the waste aluminum pop-top can comprises the following steps: through smelting, component regulation, filtering, casting and other steps. The traditional treatment mode not only has complex process, but also can generate a large amount of aluminum slag in the smelting process. The compounds such as aluminum nitride and aluminum carbide contained in the aluminum slag are easy to hydrolyze in a humid environment, and generate a large amount of flammable and harmful gases.
Therefore, the method has important practical significance for exploring a new method for recycling the aluminum scraps, carrying out efficient treatment and improving the added utilization value of the aluminum scraps.
Disclosure of Invention
In view of the deficiencies in the prior art, there is a need for a new method for recycling aluminum scrap.
A method for recycling waste aluminum comprises the following steps:
pretreating the waste aluminum;
mixing the pretreated waste aluminum with lithium carbonate molten salt, then placing the mixture into a crucible, placing the crucible into a reaction furnace, and introducing inert gas to exhaust air in the reaction furnace;
heating to a reaction temperature and introducing carbon dioxide for reaction;
collecting tail gas and solid products after reaction;
the reaction temperature is 800-950 ℃, and the partial pressure of carbon dioxide in the reaction process is not higher than twenty percent.
The method for recycling the waste aluminum comprises the steps of firstly, generating a solid product of gamma-LiAlO2，γ-LiAlO2The material has good thermal stability and molten carbonate corrosion resistance, and can be used as an electrolyte substrate material of MCFC. The method utilizes the waste aluminum to replace the original aluminum, and can greatly reduce the gamma-LiAlO2The production cost of the material can be promoted and applied in a large scale. And secondly, carbon dioxide is consumed in the reaction process, and the carbon dioxide is converted into carbon monoxide fuel, so that carbon emission reduction and cyclic utilization are realized.
Optionally, the aluminum scrap is aluminum cans.
Optionally, the pre-processing comprises the steps of:
crushing the waste aluminum, and then performing paint removal treatment on the waste aluminum.
Optionally, the crushed scrap aluminum has an average size of 2mm x 2 mm.
Optionally, the depainting treatment is to treat the waste aluminum at 500 ℃ for 20min to 30 min.
Optionally, the method further comprises:
the collected reaction tail gas is subjected to carbon dioxide removal through soda lime and is dried through silica gel.
Optionally, the crucible is a platinum crucible.
Optionally, the inert gas is argon.
Drawings
FIG. 1 is a technical flowchart of a method for recycling scrap aluminum according to the present invention.
FIG. 2 shows scrap aluminum and CO2The high temperature reaction behavior is shown in (A) as the CO generation rate curve and (B) as the metallic aluminum conversion curve.
FIG. 3 is a phase diagram of X-ray diffraction analysis of the solid product obtained in example 1.
FIG. 4 is a scanning electron microscopy topography characterization of the solid product from example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to specific embodiments. It should be understood that the detailed description and specific examples, while indicating the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The invention provides a method for recycling waste aluminum. The following description will be made by taking waste aluminum as an example of a can. Of course, it can be understood that the waste aluminum of the present invention is not limited to the pop can, but can be other waste aluminum materials with high aluminum content, and the other waste aluminum materials can be recycled by referring to the recycling method of the pop can.
The elemental composition of the can body is shown in table 1 and contains about 97wt% of metallic aluminum, as well as other alloying elements.
TABLE 1 elemental composition of Pop-top can body
| Composition (I) | Si | Mn | Cu | Fe | Mg | Al |
| wt% | 0.25 | 1.06 | 0.16 | 0.46 | 1.03 | 97.04 |
The method for recycling the waste aluminum provided by the invention, as shown in figure 1, comprises the following steps:
and S1, pretreating the waste aluminum.
In step S1, the purpose of pretreatment is to effectively ensure the proceeding of the subsequent reaction and avoid the influence of other substances in the aluminum scrap on the subsequent reaction.
In a preferred embodiment, the pre-treatment comprises the steps of: crushing the waste aluminum, and then performing paint removal treatment on the waste aluminum. Paint removal treatment can remove paint attached to the surfaces of waste aluminum such as pop cans and the like, and influence of the paint on subsequent reaction is avoided.
More specifically, the average size of the scrap after crushing was 2mm × 2 mm. This may further improve the subsequent reaction.
In a more specific embodiment, the depainting treatment is carried out by treating the aluminum scrap at 500 ℃ for 20min to 30 min. Through high-temperature treatment, the paint attached to the surface of the aluminum scrap is removed, so that the removing effect is good.
Of course, before or after crushing, a cleaning step can be optionally added according to actual conditions to remove dirt on the surface of the waste aluminum.
And S2, mixing the pretreated waste aluminum with lithium carbonate molten salt, then placing the mixture into a crucible, placing the crucible into a reaction furnace, and introducing inert gas to exhaust air in the reaction furnace.
In a preferred embodiment, the crucible is a platinum crucible.
In step S2, the inert gas is introduced to exhaust the air in the reaction furnace, so as to prevent the aluminum scrap from being oxidized by oxygen in the air during the subsequent reaction. The inert gas is preferably argon.
Preferably, high purity argon gas of 200ml/min is continuously introduced for 12 hours before the reaction, thereby blowing off the air remaining in the reaction furnace and the piping.
And S3, heating to the reaction temperature and introducing carbon dioxide for reaction.
Scrap aluminum and CO2The high temperature reaction behavior in the presence of lithium carbonate molten salt is shown in figure 2. In fig. 2, the boxes represent only scrap aluminum, i.e. no lithium carbonateIn the case of molten salts; the circle represents the condition of the waste aluminum under the action of lithium carbonate molten salt; wherein (A) is a CO generation rate curve, and (B) is a metallic aluminum conversion rate curve. The inventor of the invention discovers through research that under the participation of lithium carbonate molten salt, the waste aluminum and CO can be greatly improved within the temperature range of 850-2The reaction rate of the catalyst is improved, and the conversion rate of the waste aluminum is improved to 0.88 from the original 0.03.
In step S3, carbon dioxide and aluminum scrap undergo a redox reaction at high temperature to form an aluminum oxide film and carbon monoxide, and once a dense aluminum oxide film is formed, the reaction rate is greatly reduced. Under the participation of lithium carbonate, liquid lithium carbonate molten salt reacts with the compact alumina film on the surface of the waste aluminum to generate lithium aluminate, and the alumina film is continuously consumed and damaged; thereby promoting the overall reaction. Therefore, the conversion rate of carbon dioxide to carbon monoxide can be greatly improved under the participation of the lithium carbonate molten salt, and the substance and energy utilization rate of the whole reaction system is maximized.
After the reaction, carbon dioxide is converted to carbon monoxide and lithium carbonate is converted to gamma-LiAlO2。
In a preferred embodiment, the reaction temperature is from 800 ℃ to 950 ℃.
Alternatively, the partial pressure of carbon dioxide during the reaction should not be greater than twenty percent.
In a preferred embodiment, the reactor is heated to 900 ℃ at a rate of 5 ℃/min and the introduction of 40ml/min CO is started at 500 ℃2A gas.
And S4, collecting the tail gas and the solid products after the reaction.
In step S4, the solid product is γ -LiAlO2. Specifically, the solid product is cooled to normal temperature under an inert atmosphere and collected.
In one embodiment, the collected reaction off-gas is subjected to soda lime to remove carbon dioxide and silica gel to dry. Thereby obtaining the high-purity carbon monoxide fuel.
The method for recycling the waste aluminum comprises the steps of firstly, generating a solid product of gamma-LiAlO2，γ-LiAlO2The material has good thermal stability and molten carbonate corrosion resistance, and can be used as an electrolyte substrate material of MCFC. And gamma-LiAlO prepared by the method for recycling aluminum scrap2The material is low in cost and can be applied in large scale. And secondly, carbon dioxide is consumed in the reaction process, and the carbon dioxide is converted into carbon monoxide fuel, so that carbon emission reduction and cyclic utilization are realized. And under the participation of lithium carbonate molten salt, the conversion rate of carbon dioxide to carbon monoxide can be greatly improved, and the utilization rate of substances and energy of the whole reaction system is maximized.
By adopting the method, 2.32 tons of high-purity lithium aluminate and 1144 cubic meters of CO can be produced and obtained from one ton of aluminum pop cans, and 1.47 tons of greenhouse gas CO is consumed2And the aim of carbon emission reduction is effectively fulfilled.
The invention is further illustrated by the following examples.
Example 1
The waste aluminum pop can is crushed into aluminum sheets with the size of 2mm multiplied by 2mm, the aluminum sheets are cleaned and dried, and then the aluminum sheets are treated in a high-temperature furnace at 500 ℃ for 30min for depainting treatment.
And uniformly mixing the aluminum sheet and the lithium carbonate molten salt, placing the aluminum sheet and the lithium carbonate molten salt into a reaction furnace, introducing 200ml/min high-purity argon for 12 hours, and blowing away residual air in the reaction furnace and the pipeline. Then the temperature of the reaction furnace is increased to 900 ℃ at the heating rate of 5 ℃/min, and 40ml/min CO is introduced at 500 DEG C2The gas reacts.
And removing carbon dioxide from the generated tail gas through soda lime, drying the tail gas through silica gel, and then entering a gas chromatograph to record the change of the concentration of the carbon monoxide.
The solid product was collected and subjected to phase analysis by X-ray diffraction, the results of which are shown in fig. 3; and observing the morphological characteristics of the solid product by using a scanning electron microscope, and the result is shown in figure 4.
As can be seen from FIGS. 3 and 4, the solid product is highly pure gamma-LiAlO2A material.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (8)
1. A method for recycling waste aluminum is characterized by comprising the following steps:
pretreating the waste aluminum;
mixing the pretreated waste aluminum with lithium carbonate molten salt, then placing the mixture into a crucible, placing the crucible into a reaction furnace, and introducing inert gas to exhaust air in the reaction furnace;
heating to a reaction temperature and introducing carbon dioxide for reaction;
collecting tail gas and solid products after reaction;
the reaction temperature is 800-950 ℃, and the partial pressure of carbon dioxide in the reaction process is not higher than twenty percent.
2. The method for recycling the aluminum scrap according to claim 1, wherein the aluminum scrap is aluminum cans.
3. The method for recycling aluminum scrap according to claim 2, wherein the pretreatment comprises the steps of:
crushing the waste aluminum, and then performing paint removal treatment on the waste aluminum.
4. The method of recycling scrap aluminum in accordance with claim 3, wherein the average size of the scrap aluminum after crushing is 2mm x 2 mm.
5. The method for recycling the aluminum scrap according to claim 3, wherein the depainting treatment is to treat the aluminum scrap at 500 ℃ for 20-30 min.
6. The method for recycling aluminum scrap according to claim 1, further comprising:
the collected reaction tail gas is subjected to carbon dioxide removal through soda lime and is dried through silica gel.
7. The method of recycling scrap aluminum in accordance with claim 1 wherein the crucible is a platinum crucible.
8. The method of recycling scrap aluminum in accordance with claim 1 wherein said inert gas is argon.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911027577.0A CN110734082B (en) | 2019-10-25 | 2019-10-25 | Method for recycling waste aluminum |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911027577.0A CN110734082B (en) | 2019-10-25 | 2019-10-25 | Method for recycling waste aluminum |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110734082A CN110734082A (en) | 2020-01-31 |
| CN110734082B true CN110734082B (en) | 2021-10-22 |
Family
ID=69271639
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911027577.0A Active CN110734082B (en) | 2019-10-25 | 2019-10-25 | Method for recycling waste aluminum |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110734082B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114288837B (en) * | 2021-12-13 | 2022-09-16 | 中国科学院上海应用物理研究所 | Chemical decarburization device and chemical decarburization method for halide molten salt |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1326898A (en) * | 2001-05-24 | 2001-12-19 | 中国科学院上海硅酸盐研究所 | Preparing technology for nanometer lithium meta-aluminate for nuclear wastes recovery |
| CN101177241A (en) * | 2007-11-05 | 2008-05-14 | 昆明理工大学 | Method for preparing synthesis gas by the catforming of methyl hydride and carbonic anhydride in molten salt |
| WO2012018863A2 (en) * | 2010-08-02 | 2012-02-09 | Washington University | Synthesis of submicrometer to micrometer-sized cathode materials |
| CN102895847A (en) * | 2011-07-26 | 2013-01-30 | 武汉大学 | CO2 capturing and resourcing method |
-
2019
- 2019-10-25 CN CN201911027577.0A patent/CN110734082B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1326898A (en) * | 2001-05-24 | 2001-12-19 | 中国科学院上海硅酸盐研究所 | Preparing technology for nanometer lithium meta-aluminate for nuclear wastes recovery |
| CN101177241A (en) * | 2007-11-05 | 2008-05-14 | 昆明理工大学 | Method for preparing synthesis gas by the catforming of methyl hydride and carbonic anhydride in molten salt |
| WO2012018863A2 (en) * | 2010-08-02 | 2012-02-09 | Washington University | Synthesis of submicrometer to micrometer-sized cathode materials |
| CN102895847A (en) * | 2011-07-26 | 2013-01-30 | 武汉大学 | CO2 capturing and resourcing method |
Non-Patent Citations (2)
| Title |
|---|
| "Kinetics of the α→γ phase transformation in LiAlO2 under various atmospheres within the 1073–1173 K temperatures range";V. DANEK et al.;《JOURNAL OF MATERIALS SCIENCE》;20041231;第39卷;第2429-2435页 * |
| "四种偏铝酸锂粉体的合成";王静;《洛阳大学学报》;19991231;第14卷(第4期);第44-47页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110734082A (en) | 2020-01-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107164629A (en) | A kind of aluminium scrap base hydrogenation catalyst processing method based on microwave oxygen-enriched air roasting | |
| CN110734082B (en) | Method for recycling waste aluminum | |
| Zhang et al. | Reduction of low-grade manganese dioxide ore pellets by biomass wheat stalk | |
| CN114335781A (en) | Method for extracting precious metal from waste lithium battery | |
| KR102182845B1 (en) | METHOD OF THE Li2CO3 FROM Li2SO4 | |
| KR20160138923A (en) | Recovery method of cobalt powder from lithium-cobalt oxide | |
| Zhou et al. | Recovery of valuable metals from spent lithium-ion batteries through biomass pyrolysis gas-induced reduction | |
| CN113845286A (en) | Method for co-pyrolysis of oil-containing sludge and aluminum slag | |
| CN114024051A (en) | Method for treating electrolyte of waste lithium battery through pyrolysis | |
| CN112090397A (en) | Method for improving heat value of blast furnace tail gas by using biochar and obtaining carbon with high specific surface area | |
| JPH09227961A (en) | Treatment of zinc oxide-containing waste | |
| CN117160509A (en) | Ruthenium-loaded crystalline carbon nitride/doped nano diamond composite material and preparation method and application thereof | |
| Ma et al. | Analysis of the behavior of NaF in the vacuum carbothermal reduction of magnesium oxide | |
| CN112768798B (en) | Method for preventing impurity metal from being separated out in process of recycling waste lithium battery cathode | |
| JP2023551596A (en) | Catalytic material for pyrolysis of methane and production of hydrogen and solid carbon with virtually zero carbon emissions into the atmosphere | |
| CN106430196B (en) | A kind of method that Mn oxide gas-based reduction prepares manganess carbide | |
| CN111943151B (en) | Method for improving titanium-containing blast furnace slag carbonitride efficiency and preparing titanium carbonitride | |
| US20230307736A1 (en) | Method for Direct Recycling of Cathode Active Material in Cathode Electrode Foil Scrap in Li-Ion Battery Manufacturing | |
| CN112410821B (en) | Method for preparing high-activity ternary metal nitride hydrogen evolution catalyst by using waste aluminum foil | |
| CN113800514B (en) | Method for preparing activated carbon by using solid waste | |
| CN115974058B (en) | Preparation method and system of graphene | |
| Zhang et al. | Self-reduction of manganese-rich slag briquette containing carbon | |
| CN114335782B (en) | Method for stripping waste lithium battery anode material from aluminum foil | |
| CN107326397A (en) | CO in aluminium electrolytic flue2Resource comprehensive utilization Application way | |
| CN116242125A (en) | Ultrahigh-temperature reducing atmosphere intermediate-frequency roasting furnace, graphite material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |