CN110734082A - Method for recycling waste aluminum - Google Patents

Method for recycling waste aluminum Download PDF

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CN110734082A
CN110734082A CN201911027577.0A CN201911027577A CN110734082A CN 110734082 A CN110734082 A CN 110734082A CN 201911027577 A CN201911027577 A CN 201911027577A CN 110734082 A CN110734082 A CN 110734082A
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aluminum
recycling
reaction
scrap
waste aluminum
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CN201911027577.0A
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CN110734082B (en
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李鹏
杨墨瞳
国宏伟
闫炳基
陈栋
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Suzhou University
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Suzhou University
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    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Geology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (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 recycling method of waste aluminum, which comprises the following steps of 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, introducing inert gas to discharge air in the reaction furnace, heating to a reaction temperature, introducing carbon dioxide to react, collecting tail gas and solid products after the reaction2，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-LiAlO2MaterialThe production cost can be promoted to for application in a large scale, and then carbon dioxide is consumed in the reaction process and is converted into carbon oxide fuel, so that carbon emission reduction and recycling are realized.

Description

Method for recycling waste aluminum
Technical Field
The invention belongs to the technical field of waste aluminum recovery, and relates to a recycling method of 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 order to overcome the defects in the prior art, new methods for recycling the waste aluminum are needed.
The recycling method of kinds of 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 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 propertiesGood thermal stability and resistance to corrosion of molten carbonate, and can be used as 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 to for application in a large scale, and then carbon dioxide is consumed in the reaction process and is converted into carbon oxide fuel, so that carbon emission reduction and recycling 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 reaction temperature is from 800 ℃ to 950 ℃.
Alternatively, the partial pressure of carbon dioxide during the reaction should not be greater than twenty percent.
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
For purposes of making the objects, aspects and advantages of the present invention more apparent, the present invention is described in further detail in conjunction with the following detailed description.
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, the term "and/or" as used herein includes any and all combinations of or more of the associated listed items.
The invention provides a recycling method of waste aluminum, which is described below by taking the waste aluminum as an example of a pop can.
The elemental composition of the can body is shown in table 1 and contains about 97 wt% of metallic aluminum, as well as other alloying elements.
TABLE 1 elemental composition of Pop-top can body
Figure BDA0002247460810000031
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 , the pretreatment comprises the steps of crushing the waste aluminum, and then performing paint removal treatment on the waste aluminum, wherein the paint removal treatment can remove the paint attached to the surface of the waste aluminum such as pop cans and the like, and avoid the influence of the paint on the subsequent reaction.
More specifically, the average size of the scrap after crushing was 2mm × 2mm, which further steps improved 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 of , 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 the case where only the scrap aluminum, i.e., no lithium carbonate molten salt, is present; 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, at high temperature, the carbon dioxide and the waste aluminum undergo an oxidation-reduction reaction to generate an aluminum oxide film and carbon oxide, and once the dense aluminum oxide film is generated, the reaction rate is greatly reduced, while in the presence of lithium carbonate, the liquid lithium carbonate molten salt reacts with the dense aluminum oxide film on the surface of the waste aluminum to generate lithium aluminate, which continuously consumes and destroys the aluminum oxide film, thereby promoting the overall reaction.
After the reaction, the carbon dioxide was converted to carbon oxide, and the lithium carbonate was converted to γ -LiAlO2。
In a preferred embodiment of , the reaction temperature is in the range of 800 ℃ to 950 ℃.
Alternatively, the partial pressure of carbon dioxide during the reaction should not be greater than twenty percent.
In a preferred embodiment of , the reactor is ramped up to 900 deg.C at a ramp rate of 5 deg.C/min and 40ml/min CO is started at 500 deg.C2A 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 the embodiment, the reaction off-gas collected is subjected to soda lime to remove carbon dioxide and silica gel to obtain carbon oxide fuel with high purity.
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 scrap2Secondly, carbon dioxide is consumed in the reaction process and is converted into carbon oxide fuel, so that carbon emission reduction and recycling are realized, and the conversion rate of carbon dioxide to carbon oxide can be greatly improved under the participation of lithium carbonate molten salt, so that the utilization rate of substances and energy of the whole reaction system is maximized.
By adopting the method of the invention, tons of aluminum pop cans can be produced to obtain 2.32 tons of cansPurity lithium aluminate, 1144 cubic meters of CO, while consuming 1.47 tons of greenhouse gas CO2And the aim of carbon emission reduction is effectively fulfilled.
The invention is further illustrated at with reference to specific 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.
The resulting tail gas was subjected to soda lime to remove carbon dioxide and silica gel drying, and then subjected to gas chromatography to record changes in the concentration of carbon oxide.
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 (10)

1, kinds of aluminium scrap recycling method, characterized by, including the following step:
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.
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, wherein the reaction temperature is 800 ℃ to 950 ℃.
7. The method of claim 1, wherein the partial pressure of carbon dioxide is not higher than twenty percent during the reaction.
8. 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.
9. The method of recycling scrap aluminum in accordance with claim 1 wherein the crucible is a platinum crucible.
10. The method of recycling scrap aluminum in accordance with claim 1 wherein said inert gas is argon.
CN201911027577.0A 2019-10-25 2019-10-25 Method for recycling waste aluminum Active CN110734082B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114288837A (en) * 2021-12-13 2022-04-08 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

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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

Patent Citations (4)

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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
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114288837A (en) * 2021-12-13 2022-04-08 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
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

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