CN115433825A - Comprehensive recovery method of iron and sulfur in waste lithium battery - Google Patents
Comprehensive recovery method of iron and sulfur in waste lithium battery Download PDFInfo
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- CN115433825A CN115433825A CN202210978854.1A CN202210978854A CN115433825A CN 115433825 A CN115433825 A CN 115433825A CN 202210978854 A CN202210978854 A CN 202210978854A CN 115433825 A CN115433825 A CN 115433825A
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- iron
- sulfur
- waste lithium
- lithium batteries
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 152
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 82
- 239000011593 sulfur Substances 0.000 title claims abstract description 78
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 title claims abstract description 45
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 32
- 238000011084 recovery Methods 0.000 title claims abstract description 28
- 239000002699 waste material Substances 0.000 title claims abstract description 26
- 239000002893 slag Substances 0.000 claims abstract description 39
- KCZFLPPCFOHPNI-UHFFFAOYSA-N alumane;iron Chemical compound [AlH3].[Fe] KCZFLPPCFOHPNI-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 238000004064 recycling Methods 0.000 claims abstract description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 31
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- 238000007885 magnetic separation Methods 0.000 claims description 9
- 239000005864 Sulphur Substances 0.000 claims description 5
- 239000004411 aluminium Substances 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 2
- 235000014413 iron hydroxide Nutrition 0.000 claims description 2
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims description 2
- 239000000463 material Substances 0.000 description 36
- 239000002253 acid Substances 0.000 description 19
- 238000002386 leaching Methods 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- 239000007789 gas Substances 0.000 description 11
- 230000008901 benefit Effects 0.000 description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000001354 calcination Methods 0.000 description 7
- 239000004568 cement Substances 0.000 description 7
- 239000010881 fly ash Substances 0.000 description 6
- 239000004088 foaming agent Substances 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 5
- 238000004806 packaging method and process Methods 0.000 description 5
- 239000002440 industrial waste Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 239000010926 waste battery Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000003900 soil pollution Methods 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
Images
Classifications
-
- 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
- C22B1/02—Roasting processes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/74—Preparation
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/20—Mortars, concrete or artificial stone characterised by specific physical values for the density
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
Abstract
The invention discloses a comprehensive recovery method of iron and sulfur in waste lithium batteries, and relates to the technical field of waste lithium battery recovery. A method for recovering iron and sulfur in waste lithium batteries comprises the following steps: uniformly mixing iron-aluminum slag generated by recycling waste lithium batteries with sulfur, and roasting at 1000-1350 ℃ to obtain an iron-rich component and sulfur-containing tail gas. The method can simultaneously recover iron and sulfur in the waste lithium batteries without generating new pollution.
Description
Technical Field
The invention relates to the technical field of waste lithium battery recovery, in particular to a comprehensive recovery method of iron and sulfur in waste lithium batteries.
Background
Since the commercialization of lithium ion batteries, lithium ion batteries have been widely used due to their unique advantages such as high specific energy, small size, light weight, wide application temperature range, etc., for example, they are used in mobile phones, notebook computers, and portable devices. However, the wide use of lithium ion batteries inevitably brings a large amount of waste batteries, and if the waste batteries are discarded at will, the environment is seriously polluted, and resources are wasted.
In the related technology, valuable metals are recycled and then prepared into battery materials by wet smelting, wherein various industrial waste residues are generated indispensably, and the large amount of industrial waste residues are piled up to occupy land resources and cause serious air pollution, soil pollution and water resource pollution, while the traditional industrial waste residue treatment method (such as landfill, incineration, pyrolysis, microbial decomposition and the like) has the problems of long treatment period, secondary pollution to land and the like. The iron-aluminum slag is used as a large amount of solid waste in solid waste generated in the lithium battery recovery process, and has the characteristics of high iron content, high sulfur content and mixed components, and the existing iron-aluminum slag treatment method cannot effectively and fully recycle the sulfur component in the iron-aluminum slag, so that the economic benefit is poor, and the treatment cost is high. Therefore, a new way for recycling and comprehensive utilization of industrial waste residues is urgently needed.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides a method for recovering iron and sulfur in waste lithium batteries, which can recover iron and sulfur in iron-aluminum slag to realize iron resource utilization, the sulfur is recovered into sulfuric acid, and other impurities can be used for preparing autoclaved aerated blocks, so that the method has no secondary pollution and has good social benefit, environmental benefit and economic benefit.
The invention also provides application of the recovery method.
According to the first aspect of the invention, the method for recovering iron and sulfur in waste lithium batteries comprises the following steps:
uniformly mixing iron-aluminum slag generated by recycling waste lithium batteries with sulfur, and roasting at 1000-1350 ℃ to obtain an iron-rich component and sulfur-containing tail gas.
The recycling method provided by the embodiment of the invention has at least the following beneficial effects:
according to the recovery method, sulfur is added, so that the yield of reduced iron is increased, the sulfur content in tail gas is increased, and the cost of preparing sulfuric acid from flue gas is reduced. The prepared sulfuric acid is returned to the acid leaching treatment process, so that partial sulfur circulation can be realized, and the pressure of high-sulfur tail gas treatment and the raw material cost of the acid leaching treatment process are reduced. The iron component obtained by the method has high iron content and low sulfur content, and meets the requirements of iron smelting and iron powder plants.
The recycling method of the embodiment can fully utilize 100% of iron-aluminum slag of the waste lithium battery, realizes iron recycling, and does not generate new pollution. The tailings obtained after the iron component is enriched can be used for preparing autoclaved aerated blocks, so that value-added utilization is realized, secondary pollution is avoided in the whole process, and good social benefit, environmental benefit and economic benefit are achieved.
According to some embodiments of the invention, the process for recycling spent lithium batteries comprises: and performing acid leaching on the lithium battery powder, and removing iron and aluminum from the obtained leachate to obtain the iron and aluminum slag.
According to some embodiments of the invention, the lithium battery powder is obtained by crushing and screening waste lithium batteries.
According to some embodiments of the invention, the acid used for the acid leaching comprises at least one of sulfuric acid, hydrochloric acid.
According to some embodiments of the invention, the ferro-aluminium slag comprises at least one of astrakanite, aluminium hydroxide, iron hydroxide. Further, when sulfuric acid is used for acid leaching, sodium sulfate may be contained in the iron-aluminum slag.
According to some embodiments of the invention, the iron content in the iron-aluminium slag dry basis is between 14% and 35%.
According to some embodiments of the invention, the iron content in the iron-aluminium slag dry basis is between 21% and 28%.
According to some embodiments of the invention, the sulfur content in the iron-aluminum slag dry basis is 4% to 7.5%.
According to some embodiments of the invention, the sodium content in the iron-aluminium slag dry basis is between 3.54% and 4.72%.
According to some embodiments of the invention, the water content of the ferroaluminum slag is 35 to 55%.
According to some embodiments of the invention, the particle size of the ferroaluminum slag is less than or equal to 2cm. Therefore, the mixing uniformity of the iron-aluminum slag and the sulfur can be increased, the high-temperature reaction is more complete, and the reaction efficiency is improved.
According to some embodiments of the invention, the sulfur is 5-45% by mass based on the total mass of the iron-aluminum slag and the sulfur.
According to some embodiments of the invention, the percentage by mass of the sulphur is 8% to 42% based on the total mass of the ferroaluminium slag and the sulphur.
According to some embodiments of the invention, the mass percentage of the sulfur is 35% to 42% based on the total mass of the iron-aluminum slag and the sulfur.
According to some embodiments of the invention, the percentage by mass of the sulphur is between 40% and 42% based on the total mass of the ferroaluminium slag and the sulphur.
According to some embodiments of the invention, the firing temperature is 1100 ℃ to 1200 ℃.
According to some embodiments of the invention, the calcination time is between 5min and 70min.
According to some embodiments of the invention, the calcination time is between 10min and 60min.
According to some embodiments of the invention, the method further comprises magnetically separating the iron-rich component to obtain an iron component. Thereby, the iron component and the aluminum component can be separated.
According to some embodiments of the invention, the iron content of the iron component is higher than 65%.
According to some embodiments of the invention, the iron content of the iron component is between 65% and 90%.
According to some embodiments of the invention, the iron content of the iron component is between 70% and 85%.
According to some embodiments of the invention, the sulfur content of the iron component is 0.5% or less.
According to some embodiments of the invention, the sulfur content of the iron component is 0.3% or less.
According to some embodiments of the invention, the magnetic separation comprises a fine break. The grain diameter of the finely-broken roasted material is less than or equal to 5mm. Therefore, the magnetic separation efficiency can be improved, and the impurity content in the iron-rich component can be reduced.
According to some embodiments of the invention, the composition of the sulfur-containing tail gas comprises SO 2 、O 2 And N 2 。
According to some embodiments of the invention, the sulfur-containing tail gas comprises SO 2 The concentration is 30000mg/Nm 3 ～140000mg/Nm 3 。
According to some embodiments of the invention, the sour tail gas is used to produce sulphuric acid.
According to some embodiments of the invention, the residual tailings after the magnetic separation can be used for preparing autoclaved aerated blocks.
According to some embodiments of the invention, the method for preparing the autoclaved aerated block comprises the following steps: mixing 5-30 wt% of tailings, 25-35 wt% of cement, 15-35 wt% of fly ash and 10-15 wt% of light ceramsite to obtain a mixture; and adding 20-35 wt% of water and 0.05-0.5 wt% of foaming agent by mass of the mixture, uniformly mixing, and then sequentially pouring, molding, demolding and maintaining to obtain the autoclaved aerated block.
According to some embodiments of the invention, the curing temperature is 180 ℃ to 210 ℃.
According to some embodiments of the invention, the curing temperature is 190 ℃ to 200 ℃.
According to some embodiments of the invention, the temperature of the curing is 195 ℃.
According to some embodiments of the invention, the curing time is 7 to 9 hours.
According to some embodiments of the invention, the curing time is 8h.
According to the application of the embodiment of the second aspect of the present invention, in particular, the application of the recycling method described in the embodiment of the first aspect in recycling the waste lithium batteries is provided.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
fig. 1 is a flow chart of a method for recovering iron and sulfur from waste lithium batteries according to an embodiment of the present invention.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
The examples, in which specific conditions are not specified, were carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The sulfur used in the following examples was in the form of powder with a sulfur content of 96% or more.
The embodiment provides a method for recovering iron and sulfur in waste lithium batteries, and the specific flow is shown in figure 1.
The preparation method of the iron-aluminum slag in the following embodiment comprises the following steps: crushing and screening waste lithium batteries, separating metal iron, copper and aluminum for sale, performing acid leaching on the residual battery powder to obtain a leaching solution, adjusting the pH of the leaching solution to 3.6-4.1 by using a sodium carbonate solution, and settling iron and aluminum to obtain primary iron and aluminum slag; continuously adjusting the pH value to 4.5-5.0 to obtain secondary iron-aluminum slag.
In the following examples, the water content of the used iron-aluminum slag was 50%; based on the mass of the iron-aluminum slag dry basis, the iron content is 24.5%, the sodium content is 4.72%, the sulfur content is 6%, the aluminum content is 5.82%, and the manganese content is 5.69%.
Example 1
The embodiment provides a method for recovering iron and sulfur in waste lithium batteries, which comprises the following specific steps:
(1) Crushing the iron-aluminum slag until the diameter is less than or equal to 2cm, and uniformly stirring 2 tons of iron-aluminum slag and 538kg of sulfur to obtain a mixed material.
(2) Feeding the mixed material into a rotary kiln, and roasting at 1100 deg.C for 10min to obtain a roasted material; and finely crushing the roasted material until the particle size is less than or equal to 5mm, and then carrying out magnetic separation to obtain 287kg of magnetic high-iron material and 380kg of tailings.
The iron recovery rate reaches 92.54 percent, and the sulfur recovery rate reaches 98.40 percent. Wherein the magnetic high-iron material contains 79wt% of iron and 0.26wt% of sulfur and can be sold for sale; the sulfur content in the tailings was 0.31wt%; high sulfur tail gas (SO) generated during calcination 2 The content is 58800mg/Nm 3 ) The sulfuric acid is discharged after reaching the standard after being dedusted by an environmental protection system and oxidized to prepare acid, and the sulfuric acid with the mass fraction of 98 percent can be prepared for the acid leaching process.
(3) Mixing 20wt% of the tailings obtained in the step (2), 35wt% of cement, 34wt% of fly ash and 11wt% of light ceramsite to obtain a mixture; adding 25wt% of water and 0.08wt% of foaming agent by mass of the mixture, mixing, pouring, pre-curing, demolding, cutting and molding, feeding into an autoclave, performing autoclaved curing at 195 ℃ for 8 hours, stacking and packaging to obtain the 700-grade autoclaved aerated block building block, wherein the volume density of the autoclaved aerated block is 710kg/m 3 And the compressive strength is 3.8MPa.
Example 2
The embodiment provides a method for recovering iron and sulfur in waste lithium batteries, which comprises the following specific steps:
(1) After the iron and aluminum slag is crushed to the diameter of less than or equal to 2cm, 2 tons of iron and aluminum slag and 724kg of sulfur are evenly stirred to obtain a mixed material.
(2) Feeding the mixed material into a rotary kiln, and roasting at 1150 ℃ for 10min to obtain a roasted material; and finely crushing the roasted material until the particle size is less than or equal to 5mm, and then carrying out magnetic separation to obtain 281kg of magnetic high-iron material and 388kg of tailings.
The iron recovery rate reaches 95.20 percent, and the sulfur recovery rate reaches 98.68 percent. Wherein, the iron content of the magnetic high-iron material is 83 weight percent, and the sulfur content is 0.22 weight percent, and the magnetic high-iron material can be used for sale; the sulfur content in the tailings was 0.25wt%; high sulfur tail gas (SO) generated during calcination 2 The content is 79400mg/Nm 3 ) The sulfuric acid is discharged after reaching the standard after being dedusted by an environment-friendly system and oxidized to prepare acid, and the sulfuric acid with the mass fraction of 98 percent can be prepared for the acid leaching process.
(3) Mixing 15wt% of the tailings obtained in the step (2) with 35wt% of cement, 39wt% of fly ash and 11wt% of light ceramsite to obtain a mixture; adding 25wt% of water and 0.10wt% of foaming agent by mass of the mixture, mixing, pouring, pre-curing, demolding, cutting and molding, feeding into an autoclave, performing autoclaved curing at 195 ℃ for 8 hours, stacking and packaging to obtain the 700-grade autoclaved aerated block building block, wherein the volume density of the autoclaved aerated block is 697kg/m 3 And the compressive strength is 3.91MPa.
Example 3
The embodiment provides a method for recovering iron and sulfur in waste lithium batteries, which comprises the following specific steps:
(1) Crushing the iron-aluminum slag until the diameter is less than or equal to 2cm, and uniformly stirring 2 tons of iron-aluminum slag and 87kg of sulfur to obtain a mixed material.
(2) Feeding the mixed material into a rotary kiln, and roasting at 1150 ℃ for 60min to obtain a roasted material; and finely crushing the roasted material until the particle size is less than or equal to 5mm, and then carrying out magnetic separation to obtain 304kg of magnetic high-iron material and 365kg of tailings.
The iron recovery rate reaches 89.30 percent, and the sulfur recovery rate reaches 99.43 percent. Wherein the magnetic high-iron material contains 72wt% of iron and 0.07wt% of sulfur and can be sold for sale; the sulfur content in the tailings was 0.13wt%; high sulfur tail gas (SO) generated during calcination 2 The content is 13000mg/Nm 3 ) The acid is discharged after reaching the standard after being dedusted by an environment-friendly system and oxidized to prepare acid, and the mass fraction of the acid can be prepared to be98% sulfuric acid, used in the acid leaching process.
(3) Mixing 5wt% of the tailings obtained in the step (2), 35wt% of cement, 45wt% of fly ash and 15wt% of light ceramsite to obtain a mixture; adding 25wt% of water and 0.20wt% of foaming agent by mass of the mixture, mixing, pouring, pre-curing, demolding, cutting and molding, feeding into an autoclave, performing autoclaved curing at 195 ℃ for 8 hours, stacking and packaging to obtain the 700-grade autoclaved aerated block, wherein the volume density of the autoclaved aerated block is 688kg/m 3 And the compressive strength is 3.56MPa.
Example 4
The embodiment provides a method for recovering iron and sulfur in waste lithium batteries, which comprises the following specific steps:
(1) Crushing the iron-aluminum slag until the diameter is less than or equal to 2cm, and uniformly stirring 2 tons of iron-aluminum slag and 250kg of sulfur to obtain a mixed material.
(2) Feeding the mixed material into a rotary kiln, and roasting at 1200 ℃ for 30min to obtain a roasted material; and finely crushing the roasted material until the particle size is less than or equal to 5mm, and then carrying out magnetic separation to obtain 291kg of magnetic high-iron material and 377kg of tailings.
The iron recovery rate reaches 91.46 percent, and the sulfur recovery rate reaches 99.15 percent. Wherein the magnetic high-iron material has an iron content of 77wt% and a sulfur content of 0.13wt% and can be sold for sale; the sulfur content in the tailings was 0.17wt%; high sulfur tail gas (SO) generated during calcination 2 The content is 30500mg/Nm 3 ) The sulfuric acid is discharged after reaching the standard after being dedusted by an environmental protection system and oxidized to prepare acid, and the sulfuric acid with the mass fraction of 98 percent can be prepared for the acid leaching process.
(3) Mixing 15wt% of the tailings obtained in the step (2) with 35wt% of cement, 35wt% of fly ash and 15wt% of light ceramsite to obtain a mixture; adding 25wt% of water and 0.10wt% of foaming agent according to the mass of the mixture, mixing, pouring, pre-curing, demolding, cutting and molding, feeding into an autoclave, performing autoclave curing for 8 hours at 195 ℃, stacking and packaging to obtain the 700-grade autoclaved aerated block building block, wherein the volume density of the autoclaved aerated block is 703kg/m 3 And the compressive strength is 3.66MPa.
Example 5
The embodiment provides a method for recovering iron and sulfur in waste lithium batteries, which comprises the following specific steps:
(1) Crushing the iron-aluminum slag until the diameter is less than or equal to 2cm, and uniformly stirring 2 tons of iron-aluminum slag and 666.7kg of sulfur to obtain a mixed material.
(2) Feeding the mixed material into a rotary kiln, and roasting at 1200 ℃ for 30min to obtain a roasted material; and finely crushing the roasted material until the particle size is less than or equal to 5mm, and then carrying out magnetic separation to obtain 276kg of magnetic high-iron material and 392kg of tailings.
The iron recovery rate reaches 95.76 percent, and the sulfur recovery rate reaches 99.67 percent. Wherein, the iron content of the magnetic high-iron material is 85wt%, and the sulfur content is 0.03wt%, and the magnetic high-iron material can be sold for external use; the sulfur content in the tailings was 0.08wt%; high sulfur tail gas (SO) generated during calcination 2 The content is 72000mg/Nm 3 ) The sulfuric acid is discharged after reaching the standard after being dedusted by an environmental protection system and oxidized to prepare acid, and the sulfuric acid with the mass fraction of 98 percent can be prepared for the acid leaching process.
(3) Mixing 20wt% of the tailings obtained in the step (2), 35wt% of cement, 30wt% of fly ash and 15wt% of light ceramsite to obtain a mixture; adding 25wt% of water and 0.20wt% of foaming agent according to the mass of the mixture, mixing, pouring, pre-curing, demolding, cutting and molding, feeding into an autoclave, performing autoclave curing for 8 hours at 195 ℃, stacking and packaging to obtain the 700-grade autoclaved aerated block building block, wherein the volume density of the autoclaved aerated block is 691kg/m 3 And the compressive strength is 4.07MPa.
Comparative example 1
The comparative example provides a method for recovering iron and sulfur in waste lithium batteries, and compared with example 4, the method only comprises the following steps: replacing the roasting temperature of 1200 ℃ in the step (2) with 860 ℃.
273kg of magnetic high-iron material and 396kg of tailings are prepared in the comparative example 1, the iron content of the magnetic high-iron material is 68wt%, the sulfur content is 1.21wt%, and the iron recovery rate is 75.77%; the sulfur content in the tailings is 3.53wt%, the sulfur recovery rate is 85.60%, and when the tailings are used for preparing the autoclaved aerated block, the appearance of the autoclaved aerated block is influenced, so that the autoclaved aerated block is reddish in color, the hardening strength of cement is influenced, and the compressive strength of the autoclaved aerated block is reduced by over 25%.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the embodiments, and various changes can be made without departing from the gist of the present invention within the knowledge of those skilled in the art.
Claims (10)
1. A method for recovering iron and sulfur in waste lithium batteries is characterized by comprising the following steps:
uniformly mixing iron-aluminum slag generated by recycling waste lithium batteries with sulfur, and roasting at 1000-1350 ℃ to obtain an iron-rich component and sulfur-containing tail gas.
2. The recovery method according to claim 1, wherein the mass percentage of the sulfur is 5 to 45% based on the total mass of the iron-aluminum slag and the sulfur.
3. The recovery process of claim 1, wherein the sulfur-containing tail gas comprises SO 2 、O 2 And N 2 。
4. A recycling method according to claim 1, characterized in that the roasting temperature is 1100-1200 ℃.
5. The recovery method according to claim 1, wherein the roasting time is 5 to 70min.
6. A recycling method according to claim 5, characterized in that the roasting time is 10-60 min.
7. The recovery process of claim 1, wherein the sulfur-containing tail gas is used to produce sulfuric acid.
8. A recycling method according to claim 1, characterized in that said ferro-aluminium slag comprises at least one of astrakanite, aluminium hydroxide, iron hydroxide.
9. The recovery method according to claim 1, further comprising subjecting the iron-rich component to magnetic separation to obtain an iron component; further, the iron content in the iron component is 65-90%; preferably, the sulfur content in the iron component is less than or equal to 0.5 percent.
10. The use of a method according to any one of claims 1 to 9 for the recovery of iron and sulphur from spent lithium batteries in the recovery of spent lithium batteries.
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