Adsorbent / catalyst based on waste lithium battery recovery and preparation method and application thereof

Abstract

The invention discloses an adsorbent / catalyst based on waste lithium battery recovery and a preparation method and application thereof, and the preparation method comprises the following steps: discharging and disassembling a waste lithium battery, mixing and ball-milling the obtained positive electrode material, metal scrap, PVC and negative electrode graphite material, adding water in the ball-milling process, and carrying out mechanochemical reaction; and after the ball milling is finished, carrying out water leaching treatment on a ball milling product, drying filter residues after the water leaching treatment, and calcining in an inert atmosphere at the calcining temperature of 350-900 DEG C for 0.5-4 hours to obtain the pollutant removal adsorbent / catalyst. The process flow is completed at normal temperature and normal pressure by adopting a mechanochemical method, high-temperature operation is not needed, and the problem of high energy consumption of pyrometallurgy is avoided. Meanwhile, strong acid or strong alkali is not used, no waste liquid or toxic gas is discharged, and compared with a traditional wet metallurgy / wet modified adsorbent / catalyst process, a resource recovery and material preparation technology which is more environmentally friendly and conforms to the green and low-carbon concept is achieved.

Description

Technical Field

[0001] The present invention belongs to the technical field of flue gas purification and solid waste resource recycling and utilization, and specifically relates to an adsorbent / catalyst based on the recycling of waste lithium batteries and a preparation method and application thereof. Background Art

[0002] The statements herein merely provide background information related to the present invention and do not necessarily constitute prior art.

[0003] Industrial waste gas contains a variety of harmful pollutants, including mercury (Hg), volatile organic compounds (VOCs) and nitrogen oxides (NO x ) and other pollutants, which not only cause serious damage to the environment, but also endanger human health. Mercury is highly volatile and bioaccumulative, and can easily be transported over long distances through the atmosphere and enter the food chain; VOCs emissions can lead to photochemical smog and ozone generation, which are also toxic and irritating; NO x It is one of the main causes of acid rain and air pollution, and it can also form secondary organic aerosol (SOA) in synergy with VOCs. Faced with increasingly stringent emission standards and environmental protection requirements, how to remove these pollutants efficiently, economically and environmentally friendly has become a technical problem that needs to be solved urgently.

[0004] At present, the treatment of pollutants in industrial waste gas mainly relies on adsorbents / catalysts, but there are still many shortcomings in practical applications: (1) Carbon-based materials are good adsorbent / catalyst carriers, and are usually modified by adding transition metal oxides (such as Cu, Mn, Fe, Ce, etc.) to improve their pollutant removal performance. However, traditional modification methods (such as impregnation, chemical coprecipitation, sol-gel method) are cumbersome and time-consuming, and require additional chemical reagents, which increases production costs. At the same time, these modification methods are prone to blockage of the adsorbent / catalyst pore structure, reducing its specific surface area and removal performance. (2) Traditional modification techniques (such as impregnation, chemical coprecipitation, sol-gel method) will produce wastewater or other secondary pollutants, reducing the environmental friendliness of the process. (3) The bonding strength between carbon-based materials and transition metal oxides is not high, and active components will fall off under high temperature conditions, further affecting the sustainability of their practical applications. (4) The flue gas contains a high concentration of SO 2 and H 2 O (such as flue gas from metal smelting, oxygen-enriched combustion, etc.), and the existing adsorbents / catalysts are easily deactivated in high-sulfur and high-water environments, and their anti-sulfur and anti-water performance needs to be improved urgently.

[0005] In view of the above problems, the present invention proposes an adsorbent / catalyst of graphene-loaded nano-metal oxides prepared by recycling waste lithium batteries. This method can not only realize the efficient recovery of valuable metal lithium in waste lithium batteries, but also obtain an economical and efficient adsorbent / catalyst material suitable for removing different pollutants. The entire process is green, environmentally friendly, low-carbon and efficient, and provides a new technology with practical application prospects for the resource utilization of waste lithium batteries and environmental pollution control. Summary of the invention

[0006] In view of the deficiencies in the prior art, the purpose of the present invention is to provide an adsorbent / catalyst based on the recovery of waste lithium batteries and a preparation method and application thereof.

[0007] In order to achieve the above object, the present invention is implemented through the following technical solutions:

[0008] In a first aspect, the present invention provides a method for preparing an adsorbent / catalyst based on the recovery of waste lithium batteries, comprising the following steps:

[0009] Discharge and disassemble the waste lithium batteries, crush the obtained metal waste, mix it with positive electrode materials, PVC and negative electrode graphite materials, and ball mill them. Water is added during the ball milling process to carry out a mechanochemical reaction;

[0010] After the ball milling is completed, the ball milling product is subjected to water immersion treatment, and the filter residue after the water immersion treatment is dried and calcined in an inert atmosphere at a calcination temperature of 350-900° C. and a calcination time of 0.5-4 h to obtain an adsorbent / catalyst.

[0011] In some embodiments, the metal waste is one or a combination of copper foil, aluminum foil or stainless steel casing.

[0012] Preferably, the metal waste is a mixture of copper foil and aluminum foil, and the mass ratio of copper foil to aluminum foil is 1-2.5:1-2.5.

[0013] Preferably, the metal waste is a mixture of copper foil and stainless steel, and the mass ratio of the copper foil to the stainless steel is 1-2.5:1-2.5.

[0014] Preferably, the metal waste is a mixture of aluminum foil and stainless steel, and the mass ratio of the aluminum foil to the stainless steel is 1-2.5:1-2.5.

[0015] The experiments showed that when the metal waste is a mixture of copper foil and aluminum foil, copper foil and stainless steel, or aluminum foil and stainless steel, the lithium recovery rate is higher, and the prepared adsorbent / catalyst has a better removal effect on various pollutants such as mercury.

[0016] In some embodiments, the mass ratio of the positive electrode material, metal waste, PVC and negative electrode graphite material is 0.8-1.2:0.4-0.6:0.4-0.6:0.5-1:6:7-9:5-7 (based on the mass of the positive electrode material).

[0017] In some embodiments, the positive electrode material is lithium manganese oxide (LiMn 2 O 4 ), ternary lithium (LiNi x Co y Mn 1-x-y O 2 ), lithium iron phosphate (LiFePO 4 ) and lithium cobalt oxide (LiCoO 2 ) or a combination thereof.

[0018] In some embodiments, the PVC is waste PVC plastic.

[0019] Preferably, the waste PVC plastic comes from pipes, wires and cables or door and window profiles.

[0020] In some embodiments, during ball milling, 0.5-15 ml of water is added to each gram of the mixed material for wet milling.

[0021] Preferably, during ball milling, the ball-to-material ratio is 5-100:1, the ball milling speed is 100-900 rpm, and the ball milling time is 0.3-36 h.

[0022] In some embodiments, during the water immersion treatment, the liquid-to-solid ratio is 10-200:1; the water immersion temperature is 20-80°C, and the leaching time is 5min-4h.

[0023] In some embodiments, after the water leaching treatment, the solid and liquid are separated to obtain a lithium-rich water leaching solution, and saturated Na 2 CO 3 The solution was heated and stirred to obtain Li 2 CO 3 White precipitate. Used for lithium recovery.

[0024] In a second aspect, the present invention provides an adsorbent / catalyst based on the recovery of waste lithium batteries, which is prepared by the preparation method.

[0025] In a third aspect, the present invention provides the use of the adsorbent / catalyst based on the recovery of waste lithium batteries in the removal of flue gas pollutants.

[0026] In some embodiments, the flue gas pollutants include but are not limited to Hg 0 , NO, toluene, VOCs and SO 2 .

[0027] The beneficial effects achieved by one or more embodiments of the present invention are as follows:

[0028] (1) The present invention uses waste PVC plastic as a chlorine donor and efficiently leaches lithium in the form of LiCl through mechanochemical action. Waste PVC is widely available and inexpensive. Compared with the traditional recycling process that requires the use of expensive reagents, the lithium recovery cost is greatly reduced, and the resource utilization problem of waste PVC is effectively solved.

[0029] (2) The present invention uses the stainless steel casing of waste lithium batteries (rich in metals such as Fe, Ni, Cr, etc.), positive electrode aluminum foil (containing Al) and / or negative electrode copper foil (containing Cu) as reducing agents to promote the release of chlorine in PVC by providing free electrons, thereby reducing the need for additional additives, further reducing costs, and improving the resource utilization efficiency of solid waste.

[0030] (3) The present invention adopts wet ball milling, which effectively alleviates the problem of material sticking to the wall by adding water, ensuring more uniform ball milling, thereby improving mass transfer conditions and promoting the occurrence of lithium release reaction. At the same time, the wet operation can absorb the HCl released during the degradation of PVC that is not fully involved in the reaction, reducing the release of acidic gas.

[0031] (4) Water leaching can selectively recover lithium, while the remaining valuable metals are concentrated in the filter residue. This separation step is simple and efficient, effectively reducing the loss of valuable metals. After calcination of the filter residue, graphene-loaded metal oxide environmental functional materials were successfully prepared, further enhancing the economic value of resource utilization of waste lithium batteries.

[0032] (5) Graphite has excellent conductivity, which promotes electron transfer and is beneficial to the release of Li in the positive electrode material. In addition, the graphite surface has a certain adsorption capacity, which can capture the HCl produced by PVC to generate C-Cl functional groups. C-Cl is beneficial to the release of pollutants Hg 0 of removal.

[0033] (6) Graphene can be prepared from the negative electrode graphite powder of waste lithium batteries through ball milling and exfoliation technology. This method has the advantages of simple process and low raw material cost. The prepared graphene has a high specific surface area, which provides abundant active sites for the dispersed loading of metal oxides. It should be pointed out that nano-metal oxide particles tend to agglomerate when ball milled alone, but loading on graphene can effectively inhibit the agglomeration phenomenon and fully expose the active sites, thereby improving the performance of the adsorbent / catalyst. The flexibility of graphene can also buffer the volume change of metal oxides during use, significantly enhancing the reaction activity of the adsorbent / catalyst.

[0034] (7) When graphite is ball-milled alone, due to the strong impact and friction on graphite, although it can be exfoliated to form graphene, the strong van der Waals force will cause it to re-aggregate, especially under the condition of local temperature increase caused by ball milling. However, the nano-metal oxide particles generated by the positive electrode material and metal waste during the ball milling process can be loaded on the graphene surface, effectively hindering the re-aggregation of graphene.

[0035] (8) Ball milling and extrusion make the dispersion of nano transition metal oxides more uniform, reduce the particle size of transition metal oxides, enhance the bonding strength between transition metal oxides and carbon-based materials, avoid the shedding of transition metal oxides, and increase the service life of graphene-loaded nano metal oxides.

[0036] (9) The various metals (such as Mn, Co, Fe, Ni, Cr, Cu, Al, etc.) in graphene-loaded nanometal oxides have a strong interactive synergistic effect, avoiding SO 2 The toxic effect on active metals improves the sulfur resistance of the adsorbent / catalyst; graphene is hydrophobic and can improve the water resistance of the adsorbent / catalyst. Therefore, the adsorbent / catalyst prepared by the present invention is effective in high concentration SO 2 and H 2 O environment can show excellent stability and service life.

[0037] (10) The present invention uses a mechanochemical method to complete the process at room temperature and pressure, without the need for high-temperature operation, thus avoiding the high energy consumption problem of pyrometallurgy. At the same time, no strong acid or alkali is used, no waste liquid and toxic gas are discharged, and compared with the traditional hydrometallurgy / hydrometallurgical modified adsorbent process, a more environmentally friendly and green and low-carbon resource recovery and material preparation technology is achieved. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] The accompanying drawings in the specification, which constitute a part of the present invention, are used to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute improper limitations on the present invention.

[0039] Figure 1 It is a process flow chart of an embodiment of the present invention. DETAILED DESCRIPTION

[0040] It should be noted that the following detailed descriptions are illustrative and intended to provide further explanation of the present invention. Unless otherwise specified, all technical and scientific terms used in the present invention have the same meanings as those commonly understood by those skilled in the art to which the present invention belongs.

[0041] The present invention will be further described below in conjunction with the embodiments.

[0042] Example 1

[0043] Step 1. Use the waste lithium manganese oxide (LiMn 2 O 4 ) disassembling the battery after discharging to obtain positive electrode material powder, negative electrode copper foil, and negative electrode graphite powder;

[0044] Step 2. The positive electrode material powder, waste PVC powder, copper foil and negative electrode graphite powder are mixed and ball-milled. The specific parameters are as follows: the mass ratio of the positive electrode material powder, waste PVC powder, copper foil and graphite powder is 1:2:4:2, the water addition ratio is 3:1 (ml / g), the ball-to-material ratio is 50:1, the ball milling speed is 500rpm, and the ball milling time is 9h;

[0045] Step 3. After the ball milling is completed, the ball milling product is subjected to water leaching and filtration treatment. The water leaching conditions are: the liquid-solid ratio of water to the ball milling product is 30:1 (ml / g), the leaching temperature is 60°C, and the leaching time is 1h.

[0046] Step 4. Add saturated Na 2 CO 3 The solution was heated and stirred to obtain Li 2 CO 3 White precipitate;

[0047] Step 5: Dry the filter residue and place it in a calcining furnace at N 2 atmosphere and calcined at 500 °C for 2 h to obtain the graphene-supported nano-metal oxide adsorbent / catalyst.

[0048] The results showed that the recovery rate of Li was 90%, the leaching rate of Mn was 0.03%, and the leaching rate of Cu was 0.02%.

[0049] When Hg 0 The concentration is 80 μg / m 3 , NO concentration is 400ppm, toluene concentration is 50ug / m 3 , SO 2 The concentration is 400ppm, H 2 When the O concentration was 3wt.%, the reaction temperature was 200℃, a fixed bed test device was used, the flue gas flow rate was controlled to be 1L / min, and the adsorbent / catalyst dosage was 0.1g, Hg 0 The removal efficiencies of NO and toluene were 92%, 86% and 90%, respectively.

[0050] When Hg 0 The concentration is 80 μg / m 3 , NO concentration is 400ppm, toluene concentration is 50ug / m 3 , SO 2 The concentration is 800ppm, H 2When the O concentration was 6wt.%, the reaction temperature was 200℃, a fixed bed test device was used, the flue gas flow rate was controlled to be 1L / min, and the adsorbent / catalyst dosage was 0.1g, Hg 0 The removal efficiencies of NO and toluene were 91%, 88% and 91%, respectively.

[0051] Example 2

[0052] Step 1. Use the waste lithium manganese oxide (LiMn 2 O 4 ) disassembling the battery after discharging to obtain positive electrode material powder, negative electrode copper foil, and negative electrode graphite powder;

[0053] Step 2. The positive electrode material powder, waste PVC powder, copper foil and negative electrode graphite powder are mixed and ball-milled. The specific parameters are as follows: the mass ratio of the positive electrode material powder, waste PVC powder, copper foil and graphite powder is 1:2:4:2, the water addition ratio is 3:1 (ml / g), the ball-to-material ratio is 50:1, the ball milling speed is 700 rpm, and the ball milling time is 9 hours;

[0054] Step 3. After the ball milling is completed, the ball milling product is subjected to water leaching and filtration treatment. The water leaching conditions are: the liquid-solid ratio of water to the ball milling product is 30:1 (ml / g), the leaching temperature is 60°C, and the leaching time is 1h.

[0055] Step 4. Add saturated Na 2 CO 3 The solution was heated and stirred to obtain Li 2 CO 3 White precipitate;

[0056] Step 5: Dry the filter residue and place it in a calcining furnace at N 2 atmosphere and calcined at 500°C for 2h to obtain the graphene-supported nano-metal oxide adsorbent / catalyst material.

[0057] The results showed that the recovery rate of Li was 97%, the leaching rate of Mn was 0.04%, and the leaching rate of Cu was 0.01%.

[0058] When Hg 0 The concentration is 80 μg / m 3 , NO concentration is 400ppm, toluene concentration is 50ug / m 3 , SO 2 The concentration is 400ppm, H 2 When the O concentration was 3wt.%, the reaction temperature was 200℃, a fixed bed test device was used, the flue gas flow rate was controlled to be 1L / min, and the adsorbent / catalyst dosage was 0.1g, Hg 0 The removal efficiencies of NO and toluene were 94%, 88% and 90%, respectively.

[0059] Example 3

[0060] Step 1. Use the waste lithium manganese oxide (LiMn 2 O 4 ) disassembling the battery after discharging to obtain positive electrode material powder, negative electrode copper foil, and negative electrode graphite powder;

[0061] Step 2. The positive electrode material powder, waste PVC powder, copper foil and negative electrode graphite powder are mixed and ball-milled. The specific parameters are as follows: the mass ratio of the positive electrode material powder, waste PVC powder, copper foil and graphite powder is 1:2:4:2, the water addition ratio is 3:1 (ml / g), the ball-to-material ratio is 50:1, the ball milling speed is 500rpm, and the ball milling time is 9h;

[0062] Step 3. After the ball milling is completed, the ball milling product is subjected to water leaching and filtration treatment. The water leaching conditions are: the liquid-solid ratio of water to the ball milling product is 30:1 (ml / g), the leaching temperature is 60°C, and the leaching time is 1h.

[0063] Step 4. Add saturated Na 2 CO 3 The solution was heated and stirred to obtain Li 2 CO 3 White precipitate;

[0064] Step 5: Dry the filter residue and place it in a calcining furnace at N 2 Atmosphere and calcined at 800 °C for 2 h to obtain the graphene-supported nano-metal oxide adsorbent / catalyst material.

[0065] The results showed that the recovery rate of Li was 90%, the leaching rate of Mn was 0.03%, and the leaching rate of Cu was 0.

[0066] When Hg 0 The concentration is 80 μg / m 3 , NO concentration is 400ppm, toluene concentration is 50ug / m 3 , SO 2 The concentration is 400ppm, H 2 When the O concentration was 3wt.%, the reaction temperature was 200℃, a fixed bed test device was used, the flue gas flow rate was controlled to be 1L / min, and the adsorbent / catalyst dosage was 0.1g, Hg 0 The removal efficiencies of NO and toluene were 91%, 83% and 87% respectively.

[0067] Example 4

[0068] Compared with Example 1, the negative electrode copper foil was replaced with a mixture of copper foil and aluminum foil.

[0069] Step 1. Use the waste lithium manganese oxide (LiMn 2 O 4 ) disassembling the battery after discharging to obtain positive electrode aluminum foil, positive electrode material powder, negative electrode copper foil, and negative electrode graphite powder;

[0070] Step 2. The positive electrode material powder, waste PVC powder, copper foil / aluminum foil (a combination of the two, the mass ratio of copper foil to aluminum foil is 2:1) and the negative electrode graphite powder are mixed and ball-milled. The specific parameters are as follows: the mass ratio of the positive electrode material powder, waste PVC powder, copper foil-aluminum foil mixture and graphite powder is 1:2:4:2, the water addition ratio is 3:1 (ml / g), the ball-to-material ratio is 50:1, the ball milling speed is 500rpm, and the ball milling time is 9h;

[0071] Step 3. After the ball milling is completed, the ball milling product is subjected to water leaching and filtration treatment. The water leaching conditions are: the liquid-solid ratio of water to the ball milling product is 30:1 (ml / g), the leaching temperature is 60°C, and the leaching time is 1h.

[0072] Step 4. Add saturated Na 2 CO 3 The solution was heated and stirred to obtain Li 2 CO 3 White precipitate;

[0073] Step 5: Dry the filter residue and place it in a calcining furnace at N 2 atmosphere and calcined at 500°C for 2h to obtain the graphene-supported nano-metal oxide adsorbent / catalyst material.

[0074] The results showed that the recovery rate of Li was 96%, the leaching rate of Mn was 0.05%, the leaching rate of Cu was 0.03%, and the leaching rate of Al was 0.02%.

[0075] When Hg 0 The concentration is 80 μg / m 3 , NO concentration is 400ppm, toluene concentration is 50ug / m 3 , SO 2 The concentration is 400ppm, H 2 When the O concentration was 3wt.%, the reaction temperature was 200℃, a fixed bed test device was used, the flue gas flow rate was controlled to be 1L / min, and the adsorbent / catalyst dosage was 0.1g, Hg 0 The removal efficiencies of NO and toluene were 96%, 90% and 92% respectively.

[0076] Example 5

[0077] Step 1. Use the waste lithium manganese oxide (LiCoO 2 ) disassembling the battery after discharging to obtain positive electrode material powder, negative electrode copper foil, and negative electrode graphite powder;

[0078] Step 2. The positive electrode material powder, waste PVC powder, copper foil and negative electrode graphite powder are mixed and ball-milled. The specific parameters are as follows: the mass ratio of the positive electrode material powder, waste PVC powder, copper foil and graphite powder is 1:3:5:3, the water addition ratio is 3:1 (ml / g), the ball-to-material ratio is 50:1, the ball milling speed is 500rpm, and the ball milling time is 9h;

[0079] Step 3. After the ball milling is completed, the ball milling product is subjected to water leaching and filtration treatment. The water leaching conditions are: the liquid-solid ratio of water to the ball milling product is 30:1 (ml / g), the leaching temperature is 60°C, and the leaching time is 1h.

[0080] Step 4. Add saturated Na 2 CO 3 The solution was heated and stirred to obtain Li 2 CO 3 White precipitate;

[0081] Step 5: Dry the filter residue and place it in a calcining furnace at N 2 atmosphere and calcined at 500°C for 2h to obtain the graphene-supported nano-metal oxide adsorbent / catalyst material.

[0082] The results showed that the recovery rate of Li was 91%, the leaching rate of Co was 0.01%, and the leaching rate of Cu was 0.

[0083] When Hg 0 The concentration is 80 μg / m 3 , NO concentration is 400ppm, toluene concentration is 50ug / m 3 , SO 2 The concentration is 400ppm, H 2 When the O concentration was 3wt.%, the reaction temperature was 200℃, a fixed bed test device was used, the flue gas flow rate was controlled to be 1L / min, and the adsorbent / catalyst dosage was 0.1g, Hg 0 The removal efficiencies of NO and toluene were 98%, 92% and 94% respectively.

[0084] Example 6

[0085] The difference from Example 1 is that the negative electrode copper foil in Example 1 is replaced by aluminum foil, and the rest is the same as Example 1.

[0086] The results showed that the recovery rate of Li was 91%, the leaching rate of Mn was 0.02%, and the leaching rate of Al was 0.01%.

[0087] When Hg 0 The concentration is 80 μg / m 3, NO concentration is 400ppm, toluene concentration is 50ug / m 3 , SO 2 The concentration is 400ppm, H 2 When the O concentration was 3wt.%, the reaction temperature was 200℃, a fixed bed test device was used, the flue gas flow rate was controlled to be 1L / min, and the adsorbent / catalyst dosage was 0.1g, Hg 0 The removal efficiencies of NO and toluene were 91%, 89% and 92%, respectively.

[0088] Example 7

[0089] The difference from Example 1 is that the negative electrode copper foil in Example 1 is replaced by a stainless steel shell, and the rest is the same as Example 1.

[0090] The results showed that the recovery rate of Li was 92%, the leaching rate of Mn was 0, and the leaching rates of metals such as Fe / Ni were all lower than 0.02%.

[0091] When Hg 0 The concentration is 80 μg / m 3 , NO concentration is 400ppm, toluene concentration is 50ug / m 3 , SO 2 The concentration is 400ppm, H 2 When the O concentration was 3wt.%, the reaction temperature was 200℃, a fixed bed test device was used, the flue gas flow rate was controlled to be 1L / min, and the adsorbent / catalyst dosage was 0.1g, Hg 0 The removal efficiencies of NO and toluene were 89%, 90% and 90% respectively.

[0092] Example 8

[0093] The difference from Example 4 is that the positive electrode aluminum foil in Example 4 is replaced by a stainless steel shell, and the rest is the same as Example 4.

[0094] The results showed that the recovery rate of Li was 94%, the leaching rate of Mn was 0.03%, the leaching rate of Cu was 0.03%, and the leaching rates of metals such as Fe / Ni were all lower than 0.02%.

[0095] When Hg 0 The concentration is 80 μg / m 3 , NO concentration is 400ppm, toluene concentration is 50ug / m 3 , SO 2 The concentration is 400ppm, H 2 When the O concentration was 3wt.%, the reaction temperature was 200℃, a fixed bed test device was used, the flue gas flow rate was controlled to be 1L / min, and the adsorbent / catalyst dosage was 0.1g, Hg 0The removal efficiencies of NO and toluene were 92%, 89% and 90%, respectively.

[0096] Example 9

[0097] The difference from Example 4 is that the negative electrode copper foil in Example 4 is replaced by a stainless steel shell, and the rest is the same as Example 4.

[0098] The results showed that the recovery rate of Li was 93%, the leaching rate of Mn was 0.04%, the leaching rate of Al was 0.03%, and the leaching rates of metals such as Fe / Ni were all lower than 0.02%.

[0099] When Hg 0 The concentration is 80 μg / m 3 , NO concentration is 400ppm, toluene concentration is 50ug / m 3 , SO 2 The concentration is 400ppm, H 2 When the O concentration was 3wt.%, the reaction temperature was 200℃, a fixed bed test device was used, the flue gas flow rate was controlled to be 1L / min, and the adsorbent / catalyst dosage was 0.1g, Hg 0 The removal efficiencies of NO and toluene were 91%, 90% and 91% respectively.

[0100] Comparative Example 1

[0101] Compared with Example 1, the difference is that only the waste PVC powder is omitted, and the rest is the same as Example 1.

[0102] The results showed that the recovery rate of Li was 17%, the leaching rate of Mn was 0.01%, and the leaching rate of Cu was 0.01%.

[0103] When Hg 0 The concentration is 80 μg / m 3 , NO concentration is 400ppm, toluene concentration is 50ug / m 3 , SO 2 The concentration is 400ppm, H 2 When the O concentration was 3wt.%, the reaction temperature was 200℃, a fixed bed test device was used, the flue gas flow rate was controlled to be 1L / min, and the adsorbent / catalyst dosage was 0.1g, Hg 0 The removal efficiencies of NO and toluene were 83%, 79% and 82% respectively.

[0104] Comparative Example 2

[0105] Compared with Example 1, the difference is that only the copper foil is omitted, and the rest is the same as Example 1.

[0106] The results showed that the recovery rate of Li was 35% and the leaching rate of Mn was 0.02%.

[0107] When Hg 0 The concentration is 80 μg / m 3 , NO concentration is 400ppm, toluene concentration is 50ug / m 3 , SO 2 The concentration is 400ppm, H 2 When the O concentration was 3wt.%, the reaction temperature was 200℃, a fixed bed test device was used, the flue gas flow rate was controlled to be 1L / min, and the adsorbent / catalyst dosage was 0.1g, Hg 0 The removal efficiencies of NO and toluene were 84%, 80% and 79%, respectively.

[0108] Comparative Example 3

[0109] Compared with Example 1, the difference is that only the negative electrode graphite powder is omitted, and the rest is the same as Example 1.

[0110] The results showed that the recovery rate of Li was 88%, the leaching rate of Mn was 0.02%, and the leaching rate of Cu was 0.

[0111] When Hg 0 The concentration is 80 μg / m 3 , NO concentration is 400ppm, toluene concentration is 50ug / m 3 , SO 2 The concentration is 400ppm, H 2 When the O concentration was 3wt.%, the reaction temperature was 200℃, a fixed bed test device was used, the flue gas flow rate was controlled to be 1L / min, and the adsorbent / catalyst dosage was 0.1g, Hg 0 The removal efficiencies of NO and toluene were 86%, 83% and 82% respectively.

[0112] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A method for preparing an adsorbent / catalyst based on the recovery of waste lithium batteries, characterized in that: The steps include: Discharge and disassemble the waste lithium batteries, crush the obtained metal waste, mix it with positive electrode materials, PVC and negative electrode graphite materials, and ball mill them. Water is added during the ball milling process to carry out a mechanochemical reaction; After the ball milling is completed, the ball milling product is subjected to water immersion treatment, and the filter residue after the water immersion treatment is dried and calcined in an inert atmosphere at a calcination temperature of 350-900° C. for a calcination time of 0.5-4 h to obtain a mercury removal adsorbent / catalyst.

2. The method for preparing an adsorbent / catalyst based on waste lithium battery recovery according to claim 1, characterized in that: The metal waste is one or a combination of copper foil, aluminum foil or stainless steel casing; Preferably, the metal waste is a mixture of copper foil and aluminum foil, and the mass ratio of copper foil to aluminum foil is 1-2.5:1-2.

5. Preferably, the metal waste is a mixture of copper foil and stainless steel, and the mass ratio of copper foil to stainless steel is 1-2.5:1-2.5; Preferably, the metal waste is a mixture of aluminum foil and stainless steel, and the mass ratio of the aluminum foil to the stainless steel is 1-2.5:1-2.

5.

3. The method for preparing an adsorbent / catalyst based on waste lithium battery recovery according to claim 1, characterized in that: The mass ratio of the positive electrode material, the metal waste, the PVC and the negative electrode graphite material is 0.8-1.2:0.4-0.6:0.4-0.6:0.5-1:6:7-9:5-7.

4. The method for preparing an adsorbent / catalyst based on waste lithium battery recovery according to claim 1, characterized in that: The positive electrode material is one of lithium manganese oxide, ternary lithium, lithium iron phosphate and lithium cobalt oxide, or a combination thereof.

5. The method for preparing an adsorbent / catalyst based on waste lithium battery recovery according to claim 1, characterized in that: The PVC is waste PVC plastic; Preferably, the waste PVC plastic comes from pipes, wires and cables or door and window profiles.

6. The method for preparing an adsorbent / catalyst based on waste lithium battery recovery according to claim 1, characterized in that: When ball milling, add 0.5-15 ml of water per gram of the mixed material for wet grinding; Preferably, during ball milling, the ball-to-material ratio is 5-100:1, the ball milling speed is 100-900 rpm, and the ball milling time is 0.3-36 h.

7. The method for preparing an adsorbent / catalyst based on waste lithium battery recovery according to claim 1, characterized in that: During water immersion treatment, the liquid-solid ratio is 10-200:1; the water immersion temperature is 20-80°C, and the leaching time is 5min-4h.

8. The method for preparing an adsorbent / catalyst based on waste lithium battery recovery according to claim 1, characterized in that: After the water leaching treatment, the solid and liquid are separated to obtain a lithium-rich water leaching solution, to which a saturated Na2CO3 solution is added, heated and stirred to obtain a white Li2CO3 precipitate, which is used to recover lithium.

9. An adsorbent / catalyst based on the recovery of waste lithium batteries, characterized in that: Prepared by the preparation method described in any one of claims 1 to 8.

10. Application of the adsorbent / catalyst based on waste lithium battery recovery as claimed in claim 9 in the removal of flue gas pollutants; Preferably, the flue gas pollutants include but are not limited to Hg 0 , NO, toluene, VOCs and SO2.

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