WO2022233340A1 - Vocs combustion catalyst prepared from recycled waste ternary lithium-ion batteries, and preparation method therefor - Google Patents

Vocs combustion catalyst prepared from recycled waste ternary lithium-ion batteries, and preparation method therefor Download PDF

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WO2022233340A1
WO2022233340A1 PCT/CN2022/094388 CN2022094388W WO2022233340A1 WO 2022233340 A1 WO2022233340 A1 WO 2022233340A1 CN 2022094388 W CN2022094388 W CN 2022094388W WO 2022233340 A1 WO2022233340 A1 WO 2022233340A1
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vocs
solution
comnnio
positive electrode
electrode material
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French (fr)
Chinese (zh)
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郝郑平
黎刚刚
赵泽宇
张中申
程杰
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中国科学院大学
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/651—50-500 nm
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
    • F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
    • F23G7/07—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases in which combustion takes place in the presence of catalytic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G2209/00—Specific waste
    • F23G2209/14—Gaseous waste or fumes
    • 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
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • 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
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/84—Recycling of batteries or fuel cells

Definitions

  • the invention relates to the technical field of catalyst preparation, in particular to a VOCs combustion catalyst prepared by recycling waste ternary lithium batteries and a preparation method thereof.
  • Ternary lithium-ion batteries are widely used in the consumer electronics market, electric vehicles and grid energy storage due to their advantages of high energy density, high storage capacity and good rate performance.
  • LTIBs lithium-ion batteries
  • 80GWh the total usage capacity of lithium-ion batteries
  • Aviconi Energy the total usage capacity of lithium-ion batteries
  • ternary lithium batteries will usher in a new wave of growth demand.
  • the safe recycling and green disposal of waste ternary lithium batteries is still a key link in the development of the lithium battery industry.
  • VOCs Volatile organic compounds
  • VOCs control technologies catalytic oxidation is considered to be a technology with a wide range of applications due to its advantages of high efficiency, energy saving, and low toxic by-products.
  • transition metal oxides such as Co 3 O 4 , MnO 2 , and NiO, have shown promising potential in the catalytic oxidation of VOCs due to their excellent redox properties and good mobility of active oxygen.
  • TLIBs have relatively high-priced Co and Ni elements, if the transition metal elements in TLIBs can be recycled to prepare composite oxide VOCs catalysts, then both the resource utilization of waste TLIBs and the pollution control of VOCs will be a problem. It has better environmental and economic benefits.
  • the technical problem to be solved by the present invention is: to overcome the deficiencies of the prior art, to provide a VOCs combustion catalyst prepared by recycling waste ternary lithium batteries and a preparation method thereof. Acid-soluble metal ions ⁇ filtration to remove insoluble impurities ⁇ salt precipitation ⁇ alkaline solution modification process to obtain CoMnNiO x composite oxides containing high oxygen defects, so as to achieve efficient catalytic purification of VOCs.
  • the present invention provides a method for reusing waste ternary lithium batteries to prepare a VOCs combustion catalyst, comprising the following steps:
  • step 2) adding the positive electrode material powder obtained in step 1) to the mixed solution of strong acid and hydrogen peroxide;
  • step 3 filtering the mixed solution obtained in step 2) to remove undissolved insoluble impurities to obtain the leachate of the positive electrode material;
  • step 4) adding carbonate solution to the leaching solution obtained in step 3) to promote the precipitation of transition metals Co 2+ , Mn 2+ and Ni 2+ , followed by filtering, washing, drying and calcining to obtain CoMnNiO x composite oxide;
  • step 5 The CoMnNiO x composite oxide obtained in step 4) is added to the alkaline solution, and after stirring treatment, a composite oxide catalyst with high oxygen deficiency is obtained.
  • the obtained composite oxide catalyst with high oxygen deficiency contains at least five metal elements of cobalt, manganese, nickel, aluminum and lithium. After the alkali treatment and modification in step 5), the three metal elements of cobalt, manganese and nickel account for all the metal elements. The molar proportion of the elements is at least 99%.
  • the Al and Li elements in the composite oxide are obtained by the one-step precipitation method of alkaline solution etching.
  • the defect-enhancing effect caused by the dissolution of Al and Li cations can greatly promote the catalytic oxidation activity of VOCs of the obtained composite oxides. Therefore, the composite oxides prepared by the alkaline solution post-treatment method have the advantages of good low-temperature activity, strong stability, and suitable for various types of VOCs reactions.
  • the strong acid is nitric acid, sulfuric acid or hydrofluoric acid.
  • step 2) the mixed solution is heated to 25-90°C.
  • the carbonate solution is sodium carbonate, sodium bicarbonate, ammonium carbonate, potassium carbonate, potassium bicarbonate or ammonium bicarbonate, and the concentration is 0.1-10 mol/L.
  • the calcination temperature is 200-600°C.
  • the alkali solution is sodium hydroxide or potassium hydroxide solution, and the concentration is 0.1-5mol/L.
  • the stirring temperature is 25-95°C.
  • the present invention provides a VOCs combustion catalyst prepared by the above method.
  • the VOCs combustion catalyst has a mesoporous structure of 5-80 nm and a specific surface area of 90-200 m 2 /g.
  • the "catalytic oxidation” referred to in the present invention means that VOCs are oxidized by oxygen to carbon dioxide and water under the action of a catalyst, and do not show macroscopic flame combustion.
  • the temperature corresponding to the conversion rate of the catalytic oxidation of the target VOCs is 10%, called “light-off temperature", and denoted as T 10 ; the conversion rate of the target VOCs catalytic oxidation is 90%.
  • the corresponding temperature The temperature is called “complete transformation temperature” and is recorded as T 90 .
  • the present invention has the following beneficial effects:
  • the present invention adopts waste ternary lithium electron positive electrode material to realize CoMnNiO x composite oxide by reusing the transition metal element in it after a series of treatment processes.
  • the catalyst prepared with carbonate as precipitant is more active than oxalic acid precipitant; in addition, the alkali treatment process achieves the increase of oxygen deficiency in the composite oxide, which is in typical VOCs pollutants such as acetone, ethyl acetate and propane. It exhibits excellent catalytic activity in the catalytic combustion reaction.
  • VOCs pollutants such as acetone, ethyl acetate and propane. It exhibits excellent catalytic activity in the catalytic combustion reaction.
  • the use of waste ternary lithium battery cathode materials to prepare high-performance VOCs catalysts not only realizes the recycling of waste lithium batteries, but also has excellent application prospects for VOCs catalytic combustion.
  • Fig. 1 is the XRD pattern of the positive electrode material of ternary lithium battery and the CoMnNiO composite oxide prepared by the present invention, wherein each curve represents from bottom to top: Li( CoMnNi )O ternary obtained after mechanical disassembly, calcination and decarbonization Positive electrode material; the obtained positive electrode material was added to 1 mol/L sodium hydroxide solution, treated at 80°C for 4 h, filtered, washed and dried to obtain the positive electrode material-NaOH; the intermediate product prepared in Example 1; the product prepared in Example 2 Intermediate product; final product prepared in Example 2.
  • Example 2 is a comparison of EPR results of oxygen vacancy characterization of CoMnNiO x composite oxides before and after alkali treatment of the present invention, wherein the two curves represent the intermediate product prepared in Example 2 and the final product prepared in Example 2 from bottom to top.
  • Figure 3 shows the propane catalytic oxidation activity curves of catalysts at different treatment stages, in which the positive electrode material curve represents the Li(CoMnNi)O 2 ternary positive electrode material obtained after mechanical disassembly, calcination and decarbonization; the positive electrode material-NaOH curve represents The obtained positive electrode material was added to 1 mol/L sodium hydroxide solution, treated at 80°C for 4 h, filtered, washed and dried to obtain the positive electrode material-NaOH; the CoMnNiO x -oxalic acid curve represents the intermediate product in Example 1 ; the CoMnNiO x -sodium carbonate curve represents the intermediate product in Example 2; the CoMnNiO x -sodium carbonate-NaOH curve represents the final product in Example 2.
  • the positive electrode material curve represents the Li(CoMnNi)O 2 ternary positive electrode material obtained after mechanical disassembly, calcination and decarbonization
  • Example 4 is a graph showing the activity curves of CoMnNiO x composite oxides obtained by different precipitants for the catalytic oxidation of acetone, wherein the two curves from left to right represent the intermediate product prepared in Example 2 and the intermediate product prepared in Example 1, respectively.
  • Figure 5 shows the activity curves of the obtained CoMnNiO x composite oxide for ethyl acetate catalytic oxidation before and after alkali treatment, wherein the two curves from left to right represent the final product prepared in Example 2 and the intermediate product prepared in Example 2 respectively.
  • Figure 6 is the nitrogen adsorption and desorption curve of the catalyst, wherein the CoMnNiO x -oxalic acid curve represents the intermediate product in Example 1; the CoMnNiO x -sodium carbonate curve represents the intermediate product in Example 2; CoMnNiO x -sodium carbonate -The NaOH curve represents the final product in Example 2.
  • Fig. 7 is the pore size distribution diagram of the catalyst, wherein the CoMnNiO x -oxalic acid curve represents the intermediate product in Example 1; the CoMnNiO x -sodium carbonate curve represents the intermediate product in Example 2; CoMnNiO x -sodium carbonate-NaOH The curve represents the final product in Example 2.
  • FIG. 8 is a schematic structural diagram of a small-scale fixed-bed continuous flow reaction evaluation device of the present invention.
  • VOCs gas and oxygen entered the gas mixing device respectively, and then entered the quartz tube of the reaction furnace (model SK2-1-10K) after mixing. In the process, it contacts and reacts with the catalyst in the quartz tube, and the reacted gas enters the gas chromatograph for detection to obtain the catalytic oxidation conversion rate of VOCs gas.
  • the 40-60 mesh catalyst obtained by sieving 0.1g of tablets was put into a quartz tube (diameter 6mm), the reaction temperature was controlled by a temperature-programmed reaction furnace, and the VOCs gas was selected from three gases of propane, acetone or ethyl acetate.
  • the concentrations were 2000 ppm, 1000 ppm and 1000 ppm, respectively, and the oxygen concentration was 20%.
  • the space velocity was 18000 g ⁇ ml ⁇ h ⁇ 1 .
  • the waste ternary lithium battery is completely discharged, and the positive electrode material is separated and pulverized through shearing, screening and mechanical stripping treatment; the positive electrode material powder is added to the mixed solution of strong acid (nitric acid, sulfuric acid or hydrofluoric acid) and hydrogen peroxide and heated to 25-90° C. to promote the dissolution of metal ions in the positive electrode material; filter the mixed solution to remove undissolved insoluble impurities (conductive graphite, etc.) to obtain the leaching solution of the positive electrode material.
  • strong acid nitric acid, sulfuric acid or hydrofluoric acid
  • hydrogen peroxide hydrogen peroxide
  • a 5 mol/L oxalic acid solution was continuously added dropwise to 150 mL of the positive electrode material leaching solution until flocculent precipitation occurred. Stir vigorously for 30 min, and then stand still for aging for 12 h. The obtained precipitate is filtered with suction, washed until neutral, and dried at 100°C overnight. Finally, the obtained powder was calcined in a muffle furnace at 300° C. for 3 hours in an air atmosphere to obtain a CoMnNiO x composite metal oxide.
  • CoMnNiO x composite metal oxide was added to a 1 mol/L sodium hydroxide solution, stirred at 80° C. for 4 hours, filtered, washed and dried to obtain an oxygen-deficient composite oxide, denoted as catalyst A.
  • Catalyst A was used in the catalytic activity test of propane, acetone and ethyl acetate, respectively.
  • the preparation method of the leaching solution of the positive electrode material is the same as that in Example 1.
  • CoMnNiO x composite metal oxide was added to a 1 mol/L sodium hydroxide solution, stirred at 50°C for 8 hours, filtered, washed and dried to obtain an oxygen-deficient composite oxide, denoted as catalyst B.
  • Catalyst B was used in the catalytic activity test of propane, acetone and ethyl acetate, respectively.
  • the preparation method of the leaching solution of the positive electrode material is the same as that in Example 1.
  • a 5 mol/L ammonium carbonate solution was continuously added dropwise to 150 mL of the positive electrode material leaching solution until the pH rose to 10. Stir vigorously for 30 min, and then stand still for aging for 12 h. The obtained precipitate is filtered with suction, washed until neutral, and dried at 100°C overnight. Finally, the obtained powder was calcined in a muffle furnace at 300° C. for 3 hours in an air atmosphere to obtain a CoMnNiO x composite metal oxide.
  • CoMnNiOx composite metal oxide was added to a 1 mol/L potassium hydroxide solution, stirred at 80°C for 4 hours, filtered, washed and dried to obtain an oxygen-deficient composite oxide, denoted as catalyst C.
  • Catalyst C was used in the catalytic activity test of propane, acetone and ethyl acetate, respectively.
  • the preparation method of the leaching solution of the positive electrode material is the same as that in Example 1.
  • a 5 mol/L oxalic acid solution was continuously added dropwise to 150 mL of the positive electrode material leaching solution until flocculent precipitation occurred. Stir vigorously for 30 min, and then stand still for aging for 12 h. The obtained precipitate is filtered with suction, washed until neutral, and dried at 100°C overnight. Finally, the obtained powder was calcined in a muffle furnace at 300° C. for 3 hours in an air atmosphere to obtain a CoMnNiO x composite metal oxide, which was denoted as catalyst R1.
  • the catalyst R1 was used in the catalytic activity test of propane, acetone and ethyl acetate, respectively.
  • the preparation method of the leaching solution of the positive electrode material is the same as that in Example 1.
  • Example 2 the CoMnNiO x composite oxide prepared by using sodium carbonate as a precipitant has a higher diffraction peak than the CoMnNiO x composite oxide prepared by using oxalic acid as a precipitant in Example 1. It can be explained that the crystallinity of CoMnNiO x -sodium carbonate prepared in Example 2 is lower, and it contains more oxygen vacancy defects. Similarly, CoMnNiO x -sodium carbonate-NaOH after alkali treatment also has broad diffraction peaks, indicating that there are abundant oxygen vacancy defects.
  • Figure 4 further confirms that the catalyst prepared using carbonate as precipitant is more active than oxalic acid precipitant.
  • Figure 5 also further confirms that the alkali treatment can further improve the activity of the catalyst.
  • Figure 6 shows that the specific surface area of the VOCs combustion catalyst is 90-200 m 2 /g
  • Figure 7 shows that the catalyst has a mesoporous structure of 5-80 nm.

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Abstract

Disclosed in the present invention are a VOCs combustion catalyst prepared from recycled waste ternary lithium-ion batteries, and a preparation method therefor, which belong to the technical field of catalyst preparation. A CoMnNiOx composite oxide containing high oxygen defects is obtained by subjecting waste ternary lithium-ion batteries to the process of discharging → disassembling → mechanical exfoliation → acid dissolution of metal ions → filtration to remove insoluble impurities → salt formation and precipitation → alkali solution modification, such that efficient catalytic purification of VOCs is achieved.

Description

回用废旧三元锂电池制备的VOCs燃烧催化剂及其制备方法VOCs combustion catalyst prepared by recycling waste ternary lithium battery and preparation method thereof 技术领域technical field
本发明涉及催化剂制备技术领域，具体涉及一种回用废旧三元锂电池制备的VOCs燃烧催化剂及其制备方法。The invention relates to the technical field of catalyst preparation, in particular to a VOCs combustion catalyst prepared by recycling waste ternary lithium batteries and a preparation method thereof.
背景技术Background technique
三元锂电池(ternary lithium-ion batteries，TLIBs)因为具有能量密度大、储电容量高和倍率性能好等优点而广泛应用于消费类电子产品市场、电动汽车和电网储能等领域。据阿维森尼能源公司统计，2016年全球锂电池(LIBs)的总使用容量已经达到了80GWh，大约为六百万块单体电池。随着电动汽车需求的进一步增大，三元锂电池的将会迎来一波新的增长需求。然而，废旧三元锂电池的安全回收与绿色处置依然是锂电池行业发展的关键环节。Ternary lithium-ion batteries (TLIBs) are widely used in the consumer electronics market, electric vehicles and grid energy storage due to their advantages of high energy density, high storage capacity and good rate performance. In 2016, the total usage capacity of lithium-ion batteries (LIBs) in the world has reached 80GWh, which is about six million single cells, according to the statistics of Aviconi Energy. With the further increase in demand for electric vehicles, ternary lithium batteries will usher in a new wave of growth demand. However, the safe recycling and green disposal of waste ternary lithium batteries is still a key link in the development of the lithium battery industry.
挥发性有机物(VOCs)由于巨大的污染排放量、恶劣的环境影响和严重的人体健康危害而受到了政府和民众的广泛关注。在VOCs控制技术中，催化氧化法由于具有高效、节能和低毒害副产物等优点而被认为是一种具有广泛应用范围的技术。近年来，诸如Co 3O 4、MnO 2、NiO等过渡金属氧化物因为具有优异的氧化还原性能和良好的活性氧流动性而在VOCs催化氧化反应中展现不错的催化性能潜力。由于TLIBs中具有价格相对较高的Co和Ni元素，因此如果能够回收利用TLIBs中的过渡金属元素用来制备复合氧化物型VOCs催化剂，那么无论是废旧TLIBs的资源化利用还是VOCs的污染控制都会有着较好的环境和经济效益。 Volatile organic compounds (VOCs) have received extensive attention from the government and the public due to their huge pollution emissions, severe environmental impacts and serious human health hazards. Among VOCs control technologies, catalytic oxidation is considered to be a technology with a wide range of applications due to its advantages of high efficiency, energy saving, and low toxic by-products. In recent years, transition metal oxides, such as Co 3 O 4 , MnO 2 , and NiO, have shown promising potential in the catalytic oxidation of VOCs due to their excellent redox properties and good mobility of active oxygen. Since TLIBs have relatively high-priced Co and Ni elements, if the transition metal elements in TLIBs can be recycled to prepare composite oxide VOCs catalysts, then both the resource utilization of waste TLIBs and the pollution control of VOCs will be a problem. It has better environmental and economic benefits.
尽管中国专利CN107694559B公布了一种相似的回收废旧TLIBs正极材料制备甲苯降解催化剂的方法，但是该方法中只回收利用了较低经济价值的MnO 2，对Co、Ni元素未能进行有效利用。通常，回用的TLIBs正极材料中还含有Li、Al等对催化氧化反应具有惰性作用的金属元素，而氧空位缺陷被认为是能够有效促进复合氧化物催化活性的重要因素。因此，在废旧LIBs正极材料的回收制备催化剂过程中简便快捷的去除惰性金属元素以及提高复合氧化物上的缺陷含量对提高VOCs催化氧化活性具有重要意义。 Although Chinese patent CN107694559B discloses a similar method of recycling waste TLIBs positive electrode material to prepare toluene degradation catalyst, only MnO 2 with low economic value is recycled in this method, and Co and Ni elements cannot be effectively utilized. Usually, the recycled TLIBs cathode materials also contain metal elements such as Li and Al which are inert to the catalytic oxidation reaction, and oxygen vacancy defects are considered to be an important factor that can effectively promote the catalytic activity of composite oxides. Therefore, it is of great significance to easily and quickly remove inert metal elements and increase the defect content of composite oxides in the process of recycling waste LIBs cathode materials to prepare catalysts for improving the catalytic oxidation activity of VOCs.
发明内容SUMMARY OF THE INVENTION
本发明要解决的技术问题是：克服现有技术的不足，提供一种回用废旧三元锂电池制备的VOCs燃烧催化剂及其制备方法，废旧三元锂电池经过放电→拆解→机械剥离→酸溶金属离子→过滤除不溶杂质→成盐沉淀→碱溶液改性流程得到含有高氧缺陷的 CoMnNiO x复合氧化物，从而实现对VOCs的高效催化净化。 The technical problem to be solved by the present invention is: to overcome the deficiencies of the prior art, to provide a VOCs combustion catalyst prepared by recycling waste ternary lithium batteries and a preparation method thereof. Acid-soluble metal ions → filtration to remove insoluble impurities → salt precipitation → alkaline solution modification process to obtain CoMnNiO x composite oxides containing high oxygen defects, so as to achieve efficient catalytic purification of VOCs.
第一方面，本发明提供了一种回用废旧三元锂电池制备VOCs燃烧催化剂的方法，包括以下步骤：In a first aspect, the present invention provides a method for reusing waste ternary lithium batteries to prepare a VOCs combustion catalyst, comprising the following steps:
1)将废旧三元锂电池进行完全放电处理，经过剪切、筛选、机械剥离处理实现正极材料的分离和粉碎；1) The waste ternary lithium battery is fully discharged, and the positive electrode material is separated and pulverized through shearing, screening, and mechanical peeling treatment;
2)将步骤1)得到的正极材料粉末加入到强酸和双氧水的混合溶液中；2) adding the positive electrode material powder obtained in step 1) to the mixed solution of strong acid and hydrogen peroxide;
3)将步骤2)得到的混合溶液过滤去除未溶解的不可溶杂质，得到正极材料的浸出液；3) filtering the mixed solution obtained in step 2) to remove undissolved insoluble impurities to obtain the leachate of the positive electrode material;
4)向步骤3)所得的浸出液中加入碳酸盐溶液促进过渡金属Co 2+、Mn 2+和Ni 2+产生沉淀，随后过滤、洗涤、干燥和煅烧后得到CoMnNiO x复合氧化物； 4) adding carbonate solution to the leaching solution obtained in step 3) to promote the precipitation of transition metals Co 2+ , Mn 2+ and Ni 2+ , followed by filtering, washing, drying and calcining to obtain CoMnNiO x composite oxide;
5)将步骤4)得到的CoMnNiO x复合氧化物加入碱溶液中，搅拌处理后得到高氧缺陷的复合氧化物催化剂。 5) The CoMnNiO x composite oxide obtained in step 4) is added to the alkaline solution, and after stirring treatment, a composite oxide catalyst with high oxygen deficiency is obtained.
所得到的高氧缺陷的复合氧化物催化剂至少包含钴、锰、镍、铝、锂五种金属元素，经过步骤5)的碱处理改性后，钴、锰和镍三种金属元素占所有金属元素的摩尔比例至少为99％。The obtained composite oxide catalyst with high oxygen deficiency contains at least five metal elements of cobalt, manganese, nickel, aluminum and lithium. After the alkali treatment and modification in step 5), the three metal elements of cobalt, manganese and nickel account for all the metal elements. The molar proportion of the elements is at least 99%.
考虑到Al和Li都能够被碱溶液溶解，而Co、Mn、Ni的氧化物不能和碱溶液发生反应，因此采用碱溶液刻蚀一步沉淀法得到复合氧化物中的Al和Li元素，进一步由于Al、Li阳离子溶出导致的缺陷增强作用可以极大的促进所得复合氧化物的VOCs催化氧化活性。因此，利用碱溶液后处理方法制备的复合氧化物具有低温活性好、稳定性强、适用多种不同类型VOCs反应等优点。Considering that both Al and Li can be dissolved by the alkaline solution, and the oxides of Co, Mn, and Ni cannot react with the alkaline solution, the Al and Li elements in the composite oxide are obtained by the one-step precipitation method of alkaline solution etching. The defect-enhancing effect caused by the dissolution of Al and Li cations can greatly promote the catalytic oxidation activity of VOCs of the obtained composite oxides. Therefore, the composite oxides prepared by the alkaline solution post-treatment method have the advantages of good low-temperature activity, strong stability, and suitable for various types of VOCs reactions.
优选地，步骤2)中，所述强酸是硝酸、硫酸或者氢氟酸。Preferably, in step 2), the strong acid is nitric acid, sulfuric acid or hydrofluoric acid.
优选地，步骤2)中，将混合溶液加热到25-90℃。Preferably, in step 2), the mixed solution is heated to 25-90°C.
优选地，步骤4)中，所述碳酸盐溶液为碳酸钠、碳酸氢钠、碳酸铵、碳酸钾、碳酸氢钾或者碳酸氢铵，浓度为0.1-10mol/L。Preferably, in step 4), the carbonate solution is sodium carbonate, sodium bicarbonate, ammonium carbonate, potassium carbonate, potassium bicarbonate or ammonium bicarbonate, and the concentration is 0.1-10 mol/L.
优选地，步骤4)中，煅烧温度为200-600℃。Preferably, in step 4), the calcination temperature is 200-600°C.
优选地，步骤5)中，所述碱溶液为氢氧化钠或氢氧化钾溶液，浓度为0.1-5mol/L。Preferably, in step 5), the alkali solution is sodium hydroxide or potassium hydroxide solution, and the concentration is 0.1-5mol/L.
优选地，步骤5)中，搅拌温度为25-95℃。Preferably, in step 5), the stirring temperature is 25-95°C.
第二方面，本发明提供了利用上述方法制备得到的VOCs燃烧催化剂。In a second aspect, the present invention provides a VOCs combustion catalyst prepared by the above method.
优选地，VOCs燃烧催化剂为5-80nm的介孔结构，比表面积为90-200m 2/g。 Preferably, the VOCs combustion catalyst has a mesoporous structure of 5-80 nm and a specific surface area of 90-200 m 2 /g.
本发明所称的“催化氧化”是指VOCs在催化剂的作用下被氧气氧化为二氧化碳和水，不表现出宏观上的火焰燃烧。在催化氧化VOCs时，将目标VOCs催化氧化的转化率为10％时所对应的温度，称为“起燃温度”，记为T 10；将目标VOCs催化氧化的转化率为90％时所对应的温度，称为“完全转化温度”，记为T 90。 The "catalytic oxidation" referred to in the present invention means that VOCs are oxidized by oxygen to carbon dioxide and water under the action of a catalyst, and do not show macroscopic flame combustion. In the catalytic oxidation of VOCs, the temperature corresponding to the conversion rate of the catalytic oxidation of the target VOCs is 10%, called "light-off temperature", and denoted as T 10 ; the conversion rate of the target VOCs catalytic oxidation is 90%. The corresponding temperature The temperature is called "complete transformation temperature" and is recorded as T 90 .
本发明与现有技术相比，具有以下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
本发明采用废旧的三元锂电子正极材料经过一系列处理过程后可以实现回用其中的过渡金属元素得到CoMnNiO x复合氧化物。其中，以碳酸盐作为沉淀剂比草酸沉淀剂制备出的催化剂活性好；此外，碱处理过程实现了复合氧化物中的氧缺陷增加，其在典型VOCs污染物如丙酮、乙酸乙酯和丙烷的催化燃烧反应中展现优异的催化活性。利用废旧三元锂电池正极材料制备高性能VOCs催化剂不仅实现了废旧锂电池的资源化回收，并且具有优异的VOCs催化燃烧应用前景。 The present invention adopts waste ternary lithium electron positive electrode material to realize CoMnNiO x composite oxide by reusing the transition metal element in it after a series of treatment processes. Among them, the catalyst prepared with carbonate as precipitant is more active than oxalic acid precipitant; in addition, the alkali treatment process achieves the increase of oxygen deficiency in the composite oxide, which is in typical VOCs pollutants such as acetone, ethyl acetate and propane. It exhibits excellent catalytic activity in the catalytic combustion reaction. The use of waste ternary lithium battery cathode materials to prepare high-performance VOCs catalysts not only realizes the recycling of waste lithium batteries, but also has excellent application prospects for VOCs catalytic combustion.
附图说明Description of drawings
图1为三元锂电池正极材料和本发明制备的CoMnNiO x复合氧化物的XRD图，其中各曲线由下至上依次代表：机械拆解、煅烧除炭后得到的Li(CoMnNi)O 2三元正极材料；将得到的正极材料加入1mol/L的氢氧化钠溶液中，80℃处理4h，过滤、洗涤、干燥后得到的正极材料-NaOH；实施例1制备的中间产物；实施例2制备的中间产物；实施例2制备的最终产物。 Fig. 1 is the XRD pattern of the positive electrode material of ternary lithium battery and the CoMnNiO composite oxide prepared by the present invention, wherein each curve represents from bottom to top: Li( CoMnNi )O ternary obtained after mechanical disassembly, calcination and decarbonization Positive electrode material; the obtained positive electrode material was added to 1 mol/L sodium hydroxide solution, treated at 80°C for 4 h, filtered, washed and dried to obtain the positive electrode material-NaOH; the intermediate product prepared in Example 1; the product prepared in Example 2 Intermediate product; final product prepared in Example 2.
图2为本发明碱处理前后的CoMnNiO x复合氧化物的氧空位表征的EPR结果比较，其中两条曲线由下至上依次代表实施例2制备的中间产物、实施例2制备的最终产物。 2 is a comparison of EPR results of oxygen vacancy characterization of CoMnNiO x composite oxides before and after alkali treatment of the present invention, wherein the two curves represent the intermediate product prepared in Example 2 and the final product prepared in Example 2 from bottom to top.
图3为不同处理阶段的催化剂的丙烷催化氧化活性曲线，其中正极材料曲线代表的是机械拆解、煅烧除炭后得到的Li(CoMnNi)O 2三元正极材料；正极材料-NaOH曲线代表的是将得到的正极材料加入1mol/L的氢氧化钠溶液中，80℃处理4h，过滤、洗涤、干燥后得到的正极材料-NaOH；CoMnNiO x-草酸曲线代表的是实施例1中的中间产物；CoMnNiO x-碳酸钠曲线代表的是实施例2中的中间产物；CoMnNiO x-碳酸钠-NaOH曲线代表的是实施例2中的最终产物。 Figure 3 shows the propane catalytic oxidation activity curves of catalysts at different treatment stages, in which the positive electrode material curve represents the Li(CoMnNi)O 2 ternary positive electrode material obtained after mechanical disassembly, calcination and decarbonization; the positive electrode material-NaOH curve represents The obtained positive electrode material was added to 1 mol/L sodium hydroxide solution, treated at 80°C for 4 h, filtered, washed and dried to obtain the positive electrode material-NaOH; the CoMnNiO x -oxalic acid curve represents the intermediate product in Example 1 ; the CoMnNiO x -sodium carbonate curve represents the intermediate product in Example 2; the CoMnNiO x -sodium carbonate-NaOH curve represents the final product in Example 2.
图4为不同沉淀剂所得CoMnNiO x复合氧化物对丙酮催化氧化活性曲线，其中两条曲线由左至右分别代表实施例2制备的中间产物、实施例1制备的中间产物。 4 is a graph showing the activity curves of CoMnNiO x composite oxides obtained by different precipitants for the catalytic oxidation of acetone, wherein the two curves from left to right represent the intermediate product prepared in Example 2 and the intermediate product prepared in Example 1, respectively.
图5为碱处理前后所得CoMnNiO x复合氧化物对乙酸乙酯催化氧化活性曲线，其中 两条曲线由左至右分别代表实施例2制备的最终产物、实施例2制备的中间产物。 Figure 5 shows the activity curves of the obtained CoMnNiO x composite oxide for ethyl acetate catalytic oxidation before and after alkali treatment, wherein the two curves from left to right represent the final product prepared in Example 2 and the intermediate product prepared in Example 2 respectively.
图6是催化剂的氮气吸脱附曲线，其中CoMnNiO x-草酸曲线代表的是实施例1中的中间产物；CoMnNiO x-碳酸钠曲线代表的是实施例2中的中间产物；CoMnNiO x-碳酸钠-NaOH曲线代表的是实施例2中的最终产物。 Figure 6 is the nitrogen adsorption and desorption curve of the catalyst, wherein the CoMnNiO x -oxalic acid curve represents the intermediate product in Example 1; the CoMnNiO x -sodium carbonate curve represents the intermediate product in Example 2; CoMnNiO x -sodium carbonate -The NaOH curve represents the final product in Example 2.
图7是催化剂的孔径分布图，其中CoMnNiO x-草酸曲线代表的是实施例1中的中间产物；CoMnNiO x-碳酸钠曲线代表的是实施例2中的中间产物；CoMnNiO x-碳酸钠-NaOH曲线代表的是实施例2中的最终产物。 Fig. 7 is the pore size distribution diagram of the catalyst, wherein the CoMnNiO x -oxalic acid curve represents the intermediate product in Example 1; the CoMnNiO x -sodium carbonate curve represents the intermediate product in Example 2; CoMnNiO x -sodium carbonate-NaOH The curve represents the final product in Example 2.
图8是本发明的小型固定床连续流动反应评价装置结构示意图。8 is a schematic structural diagram of a small-scale fixed-bed continuous flow reaction evaluation device of the present invention.
具体实施方式Detailed ways
下述实施例中所用的材料、试剂等，如无特殊说明，均可从商业途径得到。The materials, reagents, etc. used in the following examples can be obtained from commercial sources unless otherwise specified.
下述实施例中所用的催化剂评价方法：Catalyst evaluation method used in the following examples:
VOCs催化氧化性能评价时，采用如图8所示的小型固定床连续流动反应评价装置，VOCs气体和氧气分别进入气体混合装置，混合后进入到反应炉(型号SK2-1-10K)的石英管中，与石英管中的催化剂接触反应，反应后的气体进入气相色谱仪中进行检测，以得出VOCs气体的催化氧化转化率。When evaluating the catalytic oxidation performance of VOCs, a small fixed-bed continuous flow reaction evaluation device as shown in Figure 8 was used. The VOCs gas and oxygen entered the gas mixing device respectively, and then entered the quartz tube of the reaction furnace (model SK2-1-10K) after mixing. In the process, it contacts and reacts with the catalyst in the quartz tube, and the reacted gas enters the gas chromatograph for detection to obtain the catalytic oxidation conversion rate of VOCs gas.
测试时，将0.1g压片过筛得到的40-60目的催化剂装入石英管中(直径6mm)，反应温度通过程序升温反应炉控制，VOCs气体选用丙烷、丙酮或乙酸乙酯三种气体，浓度分别为2000ppm、1000ppm和1000ppm，氧气浓度为20％。空速为18000g·ml·h -1。 During the test, the 40-60 mesh catalyst obtained by sieving 0.1g of tablets was put into a quartz tube (diameter 6mm), the reaction temperature was controlled by a temperature-programmed reaction furnace, and the VOCs gas was selected from three gases of propane, acetone or ethyl acetate. The concentrations were 2000 ppm, 1000 ppm and 1000 ppm, respectively, and the oxygen concentration was 20%. The space velocity was 18000 g·ml·h −1 .
实施例1Example 1
将废旧三元锂电池进行完全放电处理，经过剪切、筛选、机械剥离处理实现正极材料的分离和粉碎；将正极材料粉末加入到强酸(硝酸、硫酸或者氢氟酸)和双氧水的混合溶液中并加热至25-90℃，以促进正极材料中的金属离子的溶解；将混合溶液过滤去除未溶解的不可溶杂质(导电石墨等)，得到正极材料的浸出液。The waste ternary lithium battery is completely discharged, and the positive electrode material is separated and pulverized through shearing, screening and mechanical stripping treatment; the positive electrode material powder is added to the mixed solution of strong acid (nitric acid, sulfuric acid or hydrofluoric acid) and hydrogen peroxide and heated to 25-90° C. to promote the dissolution of metal ions in the positive electrode material; filter the mixed solution to remove undissolved insoluble impurities (conductive graphite, etc.) to obtain the leaching solution of the positive electrode material.
在150mL正极材料浸出液中不断滴加5mol/L的草酸溶液，直到有絮状沉淀产生。剧烈搅拌30min，后静止放置老化12h，所得沉淀抽滤，洗涤至中性，100℃过夜烘干。最后将所得粉末放于马弗炉中空气气氛下300℃煅烧3h，得到CoMnNiO x复合金属氧化物。 A 5 mol/L oxalic acid solution was continuously added dropwise to 150 mL of the positive electrode material leaching solution until flocculent precipitation occurred. Stir vigorously for 30 min, and then stand still for aging for 12 h. The obtained precipitate is filtered with suction, washed until neutral, and dried at 100°C overnight. Finally, the obtained powder was calcined in a muffle furnace at 300° C. for 3 hours in an air atmosphere to obtain a CoMnNiO x composite metal oxide.
将得到的CoMnNiO x复合金属氧化物加入1mol/L的氢氧化钠溶液中，80℃搅拌处理4小时，过滤、洗涤、干燥后得到氧缺陷型复合氧化物，记为催化剂A。将催化剂A分 别用于丙烷、丙酮和乙酸乙酯的催化活性测试中。 The obtained CoMnNiO x composite metal oxide was added to a 1 mol/L sodium hydroxide solution, stirred at 80° C. for 4 hours, filtered, washed and dried to obtain an oxygen-deficient composite oxide, denoted as catalyst A. Catalyst A was used in the catalytic activity test of propane, acetone and ethyl acetate, respectively.
实施例2Example 2
正极材料的浸出液的制备方法同实施例1。The preparation method of the leaching solution of the positive electrode material is the same as that in Example 1.
在150mL正极材料浸出液中不断滴加5mol/L的碳酸钠溶液，直到pH升到10。剧烈搅拌30min，后静止放置老化12h，所得沉淀抽滤，洗涤至中性，100℃过夜烘干。最后将所得粉末放于马弗炉中空气气氛下300℃煅烧3h，得到CoMnNiO x复合金属氧化物。 5 mol/L sodium carbonate solution was continuously added dropwise to 150 mL of the positive electrode material leaching solution until the pH rose to 10. Stir vigorously for 30 min, and then stand still for aging for 12 h. The obtained precipitate is filtered with suction, washed until neutral, and dried at 100°C overnight. Finally, the obtained powder was calcined in a muffle furnace at 300° C. for 3 hours in an air atmosphere to obtain a CoMnNiO x composite metal oxide.
将得到的CoMnNiO x复合金属氧化物加入1mol/L的氢氧化钠溶液中，50℃搅拌处理8小时，过滤、洗涤、干燥后得到氧缺陷型复合氧化物，记为催化剂B。将催化剂B分别用于丙烷、丙酮和乙酸乙酯的催化活性测试中。 The obtained CoMnNiO x composite metal oxide was added to a 1 mol/L sodium hydroxide solution, stirred at 50°C for 8 hours, filtered, washed and dried to obtain an oxygen-deficient composite oxide, denoted as catalyst B. Catalyst B was used in the catalytic activity test of propane, acetone and ethyl acetate, respectively.
实施例3Example 3
正极材料的浸出液的制备方法同实施例1。The preparation method of the leaching solution of the positive electrode material is the same as that in Example 1.
在150mL正极材料浸出液中不断滴加5mol/L的碳酸铵溶液，直到pH升到10。剧烈搅拌30min,后静止放置老化12h，所得沉淀抽滤，洗涤至中性，100℃过夜烘干。最后将所得粉末放于马弗炉中空气气氛下300℃煅烧3h，得到CoMnNiO x复合金属氧化物。 A 5 mol/L ammonium carbonate solution was continuously added dropwise to 150 mL of the positive electrode material leaching solution until the pH rose to 10. Stir vigorously for 30 min, and then stand still for aging for 12 h. The obtained precipitate is filtered with suction, washed until neutral, and dried at 100°C overnight. Finally, the obtained powder was calcined in a muffle furnace at 300° C. for 3 hours in an air atmosphere to obtain a CoMnNiO x composite metal oxide.
将得到的CoMnNiO x复合金属氧化物加入1mol/L的氢氧化钾溶液中，80℃搅拌处理4小时，过滤、洗涤、干燥后得到氧缺陷型复合氧化物，记为催化剂C。将催化剂C分别用于丙烷、丙酮和乙酸乙酯的催化活性测试中。 The obtained CoMnNiOx composite metal oxide was added to a 1 mol/L potassium hydroxide solution, stirred at 80°C for 4 hours, filtered, washed and dried to obtain an oxygen-deficient composite oxide, denoted as catalyst C. Catalyst C was used in the catalytic activity test of propane, acetone and ethyl acetate, respectively.
对比例1Comparative Example 1
正极材料的浸出液的制备方法同实施例1。The preparation method of the leaching solution of the positive electrode material is the same as that in Example 1.
在150mL正极材料浸出液中不断滴加5mol/L的草酸溶液，直到产生絮状沉淀。剧烈搅拌30min，后静止放置老化12h，所得沉淀抽滤，洗涤至中性，100℃过夜烘干。最后将所得粉末放于马弗炉中空气气氛下300℃煅烧3h，得到CoMnNiO x复合金属氧化物，记为催化剂R1。将催化剂R1分别用于丙烷、丙酮和乙酸乙酯的催化活性测试中。 A 5 mol/L oxalic acid solution was continuously added dropwise to 150 mL of the positive electrode material leaching solution until flocculent precipitation occurred. Stir vigorously for 30 min, and then stand still for aging for 12 h. The obtained precipitate is filtered with suction, washed until neutral, and dried at 100°C overnight. Finally, the obtained powder was calcined in a muffle furnace at 300° C. for 3 hours in an air atmosphere to obtain a CoMnNiO x composite metal oxide, which was denoted as catalyst R1. The catalyst R1 was used in the catalytic activity test of propane, acetone and ethyl acetate, respectively.
对比例2Comparative Example 2
正极材料的浸出液的制备方法同实施例1。The preparation method of the leaching solution of the positive electrode material is the same as that in Example 1.
在150mL正极材料浸出液中不断滴加5mol/L的碳酸钠溶液，直到pH升到10。剧烈搅拌30min，后静止放置老化12h，所得沉淀抽滤，洗涤至中性，100℃过夜烘干。最后将所得粉末放于马弗炉中空气气氛下300℃煅烧3h，得到CoMnNiO x复合金属氧化物，记为催化剂R2。将催化剂R2分别用于丙烷、丙酮和乙酸乙酯的催化活性测试中。 5 mol/L sodium carbonate solution was continuously added dropwise to 150 mL of the positive electrode material leaching solution until the pH rose to 10. Stir vigorously for 30 min, and then stand still for aging for 12 h. The obtained precipitate is filtered with suction, washed until neutral, and dried at 100°C overnight. Finally, the obtained powder was calcined in a muffle furnace at 300° C. for 3 hours in an air atmosphere to obtain a CoMnNiO x composite metal oxide, which was denoted as catalyst R2. The catalyst R2 was used in the catalytic activity test of propane, acetone and ethyl acetate, respectively.
下表为实施例1-3和对比例1-2制备的催化剂的VOCs催化降解活性The following table shows the catalytic degradation activities of VOCs of the catalysts prepared in Examples 1-3 and Comparative Examples 1-2
表1Table 1
Figure PCTCN2022094388-appb-000001
Figure PCTCN2022094388-appb-000001
由实施例1-3和对比例1-2的催化氧化结果可以看出，使用碳酸盐作为沉淀剂相比于使用价格昂贵的草酸具有更高的催化氧化活性，VOCs的完全转化温度有所降低。同时，通过将得到的复合金属氧化物通过碱溶液改性去除晶体中的Al和Li等金属阳离子，可以极大的增加复合金属氧化物中的氧缺陷含量(由图2的EPR结果可证明)，从而进一步地促进了催化剂的VOCs催化活性，VOCs的完全降解温度可进一步降低10-20℃。因此，我们创造性的使用碳酸盐和碱溶液改性的制备步骤将废旧三元锂电池正极材料资源化利用得到高性能的VOCs催化净化催化剂。From the catalytic oxidation results of Examples 1-3 and Comparative Examples 1-2, it can be seen that using carbonate as a precipitant has higher catalytic oxidation activity than using expensive oxalic acid, and the complete conversion temperature of VOCs is somewhat higher. reduce. At the same time, by modifying the obtained composite metal oxide by alkaline solution to remove metal cations such as Al and Li in the crystal, the oxygen defect content in the composite metal oxide can be greatly increased (as evidenced by the EPR results in Figure 2) , thereby further promoting the catalytic activity of the catalyst for VOCs, and the complete degradation temperature of VOCs can be further reduced by 10-20 °C. Therefore, we creatively used the preparation steps modified by carbonate and alkaline solution to recycle the cathode materials of waste ternary lithium batteries to obtain high-performance VOCs catalytic purification catalysts.
此外，由图1可知，实施例2中，以碳酸钠作为沉淀剂制备得到的CoMnNiO x复合氧化物，其衍射峰比实施例1以草酸作为沉淀剂制备的CoMnNiO x复合氧化物的衍射峰更宽，可以说明实施例2制备的CoMnNiO x-碳酸钠的结晶度更低，其中含有的氧空位缺陷因此会更多。同理碱处理后的CoMnNiO x-碳酸钠-NaOH也有着宽泛的衍射峰，说明有着丰富的氧空位缺陷。 In addition, it can be seen from Figure 1 that in Example 2, the CoMnNiO x composite oxide prepared by using sodium carbonate as a precipitant has a higher diffraction peak than the CoMnNiO x composite oxide prepared by using oxalic acid as a precipitant in Example 1. It can be explained that the crystallinity of CoMnNiO x -sodium carbonate prepared in Example 2 is lower, and it contains more oxygen vacancy defects. Similarly, CoMnNiO x -sodium carbonate-NaOH after alkali treatment also has broad diffraction peaks, indicating that there are abundant oxygen vacancy defects.
由图3可知：首先，通过正极材料和正极材料-NaOH的活性对比可以看出，NaOH碱溶液处理后的催化剂活性有着明显提升。其次，通过对比实施例1的CoMnNiO x-草酸，实施例2的CoMnNiO x-碳酸钠和CoMnNiO x-碳酸钠-NaOH可以发现，碳酸钠作为沉淀剂时，催化剂活性会比采用传统的草酸沉淀剂活性好，而NaOH碱处理后也进一步对催化剂的活性产生促进效益。 It can be seen from Fig. 3 that: First, the activity comparison of the positive electrode material and the positive electrode material-NaOH shows that the catalyst activity after NaOH alkaline solution treatment is significantly improved. Secondly, by comparing the CoMnNiO x -oxalic acid of Example 1, the CoMnNiO x -sodium carbonate and CoMnNiO x -sodium carbonate-NaOH of Example 2, it can be found that when sodium carbonate is used as a precipitant, the catalyst activity will be higher than the traditional oxalic acid precipitant. The activity is good, and the NaOH alkali treatment also further promotes the activity of the catalyst.
图4进一步证实了使用碳酸盐作为沉淀剂比草酸沉淀剂制备出的催化剂活性好。而图5也进一步证实了碱处理能够进一步提高催化剂的活性。Figure 4 further confirms that the catalyst prepared using carbonate as precipitant is more active than oxalic acid precipitant. Figure 5 also further confirms that the alkali treatment can further improve the activity of the catalyst.
图6表明VOCs燃烧催化剂的比表面积为90-200m 2/g，图7则表明催化剂为5-80nm的介孔结构。 Figure 6 shows that the specific surface area of the VOCs combustion catalyst is 90-200 m 2 /g, and Figure 7 shows that the catalyst has a mesoporous structure of 5-80 nm.
尽管通过参考附图并结合优选实施例的方式对本发明进行了详细描述，但本发明并 不限于此。在不脱离本发明的精神和实质的前提下，本领域普通技术人员可以对本发明的实施例进行各种等效的修改或替换，而这些修改或替换都应在本发明的涵盖范围内/任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到变化或替换，都应涵盖在本发明的保护范围之内。因此，本发明的保护范围应所述以权利要求的保护范围为准。Although the present invention has been described in detail in conjunction with the preferred embodiments with reference to the accompanying drawings, the present invention is not limited thereto. Without departing from the spirit and essence of the present invention, those of ordinary skill in the art can make various equivalent modifications or substitutions to the embodiments of the present invention, and these modifications or substitutions should all fall within the scope of the present invention/any Those skilled in the art can easily think of changes or substitutions within the technical scope disclosed by the present invention, which should all be included within the protection scope of the present invention. Therefore, the protection scope of the present invention should be based on the protection scope of the claims.

Claims (9)

  1. 回用废旧三元锂电池制备VOCs燃烧催化剂的方法，其特征在于，包括以下步骤：The method for preparing VOCs combustion catalyst by reusing waste ternary lithium battery is characterized in that, comprising the following steps:
    1)将废旧三元锂电池进行完全放电处理，经过剪切、筛选、机械剥离处理实现正极材料的分离和粉碎；1) The waste ternary lithium battery is fully discharged, and the positive electrode material is separated and pulverized through shearing, screening, and mechanical peeling treatment;
    2)将步骤1)得到的正极材料粉末加入到强酸和双氧水的混合溶液中；2) adding the positive electrode material powder obtained in step 1) to the mixed solution of strong acid and hydrogen peroxide;
    3)将步骤2)得到的混合溶液过滤去除未溶解的不可溶杂质，得到正极材料的浸出液；3) filtering the mixed solution obtained in step 2) to remove undissolved insoluble impurities to obtain the leachate of the positive electrode material;
    4)向步骤3)所得的浸出液中加入碳酸盐溶液促进过渡金属Co 2+、Mn 2+和Ni 2+产生沉淀，随后过滤、洗涤、干燥和煅烧后得到CoMnNiO x复合氧化物； 4) adding carbonate solution to the leaching solution obtained in step 3) to promote the precipitation of transition metals Co 2+ , Mn 2+ and Ni 2+ , and then filtering, washing, drying and calcining to obtain CoMnNiO x composite oxide;
    5)将步骤4)得到的CoMnNiO x复合氧化物加入碱溶液中，搅拌处理后得到高氧缺陷的复合氧化物催化剂。 5) The CoMnNiO x composite oxide obtained in step 4) is added to the alkaline solution, and after stirring treatment, a composite oxide catalyst with high oxygen deficiency is obtained.
  2. 如权利要求1所述的方法，其特征在于，步骤2)中，所述强酸是硝酸、硫酸或者氢氟酸。The method of claim 1, wherein, in step 2), the strong acid is nitric acid, sulfuric acid or hydrofluoric acid.
  3. 如权利要求1所述的方法，其特征在于，步骤2)中，将混合溶液加热到25-90℃。The method of claim 1, wherein, in step 2), the mixed solution is heated to 25-90°C.
  4. 如权利要求1所述的方法，其特征在于，步骤4)中，所述碳酸盐溶液为碳酸钠、碳酸氢钠、碳酸铵、碳酸钾、碳酸氢钾或者碳酸氢铵，浓度为0.1-10mol/L。The method of claim 1, wherein in step 4), the carbonate solution is sodium carbonate, sodium bicarbonate, ammonium carbonate, potassium carbonate, potassium bicarbonate or ammonium bicarbonate, and the concentration is 0.1- 10mol/L.
  5. 如权利要求1所述的方法，其特征在于，步骤4)中，煅烧温度为200-600℃。The method of claim 1, wherein, in step 4), the calcination temperature is 200-600°C.
  6. 如权利要求1所述的方法，其特征在于，步骤5)中，所述碱溶液为氢氧化钠或氢氧化钾溶液，浓度为0.1-5mol/L。The method of claim 1, wherein, in step 5), the alkaline solution is sodium hydroxide or potassium hydroxide solution, and the concentration is 0.1-5mol/L.
  7. 如权利要求1所述的方法，其特征在于，步骤5)中，搅拌温度为25-95℃。The method of claim 1, wherein, in step 5), the stirring temperature is 25-95°C.
  8. 利用如权利要求1-7任一项所述的方法制备得到的VOCs燃烧催化剂。The VOCs combustion catalyst prepared by the method according to any one of claims 1-7 is utilized.
  9. 如权利要求8所述的VOCs燃烧催化剂，其特征在于，VOCs燃烧催化剂为5-80nm的介孔结构，比表面积为90-200m 2/g。 The VOCs combustion catalyst according to claim 8, wherein the VOCs combustion catalyst has a mesoporous structure of 5-80 nm and a specific surface area of 90-200 m 2 /g.
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