CN113713828B - VOCs combustion catalyst prepared by recycling waste ternary lithium batteries and preparation method thereof - Google Patents
VOCs combustion catalyst prepared by recycling waste ternary lithium batteries and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- 239000012855 volatile organic compound Substances 0.000 title claims abstract description 40
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 28
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000002699 waste material Substances 0.000 title claims abstract description 21
- 238000002485 combustion reaction Methods 0.000 title claims abstract description 14
- 238000004064 recycling Methods 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000002131 composite material Substances 0.000 claims abstract description 34
- 239000003513 alkali Substances 0.000 claims abstract description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000001301 oxygen Substances 0.000 claims abstract description 18
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 18
- 230000007547 defect Effects 0.000 claims abstract description 15
- 238000001914 filtration Methods 0.000 claims abstract description 14
- 239000012535 impurity Substances 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 43
- 239000000243 solution Substances 0.000 claims description 35
- 239000007774 positive electrode material Substances 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 23
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 22
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 11
- 235000017550 sodium carbonate Nutrition 0.000 claims description 11
- 238000002386 leaching Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 239000010405 anode material Substances 0.000 claims description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 239000001099 ammonium carbonate Substances 0.000 claims description 5
- 229910052723 transition metal Inorganic materials 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 3
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 3
- 208000028659 discharge Diseases 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 238000012216 screening Methods 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 238000010008 shearing Methods 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical class Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 claims description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 28
- 230000004048 modification Effects 0.000 abstract description 5
- 238000012986 modification Methods 0.000 abstract description 5
- 229910021645 metal ion Inorganic materials 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 3
- 238000007599 discharging Methods 0.000 abstract description 2
- 230000001376 precipitating effect Effects 0.000 abstract description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 33
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 24
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 24
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000013067 intermediate product Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 235000006408 oxalic acid Nutrition 0.000 description 11
- 238000007254 oxidation reaction Methods 0.000 description 11
- 229910044991 metal oxide Inorganic materials 0.000 description 10
- 150000004706 metal oxides Chemical class 0.000 description 10
- 230000003647 oxidation Effects 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 239000001294 propane Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 7
- 230000010718 Oxidation Activity Effects 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 239000012467 final product Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 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 5
- 230000032683 aging Effects 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000007084 catalytic combustion reaction Methods 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000012716 precipitator Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 231100000206 health hazard Toxicity 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
-
- B01J35/613—
-
- B01J35/615—
-
- B01J35/647—
-
- B01J35/651—
-
- 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
Abstract
The invention discloses a VOCs combustion catalyst prepared by recycling waste ternary lithium batteries and a preparation method thereof, and belongs to the technical field of catalyst preparation. The waste ternary lithium battery is subjected to discharging, disassembling, mechanical stripping, acid-soluble metal ions, filtering and removing insoluble impurities, salifying and precipitating, and alkali solution modification to obtain CoMnNiO containing high oxygen defects x The composite oxide realizes the efficient catalytic purification of VOCs.
Description
Technical Field
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.
Background
Ternary lithium batteries (TLIBs) are widely applied to the fields of consumer electronics markets, electric automobiles, power grid energy storage and the like because of the advantages of high energy density, high storage capacity, good rate capability and the like. The total usage capacity of global lithium batteries (LIBs) of 2016 has reached 80GWh, about six million single cells, as counted by Avsenni energy company. With the further increase of the demand of electric automobiles, the ternary lithium batteries will meet the new growing demand. However, the safe recovery and green disposal of the waste ternary lithium batteries are still key links in the development of the lithium battery industry.
Volatile Organic Compounds (VOCs) are receiving considerable government and public attention due to large pollution emissions, severe environmental impact and serious human health hazards. Among VOCs control techniques, catalytic oxidation is considered as a technique having a wide range of applications due to its advantages such as high efficiency, energy saving, and low toxic by-products. In recent years, such as Co 3 O 4 、MnO 2 Oxidation of transition metals such as NiOThe catalyst has excellent oxidation-reduction performance and good active oxygen fluidity, and therefore has good catalytic performance potential in the catalytic oxidation reaction of VOCs. Because the TLIBs have relatively high-price Co and Ni elements, if the transition metal elements in the TLIBs can be recycled for preparing the composite oxide type VOCs catalyst, the method has better environmental and economic benefits in terms of recycling the waste TLIBs and pollution control of the VOCs.
Although Chinese patent CN107694559B discloses a similar method for preparing toluene degradation catalyst by recycling waste TLIBs anode materials, only MnO with lower economic value is recycled in the method 2 Co and Ni elements cannot be effectively utilized. In general, the recycled TLIBs positive electrode material further contains metal elements such as Li and Al, which have an inert effect on the catalytic oxidation reaction, and oxygen vacancy defects are considered to be important factors capable of effectively promoting the catalytic activity of the composite oxide. Therefore, the method for removing the inert metal elements and improving the defect content on the composite oxide simply, conveniently and quickly in the process of recycling the waste LIBs positive electrode materials to prepare the catalyst has important significance for improving the catalytic oxidation activity of VOCs.
Disclosure of Invention
The invention aims to solve the technical problems that: overcoming the defects of the prior art, and providing a VOCs combustion catalyst prepared by recycling waste ternary lithium batteries and a preparation method thereof, wherein the waste ternary lithium batteries are subjected to the processes of discharging, disassembling, mechanical stripping, acid-soluble metal ions, filtering and removing insoluble impurities, salifying and precipitating, and alkali solution modification to obtain CoMnNiO containing high oxygen defects x The composite oxide realizes the efficient catalytic purification of VOCs.
In a first aspect, the invention provides a method for preparing a VOCs combustion catalyst by recycling waste ternary lithium batteries, comprising the following steps:
1) Carrying out complete discharge treatment on the waste ternary lithium batteries, and carrying out shearing, screening and mechanical stripping treatment to realize separation and crushing of the positive electrode materials;
2) Adding the positive electrode material powder obtained in the step 1) into a mixed solution of strong acid and hydrogen peroxide;
3) Filtering the mixed solution obtained in the step 2) to remove undissolved insoluble impurities, thereby obtaining a leaching solution of the anode material;
4) Adding carbonate solution into the leaching solution obtained in the step 3) to promote transition metal Co 2+ 、Mn 2+ And Ni 2+ Precipitation, followed by filtration, washing, drying and calcination to give CoMnNiO x A composite oxide;
5) The CoMnNiO obtained in the step 4) is processed x Adding the composite oxide into an alkali solution, and stirring to obtain the composite oxide catalyst with high oxygen defect.
The obtained composite oxide catalyst with high oxygen defect at least comprises five metal elements of cobalt, manganese, nickel, aluminum and lithium, and after the alkali treatment modification in the step 5), the molar ratio of the three metal elements of cobalt, manganese and nickel to all the metal elements is at least 99%.
Considering that Al and Li can be dissolved by alkali solution, and oxides of Co, mn and Ni can not react with the alkali solution, the alkali solution etching one-step precipitation method is adopted to obtain Al and Li elements in the composite oxide, and further the defect enhancement effect caused by the dissolution of Al and Li cations can greatly promote the catalytic oxidation activity of VOCs of the obtained composite oxide. Therefore, the composite oxide prepared by the alkali solution post-treatment method has the advantages of good low-temperature activity, strong stability, suitability for various VOCs reactions, and the like.
Preferably, in step 2), the strong acid is nitric acid, sulfuric acid or hydrofluoric acid.
Preferably, in step 2), the mixed solution is heated to 25-90 ℃.
Preferably, in the step 4), the carbonate solution is sodium carbonate, sodium bicarbonate, ammonium carbonate, potassium bicarbonate or ammonium bicarbonate, and the concentration is 0.1-10mol/L.
Preferably, in step 4), the calcination temperature is 200-600 ℃.
Preferably, in the step 5), the alkali solution is sodium hydroxide or potassium hydroxide solution, and the concentration is 0.1-5mol/L.
Preferably, in step 5), the stirring temperature is 25-95 ℃.
In a second aspect, the present invention provides a VOCs combustion catalyst prepared by the above method.
Preferably, the VOCs combustion catalyst has a mesoporous structure of 5-80nm and a specific surface area of 90-200m 2 /g。
The term "catalytic oxidation" as used herein refers to the oxidation of VOCs by oxygen to carbon dioxide and water under the action of a catalyst, without exhibiting macroscopic flame combustion. In the catalytic oxidation of VOCs, the temperature corresponding to the target VOCs when the conversion rate of catalytic oxidation is 10% is referred to as the "light-off temperature" and is denoted as T 10 The method comprises the steps of carrying out a first treatment on the surface of the The temperature corresponding to the target VOCs with the conversion rate of 90% is called as the 'complete conversion temperature', and is marked as T 90 。
Compared with the prior art, the invention has the following beneficial effects:
the invention adopts the waste ternary lithium electron anode material to realize the recycling of transition metal elements in the waste ternary lithium electron anode material after a series of treatment processes to obtain CoMnNiO x A composite oxide. Wherein, the activity of the catalyst prepared by taking carbonate as a precipitator is better than that of the catalyst prepared by oxalic acid precipitator; in addition, the alkali treatment process achieves an increase in oxygen defects in the composite oxide, which exhibits excellent catalytic activity in catalytic combustion reactions of typical VOCs contaminants such as acetone, ethyl acetate and propane. The high-performance VOCs catalyst prepared by using the waste ternary lithium battery anode material not only realizes recycling recovery of the waste lithium battery, but also has excellent VOCs catalytic combustion application prospect.
Drawings
FIG. 1 is a ternary lithium battery positive electrode material and CoMnNiO prepared according to the present invention x XRD pattern of the composite oxide, wherein each curve is represented by, in order from bottom to top: li (CoMnNi) O obtained after mechanical disassembly and calcination for carbon removal 2 Ternary positive electrode material; adding the obtained positive electrode material into 1mol/L sodium hydroxide solution, treating for 4 hours at 80 ℃, filtering, washing and drying to obtain positive electrode material-NaOH; the intermediate product prepared in example 1; the intermediate product prepared in example 2; the final product prepared in example 2.
FIG. 2 shows CoMnNiO before and after alkali treatment according to the present invention x The EPR results of the oxygen vacancy characterization of the composite oxide are compared, wherein the two curves represent, in order from bottom to top, the intermediate product prepared in example 2, and the final product prepared in example 2.
FIG. 3 shows the propane catalytic oxidation activity curve of the catalyst at various stages of treatment, wherein the positive electrode material curve represents Li (CoMnNi) O obtained after mechanical disassembly and calcination for removal of carbon 2 Ternary positive electrode material; the positive electrode material-NaOH curve represents that the obtained positive electrode material is added into 1mol/L sodium hydroxide solution, treated for 4 hours at 80 ℃, filtered, washed and dried to obtain the positive electrode material-NaOH; coMnNiO x The oxalic acid curve represents the intermediate product of example 1; coMnNiO x The sodium carbonate curve represents the intermediate product of example 2; coMnNiO x The sodium carbonate-NaOH curve represents the final product of example 2.
FIG. 4 shows CoMnNiO obtained with different precipitants x The compound oxide versus acetone catalytic oxidation activity curves, wherein two curves represent the intermediate product prepared in example 2 and the intermediate product prepared in example 1 from left to right respectively.
FIG. 5 shows CoMnNiO obtained before and after alkali treatment x The compound oxide versus ethyl acetate catalytic oxidation activity curves, two of which represent, from left to right, the final product prepared in example 2, the intermediate product prepared in example 2, respectively.
FIG. 6 is a nitrogen adsorption and desorption curve for a catalyst in which CoMnNiO x The oxalic acid curve represents the intermediate product of example 1; coMnNiO x The sodium carbonate curve represents the intermediate product of example 2; coMnNiO x The sodium carbonate-NaOH curve represents the final product of example 2.
FIG. 7 is a pore size distribution plot of a catalyst in which CoMnNiO x The oxalic acid curve represents the intermediate product of example 1; coMnNiO x The sodium carbonate curve represents the intermediate product of example 2; coMnNiO x The sodium carbonate-NaOH curve represents the final product of example 2.
FIG. 8 is a schematic structural view of a small fixed bed continuous flow reaction evaluating apparatus according to the present invention.
Detailed Description
Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
Catalyst evaluation method used in the following examples:
when VOCs catalytic oxidation performance is evaluated, a small fixed bed continuous flow reaction evaluation device shown in fig. 8 is adopted, VOCs gas and oxygen respectively enter a gas mixing device, after mixing, enter a quartz tube of a reaction furnace (model SK 2-1-10K), contact with a catalyst in the quartz tube for reaction, and the reacted gas enters a gas chromatograph for detection, so that the catalytic oxidation conversion rate of the VOCs gas is obtained.
During testing, 0.1g of the catalyst with 40-60 meshes obtained by tabletting and sieving is filled into a quartz tube (diameter is 6 mm), the reaction temperature is controlled by a temperature programming reaction furnace, three gases of propane, acetone or ethyl acetate are adopted as VOCs gas, the concentration is 2000ppm, 1000ppm and 1000ppm respectively, and the oxygen concentration is 20%. Space velocity of 18000 g.ml.h -1 。
Example 1
Carrying out complete discharge treatment on the waste ternary lithium batteries, and carrying out shearing, screening and mechanical stripping treatment to realize separation and crushing of the positive electrode materials; adding the positive electrode material powder into a mixed solution of strong acid (nitric acid, sulfuric acid or hydrofluoric acid) and hydrogen peroxide, and heating to 25-90 ℃ to promote the dissolution of metal ions in the positive electrode material; filtering the mixed solution to remove undissolved insoluble impurities (conductive graphite and the like) and obtaining the leaching solution of the positive electrode material.
And continuously dripping 5mol/L oxalic acid solution into 150mL of positive electrode material leaching solution until flocculent precipitate is generated. Stirring vigorously for 30min, standing still, aging for 12h, filtering the obtained precipitate, washing to neutrality, and drying at 100deg.C overnight. Finally, the obtained powder is put into a muffle furnace to be calcined for 3 hours at 300 ℃ in the air atmosphere to obtain CoMnNiO x A composite metal oxide.
The obtained CoMnNiO x The composite metal oxide is added into 1mol/L sodium hydroxide solution,stirring at 80 ℃ for 4 hours, filtering, washing and drying to obtain the oxygen-deficient composite oxide, which is denoted as a catalyst A. Catalyst a was used in the catalytic activity tests for propane, acetone and ethyl acetate, respectively.
Example 2
The preparation method of the leachate of the positive electrode material is the same as in example 1.
5mol/L sodium carbonate solution is continuously added dropwise into 150mL of positive electrode material leaching solution until the pH value is increased to 10. Stirring vigorously for 30min, standing still, aging for 12h, filtering the obtained precipitate, washing to neutrality, and drying at 100deg.C overnight. Finally, the obtained powder is put into a muffle furnace to be calcined for 3 hours at 300 ℃ in the air atmosphere to obtain CoMnNiO x A composite metal oxide.
The obtained CoMnNiO x The composite metal oxide is added into 1mol/L sodium hydroxide solution, stirred at 50 ℃ for 8 hours, filtered, washed and dried to obtain the oxygen defect type composite oxide, which is denoted as a catalyst B. Catalyst B was used in the catalytic activity tests for propane, acetone and ethyl acetate, respectively.
Example 3
The preparation method of the leachate of the positive electrode material is the same as in example 1.
5mol/L ammonium carbonate solution is continuously added dropwise into 150mL of positive electrode material leaching solution until the pH value is increased to 10. Stirring vigorously for 30min, standing still, aging for 12h, filtering the obtained precipitate, washing to neutrality, and drying at 100deg.C overnight. Finally, the obtained powder is put into a muffle furnace to be calcined for 3 hours at 300 ℃ in the air atmosphere to obtain CoMnNiO x A composite metal oxide.
The obtained CoMnNiO x The composite metal oxide is added into 1mol/L potassium hydroxide solution, stirred at 80 ℃ for 4 hours, filtered, washed and dried to obtain the oxygen defect type composite oxide, which is denoted as a catalyst C. Catalyst C was used in the catalytic activity tests for propane, acetone and ethyl acetate, respectively.
Comparative example 1
The preparation method of the leachate of the positive electrode material is the same as in example 1.
Continuously dripping 5mol/L oxalic acid solution into 150mL positive electrode material leaching solution untilUntil a flocculent precipitate is produced. Stirring vigorously for 30min, standing still, aging for 12h, filtering the obtained precipitate, washing to neutrality, and drying at 100deg.C overnight. Finally, the obtained powder is put into a muffle furnace to be calcined for 3 hours at 300 ℃ in the air atmosphere to obtain CoMnNiO x The composite metal oxide is denoted as catalyst R1. Catalyst R1 was used in the catalytic activity tests for propane, acetone and ethyl acetate, respectively.
Comparative example 2
The preparation method of the leachate of the positive electrode material is the same as in example 1.
5mol/L sodium carbonate solution is continuously added dropwise into 150mL of positive electrode material leaching solution until the pH value is increased to 10. Stirring vigorously for 30min, standing still, aging for 12h, filtering the obtained precipitate, washing to neutrality, and drying at 100deg.C overnight. Finally, the obtained powder is put into a muffle furnace to be calcined for 3 hours at 300 ℃ in the air atmosphere to obtain CoMnNiO x The composite metal oxide is denoted as catalyst R2. Catalyst R2 was used in the catalytic activity tests of propane, acetone and ethyl acetate, respectively.
The following Table shows the VOCs catalytic degradation activity of the catalysts prepared in examples 1-3 and comparative examples 1-2
TABLE 1
As can be seen from the results of the catalytic oxidation of examples 1-3 and comparative examples 1-2, the use of carbonate as a precipitant has a higher catalytic oxidation activity than the use of expensive oxalic acid, and the complete conversion temperature of VOCs is reduced. Meanwhile, the obtained composite metal oxide is modified by alkali solution to remove metal cations such as Al, li and the like in the crystal, so that the oxygen defect content in the composite metal oxide can be greatly increased (as can be proved by the EPR result of FIG. 2), the catalytic activity of the VOCs of the catalyst is further promoted, and the complete degradation temperature of the VOCs can be further reduced by 10-20 ℃. Therefore, the preparation steps of modifying carbonate and alkali solution creatively utilize the anode material of the waste ternary lithium battery to obtain the high-performance VOCs catalytic purification catalyst.
Furthermore, as can be seen from FIG. 1, in example 2, coMnNiO was prepared using sodium carbonate as a precipitant x Composite oxide having diffraction peak ratio of CoMnNiO prepared in example 1 using oxalic acid as precipitant x The broader diffraction peaks of the composite oxide can be used to illustrate the CoMnNiO prepared in example 2 x Sodium carbonate has a lower crystallinity and therefore contains more oxygen vacancy defects. CoMnNiO after alkali treatment x Sodium carbonate-NaOH also has a broad diffraction peak, indicating a rich oxygen vacancy defect.
As can be seen from fig. 3: firstly, the activity comparison of the positive electrode material and the positive electrode material NaOH can show that the activity of the catalyst after being treated by NaOH alkali solution is obviously improved. Next, by CoMnNiO of comparative example 1 x Oxalic acid, coMnNiO of example 2 x Sodium carbonate and CoMnNiO x Sodium carbonate-NaOH it was found that sodium carbonate as precipitant would have better catalyst activity than conventional oxalic acid precipitants, whereas NaOH alkali treatment would have further promoting benefits on catalyst activity.
Figure 4 further demonstrates that the catalyst prepared using carbonate as the precipitant has better activity than oxalic acid precipitant. And figure 5 further demonstrates that the base treatment can further increase the activity of the catalyst.
FIG. 6 shows that the specific surface area of the VOCs combustion catalyst is 90-200m 2 FIG. 7 shows that the catalyst has a mesoporous structure of 5-80 nm.
Although the present invention has been described in detail by way of preferred embodiments with reference to the accompanying drawings, the present invention is not limited thereto. Various equivalent modifications and substitutions may be made in the embodiments of the present invention by those skilled in the art without departing from the spirit and scope of the present invention, and it is intended that all such modifications and substitutions be within the scope of the present invention/be within the scope of the present invention as defined by the appended claims. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (9)
1. The method for preparing the VOCs combustion catalyst by recycling the waste ternary lithium battery is characterized by comprising the following steps of:
1) Carrying out complete discharge treatment on the waste ternary lithium batteries, and carrying out shearing, screening and mechanical stripping treatment to realize separation and crushing of the positive electrode materials;
2) Adding the positive electrode material powder obtained in the step 1) into a mixed solution of strong acid and hydrogen peroxide;
3) Filtering the mixed solution obtained in the step 2) to remove undissolved insoluble impurities, thereby obtaining a leaching solution of the anode material;
4) Adding carbonate solution into the leaching solution obtained in the step 3) to promote transition metal Co 2+ 、Mn 2+ And Ni 2+ Precipitation, followed by filtration, washing, drying and calcination to give CoMnNiO x A composite oxide;
5) The CoMnNiO obtained in the step 4) is processed x Adding the composite oxide into an alkali solution, and stirring to obtain the composite oxide catalyst with high oxygen defect.
2. The method of claim 1, wherein in step 2), the strong acid is nitric acid, sulfuric acid, or hydrofluoric acid.
3. The method according to claim 1, wherein in step 2), the mixed solution is heated to 25-90 ℃.
4. The method of claim 1, wherein in step 4), the carbonate solution is sodium carbonate, sodium bicarbonate, ammonium carbonate, potassium bicarbonate or ammonium bicarbonate at a concentration of 0.1 to 10mol/L.
5. The method according to claim 1, wherein in step 4), the calcination temperature is 200 to 600 ℃.
6. The method according to claim 1, wherein in step 5), the alkali solution is sodium hydroxide or potassium hydroxide solution at a concentration of 0.1 to 5mol/L.
7. The method according to claim 1, wherein in step 5), the stirring temperature is 25 to 95 ℃.
8. A VOCs combustion catalyst prepared by the method of any one of claims 1-7.
9. The VOCs combustion catalyst of claim 8, wherein the VOCs combustion catalyst has a mesoporous structure of 5-80nm and a specific surface area of 90-200m 2 /g。
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