CN115504537A - Waste liquid treatment method for wet-process coated anode material - Google Patents
Waste liquid treatment method for wet-process coated anode material Download PDFInfo
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The application provides a waste liquid treatment method for a wet-process coated anode material, which comprises the following steps: providing a suspension comprising a positive electrode material and a coating solution comprising a soluble salt, wherein the soluble salt comprises at least one of a metal compound or a fluorine-containing salt; mixing the suspension and the coating solution, reacting to obtain a reaction solution, and carrying out solid-liquid separation to obtain a waste liquid; pumping the waste liquid and the extract liquid into a first microchannel reactor from different ports respectively for extraction reaction for 0.05-5min, inputting the reacted first mixed liquid into a first liquid separation tower, and separating out an organic phase loaded with metal ions and wastewater; and pumping the organic phase and the acid solution loaded with the metal ions into a second microchannel reactor from different ports respectively for carrying out back extraction reaction for 0.05-5min to obtain a second mixed solution, inputting the second mixed solution into a second liquid separation tower, and separating the second mixed solution from the second liquid separation tower to obtain an extraction liquid and a metal salt solution.
Description
Technical Field
The application relates to the technical field of waste liquid treatment, in particular to a waste liquid treatment method for wet-process coating of a positive electrode material.
Background
With the rapid rise of new energy industries, the lithium battery cathode material has wider and wider application. The lithium battery anode material mainly comprises a ternary anode material (NCM, NCA), lithium iron phosphate (LFP) and Lithium Cobaltate (LCO). The three anode materials show different electrochemical performances due to the difference of respective element compositions and material structures. Lithium cobaltate is widely applied to the fields of 3C, electric vehicles, electric tools, energy storage, wearable electronic products and the like due to high capacity, high compaction density and high energy density. The lithium iron phosphate has the characteristics of high cycle performance, high safety performance, low cost, environmental friendliness and the like, so that the lithium iron phosphate has a prominent application prospect in power lithium ion batteries. The ternary positive electrode material has the characteristics of high energy density and excellent cycle performance, and is widely applied to the large-scale power battery market of electric vehicles and the like.
However, the above-mentioned cathode material in a lithium ion battery is susceptible to phase transition at high voltage, which causes problems of deterioration of cycle performance, structural collapse of the material, and mixed arrangement of metal cations, resulting in poor rate performance, excessive lithium removal capacity decrease, and high-temperature gassing.
In order to solve the problems under high voltage, a layer of metal oxide can be coated on the surface of the anode material, and the metal oxide can play a role in stabilizing the structure and improve the phenomenon that the anode material in the lithium ion battery has phase change under high voltage. At present, the anode material is modified by a dry coating method. The dry coating is to realize the coating of the anode material by forming a solid solution by the coating solution and the anode material at high temperature, and belongs to high-temperature solid-phase sintering, and the dry coating is difficult to uniformly coat the anode material.
The wet coating achieves the purpose of coating the anode material by using the coating solution on the surface of the anode material through liquid phase reaction, and effectively solves the problem of poor uniformity of the dry coating. The wet coating requires that the anode material is prepared into suspension and added into a reaction kettle for coating reaction. In the wet coating process, the mixed liquid synthesized in the reaction kettle is subjected to solid-liquid separation, and the separated solid is further treated to obtain the coated anode material, however, the waste liquid of the solid-liquid separation needs to be extracted and recovered by an extraction tank and an extraction tower, and the extraction flow of the extraction and recovery mode is long, and the extraction efficiency is low.
Disclosure of Invention
In view of the above, the present application provides a method for treating waste liquid of a wet-process coated positive electrode material.
In order to achieve the above object, the present application provides a waste liquid treatment method for wet coating a positive electrode material, the waste liquid treatment method comprising: providing a suspension comprising a positive electrode material and a coating solution comprising soluble salts, wherein the soluble salts comprise at least one of metal compounds or fluorine-containing salts, and the metal compounds comprise at least one of metal sulfates, metal acetates, metal nitrates, metal chlorides or fluorine-containing salts; mixing the suspension and the coating solution and reacting to obtain a reaction solution; carrying out solid-liquid separation on the reaction liquid to obtain waste liquid;
pumping the waste liquid and the extraction liquid into a first microchannel reactor from different ports respectively for extraction reaction, wherein the reaction time of the waste liquid and the extraction liquid in the first microchannel reactor is 0.05-5min, inputting a first mixed solution after the reaction into a first liquid separation tower, and separating an organic phase loaded with metal ions and wastewater from the first liquid separation tower by the first mixed solution;
pumping the organic phase loaded with the metal ions and the acid solution into a second microchannel reactor from different ports respectively for carrying out back extraction reaction, wherein the organic phase loaded with the metal ions and the acid solution react in the second microchannel reactor for 0.05-5min to obtain a second mixed solution, inputting the second mixed solution into a second liquid separation tower, and separating the second mixed solution from the second liquid separation tower to obtain the extraction liquid and the metal salt solution.
In some embodiments, the reaction temperature of the spent liquor and the extract in the first microchannel reactor is from 25 ℃ to 50 ℃.
In some embodiments, the first microchannel reactor and the second microchannel reactor each have a feed end internal diameter of 2 to 20mm and a discharge end internal diameter of 2 to 40mm.
In some embodiments, the pressure within the first microchannel reactor is from 0.10 to 1Mpa.
In some embodiments, the pressure within the second microchannel reactor is from 0.10 to 1Mpa.
In some embodiments, the waste liquid treatment method further comprises: and adding an alkaline solution into the metal salt solution, and adjusting the pH of the metal salt solution to be the same as that of the coating solution.
In some embodiments, the step of mixing and reacting the suspension and the coating solution specifically comprises: and pumping the suspension and the coating solution into a third microchannel reactor from different ports respectively, wherein the suspension and the coating solution react in the third microchannel reactor for 0.5-20min.
In some embodiments, the reaction temperature of the suspension and the coating solution in the third microchannel reactor is 30 to 80 ℃.
In some embodiments, the acid solution is any one of sulfuric acid, acetic acid, nitric acid, hydrochloric acid, oxalic acid, and the anion of the acid solution is the same as the anion in the coating solution.
In some embodiments, the extraction solution comprises one of bis (2-ethylhexyl) phosphate, mono-2-ethylhexyl 2-phosphate, a primary secondary amine, tributyl phosphate, or bis (2, 4-trimethylpentyl) phosphinic acid.
In this application, after accomplishing the cladding of cathode material, the separation obtains the waste liquid, extract the waste liquid through first microchannel reactor, in order to extract the metal ion in the waste liquid to the extraction liquid, obtain the organic phase of load metal ion, and further in the organic phase metal ion strip of load metal ion to the acid solution through second microchannel reactor, obtain metal salt solution and extraction liquid, metal salt solution can be utilized as cladding solution once more, the extraction liquid can be regarded as once more to the extractant of recovery, realize metal ion's recovery and reuse. Meanwhile, the first microchannel reactor and the second microchannel reactor enable the molecular diffusion distance between two-phase fluids to be reduced under the shearing force action between the inner wall of the microchannel reactor and the two-phase fluids, so that the mass transfer rate between the two-phase fluids is improved, the ion exchange reaction between the two-phase fluids is rapidly realized through interface diffusion, the recovery rate of metal ions is further improved, the extraction and back extraction time is shortened, and the extraction efficiency is improved; moreover, the first micro-channel reactor and the second micro-channel reactor are simple in structure, and the process of the waste liquid treatment method can be simplified.
Description of the main elements
Third microchannel reactor 350
Extraction liquid tank 120
First microchannel reactor 150
First liquid separation tower 160
Second microchannel reactor 250
Second liquid separation tower 260
Drawings
Fig. 1 is a schematic flow diagram of a waste liquid treatment method provided by the present application.
Detailed Description
The following describes embodiments of the present invention in detail. The embodiments described below with reference to the accompanying drawings are illustrative only for the purpose of explaining the present invention, and are not to be construed as limiting the present invention.
In the description of the specification, reference to the description of "one embodiment," "some embodiments," "an example," "a specific example," or "some examples" or the like means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The application provides a waste liquid treatment method for a wet-process coated positive electrode material, which comprises the following steps:
s1, providing a positive electrode material, adding the positive electrode material into a first solvent, and stirring to obtain a suspension; providing a coating solution, wherein the coating solution comprises a soluble salt and a second solvent, the soluble salt comprises at least one of a metal compound or a fluorine-containing salt, and the metal compound comprises at least one of a metal sulfate, a metal acetate, a metal nitrate or a metal chloride.
In some embodiments, the metallic element in the metallic compound comprises one or more of titanium, aluminum, tungsten, yttrium, lanthanum, nickel, hafnium, manganese, copper, or zirconium. The second solvent includes water. Wherein the fluorine-containing salt may be ammonium fluoride. The tungstate may be ammonium tungstate.
In some embodiments, the first solvent comprises one or more of water, methanol, ethanol, isopropanol, n-butanol, isobutanol, cycloethanol, acetone, cyclohexanol, diethyl phthalate, glycerol, quinoline, and 2-ethylhexanol.
In some embodiments, the positive electrode material is one of a ternary or quaternary positive electrode material, a lithium-rich manganese-based positive electrode material, lithium cobaltate, lithium manganate, sodium cobaltate, and lithium iron phosphate positive electrode material.
In the turbid liquid of this application, because during the cathode material who prepares among the prior art, add alkali lye in the raw materials, through high temperature sintering back, make the cathode material surface can remain alkali, consequently, the cathode material's in the turbid liquid surface can produce a large amount of hydroxyl ions, can react with the metal compound of follow-up joining and form the precipitated salt.
In some embodiments, the solid-liquid volume ratio in the suspension is 1 to 4, in this range to better disperse the positive electrode material in water. If the solid-liquid volume ratio in the suspension is greater than 4, the content of the positive electrode material in the suspension is too high, which affects the dispersibility of the positive electrode material and causes the positive electrode material in the subsequent suspension to agglomerate. If the volume ratio of solid to liquid in the suspension is less than 1, the solid content in the suspension is low, a large amount of water is generated in the subsequent treatment process, and the production efficiency is reduced.
In some embodiments, an alkaline solution, such as at least one of sodium hydroxide (e.g., liquid alkali), potassium hydroxide, or ammonia, is further added to the suspension to adjust the pH of the suspension to 8-13, thereby improving the coating stability of the subsequent coating solution and the positive electrode material in the suspension. In some embodiments, the pH may be 8,9, 10, 11, 12, or 13.
In some embodiments, the concentration of the coating solution is 0.5 to 2mol/L. The concentration of the coating solution is set according to the coating amount of the subsequent composite material.
S2, referring to the figure 1, mixing the suspension and the coating solution and reacting to obtain a reaction solution; and carrying out solid-liquid separation on the reaction liquid to obtain filter residue and waste liquid.
In some embodiments, drying the filter residue to obtain an intermediate, placing the intermediate in an air atmosphere at 500-1000 ℃, and sintering for 4-8h to obtain the composite material.
In some embodiments, the suspension and the coating solution are pumped into a third microchannel reactor 350 from different ports, respectively, and the suspension and the coating solution are subjected to a coating reaction in the third microchannel reactor 350 for 0.5-20min to obtain the reaction solution, and the reaction solution flows out from a discharge end of the third microchannel reactor 350.
In this step, the suspension and the coating solution are mixed in the third microchannel reactor 350, and hydroxide on the surface of the positive electrode material in the suspension and metal ions of the metal compound undergo a coprecipitation reaction to form a uniform precipitated salt on the surface of the positive electrode material, or a fluorine-containing salt (such as ammonium fluoride) in the coating solution is directly adsorbed onto the surface of the positive electrode material, so that the surface of the positive electrode material is coated with a layer of coating film, that is, the coating of the positive electrode material is completed in the third microchannel reactor 350.
Simultaneously, in this application, can also realize the incessant feeding of turbid liquid and cladding solution and the incessant ejection of compact of the mixed liquid after the reaction through adopting third microchannel reactor 350, realize the continuous mobility production of cladding cathode material, carry out the cladding to the cathode material who lasts to add.
In some embodiments, the reaction time may be 0.5min, 1min, 2min, 3min, 5min, 8min, 10min, 12min, 15min, or 20min.
In some embodiments, the reaction temperature of the suspension and the coating solution in the third microchannel reactor 350 is 30-80 ℃. At this temperature the mixing effect can be further improved. In some embodiments, the third microchannel reactor 350 can be heated by a water bath. Meanwhile, in the present application, when the third microchannel reactor 350 is at the above temperature, the coating of the cathode material is achieved by means of co-precipitation.
In some embodiments, the third microchannel reactor 350 may be designed in a "T" or "Y" configuration.
In some embodiments, the third microchannel reactor 350 has an inner diameter of 2 to 20mm at both feed ends and an inner diameter of 2 to 40mm at the discharge end. Wherein the inner diameters of the two feeding ends are the same and are respectively 5mm,8mm,10mm,15 mm or 20mm, and the inner diameter of the discharging end is 7mm,10mm,20 mm and 40mm.
In some embodiments, a solid-liquid separator is used to separate the reject and reject, wherein the pneumatic valve in the solid-liquid separator is operated for a set time of 0.5 to 60 min/time.
In some embodiments, the reaction solution is allowed to stand for 0.5-60min before solid-liquid separation is performed to further stabilize the combination of the cathode material and the coating solution. In some embodiments, the filter residue may be washed with clean water to wash excess coating solution.
In some embodiments, the temperature for drying the filter residue is 60-120 ℃, and the drying time is 2-12h.
And in the air atmosphere, placing the intermediate in 500-1000 ℃ and sintering for 4-8h to form a coating layer on the surface of the positive electrode material. The composite material comprises a positive electrode material and a coating layer formed on the surface of the positive electrode material, wherein the coating layer comprises one of oxide, metal salt and fluorine-containing salt (such as lithium fluoride), and the composite material is obtained.
In some embodiments, the soluble salt content in the coating on the surface of the cathode material is 200-5000ppm, and the thickness of the coating layer is 5-50nm. For example, the coating may have a thickness of 5nm, 10nm, 15nm, 20nm, 25nm, 30nm, 40nm, or 50nm. If the thickness of the clad layer is more than 50nm, the diffusion of lithium ions is inhibited due to the excessively large thickness of the clad layer.
In some embodiments, the intermediate is subjected to two sinters, the primary sinter product being mixed with lithium carbonate in a ratio of 1:0.05-1:0.25, adding lithium carbonate, and sintering at high temperature to further increase the lithium content in the coating layer in the composite material.
And S3, pumping the waste liquid and the extraction liquid into a first microchannel reactor 150 from different ports respectively for extraction reaction, wherein the reaction time of the waste liquid and the extraction liquid in the first microchannel reactor 150 is 0.05-5min, inputting a reacted first mixed liquid into a first liquid separation tower 160, and separating an organic phase loaded with metal ions and wastewater from the first liquid separation tower 160 by the first mixed liquid.
In this step, under the action of the shearing force between the inner wall of the microchannel of the first microchannel reactor 150 and the waste liquid and the extract, the diffusion distance between molecules of the waste liquid and the extract is reduced, so that the molecules of the waste liquid and the extract rapidly realize ion exchange, and the metal ions in the waste liquid are extracted into the extract and separated by the first liquid separation tower 160 to obtain the metal ion-loaded organic phase.
In some embodiments, the pressure in the first microchannel reactor 150 is 0.10-1Mpa, which further increases the molecular diffusion rate between the waste liquid and the extract liquid, and increases the mass transfer rate between the waste liquid and the extract liquid. In some embodiments, the pressure within the first microchannel reactor 150 may be 0.10Mpa, 0.2Mpa, 0.3Mpa, 0.5Mpa, 0.7Mpa, 0.9Mpa, or 1Mpa.
In some embodiments, the reaction temperature of the waste stream and the extract in the first microchannel reactor 150 is 25-50 ℃, which further increases the mass transfer rate between the waste stream and the extract, and increases the extraction efficiency.
In some embodiments, the extraction solution comprises one of bis (2-ethylhexyl) phosphate (P204), mono-2-ethylhexyl 2-phosphate (P507), a secondary primary amine, tributyl phosphate (TBP), or bis (2, 4-trimethylpentyl) phosphinic acid (Cynaex 272).
S4, pumping the organic phase loaded with the metal ions and the acid solution into a second microchannel reactor 250 from different ports respectively for carrying out back extraction reaction, wherein the organic phase loaded with the metal ions and the acid solution react in the second microchannel reactor 250 for 0.05-5min to obtain a second mixed solution, inputting the second mixed solution into a second liquid separation tower 260, separating the second mixed solution from the second liquid separation tower 260 to obtain an extractant and a metal salt solution, wherein the metal salt solution can be used as the coating solution again to coat the anode material, and the extractant is used as the extraction solution again to extract the metal ions.
In this step, under the action of the shearing force between the inner wall of the microchannel of the second microchannel reactor 250 and the organic phase loaded with metal ions and the acid solution, the molecules of the organic phase loaded with metal ions and the acid solution rapidly realize ion exchange, so as to strip the metal ions in the organic phase loaded with metal ions into the acid solution, and the recovered extractant and the metal salt solution are obtained through separation in the second liquid separation column 260. The recovered extractant and metal salt solution can be reused, and the utilization efficiency of metal ions and extraction liquid is improved.
In some embodiments, the acid solution is any one of sulfuric acid, acetic acid, nitric acid, hydrochloric acid, and an anion of the acid solution is the same as an anion in the coating solution to obtain a corresponding coating solution.
In some embodiments, an alkaline solution is further added to the metal salt solution, and the pH of the metal salt solution is adjusted to be the same as the pH of the coating solution, so that the obtained metal salt solution can directly flow back to the tank of the coating solution.
In some embodiments, the pressure within the second microchannel reactor 250 is between 0.10Mpa and 1Mpa, further increasing the mass transfer rate between the metal ion-loaded organic phase and the acid solution. In some embodiments, the pressure within the second microchannel reactor 250 can be 0.10Mpa, 0.2Mpa, 0.3Mpa, 0.5Mpa, 0.7Mpa, 0.9Mpa, or 1Mpa.
In some embodiments, the first microchannel reactor 150 and the second microchannel reactor 250 each have a feed end internal diameter of 2 to 20mm and a discharge end internal diameter of 2 to 40mm. Within this range to improve the efficiency of extraction and stripping.
Referring to fig. 1, the method for treating waste liquid of the present application specifically includes accommodating the suspension in the suspension tank 310, accommodating the coating solution in the coating solution tank 320, and pumping the suspension and the coating solution from the corresponding suspension tank 310 and coating solution tank 320 into the third microchannel reactor 350 by the first pump 330 and the second pump 340, respectively. The outlet end of the third microchannel reactor 350 is connected to a pneumatic valve 360. The outlet end of the pneumatic valve 360 is connected to a waste tank 110. And mixing the suspension and the coating solution in a third microchannel reactor 350 and reacting to obtain a reaction solution. The reaction liquid is separated by the pneumatic valve 360 to obtain waste liquid, and the waste liquid is collected in the waste liquid groove body 110.
The waste liquid tank 110 is further connected with a first microchannel reactor 150, and the first microchannel reactor 150 is further connected with an extraction liquid tank 120. The waste liquid tank 110 and the extraction liquid tank 120 are connected to the same end of the first microchannel reactor 150, a third pump 130 is connected between the waste liquid tank 110 and the first microchannel reactor 150, and a fourth pump 140 is connected between the extraction liquid tank 120 and the first microchannel reactor 150. The waste liquid in the waste liquid tank 110 and the extract liquid in the extract liquid tank 120 are respectively pumped into the first microchannel reactor 150 by the third pump 130 and the fourth pump 140 at the same time for extraction reaction, so as to obtain a first mixed liquid. The first microchannel reactor 150 is further connected to the first fractionating tower 160, and the first mixed liquid flows into the first fractionating tower 160 from the first microchannel reactor 150 to obtain the metal ion-loaded organic phase and the wastewater. The first fractionating tower 160 is connected to an organic phase tank 210, and the organic phase loaded with metal ions is collected in the organic phase tank 210.
The organic phase tank 210 is further connected to a second microchannel reactor 250, and the second microchannel reactor 250 is further connected to an acid solution tank 220. The organic phase tank 210 and the acid solution tank 220 are connected to the same end of the second microchannel reactor 250, and a fifth pump 230 is connected between the organic phase tank 210 and the second microchannel reactor 250, and a sixth pump 240 is connected between the acid solution tank 220 and the second microchannel reactor 250. The organic phase loaded with metal ions in the organic phase tank 210 and the acid solution in the acid solution tank 220 are simultaneously pumped into the second microchannel reactor 250 through the fifth pump 230 and the sixth pump 240 respectively to perform a back extraction reaction, so as to obtain a second mixed solution. The second microchannel reactor 250 is also connected to a second split column 260. The second liquid dividing tower 260 is further connected with the coating solution tank 320 and the extraction solution tank 120, and the second mixed liquid flows into the second liquid dividing tower 260 from the second microchannel reactor 250 to be separated to obtain the extractant and the metal salt solution. The extractant is recovered into the extraction liquid tank 120, and the metal salt solution is recovered into the coating solution tank 320.
In this application, after accomplishing the cladding of cathode material, the separation obtains the waste liquid, extract the waste liquid through first microchannel reactor 150, in order to extract the metal ion in the waste liquid to the extraction liquid, obtain the organic phase of load metal ion, and further in the organic phase metal ion strip of load metal ion to the acid solution through second microchannel reactor 250, obtain metal salt solution and the extractant of retrieving, metal salt solution can be utilized as cladding solution once more, the extractant of retrieving can be as the extraction liquid once more, realize the recovery and the reuse to metal ion. Meanwhile, under the action of the shearing force between the inner wall of the microchannel reactor and the two-phase fluid, the molecular diffusion distance between the two-phase fluid is reduced by the first microchannel reactor 150 and the second microchannel reactor 250, so that the mass transfer rate between the two-phase fluid is increased, the ion exchange reaction between the two-phase fluid is rapidly realized through interfacial diffusion, the recovery rate of metal ions is increased, the extraction and back extraction time is shortened, and the extraction efficiency is increased; moreover, the first microchannel reactor 150 and the second microchannel reactor 250 have simple structures, and the process of the waste liquid treatment method can be simplified.
In the application, by the waste liquid treatment method for coating the anode material by the wet method, a closed-loop system is formed by coating, extracting and back-extracting, and the metal ions and the extraction liquid can be recycled.
The scheme of the invention will be explained with reference to the following examples. It will be appreciated by those skilled in the art that the following examples are illustrative only and are not to be construed as limiting the invention. Unless otherwise handled, reagents, software and equipment not specifically handled in the following examples are conventional commercially available products or open sources.
Example 1
20kg of a ternary cathode material Li (Ni) 0.71 Co 0.05 Mn 0.24 )O 2 Adding the mixture into salt-free water, stirring uniformly to prepare a suspension with a solid-to-liquid ratio of 1.
58g of aluminum sulfate and 218g of ammonium tungstate solid are dissolved in salt-free water to prepare a solution with the concentration of 2mol/L as a coating solution. And (3) placing the third microchannel reactor in a water bath at 50 ℃ for heat preservation, pumping the prepared suspension and the prepared coating solution into the third microchannel reactor at the flow rate of 20ml/min respectively for coating reaction, wherein the reaction time of the suspension and the coating solution in the third microchannel reactor is 1min, and the reacted mixed solution flows out from the discharge end of the third microchannel reactor.
And (3) allowing the mixed solution to enter a solid-liquid separator under the regulation of a pneumatic valve for standing and separating for 30min to obtain filter residues and waste liquid, and washing and drying the filter residues to obtain an intermediate. And (3) placing the intermediate in an air atmosphere at 500 ℃ and sintering for 6h to obtain the composite material.
Pumping the waste liquid and the solution composed of secondary carbon primary amine and a P204 mixed extracting agent into a first microchannel reactor at the flow rate of 10ml/min for extraction reaction, wherein the pressure in the first microchannel reactor is 0.16Mpa, and the extraction reaction time is 2min. Inputting the reacted extraction solution into a first liquid separation tower, layering the reacted extraction solution, discharging the wastewater from the lower water phase layer, and obtaining an organic phase loaded with tungstate ions and aluminum ions from the upper water phase layer.
Pumping the organic phase loaded with metal ions and 500ml of 1mol/L sulfuric acid into a second microchannel reactor at the flow rate of 5ml/min respectively for carrying out back extraction reaction, wherein the pressure in the second microchannel reactor is 0.16Mpa, the back extraction reaction time is 1min, and then inputting the back extracted solution into a second liquid separation tower to obtain the recovered extractant, aluminum sulfate and tungstate solution. The recovered extractant returns to the extraction liquid tank to be used as extraction liquid for extracting metal ions again.
Example 2
20kg of a ternary cathode material Li (Ni) 0.71 Co 0.05 Mn 0.24 )O 2 Is added toAnd uniformly stirring the mixture in saline to prepare a suspension with a solid-to-liquid ratio of 1, and slowly adding liquid alkali and ammonia water to adjust the precise pH value to 11.6.
Lanthanum nitrate is dissolved in water to prepare a solution with the concentration of 1mol/L as a coating solution. And (3) placing the third micro-channel reactor in a water bath at 50 ℃ for heat preservation, then pumping the prepared suspension and the prepared coating solution into the third micro-channel reactor at the flow rate of 10ml/min respectively for coating reaction, wherein the suspension and the coating solution react in the third micro-channel reactor for 2min, and the reacted mixed solution flows out from the discharge end of the third micro-channel reactor.
And (3) allowing the mixed solution to enter a solid-liquid separator under the regulation of a pneumatic valve, standing and separating for 40min to obtain filter residues and waste liquid, and washing and drying the filter residues to obtain an intermediate. And (3) placing the intermediate in an air atmosphere at 500 ℃ and sintering for 5h to obtain the composite material.
Pumping the waste liquid and the P507 extract liquid into a first micro-channel reactor at the flow rate of 12ml/min respectively for extraction reaction, wherein the pressure in the first micro-channel reactor is 0.16Mpa, and the extraction reaction time is 0.8min. Inputting the reacted extraction solution into a first liquid separation tower, layering the reacted extraction solution, discharging the wastewater from the lower layer of the aqueous phase, and obtaining the organic phase loaded with lanthanum metal ions from the upper layer of the aqueous phase.
Pumping the organic phase loaded with lanthanum metal ions and 500ml of 1mol/L dilute nitric acid into a second microchannel reactor at the flow rate of 10ml/min respectively to carry out back extraction reaction, wherein the pressure in the second microchannel reactor is 0.16Mpa, the back extraction reaction time is 0.5min, and then inputting the back-extracted solution into a second liquid separation tower to obtain the recovered extractant and the recovered lanthanum nitrate solution. The recovered extractant returns to the extraction liquid tank to be used as extraction liquid for extracting metal ions again.
Example 3
Adding 2kg of lithium cobaltate cathode material into salt-free water, uniformly stirring the mixture to prepare a suspension with a solid-to-liquid ratio of 1.5, and slowly adding liquid alkali and ammonia water to adjust the precise pH value to 11.5.
13.5g of yttrium nitrate was dissolved in 100mL of brine-free water as a coating solution. And (3) placing the third microchannel reactor in a water bath at 60 ℃ for heat preservation, pumping the prepared suspension and the prepared coating solution into the third microchannel reactor at the flow rate of 10ml/min respectively for coating reaction, wherein the suspension and the coating solution react in the third microchannel reactor for 2min, and the reacted mixed solution flows out from the discharge end of the third microchannel reactor.
And (3) allowing the mixed solution to enter a solid-liquid separator under the regulation of a pneumatic valve for standing and separating for 30min to obtain filter residues and waste liquid, and washing and drying the filter residues to obtain an intermediate. And (3) placing the intermediate in an air atmosphere at 600 ℃, sintering for 8h, and naturally cooling to obtain the composite material.
Pumping the waste liquid and the P204 extraction liquid into a first micro-channel reactor at the flow rate of 10ml/min respectively for extraction reaction, wherein the pressure in the first micro-channel reactor is 0.16Mpa, and the extraction reaction time is 1min. Inputting the reacted extraction solution into a first liquid separation tower, layering the reacted extraction solution, discharging the wastewater from the lower layer of the aqueous phase, and obtaining the organic phase loaded with metal ions from the upper layer of the aqueous phase.
Pumping the yttrium-loaded organic phase and 100ml of 0.5mol/L dilute nitric acid into a second microchannel reactor at the flow rate of 5ml/min respectively to carry out back extraction reaction, wherein the pressure in the second microchannel reactor is 0.16Mpa, the residence time of the back extraction reaction is 3min, and then inputting the back-extracted solution into a second liquid separation tower to obtain the recovered extractant P204 and yttrium nitrate solution. The recovered extractant returns to the extraction liquid tank to be used as extraction liquid for extracting metal ions again.
Example 4
Adding 2kg of lithium cobaltate cathode material into brine, uniformly stirring to prepare a suspension with a solid-to-liquid ratio of 2.
Dissolving yttrium nitrate and lanthanum nitrate into salt-free water to prepare 1mol/L yttrium nitrate solution as a coating solution. And (3) placing the third micro-channel reactor in a water bath at 65 ℃ for heat preservation, then pumping the prepared suspension and the prepared coating solution into the third micro-channel reactor at the flow rate of 10ml/min respectively for coating reaction, wherein the suspension and the coating solution react in the third micro-channel reactor for 4min, and the reacted mixed solution flows out from the discharge end of the third micro-channel reactor.
And (3) allowing the mixed solution to enter a solid-liquid separator under the regulation of a pneumatic valve for standing and separating for 10min to obtain filter residue and waste liquid, and washing and drying the filter residue to obtain an intermediate. And (3) placing the intermediate in an air atmosphere at 600 ℃, sintering for 8h, and naturally cooling to obtain the composite material.
Pumping the waste liquid and the P204 extract liquid into a first microchannel reactor at the flow rate of 5ml/min respectively for extraction reaction, wherein the pressure in the first microchannel reactor is 0.16Mpa, and the extraction reaction time is 2min. Inputting the reacted extraction solution into a first liquid separation tower, layering the reacted extraction solution, discharging the wastewater from the lower water phase layer, and obtaining the organic phase loaded with yttrium metal ions from the upper water phase layer.
Pumping the organic phase loaded with yttrium and lanthanum metal ions and 100ml of 1mol/L dilute nitric acid into a second microchannel reactor at the flow rate of 10ml/min respectively for carrying out back extraction reaction, wherein the pressure in the second microchannel reactor is 0.16Mpa, the back extraction reaction time is 2min, and then inputting the back extracted solution into a second liquid separation tower to obtain the recovered extractant P204 and yttrium nitrate and lanthanum nitrate salt solutions. And adding a liquid alkali solution into the metal salt solution to ensure that the pH of the metal salt solution is consistent with that of the coating solution, and conveying the metal salt solution into a tank for storing the coating solution for cyclic utilization. The recovered extractant returns to the extraction liquid tank to be used as extraction liquid for extracting metal ions again.
Example 5
Adding 2kg of lithium cobaltate cathode material into the salt-free water, uniformly stirring the mixture to prepare a suspension with a solid-to-liquid ratio of 2.
Dissolving hafnium nitrate and lanthanum nitrate into salt-free water to prepare 1mol/L hafnium nitrate solution as a coating solution. And (3) placing the third micro-channel reactor in a water bath at 50 ℃ for heat preservation, then pumping the prepared suspension and the prepared coating solution into the third micro-channel reactor at the flow rate of 15ml/min respectively for coating reaction, wherein the suspension and the coating solution react in the third micro-channel reactor for 3min, and the reacted mixed solution flows out from the discharge end of the third micro-channel reactor.
And (3) allowing the mixed solution to enter a solid-liquid separator under the regulation of a pneumatic valve for standing and separating for 10min to obtain filter residue and waste liquid, and washing and drying the filter residue to obtain an intermediate. And (3) placing the intermediate in an air atmosphere at 600 ℃, sintering for 8h, and naturally cooling to obtain the composite material.
Pumping the waste liquid and the TBP extract into a first microchannel reactor at the flow rate of 10ml/min for extraction reaction, wherein the pressure in the first microchannel reactor is 0.16Mpa, and the extraction reaction time is 3min. Inputting the reacted extraction solution into a first liquid separation tower, layering the reacted extraction solution, discharging the wastewater from the lower water phase layer, and obtaining the organic phase loaded with lanthanum metal ions from the upper water phase layer.
Pumping the organic phase loaded with lanthanum and hafnium metal ions and 200ml of 1mol/L dilute nitric acid into a second microchannel reactor at the flow rate of 6ml/min respectively for carrying out back extraction reaction, wherein the internal pressure of the second microchannel reactor is 0.16Mpa, the residence time of the back extraction reaction is 3min, and then inputting the back extracted solution into a second liquid separation tower to obtain the recovered extractant and lanthanum nitrate and hafnium nitrate solutions. The recovered extractant returns to the extraction liquid tank to be used as extraction liquid for extracting metal ions again.
Comparative example 1
The difference from example 3 is that an extraction tank is used for extraction and back extraction, the extraction and back extraction time is 10min, and the rest conditions are the same as example 3.
Comparative example 2
The difference from example 3 was that the stripping was carried out in an extraction tank for 10min, and the other conditions were the same as in example 3.
The content of metal ions in the waste liquid is tested through an Inductively Coupled Plasma (ICP) or atomic absorption tester, and then the content of metal elements in the coating layer is calculated through the concentration difference of the metal ions in the coating solution and the waste liquid. And the metal ion concentration in the metal salt solution is also tested by an Inductive Coupling Plasma (ICP) or atomic absorption tester, and the recovery rate of the metal elements in the metal salt solution can be calculated by the concentration difference of the metal ions in the waste liquid and the metal salt solution.
The reaction conditions for examples 1-5 and comparative examples 1-3 provided herein are shown in table 1 below:
TABLE 1 reaction conditions of examples 1 to 5 and comparative examples 1 to 3
As can be seen from table 1, after the cathode material is coated by the third microchannel reactor in the wet process, the content of the metal element in the coating layer is higher. Compared with the comparative examples 1-2, the recovery rate of the metal ions recovered from the waste liquid can be further improved through the first microchannel reactor and the second microchannel reactor in the embodiments 1-5 of the application, the recovery rate can reach more than 92%, the rare precious metals can be recycled, and the discharge of metal waste water is reduced; and the extraction and the back extraction can be completed in a short time. In addition, the waste liquid treatment method is simple in process, clear in flow of the coating-extraction-back-extraction system, convenient to operate and easy for industrial production.
Although the present invention has been described in detail with reference to the above embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the invention.
Claims (10)
1. A waste liquid treatment method for a wet-process coated positive electrode material is characterized by comprising the following steps:
providing a suspension comprising a positive electrode material and a coating solution comprising soluble salts, wherein the soluble salts comprise at least one of metal compounds or fluorine-containing salts, and the metal compounds comprise at least one of metal sulfates, metal acetates, metal nitrates, metal chlorides or fluorine-containing salts;
mixing the suspension and the coating solution and reacting to obtain a reaction solution;
carrying out solid-liquid separation on the reaction liquid to obtain waste liquid;
pumping the waste liquid and the extract liquor into a first microchannel reactor from different ports respectively for extraction reaction, wherein the reaction time of the waste liquid and the extract liquor in the first microchannel reactor is 0.05-5min, inputting a first mixed solution after reaction into a first liquid separation tower, and separating an organic phase loaded with metal ions and wastewater from the first liquid separation tower by the first mixed solution;
and respectively pumping the organic phase loaded with the metal ions and the acid solution from different ports into a second microchannel reactor for carrying out back extraction reaction, wherein the reaction time of the organic phase loaded with the metal ions and the acid solution in the second microchannel reactor is 0.05-5min, so as to obtain a second mixed solution, inputting the second mixed solution into a second liquid separation tower, and separating the second mixed solution from the second liquid separation tower, so as to obtain an extraction liquid and a metal salt solution.
2. The method of claim 1, wherein the reaction temperature of the waste stream and the extract in the first microchannel reactor is in the range of 25 ℃ to 50 ℃.
3. The liquid waste treatment method of claim 1, wherein the first microchannel reactor and the second microchannel reactor each have a feed end inside diameter of 2 to 20mm and a discharge end inside diameter of 2 to 40mm.
4. The liquid waste treatment method of claim 1, wherein the pressure within the first microchannel reactor is between 0.10Mpa and 1Mpa.
5. The method of claim 1, wherein the pressure within the second microchannel reactor is between 0.10Mpa and 1Mpa.
6. The liquid waste treatment method according to claim 1, further comprising: and adding an alkaline solution into the metal salt solution, and adjusting the pH of the metal salt solution to be the same as that of the coating solution.
7. The method for treating waste liquid according to claim 1, wherein the step of mixing and reacting the suspension and the coating solution specifically comprises:
and pumping the suspension and the coating solution into a third microchannel reactor from different ports respectively, wherein the suspension and the coating solution react in the third microchannel reactor for 0.5-20min.
8. The method of claim 7, wherein the reaction temperature of the suspension and the coating solution in the third microchannel reactor is 30-80 ℃.
9. The method for treating waste liquid according to claim 1, wherein the acid solution is any one of sulfuric acid, acetic acid, nitric acid and hydrochloric acid, and an anion of the acid solution is the same as an anion of the coating solution.
10. The method of treating a waste liquid according to claim 1, wherein the extraction liquid comprises one of bis (2-ethylhexyl) phosphate, mono-2-ethylhexyl phosphate, secondary primary amine, tributyl phosphate, or bis (2, 4-trimethylpentyl) phosphinic acid.
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