CN116081658B - Purification method for preparing industrial grade lithium carbonate from electrolytic waste residues - Google Patents
Purification method for preparing industrial grade lithium carbonate from electrolytic waste residues Download PDFInfo
- Publication number
- CN116081658B CN116081658B CN202310109894.7A CN202310109894A CN116081658B CN 116081658 B CN116081658 B CN 116081658B CN 202310109894 A CN202310109894 A CN 202310109894A CN 116081658 B CN116081658 B CN 116081658B
- Authority
- CN
- China
- Prior art keywords
- stirring
- adsorbent
- beaker
- lithium carbonate
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
- B01J20/205—Carbon nanostructures, e.g. nanotubes, nanohorns, nanocones, nanoballs
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28019—Spherical, ellipsoidal or cylindrical
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28042—Shaped bodies; Monolithic structures
- B01J20/28045—Honeycomb or cellular structures; Solid foams or sponges
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a purification method for preparing industrial lithium carbonate from electrolytic waste residues, and belongs to the technical field of lithium recovery and purification. The invention is used for solving the technical problems of long process flow and complicated operation of recycling a large amount of hydrogen fluoride gas generated in the lithium extraction process of electrolytic aluminum waste residues in the prior art, and discloses a purification method for preparing industrial grade lithium carbonate from electrolytic waste residues, which comprises the following steps: adding the electrolytic aluminum waste residue into a pulverizer, pulverizing, and sieving with 80 mesh sieve to obtain fine powder. According to the invention, the chitosan is modified by the 2-hydroxymethyl-12-crown-4 and then the carboxylated multi-carbon nano tube is doped to prepare the porous adsorbent with large adsorption capacity, after the electrolytic aluminum waste residue is subjected to burning treatment, alkali liquor is used for extracting lithium in the electrolytic aluminum waste residue, the adsorbent is used for adsorbing the lithium, and the lithium carbonate is prepared after acid water elution, so that the adsorbent can be used for multiple cyclic elution, the process flow is short, hydrogen fluoride gas is not generated, and the operation is simple.
Description
Technical Field
The invention relates to the technical field of lithium recovery and purification, in particular to a purification method for preparing industrial grade lithium carbonate from electrolytic waste residues.
Background
In the electrolytic production of aluminum, besides cryolite, some fluoride or chloride and other salts are added into the electrolyte, so as to improve the property of the electrolyte and achieve the purposes of improving the current efficiency and reducing the energy consumption, and one of the common additives is lithium fluoride. The lithium-containing anhydrous aluminum fluoride and the lithium-containing cryolite have good use effect in the aluminum electrolysis enterprises at present, and can effectively reduce the initial temperature of the electrolyteThe fluorine emission is reduced, and the energy saving and consumption reduction effects of an electrolytic aluminum enterprise are promoted. A great amount of lithium is enriched in the electrolytic aluminum waste slag, and the lithium content in the electrolytic aluminum waste slag can reach 1% -3% (Li is used) + Meter).
In the prior art, a Chinese patent with publication number of CN113718107A discloses a method for efficiently extracting lithium from lithium-rich aluminum electrolyte waste residues and preparing anhydrous aluminum fluoride. The invention prepares anhydrous AlF by directly contacting HF gas generated by curing and volatilizing concentrated sulfuric acid with an organic phase loaded with aluminum after dust removal and impurity removal 3 Synthesis of Anhydrous AlF 3 High purity and the obtained anhydrous AlF 3 Can return to the aluminum electrolysis process to be used as a cosolvent, thereby realizing the recycling of aluminum fluoride. According to the invention, the sodium Fumei solution is used as a precipitator for deep purification to remove calcium, magnesium and aluminum, the impurity element removal effect is thorough, and the raw materials are prepared for the step of precipitating lithium by sodium carbonate. The method can efficiently recycle various components in the lithium-rich aluminum electrolyte waste residue treatment process, fully recycle waste materials and simultaneously generate no new pollution. The lithium extraction method can generate hydrofluoric acid with strong corrosiveness in the sulfuric acid curing process, can generate serious corrosion on equipment, and can recover lithium through lithium precipitation and deep lithium removal after precipitating impurity ions in the lithium extraction process, and has the advantages of long process flow, high equipment energy consumption and complex operation.
In view of the technical drawbacks of this aspect, a solution is now proposed.
Disclosure of Invention
The invention aims to provide a purification method for preparing industrial grade lithium carbonate from electrolytic waste residues, which is used for solving the technical problems that in the prior art, a large amount of hydrogen fluoride gas is generated in the process of purifying and processing lithium in electrolytic aluminum waste residues, lithium is required to be recovered in the steps of depositing lithium, deeply removing lithium and the like after impurity ions are settled in the process of recovering and purifying lithium, and the recovery process flow of the lithium is long and the operation is complicated.
The aim of the invention can be achieved by the following technical scheme:
a purification method for preparing industrial grade lithium carbonate by using electrolytic waste residues comprises the following steps:
s1, adding electrolytic aluminum waste residues into a pulverizer, pulverizing, and sieving with a 80-mesh sieve to obtain fine powder;
s2, uniformly mixing the fine powder with sodium carbonate, adding the mixture into a muffle furnace, setting the temperature to be 750-850 ℃, and preserving the heat for 2-3 hours to obtain calcined fine powder;
s3, adding the calcined fine powder and the alkaline solution into a beaker, stirring, raising the temperature of the beaker to 80-90 ℃, preserving the heat for 4-6 hours, and filtering to obtain a leaching solution;
s4, adjusting the pH value of the leaching solution to be 7-8 by using a hydrochloric acid aqueous solution, adding an adsorbent into the leaching solution, mixing for 1.5-2.5 hours, filtering, and separating the adsorbent from the leaching solution to obtain a saturated adsorbent;
s5, transferring the saturated adsorbent into a beaker, adding a hydrochloric acid aqueous solution with the concentration of 1mol/L into the beaker, soaking for 50-70min, filtering, adding a sodium carbonate aqueous solution into the filtrate, adjusting the pH value of the system to be 10-12, raising the temperature of the beaker to 70-80 ℃, stirring for 30-50min, and performing post-treatment to obtain the industrial grade lithium carbonate.
The synthesis reaction principle of lithium carbonate is as follows:
2Li + +Na 2 CO 3 ＝Li 2 CO 3 ↓+2Na +
further, the weight ratio of the fine powder to the sodium carbonate is 5:2.
Further, the mixing in the step S4 is stirring, the stirring speed is 400-460r/min, and the mixing temperature is room temperature.
Further, the preparation of the adsorbent comprises the following steps:
a1, adding 2-hydroxymethyl-12-crown-4, sodium hydride and N, N-dimethylformamide into a three-neck flask protected by nitrogen, stirring, raising the temperature of the three-neck flask to 60-70 ℃, reacting for 2-3h, adding epoxybromopropane into the three-neck flask, keeping the temperature at 60-70 ℃, and reacting for 72-76h to obtain a dripping liquid;
the reaction principle of the synthesis of the dropping liquid is as follows;
a2, adding chitosan and 2wt% acetic acid aqueous solution into a three-neck flask, stirring until the system is dissolved, dropwise adding liquid into the three-neck flask by using a constant-pressure dropping funnel, reacting for 26-28h at room temperature, and performing post-treatment to obtain modified chitosan;
the reaction principle of the synthesis of the modified chitosan is as follows:
a3, adding the modified chitosan and 2wt% acetic acid aqueous solution into a three-neck flask, stirring until the system is dissolved, adding carboxylated multi-wall carbon nanotubes into the three-neck flask, performing ultrasonic dispersion for 2h, adding 50wt% benzaldehyde ethanol solution into the three-neck flask, and stirring for 30-50min to obtain a disperse phase;
and A4, adding Tween 80, cyclohexane and liquid paraffin into a beaker, rapidly stirring, conveying the dispersibility into the beaker at a constant speed by using a peristaltic pump, then dropwise adding glutaraldehyde into the beaker, stirring for 3-5h, and performing post-treatment to obtain the adsorbent.
Further, the weight ratio of the 2-hydroxymethyl-12-crown-4, sodium hydride, N-dimethylformamide to the epoxybromopropane is 2:1:6:1.3.
Further, the weight ratio of the chitosan, the 2wt% acetic acid aqueous solution and the dropping liquid is 2:7:4, and the post-treatment operation of the step A2 comprises the following steps: transferring the reaction solution into a rotary evaporation bottle, using a rotary evaporator, distilling under reduced pressure at 65-75deg.C until no liquid flows out, adding purified water into the rotary evaporation bottle, stirring for 30-50min, filtering, transferring the filter cake into a vacuum drying oven at 60-80deg.C, and drying for 8-10 hr to obtain modified chitosan.
Further, the weight ratio of the modified chitosan, the 2wt% acetic acid aqueous solution, the carboxylated multi-wall carbon nanotubes and the 50wt% benzaldehyde ethanol solution is 1:10:0.1:2.
Further, the weight ratio of tween 80, cyclohexane, liquid paraffin and glutaraldehyde is 1:8:5:1.5, and the post-treatment operation in the step A4 comprises the following steps: after the reaction is finished, filtering, mixing a filter cake with a 50wt% cyclohexane ethanol solution, adding the mixture into a beaker, performing ultrasonic dispersion for 40-60min, filtering, transferring the filter cake into a three-mouth flask containing 0.1mol/L hydrochloric acid aqueous solution, stirring, raising the temperature of the three-mouth flask to 45-55 ℃, reacting for 2-3h, filtering, eluting the filter cake to be neutral by purified water, transferring the filter cake into a vacuum drying oven with the temperature of 60-80 ℃ and drying for 8-10h to obtain the adsorbent.
Further, the post-processing operation of step S5 includes: filtering, leaching with purified water, pumping, transferring the filter cake into an oven with the temperature of 60-80 ℃ and drying for 6-8h to obtain the industrial grade lithium carbonate.
The invention has the following beneficial effects:
1. according to the purification method for preparing industrial lithium carbonate from the electrolytic waste residue, when lithium in the electrolytic aluminum waste residue containing lithium is recovered, the electrolytic aluminum waste residue is crushed and then is uniformly mixed with sodium carbonate, and the sodium carbonate can promote the insoluble substances in the electrolytic aluminum waste residue to be converted into compounds which are easy to dissolve out at high temperature, so that the structure and the structure of the finely-ground powder are improved, and the Li in the finely-ground powder is enabled + 、Al 3+ 、Na + The plasma metal ions are more easily leached and extracted, fluorine in the electrolytic waste residue exists in the form of calcium fluoride, and Al is in alkaline environment 3+ Form aluminum hydroxide precipitate, li + Forming lithium hydroxide which is easily dissolved in water, thereby Li + Extracted from electrolyte waste residue and uses adsorbent to extract Li from leaching solution + The selective adsorption is carried out, the recovery purity of lithium carbonate is improved, the organic matters in the electrolytic aluminum waste residue can be removed through high-temperature burning, and the degradation of the cyclic adsorption regeneration performance of the adsorbent caused by the adsorption of the organic matters in the electrolytic aluminum waste residue by the adsorbent is prevented.
2. The invention relates to a purification method for preparing industrial lithium carbonate by electrolyzing waste residues, which is characterized in that 2-hydroxymethyl-12-crown-4 and epoxybromopropane are used for capturing hydrogen ions with negative charges on sodium hydride under the condition of taking the sodium hydride as a catalystObtaining positive charge hydrogen ions of active hydroxyl groups on 2-hydroxymethyl-12-crown-4 to form oxygen anions, under alkaline environment, attacking two carbon atoms near oxygen atoms in epoxy groups by nucleophilic reagent to induce epoxy groups on epoxy bromopropane to generate ring opening reaction, grafting epoxy bromopropane onto 2-hydroxymethyl-12-crown-4, breaking carbon bromine bond on epoxy bromopropane in acidic environment to generate bromine substitution reaction with amino groups or hydroxyl groups on chitosan, grafting 2-hydroxymethyl-12-crown-4 onto chitosan to prepare modified chitosan, wherein 2-hydroxymethyl-12-crown-4 can react with Li + Complexation occurs but Na cannot be complexed + 、K + By combining Li + Strongly binds to 2-hydroxymethyl-12-crown-4, thereby achieving Li + For selective adsorption purposes, the active groups on the surface of the modified chitosan are protonated in an acidic environment of the adsorbent, and H is in solution + Will be in contact with Li + Competing adsorption sites, the adsorption capacity of the adsorbent in an acidic environment is minimized, so that Li can be soaked by acid water + Desorption is resolved from the adsorbent, and the adsorbent is activated and recycled.
3. According to the purification method for preparing industrial grade lithium carbonate from electrolytic waste residues, after the chitosan is modified, the modified chitosan can be used for preparing Li + Selectively adsorbing, namely uniformly dispersing carboxylated multi-wall carbon nano-tubes into the modified chitosan after the modified chitosan is dissolved to prepare a disperse phase, uniformly injecting tween 80, cyclohexane and liquid paraffin into a beaker, adding the disperse phase into the beaker, continuously shearing and separating the mixture into liquid drops under the action of a certain rotating speed to prepare the adsorbent with a microsphere structure, wherein the modified chitosan and the carboxylated multi-wall carbon nano-tubes have ultrahigh specific surface area, and the carboxylated multi-wall carbon nano-tubes have the characteristics of hollow and lamellar nano-scale structures, and sponge-shaped pores are formed on the surface and inside of the adsorbent to increase the Li of the adsorbent + Is used as a catalyst.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in connection with the embodiments, and it is obvious that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The purification method for preparing industrial grade lithium carbonate from electrolytic waste residues provided by the embodiment comprises the following steps:
s1, crushing
Adding electrolytic aluminum waste residues into a pulverizer for pulverization, and sieving with a 80-mesh sieve to obtain fine powder;
s2, roasting
Weighing the following components in parts by weight: mixing 2000g of fine powder with 800g of sodium carbonate uniformly, adding the mixture into a muffle furnace, setting the temperature to 750 ℃, and preserving heat for 2 hours to obtain roasting fine powder;
s3, leaching
Weighing the following components in parts by weight: adding 2000g of roasting fine powder and 8kg of 10wt% sodium hydroxide aqueous solution into a beaker, stirring, raising the temperature of the beaker to 80 ℃, preserving heat for 4 hours, and filtering to obtain leaching liquid;
s4, preparing an adsorbent
The preparation of the adsorbent comprises the following steps:
a1, weighing: adding 100g of sodium hydride, 4200g of 2-hydroxymethyl-12-crown-12-and 600g of N, N-dimethylformamide into a three-neck flask protected by nitrogen, stirring, raising the temperature of the three-neck flask to 60 ℃, reacting for 2 hours, adding 130g of epibromohydrin into the three-neck flask, keeping the temperature at 60 ℃, and reacting for 72 hours to obtain a dripping solution;
a2, weighing: adding 500g of chitosan and 4kg of 2wt% acetic acid aqueous solution into a three-neck flask, stirring until the system is clear, using a constant-pressure dropping funnel to drop 1030g of dropping liquid into the three-neck flask, reacting for 26 hours at room temperature, transferring the reaction liquid into a rotary evaporation bottle, using a rotary evaporator, distilling under reduced pressure at 65 ℃ until no liquid flows out, adding 5kg of purified water into the rotary evaporation bottle, stirring for 30 minutes, filtering, transferring a filter cake into a vacuum drying oven at 60 ℃ and drying for 8 hours to obtain modified chitosan;
a3, weighing: adding 100g of modified chitosan and 1000g of 2wt% acetic acid aqueous solution into a three-neck flask, stirring until the system is dissolved, adding 10g of carboxylated multi-wall carbon nanotubes into the three-neck flask, performing ultrasonic dispersion for 2h, adding 200g of 50wt% benzaldehyde ethanol solution into the three-neck flask, and stirring for 30min to obtain a dispersed phase;
a4, weighing: 200g of Tween 80, 1600g of cyclohexane and 1000g of liquid paraffin are added into a beaker, quick stirring is carried out, a peristaltic pump is used for conveying the dispersibility into the beaker at a constant speed, then 300g of glutaraldehyde is dripped into the beaker, stirring is carried out for 3 hours, filtration is carried out, a filter cake and 900g of 50wt% cyclohexane ethanol solution are mixed and added into the beaker, ultrasonic dispersion is carried out for 40-60 minutes, filtration is carried out, the filter cake is transferred into a three-neck flask containing 0.1mol/L hydrochloric acid aqueous solution, the temperature of the three-neck flask is increased to 45 ℃ for 2 hours, filtration is carried out, the filter cake is leached to be neutral by purified water, and the filter cake is transferred into a vacuum drying box with the temperature of 60 ℃ for drying for 8 hours, thus obtaining the adsorbent.
S5, adsorption
Adjusting the pH=7 of the leaching solution by using a hydrochloric acid aqueous solution with the concentration of 1mol/L, adding 500g of adsorbent into the leaching solution, stirring at the room temperature for 1.5h at the rotating speed of 400r/min, filtering, and separating the adsorbent from the leaching solution to obtain a saturated adsorbent;
s6, preparing potassium carbonate
Transferring the saturated adsorbent into a beaker, adding 1kg of 1mol/L hydrochloric acid aqueous solution into the beaker, soaking for 50min, filtering, adding 25wt% sodium carbonate aqueous solution into the filtrate, adjusting the pH value of the system to be 10, raising the temperature of the beaker to 70 ℃, stirring for 30min, filtering, leaching by using purified water, pumping, transferring the filter cake into an oven with the temperature of 60 ℃ and drying for 6h to obtain the industrial grade lithium carbonate.
Example 2
The purification method for preparing industrial grade lithium carbonate from electrolytic waste residues provided by the embodiment comprises the following steps:
s1, crushing
Adding electrolytic aluminum waste residues into a pulverizer for pulverization, and sieving with a 80-mesh sieve to obtain fine powder;
s2, roasting
Weighing the following components in parts by weight: mixing 2000g of fine powder with 800g of sodium carbonate uniformly, adding the mixture into a muffle furnace, setting the temperature to 800 ℃, and preserving heat for 2.5h to obtain roasting fine powder;
s3, leaching
Weighing the following components in parts by weight: adding 2000g of roasting fine powder and 8kg of 10wt% sodium hydroxide aqueous solution into a beaker, stirring, raising the temperature of the beaker to 850 ℃, preserving heat for 5 hours, and filtering to obtain leaching liquid;
s4, preparing an adsorbent
The preparation of the adsorbent comprises the following steps:
a1, weighing: adding 100g of sodium hydride, 4200g of 2-hydroxymethyl-12-crown-12-and 600g of N, N-dimethylformamide into a three-neck flask protected by nitrogen, stirring, raising the temperature of the three-neck flask to 65 ℃, reacting for 2.5h, adding 130g of epoxybromopropane into the three-neck flask, keeping the temperature at 65 ℃, and reacting for 74h to obtain a dripping solution;
a2, weighing: adding 500g of chitosan and 4kg of 2wt% acetic acid aqueous solution into a three-neck flask, stirring until the system is clear, using a constant-pressure dropping funnel to drop 1030g of dropping liquid into the three-neck flask, reacting for 27h at room temperature, transferring the reaction liquid into a rotary evaporation bottle, using a rotary evaporator, distilling under reduced pressure at the temperature of 70 ℃ until no liquid flows out, adding 5kg of purified water into the rotary evaporation bottle, stirring for 40min, filtering, transferring a filter cake into a vacuum drying oven at the temperature of 70 ℃ and drying for 9h to obtain modified chitosan;
a3, weighing: adding 100g of modified chitosan and 1000g of 2wt% acetic acid aqueous solution into a three-neck flask, stirring until the system is dissolved, adding 10g of carboxylated multi-wall carbon nanotubes into the three-neck flask, performing ultrasonic dispersion for 2h, adding 200g of 50wt% benzaldehyde ethanol solution into the three-neck flask, and stirring for 40min to obtain a dispersed phase;
a4, weighing: 200g of Tween 80, 1600g of cyclohexane and 1000g of liquid paraffin are added into a beaker, quick stirring is carried out, a peristaltic pump is used for conveying the dispersibility into the beaker at a constant speed, then 300g of glutaraldehyde is dripped into the beaker, stirring is carried out for 4 hours, filtration is carried out, a filter cake and 900g of 50wt% cyclohexane ethanol solution are mixed and added into the beaker, ultrasonic dispersion is carried out for 50 minutes, filtration is carried out, the filter cake is transferred into a three-neck flask containing 0.1mol/L hydrochloric acid aqueous solution, the temperature of the three-neck flask is increased to 50 ℃, reaction is carried out for 2.5 hours, filtration is carried out, the filter cake is leached to be neutral by purified water, and the filter cake is transferred into a vacuum drying box with the temperature of 70 ℃ for drying for 9 hours, thus obtaining the adsorbent.
S5, adsorption
Adjusting the pH=7.5 of the leaching solution by using a hydrochloric acid aqueous solution with the concentration of 1mol/L, adding 500g of adsorbent into the leaching solution, stirring at the room temperature for 2 hours at the rotating speed of 430r/min, filtering, and separating the adsorbent from the leaching solution to obtain a saturated adsorbent;
s6, preparing potassium carbonate
Transferring the saturated adsorbent into a beaker, adding 1kg of 1mol/L hydrochloric acid aqueous solution into the beaker, soaking for 60min, filtering, adding 25wt% sodium carbonate aqueous solution into the filtrate, adjusting the pH value of the system to be 11, raising the temperature of the beaker to 75 ℃, stirring for 40min, filtering, leaching by using purified water, pumping, transferring the filter cake into an oven with the temperature of 70 ℃ and drying for 7h to obtain the industrial grade lithium carbonate.
Example 3
The purification method for preparing industrial grade lithium carbonate from electrolytic waste residues provided by the embodiment comprises the following steps:
s1, crushing
Adding electrolytic aluminum waste residues into a pulverizer for pulverization, and sieving with a 80-mesh sieve to obtain fine powder;
s2, roasting
Weighing the following components in parts by weight: mixing 2000g of fine powder with 800g of sodium carbonate uniformly, adding the mixture into a muffle furnace, setting the temperature to 850 ℃, and preserving heat for 3 hours to obtain roasting fine powder;
s3, leaching
Weighing the following components in parts by weight: adding 2000g of roasting fine powder and 8kg of 10wt% sodium hydroxide aqueous solution into a beaker, stirring, raising the temperature of the beaker to 90 ℃, preserving heat for 6 hours, and filtering to obtain leaching liquid;
s4, preparing an adsorbent
The preparation of the adsorbent comprises the following steps:
a1, weighing: adding 100g of sodium hydride, 4200g of 2-hydroxymethyl-12-crown-12-and 600g of N, N-dimethylformamide into a three-neck flask protected by nitrogen, stirring, raising the temperature of the three-neck flask to 70 ℃, reacting for 3 hours, adding 130g of epibromohydrin into the three-neck flask, keeping the temperature at 70 ℃, and reacting for 76 hours to obtain a dripping solution;
a2, weighing: adding 500g of chitosan and 4kg of 2wt% acetic acid aqueous solution into a three-neck flask, stirring until the system is clear, using a constant pressure dropping funnel to drop 1030g of dropping liquid into the three-neck flask, reacting for 28h at room temperature, transferring the reaction liquid into a rotary evaporation bottle, using a rotary evaporator, distilling under reduced pressure at the temperature of 75 ℃ until no liquid flows out, adding 5kg of purified water into the rotary evaporation bottle, stirring for 50min, filtering, transferring a filter cake into a vacuum drying oven at the temperature of 80 ℃ and drying for 10h to obtain modified chitosan;
a3, weighing: adding 100g of modified chitosan and 1000g of 2wt% acetic acid aqueous solution into a three-neck flask, stirring until the system is dissolved, adding 10g of carboxylated multi-wall carbon nanotubes into the three-neck flask, performing ultrasonic dispersion for 2h, adding 200g of 50wt% benzaldehyde ethanol solution into the three-neck flask, and stirring for 50min to obtain a dispersed phase;
a4, weighing: 200g of Tween 80, 1600g of cyclohexane and 1000g of liquid paraffin are added into a beaker, quick stirring is carried out, a peristaltic pump is used for conveying the dispersibility into the beaker at a constant speed, then 300g of glutaraldehyde is dripped into the beaker, stirring is carried out for 5 hours, filtration is carried out, a filter cake and 900g of 50wt% cyclohexane ethanol solution are mixed and added into the beaker, ultrasonic dispersion is carried out for 60 minutes, filtration is carried out, the filter cake is transferred into a three-neck flask containing 0.1mol/L hydrochloric acid aqueous solution, the temperature of the three-neck flask is increased to 55 ℃, reaction is carried out for 2-3 hours, filtration is carried out, the filter cake is leached to be neutral by purified water, and the filter cake is transferred into a vacuum drying box with the temperature of 80 ℃ for drying for 10 hours, thus obtaining the adsorbent.
S5, adsorption
Adjusting the pH=8 of the leaching solution by using a hydrochloric acid aqueous solution with the concentration of 1mol/L, adding 500g of adsorbent into the leaching solution, stirring at the room temperature for 2.5h at the rotating speed of 460r/min, filtering, and separating the adsorbent from the leaching solution to obtain a saturated adsorbent;
s6, preparing potassium carbonate
Transferring the saturated adsorbent into a beaker, adding 1kg of 1mol/L hydrochloric acid aqueous solution into the beaker, soaking for 70min, filtering, adding 25wt% sodium carbonate aqueous solution into the filtrate, adjusting the pH value of the system to be=12, raising the temperature of the beaker to 80 ℃, stirring for 50min, filtering, leaching by using purified water, pumping, transferring the filter cake into an oven with the temperature of 80 ℃ for drying for 8h, and obtaining the industrial grade lithium carbonate.
Comparative example 1
The difference between this comparative example and example 3 is that the modified chitosan in step A3 is replaced by chitosan in equal amounts.
Comparative example 2
The present comparative example is different from example 3 in that the multiwall carbon nanotubes were not added in step A3.
Comparative example 3
The present comparative example is different from example 3 in that step S2 is eliminated and the fine powder is not subjected to the calcination treatment.
Testing performance;
the purification method for preparing industrial grade lithium carbonate from electrolytic waste residues provided in examples 1-3 and comparative examples 1-3 was used for detecting recovery rate and purity of lithium in electrolytic waste residues and adsorption regeneration performance of adsorbent, and elements in electrolytic aluminum waste residues used in the test include: 40% -50% of F, 10% -20% of Al, 20% -30% of Na, 2% -5% of Ca, 1% -3% of Li and the balance of other impurities, wherein the purity of the lithium carbonate is as defined in standard GB/T11064.1-2013 of lithium carbonate, lithium hydroxide monohydrate and lithium chloride chemical analysis method part 1: determination of lithium carbonate content acid-base titration method, determination of lithium carbonate mass percent, determination of lithium recovery rate is to calculate the adsorption rate by measuring the concentration change of lithium element in leaching solution before and after leaching through an inductively coupled plasma atomic emission spectrometer (ICP), adsorption regeneration performance test of the adsorbent is to perform 10 times of adsorption and elution cycle experiments on the adsorbent, and determination of the concentration change of lithium element in tenth leaching solution before and after leaching, wherein specific test results are shown in the following table:
from the analysis of the performance test data in the above table, it is known that:
as can be seen from the analysis of the data of examples 1-3, the present invention prepares the P-Li by grafting 2-hydroxymethyl-12-crown-4 onto chitosan + Selectively adsorbed modified chitosan, and preparing adsorbent with microporous structure and large adsorption capacity by doping carboxylated multi-carbon nano tube, and for Li in leaching solution + Selective adsorption is carried out, effectively improving Li + The recovery efficiency of (2) and the purity of lithium carbonate, and the adsorption capacity of the adsorbent is small under the acidic condition, and the Li can be soaked by acid water + The desorption is resolved from the adsorbent, the adsorbent is activated and recycled, and organic matters in the electrolytic aluminum waste residue can be effectively removed by crushing the electrolytic aluminum waste residue and roasting the crushed electrolytic aluminum waste residue, so that insoluble matters in the electrolytic aluminum waste residue are promoted to be converted into compounds which are easy to dissolve out, the structure and the structure of the fine powder are improved, and Li is promoted + Leaching out of electrolytic aluminum waste residue, and making the adsorbent circularly elute Li ten times + Still has good adsorption rate.
The foregoing is merely illustrative and explanatory of the invention, as it is well within the scope of the invention as claimed, as it relates to various modifications, additions and substitutions for those skilled in the art, without departing from the inventive concept and without departing from the scope of the invention as defined in the accompanying claims.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean 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 present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. 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 preferred embodiments of the invention disclosed above are intended only to assist in the explanation of the invention. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise form disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best understand and utilize the invention. The invention is limited only by the claims and the full scope and equivalents thereof.
Claims (7)
1. The purification method for preparing the industrial grade lithium carbonate by using the electrolytic waste residues is characterized by comprising the following steps of:
s1, adding electrolytic aluminum waste residues into a pulverizer, pulverizing, and sieving with a 80-mesh sieve to obtain fine powder;
s2, uniformly mixing the fine powder with sodium carbonate, adding the mixture into a muffle furnace, setting the temperature to be 750-850 ℃, and preserving the heat for 2-3 hours to obtain calcined fine powder;
s3, adding the calcined fine powder and the alkaline solution into a beaker, stirring, raising the temperature of the beaker to 80-90 ℃, preserving the heat for 4-6 hours, and filtering to obtain a leaching solution;
s4, adjusting the pH value of the leaching solution to be 7-8 by using a hydrochloric acid aqueous solution, adding an adsorbent into the leaching solution, mixing for 1.5-2.5 hours, filtering, and separating the adsorbent from the leaching solution to obtain a saturated adsorbent;
s5, transferring the saturated adsorbent into a beaker, adding a hydrochloric acid aqueous solution with the concentration of 1mol/L into the beaker, soaking for 50-70min, filtering, adding a sodium carbonate aqueous solution into the filtrate, adjusting the pH value of the system to be 10-12, raising the temperature of the beaker to 70-80 ℃, stirring for 30-50min, and performing post-treatment to obtain industrial-grade lithium carbonate;
the preparation of the adsorbent comprises the following steps:
a1, adding 2-hydroxymethyl-12-crown-4 ether, sodium hydride and N, N-dimethylformamide into a three-neck flask protected by nitrogen, stirring, heating the three-neck flask to 60-70 ℃, reacting for 2-3h, adding epoxybromopropane into the three-neck flask, keeping the temperature at 60-70 ℃, and reacting for 72-76h to obtain a dripping liquid;
a2, adding chitosan and 2wt% acetic acid aqueous solution into a three-neck flask, stirring until the system is dissolved, dropwise adding liquid into the three-neck flask by using a constant-pressure dropping funnel, reacting for 26-28h at room temperature, and performing post-treatment to obtain modified chitosan;
a3, adding the modified chitosan and 2wt% acetic acid aqueous solution into a three-neck flask, stirring until the system is dissolved, adding carboxylated multi-wall carbon nanotubes into the three-neck flask, performing ultrasonic dispersion for 2h, adding 50wt% benzaldehyde ethanol solution into the three-neck flask, and stirring for 30-50min to obtain a disperse phase;
a4, adding Tween 80, cyclohexane and liquid paraffin into a beaker, rapidly stirring, conveying the dispersed phase into the beaker at a constant speed by using a peristaltic pump, then dropwise adding glutaraldehyde into the beaker, stirring for 3-5h, and performing post-treatment to obtain an adsorbent; the weight ratio of tween 80, cyclohexane, liquid paraffin and glutaraldehyde is 1:8:5:1.5, and the post-treatment operation comprises the following steps: after the reaction is finished, filtering, mixing a filter cake with a 50wt% cyclohexane ethanol solution, adding the mixture into a beaker, performing ultrasonic dispersion for 40-60min, filtering, transferring the filter cake into a three-mouth flask containing 0.1mol/L hydrochloric acid aqueous solution, stirring, raising the temperature of the three-mouth flask to 45-55 ℃, reacting for 2-3h, filtering, eluting the filter cake to be neutral by purified water, transferring the filter cake into a vacuum drying oven with the temperature of 60-80 ℃ and drying for 8-10h to obtain the adsorbent.
2. The purification method for preparing industrial grade lithium carbonate from electrolytic waste residue according to claim 1, wherein the weight ratio of the fine powder to sodium carbonate is 5:2.
3. The purification method for preparing industrial grade lithium carbonate from electrolytic waste residue according to claim 1, wherein the mixing in the step S4 is stirring, the stirring speed is 400-460r/min, and the mixing temperature is room temperature.
4. The purification method for preparing industrial grade lithium carbonate from electrolytic waste residues according to claim 1, wherein the weight ratio of 2-hydroxymethyl-12-crown-4 ether, sodium hydride, N-dimethylformamide and epibromohydrin is 2:1:6:1.3.
5. The purification method for preparing industrial grade lithium carbonate from electrolytic waste residue according to claim 1, wherein the weight ratio of chitosan, 2wt% acetic acid aqueous solution and dropwise added solution is 2:7:4, and the post-treatment operation of step A2 comprises: transferring the reaction solution into a rotary evaporation bottle, using a rotary evaporator, distilling under reduced pressure at 65-75deg.C until no liquid flows out, adding purified water into the rotary evaporation bottle, stirring for 30-50min, filtering, transferring the filter cake into a vacuum drying oven at 60-80deg.C, and drying for 8-10 hr to obtain modified chitosan.
6. The purification method for preparing industrial grade lithium carbonate from electrolytic waste residues according to claim 1, wherein the weight ratio of the modified chitosan, the 2wt% acetic acid aqueous solution, the carboxylated multi-wall carbon nanotubes and the 50wt% benzaldehyde ethanol solution is 1:10:0.1:2.
7. The purification method for preparing industrial grade lithium carbonate from electrolytic waste residue according to claim 1, wherein the post-treatment operation of step S5 comprises: filtering, leaching with purified water, pumping, transferring the filter cake into an oven with the temperature of 60-80 ℃ and drying for 6-8h to obtain the industrial grade lithium carbonate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310109894.7A CN116081658B (en) | 2023-02-14 | 2023-02-14 | Purification method for preparing industrial grade lithium carbonate from electrolytic waste residues |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310109894.7A CN116081658B (en) | 2023-02-14 | 2023-02-14 | Purification method for preparing industrial grade lithium carbonate from electrolytic waste residues |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116081658A CN116081658A (en) | 2023-05-09 |
| CN116081658B true CN116081658B (en) | 2023-09-08 |
Family
ID=86202369
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310109894.7A Active CN116081658B (en) | 2023-02-14 | 2023-02-14 | Purification method for preparing industrial grade lithium carbonate from electrolytic waste residues |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116081658B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019099901A (en) * | 2017-12-05 | 2019-06-24 | ティーエムシー株式会社 | Method for recovering lithium from lithium-containing solution |
| WO2019221932A1 (en) * | 2018-05-15 | 2019-11-21 | Energysource Minerals Llc | Process for selective adsorption and recovery of lithium from natural and synthetic brines |
| CN111115665A (en) * | 2020-01-15 | 2020-05-08 | 郑州大学 | Method for recycling lithium-potassium-rich aluminum electrolyte |
| CN112778553A (en) * | 2021-01-04 | 2021-05-11 | 常州大学 | Crown ether modified chitosan nano fiber membrane and preparation method and application thereof |
| CN114031099A (en) * | 2021-11-19 | 2022-02-11 | 东北大学 | Acidification roasting method for efficiently treating aluminum electrolysis solid waste |
| CN115216645A (en) * | 2022-07-09 | 2022-10-21 | 江西志存锂业有限公司 | Method for extracting lithium from electrolytic aluminum waste slag by mixed salt calcination method |
-
2023
- 2023-02-14 CN CN202310109894.7A patent/CN116081658B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019099901A (en) * | 2017-12-05 | 2019-06-24 | ティーエムシー株式会社 | Method for recovering lithium from lithium-containing solution |
| WO2019221932A1 (en) * | 2018-05-15 | 2019-11-21 | Energysource Minerals Llc | Process for selective adsorption and recovery of lithium from natural and synthetic brines |
| CN111115665A (en) * | 2020-01-15 | 2020-05-08 | 郑州大学 | Method for recycling lithium-potassium-rich aluminum electrolyte |
| CN112778553A (en) * | 2021-01-04 | 2021-05-11 | 常州大学 | Crown ether modified chitosan nano fiber membrane and preparation method and application thereof |
| CN114031099A (en) * | 2021-11-19 | 2022-02-11 | 东北大学 | Acidification roasting method for efficiently treating aluminum electrolysis solid waste |
| CN115216645A (en) * | 2022-07-09 | 2022-10-21 | 江西志存锂业有限公司 | Method for extracting lithium from electrolytic aluminum waste slag by mixed salt calcination method |
Non-Patent Citations (1)
| Title |
|---|
| High specific surface crown ether modified chitosan nanofiber membrane by low-temperature phase separation for efficient selective adsorption of lithium;Qian Cheng et al.;Separation and Purification Technology;第262卷;1-10 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116081658A (en) | 2023-05-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102212697B (en) | Tungsten slag treatment method | |
| CN103086405B (en) | Clean production method of battery level lithium carbonate | |
| CN110885090A (en) | Method for preparing battery-grade lithium carbonate by using lepidolite as raw material through one-step method | |
| CN106129511A (en) | A kind of method of comprehensively recovering valuable metal from waste and old lithium ion battery material | |
| CN102828025B (en) | Method for extracting V2O5 from stone coal navajoite | |
| CN112919507B (en) | Method for extracting lithium salt from aluminum electrolyte | |
| CN104745823B (en) | Method for recycling lithium from waste lithium ion battery | |
| CN109167118B (en) | Comprehensive utilization method of lithium iron phosphate battery electrode material | |
| CN111926195B (en) | Method for preparing high-purity platinum powder from platinum alloy waste | |
| CN107381604A (en) | A kind of method that lithium carbonate is reclaimed from ferric phosphate lithium cell | |
| CN111471864A (en) | Method for recovering copper, aluminum and iron from waste lithium ion battery leachate | |
| CN111455177B (en) | Method for recovering valuable metals of lithium battery positive electrode material by using saccharides and hydrogen peroxide | |
| CN115287469B (en) | Method for selectively extracting lithium from clay-type lithium ore | |
| CN110835687B (en) | Method for extracting rubidium and cesium from steel smoke dust and/or volatile dust | |
| CN113415793A (en) | Method for preparing high-purity iron phosphate from lithium iron phosphate battery waste | |
| CN113186400A (en) | Method for recovering valuable metal from lithium ion battery | |
| CN113548701A (en) | Preparation and application method of lithium ion sieve | |
| CN109850935B (en) | Method for preparing thallium chloride by using thallium-containing acidic wastewater of smelting plant as raw material | |
| CN116553502A (en) | Method for effectively recycling anode material of waste lithium iron phosphate battery | |
| CN103014334B (en) | Method for replacement dissolution of bastnaesite (bastnasite) | |
| CN116081658B (en) | Purification method for preparing industrial grade lithium carbonate from electrolytic waste residues | |
| Han et al. | Recycling of lithium and fluoride from LiF wastewater from LiF synthesis industry by solvent extraction | |
| CN110106356B (en) | Method for separating lithium from salt lake brine by using powder type titanium ion exchanger | |
| CN108866354B (en) | Method for efficiently extracting vanadium from vanadium-containing ore | |
| CN115404362A (en) | Method for efficiently separating and recovering tungsten from tungsten slag |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |