CN109047285B - Method and system for converting sodium-containing and fluorine-containing compounds in waste cathode carbon blocks of aluminum electrolytic cell - Google Patents
Method and system for converting sodium-containing and fluorine-containing compounds in waste cathode carbon blocks of aluminum electrolytic cell Download PDFInfo
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- CN109047285B CN109047285B CN201810867560.5A CN201810867560A CN109047285B CN 109047285 B CN109047285 B CN 109047285B CN 201810867560 A CN201810867560 A CN 201810867560A CN 109047285 B CN109047285 B CN 109047285B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B5/00—Operations not covered by a single other subclass or by a single other group in this subclass
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D1/00—Oxides or hydroxides of sodium, potassium or alkali metals in general
- C01D1/04—Hydroxides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D7/00—Carbonates of sodium, potassium or alkali metals in general
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/20—Halides
- C01F11/22—Fluorides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/26—Magnesium halides
- C01F5/28—Fluorides
Abstract
The invention relates to a method and a system for converting sodium-containing and fluorine-containing compounds in waste cathode carbon blocks of an aluminum electrolytic cell. The conversion method of the invention comprises the steps of converting sodium-containing compounds in the waste cathode carbon blocks of the aluminum electrolytic cell into soluble sodium compounds without fluorine, converting fluorine-containing compounds into insoluble and harmless mineral fluorine compounds, and oxidizing cyanogen-containing compounds into harmless N by using a conversion agent through mechanochemical conversion reaction in a conversion mill2Or NH3And CO2Thereby completely removing the harm of fluoride and cyanide in the waste cathode carbon block for aluminum electrolysis. The conversion system comprises waste cathode carbon block crushing equipment, grinding equipment, a conversion mill, a stirring reactor and solid-liquid separation equipment which are sequentially connected, the solid-liquid separation equipment is directly connected with concentration or crystallization equipment and drying or heat treatment equipment, and the drying or heat treatment equipment is connected with crushing equipment. The invention has simple process, easy large-scale production, low production cost, no three-waste pollution and environmental protection.
Description
Technical Field
The invention relates to a method and a system for converting sodium-containing and fluorine-containing compounds in waste cathode carbon blocks of an aluminum electrolytic cell, belonging to the technical field of harmless and resource utilization of solid wastes in the electrolytic aluminum industry.
Background
The aluminum electrolysis capacity is about 4500 ten thousand tons, the actual yield exceeds 3600 ten thousand tons and accounts for more than 50 percent of the global aluminum electrolysis capacity in China by 2017. In the process of aluminum electrolysis production, the carbon cathode expands due to the permeation of fluorine-containing salt, and further causes the damage and the rejection of the electrolytic cell. The aluminum electrolytic cell generally needs to be stopped for overhaul after about 4 to 6 years of use, all waste cell lining materials (overhaul residues for short) are taken out, and the waste cathode carbon blocks account for about 50 percent of the overhaul residues. The overhaul slag is solid waste inevitable in the production process of electrolytic aluminum, and 10-30 kg of overhaul slag is generated for each 1 ton of electrolytic aluminum. Electrolytic aluminum overhaul slag under the name of national hazardous wasteRecords specify hazardous solid waste (category: HW48), waste liners have been listed under national records of hazardous waste, HW32 inorganic fluoride waste, HW33 inorganic cyanide waste. The carbon material in the waste cathode carbon block for aluminum electrolysis accounts for 30-70 percent, and the rest is electrolyte and mainly Na3[AlF6]、NaF、CaF2、MgF2、LiF、AlF3、NaCN、Na4[Fe(CN)6]Etc., and also small amounts of Al and Al4C3AlN and Na, which are soluble and reactive with water to produce HF, HCN and H2、CH4、NH3And the harmful or flammable gases, fluorine-containing and cyanogen-containing compounds, which enter the environment, can cause great harm to the health and growth of human beings, animals and plants.
The waste cathode carbon block is a valuable resource rich in highly graphitized carbon and fluorine-containing electrolyte. Therefore, how to thoroughly eliminate the harm of fluoride and cyanide in the waste cathode carbon block of the aluminum electrolytic cell and realize the harmlessness and resource recycling of the waste cathode carbon block of the aluminum electrolytic cell is an industry difficult problem which needs to be overcome urgently, and the experts and production line personnel in the industry conduct years of continuous research and research aiming at the difficult problem.
CN106745137A, CN106077038A, CN106077040A, CN106587122A, CN101817521A, CN106086938A and CN105821445A of the invention propose to treat aluminum electrolysis waste cathode carbon or aluminum electrolysis waste by adopting an alkaline leaching or ultrasonic-assisted flotation and pressurization alkaline leaching method, crush the waste, carry out flotation and magnetic separation to obtain carbon powder A, add alkali liquor to the carbon powder A to dissolve fluoride, add CO into the solution to dissolve fluoride2Separating out cryolite, and performing secondary flotation on the carbon powder A to obtain high-purity carbon powder.
The invention CN106077037A, CN106077036A, CN106180118A and CN101984984A in China propose to treat the aluminum electrolysis waste cathode carbon or overhaul residues by adopting an acid treatment or ultrasonic-assisted flotation pressurization acid treatment method.
The invention CN107162061A of China proposes a method of combining alkali leaching, acid leaching and fly ash to carry out harmless treatment and resource utilization on the waste cathode carbon of the aluminum electrolytic cell.
Chinese inventions CN106064813A and CN105964659A propose that waste cathode carbon powder is subjected to heat preservation and decyanation at 200-400 ℃, decyanation materials are subjected to flotation separation to obtain carbon slag and electrolyte slag, the electrolyte slag is heated at 550-800 ℃ to remove carbon impurities to obtain electrolyte powder, the carbon slag is subjected to alkali leaching to remove soluble substances to obtain carbon powder with high purity, and CO is introduced into alkali leaching filtrate2Separating out the mixture of cryolite and aluminum hydroxide.
The Chinese invention CN102989744A provides a recycling method of mixed slag of overhaul groove slag of an electrolytic cell, which is used for sorting the overhaul groove slag of the electrolytic cell to respectively obtain an electrolyte lump material, a cathode bar, a waste cathode carbon block, a waste refractory brick, a waste heat-insulating plate, waste ramming paste and residual mixed slag; and (3) grinding the sorted mixed slag, then performing flotation to select carbon powder and refractory materials, and preparing the residual powder into a slagging agent. And drying the carbon powder, and then calcining at 1700-1900 ℃ to gasify sodium fluoride and sulfur in the carbon powder to obtain the high-purity carbon powder. And drying the refractory material, and then calcining at 1700-1900 ℃ to gasify sodium fluoride in the refractory material to obtain the high-purity refractory material.
Chinese invention CN105772486A proposes to soak the waste cathode carbon powder in aluminum electrolytic cell with water, leach soluble cyanide, and add hydrogen peroxide, stabilizer (selected from citric acid, tartaric acid, ethylenediamine tetraacetic acid, aminotrimethylene phosphonic acid, polyacrylic acid, maleic acid, borax, ammonium carbonate, ammonium bicarbonate, ammonium acetate and ammonium citrate) and catalyst (selected from ZnO, CuO and Fe)3O4、WO3Middle) and then reacted at 30-70 ℃ to decompose cyanide oxidation products into CO2、NH3A gas.
Chinese invention CN105327933A provides a method for treating waste cell lining of aluminum electrolysis cell based on chemical precipitation and oxidation reduction reaction, which comprises crushing and grinding the waste cell lining, adding sodium hypochlorite solution, controlling the pH value of alkalescence to 7.0-8.5, removing cyanide and sodium hypochlorite solution through oxidation reduction reaction, and reacting with lime water to generate insoluble CaF2。
China invention CN107377592A provides a harmless treatment device and a treatment method for aluminum electrolysis waste cell liners, which comprises the steps of grinding the aluminum electrolysis waste cell liners, adding the ground aluminum electrolysis waste cell liners into a reaction bin, sequentially adding water, a fluorine removal agent (comprising quicklime, hydrated lime or calcium chloride) or a cyanogen removal agent (bleaching powder) and a neutralizing agent (mixed acid), and simultaneously carrying out feeding, reaction and discharging to form a continuous harmless treatment process for the aluminum electrolysis waste cell liners.
Chinese invention CN105964660A provides a method for innocent treatment of aluminum cell waste cell lining, which comprises crushing the aluminum cell waste cell lining, heating in a muffle furnace at a constant temperature of 200-400 ℃ for a certain time to remove cyanogen, adding CaCl into the cyanogen-removed waste cell lining2、Ca3(NO3)2、CaBr2、Ca(ClO4)2Performing salt leaching treatment in the water solution, filtering after stirring and leaching, burying or storing filter residues, and recycling the filtrate as a salt leaching solution.
The invention CN105728440A in China provides an aluminum cell overhaul residue harmless treatment system and a treatment method, the system comprises a leaching bin and a reaction bin which is connected with the leaching bin and is used for carrying out cyanogen and fluorine removal treatment, the cyanogen removal agent is one or more of sodium chlorate, bleaching powder, hydrogen peroxide, bleaching powder essence and chlorine dioxide, and the fluorine removal agent is one or more of calcium chloride, aluminum chloride, magnesium chloride, calcium hydroxide and calcium oxide.
Chinese invention CN106166560A proposes a method for treating waste cathode carbon blocks, which comprises leaching the overhaul residues of an electrolytic cell with water to obtain leached cathode carbon blocks and leachate, reacting the leachate with quicklime, lime milk, carbide slag or calcium chloride, and then performing liquid-solid separation, returning the filtrate to the leaching step for recycling, and stacking filter cakes or using the filter cakes as raw materials for preparing calcium fluoride.
Chinese invention CN107313073A proposes a method for heap leaching treatment of waste cathode linings of aluminum electrolysis cells, which comprises the steps of respectively crushing and screening insulating bricks, castable, anti-seepage materials and carbon materials in waste cathode linings separated from overhaul tank slag of the aluminum electrolysis cells, mixing the crushed waste insulating bricks, castable and anti-seepage materials, and then treating the mixture together, and treating the carbon materials separately; pre-leaching, heap leaching and washing the crushed material by adopting hydrogen peroxideFilter pressing after water decyanation treatment; introducing CO into the filtrate2The gas is subjected to carbonation and neutralization treatment and then concentrated, crystallized and recovered to obtain fluorine-containing NaHCO3And fluorine-containing Na2CO3NaF.
The Chinese invention CN106517209A provides a method for processing waste cathodes of aluminum cell liners, which comprises the steps of adding carbon materials and quartz sand into the waste cathodes of the aluminum cell liners, carrying out high-temperature carbothermic reduction to generate SiC, forming melt sinking by cryolite and carrying out solid-liquid separation on SiC, evaporating fluoride salt in furnace gas and carrying out gas-solid separation on the generated SiC to respectively prepare SiC, the cryolite melt and fluoride salt.
The invention CN107904621A of China proposes a regeneration treatment method of waste cathode carbon blocks of an aluminum electrolytic cell, and the main treatment process comprises crushing, screening, toxicity inhibition, batching and pressure-controlled heat treatment. After the aluminum cell waste cathode carbon block material is crushed and screened, adding toxicity inhibitors such as hydrogen peroxide, potassium permanganate, hypochlorite and the like, then adding carbon materials such as anthracite, calcined petroleum coke, waste anode carbon blocks, anode scraps and the like as furnace entering raw materials, placing the raw materials in a resistance furnace for heat treatment under the conditions of normal pressure (1200-1800 ℃) or controlled pressure (1000-1600 ℃ and 0.01-0.5 atm), cooling and crystallizing the volatilized fluoride in the flue gas for recovery, and enabling the carbon content of the furnace slag to reach 99% and being capable of being used for producing various carbon products.
The invention CN106147910A of China provides a system and a method for producing high-graphite anthracite by using electrolytic aluminum waste cathode carbon blocks, wherein the system comprises a crushing and screening unit, an automatic feeding unit, an ultrahigh temperature calcination unit, a finished product cooling unit and a packaging unit. The graphitization degree of the finished product material is more than or equal to 90% by adopting a method of improving the graphitization degree of the waste cathode carbon block of the electrolytic aluminum under the ultra-high temperature state of 2300-3000 ℃, and the volatile components contained in the raw materials can be completely decomposed under the ultra-high temperature state.
China invention CN100542702C uses waste cathode carbon blocks of aluminum electrolytic cell and SiO-rich2And Al2O3Mixing the fly ash, roasting, and using H to treat the treated material2SO4And lime decomposition treatment, so that the waste cathode carbon blocks of the aluminum electrolytic cell are harmlessly utilized as resources.
Chinese CN101054693A mixes and presses waste cathode carbon powder of an aluminum electrolytic cell and an organic binder into a cluster, and then carries out roasting treatment at 650-900 ℃ for 4-6 hours to completely oxidize carbon to obtain an electrolyte product with the concentration of more than 97.5%.
The CN107628614A of the invention in China calcines the waste cathode of the electrolytic aluminum at 1200-1700 ℃, separates carbon from fluoride, oxide and cyanide in the waste cathode, and realizes harmless and resource utilization.
The invention CN105642649A, CN106185818A and CN106269787A in China treat the waste cathode carbon block of the electrolytic aluminum under the conditions of ultrahigh temperature of more than 2000 ℃ and vacuum, volatilize fluoride in the carbon block, decompose cyanide in the carbon block, the fluoride and the cyanide in the cathode, and effectively separate and decompose the carbon, the fluoride and the cyanide in the cathode, thereby realizing harmless and resource utilization.
From the prior technical results, the harmless and resource treatment and utilization of the waste cathode carbon block of the aluminum electrolytic cell are divided into two main categories, namely wet treatment of aqueous solution and pyrogenic treatment at high temperature. The wet treatment also involves water washing (leaching), alkali method, acid-alkali combination method and flotation process, mainly aims at recovering electrolyte and carbon material, and adopts oxidant to decompose cyanide into harmless gas substance in the wet treatment. The pyrogenic process treatment technology mainly aims at harmlessness, or can effectively utilize the calorific value resource of the waste cathode based on the fact that the carbon content of the waste cathode is more than 50%; or the electrolyte is melted, permeated and separated to be recovered; or converting the fluoride into HF and then carrying out absorption conversion utilization; or converting the electrolyte into harmless and insoluble fluorine mineral by adding a conversion aid; or the carbon material and the electrolyte are respectively recycled by adopting a high-temperature vacuum technology. In the pyrogenic process, cyanide-containing compounds are oxidatively decomposed at high temperatures into harmless gaseous substances.
The wet treatment and the fire treatment of the waste cathode carbon block of the aluminum electrolytic cell still have a plurality of problems which need to be solved urgently.
The current wet processing technology has at least the following main problems: firstly, a large amount of salt-containing and fluorine-containing wastewater generated is not effectively treated, resulting in secondary pollutionDyeing; generated H2、CH4、NH3The gas is not controlled and utilized and the HF produced causes serious pollution. Secondly, the recovered electrolyte and carbon material have too high impurity content to be directly utilized. Thirdly, the process route is complicated, the technology is complex, the equipment corrosion is serious, and the treatment cost is too high. Fourthly, the difficulty of controlling the process parameters is high due to the influence of factors such as the difference of the capacity and the age of the electrolytic aluminum tank, the fluctuation of components, the granularity of powder and the like.
The current fire treatment technology has at least the following main problems: first, the off-gas that produces large amounts of entrained HF and dust needs to be treated. Second, the electrolyte salt is not completely recovered and remains in the carbonaceous material or slag requiring further treatment. Thirdly, the low-melting point electrolyte salt is melted and agglomerated in the furnace, so that the residual quantity of the carbon material is large due to incomplete oxidation and combustion, and the melting and agglomeration in the furnace cause the deterioration of the production working condition and the poor production stability. Fourth, the reaction mass is difficult to achieve uniform mixing at the molecular level, resulting in incomplete conversion reactions. Fifthly, the equipment is seriously corroded and the energy consumption for treatment is high.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method and a system for converting sodium-containing and fluorine-containing compounds in waste cathode carbon blocks of an aluminum electrolytic cell. The invention has the characteristics of convenient control of the production process, easy industrial stable production, low production cost, no three-waste pollution, no equipment corrosion and the like.
The invention is realized by the following technical scheme:
a method for converting sodium-containing and fluorine-containing compounds in the waste cathode carbon blocks of an aluminum electrolytic cell comprises the steps of converting the sodium-containing compounds in the waste cathode carbon blocks of the aluminum electrolytic cell into soluble sodium compounds without fluorine, converting the fluorine-containing compounds into insoluble and harmless mineral fluorine compounds, and oxidizing the cyanogen-containing compounds into harmless N by using a conversion agent through mechanochemical conversion reaction in a conversion mill2Or NH3And CO2Thereby completely removing the harm of fluoride and cyanide in the aluminum electrolysis waste cathode carbon block; the conversion system comprises waste cathode carbon block crushing equipment and grinding powder which are connected in sequenceThe equipment, the conversion mill, the stirring reactor and the solid-liquid separation equipment, wherein the solid-liquid separation equipment is directly connected with the concentration or crystallization equipment and the drying or heat treatment equipment, and the drying or heat treatment equipment is connected with the crushing equipment. The method has the characteristics of simple process, easy large-scale production, low production cost, no three-waste pollution, environmental friendliness and the like. The invention can realize the treatment targets of harmlessness, resource utilization and final polarization of the waste cathode carbon block of the aluminum electrolytic cell.
A method for converting sodium-containing and fluorine-containing compounds in waste cathode carbon blocks of an aluminum electrolytic cell comprises the following partial or all steps (the sequence of the following steps is convenient for expression and does not directly indicate the precedence relationship, and the steps specifically comprise which parts are subject to the logical description or logical relationship in the characters):
(1) crushing, grinding, screening and homogenizing the waste cathode carbon blocks of the aluminum electrolytic cell to obtain waste cathode carbon powder with the particle size less than or equal to 200 mu m; analyzing and determining the mole number or mass of sodium and fluorine in the unit mass of the waste cathode carbon powder; analyzing and determining CN in unit mass of waste cathode carbon powder-The number of moles or mass of ions;
adding the grinding body into the conversion mill, and then carrying out air evacuation or N on the conversion mill2Replacement, namely adding the measured waste cathode carbon powder into a conversion mill, controlling the mass ratio of the waste cathode carbon powder to a grinding body to be 1 (0.2-10), adding the measured water into the conversion mill, and controlling the solid-liquid mass ratio of the waste cathode carbon powder to the water to be 1 (1-10);
adding a conversion agent into a conversion mill according to the amount of 1-3 times of the stoichiometric ratio of the chemical reaction for converting the sodium-containing and fluorine-containing compounds in the waste cathode carbon powder into corresponding products, or according to the amount of 5-80% of the mass of the waste cathode carbon powder;
adding a grinding aid into a conversion mill according to the mass of 0-1% of the waste cathode carbon powder;
(2) after the step (1) is finished, starting the conversion mill, controlling the rotation speed of the conversion mill to be 10-1000 rpm, and controlling the conversion temperature to be 10-110 ℃; in the conversion process, the slurry is sampled and analyzed and checked in batches at regular time until Na in the solid phase substance of the slurry+The ion content meets the enterprise standard and the soluble F-Ion contentStopping the conversion grinding when the national emission standard is met;
(3) after the step (2) is finished, transferring the slurry into a stirring reactor (a reaction kettle, a reaction tank or a reaction tank) for gel breaking and aging treatment, wherein the temperature is controlled to be 60-150 ℃, and the treatment time is 0.5-5 h;
(4) carrying out solid-liquid separation on the slurry obtained in the step (3) by adopting a filtering or centrifugal separation mode, repeatedly carrying out dispersion washing and solid-liquid separation on a water-containing solid-phase substance in a conversion mill or a stirring reactor (a reaction kettle or a reaction tank) by taking water as a washing agent according to the solid-liquid mass ratio of 1 (1-10) for a plurality of times until the content of soluble ions in the solid-phase substance meets the enterprise standard, combining separation liquids, and respectively obtaining a mixture of wet fluorine-containing mineral substances and carbon, namely a dilute solution of the water-containing solid-phase substance and a soluble mixture;
(5) drying or carrying out heat treatment on the aqueous solid phase obtained in the step (4) at the temperature of 80-300 ℃ for 1-10 h, and then crushing to obtain a mixed powder material of a fluorine-containing mineral substance and carbon, wherein the average particle size of the mixed powder material is less than or equal to 20 microns, and the mixed material can be sold as a commodity or further separated and purified to obtain a high-quality carbon material and a fluoride mineral substance raw material;
placing the mixed powder material containing the fluorine-containing mineral substances and carbon in an air atmosphere and a high-temperature furnace at the temperature of 700-1200 ℃ for calcining for 0.5-5 h, wherein the carbon component is completely oxidized and combusted, and the residue of the mixed powder material is a mixture containing the fluorine-containing mineral substances;
(6) concentrating or crystallizing the mixture dilute solution obtained in the step (4) to obtain a mixture concentrated solution or a solid-phase mixture, or further separating and purifying Na, K, Li, Al, Mg and Ca compounds in the mixture to obtain a series of compound raw materials with higher quality and value;
(7) according to CN in waste cathode carbon powder-Conversion of ions to N2Or NH3And CO2In an amount of 1 to 5 times of the stoichiometric ratio of the chemical reaction, or in an amount of 0.1 to 10% by mass of the waste cathode carbon powder, a cyanide conversion agent is added to either the step (2), the step (3) or the step (6) to oxidatively convert a cyanide-containing compound into harmless N2Or NH3And CO2The analysis and check are carried out on the transformation system in batches and at regular time until CN in the system-The conversion reaction is stopped when the ion content meets the national emission standard;
(8) the NH generated in the step (2) or the step (3) or the step (6)3、CO2、H2And (4) carrying out absorption conversion and drying on the O gas, and collecting the generated reducing gas or directly oxidizing and burning the reducing gas.
Al and Al exist in the waste cathode carbon block of the aluminum electrolytic cell4C3AlN, Na, etc., and combustible gases (including H) generated by the reaction taking part in the conversion reaction2、CH4、NH3Etc.) is the reducing gas in the step (8).
In the conversion mill, high-energy mechanical force synchronously acts on the mechanochemical conversion reaction of the sodium-containing compound and the fluorine-containing compound, so that solid particles are continuously ground, milled and converted, reactants and products are continuously updated and stripped from carbon particles, and the conversion reaction is quickly and completely finished.
Further, in all the steps, the pH is controlled to be not less than 6, no protonic acid substance is used, and the sodium and fluorine compound conversion agent, cyanide conversion agent and grinding aid substance are used without chlorine element.
Further, the main elements of the waste cathode carbon block are more than two of C (including graphitized C and non-graphitized C), Na, F, Al, Ca, O, N, Li, Mg, Si, K and Fe; the sodium-containing compound comprises NaF and Na3AlF6、NaCN、Na4[Fe(CN)6]Two or more of (1); the fluorine-containing compound comprises NaF and Na3AlF6、AlF3、LiF、CaF2、MgF2And KF.
Further, the conversion agent of the sodium-containing compound and the fluorine-containing compound comprises one or more than two of oxides, hydroxides, sulfates, nitrates, carbonates, acetates and citrates corresponding to the elements of Ca, Al, Mg, Sr, Ba, La and Ce.
After being converted by the converting agent, the sodium-containing compounds in the waste cathode carbon powder are converted into corresponding non-fluorine-containing soluble sodium-containing compounds including NaOH and Na2SO4、NaNO3、NaOAc、Na2CO3、Na3C6H5O7、Na2AlO4、Na[Al(OH)6]2(OH)3、NaAlSi2O6、Na2(H2SiO4)·7H2O、Na6Si8O19、Na2Al2SiO6、Na2Si2O5、Na2SiO3One or more than two of them.
The corresponding insoluble and harmless mineral fluoride including CaF converted from fluorine-containing compound in the waste cathode carbon powder by using the conversion agent2、MgF2、AlF3、SrF2、BaF2、CaF2、LaF3、CeF3、CeF4One or more than two of them.
Further, the cyanide conversion agent comprises Na2CO3·1.5H2O2、K2CO3·1.5H2O2、Na2O2、K2O2、CaO2、SrO2、BaO2、H2O2、(NH4)2S2O8、Na2S2O8、K2S2O8、KMnO4、O2、O3One or more than two of them.
Further, the grinding aid comprises one or more of polymeric polyol, polymeric alcohol amine, triisopropanolamine, ethylene glycol, propylene glycol, glycerol, diethylene glycol, triethanolamine, amide, stearic acid, oleic acid, sodium hexametaphosphate and sodium stearate.
Furthermore, the transforming agent and the grinding aid are added in a solid, aqueous solution or gas state in a one-time adding mode, a batch adding mode or a continuous adding mode.
A conversion system for sodium-containing and fluorine-containing compounds in waste cathode carbon blocks of an aluminum electrolytic cell comprises waste cathode carbon block crushing equipment, powder grinding equipment, a conversion mill, a stirring reactor and solid-liquid separation equipment which are sequentially connected, wherein the solid-liquid separation equipment is directly connected with concentration or crystallization equipment and drying or heat treatment equipment, and the drying or heat treatment equipment is connected with crushing equipment.
Further, the device also comprises a condensing device which is connected with the concentrating or crystallizing device.
And further, the tail gas collecting and absorbing device is further included and is connected with the powder grinding device, the conversion mill, the stirring reactor and the condensing device.
Furthermore, the device also comprises storage equipment, wherein the storage equipment comprises a powder material storage device connected with the crushing equipment and a concentrated solution or crystallized product storage device.
Further, the device comprises analytical instrument equipment, wherein the analytical instrument equipment is used for analyzing and detecting samples taken from a grinding device, a conversion mill, a stirring reactor, a concentration or crystallization device, a drying or heat treatment device and a storage device.
Further, the waste cathode carbon block crushing equipment comprises a jaw crusher, a cone crusher, a column crusher, a double-shaft crusher or an impact type fine crusher.
Furthermore, the milling equipment comprises a column mill, a Raymond mill, a vertical mill, an air swept mill or a roller press and a homogenization device matched with the milling equipment for powder selection and screening, so that the waste cathode carbon powder with uniform composition and particles less than or equal to 200 mu m is obtained.
Further, the concentration or crystallization equipment is a multi-effect evaporation concentration or crystallization device, is used for concentrating or crystallizing a separation liquid of a soluble mixture obtained by solid-liquid separation, and relates to heat energy supply, heat exchange and condensation of an evaporation phase, recycling of condensed water, delivery of a concentrated solution or a crystallized substance and the like.
The tail gas collecting and absorbing equipment is used for crushing, grinding and homogenizing, converting, breaking and washing, concentrating, crystallizing and the likeAnd collecting and absorbing the tail gas. The material component in the tail gas comprises H2O、NH3、CO2、H2、CH4、N2And trace amounts of dust; in which the gas phase H2Recycling O by condensation, NH3、CO2The dust is absorbed and utilized by an absorbent, and the combustible gas H2、CH4Collected for storage or entered into a combustion furnace for use as fuel.
The analytical instrument is used for material component detection, material conversion effect and content control detection, product quality detection and environmental protection emission standard monitoring in all links of the production process.
Further, the conversion mill is a modified airtight ball mill, and a mill body is provided with a grinding body inlet and outlet, a powder inlet, a liquid material inlet, a gas outlet, a slurry outlet, a cleaning emptying port, a gas sampling port and a slurry sampling port; the grinding body is one or more than two of corundum balls, zirconia balls, ceramic balls, steel balls, stainless steel balls and alloy balls.
The invention has the beneficial effects that:
(1) the invention has the characteristics of convenient control of the process, easy industrial stable production, low production cost, no three-waste pollution, no equipment corrosion and the like.
(2) The invention solves the problems and the defects of the existing wet treatment and fire treatment production process. Provides an advanced and systematic solution for the harmlessness and resource recycling of the aluminum electrolysis waste cathode carbon blocks.
Drawings
FIG. 1 is a schematic process flow diagram of the conversion process of the present invention.
Fig. 2 is a schematic structural diagram of a system employed in the present invention.
FIG. 3 is an X-ray diffraction pattern of the used cathode carbon block of the aluminum electrolytic cell used in example 1.
FIG. 4 is an X-ray diffraction chart of a mixed powder material B obtained in example 1.
FIG. 5 is a thermogram of the mixed powder material B obtained in example 1.
Detailed Description
The following examples further illustrate the technical solutions of the present invention, but the present invention is not limited to the examples and is not intended to limit the scope of the present invention.
As shown in fig. 2, the system of the present invention comprises a waste cathode carbon block crushing device 1, a milling device 2, a conversion mill 3, a stirring reactor 4 and a solid-liquid separation device 5 which are connected in sequence, wherein the solid-liquid separation device 5 is directly connected with a concentration or crystallization device 7 and a drying or heat treatment device 6, and the drying or heat treatment device 6 is connected with a crushing device 8; still include condensing equipment 9, tail gas collection absorption apparatus 10 and storage equipment, condensing equipment 9 is connected with concentration or crystallization apparatus 7, and tail gas collection absorption apparatus 10 all is connected with milling equipment 2, conversion mill 3, stirring reactor 4, condensing equipment 9, and storage equipment includes the storage device 12 of the powder material storage device 11 and concentrate or crystallization product that is connected with crushing apparatus.
The device also comprises analytical instrument equipment, and the analytical instrument equipment is used for analyzing and detecting samples taken from the devices such as a grinding device, a conversion mill, a stirring reactor, a concentration or crystallization device, a drying or heat treatment device and the like.
The waste cathode carbon block crushing equipment comprises a jaw crusher, a cone crusher, a column crusher, a double-shaft crusher or an impact type fine crusher.
The milling equipment comprises a column mill, a Raymond mill, a vertical mill, a wind sweeping mill or a roller press and a homogenization device matched with the milling equipment for powder selection and screening, so that the waste cathode carbon powder with uniform composition and particles less than or equal to 200 mu m is obtained.
The concentrating or crystallizing equipment is a multi-effect evaporating concentrating or crystallizing device, is used for concentrating or crystallizing a separation liquid of a soluble mixture obtained by solid-liquid separation, and relates to heat energy supply, heat exchange and condensation of an evaporation phase, recycling of condensed water, delivery of a concentrated solution or a crystallized substance and the like.
The tail gas collecting and absorbing equipment is used for collecting and absorbing tail gas generated in the processes of crushing, grinding and homogenizing, conversion reaction, gel breaking and washing, concentration, crystallization and the like. The material component in the tail gas comprises H2O、NH3、CO2、H2、CH4、N2And trace amounts of dust; in which the gas phase H2Recycling O by condensation, NH3、CO2The dust is absorbed and utilized by an absorbent, and the combustible gas H2、CH4Collected for storage or entered into a combustion furnace for use as fuel.
The conversion mill is a modified airtight ball mill, and a mill body is provided with a grinding body inlet and outlet, a powder inlet, a liquid material inlet, a gas outlet, a slurry outlet, a cleaning emptying port, a gas sampling port and a slurry sampling port; the grinding body is one or more than two of corundum balls, zirconia balls, ceramic balls, steel balls, stainless steel balls and alloy balls.
Example 1
(1) The waste cathode carbon blocks of the aluminum electrolytic cell are crushed in a high-speed crusher, sieved by a 200-mesh sieve, and the waste cathode carbon powder of the undersize material is adopted to carry out the mechanochemical conversion of the compounds containing sodium and fluorine. Determining the mass content of sodium and fluorine elements in the unit mass of the aluminum electrolytic cell waste cathode carbon powder by adopting a chemical analysis method, and determining CN in the unit mass of the aluminum electrolytic cell waste cathode carbon powder by adopting the chemical analysis method-Mass content of ions.
(2) 200g of corundum balls are added into a conversion mill, and 100g of waste cathode carbon powder and 44g of CaSO are weighed4·2H2O、3g Ca(OH)2Adding into a conversion mill, mixing, and adding N2Displacing air from the inversion mill and adding 300g H to the inversion mill2And O. Starting the conversion mill, wherein the rotating speed is 500rpm, the temperature is 30 ℃, and the conversion reaction time is 3 h.
Transferring the slurry to a stirring reactor after the conversion reaction, wherein the stirring speed is 1000rpm, the temperature is 95 ℃, and Na with the mass percentage concentration of 10 percent is dropwise added into the system during the stirring reaction2CO3·1.5H2O215g of the solution is stirred at constant temperature and reacted for 90min, and then the reaction is stopped.
Respectively passing the tail gas generated in the step (1) and the step (2) through an absorber using water as an absorbent and Ca (OH)2Is an absorber of an absorbent, wherein NH3、CO2The dust is absorbed H2、CH4And (4) carrying out combustion oxidation.
(3) Carrying out negative pressure suction filtration on the slurry after the stirring reaction, transferring the filter cake into a conversion mill after suction filtration, and adding 200g H2Dispersing, washing and then pumping filtration of O in a conversion mill, repeatedly washing and pumping filtration until the final filtrate uses 2mol/L BaCl2The solution was checked for precipitate and the filtrates were combined.
The filtrate was evaporated under reduced pressure, concentrated and crystallized and dried in a vacuum oven at 100 ℃ for 10h to give a soluble mixture A.
(4) Drying the water-containing filter cake at 100 ℃ under normal pressure for 20h, crushing the dried product to obtain a mixed powder material B of the fluorine-containing mineral substance and carbon, and calcining the mixed powder material of the fluorine-containing mineral substance and carbon at 900 ℃ for 3h to obtain a fluorine-containing mineral substance C without carbon.
As can be seen from FIG. 3, the main phase components of the waste cathode carbon block of the aluminum electrolytic cell used in example 1 are C, NaF and Na3AlF6、CaF2、LiF、MgF2、AlN。
As can be seen from FIG. 4, the main component of the mixed powder material B of fluorine-containing mineral and carbon obtained by the treatment of example 1 was C, CaF2、MgF2、Al2O3、SiO2、CaO、CaSO4NaF and Na of waste cathode carbon block of aluminum electrolytic cell3AlF6、AlF3LiF and other components are completely converted into mineral CaF2And MgF2。
From the thermal analysis of the mixed powder material B in FIG. 5, it was found that the residue ratio at 900 ℃ was 46.4% and the burn-out ratio was 53.6%.
From these test analysis data it can be seen that: example 1 realizes the complete conversion of sodium-containing and fluorine-containing compounds in the waste cathode carbon block of the aluminum electrolytic cell, and thoroughly removes the harm of fluoride and cyanide in the waste cathode carbon block of the aluminum electrolytic cell.
Example 2
(1) Crushing the waste cathode carbon blocks of the aluminum electrolytic cell in a high-speed crusher, sieving by a 200-mesh sieve, and adopting the sieveThe lower material is subjected to mechanochemical conversion of sodium-containing and fluorine-containing compounds. Determining the mass content of sodium and fluorine elements in the unit mass of the aluminum electrolytic cell waste cathode carbon powder by adopting a chemical analysis method, and determining CN in the unit mass of the aluminum electrolytic cell waste cathode carbon powder by adopting the chemical analysis method-Mass content of ions.
(2) Adding 300g of corundum balls into a conversion mill, weighing 100g of waste cathode carbon powder, 35g of CaO and 1g of polyvinyl alcohol, adding into the conversion mill, uniformly mixing, and adding N2Displacing air from the inversion mill and adding 400g H to the inversion mill2And O. The conversion mill is started, the rotating speed is 800rpm, the temperature is 40 ℃, and the conversion reaction time is 2 hours.
Transferring the slurry to a stirring reactor after the conversion reaction, wherein the stirring speed is 900rpm, the temperature is 105 ℃, and when the stirring reaction is carried out, adding 8 percent K by mass into the system2S2O8The reaction was stopped by stirring the solution (25 g) at constant temperature for 100 min.
Respectively passing the tail gas generated in the step (1) and the step (2) through an absorber using water as an absorbent and an absorber using CaO as an absorbent, wherein NH is3、CO2The dust is absorbed H2、CH4And (4) carrying out combustion oxidation.
(3) Carrying out negative pressure suction filtration on the slurry after the stirring reaction, transferring a filter cake into a conversion mill after suction filtration, and adding 300g H2Dispersing, washing and then pumping filtration of O in a conversion mill, repeatedly washing and pumping filtration until the final filtrate uses 2mol/L NH4Solution F was checked for precipitate and the filtrates were combined.
The filtrate was evaporated under reduced pressure, concentrated and crystallized and dried in a vacuum oven at 100 ℃ for 10h to give a soluble mixture A.
(4) Drying the water-containing filter cake at 100 ℃ under normal pressure for 20h, crushing the dried product to obtain a mixed powder material B of the fluorine-containing mineral substance and carbon, and calcining the mixed powder material of the fluorine-containing mineral substance and carbon at 900 ℃ for 3h to obtain a fluorine-containing mineral substance C without carbon.
Experimental results show that the example 2 realizes the complete conversion of sodium-containing and fluorine-containing compounds in the waste cathode carbon blocks of the aluminum electrolytic cell, and thoroughly removes the harm of fluoride and cyanide in the waste cathode carbon blocks of the aluminum electrolytic cell.
Example 3
(1) The waste cathode carbon blocks of the aluminum electrolytic cell are crushed in a high-speed crusher, sieved by a 200-mesh sieve, and the undersize products are adopted to carry out the mechanochemical conversion of sodium-containing and fluorine-containing compounds. Determining the mass content of sodium and fluorine elements in the unit mass of the aluminum electrolytic cell waste cathode carbon powder by adopting a chemical analysis method, and determining CN in the unit mass of the aluminum electrolytic cell waste cathode carbon powder by adopting the chemical analysis method-Mass content of ions.
(2) 200g of corundum balls are added into a conversion mill, 100g of waste cathode carbon powder and 50g of MgSO4Adding into a conversion mill, mixing, and adding N2Displacing air from the inversion mill and adding 350g H to the inversion mill2And O. Starting the conversion mill, wherein the rotating speed is 900rpm, the temperature is 50 ℃, and the conversion reaction time is 4 hours.
Transferring the slurry to a stirring reactor after the conversion reaction, wherein the stirring speed is 700rpm, the temperature is 110 ℃, and Na with the mass percentage concentration of 5 percent is dropwise added into the system during the stirring reaction2S2O830g of the solution is stirred at constant temperature and the reaction is stopped for 110 min.
Respectively passing the tail gas generated in the step (1) and the step (2) through an absorber using water as an absorbent and Ca (OH)2Is an absorber of an absorbent, wherein NH3、CO2The dust is absorbed H2、CH4And (4) carrying out combustion oxidation.
(3) Carrying out negative pressure suction filtration on the slurry after the stirring reaction, transferring the filter cake into a conversion mill after suction filtration, and adding 200g H2Dispersing, washing and then pumping filtration of O in a conversion mill, repeatedly washing and pumping filtration until the final filtrate uses 2mol/L BaCl2The solution was checked for precipitate and the filtrates were combined.
The filtrate was evaporated under reduced pressure, concentrated and crystallized and dried in a vacuum oven at 100 ℃ for 10h to give a soluble mixture A.
(4) Drying the water-containing filter cake at 100 ℃ under normal pressure for 20h, crushing the dried product to obtain a mixed powder material B of the fluorine-containing mineral substance and carbon, and calcining the mixed powder material of the fluorine-containing mineral substance and carbon at 900 ℃ for 3h to obtain a fluorine-containing mineral substance C without carbon.
Experimental results show that the example 3 realizes the complete conversion of sodium-containing and fluorine-containing compounds in the waste cathode carbon blocks of the aluminum electrolytic cell, and thoroughly removes the harm of fluoride and cyanide in the waste cathode carbon blocks of the aluminum electrolytic cell.
Claims (9)
1. A method for converting sodium-containing compounds and fluorine-containing compounds in waste cathode carbon blocks of an aluminum electrolytic cell is characterized by comprising the following steps:
(1) crushing, grinding, screening and homogenizing the waste cathode carbon blocks of the aluminum electrolytic cell to obtain the waste cathode carbon powder of the aluminum electrolytic cell with particles less than or equal to 200 mu m; analyzing and determining the mole number or mass of sodium and fluorine in the unit mass of the waste cathode carbon powder of the aluminum electrolytic cell; analysis and determination of CN in unit mass of waste cathode carbon powder of aluminum electrolytic cell-The number of moles or mass of ions;
adding the grinding body into the conversion mill, and then carrying out air evacuation or N on the conversion mill2Replacement, namely adding measured aluminum cell waste cathode carbon powder into a conversion mill, controlling the mass ratio of the aluminum cell waste cathode carbon powder to a grinding body to be 1 (0.2-10), adding measured water into the conversion mill, and controlling the solid-liquid mass ratio of the aluminum cell waste cathode carbon powder to the water to be 1 (1-10);
adding a conversion agent of a sodium-containing compound and a fluorine-containing compound into a conversion mill according to the amount which is 1-3 times of the stoichiometric ratio of the chemical reaction of converting the sodium-containing compound and the fluorine-containing compound in the waste cathode carbon powder of the aluminum electrolytic cell into corresponding products or according to the amount which is 5-80% of the mass of the waste cathode carbon powder of the aluminum electrolytic cell;
adding a grinding aid into a conversion mill according to the mass of 0-1% of the waste cathode carbon powder of the aluminum electrolytic cell;
(2) after the step (1) is finished, starting the conversion mill, controlling the rotation speed of the conversion mill to be 10-1000 rpm, and controlling the conversion temperature to be 10-110 ℃; in the conversion process, the slurry is sampled and analyzed and checked in batches at regular time until Na in the solid phase substance of the slurry+The ion content meets the enterprise standard and the soluble F-Stopping the conversion grinding when the ion content meets the national emission standard;
(3) after the step (2) is completed, transferring the slurry into a stirring reactor for gel breaking and aging treatment, controlling the temperature to be 60-150 ℃ and the treatment time to be 0.5-5 h;
(4) carrying out solid-liquid separation on the slurry obtained in the step (3) by adopting a filtering or centrifugal separation mode, repeatedly carrying out dispersion washing and solid-liquid separation on a water-containing solid-phase substance in a conversion mill or a stirring reactor by taking water as a washing agent according to the solid-liquid mass ratio of 1 (1-10) until the content of soluble ions in the solid-phase substance meets the enterprise standard, combining separation liquids, and respectively obtaining a mixture of wet fluorine-containing mineral substances and carbon, namely a dilute solution of the water-containing solid-phase substance and the soluble mixture;
(5) drying or heat-treating the water-containing solid phase substance obtained in the step (4) at the temperature of 80-300 ℃ for 1-10 h, and then crushing to obtain a mixed powder material of the fluorine-containing mineral substance and carbon;
placing the mixed powder material containing the fluorine-containing mineral substances and carbon in an air atmosphere and a high-temperature furnace at the temperature of 700-1200 ℃ for calcining for 0.5-5 h, wherein the carbon component is completely oxidized and combusted, and the residue of the mixed powder material is a mixture containing the fluorine-containing mineral substances;
(6) concentrating or crystallizing the mixture dilute solution obtained in the step (4) to obtain a mixture concentrated solution or a solid phase mixture;
(7) according to CN in waste cathode carbon powder-Conversion of ions to N2Or NH3And CO2In an amount of 1 to 5 times of the stoichiometric ratio of the chemical reaction, or in an amount of 0.1 to 10% by mass of the waste cathode carbon powder, a cyanide conversion agent is added to either the step (2), the step (3) or the step (6) to oxidatively convert a cyanide-containing compound into harmless N2Or NH3And CO2The analysis and check are carried out on the transformation system in batches and at regular time until CN in the system-The conversion reaction is stopped when the ion content meets the national emission standard;
(8) the NH generated in the step (2) or the step (3) or the step (6)3、CO2、H2And (4) carrying out absorption conversion and drying on the O gas, and collecting the generated reducing gas or directly oxidizing and burning the reducing gas.
2. The method for converting sodium-containing compounds and fluorine-containing compounds in the waste cathode carbon blocks of an aluminum electrolysis cell according to claim 1, wherein in all the steps, the pH is controlled to be not less than 6, no protonic acid substance is used, and a conversion agent of sodium-containing compounds and fluorine-containing compounds, a cyanide conversion agent and a grinding aid substance are used, and chlorine elements are not contained.
3. The method for converting sodium-containing compounds and fluorine-containing compounds in the waste cathode carbon blocks of the aluminum electrolytic cell according to claim 1, wherein the main elements of the waste cathode carbon blocks are two or more of C, Na, F, Al, Ca, O, N, Li, Mg, Si, K and Fe; the sodium-containing compound comprises NaF and Na3AlF6、NaCN、Na4[Fe(CN)6]Two or more of (1); the fluorine-containing compound comprises NaF and Na3AlF6、AlF3、LiF、CaF2、MgF2And KF.
4. The method for converting sodium-containing compounds and fluorine-containing compounds in the waste cathode carbon blocks of an aluminum electrolytic cell according to claim 1, wherein the converting agent for the sodium-containing compounds and the fluorine-containing compounds comprises one or more of oxides, hydroxides, sulfates, nitrates, carbonates, acetates or citrates corresponding to each element of Ca, Al, Mg, Sr, Ba, La or Ce.
5. The method as claimed in claim 1, wherein the cyanide conversion agent comprises Na2CO3·1.5H2O2、K2CO3·1.5H2O2、Na2O2、K2O2、CaO2、SrO2、BaO2、H2O2、(NH4)2S2O8、Na2S2O8、K2S2O8、KMnO4、O2、O3One or more than two of them.
6. The method for converting sodium-containing compounds and fluorine-containing compounds in the waste cathode carbon blocks of the aluminum electrolytic cell according to claim 1, wherein the grinding aid comprises one or more of polymeric polyol, polymeric alcohol amine, triisopropanolamine, ethylene glycol, propylene glycol, glycerol, diethylene glycol, triethanolamine, amide, stearic acid, oleic acid, sodium hexametaphosphate and sodium stearate.
7. The method for converting sodium-containing compounds and fluorine-containing compounds in the waste cathode carbon blocks of the aluminum electrolytic cell according to claim 1, wherein the conversion agent of the sodium-containing compounds and the fluorine-containing compounds, the cyanide conversion agent and the grinding aid are added in a solid, aqueous solution or gas state by a single addition, or in batches, or continuously.
8. A conversion system for sodium-containing compounds and fluorine-containing compounds in waste cathode carbon blocks of an aluminum electrolytic cell is characterized by comprising waste cathode carbon block crushing equipment, grinding equipment, a conversion mill, a stirring reactor and solid-liquid separation equipment which are sequentially connected, wherein the solid-liquid separation equipment is directly connected with concentration or crystallization equipment and drying or heat treatment equipment, and the drying or heat treatment equipment is connected with the crushing equipment; still include condensing equipment, tail gas collection absorption equipment, storage equipment and analytical instrument equipment, condensing equipment is connected with concentrated or crystallization equipment, tail gas collection absorption equipment and milling equipment, the conversion grinds, stirring reactor, condensing equipment all is connected, storage equipment includes the storage device of the powder material storage device and concentrate or the crystallization product that are connected with crushing apparatus, analytical instrument equipment is to getting from milling equipment, the conversion grinds, stirring reactor, concentrated or crystallization equipment, drying or heat treatment equipment, the sample of storage equipment carries out the analysis and detection.
9. The system for converting sodium-containing compounds and fluorine-containing compounds in the waste cathode carbon blocks of the aluminum electrolytic cell according to claim 8, wherein the waste cathode carbon block crushing equipment is a jaw crusher, a cone crusher, a column crusher, a double-shaft crusher or an impact type fine crusher; the milling equipment is a column mill, a Raymond mill, a vertical mill, a wind sweeping mill or a roller press and homogenization equipment matched with the milling equipment for powder selection and screening; the concentration or crystallization equipment is a multi-effect evaporation concentration or crystallization device; the conversion mill is a modified airtight ball mill, and a mill body is provided with a grinding body inlet and outlet, a powder inlet, a liquid material inlet, a gas outlet, a slurry outlet, a cleaning emptying port, a gas sampling port and a slurry sampling port; the grinding body is one or more than two of corundum balls, zirconia balls, ceramic balls, steel balls and alloy balls.
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| CN113249576B (en) * | 2021-04-20 | 2022-11-11 | 沈阳铝镁设计研究院有限公司 | Waste cathode carbon block, fluoride and metal sodium recovery processing equipment and use method |
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