NL2033897B1 - Method for synchronously leaching rare earth, fluorine and lithium acid leaching solution from rare earth electrolytic molten salt slag - Google Patents

Method for synchronously leaching rare earth, fluorine and lithium acid leaching solution from rare earth electrolytic molten salt slag Download PDF

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NL2033897B1
NL2033897B1 NL2033897A NL2033897A NL2033897B1 NL 2033897 B1 NL2033897 B1 NL 2033897B1 NL 2033897 A NL2033897 A NL 2033897A NL 2033897 A NL2033897 A NL 2033897A NL 2033897 B1 NL2033897 B1 NL 2033897B1
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rare earth
leaching
fluorine
slag
acid
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NL2033897A (en
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Wen Hao
Tong Zhifang
Wang Jiaxing
Ye Chunlin
Xie Zhaoxun
Xu Congcong
Hu Xiaofei
Li Huiquan
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Univ Jiangxi Sci & Technology
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10—Obtaining alkali metals
    • C22B26/12—Obtaining lithium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C22B7/007—Wet processes by acid leaching
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00—Halogens; Halogen acids
    • C01B7/19—Fluorine; Hydrogen fluoride
    • C01B7/20—Fluorine
    • 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
    • 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
    • C01F17/00—Compounds of rare earth metals
    • C01F17/10—Preparation or treatment, e.g. separation or purification
    • 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
    • C01F17/00—Compounds of rare earth metals
    • C01F17/20—Compounds containing only rare earth metals as the metal element
    • C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
    • 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
    • C01F7/00—Compounds of aluminium
    • C01F7/48—Halides, with or without other cations besides aluminium
    • C01F7/50—Fluorides
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/02—Roasting processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B59/00—Obtaining rare earth metals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

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  • General Life Sciences & Earth Sciences (AREA)
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  • Manufacture And Refinement Of Metals (AREA)
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Abstract

The present invention relates to a recycling technology of metallurgical secondary resources, in particular to a Hoethod for synchronously leaching rare earth, fluorine and lithium acid leaching solution from rare earth electrolytic molten salt slag. The present invention. mixes the rare earth electrolytic molten salt slag with calcium oxide and aluminum sulfate, and then cooperative roasting is performed, so that rare earth fluoride in the slag reacts with. the calciuHL oxide to generate rare earth oxide that is easily soluble in acid and calcium fluoride that is slightly soluble in acid. The calcium fluoride generated and unreacted lithium fluoride in the rare earth electrolytic molten salt slag react with the aluminum sulfate at a high temperature.

Description

METHOD FOR SYNCHRONOUSLY LEACHING RARE EARTH, FLUORINE AND LITHIUM
ACID LEACHING SOLUTION FROM RARE EARTH ELECTROLYTIC MOLTEN SALT
SLAG
TECHNICAL FIELD
The present invention relates to a recycling technology of metallurgical secondary resources, in particular to a method for synchronously leaching rare earth, fluorine and lithium acid leaching solution from rare earth electrolytic molten salt slag.
BACKGROUND ART
At present, single rare earth metals and functional rare earth alloys are mainly produced by a molten salt electrolysis process of a fluoride system. The annual output of the rare earth metals produced by the electrolysis process is about 35,000-45,000 tons, and the annual output of an electrolytic molten salt slag generated is about 2,200 tons. In the production process, the re- covery rate of rare earth is only 85-93%, the lost rare earth mainly exists in the molten salt slag in the form of fluorides, the contents of rare earth, lithium, fluorine in the slag may reach 10%-80%, about 5%, and 5%-20% respectively. It is well-known that rare earth, lithium and fluorine are strategic resources in
China. Therefore, it is of great economic value and strategic sig- nificance to comprehensively and efficiently recover rare earth, lithium and fluorine from the rare earth electrolytic molten salt slag.
At present, the recycling of the rare earth molten salt slag mainly focuses on the recovery of rare earth elements in the slag.
In a first method, concentrated sulfuric acid is used to strength- en roasting of the molten salt slag, to obtain soluble rare earth sulfate, and after a series of processes such as extraction puri- fication, crystallization precipitation and burning, the rare earth is finally recovered in the form of rare earth oxide. Alt- hough the first method is simple and large in treatment capacity, the roasting process may generate a hydrogen fluoride gas, and it is harmful to the environment and human body. At the same time, fluorine is not effectively recycled. In a second method, a calci- um hydroxide is used as a fluorine fixing agent due to the differ- ent affinity between fluorine and calcium and rare earth, a rare earth fluoride is replaced as the rare earth oxide that is easily soluble in acid, and then after acid leaching, extraction and pre- cipitation, the rare earth oxide is obtained. The second method is short in process flow and higher in rare earth recovery rate, but a leached residue generated after leaching and separating is cal- cium fluoride residue, it may harm the environment, and fluorine is not used as one resource. In a third method, a sodium silicate is used as an additive through using the characteristics of a rare earth silicate that is insoluble in water but soluble in hydro- chloric acid, so that the rare earth fluoride is converted into the rare earth silicate that is soluble in acid and sodium fluo- ride that is easily soluble in the water. Fluorine is firstly re- moved by water washing, and then the rare earth is leached by ac- id-leaching the rare earth silicate with hydrochloric acid. The third method is simple in operation and short in process flow.
However, in the process of rare earth leaching, a large amount of siliceous impurities may be introduced, and a large amount of the fluoride-containing wastewater may be generated, which may harm the environment, and fluorine is not used as one resource.
In conclusion, the prior art for the utilization of the rare earth electrolytic molten salt slag is mainly to leach the rare earth from the molten salt slag, the extraction of useful compo- nents such as lithium and fluorine in the slag is rarely consid- ered, but rare earth, lithium and fluorine are important strategic resources in China. Therefore, it is very necessary and of great economic value and strategic significance to find a method for synchronously and efficiently extracting useful components such as rare earth, fluorine and lithium from the rare earth electrolytic molten salt slag.
SUMMARY
A purpose of the present invention is to provide a method for synchronously leaching rare earth, fluorine and lithium acid leaching solution from rare earth electrolytic molten salt slag.
At a certain temperature, rare earth electrolytic molten salt slag opens action bonds of all rare earth fluorides, lithium fluorides and other fluorides by the synergistic complexation of calcium ox- ide and aluminum sulfate, rare earth, lithium and fluorine ele- ments are all released, and the simultaneous efficient leaching of rare earth, lithium and fluorine is achieved by acid leaching.
Technical schemes of the present invention provide a method for synchronously leaching rare earth, fluorine and lithium acid leaching solution from rare earth electrolytic molten salt slag, including the following steps: (1) slag drying: putting the massive rare earth electrolytic molten salt slag into an oven and drying at 100°C-120°C for 24 h-48 h; (2) crushing and grinding: crushing the dried slag in step (1) by a crusher for the first time before using a ball mill to grind the slag to a particle size of more than 200 meshes for use; (3) mixing: mixing the ground slag in step (2) with aluminum sulfate octadecahydrate and calcium oxide according to a mass ra- tio of 10-20:25-35:4-8 uniformly to form a master batch; (4) roasting: putting the master batch in step (3) into a tubular furnace for roasting, herein the roasting temperature is controlled at 700°C-200°C, the roasting time is 1 h-5 h, and main chemical reactions in the roasting process are as follows: 2REF; +3Ca0-3CaF,+RE.0;
CaF; +Al: {S04) 3>CaSO,+AlF;
GLiF+Al- (S04)}2>3Li;SO,+2AlF;, (5) leaching: ball-milling the roasted material in step (4) and sieving with a 200-mesh sieve, to obtain powder, putting the powder into a reaction tank, slowly adding sulfuric acid or hydro- chloric acid with a concentration of 1-4 mol/L at a uniform speed, immersing the powder into acid solution, reacting for 2-5 h under a condition of 70°C-95°C, and continuously stirring at a rotation speed of 300 r/min, where a mass-volume solid-liquid ratio of pow- der to sulfuric acid or hydrochloric acid is 1:7.5-15; and (6) filtering: filtering the reacted slurry in step (5), to obtain acid leaching solution containing rare earth, fluorine and lithium and a filter cake, herein after the filter cake is washed by dilute sulfuric ac- id or hydrochloric acid with a concentration of 0.1-0.5 mol/L for 2-3 times, washing solution and residue are obtained, the washing solution is used to prepare sulfuric acid or hydrochloric acid so- lution for leaching in step (5), the phase of the residue is cal- cium sulfate and hydrated calcium sulfate, which are used as raw materials for building materials and cement, and calcium fluoride waste residue and fluoride-containing wastewater are not generat- ed.
The drying temperature of step (1) is preferably 100°C, and the drying time is preferably 48 h.
The mass ratio of slag and aluminum sulfate octadecahydrate and calcium oxide in step (3) is preferably 10:28-34:6-8.
The roasting temperature in step (4) is preferably 800°C- 900°C, and the roasting time is preferably 2-3 h.
The concentration of sulfuric acid or hydrochloric acid in step (5) is preferably 3-4 mol/L, and a mass-volume solid-liquid ratio of powder to sulfuric acid or hydrochloric acid is prefera- bly 1:10-12.5.
Beneficial effects of the present invention:
On the one hand, compared with an existing process, the pre- sent invention leaches the rare earth from rare earth electrolytic molten salt slag, and synchronously leaches useful components in the slag such as fluorine and lithium, the multi-component syn- chronous leaching of rare earth, fluorine and lithium as the stra- tegic resources in China is achieved, and the leaching rates of neodymium, praseodymium, gadolinium, lithium and fluorine in the rare earth electrolytic molten salt slag are as high as 97.34%, 95.37%, 94.89%, 97.37% and 95.35% respectively (shown in Embodi- ment 4). On the other hand, the present invention mixes the rare earth electrolytic molten salt slag with calcium oxide and alumi- num sulfate, and then cooperative roasting is performed, so that a rare earth fluoride in the slag reacts with the calcium oxide to generate rare earth oxide that is easily soluble in acid and cal-
cium fluoride that is slightly soluble in acid. The calcium fluo- ride generated and unreacted lithium fluoride in the rare earth electrolytic molten salt slag react with the aluminum sulfate at a high temperature, so that fluorine in the calcium fluoride and 5 lithium fluoride may be converted into a fluorine-aluminum complex that is easily soluble in acid. Then, by sulfuric ac- id/hydrochloric acid leaching, rare earth, fluorine and lithium in the slag are leached and dissolved in sulfuric acid/hydrochloric acid solution, herein fluorine exists in the solution in the form of fluorine-aluminum complex, thereby rare earth, fluorine and lithium acid leaching solution is obtained. There is no calcium fluoride waste residue and fluoride-containing wastewater generat- ed in the whole process, and there is no fluoride-containing "three wastes" problem in an existing recovery technology.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an X-ray diffraction (XRD) diagram of a residue in a step (6) of the present invention.
DETAILED DESCRIPTION OF THE EMBODIMENTS
In embodiments, rare earth electrolytic molten salt slag pro- duced by a certain domestic rare earth electrolysis plant is used as a raw material, and its raw material components are shown in
Table 1.
Table 1: Main chemical components of rare earth electrolytic molten salt slag
Mass®% 18.72 9.42 12.77 0.85 1.3
Embodiment 1: 2 kg of the rare earth electrolytic molten salt slag was tak- en, dried in an oven for 48 h under a condition of 100°C, after being dried, it was crushed for the first time by a crusher, and then the slag was ground to a particle size of 200 meshes by a ball mill. Then, powder was fully ball-milled and mixed with alu-
minum sulfate octadecahydrate and calcium oxide in the ball mill according to a mass ratio of 10:33.5:6.25, a mixed material was poured into a corundum crucible, and roasted at a temperature of 825°C for 4 h in a tubular furnace, and after a roasted material was cooled, it was ball-milled and sieved with a 200-mesh sieve.
The roasted material after grinding was put into a reaction tank, sulfuric acid with a concentration of 4 mol/L was slowly added ac- cording to a solid-liquid ratio (mass-volume ratio) of the powder to sulfuric acid of 1:10, and then it was continuously reacted at 95°Cfor 4 h at a stirring speed of 300 r/min. After the reaction, slurry was filtered to obtain acid leaching solution containing rare earth, fluorine and lithium and a filter cake. After the fil- ter cake was washed for 2-3 times by a dilute sulfuric acid with a concentration of 0.1-0.5 mol/L, washing solution and residue were obtained, the washing solution was used to prepare sulfuric acid solution for leaching, the phase of the residue was calcium sul- fate and hydrated calcium sulfate, and was used as a raw material for building material and cement, and calcium fluoride waste resi- due and fluoride-containing wastewater were not generated.
Calculation results of the leaching rates showed that under this condition, the leaching rates of neodymium, praseodymium, gadolinium, lithium and fluorine in the rare earth electrolytic molten salt slag were 93.61%, 91.24%, 90.73%, 96.51% and 95.11% respectively.
Embodiment 2: 2 kg of the rare earth electrolytic molten salt slag was tak- en, dried in an oven for 48 h under a condition of 100°C, after being dried, it was crushed for the first time by a crusher, and then the slag was ground to a particle size of 200 meshes by a ball mill. Then, powder was fully ball-milled and mixed with alu- minum sulfate octadecahydrate and calcium oxide in the ball mill according to a mass ratio of 10:31.25:6.25, a mixed material was poured into a corundum crucible, and roasted at a temperature of 900°C for 2 h in a tubular furnace, and after a roasted material was cooled, it was ball-milled and sieved with a 200-mesh sieve.
The roasted material after grinding was put into a reaction tank,
sulfuric acid with a concentration of 3 mol/L was slowly added ac- cording to a solid-liquid ratio (mass-volume ratio) of the powder to sulfuric acid of 1:10, and then it was continuously reacted at 80°Cfor 4 h at a stirring speed of 300 r/min. After the reaction, slurry was filtered to obtain acid leaching solution containing rare earth, fluorine and lithium and a filter cake. After the fil- ter cake was washed for 2-3 times by a dilute sulfuric acid with a concentration of 0.1-0.5 mol/L, washing solution and residue were obtained, the washing solution was used to prepare sulfuric acid solution for leaching, the phase of the residue was calcium sul- fate and hydrated calcium sulfate, and was used as a raw material for building material and cement, and calcium fluoride waste resi- due and fluoride-containing wastewater were not generated.
Calculation results of the leaching rates showed that under this condition, the leaching rates of neodymium, praseodymium, gadolinium, lithium and fluorine in the rare earth electrolytic molten salt slag were 92.47%, 91.56%, 91.08%, 96.69% and 96.8% re- spectively.
Embodiment 3: 2 kg of the rare earth electrolytic molten salt slag was tak- en, dried in an oven for 48 h under a condition of 100°C, after being dried, it was crushed for the first time by a crusher, and then the slag was ground to a particle size of 200 meshes by a ball mill. Then, powder was fully ball-milled and mixed with alu- minum sulfate octadecahydrate and calcium oxide in the ball mill according to a mass ratio of 10:31.25:6.25, a mixed material was poured into a corundum crucible, and roasted at a temperature of 900°C for 2 h in a tubular furnace, and after a roasted material was cooled, it was ball-milled and sieved with a 200-mesh sieve.
The roasted material after grinding was put into a reaction tank, sulfuric acid with a concentration of 4 mol/L was slowly added ac- cording to a solid-liquid ratio (mass-volume ratio) of the powder to sulfuric acid of 1:10, and then it was continuously reacted at 90°Cfor 4 h at a stirring speed of 300 r/min. After the reaction, slurry was filtered to obtain acid leaching solution containing rare earth, fluorine and lithium and a filter cake. After the fil-
ter cake was washed for 2-3 times by a dilute sulfuric acid with a concentration of 0.1-0.5 mol/L, washing solution and residue were obtained, the washing sclution was used to prepare sulfuric acid solution for leaching, the phase of the residue was calcium sul- fate and hydrated calcium sulfate, and was used as a raw material for building material and cement, and calcium fluoride waste resi- due and fluoride-containing wastewater were not generated.
Calculation results of the leaching rates showed that under this condition, the leaching rates of neodymium, praseodymium, gadolinium, lithium and fluorine in the rare earth electrolytic molten salt slag were 95.83%, 96.50%, 93.06%, 95.52% and 94.85% respectively.
Embodiment 4: 2 kg of the rare earth electrolytic molten salt slag was tak- en, dried in an oven for 48 h under a condition of 100°C, after being dried, it was crushed for the first time by a crusher, and then the slag was ground to a particle size of 200 meshes by a ball mill. Then, powder was fully ball-milled and mixed with alu- minum sulfate octadecahydrate and calcium oxide in the ball mill according to a mass ratio of 10:31.25:6.25, a mixed material was poured into a corundum crucible, and roasted at a temperature of 900°C for 2 h in a tubular furnace, and after a roasted material was cooled, it was ball-milled and sieved with a 200-mesh sieve.
The roasted material after grinding was put into a reaction tank, sulfuric acid with a concentration of 3 mol/L was slowly added ac- cording to a solid-liquid ratio (mass-volume ratio) of the powder to sulfuric acid of 1:10, and then it was continuously reacted at 90°Cfor 4 h at a stirring speed of 300 r/min. After the reaction, slurry was filtered to obtain acid leaching solution containing rare earth, fluorine and lithium and a filter cake. After the fil- ter cake was washed for 2-3 times by a dilute sulfuric acid with a concentration of 0.1-0.5 mol/L, washing solution and residue were obtained, the washing solution was used to prepare sulfuric acid solution for leaching, the phase of the residue was calcium sul- fate and hydrated calcium sulfate, and was used as a raw material for building material and cement, and calcium fluoride waste resi-
due and fluoride-containing wastewater were not generated.
Calculation results of the leaching rates showed that under this condition, the leaching rates of neodymium, praseodymium, gadolinium, lithium and fluorine in the rare earth electrolytic molten salt slag were 97.34%, 95.37%, 24.89%, 97.37% and 95.35% respectively.
The leaching solution (acid leaching solution) may be used as a raw material to recover rare earth, lithium and fluorine in acid leaching solution step by step by a subsequent process, to obtain a rare earth sulfate double salt, a cryolite and a battery-grade lithium carbonate respectively, and finally the comprehensive and efficient recycling of rare earth, lithium and fluorine in the ra- re earth electrolytic molten salt slag are achieved.

Claims (6)

CONCLUSIESCONCLUSIONS 1. Werkwijze voor het synchroon uitlogen van zeldzame aarde-, flu- or- en lithiumzuur-uitloogoplossing uit de elektrolytisch gesmol- ten zoutslak van zeldzame aarde, gekenmerkt doordat de werkwijze de volgende stappen omvat: (1) slakken drogen: het plaatsen van de massieve zeldzame aarde elektrolytisch gesmolten zoutslakken in een oven en drogen bij 100 °C tot 120 °C gedurende 24 uur tot 48 uur; {2} breken en malen: het voor de eerste keer breken van de ge- droogde slak in stap (1) door een breker alvorens een kogelmolen te gebruiken om de slak te malen tot een deeltjesgrootte van meer dan 200 mesh voor gebruik; (3) mengen: het uniform mengen van de gemalen slak in stap (2) met aluminiumsulfaatoctadecahydraat en calciumoxide volgens een massa- verhouding van (10 tot 20): (25 tot 35):{4 tot 8) om een master- batch te vormen; (4) roosteren: de masterbatch in stap (3) in een buisoven plaatsen om te roosteren, waarbij de roostertemperatuur wordt geregeld op 700 °C tot 900 °C, de roostertijd 1 uur tot 5 uur is en de belang- rijkste chemische reacties in het roosterproces als volgt zijn: 2REF; +3Ca0-3CaF:+RE;03 CaF; +Al; (504) 3>CaS0,:+Al1Fs GLiF+Al: (S04)}3>3Li:S0,+2AlF;3; (5) uitlogen: het geroosterde materiaal in stap (4) in een kogel- molen malen en zeven met een zeef van 200 mesh om poeder te ver- krijgen, het poeder in een reactietank doen, het langzaam toevoe- gen van zwavelzuur of zoutzuur met een concentratie van 1 tot 4 mol/L bij een eenvormige snelheid, het onderdompelen van het poe- der in zure oplossing , het laten reageren gedurende 2 tot 5 h onder een omstandigheid van 70 °C tot 35 °C, en het onophoudelijk roeren bij een omwentelingssnelheid van 300 r/min, waarbij een massa-volume vaste stof-vloeistofverhouding van poeder tot zwavel- zuur of zoutzuur 1: (7,5 tot 15) is; en (6) filteren: filteren van de gereageerde slurry in stap (5), om een zure uitloogoplossing te verkrijgen die zeldzame aarde, fluor en lithium en een filterkoek bevat, waarbij nadat de filterkoek 2 tot 3 keer is gewassen met verdund zwavelzuur of zoutzuur met een concentratie van 0,1 tot 0,5 mol/L, wasoplossing en residu worden verkregen, de wasoplossing wordt ge- bruikt om zwavelzuur of zoutzuuroplossing te bereiden ten behoeve van uitloging in stap (5), de fase van het residu is calciumsul- faat en gehydrateerd calciumsulfaat, die worden gebruikt als grondstoffen voor bouwmaterialen en cement, en er worden geen cal- ciumfluorideafvalresidu en fluoridehoudend afvalwater gegenereerd.1. Method for synchronously leaching rare earth, fluorine and lithium acid leaching solution from electrolytically molten rare earth salt slag, characterized in that the method includes the following steps: (1) slag drying: placing the solid rare earth electrolytically molten salt slag in a furnace and drying at 100°C to 120°C for 24 hours to 48 hours; {2} crushing and grinding: crushing the dried slag in step (1) for the first time by a crusher before using a ball mill to grind the slag to a particle size of more than 200 mesh before use; (3) mixing: uniformly mixing the ground slag in step (2) with aluminum sulfate octadecahydrate and calcium oxide according to a mass ratio of (10 to 20): (25 to 35): {4 to 8) to form a master batch forms; (4) roasting: placing the masterbatch in step (3) into a tube oven for roasting, where the roasting temperature is controlled at 700°C to 900°C, the roasting time is 1 hour to 5 hours, and the main chemical reactions in the scheduling process is as follows: 2REF; +3Ca0-3CaF:+RE;03 CaF; +Al; (504) 3>CaS0,:+Al1Fs GLiF+Al: (SO4)}3>3Li:S0,+2AlF;3; (5) leaching: grinding the roasted material in step (4) in a ball mill and sieving with a 200 mesh sieve to obtain powder, putting the powder into a reaction tank, slowly adding sulfuric acid or hydrochloric acid at a concentration of 1 to 4 mol/L at a uniform rate, immersing the powder in acidic solution, allowing it to react for 2 to 5 hours under a condition of 70 °C to 35 °C, and stirring continuously at a rotational speed of 300 rpm, where a mass-volume solid-liquid ratio of powder to sulfuric acid or hydrochloric acid is 1: (7.5 to 15); and (6) filtering: filtering the reacted slurry in step (5), to obtain an acidic leaching solution containing rare earth, fluorine and lithium and a filter cake, after washing the filter cake 2 to 3 times with dilute sulfuric acid or hydrochloric acid with a concentration of 0.1 to 0.5 mol/L, washing solution and residue are obtained, the washing solution is used to prepare sulfuric acid or hydrochloric acid solution for leaching in step (5), the residue phase is calcium sul - phate and hydrated calcium sulphate, which are used as raw materials for building materials and cement, and no calcium fluoride waste residue and fluoride-containing wastewater are generated. 2. Werkwijze voor het synchroon uitlogen van zeldzame aarde-, flu- or- en lithiumzuur-uitloogoplossing uit de elektrolytisch gesmol- ten zoutslak van zeldzame aarde volgens conclusie 1, met het ken- merk, dat de droogtemperatuur van stap (1) bij voorkeur 100 °C is, en de droogtijd bij voorkeur 48 uur is.A method for synchronously leaching rare earth, fluorine and lithium acid leaching solution from the electrolytically molten rare earth salt slag according to claim 1, characterized in that the drying temperature of step (1) is preferably 100 °C, and the drying time is preferably 48 hours. 3. Werkwijze voor het synchroon uitlogen van zeldzame aarde-, flu- or- en lithiumzuur-uitlcoogoplossing uit de elektrolytisch gesmol- ten zoutslak van zeldzame aarde volgens conclusie 1, met het ken- merk, dat een massaverhouding van slak en aluminiumsulfaat- octadecahydraat en calciumoxide in stap (3) bij voorkeur 10: (28 tot 34):(6 tot 8) is.A method for synchronously leaching rare earth, fluorine and lithium acid leaching solution from the electrolytically molten rare earth salt slag according to claim 1, characterized in that a mass ratio of slag and aluminum sulphate octadecahydrate and calcium oxide in step (3) is preferably 10: (28 to 34): (6 to 8). 4. Werkwijze voor het synchroon uitlogen van zeldzame aarde-, flu- or- en lithiumzuur-uitloogoplossing uit de elektrolytisch gesmol- ten zoutslak van zeldzame aarde volgens conclusie 1, met het ken- merk, dat de roostertemperatuur in stap (4) bij voorkeur 800 °C tot 900 °C is, en de braadtijd is bij voorkeur 2 tot 3 uur.A method for synchronously leaching rare earth, fluorine and lithium acid leaching solution from the electrolytically molten rare earth salt slag according to claim 1, characterized in that the roasting temperature in step (4) is preferably 800 °C to 900 °C, and the roasting time is preferably 2 to 3 hours. 5. Werkwijze voor het synchroon uitlogen van zeldzame aarde-, flu- or- en lithiumzuur-uitloogoplossing uit de elektrolytisch gesmol- ten zoutslak van zeldzame aarde volgens conclusie 1, met het ken- merk, dat de concentratie van zwavelzuur of zoutzuur in stap (5) bij voorkeur 3 tot 4 mol/L, en een massa-volume vaste stof- vloeistofverhouding van poeder tot zwavelzuur of zoutzuur bij voorkeur 1:{(10 tot 12,5) is.A method for synchronously leaching rare earth, fluorine and lithium acid leaching solution from the electrolytically molten rare earth salt slag according to claim 1, characterized in that the concentration of sulfuric acid or hydrochloric acid in step ( 5) preferably 3 to 4 mol/L, and a mass-volume solid-liquid ratio of powder to sulfuric acid or hydrochloric acid is preferably 1:{(10 to 12.5). 6. Werkwijze voor het synchroon uitlogen van zeldzame aarde-, flu- or- en lithiumzuur-uitloogoplossing uit de elektrolytisch gesmol- ten zoutslak van zeldzame aarde volgens conclusie 1, met het ken- merk, dat de belangrijkste chemische componenten van de elektroly- tisch gesmolten zoutslak van zeldzame aarde de volgende zijn: u u u ”A method for synchronously leaching rare earth, fluorine and lithium acid leaching solution from the electrolytically molten rare earth salt slag according to claim 1, characterized in that the main chemical components of the electrolytically molten rare earth salt slag are: u u u”
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