CN1721559A - Process for comprehensive recovery of rare earth and thorium from rare earth ore - Google Patents
Process for comprehensive recovery of rare earth and thorium from rare earth ore Download PDFInfo
- Publication number
- CN1721559A CN1721559A CNA2005100852303A CN200510085230A CN1721559A CN 1721559 A CN1721559 A CN 1721559A CN A2005100852303 A CNA2005100852303 A CN A2005100852303A CN 200510085230 A CN200510085230 A CN 200510085230A CN 1721559 A CN1721559 A CN 1721559A
- Authority
- CN
- China
- Prior art keywords
- rare earth
- thorium
- iron
- acid
- phosphorus
- 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.)
- Granted
Links
Images
Classifications
-
- 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
Abstract
The RE mineral smelting and separating process includes the following steps: mixing mixed RE concentrate or monazite RE mineral with concentrated sulfuric acid and iron containing assistant and roasting in controlled condition to make RE, Th, Fe, P, etc. form water or dilute acid solution soluble matter; leaching the roasted mineral with water or dilute acid solution and filtering to obtain low radioactive slag and water leached liquid; neutralizing and filtering the water leached liquid to enrich Th, Fe, P, etc. inside slag; extracting the sulfuric acid solution of RE with non-saponified P204 (D2EHPA) or P204 containing mixed extractant to obtain RE; dissolving That-Fe-P slag and extracting to recover Th, neutralizing raffinate to recover ferrous phosphate and returning the mother liquid containing small amount of RE to leaching mineral. The said process is simple, flexible, low in chemical material consumption, suitable for large scale production, high in recovering efficiency of RE, Th, Fe, P, etc. and environment friendly.
Description
Technical Field
The invention relates to a smelting separation process method of rare earth ore. Mixing mixed rare earth concentrate (a mixture of bastnaesite and monazite) or monazite rare earth ore with concentrated sulfuric acid and an iron-containing auxiliary agent, and roasting at a proper temperature and time to form water-soluble or dilute acid substances of rare earth, thorium, part of iron and phosphorus valuable elements; leaching roasted ore with water or dilute acid, and directly filtering to obtain low-radioactivity slag and water leaching solution; neutralizing and filtering the water leaching solution to enrich thorium, iron, phosphorus and the like in slag, recovering thorium through acid dissolution and extraction, and neutralizing and recovering iron phosphate through raffinate; the obtained pure sulfuric acid rare earth solution is directly extracted and separated by unsaponifiable P204(D2EHPA) or mixed extractant containing P204.
Background
At present, the industrial treatment process of the mixed rare earth concentrate comprises a sulfuric acid roasting method and a caustic soda method, wherein more than 90 percent of the mixed rare earth concentrate is treated by adopting a high-temperature sulfuric acid reinforced roasting method.
The low-temperature sulfuric acid roasting method for smelting mixed rare earth concentrate process developed in 70 s of 20 th century by Beijing institute of nonferrous metals research, Gansu rare earth company and other units, and applied to industrial production of rare earth (see the following document for details) [1]]Zhanggucheng et al, abstracted compilation of annual meeting papers of the Chinese society for metals in 1980, Beijing, P54; [2]Romoto, ministration of the world, fourth national rare earth chemistry and hydrometallurgy society, proceedings abstract (supra), 1987, second part, P10; [3]Xu Xiong constitution eds, rare earths, 2 nd edition (supra), Metallurgical Press, 2002, P401, P408). The process mixes the mixed rare earth concentrate with the REO content of more than 30 percent with sulfuric acid in advance to form slurry, the mineral acid ratio is 1: 1.7, then the slurry flows into an external heating type rotary kiln to be decomposed at the temperature of 200-300 ℃, the reaction time is 1.5-3.0 h, and the residual acid is not driven to the full in the decomposition process. Directly leaching roasted ore from a rotary kiln by using water, controlling REO to be 40-45 g/L and H2SO40.5 to 0.8 mol/L.
During the roasting process, RE, P, Fe, Th and other material in the ore are decomposed into sulfate and other soluble salt, which enters into water solution, and the alkali earth metal sulfate is left in the slag. The decomposition rate of the concentrate is 95-97%. The reaction is as follows:
the rare earth sulfate water extract obtained by the method has high acidity and contains a large amount of impurities such as iron, phosphorus and the like, and the impurities are separated from the rare earth by adopting a double-salt precipitation alkali conversion method. The method has the advantages of complex flow, low rare earth yield, discontinuous process and difficult recovery of radioactive thorium dispersed in slag and wastewater.
In order to recover thorium in rare earth ore, some domestic rare earth science and technology workers develop a primary ammonium thorium extraction process on the basis of a low-temperature sulfuric acid roasting process. Thorium extraction is carried out on the water leaching solution by using primary ammonium, and the raffinate is subjected to rare earth fishing by using the primary ammonium to remove iron and phosphorus; naphthenic acid is extracted and transformed to remove sulfate radical, and finally P507 is adopted to extract and separate rare earth (4) rare earth chemical collection, Changchun chemical institute, 1982, science publishing company). The process has the advantages that the thorium in the rare earth ore can be recovered, and the main problems are as follows: (1) because the roasting temperature of the concentrate is low, the residual acid content of the roasted ore is high, the roasted ore is damp and easy to adhere to the kiln wall, and the continuous production is influenced; (2) the impurities such as iron and phosphorus in the raffinate obtained after thorium extraction by primary amine are high, the acidity is over 0.6mol/L, rare earth cannot be directly extracted and separated, iron and phosphorus in the rare earth must be removed by primary amine extraction, the acidity of the raffinate reaches about 0.8mol/L, a large amount of alkali is consumed to neutralize the spent acid, and the back extract is subjected to naphthenic acid fishing of rare earth transformation to remove sulfate radical and then is extracted and separated by P507; (3) the process needs three kinds of extractants, and the loss of the extractants is large. The process is complex, large in chemical material consumption and high in cost, so that the process is not applied to industry all the time. The process flow is shown in figure 1.
The process adopted in the industry at present is a process for decomposing mixed rare earth concentrate by a sulfuric acid enhanced roasting method developed by the institute of nonferrous metals of Beijing in the early 80 s ([3]]The xu-xu constitution is compiled, rare earth,2 nd edition (on the book), the publication of metallurgical industry, 2002, P401, P408), simplify the process for producing rare earth chloride by decomposing mixed rare earth concentrate with sulfuric acid method, reduce the production cost. The process mixes the rare earth concentrate with excessive concentrated sulfuric acid and then carries out high-temperature reinforced roasting at 400-500 ℃, so that impurities such as thorium, iron, phosphorus and the like form insoluble phosphate or pyrophosphate to enter slag, the roasting time is prolonged, and H in roasted ore is treated2SO4Drive away as far as possible to ensure H2SO4The content is less than 7 percent, and the acidity of the water extract0.05-0.15 mol/L, and the rare earth enters the water leaching solution as soluble sulfate. The main reaction is as follows:
when the reaction temperature reaches 300 ℃, the phosphoric acid generated by the decomposition reaction is dehydrated to form pyrophosphoric acid, and the pyrophosphoric acid reacts with thorium and calcium to form pyrophosphate which is difficult to dissolve in water.
When the reaction temperature is about 328 ℃, the sulfuric acid is decomposed.
When the reaction temperature reaches 400 ℃, Fe2(SO4)3Decomposed into salt-based ferric sulfate which is hardly soluble in water, and the pyrophosphoric acid is further dehydrated.
The roasted ore water extract is neutralized by magnesium oxide, calcium oxide or calcium carbonate to remove trace impurities such as iron, thorium, phosphorus and the like, pure sulfuric acid rare earth solution is obtained, rare earth is directly extracted and separated or ammonium bicarbonate precipitation method is adopted to produce rare earth carbonate, and then single or composite rare earth compounds are prepared by hydrochloric acid dissolution and P507 extraction separation. The process flow is shown in figure 2.
The disadvantages of the process are as follows: valuable elements such as iron, thorium, phosphorus and the like are all put into the leached slag and cannot be recovered, and particularly, thorium is enriched in the slag, so that the radioactivity of the slag exceeds the standard, and the environmental pollution is caused.
Disclosure of Invention
The invention aims to provide a comprehensive recovery process method of rare earth and thorium in rare earth ore. The process method is simple and reasonable, has high recovery rate of rare earth and thorium, is easy to realize large-scale production, and has strong adaptability to the grade and the variety of rare earth ores; the organic phase does not need ammonium salt or sodium salt saponification in the whole extraction process,ammonia nitrogen wastewater is not generated, and the consumption of chemical materials is low. The process method can effectively recover rare earth, thorium, iron and phosphorus valuable elements, can eliminate the pollution of thorium, ammonia, nitrogen and the like to the environment, and is an environment-friendly process flow.
In order to achieve the purpose, the invention adopts the following technical scheme:
a process method for comprehensively recovering rare earth and thorium from rare earth ore comprises the following steps:
(1) mixing the mixed rare earth concentrate, namely a mixture of bastnaesite and monazite or the monazite rare earth ore, concentrated sulfuric acid and an iron-containing auxiliary agent, and then roasting to enable rare earth, thorium, part of valuable elements such as iron, phosphorus and the like to form soluble salts, namely roasted ore;
(2) leaching roasted ore with water or dilute acid, and directly filtering to obtain low-radioactivity slag and water leaching solution;
(3) neutralizing and filtering the water leaching solution to enrich thorium, iron, phosphorus and the like in the slag to respectively obtain iron-phosphorus thorium slag and a pure rare earth sulfate solution;
in the process method, the iron-phosphorus-thorium solution obtained by dissolving the iron-phosphorus-thorium slag obtained in the step (3) with inorganic acid is extracted to recover thorium, raffinate is used for neutralizing and recovering iron phosphate and is used as an additive for preparing a rare earth phosphate fertilizer, and mother liquor is returned to leaching.
In the process method, the pure sulfuric acid rare earth solution obtained in the step (3) is directly extracted and separated by adopting unsaponifiable P204 or a mixed extractant containing P204.
In the process method, in the step (1), the iron-containing auxiliary agent is iron oxide, iron ore or iron slag, the adding amount is determined according to the composition of the ore, and Fe/P in the mixture of the ore and the iron auxiliary agent is 2-8 (weight ratio).
In the process of the present invention, in the step (2), Fe/P in the leachate is 2 to 5 (by weight). The Fe/P ratio in the leachate is preferably about 3.
In the process method, in the step (1), the use amount of concentrated sulfuric acid is 1-1.8 of sulfuric acid/ore weight ratio, the roasting temperature is 260-380 ℃, the roasting time is 1-8 hours, and the residual acid of the roasted ore is controlled at 2-20 wt%.
In the process method of the invention, in the step (1), the roasting temperature is preferably 280-310 ℃, and the residual acid of the roasted ore is preferably controlled to be less than 10% by weight, and more preferably controlled to be 3-10% by weight.
In the process method, in the step (2), the roasted ore is immersed in water, and the water consumption is 5-18: 1 of the weight ratio of water to the roasted ore; or soaking with dilute acid, wherein the dilute acid is 0.05-0.6 mol/L of one or more of sulfuric acid, hydrochloric acid or nitric acid, and the weight ratio of the dilute acid to the roasted ore is 5-18: 1; leaching temperatures are 10-60 ℃ respectively, and leaching time is 1-8 hours respectively; the rare earth concentration (REO) of the leached leaching solution is controlled within the range of 20-50 g/l.
In the process method, in the step (3), the water extract is neutralized to pH3.5-5 by one or a mixture of two of magnesia, magnesite, dolomite, magnesia and brucite.
In the process method, during the process of dissolving the iron-phosphorus thorium slag by the inorganic acid, the iron-phosphorus thorium slag is dissolved by 0.5-12 mol/L nitric acid or hydrochloric acid, and the acidity of the solution is 0.1-6 mol/L.
In the process method, the acidity of the solution is preferably 0.3-1 mol/L after the iron-phosphorus thorium slag is dissolved by the nitric acid or the hydrochloric acid.
In the process method, the iron-phosphorus-thorium solution obtained by dissolving the iron-phosphorus-thorium slag through inorganic acid is prepared by fractionating and extracting thorium through P350 or TBP, wherein the concentration of P350 or TBP is 5-50% by volume, the extraction level is 3-15 levels, the washing level is 3-15 levels, the back extraction level is 3-10 levels, the ratio of an organic phase, a material liquid, a washing liquid and a back extraction liquid is 0.1-5: 1: 0.1-1: 0.05-1, the washing liquid and the back extraction acid are dilute nitric acid or hydrochloric acid, the acidity is 5-0.5 mol/L, the back extraction liquid is concentrated and crystallized to prepare thorium nitrate or thorium chloride with the concentration of more than 99.9%, and the back extraction liquid can also be calcined by oxalic acid precipitation to prepare thorium oxide.
In the process method, the pure rare earth sulfate solution is a pure rare earth sulfate solution containing REO 20-50 g/L and having a pH value of 3.5-5, the non-saponified P204 or the mixed extracting agent containing P204 is directly used and is 0.5-1.5 mol/L of non-saponified P204(D2EHPA) or the mixed extracting agent prepared from one of P204 and P507(HEH/EHP), C272, C301, C302 and HEOPPA, and the process for extracting and separating rare earth comprises the following steps: performing cerium/praseodymium and praseodymium/neodymium extraction grouping by using the mixed extractant, and performing neodymium/samarium extraction grouping by directlyfeeding the loaded rare earth organic phase to obtain praseodymium-neodymium or neodymium chloride and samarium-europium-gadolinium enriched materials; neutralizing raffinate containing lanthanum, cerium or lanthanum, cerium and praseodymium to the pH value of 2-5, extracting by using unsaponifiable P204, and performing back extraction by using hydrochloric acid or nitric acid to produce lanthanum, cerium, praseodymium, rare earth chloride or rare earth nitrate; or grouping neodymium/samarium, carrying out hydrochloric acid back extraction on the loaded rare earth organic phase to obtain a samarium-europium-gadolinium enriched material, neutralizing raffinate to the pH value of 2-5, and extracting by using nonsaponifiable P204 to prepare the lanthanum-cerium-praseodymium-neodymium rare earth chloride. The above compounds can also be further extracted and separated to prepare single rare earth oxides of 99-99.999% purity, such as lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium and the like.
The concentrated sulfuric acid used in the present invention has a concentration of>92% by volume.
The mixed rare earth concentrate (the mixture of the bastnaesite and the monazite) or the monazite rare earth ore is mixed with concentrated sulfuric acid and an iron-containing auxiliary agent and then roasted under a certain condition, so that valuable elements such as rare earth, thorium, partial iron, phosphorus and the like form water or dilute acid soluble substances, and the residual acid of the roasted ore is lower; leaching roasted ore with water or dilute acid, and directly filtering, wherein the water leaching residue is a low-radioactive substance and can be directly stacked; neutralizing and filtering the water leaching solution, and enriching thorium, iron, phosphorus and the like in the slag; obtaining pure sulfuric acid rare earth solution, and directly extracting and separating rare earth by using P204 or a mixed extractant containing P204; dissolving iron-phosphorus-thorium slag by acid to obtain an iron-phosphorus-thorium solution, extracting and recovering thorium, neutralizing and recovering iron phosphate from raffinate to be used as an additive for preparing a rare earth phosphate fertilizer, and returning mother liquor to leaching.
The invention has the advantages that: 1) when the rare earth ore is decomposed by sulfuric acid roasting method, a certain quantity of additive containing rare earth is addedIron auxiliary agent, and controlling acid dosage, roasting temperature and roasting time to ensure that rare earth and thorium are almost completely leached and obtain sulfuric acid rare earth leachate with low acid content, so that the water leaching residue basically contains no radioactive element thorium, and the radioactivity ratio is less than 7 multiplied by 104Bq/kg, can be directly stockpiled; 2) Fe/P in the leaching solution is more than 3, so that the loss of rare earth generated by phosphate precipitation during neutralization and impurity removal is avoided, and the recovery rate of the rare earth is improved; 3) the water extract is neutralized by magnesium oxide, thorium, iron and phosphorus are enriched in slag and separated from rare earth, so that the subsequent rare earth separation and purification process is simplified; 4) thorium iron phosphorus slag is dissolved by acid, thorium is enriched by about ten times, equipment and plants for extracting and purifying thorium are greatly reduced, protection is facilitated, the process for extracting and purifying thorium by TBP or P350 is advanced, the thorium recovery rate is more than 95%, and the thorium purity is more than 99.9%; 5) the sulfuric acid rare earth solution directly adopts unsaponified P204 or mixed extractant containing P204 to perform cerium praseodymium or praseodymium neodymium group extraction, and the loaded organic phase directly performs neodymium samarium groupextraction, so that neodymium or praseodymium neodymium chloride and samarium gadolinium enriched materials can be obtained, and the neutralization and filtration processes of the rare earth extraction and separation process of the original P204-sulfuric acid system are saved, thereby simplifying the process; 6) an ammonium bicarbonate precipitation transformation process is omitted, organic phase does not need ammonium salt or sodium salt saponification in the whole extraction process, ammonia nitrogen wastewater is not generated, and the consumption of chemical materials is low; 7) the invention has simple and flexible whole process flow, high recovery rate of rare earth and thorium, low cost, easy realization of large-scale production and strong adaptability to the grade and the variety of rare earth ores. The process not only can effectively recover rare earth, thorium and partial valuable elements of iron and phosphorus, but also eliminates the pollution of thorium, ammonia, nitrogen and the like to the environment, and is an environment-friendly process flow.
Drawings
FIG. 1 is a process flow chart of low-temperature sulfuric acid roasting and primary ammonium thorium extraction
FIG. 2 is a flow chart of a concentrated sulfuric acid enhanced roasting process
FIG. 3 is a flow chart of the process for comprehensively recovering rare earth and thorium by roasting concentrated sulfuric acid
Detailed Description
This is explained in detail below with reference to fig. 3.
The process for comprehensively recovering rare earth and thorium from rare earth ore adopts the following specific technical scheme:
1. adding a certain amount of iron oxide, iron ore or iron slag (the adding amount is determined according to the composition of ore, the Fe/P in the mixture of ore and iron auxiliary agent is 2-8 (weight ratio) so that the Fe/P in the leaching solution is about 3), mixing with 1-1.8 times of concentrated sulfuric acid (more than 92%, sulfuric acid/ore and weight ratio), roasting at the temperature of 260-380 ℃ for 1-8 hours, controlling the residual acid of the roasted ore to be 2-20 wt%, preferably below 10 wt%, and ensuring that elements such as rare earth and thorium and the like generate substances which are soluble in water or dilute acid. The key point of decomposing rare earth ore by the sulfuric acid roasting method is to well combine the acid dosage, the roasting temperature and the roasting time to ensure that rare earth and thorium are almost completely leached and obtain sulfuric acid rare earth leachate with lower acid content.
2. Soaking roasted ore in water, wherein the water consumption is 5-18: 1 of the weight ratio of water to the roasted ore; or soaking with dilute acid, wherein the dilute acid is 0.05-0.6 mol/L of one or two mixed acids of sulfuric acid, hydrochloric acid or nitric acid, and the weight ratio of the dilute acid to the roasted ore is 5-18: 1; leaching temperatures are 10-60 ℃ respectively, and leaching time is 1-8 hours respectively; the rare earth concentration (REO) of the leached leaching solution is controlled within the range of 20-50 g/l.
3. Filtering the slurry, washing the residue with water for 1-3 times, and returning the washing water to leaching ore to obtain leached residue which is low-radioactive substance and can be directly stockpiled.
4. And neutralizing the water extract with one or two of magnesia, magnesite, magnesia, dolomite and brucite to pH 3.5-5 to precipitate thorium, iron and phosphorus into thorium phosphate, iron phosphate or thorium hydroxide and iron hydroxide, and filtering to obtain iron-phosphorus thorium slag and a pure rare earth sulfate solution.
5. Dissolving iron-phosphorus thorium residue with 0.5-12 mol/L nitric acid or hydrochloric acid, wherein the acidity of the solution is 0.1-6 mol/L, preferably 0.3-1 mol/L.
6. And purifying thorium from the obtained iron-phosphorus-thorium solution by adopting a P350 or TBP extraction method, wherein the concentration of P350 or TBP is 5-50 vol%, the extraction grade is 3-15, the washing grade is 3-15, and the back extraction grade is 3-10, the ratio (organic phase: feed liquid: acid washing: back extraction acid) is 0.1-5: 1: 0.1-1: 0.05-1, the acid washing and back extraction acid is dilute nitric acid or hydrochloric acid, and the acidity is 5-0.5 mol/L. The back extraction liquid is concentrated and crystallized to prepare thorium nitrate or thorium chloride with the concentration of over 99.9 percent, and the back extraction liquid can also be used for producing thorium oxide by an oxalic acid precipitation method, and the recovery rate of thorium is more than 95 percent.
7. The raffinate after thorium extraction is neutralized and precipitated by one or two mixtures of magnesia, magnesite, magnesia, dolomite and brucite to obtain iron phosphate concentrate containing a small amount of rare earth, which can be used as an additive for producing rare earth phosphate fertilizer, and the mother liquor is returned to the leaching to recover rare earth.
8. Directly adopting a non-saponified P204(D2EHPA) or a mixed extractant prepared from one of P204 and P507(HEH/EHP), C272, C301, C302 and HEOPPA in an amount of 0.5-1.5 mol/L to carry out cerium/praseodymium and praseodymium/neodymium extraction grouping on a pure rare earth sulfate solution (the rare earth concentration (REO) is 20-50 g/L, and the pH is 3.5-5), and directly feeding a loaded rare earth organic phase to carry out neodymium/samarium extraction grouping, thus obtaining a praseodymium-neodymium or neodymium chloride and a samarium-gadolinium enrichment; neutralizing raffinate containing lanthanum, cerium or lanthanum, cerium and praseodymium to the pH value of 2-5, extracting by using unsaponifiable P204, and performing back extraction by using hydrochloric acid or nitric acid to produce lanthanum, cerium, praseodymium, rare earth chloride or rare earth nitrate; or grouping neodymium/samarium, carrying out hydrochloric acid back extraction on the loaded rare earth organic phase to obtain a samarium-europium-gadolinium enriched material, neutralizing raffinate to the pH value of 2-5, and extracting by using nonsaponifiable P204 to prepare the lanthanum-cerium-praseodymium-neodymium rare earth chloride. The above compounds can also be further extracted and separated to prepare single rare earth oxides of 99-99.999% purity, such as lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium and the like.
Example 1
1000 g of Baotou mixed rare earth concentrate (rare earth content REO 51%, Fe3.1%, P2.6%, ThO)20.21%) and 70g Fe2O31200 g of concentrated sulfuric acid (more than 92 percent) are mixed and roasted for 3 hours at the temperature of 310 ℃ to obtain 1470 g of roasted ore, the acid content of the ore is 4 percent, 10000ml of dilute sulfuric acid of 0.1mol/L is used for leaching for 3 hours at the temperature of 40 ℃, the ore is filtered, the slag is washed by 1500ml of water and dried to obtain 420 g of dry slag, and the radioactivity ratio activity is less than 4 multiplied by 104Bq/kg. 11390ml of aqueous extract was obtained, which had the following composition: REO 42.8g/l, ThO20.181g/l，Fe 6.15g/l，P2.1g/l，CaO 1.2g/l，H+0.26 mol/L. The recovery rate of rareearth is 95.58 percent, and the recovery rate of thorium is 98.2 percent.
Neutralizing the water extract with magnesium oxide to pH4 to allow thorium, iron and phosphorus to generate thorium phosphate, iron phosphate or thorium hydroxide, and iron hydroxide precipitate, filtering, and washing to obtain 225 g (REO 9.85%, ThO) of iron-phosphorus thorium residue20.90%) and 11630ml of pure rare earth sulfate solution, which had the following composition: REO 40.01g/l, ThO20.003g/l, Fe 0.01g/l, P0.001 g/l. By the process, the total recovery rate of rare earth is 91.24%, and the total recovery rate of thorium is 96.6%.
Dissolving iron phosphorus thorium residue with 500ml 6.5 mol/L nitric acid, filtering, washing to obtain 550ml solution with acidity of 0.6mol/L, ThO2The content was 3.68g/l, REO 41.36 g/l. The solution is extracted by 15 percent TBP, the extraction grade is 8 grades, the washing grade is 10 grades, and the back extraction grade is 6 grades, the phase ratio (organic phase: feed liquid: washing liquid: back extraction liquid) is 0.3: 1: 0.2: 0.10, the washing liquid is dilute nitric acid with the pH value of 5, and the back extraction acid is 0.1mol/L dilute nitric acid. 50ml of stripping solution is obtained and is distilled and concentrated to obtain 4.25 g of thorium nitrate (2.01 g calculated by ThO 2), the purity is 99.92%, the content of REO is 0.043%, Fe2O30.025% and P2O50.01%, and the total recovery rate of thorium is 95.7 l.
The raffinate after thorium extraction is neutralized to pH4 by magnesium oxide to obtain 196.6 g of ferric phosphate which can be used as an additive for producing rare earth phosphate fertilizer.
Example 2
Pure rare earth sulfate solution (REO 40.01g/l, ThO)20.003g/L, Fe 0.01g/L, P0.001g/L, pH4.2) using a mixed extractant containing 80% of 1mol/L non-saponified P204 and 20% of 1mol/L non-saponified P507 to perform cerium/praseodymium grouping, extracting for 2L, washing for 30 stages, and washing with 0.5mol/L sulfuric acid; directly entering a neodymium/samarium extraction grouping section without back extraction of a loaded rare earth organic phase, extracting 9 grades, washing 13 grades and back extraction 8 grades, extracting by adopting the mixed extracting agent, and continuously back extracting and washing by using 6mol/L hydrochloric acid to obtain praseodymium-neodymium chloride (cerium oxide is less than 0.05 percent and samarium oxide is less than 0.01 percent) and samarium-europium-gadolinium chloride (neodymium oxide is less than 0.1 percent); after the raffinate containing lanthanum and cerium is neutralized to PH2, non-saponified P204 of 1.5mol/L is adopted to carry out 5-level extraction and 2-level water washing, and the loaded lanthanum and cerium organic phase is subjected to 5-level hydrochloric acid back extraction to obtain lanthanum and cerium rare earth chloride (the content of praseodymium oxide is less than 0.1%).
Example 3
Pure rare earth sulfate solution (REO 40.01g/l, ThO)20.003g/L, 0.01g/L of Fe, 0.001g/L, pH4.2) adopting a mixed extractant of 70% of 1mol/L unsaponifiable P204 and 30% of 1mol/L unsaponifiable P507 to carry out neodymium/samarium grouping, extraction 11 stages, washing 15 stages and back extraction 8 stages, washing by adopting 0.5mol/L sulfuric acid and back extraction by 6mol/L hydrochloric acid to obtain samarium-europium-gadolinium chloride (neodymium oxide is less than 0.1%); the raffinate containing lanthanum, cerium, praseodymium and neodymium is neutralized to PH4 by magnesium oxide, then 1.3mol/L unsaponifiable P204 is extracted by 6, 2-grade water washing is carried out, and the loaded lanthanum, cerium and lanthanum organic phase is back extracted by 6-grade hydrochloricacid to obtain lanthanum, cerium, praseodymium and neodymium rare earth chloride (the samarium oxide content is less than 0.005%).
Example 4
1000 g of Baotou mixed rare earth concentrate (rare earth content REO 51%, Fe 3.1%, P2.6%, ThO)20.21%) and 80 g Fe2O31300 g of concentrated sulfuric acid, mixing and roasting at 290 ℃ for 3 hours to obtain 1510 g of roasted ore with the acid content of 8 percent, leaching the roasted ore with 11000ml of water at 40 ℃ for 3 hours, filtering, washing the slag with 1000ml of water for 2 times to obtain 407 g of dry slag with the radioactivity ratio of less than 4 multiplied by 104Bq/kg. 11760ml of aqueous extract was obtained, which had the following composition: REO 41.70g/l, ThO20.176g/l，Fe 6.95g/l，P 2.21g/l，CaO 1.3g/l，H+0.41 mol/L. The recovery rate of rare earth is 96.16%, and the recovery rate of thorium is 98.5%.
The water extract is neutralized to pH4 with magnesite, so that thorium, iron and phosphorus are generated into thorium phosphate, iron phosphate or thorium hydroxide and iron hydroxide precipitates, and 238 g of iron-phosphorus thorium slag (REO 9.88%, ThO) is obtained by filtering and washing20.85%) and 11950ml of pure rare earth sulfate solution, which has the following composition: REO 39.07g/l, ThO20.003g/l, Fe 0.01g/l, P0.001 g/l. By the process, the total recovery rate of rare earth is 91.55 percent, and the total recovery rate of thorium is 96.83 percent.
The method for dissolving, extracting and separating the iron-phosphorus thorium slag is the same as the example 1, and the method for extracting and separating the rare earth sulfate solution is the same as the examples 2 and 3.
Example 5
1000 g of Australian monazite rare earth concentrate (rare earth content REO 45%, Fe)2O327.5％，P2O518.7％，ThO20.27%) and 40 g of iron slag (containing Fe)2O357%) and 1500 g of concentrated sulfuric acid, and roasting the mixture at 340 ℃ for 5 hours to obtain 1460 g of roasted ore,the acid content was 6%, and the residue was leached with 12000ml of water at 30 ℃ for 2 hours, filtered and the residue washed with 2000ml of water to give 13728ml of a leach solution consisting of: REO 31.24g/l, ThO20.193g/l, Fe 7.4g/l, P2.8 g/l. The recovery rate of rare earth is 95.31%, and the recovery rate of thorium is 98.0%.
The leaching solution is neutralized by magnesium oxide to pH3.8, thorium, iron and phosphorus are generated into thorium phosphate, iron phosphate or thorium hydroxide and iron hydroxide precipitates, and 327 g (REO 6.61%, ThO) of iron-phosphorus thorium slag is obtained after filtration and washing20.80%) and 14280ml of pure rare earth sulfate solution, which has the following composition: nREO 28.52g/l, ThO20.002g/l, Fe 0.03g/l, P0.001 g/l. The recovery rate of rare earth in the working procedure is 94.96%, and the recovery rate of thorium is 98.92%.
The method for dissolving, extracting and separating the iron-phosphorus thorium slag is the same as the example 1, and the method for extracting and separating the rare earth sulfate solution is the same as the examples 2 and 3.
Example 6
1000 g of Australian monazite rare earth ore (rare earth content REO 19.72%, Fe)2O343.5％，P2O58.73％，ThO20.1%) and 1500 g of concentrated sulphuric acid, roasting at 340 ℃ for 3 hours to obtain 1560 g of roasted ore with an acid content of 8%, leaching with 10000ml of water at 30 ℃ for 2 hours, filtering, washing the residue with 1500ml of water toobtain 11228ml of leachate consisting of: REO 16.24g/l, ThO20.086g/l, Fe 6.3g/l, P1.8 g/l. The recovery rate of rare earth is 93.39%, and the recovery rate of thorium is 97.0%.
The method for neutralizing, filtering, dissolving iron-phosphorus thorium slag and extracting and separating the leachate is the same as that of example 1, and the method for extracting and separating the rare earth sulfate solution is the same as that of examples 2 and 3.
Claims (13)
1. A process method for comprehensively recovering rare earth and thorium from rare earth ore is characterized by comprising the following steps:
(1) mixing the mixed rare earth concentrate, namely a mixture of bastnaesite and monazite or the monazite rare earth ore, concentrated sulfuric acid and an iron-containing auxiliary agent, and then roasting to enable rare earth, thorium, part of valuable elements such as iron, phosphorus and the like to form soluble salts, namely roasted ore;
(2) leaching roasted ore with water or dilute acid, and directly filtering to obtain low-radioactivity slag and water leaching solution;
(3) neutralizing and filtering the water leaching solution to enrich thorium, iron, phosphorus and the like in the slag, and respectively obtaining iron-phosphorus thorium slag and pure rare earth sulfate solution.
2. The process of claim 1, wherein the iron-phosphorus-thorium solution obtained by dissolving the iron-phosphorus-thorium slag obtained in step (3) with inorganic acid is subjected to extraction and thorium recovery, and the iron phosphate is neutralized and recovered in raffinate, and is used as an additive for preparing a rare earth phosphate fertilizer, and the mother liquor is returned to leaching.
3. The process of claim 1, wherein the pure sulfuric acid rare earth solution obtained in step (3) is directly extracted and separated from rare earth by using unsaponifiable P204 or a mixed extractant containing P204.
4. The process according to claim 1, wherein in the step (1), the iron-containing auxiliary is iron oxide, iron ore or iron slag, and the addition amount is determined according to the composition of the ore, so that the Fe/P ratio in the mixture of the ore and the iron auxiliary is 2-8 (weight ratio).
5. The process according to claim 1, wherein in the step (2), the Fe/P ratio in the leachate is 2-5 (by weight).
6. The process method as claimed in claim 1, wherein in the step (1), the concentrated sulfuric acid is used in an amount of 1-1.8 by weight of sulfuric acid/ore, the roasting temperature is 260-380 ℃, the roasting time is 1-8 hours, and the residual acid of the roasted ore is controlled to be 2-20% by weight.
7. The process according to claim 6, wherein in the step (1), the roasting temperature is 280-310 ℃, and the residual acid of the roasted ore is controlled to be 3-10 wt%.
8. The process method as claimed in claim 1, wherein in the step (2), the roasted ore is immersed in water, and the water consumption is 5-18: 1 of the weight ratio of water to the roasted ore; or soaking with dilute acid, wherein the dilute acid is 0.05-0.6 mol/L of one or more of sulfuric acid, hydrochloric acid or nitric acid, and the weight ratio of the dilute acid to the roastedore is 5-18: 1; leaching temperatures are 10-60 ℃ respectively, and leaching time is 1-8 hours respectively; the rare earth concentration (REO) of the leached leaching solution is controlled within the range of 20-50 g/l.
9. The process method as claimed in claim 1, wherein in the step (3), the water extract is neutralized to pH 3.5-5 by one or a mixture of two of magnesia, magnesite, dolomite, magnesia and brucite.
10. The process of claim 2, wherein during the dissolution of iron-phosphorus thorium slag with inorganic acid, the iron-phosphorus thorium slag is dissolved with 0.5-12 mol/L nitric acid or hydrochloric acid, and the acidity of the solution is 0.1-6 mol/L.
11. The process of claim 10, wherein the acidity of the solution obtained by dissolving iron-phosphorus thorium residue in said nitric acid or hydrochloric acid is 0.3-1 mol/L.
12. The process method as claimed in claim 2, wherein the iron-phosphorus-thorium solution obtained by dissolving the iron-phosphorus-thorium slag with the inorganic acid is prepared by fractionating and extracting thorium by using P350 or TBP, the concentration of P350 or TBP is 5-50 vol%, the extraction level is 3-15 levels, the washing level is 3-15 levels, and the back extraction level is 3-10 levels, the ratio of an organic phase, a material liquid, a washing liquid and a back extraction liquid is 0.1-5: 1: 0.1-1: 0.05-1, the washing liquid and the back extraction acid are dilute nitric acid or hydrochloric acid, the acidity is pH 5-0.5 mol/L, the back extraction liquid is concentrated and crystallized to prepare nitric acid or thorium chloride with the concentration of over 99.9%, and the back extraction liquid can also be calcined by using oxalic acid to prepare thorium oxide.
13. The process of claim 3, wherein the pure rare earth sulfate solution is a pure rare earth sulfate solution with REO 20-50 g/L and pH 3.5-5, the non-saponified P204 or the mixed extractant containing P204 directly used is 0.5-1.5 mol/L non-saponified P204(D2EHPA) or a mixed extractant prepared from one of P204 and P507(HEH/EHP), C272, C301, C302 and HEOPPA, and the process of extracting and separating rare earth comprises: performing cerium/praseodymium and praseodymium/neodymium extraction grouping by using the mixed extractant, and performing neodymium/samarium extraction grouping by directly feeding the loaded rare earth organic phase to obtain praseodymium-neodymium or neodymium chloride and samarium-europium-gadolinium enriched materials; neutralizing raffinate containing lanthanum, cerium or lanthanum, cerium and praseodymium to the pH value of 2-5, extracting by using unsaponifiable P204, and performing back extraction by using hydrochloric acid or nitric acid to produce lanthanum, cerium, praseodymium, rare earth chloride or rare earth nitrate; or grouping neodymium/samarium, carrying out hydrochloric acid back extraction on the loaded rare earth organic phase to obtain a samarium-europium-gadolinium enriched material, neutralizing raffinate to the pH value of 2-5, and extracting by using nonsaponifiable P204 to prepare the lanthanum-cerium-praseodymium-neodymium rare earth chloride. The above compounds can also be further extracted and separated to prepare single rare earth oxides of 99-99.999% purity, such as lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium and the like.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100852303A CN100348748C (en) | 2004-12-15 | 2005-07-21 | Process for comprehensive recovery of rare earth and thorium from rare earth ore |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200410098656 | 2004-12-15 | ||
| CN200410098656.8 | 2004-12-15 | ||
| CNB2005100852303A CN100348748C (en) | 2004-12-15 | 2005-07-21 | Process for comprehensive recovery of rare earth and thorium from rare earth ore |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1721559A true CN1721559A (en) | 2006-01-18 |
| CN100348748C CN100348748C (en) | 2007-11-14 |
Family
ID=35912164
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100852303A Active CN100348748C (en) | 2004-12-15 | 2005-07-21 | Process for comprehensive recovery of rare earth and thorium from rare earth ore |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100348748C (en) |
Cited By (44)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100424200C (en) * | 2007-02-05 | 2008-10-08 | 扬州大学 | Method for hypersonic rare earth leaching |
| WO2009021389A1 (en) * | 2007-08-10 | 2009-02-19 | Grirem Advanced Materials Co., Ltd. | A PROCESS OF SMELTING MONAZITE RARE EARTH ORE RICH IN Fe |
| CN101633980A (en) * | 2008-07-23 | 2010-01-27 | 甘肃稀土新材料股份有限公司 | Roasting process of sulfuric acid of rare-earth ore |
| AU2008286599B2 (en) * | 2007-08-10 | 2010-11-18 | Grirem Advanced Materials Co., Ltd. | A metallurgical process for iron-rich monazite rare earth ore or concentrate |
| CN101876007B (en) * | 2009-12-14 | 2012-01-11 | 五矿（北京）稀土研究院有限公司 | Method for separating rare earth sulfate solution by saponifiable extraction |
| CN102399999A (en) * | 2010-09-15 | 2012-04-04 | 北京有色金属研究总院 | Comprehensive recovery process for rare earth and strontium intergrowth multi-metal ore |
| CN102534269A (en) * | 2012-03-26 | 2012-07-04 | 乐山盛和稀土股份有限公司 | Method for comprehensively recycling various rare earth from rare earth materials containing fluorine |
| WO2012093170A1 (en) | 2011-01-06 | 2012-07-12 | Areva Mines | Dissolution and recovery of at least one element nb or ta and of at least one other element u or rare earth elements from ores and concentrates |
| CN102758083A (en) * | 2012-08-01 | 2012-10-31 | 中冶东方工程技术有限公司 | Method for transforming rare earth concentrated sulfuric acid roasted ores |
| CN102864319A (en) * | 2011-10-08 | 2013-01-09 | 中国恩菲工程技术有限公司 | Method for leaching rare earth elements from nickel oxide ore |
| CN103074504A (en) * | 2012-09-29 | 2013-05-01 | 内蒙古机电职业技术学院 | Electrical heating internal resistance electric melting method for decomposing mixed rare earth ore concentrate and electric heating decomposer thereof |
| CN103540746A (en) * | 2012-07-12 | 2014-01-29 | 中国科学院过程工程研究所 | Method of separating lanthanum from rare earth nitrate slurry as well as rare earth ore concentrate separation method |
| WO2014082461A1 (en) * | 2012-11-27 | 2014-06-05 | 益阳鸿源稀土有限责任公司 | Monazite ballast separation and recovery method |
| CN104046804A (en) * | 2014-06-25 | 2014-09-17 | 包头华美稀土高科有限公司 | Method for improving concentration of rear earth in lixivium of rear-earth concentrated sulfuric acid roasted ore |
| CN104962762A (en) * | 2015-07-22 | 2015-10-07 | 中国恩菲工程技术有限公司 | Processing method of fine bastnaesite |
| US20150329940A1 (en) * | 2014-05-15 | 2015-11-19 | Vale S.A. | System and process for selective rare earth extraction with sulphur recovery |
| CN105517713A (en) * | 2015-01-08 | 2016-04-20 | 中国地质科学院矿产综合利用研究所 | Method for enriching monazite apatite paragenic ore |
| CN105568006A (en) * | 2015-12-31 | 2016-05-11 | 包头稀土研究院 | Method for cleaning smelted mixed rare earth concentrate by concentrated sulfuric acid |
| CN105668888A (en) * | 2015-12-31 | 2016-06-15 | 包头稀土研究院 | Low-grade mixed rare earth ore concentrate chemical dressing and chemical dressing waste water resource comprehensively recycling method |
| WO2016090808A1 (en) * | 2014-12-11 | 2016-06-16 | 中国科学院长春应用化学研究所 | Use of amino group-containing neutral phosphine extraction agent for extraction and separation of thorium, and method |
| WO2016202257A1 (en) * | 2015-06-19 | 2016-12-22 | 有研稀土新材料股份有限公司 | Method for recovering phosphorus and rare earth from rare earth-containing phosphate ore, and substance containing rare earth phosphate |
| CN106319218A (en) * | 2015-06-16 | 2017-01-11 | 有研稀土新材料股份有限公司 | Method for recovering rare earth, aluminum and silicon from rare earth-containing aluminum and silicon wastes |
| CN106381406A (en) * | 2015-07-28 | 2017-02-08 | 永州市湘江稀土有限责任公司 | Technology for extraction and separation of thorium and rare earth |
| CN106957966A (en) * | 2016-01-12 | 2017-07-18 | 厦门稀土材料研究所 | A kind of method that thorium and rare earth element are reclaimed from rare earth waste |
| CN106978532A (en) * | 2017-03-15 | 2017-07-25 | 包头稀土研究院 | The method that the concentrated sulfuric acid extracts fluorine-containing rare-earth mineral middle rare earth, fluorine and thorium |
| CN107208177A (en) * | 2014-07-21 | 2017-09-26 | 搜索矿物公司 | The acidleach of rare earth element is carried |
| CN107557576A (en) * | 2017-08-15 | 2018-01-09 | 广东省稀有金属研究所 | A kind of method of the Extraction of rare earth from halmeic deposit |
| CN107675000A (en) * | 2017-09-05 | 2018-02-09 | 中国科学院长春应用化学研究所 | Regulate and control heavy rare-earth extraction separating technology extraction equilibrium acidity and the method for extracting series |
| CN106978531B (en) * | 2017-03-15 | 2018-12-14 | 包头稀土研究院 | The method that soda acid joint decomposes mixed rare earth concentrate |
| CN110642276A (en) * | 2019-11-11 | 2020-01-03 | 南昌航空大学 | Method for preparing 6N-grade magnesium chloride solution |
| CN110756162A (en) * | 2019-10-24 | 2020-02-07 | 中国科学院城市环境研究所 | Synthesis of P5O7 composite carbon fiber material and method for adsorbing and separating indium in liquid crystal panel by using same |
| CN111020188A (en) * | 2019-12-04 | 2020-04-17 | 厦门稀土材料研究所 | Extracting agent and preparation method and application thereof |
| CN111020196A (en) * | 2019-12-04 | 2020-04-17 | 厦门稀土材料研究所 | Method for separating thorium and enriching rare earth from radioactive waste residue leachate based on POAA |
| CN111394599A (en) * | 2020-04-01 | 2020-07-10 | 四川江铜稀土有限责任公司 | Method for recovering rare earth from iron thorium slag in bastnaesite acid leaching process |
| CN112534072A (en) * | 2018-08-10 | 2021-03-19 | 有研稀土新材料股份有限公司 | Smelting separation process for treating rare earth concentrate by combined method |
| CN114127319A (en) * | 2019-03-27 | 2022-03-01 | 多伦多大学管理委员会 | Method for recovering target metal from iron or steel slag using at least one of carbothermic process and pyrometallurgical-hydrometallurgical process |
| CN114293012A (en) * | 2022-01-04 | 2022-04-08 | 内蒙古包钢和发稀土有限公司 | Method for reducing iron and aluminum content in rare earth sulfate leaching solution |
| CN115029546A (en) * | 2022-05-07 | 2022-09-09 | 包头稀土研究院 | Method for treating mixed rare earth ore |
| CN115058609A (en) * | 2022-06-20 | 2022-09-16 | 中国科学院地球化学研究所 | Method for leaching rare earth in basalt weathering crust |
| CN115210393A (en) * | 2020-03-06 | 2022-10-18 | 雅苒国际集团 | Process for selective separation of thorium and cerium from solid concentrates containing thorium and cerium and one or more other rare earth metals and acidic rare earth solutions thereof |
| CN115323177A (en) * | 2022-08-11 | 2022-11-11 | 甘肃稀土新材料股份有限公司 | Method for extracting rare earth from rare earth waste by low-temperature intensified roasting method |
| CN115449624A (en) * | 2022-08-11 | 2022-12-09 | 甘肃稀土新材料股份有限公司 | Method for treating high-iron low-phosphorus rare earth ore |
| CN116987893A (en) * | 2023-08-10 | 2023-11-03 | 长沙市丰程有色金属材料有限责任公司 | Method for recycling monazite slag |
| CN117186777A (en) * | 2023-11-07 | 2023-12-08 | 琥崧科技集团股份有限公司 | Polishing solution applied to semiconductor industry and preparation method thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1219305A (en) * | 1968-03-21 | 1971-01-13 | Dow Chemical Co | Separating thorium from rare earth metals |
| CN1009332B (en) * | 1986-08-23 | 1990-08-29 | 北京有色金属研究总院 | Extracting and separating rear earth element from sulfuric acid system |
| FR2678644A1 (en) * | 1991-07-02 | 1993-01-08 | Rhone Poulenc Chimie | Process for overall recovery of the thorium and of the rare earths in a nitrate medium |
| FR2826667A1 (en) * | 2001-06-29 | 2003-01-03 | Rhodia Elect & Catalysis | Treatment of rare earth mineral with high iron content for recuperation of rare earth metals as an aqueous solution involves reacting the mineral with sulfuric acid, firing, mixing the calcined material with aqueous solution, and separating |
| CN1162558C (en) * | 2002-07-09 | 2004-08-18 | 中国科学院长春应用化学研究所 | Process for extracting and separating thorium and extracting rare earth chloride from sulfuric and phosphoric mixed acid system |
| CN1173050C (en) * | 2002-09-25 | 2004-10-27 | 包头稀土研究院 | Low-temperature roasting and decomposing process of rare earth heading concentrated sucfuric acid |
-
2005
- 2005-07-21 CN CNB2005100852303A patent/CN100348748C/en active Active
Cited By (62)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100424200C (en) * | 2007-02-05 | 2008-10-08 | 扬州大学 | Method for hypersonic rare earth leaching |
| WO2009021389A1 (en) * | 2007-08-10 | 2009-02-19 | Grirem Advanced Materials Co., Ltd. | A PROCESS OF SMELTING MONAZITE RARE EARTH ORE RICH IN Fe |
| AU2008286599B2 (en) * | 2007-08-10 | 2010-11-18 | Grirem Advanced Materials Co., Ltd. | A metallurgical process for iron-rich monazite rare earth ore or concentrate |
| CN101633980A (en) * | 2008-07-23 | 2010-01-27 | 甘肃稀土新材料股份有限公司 | Roasting process of sulfuric acid of rare-earth ore |
| CN101876007B (en) * | 2009-12-14 | 2012-01-11 | 五矿（北京）稀土研究院有限公司 | Method for separating rare earth sulfate solution by saponifiable extraction |
| CN102399999B (en) * | 2010-09-15 | 2016-01-20 | 有研稀土新材料股份有限公司 | A kind of rare earth and strontium association polymetallic ore comprehensive recycling process altogether |
| CN102399999A (en) * | 2010-09-15 | 2012-04-04 | 北京有色金属研究总院 | Comprehensive recovery process for rare earth and strontium intergrowth multi-metal ore |
| WO2012093170A1 (en) | 2011-01-06 | 2012-07-12 | Areva Mines | Dissolution and recovery of at least one element nb or ta and of at least one other element u or rare earth elements from ores and concentrates |
| CN102864319A (en) * | 2011-10-08 | 2013-01-09 | 中国恩菲工程技术有限公司 | Method for leaching rare earth elements from nickel oxide ore |
| CN102864319B (en) * | 2011-10-08 | 2015-02-04 | 中国恩菲工程技术有限公司 | Method for leaching rare earth elements from nickel oxide ore |
| CN102534269A (en) * | 2012-03-26 | 2012-07-04 | 乐山盛和稀土股份有限公司 | Method for comprehensively recycling various rare earth from rare earth materials containing fluorine |
| CN103540746B (en) * | 2012-07-12 | 2015-06-03 | 中国科学院过程工程研究所 | Method of separating lanthanum from rare earth nitrate slurry as well as rare earth ore concentrate separation method |
| CN103540746A (en) * | 2012-07-12 | 2014-01-29 | 中国科学院过程工程研究所 | Method of separating lanthanum from rare earth nitrate slurry as well as rare earth ore concentrate separation method |
| CN102758083A (en) * | 2012-08-01 | 2012-10-31 | 中冶东方工程技术有限公司 | Method for transforming rare earth concentrated sulfuric acid roasted ores |
| CN102758083B (en) * | 2012-08-01 | 2014-09-03 | 中冶东方工程技术有限公司 | Method for transforming rare earth concentrated sulfuric acid roasted ores |
| CN103074504A (en) * | 2012-09-29 | 2013-05-01 | 内蒙古机电职业技术学院 | Electrical heating internal resistance electric melting method for decomposing mixed rare earth ore concentrate and electric heating decomposer thereof |
| WO2014082461A1 (en) * | 2012-11-27 | 2014-06-05 | 益阳鸿源稀土有限责任公司 | Monazite ballast separation and recovery method |
| US9657369B2 (en) | 2012-11-27 | 2017-05-23 | Yiyang Hongyuan Rare Earth Co., Ltd | Monazite ballast separation and recovery method |
| US20150329940A1 (en) * | 2014-05-15 | 2015-11-19 | Vale S.A. | System and process for selective rare earth extraction with sulphur recovery |
| KR102553461B1 (en) * | 2014-05-15 | 2023-07-07 | 발레 에스.에이. | System and process for selective rare earth extraction with sulfur recovery |
| US10597754B2 (en) * | 2014-05-15 | 2020-03-24 | Vale S.A. | System and process for selective rare earth extraction with sulphur recovery |
| KR20170007423A (en) * | 2014-05-15 | 2017-01-18 | 발레 에스.에이. | System and process for selective rare earth extraction with sulfur recovery |
| CN104046804A (en) * | 2014-06-25 | 2014-09-17 | 包头华美稀土高科有限公司 | Method for improving concentration of rear earth in lixivium of rear-earth concentrated sulfuric acid roasted ore |
| CN107208177A (en) * | 2014-07-21 | 2017-09-26 | 搜索矿物公司 | The acidleach of rare earth element is carried |
| US10273562B2 (en) | 2014-07-21 | 2019-04-30 | Search Minerals Inc. | Acid leaching of rare earth minerals |
| WO2016090808A1 (en) * | 2014-12-11 | 2016-06-16 | 中国科学院长春应用化学研究所 | Use of amino group-containing neutral phosphine extraction agent for extraction and separation of thorium, and method |
| US10081554B2 (en) | 2014-12-11 | 2018-09-25 | Changchun Institute Of Applied Chemistry, Chinese Academy Of Sciences | Use of amino-containing neutral phosphine extractant in extraction and separation of thorium and process of using same |
| WO2016109966A1 (en) * | 2015-01-08 | 2016-07-14 | 中国地质科学院矿产综合利用研究所 | Enrichment method for monazite-apatite paragenesis mineral |
| US10006102B2 (en) | 2015-01-08 | 2018-06-26 | Institute Of Multipurpose Utilization Of Mineral Resources | Monazite and apatite paragenetic ore enrichment method |
| CN105517713A (en) * | 2015-01-08 | 2016-04-20 | 中国地质科学院矿产综合利用研究所 | Method for enriching monazite apatite paragenic ore |
| CN106319218A (en) * | 2015-06-16 | 2017-01-11 | 有研稀土新材料股份有限公司 | Method for recovering rare earth, aluminum and silicon from rare earth-containing aluminum and silicon wastes |
| US10280482B2 (en) | 2015-06-16 | 2019-05-07 | Grirem Advanced Materials Co., Ltd. | Method of recovering rare earth aluminum and silicon from rare earth-containing aluminum-silicon scraps |
| WO2016202257A1 (en) * | 2015-06-19 | 2016-12-22 | 有研稀土新材料股份有限公司 | Method for recovering phosphorus and rare earth from rare earth-containing phosphate ore, and substance containing rare earth phosphate |
| CN104962762A (en) * | 2015-07-22 | 2015-10-07 | 中国恩菲工程技术有限公司 | Processing method of fine bastnaesite |
| CN106381406A (en) * | 2015-07-28 | 2017-02-08 | 永州市湘江稀土有限责任公司 | Technology for extraction and separation of thorium and rare earth |
| CN105568006A (en) * | 2015-12-31 | 2016-05-11 | 包头稀土研究院 | Method for cleaning smelted mixed rare earth concentrate by concentrated sulfuric acid |
| CN105668888B (en) * | 2015-12-31 | 2018-06-22 | 包头稀土研究院 | The method that waste water resource synthetical recovery is selected in low-grade mixed rare earth concentratesization choosing and change |
| CN105668888A (en) * | 2015-12-31 | 2016-06-15 | 包头稀土研究院 | Low-grade mixed rare earth ore concentrate chemical dressing and chemical dressing waste water resource comprehensively recycling method |
| CN106957966A (en) * | 2016-01-12 | 2017-07-18 | 厦门稀土材料研究所 | A kind of method that thorium and rare earth element are reclaimed from rare earth waste |
| CN106978531B (en) * | 2017-03-15 | 2018-12-14 | 包头稀土研究院 | The method that soda acid joint decomposes mixed rare earth concentrate |
| CN106978532A (en) * | 2017-03-15 | 2017-07-25 | 包头稀土研究院 | The method that the concentrated sulfuric acid extracts fluorine-containing rare-earth mineral middle rare earth, fluorine and thorium |
| CN107557576A (en) * | 2017-08-15 | 2018-01-09 | 广东省稀有金属研究所 | A kind of method of the Extraction of rare earth from halmeic deposit |
| CN107675000A (en) * | 2017-09-05 | 2018-02-09 | 中国科学院长春应用化学研究所 | Regulate and control heavy rare-earth extraction separating technology extraction equilibrium acidity and the method for extracting series |
| CN112534072A (en) * | 2018-08-10 | 2021-03-19 | 有研稀土新材料股份有限公司 | Smelting separation process for treating rare earth concentrate by combined method |
| CN114127319A (en) * | 2019-03-27 | 2022-03-01 | 多伦多大学管理委员会 | Method for recovering target metal from iron or steel slag using at least one of carbothermic process and pyrometallurgical-hydrometallurgical process |
| CN110756162A (en) * | 2019-10-24 | 2020-02-07 | 中国科学院城市环境研究所 | Synthesis of P5O7 composite carbon fiber material and method for adsorbing and separating indium in liquid crystal panel by using same |
| CN110642276B (en) * | 2019-11-11 | 2022-01-25 | 南昌航空大学 | Method for preparing 6N-grade magnesium chloride solution |
| CN110642276A (en) * | 2019-11-11 | 2020-01-03 | 南昌航空大学 | Method for preparing 6N-grade magnesium chloride solution |
| CN111020188A (en) * | 2019-12-04 | 2020-04-17 | 厦门稀土材料研究所 | Extracting agent and preparation method and application thereof |
| CN111020196A (en) * | 2019-12-04 | 2020-04-17 | 厦门稀土材料研究所 | Method for separating thorium and enriching rare earth from radioactive waste residue leachate based on POAA |
| CN115210393A (en) * | 2020-03-06 | 2022-10-18 | 雅苒国际集团 | Process for selective separation of thorium and cerium from solid concentrates containing thorium and cerium and one or more other rare earth metals and acidic rare earth solutions thereof |
| CN111394599A (en) * | 2020-04-01 | 2020-07-10 | 四川江铜稀土有限责任公司 | Method for recovering rare earth from iron thorium slag in bastnaesite acid leaching process |
| CN114293012A (en) * | 2022-01-04 | 2022-04-08 | 内蒙古包钢和发稀土有限公司 | Method for reducing iron and aluminum content in rare earth sulfate leaching solution |
| CN114293012B (en) * | 2022-01-04 | 2024-02-02 | 内蒙古包钢和发稀土有限公司 | Method for reducing iron and aluminum content in rare earth sulfate leaching solution |
| CN115029546B (en) * | 2022-05-07 | 2024-01-23 | 包头稀土研究院 | Treatment method of mixed rare earth ore |
| CN115029546A (en) * | 2022-05-07 | 2022-09-09 | 包头稀土研究院 | Method for treating mixed rare earth ore |
| CN115058609A (en) * | 2022-06-20 | 2022-09-16 | 中国科学院地球化学研究所 | Method for leaching rare earth in basalt weathering crust |
| CN115449624A (en) * | 2022-08-11 | 2022-12-09 | 甘肃稀土新材料股份有限公司 | Method for treating high-iron low-phosphorus rare earth ore |
| CN115323177A (en) * | 2022-08-11 | 2022-11-11 | 甘肃稀土新材料股份有限公司 | Method for extracting rare earth from rare earth waste by low-temperature intensified roasting method |
| CN116987893A (en) * | 2023-08-10 | 2023-11-03 | 长沙市丰程有色金属材料有限责任公司 | Method for recycling monazite slag |
| CN117186777A (en) * | 2023-11-07 | 2023-12-08 | 琥崧科技集团股份有限公司 | Polishing solution applied to semiconductor industry and preparation method thereof |
| CN117186777B (en) * | 2023-11-07 | 2024-01-26 | 琥崧科技集团股份有限公司 | Polishing solution applied to semiconductor industry and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100348748C (en) | 2007-11-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1721559A (en) | Process for comprehensive recovery of rare earth and thorium from rare earth ore | |
| US20230115288A1 (en) | Processing for the extraction of rare earth elements | |
| US9752213B2 (en) | Method for comprehensively recovering rare earth elements and fluorine element in a bastnaesite treatment process | |
| CN106319218B (en) | Method for recovering rare earth, aluminum and silicon from rare earth-containing aluminum-silicon waste | |
| CN101319275B (en) | Process for solvent extraction separation purification of rare earth element | |
| CN100584967C (en) | Method for separating highly-pure rare-earth oxide from rare earth mine for reinforced baking by sulfuric acid | |
| CN104294063B (en) | The method of low concentration of rare earth solution extraction and recovery rare earth | |
| RU2293134C1 (en) | Process for extracting rare-earth metals and yttrium from coals and ash-slag waste material of coal burning | |
| CN104928475B (en) | A kind of recovery method of the aluminium scrap silicon containing rare earth | |
| CN101363079A (en) | Smelting method of iron rich mengite rare-earth mine | |
| CN101970700B (en) | Application of aqueous solution of magnesium bicarbonate and/or calcium bicarbonate in the process of extraction separation and purification of metals | |
| CN106636689B (en) | A kind of method of Extraction of rare earth in precipitation slag from RE waste water pond | |
| CN101294244B (en) | Technique for extraction separation of quadravalence cerium, thorium, fluorine and cerium less tervalence rare earth from sulphuric acid rare earth solution | |
| CN1730680A (en) | Rare-earth element extraction separation process using nonsaponifying organic extractant | |
| CN104928504B (en) | A kind of recovery method of aluminium scrap silicon middle rare earth | |
| CN102676853A (en) | Rare earth separation method with material linkage cyclic utilization function | |
| WO2009021389A1 (en) | A PROCESS OF SMELTING MONAZITE RARE EARTH ORE RICH IN Fe | |
| CN1804063A (en) | Process for extracting rare earth element by non-saponifiable phosphorous mixing extractant | |
| CN1384214A (en) | Carbon reducting roast process of producing RE chloride with mixed RE concentrate | |
| CN1683569A (en) | Process for decomposing bactnaesite by hydrochloric acid method | |
| CN112063862A (en) | Extractant for rare earth enrichment and application thereof | |
| CN105861828B (en) | A kind of rare earth complex chemical compound containing rare earth hydrate and rare earth carbonate and preparation method thereof | |
| CN104651613B (en) | A kind of method that rare earth is separated and recovered from useless rare-earth type Y molecular sieve catalyst | |
| CN101343064B (en) | Preparation method for separating and purifying silicon dioxide and cerous chlorate from seeing stone waste material | |
| CN113373326A (en) | Method for preparing pure rare earth sulfate solution |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Free format text: FORMER OWNER: GRIREM ADVANCED MATERIALS CO., LTD. Effective date: 20130802 Owner name: GRIREM ADVANCED MATERIALS CO., LTD. Free format text: FORMER OWNER: BEIJING CENTRAL INST.OF THE NONFERROUS METAL Effective date: 20130802 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20130802 Address after: 100088, 2, Xinjie street, Beijing Patentee after: Grirem Advanced Materials Co., Ltd. Address before: 100088, 2, Xinjie street, Beijing Patentee before: General Research Institute for Nonferrous Metals Patentee before: Grirem Advanced Materials Co., Ltd. |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20210909 Address after: 614300 No. 13, Yang Zhu Ba Road, Ebian Yi Autonomous County, Leshan City, Sichuan Patentee after: LESHAN GRIREM ADVANCED MATERIALS Co.,Ltd. Address before: 100088, 2, Xinjie street, Beijing Patentee before: GRIREM ADVANCED MATERIALS Co.,Ltd. |
|
| TR01 | Transfer of patent right |