CN111559755B - Production method of low-calcium lanthanum carbonate - Google Patents
Production method of low-calcium lanthanum carbonate Download PDFInfo
- Publication number
- CN111559755B CN111559755B CN202010510766.XA CN202010510766A CN111559755B CN 111559755 B CN111559755 B CN 111559755B CN 202010510766 A CN202010510766 A CN 202010510766A CN 111559755 B CN111559755 B CN 111559755B
- Authority
- CN
- China
- Prior art keywords
- solution
- calcium
- carbonate
- lanthanum
- rare earth
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses a production method of low-calcium lanthanum carbonate, which comprises the following steps: s1, adding dilute sulfuric acid into the mixed rare earth chloride solution to carry out calcium and barium removal treatment; s2, adding barium chloride into the filtrate to remove sulfate radicals, and extracting and separating the mixed rare earth chloride solution to obtain a lanthanum chloride solution; s3, adding lanthanum carbonate seed crystals and carbonate solution into the lanthanum chloride solution, controlling the pH of the solution to be 6-6.6, and performing primary precipitation; s4, adding soluble bicarbonate salt into the solution to carry out secondary precipitation; and S5, filtering to obtain filter residues, washing the filter residues with water, centrifuging, drying, packaging and storing. According to the invention, calcium impurities in lanthanum carbonate are removed, unreacted rare earth in the solution is recovered, the calcium content of lanthanum carbonate is reduced to below 500ppm, the market requirement is met, and the defects of the prior art are overcome.
Description
Technical Field
The invention relates to the technical field of rare earth hydrometallurgy, in particular to a production method of low-calcium lanthanum carbonate.
Background
At present, the rare earth market is increasingly low, so that the rare earth products need to have a market, the quality of the rare earth products needs to be improved, and particularly for lanthanum products which are relatively popular, the rare earth products have no market if the quality is not improved. The bastnaesite used at present is a product (rare earth concentrate for short) obtained by a magnetic separation and flotation combined beneficiation method, and contains certain calcium fluoride or calcium carbonate and other calcium-containing non-rare earth impurities inevitably in the beneficiation procedure, about 60% of calcium in the rare earth concentrate enters a rare earth chloride product after the rare earth concentrate is treated by an acid-base combination method, then about 20% of the calcium impurities can be thrown away during rare earth saponification through extraction separation, the calcium impurities which are not removed are finally enriched into a lanthanum chloride feed liquid, and then a precipitating agent such as sodium carbonate, ammonium bicarbonate, sodium bicarbonate and the like is used for precipitation, so that lanthanum carbonate with the calcium oxide content of 1000-. Therefore, in order to meet the requirements of customers, the existing enterprises establish a lanthanum fishing calcium removing line, and the lanthanum carbonate is produced after carbon deposition, so that the lanthanum carbonate product suitable for the requirements of customers can be produced, but the production cost can be increased, and the cost of producing rare earth oxide per ton can be increased by about 3500 yuan. The market price of the lanthanum carbonate rare earth is not high, and the cost investment is increased, so that the economic value of the lanthanum carbonate is lower.
The existing enterprises also utilize a stepwise precipitation method, namely the pH value of the end point of precipitation is controlled to be 6 in the precipitation process, so that part of calcium impurities can be discarded, but part of rare earth is easily lost, and meanwhile, the method is easily influenced by the content of lanthanum chloride and calcium oxide to influence the quality of lanthanum carbonate.
Chinese patent CN110408778A discloses a method for precipitating heavy rare earth by mixing sodium carbonate and sodium bicarbonate, which is to obtain a precipitation solvent by mixing the sodium carbonate and the sodium bicarbonate, then add the precipitation solvent into rare earth feed liquid, precipitate and separate out erbium carbonate by adopting a coprecipitation mode, wherein the pH value of the precipitation solvent is 6.5-7. When sodium carbonate and sodium bicarbonate are added into rare earth feed liquid together, the bicarbonate reacts with metal cations to generate carbonate precipitates preferentially due to the instability of bicarbonate, then carbonate reacts with the metal cations to generate carbonate precipitates, at the moment, the precipitates contain rare earth carbonate precipitates and non-rare earth impurities such as calcium carbonate, the impurity content of rare earth carbonate products is possibly high, and the bicarbonate can reduce the carbonate in the solution (CO exists) in the reaction process (the bicarbonate has CO) 2 And generation), which inevitably leads to incomplete solution precipitation, a small amount of rare earth still directly transfers waste without participating in reaction, although the rare earth yield is claimed to be not less than 99%, the method obviously has the defect of rare earth waste, the beneficial effect is doubtful, and meanwhile, the method can not solve the problem of calcium content in the rare earth carbonate product.
Chinese patent CN102936029A discloses a method for precipitating rare earth carbonate, and specifically discloses the following methods: (1) adding the rare earth feed liquid into a reaction kettle; (2) adding a sodium carbonate solution into the rare earth feed liquid under the condition of stirring, and precipitating rare earth metal ions in the supernatant until the concentration is 0.2-0.002 mol/L; (3) using sodium bicarbonate solution as precipitant, continuing precipitation until the pH value of the supernatant is 6-7; (4) and dehydrating and washing the precipitate to obtain the rare earth carbonate. The method is used for reducing the content of non-precipitated rare earth ions in the precipitation mother liquor, improving the yield of the product and simultaneously reducing the content of calcium and magnesium ions. However, the method does not consider the calcium content range in the initial rare earth feed liquid or the pH value of the solution when the rare earth feed liquid reacts with sodium carbonate, so that the calcium content in the actually obtained rare earth carbonate product is higher than the theoretical value, especially the lanthanum chloride feed liquid rich in a large amount of calcium salt, when the method is adopted for treatment, the calcium content in the obtained lanthanum carbonate product is not smaller than 0.05 percent as alleged in the patent, but is in the range of 1000-2500 ppm, the concentration of rare earth ions in the mother liquid is also higher than the alleged value, when the rare earth carbonate is precipitated, the generation of calcium carbonate precipitate is related to the pH value of the solution, if the pH value of the solution in the early stage of the reaction is accurately controlled, the generation of calcium carbonate precipitate is inhibited as much as possible, even if the sodium bicarbonate is added in the later stage of the reaction, a certain amount of calcium carbonate precipitate is still included in the precipitate, especially when the calcium content in the solution is larger (the content is 9-14 g/L), the more calcium carbonate precipitates are mixed in the precipitates, and the calcium content of the rare earth carbonate product exceeds the standard finally, so that the method can effectively remove calcium and magnesium impurities in the rare earth carbonate, but the removal effect is not ideal, and the obtained rare earth carbonate product cannot meet the market requirement.
Disclosure of Invention
The invention aims to: aiming at the existing problems, the invention provides a production method of low-calcium lanthanum carbonate, which is improved on the basis of the original carbon precipitation method, firstly, the mixed rare earth chloride solution is subjected to pre-calcium removal treatment to control the calcium content in the lanthanum chloride solution, then, the carbonate solution is added into the lanthanum chloride solution, the pH value is controlled, then, soluble bicarbonate is added, calcium impurities mixed in the lanthanum carbonate are removed through the modes of pre-calcium removal, pH value control and twice precipitation, meanwhile, unreacted rare earth in the solution is recovered, and the calcium content of the lanthanum carbonate is reduced to be below 500ppm, so that the market requirement is met, and the defects of the prior art are overcome.
The technical scheme adopted by the invention is as follows: a production method of low-calcium lanthanum carbonate is characterized by comprising the following steps:
s1, treating the bastnaesite by an acid-base combination method to obtain a lead-removed mixed rare earth chloride solution, adding dilute sulfuric acid into the mixed rare earth chloride solution to remove calcium and barium, and filtering to obtain a filtrate;
s2, adding a proper amount of barium chloride into the filtrate to remove sulfate ions in the solution, filtering to obtain a mixed rare earth chloride solution, and extracting and separating the mixed rare earth chloride solution to obtain a lanthanum chloride solution;
s3, adding lanthanum carbonate seed crystals and carbonate solution into the lanthanum chloride solution, controlling the pH of the solution to be 6-6.6, and performing primary precipitation;
s4, after the precipitation is finished, adding soluble bicarbonate salt into the solution for secondary precipitation;
and S5, after the second precipitation is finished, filtering to obtain filter residues, washing the filter residues with water, centrifugally drying, packaging and warehousing.
In the method, the bastnaesite is treated by an acid-base combination method to produce a mixed rare earth chloride solution, the calcium content (calculated by calcium oxide) in the solution is generally 9-14 g/L, if the solution is not treated, the solution is directly extracted and separated, the calcium content in the obtained lanthanum chloride solution is higher than 5g/L, and when secondary precipitation treatment is carried out, the calcium content in lanthanum carbonate is between 1000 and 2500ppm, so that the market demand can not be met. The inventor finds out through multiple experimental researches that: in order to make the calcium content in lanthanum carbonate below 500ppm, provided that the calcium content of the lanthanum chloride solution is controlled, and specifically the calcium content is below 3.5g/L, the calcium content of the mixed rare earth chloride solution before extraction separation treatment is required to be below 5g/L, in order to meet the calcium requirement, the inventor carries out pre-calcium removal treatment on the mixed rare earth solution, namely, the methods of S1 and S2 are adopted, and the reaction principle is as follows:
Ba 2+ +SO 4 2－ ＝BaSO 4 ↓
Ca 2+ +SO 4 2－ ＝CaSO 4 ↓
during the calcium and barium removing treatment, because the content of barium is less, the addition amount of the dilute sulfuric acid is excessive by 20 percent of the theoretical amount of calcium impurities, and in order to ensure the calcium removing effect, the pH value is required to be kept between 4 and 4.5 in the process. Correspondingly, because calcium sulfate is slightly soluble, only partial calcium removal can be realized, after the calcium removal is finished, the excess sulfate radical is removed by barium chloride, in the sulfate radical removal process, the temperature of the whole system is controlled to be more than 60 ℃, and the calcium impurity removal process is carried out at normal temperature. After the pre-calcium removal treatment, the calcium content in the mixed rare earth chloride solution is generally less than 5g/L, and after the mixed rare earth chloride solution is extracted and separated, the calcium content in the obtained lanthanum chloride solution is less than 3.5g/L, so that the precondition of secondary precipitation is met.
Furthermore, the inventor finds that the calcium content in the lanthanum chloride solution directly affects the calcium content of the product, namely affects the treatment effect of secondary precipitation, and also directly concerns the treatment difficulty of the secondary precipitation, when the calcium content in the lanthanum chloride solution is higher than 3.5g/L, during secondary precipitation, the addition amount of carbonate and bicarbonate needs to be controlled to be very accurate, and trace excess or deficiency can obviously affect the precipitation effect, and meanwhile, the accurate control requirement is provided for the pH value, the allowable pH value floating range is narrow, the operation difficulty is high, and the correlation relationship is repeatedly verified in the test, so that the calcium content control of the lanthanum chloride solution is particularly important.
Further, the inventors found that the control of the pH during the secondary precipitation treatment, which is the control of free Ca in the solution, is very important 2+ Start and CO 3 2－ Important condition for the reaction to form precipitate, and free Ca when the pH value of the solution is 6-6.6 2+ Start and CO 3 2－ The reaction forms a precipitate, and the addition of the carbonate solution is stopped, at which point most of the CO is present 3 2－ Precipitate with lanthanum ion, and thenThe principle is as follows:
carbon precipitation reaction: 2La 3+ +3CO 3 2－ ＝La 2 (CO 3 ) 3 ↓
After the first precipitation is finished, adding bicarbonate soluble salt into the solution, wherein the bicarbonate ions have two functions in the solution: firstly, the calcium ions mixed with lanthanum carbonate and the generated calcium carbonate precipitate react to generate soluble calcium bicarbonate, so that the calcium mixed with lanthanum carbonate is separated; secondly, under the pH solution system, bicarbonate radical and free rare earth ions are combined to generate carbonate sediment, and the reaction principle is as follows:
2La 3+ +6HCO 3 － ＝La 2 (CO 3 ) 3 ↓+3CO 2 ↑+3H 2 O
under the strict control of calcium content and pH value, by means of twice precipitation, unreacted rare earth in the solution is recovered while calcium impurities mixed in lanthanum carbonate are removed, the calcium content of lanthanum carbonate is reduced to below 500ppm, the qualification rate is over 95 percent, and the market requirement is met.
In the method of the present invention, in order to precisely control the precipitation system, it is experimentally determined that Ca is free in the solution at a pH of 6.2 to 6.6, more preferably at a pH of about 6.4 2+ Start and CO 3 2－ And (3) generating a precipitate after the reaction, stopping adding the carbonate solution, minimizing calcium carbonate precipitate in the first precipitation, minimizing free rare earth ions in the solution, and facilitating subsequent further precipitation treatment.
Further, the carbonate solution is sodium carbonate or/and potassium carbonate solution, preferably sodium carbonate solution, and the bicarbonate soluble salt is sodium bicarbonate or/and potassium bicarbonate, preferably sodium bicarbonate.
Further, in S1, the concentration of the lanthanum chloride solution is 80-100g/L, and the reaction temperature is 40-55 ℃.
Further, the content of calcium in the lanthanum chloride solution is not more than 3.5g/L in terms of the content of calcium oxide.
Further, the filter residue obtained in S1 and S2 is transferred to a process for recovering rare earth and is continuously treated.
In summary, due to the adoption of the technical scheme, compared with the prior art, the invention has the beneficial effects that:
1. compared with the existing lanthanum fishing and calcium removing process, in order to obtain a low-calcium lanthanum carbonate product, the existing lanthanum fishing and calcium removing process is characterized in that an extraction tank is added during extraction and separation, lanthanum chloride solution in an extraction section is extracted and separated again to achieve the purpose of removing calcium impurities in lanthanum chloride, and then a lanthanum carbonate product meeting the requirements of customers is obtained through precipitation, equipment and raw material investment are increased compared with the original production process, the production cost is increased, the method can produce the lanthanum carbonate product meeting the requirements of customers (on the basis of the original carbon deposition process) without increasing equipment and extra raw and auxiliary materials, and the cost control method is obviously more advantageous;
2. compared with the existing fractional precipitation method, namely the pH value is controlled to control precipitation, the method can produce lanthanum carbonate products meeting the requirements of customers, but the method is easy to cause the loss of rare earth chloride (free lanthanum ions exist in the solution) and is easy to be influenced by the calcium content in the solution so as to cause the calcium content in the produced lanthanum carbonate to be unstable, but the method can obtain the lanthanum carbonate products with stable calcium content and meeting the requirements of customers without losing part of the lanthanum ions, and has more advantages in yield and product quality;
3. the method is improved on the basis of the original stepwise carbon precipitation method, the mixed rare earth chloride solution is subjected to pre-calcium removal treatment to control the calcium content in the lanthanum chloride solution, then the carbonate solution is added into the lanthanum chloride solution, the pH value is controlled, then the soluble salt of hydrogen carbonate is added, and the calcium content of lanthanum carbonate can be controlled below 500ppm by means of pre-calcium removal, accurate pH value control and twice precipitation, so that the market requirement is met, the defects of the prior art are overcome, and the production cost and the product advantages are obvious.
Drawings
FIG. 1 is a flow chart of a beneficiation process of rare earth fluorocarbon ore concentrate related by the invention;
FIG. 2 is a process flow diagram of rare earth concentrate treatment by acid-base combination method according to the present invention;
FIG. 3 is a flow chart of the pre-decalcification treatment process of the lead-removing mixed rare earth chloride solution of the invention;
FIG. 4 is a flow chart of the secondary precipitation process for producing low-calcium lanthanum carbonate according to the present invention.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
As shown in fig. 1, the beneficiation process of the rare earth fluorocarbon-cerium ore concentrate according to the present invention is approximately:
the method comprises the steps of obtaining heavy mineral separation and heavy mineral separation tailings from raw ores through gravity separation, obtaining magnetic separation concentrates and permanent magnet tailings from middlings through magnetic separation, and obtaining flotation concentrates and flotation tailings through enrichment and flotation of the permanent magnet tailings and the heavy mineral separation tailings. The content of REO in the flotation concentrate obtained by adopting the beneficiation process is generally not less than 65 percent, wherein the content of calcium-containing non-rare earth impurities such as calcium fluoride, calcium carbonate and the like is generally 0.6 to 1.5 percent.
As shown in fig. 2, the process of treating the flotation concentrate (rare earth concentrate) by the acid-base combination method is roughly as follows:
after the rare earth concentrate is oxidized and roasted, the rare earth concentrate is sequentially subjected to acid leaching, tempering, concentration and other treatments to obtain a cerium-poor solution and a cerium-poor enrichment, the cerium-poor enrichment is dried, packaged and warehoused, and the cerium-poor solution is extracted and separated to respectively obtain rare earth chloride feed liquids (the prior art is not described too much), such as a cerium chloride solution, a lanthanum chloride solution, a praseodymium neodymium chloride solution and the like. In the process, as lanthanum ions are + 3-valent cations, about 85% of calcium impurities in the solution can be enriched in the lanthanum chloride solution during extraction and separation, so that the calcium content in the lanthanum chloride solution is far higher than that in other rare earth chloride solutions, and the calcium content in the lanthanum chloride solution is generally not less than 2% based on the finally formed calcium oxide, therefore, only the lanthanum chloride solution is required to be subjected to calcium removal treatment.
As shown in FIG. 3, the pre-decalcification treatment process of the lead-removing mixed rare earth chloride solution comprises the following steps:
s1, adding dilute sulfuric acid (the concentration is not specially required and is suitable) into the lead-removing mixed rare earth chloride solution obtained by the acid-base combination treatment, wherein the addition amount of the dilute sulfuric acid is 20% excessive of the theoretical amount of calcium impurities, in order to ensure the calcium removal effect, the pH value is kept between 4 and 4.5 in the process, the reaction is carried out at normal temperature, after the calcium and barium removal treatment, filtering is carried out to obtain filtrate, and the filter residue is transferred to the rare earth recovery process for continuous treatment;
s2, heating the filtrate to about 60 ℃, adding barium chloride into the filtrate to remove sulfate ions in the solution, filtering to obtain a mixed rare earth chloride solution, transferring filter residues to a rare earth recycling process for continuous treatment, and extracting and separating the mixed rare earth chloride solution to obtain a lanthanum chloride solution. After the pre-calcium removal treatment, the calcium content of the original lanthanum chloride solution is reduced from more than 5g/L to less than 3.5g/L, and the pre-calcium removal effect is obvious.
As shown in fig. 4, the method for producing low-calcium lanthanum carbonate by using the lanthanum chloride solution obtained after the pre-calcium removal treatment as a raw material comprises the following steps:
s1, diluting the lanthanum chloride solution to about 80-100g/L, then adding a certain amount of lanthanum carbonate seed crystals to promote the generation of lanthanum carbonate precipitates, and heating to 40-55 ℃ for later use;
s2, preparing a sodium carbonate solution (preferably 150g/L) with the concentration of 120-160 g/L, adding the sodium carbonate solution into the lanthanum chloride solution of S1, observing and controlling the pH of the solution to be about 6.4, and then stopping adding the carbonate solution to perform primary precipitation;
s3, adding solid sodium bicarbonate into the solution, controlling the pH of the solution system to be about 6.4, and carrying out secondary precipitation;
and S4, after the second precipitation is finished, filtering to obtain filter residues, washing the filter residues with water, centrifuging, drying, packaging and warehousing to obtain the lanthanum carbonate product with the calcium content of less than 500 ppm.
In the above, the parameters of concentration, temperature, etc. are specifically selected according to the actual conditions, but the pH should be within a small range of about 6.4, preferably not exceeding the range of 6-7.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (4)
1. A production method of low-calcium lanthanum carbonate is characterized by comprising the following steps:
s1, treating the bastnaesite by an acid-base combination method to obtain a lead-removed mixed rare earth chloride solution, adding dilute sulfuric acid into the mixed rare earth chloride solution to remove calcium and barium, and filtering to obtain a filtrate;
s2, adding a proper amount of barium chloride into the filtrate to remove sulfate ions in the solution, filtering to obtain a mixed rare earth chloride solution, extracting and separating the mixed rare earth chloride solution to obtain a lanthanum chloride solution, wherein the content of calcium in the lanthanum chloride solution is not more than 3.5g/L in terms of the content of calcium oxide;
s3, adding lanthanum carbonate seed crystals and carbonate solution into the lanthanum chloride solution, controlling the pH value of the solution to be 6-6.6, and performing primary precipitation, wherein when the pH value is 6.2-6.6, the addition of the carbonate solution is stopped;
s4, after the precipitation is finished, adding soluble bicarbonate salt into the solution for secondary precipitation;
and S5, after the second precipitation is finished, filtering to obtain filter residues, washing the filter residues with water, centrifugally drying, packaging and warehousing.
2. The method for producing low-calcium lanthanum carbonate according to claim 1, wherein the carbonate solution is sodium carbonate or/and potassium carbonate solution, and the bicarbonate-soluble salt is sodium bicarbonate or/and potassium bicarbonate.
3. The method for producing lanthanum carbonate with low calcium content according to claim 2, wherein the concentration of the lanthanum chloride solution is 80-100g/L in S1, and the reaction temperature is 40-55 ℃.
4. The method for producing lanthanum carbonate with low calcium content as claimed in claim 3, wherein the filter residue obtained in S1 and S2 is transferred to the process of recovering rare earth for further treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010510766.XA CN111559755B (en) | 2020-06-08 | 2020-06-08 | Production method of low-calcium lanthanum carbonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010510766.XA CN111559755B (en) | 2020-06-08 | 2020-06-08 | Production method of low-calcium lanthanum carbonate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111559755A CN111559755A (en) | 2020-08-21 |
| CN111559755B true CN111559755B (en) | 2022-08-05 |
Family
ID=72068651
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010510766.XA Active CN111559755B (en) | 2020-06-08 | 2020-06-08 | Production method of low-calcium lanthanum carbonate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111559755B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113249597A (en) * | 2020-09-14 | 2021-08-13 | 江西明达功能材料有限责任公司 | Method for purifying rare earth solution |
| CN113667842B (en) * | 2021-07-14 | 2022-09-20 | 四川省冕宁县方兴稀土有限公司 | Method for removing non-rare earth impurities in rare earth hydrometallurgy |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1077546C (en) * | 1998-06-04 | 2002-01-09 | 葛新芳 | Method for producing mixed rare-earth chloride |
| CN101633518A (en) * | 2008-07-23 | 2010-01-27 | 甘肃稀土新材料股份有限公司 | Preparation method of lanthanum oxide low in calcium by removing calcium chemically |
| ES2407993T3 (en) * | 2009-05-15 | 2013-06-17 | Natco Pharma Limited | Procedure for the preparation of lanthanum carbonate dihydrate |
| CN102936029B (en) * | 2012-11-30 | 2014-07-09 | 淄博包钢灵芝稀土高科技股份有限公司 | Method for precipitating rare earth carbonate |
| CN104355433B (en) * | 2014-12-05 | 2016-04-06 | 中国地质科学院矿产综合利用研究所 | Method for treating rare earth comprehensive wastewater by forward osmosis membrane separation |
| WO2017015435A1 (en) * | 2015-07-21 | 2017-01-26 | Hazen Research, Inc. | Recovery of rare earths from concentrates containing fluorine |
| CN108796247A (en) * | 2018-07-11 | 2018-11-13 | 钢研集团稀土科技有限公司 | The minimizing technology of calcium strontium foreign ion in a kind of rare earth feed liquid |
| CN110760705A (en) * | 2019-12-10 | 2020-02-07 | 四川省乐山锐丰冶金有限公司 | Novel method for rare earth extraction organic phase saponification by using alkaline earth metal in bastnaesite concentrate |
-
2020
- 2020-06-08 CN CN202010510766.XA patent/CN111559755B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN111559755A (en) | 2020-08-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101021454B1 (en) | Method for recovering rare metals in a zinc leaching process | |
| US6171564B1 (en) | Process for extraction of metal from an ore or concentrate containing nickel and/or cobalt | |
| CN111636002B (en) | Method for removing fluorine from rare earth chloride mixed solution obtained by acid-base combination treatment | |
| BG62180B1 (en) | Chloride assisted hydrometallurgical extraction of nickel and cobalt from sulphide ores | |
| CN111559755B (en) | Production method of low-calcium lanthanum carbonate | |
| JP2019508587A5 (en) | ||
| US6692709B2 (en) | Preparation and use of organic extractant for recovery of metal ions from aqueous solutions | |
| US3691038A (en) | Process for the recovery of zinc from zinc- and iron-containing materials | |
| AU2016315207B2 (en) | Scandium oxide manufacturing method | |
| KR20120083529A (en) | Method for the removal of chloride from zinc sulphate solution | |
| EP1020537B1 (en) | Separation and concentration method for recovering gallium and indium from solutions by jarosite precipitation | |
| US3189407A (en) | Method of recovering lithium from lepidolite | |
| CN111748702B (en) | Method for preparing vanadium oxide and circulating sodium and ammonium by using vanadium solution | |
| CN107099672B (en) | The recovery method of the fume from steel making containing zinc | |
| CN111394599A (en) | Method for recovering rare earth from iron thorium slag in bastnaesite acid leaching process | |
| US4071422A (en) | Process for concentrating and recovering gallium | |
| US2647831A (en) | Preparation of pure copper metal from nonferrous metal-bearing scrap | |
| CN115927884A (en) | Defluorination method for rare earth ore leaching solution | |
| CA1136086A (en) | Electrolytic extraction of gallium from alkali metal aluminate including two-stage carbonatation | |
| CN116287682A (en) | Method for removing fluorine from rare earth concentrate | |
| JP2004531643A (en) | Method for removing calcium from a sulfate solution in a zinc process | |
| US1377822A (en) | Treatment of iron ores | |
| JPH07188793A (en) | Method for recovering valuable metal and calcium fluoride from waste liquid of pickling stage | |
| US1514153A (en) | Metallurgical process | |
| US2796342A (en) | Process for recovering copper by chemical precipitation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |